CN101443919B

CN101443919B - Method for forming absorber layer, precursor material for forming absorber layer and solar cell

Info

Publication number: CN101443919B
Application number: CN200780014617.7A
Authority: CN
Inventors: 耶罗恩·K·J·范杜伦; 克雷格·R·莱德赫尔姆; 马修·R·鲁滨逊
Original assignee: Individual
Current assignee: Individual
Priority date: 2006-02-23
Filing date: 2007-02-23
Publication date: 2014-03-05
Anticipated expiration: 2027-02-23
Also published as: EP1997150A2; CN101443919A; JP2013033987A; WO2007101138A2; JP2009528682A; CN103824896A; WO2007101138A9; WO2007101138A3

Abstract

Methods and devices are provided for transforming non-planar or planar precursor materials in an appropriate vehicle under the appropriate conditions to create dispersions of planar particles with stoichiometric ratios of elements equal to that of the feedstock or precursor materials, even after selective forces settling. In particular, planar particles disperse more easily, form much denser coatings (or form coatings with more interparticle contact area), and anneal into fused, dense films at a lower temperature and/or time than their counterparts made from spherical nanoparticles. These planar particles may be nanoflakes that have a high aspect ratio. The resulting dense films formed from nanoflakes are particularly useful in forming photovoltaic devices. In one embodiment, at least one set of the particles in the ink may be inter-metallic flake particles (microflake or nanoflake) containing at least one group IB-IIIA inter-metallic alloy phase.

Description

Form method, the precursor material that is used to form absorbed layer and the solar cell of absorbed layer

Invention field

Relate generally to semiconductor film of the present invention, relates more specifically to the manufacture of the solar cell of the semiconductor film of use based on IB-IIIA-VIA compound.

Background of invention

Solar cell and solar energy module are electricity by sunlight conversion.These electronic devices use traditionally silicon (Si) as light absorption semi-conducting material with relatively costly production technology manufacture.For making solar cell feasible more economically, developed following solar cell device structure: this structure can be utilized film at an easy rate, light absorption semi-conducting material for example copper indium gallium sulphur for diselenide, Cu (In, Ga) (S, Se) ₂, also referred to as CI (G) S (S).This class solar cell has the p-type absorbed layer being clipped between backplate layer and N-shaped knot pairing layer conventionally.Backplate layer is usually Mo, and knot pairing is usually CdS.On knot pairing layer, form for example zinc oxide (ZnO of transparent conductive oxide (TCO) _x), conventionally used as transparency electrode.The verified power conversion efficiency having over 19% of CIS based solar battery.

Cost effectively builds large area CIGS based solar battery or the challenge of module Zhong center is, within the element of cigs layer must be in narrow stoichiometric proportion on the nanometer of all three dimensions, be situated between sight and macro length yardstick, so that the battery or the module that produce have high efficiency.Yet use traditional vacuum-based depositing operation to be difficult to realize accurate stoichiometric composition in relatively large Substrate Area.For example, by sputter or evaporation, be difficult to deposition and contain compound and/or the alloy more than a kind of element.These two kinds of technology depend on the deposition process that is subject to sight line and the restriction of limited area sources, trend towards producing bad surface coverage.Sight line track and limited area sources can produce the non-homogeneous distributed in three dimensions of element and/or in large area, produce bad film thickness uniformity in all three dimensions.These heterogeneities can occur in nanometer, be situated between sight and/or macro-scale.This type of heterogeneity also changes the local stoichiometric condition ratio of absorbed layer, reduces the potential power conversion efficiency of completed cell or module.

Developed the alternative method of traditional vacuum base deposition technique.Particularly, using antivacuum semiconductor printing technology in flexible substrate, to prepare solar cell provides the height cost of conventional vacuum moulding machine solar cell effectively to substitute.For example, T.Arita and colleague thereof [20thIEEE PV Specialists Conference, 1988, the 1650th page] antivacuum screen printing technique described, this technology comprise with the ratio of components of 1:1:2, pure Cu, In and Se powder are mixed and grind and form can silk screen printing thickener, this thickener of silk screen printing on substrate, and this film of sintering is to form compound layer.They report, although they start with simple substance Cu, In and Se powder, after grinding steps, thickener contains Cu-In-Se ₂phase.Yet the solar cell of being manufactured by sinter layer has low-down efficiency, because the structure of these absorbents and electronic property are poor.

A.Vervaet etc. have also reported the silk screen printing Cu-In-Se that is deposited as film ₂[9thEuropean Communities PV Solar Energy Conference, 1989, the 480 pages], wherein by the Cu-In-Se of micron-scale ₂powder makes thickener that can silk screen printing for preparation together with the Se of micron-scale powder.The formed layer of the at high temperature antivacuum silk screen printing of sintering.The difficulty of this method is to find to be suitable for fine and close Cu-In-Se ₂film formed flux.The solar cell of making even so has bad conversion efficiency, but manufacture solar cell by printing and other antivacuum technology, remains promising.

In described field and certainly, in the antivacuum precursor of CIGS field, there is a kind of general idea, be that best dispersion and coating contain spheric granules and with regard to dispersion stability and film are filled, particularly when relating to nano particle, any other shape is so not desirable.Therefore, dispersion chemistry man and coating engineer for technique and theory relate to spheric granules.Due to the antivacuum precursor of CIGS, especially comprise simple metal those precursors in the high density of metal used, the very little size of instructions for use of spheric granules is to obtain the medium fully disperseing.So requiring every kind of component to have similar size, this keeps the stoichiometric proportion of expectation, because otherwise first sedimentation of large particle.In addition, spherical is considered to can be used for realizing the high bulk density based on filler cells/volume, even but under high density, spheroid is also only in point of contact contact, and this represents the mark of surface area between very little particle.In addition,, if expect that in produced film good atom mixes, expect that the flocculation of minimum degree is assembled to reduce.

Due to the problems referred to above, the such little spherical nanoparticle that many expert's desired size of antivacuum precursor CIGS circle can reach for them.Although the use of traditional spheroidal nano particle remains promising, but leave many basic challenges, for example, with high yield and low cost (especially by CIGS precursor material), obtain the difficult of enough little spherical nanoparticle aspect or reproducibly obtain the difficulty of high quality film aspect.In addition, between spheric granules contact point place compared with surface area between granule, may hinder the fast processing of these particles because kinetics depends on intergranular surface area Exposure in many aspects.

Summary of the invention

Embodiment of the present invention solve at least some above-mentioned shortcomings.The invention provides the use of aspherical particle in the formation of high-quality precursor layer that is processed into dense film.The dense film producing can be useful in multiple industry and application, comprising being still not limited to the manufacture of photovoltaic device and solar cell.More specifically, the present invention is applied to the formation of precursor layer for thin-film solar cells especially.The preparation of the coating that the invention provides dispersion more effective and that simplify and produce.Be to be understood that the present invention can generally be applied to relate to any technique from dispersion deposition materials.At least some in these and other objects as herein described will be met by each embodiment of the present invention.

In one embodiment of the present invention, a kind of method that changes under proper condition on-plane surface and/or plane precursor metal in suitable carrier is provided, though with produce after selectivity sedimentation element chemistry metering than also with the dispersion of the plane particle equating in charging or precursor metal.Especially, have been found that plane particle as herein described is easy to disperse, but form much fine and close coating and there is the made coating of the spherical nanoparticle of similar composition different shape substantially compare low temperature and/or the film forming of annealing under the less time with them.In one embodiment of the present invention, stabilising dispersions is to keep disperseing to continue to be enough to make substrate to obtain the dispersion of a period of time of coating.In one embodiment, this may relate to stirring and keeps particle to be dispersed in dispersion.In other embodiments, but this may relate to sedimentation can be by the dispersion stirring and/or other method is disperseed again while being carved in use.

In another embodiment of the present invention, a kind of method that comprises preparation particle ink is provided, wherein all particle is all nano flake (nanoflake) substantially.In one embodiment, in all particles, at least about 95% (in the total weight of all particles), be nano flake.In one embodiment, in all particles, at least about 99% (in the total weight of all particles), be nano flake.In one embodiment, all particles are nano flakes.In another embodiment, all particles are micron thin slice and/or nano flake.Substantially each nano flake contains at least one from the element of IB, IIIA and/or VIA family, and the total amount of the IB comprising in wherein said ink, IIIA and/or VIA family element makes this ink at least for IBHe IIIA family element, have element chemistry metering ratio expectation or that approach expectation.Described method comprises with this ink coats substrate to form precursor layer and to process this precursor layer to form dense film in appropriate atmosphere.Described dense film can be for the formation of the semiconductor absorber of photovoltaic device.This film can consist of the fusing form of the precursor layer that comprises a plurality of non-molten individual particles that contain.

In another embodiment of the present invention, a kind of material that comprises a plurality of nano flakes is provided, the material of described a plurality of nano flakes forms and contains at least one from the element of IB, IIIA and/or VIA family.By grinding or pulverize the precursor granules that consists of feature with precursor, prepare described nano flake, this precursor forms ductility (the better ductility that provides enough, see that patent is below) to form flat shape from the original shape of on-plane surface and/or plane when grinding or pulverize, and the total amount of the IB, the IIIA that wherein comprise in the precursor granules merging and/or VIA family element at least for IBHe IIIA family element, be in element chemistry metering expectation or that approach expectation than under.In one embodiment, plane be included in two dimensions wide in all other dimensions those situations of thin particle.Grinding can make substantially all precursor granules be transformed into nano flake.As selection, grind and to make at least 50% precursor granules be transformed into nano flake.Grinding can carry out preparing anaerobic nano flake in oxygen-free atmosphere.Grinding can carry out preparing anaerobic nano flake in inert gas environment.These aspherical particles can be the nano flakes that full-size (thickness and/or length and/or width) is greater than about 20nm, because tend to than this less size the solar cell that generation efficiency is lower.Grinding can also be allowed and grind the particle consisting of low melting material through cold quenching and carrying out at the temperature lower than room temperature.In other embodiments, grinding can at room temperature be carried out.As selection, grinding can carry out obtaining the material ductility of expectation at the temperature higher than room temperature.In one embodiment of the present invention, the material of feed particles composition preferably demonstrates and makes nonplanar feed particles under proper temperature, be configured as the ductility of the nano flake of plane substantially.In one embodiment, described nano flake has at least one smooth surface substantially.

In another embodiment of the present invention, a kind of solar cell is provided, and it comprises substrate, the backplate forming on described substrate, the p-type semiconductive thin film forming in described backplate, formation to form the N-shaped semiconductive thin film of pn knot and the transparency electrode forming on described N-shaped semiconductive thin film together with described p-type semiconductive thin film.Described p-type semiconductive thin film is produced by the formed dense film of a plurality of nano flakes by processing, the material of described nano flake forms and contains at least one from the element of IB, IIIA and/or VIA family, and the film that wherein produced has 26% or less voidage.In one embodiment, this numerical value can be filled the free volume of spheroid so that voidage reduces to minimum based on different-diameter.In another embodiment of the present invention, described dense film has approximately 30% or less voidage.In other embodiments, voidage is approximately 20% or less.In other embodiments, voidage is approximately 10% or less.

In another embodiment of the present invention, provide a kind of method by use with the granulated film forming of special properties.Described character can distribute based on size, shape, composition and form between particle.As limiting examples, described particle can be the nano flake within the scope of desired size.In nano flake, form can comprise unbodied particle, crystalline particle, than the particle of amorphous more crystalline state and than the more unbodied particle of crystalline state.Described character can also be based on forming between particle and form distribution.In one embodiment of the present invention, be to be understood that the form that produced thin slice has is that described thin slice is compared less crystalline state with the feed material that forms this thin slice.Thin slice be have at least one substantially flat surfaces particle and also can comprise nano flake and/or micron thin slice.

In another embodiment of the present invention, described method comprises preparation particle ink, wherein approximately 50% or more particle (in the total weight of all particles) be contain separately at least one from the element of IB, IIIA and/or VIA family and there is the thin slice of aspheric flat shape, the total amount of the IB comprising in wherein said ink, IIIA and/or VIA family element makes this ink have the element chemistry metering ratio of expectation.In another embodiment, the numbers of particles that term " 50% or more " can be based on total number of particles in relatively described ink.In another embodiment, at least about 75% or more particle (by weight or by number) be nano flake.Described method comprises with this ink coats substrate to form precursor layer and to process this precursor layer to form film under suitable process conditions.Described film can be for the formation of the semiconductor absorber of photovoltaic device.Be to be understood that suitable treatment conditions can include, but are not limited to atmosphere composition, pressure and/or temperature.In one embodiment, all particle is the thin slice with aspheric flat shape substantially.In one embodiment, in all particles, at least about 95% (in all particle weight that merge), be thin slice.In another embodiment, at least 99% in all particles (in all particle weight that merge) are thin slices.Described thin slice can be comprised of nano flake.In other embodiments, described thin slice can be comprised of micron thin slice and nano flake.

The flat shape that is to be understood that described nano flake can provide many advantages.As limiting examples, flat shape can produce larger surface area contact between adjacent nano flake, this compares the film made with the precursor layer of ink that uses spherical nanoparticle, wherein this nano particle has that substantially similar material forms and this ink other side is substantially identical with ink of the present invention, and dense film forms under lower temperature and/or short period.The flat shape of described nano flake also can produce larger surface area contact between adjacent nano flake, this make with use other side substantially the made film of the precursor layer of the spherical nanoparticle ink identical with ink of the present invention compare, this dense film forms under the annealing temperature of low at least 50 ℃.

The flat shape of described nano flake can produce with respect to adjacent spherical nanoparticle larger surface area contact between adjacent nano flake, and the prepared film of precursor layer forming with ink of the present invention is thus compared the atom mixing that promotes raising.Compare with using the other side prepared film of precursor layer that the spherical nanoparticle ink of the same composition identical with ink of the present invention forms substantially, the flat shape of described nano flake produces higher bulk density in dense film.

The flat shape of described nano flake can also produce the bulk density at least about 76% in precursor layer.The flat shape of this nano flake can produce at least 80% bulk density in precursor layer.The flat shape of this nano flake can produce at least 90% bulk density in precursor layer.The flat shape of this nano flake can produce at least 95% bulk density in precursor layer.Bulk density can be mass/volume, solid/volume or non-void/volume.

The flat shape of described nano flake produces the crystallite dimension at least about 1 μ m in the semiconductor absorber of photovoltaic device.The flat shape of this nano flake can produce at least one dimension the crystallite dimension at least about 2.0 μ m in the semiconductor absorber of photovoltaic device.In other embodiments, described nano flake produces at least one dimension the crystallite dimension at least about 1.0 μ m in the semiconductor absorber of photovoltaic device.In other embodiments, described nano flake produces at least one dimension the crystallite dimension at least about 0.5 μ m in the semiconductor absorber of photovoltaic device.The flat shape of this nano flake can produce the wide crystallite dimension at least about 0.3 μ m in the semiconductor absorber of photovoltaic device.In other embodiments, when one or more in following copper selenide, indium selenide or gallium selenide of described nano flake form, the flat shape of nano flake can produce the wide crystallite dimension at least about 0.3 μ m in the semiconductor absorber of photovoltaic device.

The flat shape of described nano flake provides the material character of avoiding the quick and/or preferential sedimentation of particle when forming precursor layer.The flat shape of this nano flake provides the material character of avoiding having the quick and/or preferential sedimentation of nano flake that different materials forms when forming precursor layer.The flat shape of this nano flake provides the material character of avoiding having the quick and/or preferential sedimentation of the nano flake of varying particle size when forming precursor layer.The flat shape of this nano flake provides to be avoided the material character of nano flake gathering and makes thus the fine dispersion soln of nano flake become possibility in ink.

The flat shape of described nano flake provides the material character of the less desirable gathering of nano flake of avoiding particular types in ink and makes thus the dispersed solution of nano flake become possibility.The flat shape of this nano flake provides the material character of the less desirable gathering of nano flake of avoiding certain material composition in ink and makes thus the dispersed solution of nano flake become possibility.The flat shape of this nano flake provides the material character of the nano flake gathering of avoiding specific phase separation in the precursor layer producing at ink.This nano flake has between the nano flake that reduces in ink and carrier fluid the capillary material character on interface to improve dispersion quality.

In one embodiment of the present invention, can be by utilizing low-molecular-weight dispersant to prepare ink, due to the favourable interaction of the flat shape of this dispersant and nano flake, comprising of it is effective.Can be by utilizing carrier fluid without dispersant preparation ink.The flat shape of described nano flake provides with the other side prepared film of precursor layer that the spherical nanoparticle ink identical with ink of the present invention forms substantially and compares and allow IIIA family material more homodisperse material character in whole dense film.In another embodiment, described nano flake can have random flat shape and/or random distribution of sizes.

Described nano flake can have non-random flat shape and/or non-random distribution of sizes.This nano flake can have length and/or the maximum transverse size that is less than about 500nm and is greater than about 20nm separately.This nano flake can have length and/or the maximum transverse size of the about 50nm of about 300nm-separately.Described nano flake can have about 100nm or less thickness separately.In other embodiments, the length of smooth nano flake is the about 1nm of about 500nm-.As a kind of limiting examples, nano flake can have length and/or the maximum transverse size of the about 10nm of about 300nm-.In other embodiments, nano flake can have the thickness of the about 20nm of about 200nm-.In another embodiment, these nano flakes can have the thickness of the about 10nm of about 100nm-.In one embodiment, these nano flakes can have the thickness of the about 20nm of about 200nm-.Nano flake can have the thickness that is less than about 50nm separately.Nano flake can have the thickness that is less than about 20nm.Nano flake can have at least about 5 or larger aspect ratio.Nano flake can have at least about 10 or larger aspect ratio.Nano flake has at least about 15 or larger aspect ratio.

Described nano flake can be oxygen-free.This nano flake can be single metal.This nano flake can ShiIB, IIIA family element alloy.This nano flake can ShiIB, IIIA family element bianry alloy.This nano flake can ShiIB, IIIA family element ternary alloy three-partalloy.This nano flake can be the quaternary alloy of IB, IIIA and/or VIA family element.This nano flake can ShiIB family-chalcogenide particle and/or IIIA family-chalcogenide particle.In addition, described particle can be the particle that is substantially free of oxygen, and it can comprise and contains those particles that are less than about 1wt% oxygen.Other embodiments can be used has the material that is less than about 5wt% oxygen.Other embodiments can be used has the material that is less than about 3wt% oxygen.Other embodiments can be used has the material that is less than about 2wt% oxygen.Other embodiments can be used has the material that is less than about 0.5wt% oxygen.Other embodiments can be used has the material that is less than about 0.1wt% oxygen.

In one embodiment of the present invention, described coating step at room temperature carries out.This coating step can carry out under atmospheric pressure.Described method may further include selenium film is deposited in dense film.This treatment step can be by promoting by following at least one heat treatment technics: laser beam is processed, is exposed to pulse heat or by the heating of IR lamp and/or similar or relevant method.Described processing can comprise by precursor layer be heated to be greater than approximately 375 ℃ but the temperature that are less than substrate fusion temperature continue to be less than the time of 15 minutes.This processing can comprise by precursor layer be heated to be greater than approximately 375 ℃ but the temperature that is less than substrate fusion temperature continues 1 minute or time still less.

In another embodiment of the present invention, but processing can comprise and precursor layer is heated to annealing temperature is less than that substrate fusion temperature continues 1 minute or the time still less.Described appropriate atmosphere can comprise nitrogen atmosphere.In another embodiment of the present invention, described appropriate atmosphere comprises blanket of nitrogen.In another embodiment, described appropriate atmosphere comprises carbon monoxide atmosphere.This appropriate atmosphere can form by having the atmosphere that is less than approximately 10% hydrogen.This appropriate atmosphere can be comprised of the atmosphere containing selenium.This appropriate atmosphere can be comprised of the atmosphere of non-oxygen chalcogen.In one embodiment of the present invention, described appropriate atmosphere can be comprised of selenium atmosphere, and this selenium atmosphere provides the dividing potential drop of the selenium steam pressure being more than or equal in precursor layer.In another embodiment, described appropriate atmosphere can be comprised of the non-oxygen atmosphere that contains chalcogen steam, this chalcogen steam divides and depresses so that the loss of precursor layer chalcogen minimizes at the chalcogen that is more than or equal to the chalcogen vapour pressure under treatment temperature and processing pressure, and wherein this processing pressure is non-vacuum pressure.In another embodiment, chalcogen atmosphere can be used together with one or more binary chalcogenides (arbitrary shape or form), its chalcogen that is in the chalcogen vapour pressure being more than or equal under treatment temperature and processing pressure divides to be depressed so that the loss of precursor layer chalcogen minimizes, and wherein optionally this processing pressure is non-vacuum pressure.

In another embodiment of the present invention, before the step of preparation ink, comprise the step of manufacturing nano flake.Described manufacturing step comprises provides the feed particles that contains at least one IB, IIIA and/or VIA family element, the composition that wherein each feed particles has enough ductility to be substantially to form flat shape from on-plane surface original shape, and grinds this feed particles at least to make the thickness of each particle be reduced to less than 100nm.Grinding steps can carry out manufacturing the nano flake of anaerobic substantially in oxygen-free atmosphere.Described substrate can be rigid substrate.Described substrate can be flexible substrate.This substrate can be aluminum substrates or polymer substrate, and it is to use commercially available net to be coated with the flexible substrate in reel-to-reel (roll-to-roll) method (continuous or segmentation) of system.Rigid substrate can form by being selected from least one following material: any single or multiple combination of glass, solar energy glass, low iron glass, green glass, soda-lime glass, steel, stainless steel, aluminium, polymer, pottery, metallic plate, metallized ceramic plate, metallized polymeric plate, metallized glass plate and/or above-mentioned material.Described substrate can be under different temperatures with precursor layer in processing procedure.This can melt or the unsettled material that becomes so that substrate can be used under the treatment temperature of precursor layer.Optionally, this can relate to positive cooling this substrate in processing procedure.

In another embodiment of the present invention, a kind of method of preparing particle ink is provided, wherein most of particle is contain separately at least one from the element of IB, IIIA and/or VIA family and have the nano flake of aspheric flat shape, and the total amount of the IB comprising in wherein said ink, IIIA and/or VIA family element makes this ink have the element chemistry metering ratio of expectation.Described method can comprise with this ink coats substrate to form precursor layer and to process this precursor layer to be formed for the dense film of the semiconductor absorber growth of photovoltaic device.In one embodiment, at least 60% particle (by weight or by number) is nano flake.In another embodiment, at least 70% particle (by weight or by number) is nano flake.In another embodiment, at least 80% particle (by weight or by number) is nano flake.In another embodiment, at least 90% particle (by weight or by number) is nano flake.In another embodiment, at least 95% particle (by weight or by number) is nano flake.

In another embodiment, liquid ink can be manufactured with one or more liquid metals.For example, ink can by the liquid state of gallium and/or indium and/or molten mixture is initial be manufactured.Then copper nano particles can be joined in mixture, then this mixture can be used as ink/thickener.Copper nano particles can be buied.As selection, can regulate the temperature (for example cooling) of Cu-Ga-In mixture until solid formation.Can be at this temperature by solid abrasive for example, until there is little nano particle (being less than 5nm).Can by for example before annealing, during or be exposed to afterwards under selenium steam and selenium joined in ink and/or the formed film of this ink.

In another embodiment of the present invention, a kind of technique of the dispersion that comprises the solid-state and/or liquid particles of preparation is described, this particle comprises IB and/or IIIA family element and at least one VIA family element optionally.Described technique comprise this dispersion of deposition on substrate to form layer and make this layer of reaction to form film in appropriate atmosphere on substrate.In this technique, at least one group of particle is the intermetallic particle that contains at least one IB-IIIA family intermetallic phase.Any above-mentioned embodiment can be used the thin slice that contains intermetallic phase as described herein (micron thin slice or nano flake).

In another embodiment of the present invention, a kind of composition is provided, it comprises a plurality of IB of containing and/or IIIA family element and the particle of at least one VIA family element optionally.At least one group of particle contains at least one IB-IIIA family intermetallic phase.

In another embodiment of the present invention, described method can comprise that preparation comprises IB and/or IIIA family element and the dispersion of the particle of at least one VIA family element optionally.The method can comprise this dispersion of deposition on substrate to form layer and make this layer of reaction to form film in appropriate atmosphere on substrate.At least one group of IB-IIIA family alloy phase that particle contains PinIB family.The contribution of the particle of ，Pin IB family is less than the IB family element existing in all particles of about 50mol% in some embodiments.The IB-IIIA family alloy phase particle of described PinIB family can be a kind of unique source in IIIA family element.The IB-IIIA family alloy phase particle of described PinIB family can contain intermetallic phase and can be a kind of unique source in IIIA family element.The IB-IIIA family alloy phase particle of described PinIB family can contain intermetallic phase and be a kind of unique source in IIIA family element.The IB-IIIA family alloy phase particle of described PinIB family can be Cu ₁in ₂particle and be unique source of the indium in material.

Be to be understood that any in aforementioned films and/or final compound can comprise IB-IIIA-VIA compounds of group.Described reactions steps can be included in appropriate atmosphere and heat described layer.Described deposition step can comprise uses dispersion coated substrate.At least one group of particle in this dispersion can be nanometer bead form.At least one group of particle in this dispersion can be nanometer bead form and contain at least one IIIA family element.At least one group of particle in this dispersion can be the nanometer bead form of the IIIA family element that comprises simple substance form.In some embodiments of the present invention, described intermetallic phase is not end border solid solution phase.In some embodiments of the present invention, described intermetallic phase is not solid solution phase.Described intermetallic particle can be contributed the IB family element existing in all particles that is less than about 50mol%.Described intermetallic particle can be contributed the IIIA family element existing in all particles that is less than about 50mol%.Described intermetallic particle can be contributed the IB family element that is less than about 50mol% and the IIIA family element that is less than about 50mol% in the dispersion on being deposited on substrate.Described intermetallic particle can the dispersion on being deposited on substrate in contribution be less than the IB family element of about 50mol% and more than the IIIA family element of about 50mol%.Described intermetallic particle can be contributed the IB family element and the IIIA family element that is less than about 50mol% more than about 50mol% in the dispersion on being deposited on substrate.The integral molar quantity of the element of aforementioned any molar percentage in can all particles based on existing in described dispersion.In some embodiments, at least some particles have platelet (platelet) shape.In some embodiments, to have sheet crystalline for most of particle.In other embodiments, substantially all particle to have sheet crystalline.

For any in previous embodiments, the intermetallic material of using under the present invention is binary material.This intermetallic material can be ternary material.This intermetallic material can comprise Cu ₁in ₂.This intermetallic material can comprise Cu ₁in ₂the composition of δ phase.This intermetallic material can comprise Cu ₁in ₂the phase that limits of δ phase and Cu16In9 between composition.This intermetallic material can comprise Cu ₁ga ₂.This intermetallic material can comprise Cu ₁ga ₂intermediate solid solution.This intermetallic material can comprise Cu ₆₈ga ₃₈.This intermetallic material can comprise Cu ₇₀ga ₃₀.This intermetallic material can comprise Cu ₇₅ga ₂₅.This intermetallic material can comprise end border solid solution and the Cu-Ga composition that is only second to the phase between its intermediate solid solution.The Cu-Ga that this intermetallic material can comprise γ 1 phase forms (the about 39.8wt%Ga of about 31.8-).The Cu-Ga that this intermetallic material can comprise γ 2 phases forms (the about 39.9wt%Ga of about 36.0-).The Cu-Ga that this intermetallic material can comprise γ 3 phases forms (the about 44.9wt%Ga of about 39.7-).The Cu-Ga that this intermetallic material can comprise the phase between γ 2 and γ 3 forms.This intermetallic material can comprise the Cu-Ga composition of the phase between end border solid solution and γ 1.The Cu-Ga that this intermetallic material can comprise θ phase forms (the about 68.7wt%Ga of about 66.7-).This intermetallic material can comprise the Cu-Ga of rich Cu.Gallium can be used as IIIA family element and introduces with the form of suspension of nanometer bead.Gallium nanometer bead can form by produce the emulsion of liquid gallium in solution.Gallium nanometer bead can be by producing in the following quenching of room temperature.

According to any the technique in previous embodiments of the present invention, can comprise by stirring, mechanical device, calutron, Vltrasonic device and/or add dispersant and/or emulsifying agent keeps or improves the dispersion of liquid gallium in solution.This technique can comprise that adding one or more is selected from the mixture of following simple substance particle: aluminium, tellurium or sulphur.Described appropriate atmosphere can contain selenium, sulphur, tellurium, H ₂, CO, H ₂se, H ₂s, Ar, N ₂or its combination or mixture.This appropriate atmosphere can contain following at least one: H ₂, CO, Ar and N ₂.One class or multiclass particle can be doped with one or more inorganic material.Optionally, the particle doped inorganic material that has one or more to be selected from aluminium (Al), sulphur (S), sodium (Na), potassium (K) or lithium (Li) of a class or multiclass.

Optionally, embodiment of the present invention can comprise not having and can form immediately the copper source of alloy with In and/or Ga.A kind of selection can be the copper that uses (slightly) oxidation.Another kind of selection can be to use CuxSey.Attention, for the copper approach of (slightly) oxidation, may need reduction step.Substantially, if use elemental copper in liquid In and/or Ga, the speed of the process between ink preparation and coating should enough will produce the size of coating in uneven thickness so that particle grows into.

Be to be understood that temperature range can be substrate temperature scope because substrate normally should more than fusing point not heat at it unique one.The material of minimum fusing point in this applicable substrate, i.e. Al and other suitable substrate.

With reference to remainder and the accompanying drawing of specification, to more understandings of characteristic of the present invention and advantage, can become obvious.

Accompanying drawing explanation

Figure 1A-1D is the schematic sectional view that explanation is manufactured according to the film of one embodiment of this invention.

Fig. 2 A and 2B are according to the enlarged side view of the nano flake of one embodiment of this invention and amplification plan view.

Fig. 2 C is according to the amplification plan view of the micron thin slice of one embodiment of this invention.

Fig. 3 shows according to the schematic diagram of the grinding system of one embodiment of this invention.

Fig. 4 shows according to the schematic diagram of the reel-to-reel manufacturing system of one embodiment of this invention.

Fig. 5 shows according to the sectional view of the photovoltaic device of one embodiment of this invention.

Fig. 6 shows according to the flow chart of the method for one embodiment of this invention.

Fig. 7 shows according to the module with a plurality of photovoltaic devices of one embodiment of this invention.

Fig. 8 A-8C shows the schematic diagram of the plane particle using together with spheric granules according to one embodiment of this invention.

Fig. 9 A-9D shows the schematic diagram of the discontinuous printed layers in the chalcogen source of using together with plane particle according to one embodiment of this invention.

Fig. 9 E shows according to the particle with chalcogen shell of one embodiment of this invention.

Figure 10 A-10C shows according to the use of the chalcogenide plane particle of one embodiment of this invention.

Figure 11 A-11C shows according to the nucleating layer of one embodiment of this invention.

Figure 12 A-12C shows and can be used for being prepared into by thermal gradient the schematic diagram of the device of stratum nucleare.

Figure 13 A-13F shows according to the use of the chemical gradient of one embodiment of this invention.

Figure 14 shows according to reel-to-reel system of the present invention.

Figure 15 A shows the schematic diagram that uses the system of chalcogen steam ambient according to one embodiment of this invention.

Figure 15 B shows the schematic diagram that uses the system of chalcogen steam ambient according to one embodiment of this invention.

Figure 15 C shows the schematic diagram that uses the system of chalcogen steam ambient according to one embodiment of this invention.

Figure 16 A shows a kind of embodiment of the system of using together with rigid substrate according to one embodiment of this invention.

Figure 16 B shows a kind of embodiment of the system of using together with rigid substrate according to one embodiment of this invention.

Figure 17-19 demonstration forms film according to embodiment of the present invention by intermetallic material.

Figure 20 shows according to embodiment of the present invention, with a plurality of layers, to form the sectional view of film.

Figure 21 shows the feed material of processing according to embodiment of the present invention.

Figure 22 A and 22B show according to the feature of the thin slice of embodiment of the present invention.

Figure 23 A and 23B show the feature of platelet.

Embodiment

Be to be understood that general description and following detailed description are above all exemplary and explanat and are not the restriction to claimed invention.Can notice, during for specification and appended claims, singulative " ", " a kind of " and " being somebody's turn to do " comprise plural object, unless context is separately indicated clearly.Therefore, for example, mention that " a kind of material " can comprise the mixture of material, mention that " a kind of compound " can comprise multiple compounds, etc.Therefore the list of references of quoting herein is all incorporated to by reference, unless reached the degree that they conflict with the instruction of clearly setting forth in this specification.

In this specification and following claim book, will be with reference to some terms, it should be defined as has following meanings:

" optional " or " optionally " means that described situation can occur or can not occur afterwards, so this description comprises the situation of this situation generation and the situation that this situation does not occur.For example, if device optionally comprises the feature of barrier film, this means that this barrier film feature can exist or can not exist, and, therefore, this description had not only comprised that wherein device had the structure of barrier film feature but also comprises the wherein non-existent structure of barrier film feature.

According to embodiment of the present invention, by first preparing, contain separately at least one from the ink of the aspherical particle of IB, IIIA and/or VIA family element, with this ink coats substrate, to form precursor layer, and heat this precursor layer to form dense film, can manufacture the active layer of photovoltaic device.Optionally, be to be understood that in some embodiments, may do not need the densification of precursor layer, if particularly precursor material be anaerobic and/or anaerobic substantially.Therefore,, if described particle is processed and anaerobic without air, can optionally skip over heating steps.In a preferred embodiment, described aspherical particle is the shape nano flake of plane substantially.Can in appropriate atmosphere, process dense film to form IB-IIIA-VIA compounds of group.The IB-IIIA-VIA compounds of group producing is formula CuIn preferably _(1-x)ga _xs _{2 (1-y)}se _2ycu, In, Ga and selenium (Se) or the compound of sulphur S, wherein 0≤x≤1 and 0≤y≤1.Be to be understood that in addition produced IB-IIIA-VIA compounds of group can be formula Cu _zin _(1-x)ga _xs _{2 (1-y)}se _2ycu, In, Ga and selenium (Se) or the compound of sulphur S, wherein 0.5≤z≤1.5,0≤x≤1.0 and 0≤y≤1.0.

Be to be understood that IB, IIIA HeVIA family element beyond Cu, In, Ga, Se and S also can be included in the explanation of IB-IIIA-VIA material as herein described, and hyphen ("-" for example, in Cu-Se or Cu-In-Se) use do not represent compound, but show the mixture that coexists of the element that connected by this hyphen.Will also be understood that IB family is sometimes called as 11Zu， IIIA family and is sometimes called as 13Zu，Er VIA family and is sometimes called as 16 families.In addition, VIA (16) family element is called as chalcogen sometimes.In embodiments of the invention, in the situation that some elements can combinations with one another or are replaced each other, for example In and Ga, or Se, and S, in this area, commonly in one group of bracket, comprise the element that those can combine or exchange, for example (In, Ga) or (Se, S).Description in this specification adopts this convenient measure sometimes.Finally, also for convenience's sake, the chemical symbol of conventionally accepting with it is discussed these elements.The IB family element that is applicable to the inventive method comprises copper (Cu), silver (Ag) and gold (Au).Preferably IB family element is copper (Cu).The IIIA family element that is applicable to the inventive method comprises gallium (Ga), indium (In), aluminium (Al) and thallium (Tl).Preferably IIIA family element is gallium (Ga) or indium (In).The VIA family element of paying close attention to comprises selenium (Se), sulphur (S) and tellurium (Te), and preferably VIA family element is Se and/or S.Be to be understood that and can also use above-mentioned any mixture, for example but be not limited to alloy, solid solution and compound.

Form the method for film

Referring now to Fig. 1, a kind of method that forms semiconductor film according to the present invention will be described.The present embodiment that is to be understood that invention forms semiconductor film by antivacuum technology.Yet other embodiment can form this film under vacuum environment, and use the present invention of aspherical particle to be not limited only to antivacuum paint-on technique.

As seen in Figure 1A, substrate 102 is provided, will form precursor layer 106 (seeing Figure 1B) thereon.As nonrestrictive example, substrate 102 can by metal for example aluminium make.In other embodiments, metal for example still can be not limited to stainless steel, molybdenum, titanium, copper, metallized plastic film or aforesaid combination as substrate 102.Substrate as an alternative includes, but are not limited to pottery, glass etc.Any these substrates can be the forms of paper tinsel, sheet material, volume etc. or its combination.According to the material of substrate 102, what come in handy is with contact layer 104, to cover the surface of substrate 102, thereby promote substrate 102 and need electrically contacting between absorbed layer formed thereon, thereby and/or the reactivity of restriction substrate 102 in subsequent step, and/or in order to promote more high-quality absorber growth.As limiting examples, when substrate 102 is made of aluminum, contact layer 104 can be but be not limited to molybdenum layer.With regard to current discussion, contact layer 104 can be regarded as to a part for substrate.Therefore,, if use contact layer 104, any discussion that forms or arrange a kind of material or material layer on substrate 102 is included in and on contact layer 104, arranges or form described material or layer.Optionally, in order to insulate or other object can also be used other material layer and still regard as a part for substrate 102 together with contact layer 104.Be to be understood that contact layer 104 can comprise more than one type or more than one discontinuous material layer.Optionally, some embodiments can be by following any one and/or combination for contact layer: copper, aluminium, chromium, molybdenum, vanadium etc. and/or iron-cobalt alloy.Optionally, can comprise that diffusion impervious layer 103 (showing with diplopia) and layer 103 can be conduction or nonconducting.As limiting examples, layer 103 can be in multiple material any composition, these materials include, but are not limited to chromium, vanadium, tungsten or compound for example nitride (comprising tantalum nitride, tungsten nitride, titanium nitride, silicon nitride, zirconium nitride and/or hafnium nitride), oxide (comprising Al203 or SiO2), carbide (comprising SiC) and/or aforesaid any single or Multiple Combination.Optionally, diffusion impervious layer 105 (showing with diplopia) can be in substrate 102 downside and by such as but be not limited to following material and form: chromium, vanadium, tungsten or compound be nitride (comprising tantalum nitride, tungsten nitride, titanium nitride, silicon nitride, zirconium nitride and/or hafnium nitride), oxide (comprising Al203 or SiO2), carbide (comprising SiC) and/or aforesaid any single or Multiple Combination for example.Can make layer 103 and/or 105 be applicable to using with together with any of embodiment described herein.

Referring now to Figure 1B, by using such as the dispersion coated substrate 102 that is still not limited to ink, on substrate 102, form precursor layer 106.As a kind of limiting examples, described ink can comprise the carrier fluid mixing with nano flake 108 and have the rheological characteristic that ink can be applied on substrate 102.In one embodiment, the present invention can use and mix with carrier and the dried powder of sonicated before applying.Optionally, ink can be prepared directly from grinder.In the situation that mixing a plurality of thin slice composition, product can be mixed by various grinders.This mixing can be carried out sonicated, but can use the stirring of other form and/or other grinder.But the ink that is used for forming precursor layer 106 for example can contain aspherical particle 108 be not limited to nano flake.Be to be understood that in addition this ink can be optionally used aspheric and spherical particle with any in various relative scales simultaneously.

Figure 1B comprises the close up view of the nano flake 108 in precursor layer 106, as seen in enlarged image.Nano flake has aspherical and substantially smooth at least simultaneously.The more detailed view of a kind of embodiment of nano flake 108 can find in Fig. 2 A and 2B.Nano flake can be defined as length and/or maximum transverse size to be about 500nm or less to have at least one particle of flat surfaces substantially, and this particle has approximately 2 or larger aspect ratio.In one embodiment, this length and/or maximum transverse size are the about 1nm of about 400nm-.In another embodiment, this length and/or maximum transverse size are the about 10nm of about 300nm-.In another embodiment, this length and/or maximum transverse size are the about 20nm of about 200nm-.In another embodiment, this length and/or maximum transverse size are the about 200nm of about 500nm-.In other embodiments, nano flake is that thickness is that the about 100nm of about 10-and length are the structure of the plane substantially of the about 500nm of about 20nm-.

Be to be understood that different types of nano flake 108 can be used for forming precursor layer 106.In a limiting examples, this nano flake is simple substance nano flake, namely only has the nano flake of single atomic species.Nano flake can be the single metallic particles of Cu, Ga, In or Se.Some ink can only have a kind of nano flake.Other ink can have the nano flake that two or more in the following areas can be different: material forms and/or other character is for example still not limited to shape, size, internal structure (centronucleus for example being surrounded by one or more shells), external skin (be at this moment more illustrative, can use for example wording of core-shell) etc.In one embodiment, the ink for precursor layer 106 can contain the nano flake that comprises one or more IB family elements and the nano flake that comprises one or more different IIIA family elements.Preferably, precursor layer (106) cupric, indium and gallium.In another embodiment, precursor layer 106 can be the layer of cupric, indium and the gallium of anaerobic.Optionally, the elemental ratio in precursor layer can be so that this layer forms CuIn when processing _xga _1-xcompound, 0≤x≤1 wherein.Those skilled in the art will recognize that other IB family element can replace Cu and other IIIA family element can replace In and Ga.Optionally, precursor can also contain Se, for example, be still not limited to Cu-In-Ga-Se sheet.If precursor is oxygen-free and do not need densification this is feasible.In other embodiments, precursor material can contain the nano flake of IB, IIIA HeVIA family element.In a limiting examples, precursor can contain Cu-In-Ga-Se nano flake, if form this nano flake and do not need film forming densification before without air, this can be particularly advantageous.

Optionally, the nano flake in ink 108 can be alloy nano thin slice.In a limiting examples, this nano flake can be for example Cu-In, In-Ga or Cu-Ga of binary alloy nano thin slice.As an alternative, this nano flake can ShiIB, IIIA family element the bianry alloy of bianry alloy ,IB, VIA family element and/or the bianry alloy of IIIA ,VIA family element.In other embodiments, this particle can be the ternary alloy three-partalloy of IB, IIIA and/or VIA family element.For example, this particle can be any above-mentioned element ternary alloy three-partalloy particle such as but be not limited to Cu-In-Ga.In other embodiments, ink can contain the particle as the quaternary alloy of IB, IIIA and/or VIA family element.Some embodiments can have quaternary or polynary nanometer thin slice.This ink can also combine different types of nano flake such as being still not limited to simple substance nano flake and alloy nano thin slice etc.In one embodiment, be used to form the nano flake of precursor layer 106 preferably oxygen-free except the amount that those inevitably exist as impurity.Optionally, this nano flake contains the oxygen that is less than about 0.1wt%.In other embodiments, nano flake contains the oxygen that is less than about 0.5wt%.In other embodiments, nano flake contains the oxygen that is less than about 1.0wt%.In another embodiment, nano flake contains the oxygen that is less than about 3.0wt%.In other embodiments, nano flake contains the oxygen that is less than about 5.0wt%.

Optionally, the nano flake 108 in ink can be chalcogenide particle, for example, be still not limited to IBZu Huo IIIA family selenides.In a limiting examples, this nano flake can be and one or more IB families (new style: the element IB family chalcogenide that for example copper (Cu), silver (Ag) and gold (Au) form 11 families).Example includes, but are not limited to Cu _xse _y, wherein x is that about 1-10 and y are about 1-10.In some embodiments of the present invention, x<y.As selection, some embodiments can have the selenides of richer selenium, for example, be still not limited to Cu ₁se _x(wherein x>1).This can provide the selenium of increase to originate, as submitted on February 23rd, 2006 and whole middle discuss such of U.S. Patent application 11/243,522 (attorney docket NSL-046) common transfer, common pending trial that is incorporated to by reference this paper.In another limiting examples, nano flake can be and one or more IIIA families (new style: the element IIIA family chalcogenide that for example aluminium (Al), indium (In), gallium (Ga) and thallium (Tl) form 16 families).Example comprises In _xse _yand Ga _xse _y, wherein x is that about 1-10 and y are about 1-10.Further, nano flake can be IB-IIIA family-chalcogenide compound of one or more IB family elements, one or more IIIA family elements and one or more chalcogens.Example comprises CuInGa-Se ₂.Other embodiments can with another VIA family element for example but the combination that is not limited to sulphur or multiple VIA family element for example sulphur and selenium the two replace selenides composition.

Be to be understood that for ink of the present invention and can comprise the chalcogenide nano flake more than a type.For example, some can comprise the nano flake from IB family-chalcogenide and IIIA family-chalcogenide.Can comprise from the nano flake with the different I B family-chalcogenide of different chemical metering ratio in addition.Can comprise from the nano flake with the different I IIA family-chalcogenide of different chemical metering ratio in addition.

Optionally, the nano flake in ink 108 can also be the particle of at least one solid solution.In a limiting examples, this nanometer powder can contain copper-gallium solid solution pellet, and at least one in indium particle, indium-gallium solid solution pellet, copper-indium solid solution pellet and copper particle.As selection, this nanometer powder can contain copper particle and indium-gallium solid solution pellet.

One of advantage of using nano flake base dispersion is, by forming the order of the thinner sublayer of precursor layer when merging, forms precursor layer, can change from top to bottom the concentration of element in precursor layer 106.Can deposition materials to form first, second layer or sublayer subsequently, and at least one appropriate atmosphere reaction to form the corresponding composition of active layer.In another embodiment, can when deposited seed layer, make this sublayer reaction.Forming each sublayer can change with the relative concentration of element of the nano flake of ink.Therefore, for example, the gallium concentration in absorbed layer can change with the degree of depth in absorbed layer.Precursor layer 106 (or selected components sublayer, if any) can form by the controlled overall with expectation stoichiometric proportion the precursor material deposition of configuration.About finding in submitting and be all incorporated to by reference for all objects U.S. Patent application 11/243,492 (attorney docket NSL-040) common transfer herein, common pending trial on October 3rd, 2005 by more details of a kind of method of sublayer order constituting layer.

Be to be understood that described film can be by dispersion, for example but be not limited to ink, thickener or coating made layer.Can the layer of dispersion be applied on substrate and anneal to form precursor layer 106.The anaerobic nano flake that for example can contain IBZu, IIIA family element by formation and mix these nano flakes and they are joined and prepare dispersion in carrier, this carrier can comprise carrier fluid (but be for example not limited to solvent) and any additive.

Conventionally, can for example, by by nano flake, together with (optionally), other some combination that is usually used in preparing the composition of ink is dispersed in the carrier that contains dispersant (surfactant or polymer) and forms ink.In such schemes more of the present invention, without dispersant or other additive preparation ink.Carrier fluid can be water-based (water base) or non-aqueous (organic) solvent.Other composition do not comprise dispersant, binding agent, emulsifying agent, defoamer, drier, solvent, filler, replenishers, thickener, film adjusting agent, antioxidant with limiting, flow and all flat agent, plasticizer and anticorrisive agent.Can under various combinations, add these compositions to improve film quality and to optimize the paintability of this nano flake dispersion.The alternative method of mixing nano flake and preparing dispersion by the nano flake of these mixing subsequently can be, prepare each independent type nano flake independent dispersion and also subsequently these dispersions are mixed.Should be appreciated that due to the flat shape of described nano flake and the favourable interaction of carrier fluid, some embodiments of described ink can be by utilizing carrier fluid and preparing without dispersant.

Can on substrate 102, by dispersion, form precursor layer 106 by any in the various paint-on techniques based on solution, these technology include, but are not limited to wet coating, spraying, spin coating, scraper applies, contact print, top charging reversal printing, bottom feed reversal printing, nozzle material-feeding reversal printing, intaglio printing, nick printing, the printing of reversion nick, comma directly prints (comma direct printing), roller coat, slit die extrusion covers, Meyer bar type applies, flanging directly applies (lip direct coating), two flanging directly apply, capillary applies, ink jet printing, jet deposition, jet deposition etc., and the combination of above-mentioned and/or correlation technique.No matter how are particle size or size, aforementioned content goes for any embodiment herein.

In some embodiments, can by extra chalcogen, alloying pellet or simple substance particle, for example micron or the chalcogen powder of submicron-scale be sneaked in the dispersion that contains nano flake to nano flake and extra chalcogen are deposited simultaneously.As an alternative can deposition containing before or after the dispersion of nano flake in the coating step based on solution independently by chalcogen powder deposition on substrate.In another embodiment, IIIA family element material for example still can be not limited to gallium drop mixes with thin slice.This is described more fully in submitting and be all incorporated to by reference U.S. Patent application 11/243,522 (attorney docket NSL-046) common transfer herein, common pending trial on February 23rd, 2006.This can produce extra play 107 (showing with diplopia in Fig. 1 C).Optionally, can add by following combination in any extra chalcogen: any chalcogen source that (1) can liquid deposition, for example sneak in precursor layer or conduct Se or S nanometer or micron-scale powder that independently layer deposits, (2) chalcogen (for example Se or S) evaporation, (3) H ₂se (H ₂s) atmosphere, (4) chalcogen (for example Se or S) atmosphere, (5) H ₂atmosphere, (6) Organic Selenium atmosphere, for example diethyl selenide or other organo metallic material, the reducing atmosphere that (7) are other, for example CO, and (8) heat treatment.The nano flake providing as Se/ (Cu+In+Ga+Se) can be about 0-approximately 1000 with the stoichiometric proportion of extra chalcogen.

The solution-based deposition of the nano flake mixture that attention proposes not necessarily must be undertaken by deposit these mixtures in one step.In some embodiments of the present invention, can by successively in two or more steps deposition there are different IB-, the IIIA-that form and the nano flake dispersion of chalcogen base particulate is carried out coating step.For example, first the method can deposit the dispersion that contains InSe nanometer thin slice (ratio for example with approximately 1 In/Se), and deposit subsequently the dispersion of copper selenide nano flake (ratio for example with approximately 1 Cu/Se) and gallium selenide nano flake (ratio for example with approximately 1 Ga/Se), then optionally deposit the dispersion of Se.This can produce the lamination of three solution-based sedimentary deposits, they can be sintered together.As selection, can under deposition, before one deck, heat or each layer of sintering.Many different orders are possible.For example, can be as mentioned above w>=0 (being more than or equal to zero) therein, the Cu of x>=0 (being more than or equal to zero) and y>=0 (being more than or equal to zero) _win _xga _yevenly, compacted zone top forms In _xga _yse _zlayer, wherein x>=0 (being more than or equal to zero), y>=0 (being more than or equal to zero) and z>=0 (being more than or equal to zero), and subsequently this two-layer transformation (sintering) is become to CIGS.As selection, Cu _win _xga _ylayer can be at In _xga _yse _zevenly, compacted zone top forms and subsequently this two-layer transformation (sintering) become to CIGS.

In substituting embodiment, nano flake base dispersion as above can further comprise simple substance IB and/or IIIA nano particle (for example metallic forms).These nano particles can be nano flake form, or optionally take other shape for example but be not limited to spherical, elliposoidal, ellipse, cube or other molded non-planar.These particles can also comprise emulsion, melted material, mixture etc. except solid.Cu for example _xin _yga _zse _umaterial, u>0 (be greater than zero) wherein, x>=0 (being more than or equal to zero), y>=0 (being more than or equal to zero) and z>=0 (being more than or equal to zero), can be merged into dispersion with extra selenium source (or other chalcogen) and gallium, this dispersion forms film on substrate by sintering.Can for example by produce at first the emulsion of liquid-gallium in solution, form gallium nano particle and/or nanometer bead and/or nano-liquid droplet.Can be with or without gallium metal in the solvent of emulsifying agent this metal that heats to liquefy by gallium metal or at tool, then by its sonicated and/or mechanical agitation under the existence of solvent in addition.Can under being with or without the existence of solvent of surfactant, dispersant and/or emulsifying agent, stir with machinery, electromagnetism or acoustically tool.Then gallium nanometer bead and/or nano-liquid droplet can operate by solid particulate, by quenching in being equal to or less than the environment of room temperature to change liquid-gallium nanometer bead into solid gallium nano particle.In the common transfer U.S. Patent application 11/081,163 that is entitled as " Metallic Dispersion " of Matthew R.Robinson and Martin R.Roscheisen, describe this technology in detail, by reference its whole disclosures are incorporated to herein.

Attention can by before liquid deposition and/or one or more precursor layer sintering, during or afterwards with below combination in any optimize the method: any chalcogen source that (1) can liquid deposition, for example sneak in precursor layer or conduct Se or S nanometer powder that independently layer deposits, (2) chalcogen (for example Se or S) evaporation, (3) H ₂se (H ₂s) atmosphere, (4) chalcogen (for example Se or S) atmosphere, (5) containing the atmosphere of Organic Selenium, diethyl selenide for example, (6) H ₂atmosphere, the reducing atmosphere that (7) are other, CO for example, (8) wet-chemical reduction step, and (9) heat treatment.

Referring now to Fig. 1 C, then can in appropriate atmosphere, process precursor layer 106 to form film.This film can be dense film.In one embodiment, this comprises precursor layer 106 is heated to and is enough to temperature that ink (ink of deposition) is changed.Attention solvent and possible dispersant are removed by dry.This temperature can be approximately 375 ℃-Yue 525 ℃ (for safe temperature scopes of processing on aluminium foil or high temperature polymer substrate).Processing can be carried out under the various temperature within the scope of this, for example, be still not limited to 450 ℃.In other embodiments, the temperature at substrate place can be approximately 400 ℃-Yue 600 ℃ in precursor layer level, but temperature is lower on substrate.If remove some step, the duration of processing can also be reduced by least to approximately 20%.Heating can be carried out in the scope of approximately 4 minutes-Yue 10 minutes.In one embodiment, pack processing continues to be less than the time of approximately 15 minutes containing precursor layer being heated to be greater than approximately 375 ℃ of temperature that are still less than substrate fusion temperature.In another embodiment, pack processing is still less than lasting 1 minute of the temperature of substrate fusion temperature or time still less containing precursor layer being heated to be greater than approximately 375 ℃.In another embodiment, pack processing is still less than lasting approximately 1 minute of substrate fusion temperature or time still less containing precursor layer being heated to annealing temperature.Treatment step can also promote by the heat treatment technics by least one following technique: pulse heat is processed, is exposed to laser beam or heats and/or similar or relevant technique by IR lamp.

The atmosphere relevant with annealing steps in Fig. 1 C also can change.In one embodiment, appropriate atmosphere comprises the atmosphere containing over approximately 10% hydrogen.Appropriate atmosphere comprises carbon monoxide atmosphere in another embodiment.Yet the oxygen content existing in described particle is very low or do not have in the other embodiments of oxygen, appropriate atmosphere can be blanket of nitrogen, argon atmospher or have the atmosphere that is less than approximately 10% hydrogen.These other atmosphere can be favourable so that preparation during material processed become may be improved.

Although pulse heat is processed and is conventionally remained promising, for example numerous challenges of directional plasma arc systems face of some pulse heat process instrumentation.In this instantiation, being enough to provide the heat treated directional plasma arc of pulse system is the system of the intrinsic heaviness that running cost is high.The power of this directional plasma arc system requirements certain level, this power makes whole system high cost and to the quite large cost of manufacture process increase on energy.Directional plasma arc also demonstrates lag time long between pulse and therefore makes this system be difficult to coordinate and synchronize with continuous reel-to-reel system.The time that this system recharges cost between pulse also produces very slow system or uses the system of more directional plasma arcs, and this increases sharply system cost.

In some embodiments of the present invention, can use the device of other applicable rapid thermal treatment, they comprise the pulse layer using under adiabatic model (the Shtyrokov E I for annealing, Sov.Phys.Semicond.91309), continuous wave laser (10-30W conventionally) (FerrisS D1979Laser-Solid Interactions and Laser Processing (New York:AIP)), pulsed electron bundle device (Kamins T I1979Appl.Phys.Leti.35282-5), scanning electron beam system (McMahon R A1979J.Vac.Sci.Techno.161840-2) (Regolini J L1979Appl.Phys.Lett.34410), other beam system (Hodgson R T1980Appl.Phys.Lett.37187-9), graphite cake heater (Fan J C C1983Mater.Res.Soc.Proc.4751-8) (M W Geis1980Appl.Phys.Lett.37454), lamp system (Cohen R L1978Appl.Phys.Lett.33751-3), and scanning hydrogen flame system (Downey D F1982Solid State Technol.2587-93).In some embodiments of the present invention, can use nondirectional low density systems.As selection, other known pulse heating technology is also at United States Patent (USP) 4,350, described in 537 and 4,356,384.In addition, be to be understood that as expired United States Patent (USP) 3,950,187 (" Method and apparatus involvingpulsed electron beam processing of semiconductor devices ") and 4, the pulsed electron beam that relates to solar cell described in 082,958 (" Apparatus involving pulsed electron beamprocessing of semiconductor devices ") process and the method and apparatus of rapid thermal treatment in public field and be known.United States Patent (USP) 4,729,962 also describe the another kind of known method for the rapid thermal treatment of solar cell.Above-mentioned can be individually or with above-mentioned or other similar treatment technology and various embodiments of the present invention are single or Multiple Combination application.

It should be noted that and use nano flake to be conventionally created in than the low precursor layer that sinters solid layer at the temperature of 50 ℃ into that reaches of the corresponding layer of spherical nanoparticle.This part is due to surface area contact larger between particle.

In certain embodiments of the invention, precursor layer 106 (or in its sublayer any) can order or annealing simultaneously.Described annealing can quickly heat up to the plateau temperature range of approximately 200 ℃-Yue 600 ℃ from ambient temperature by substrate 102 and precursor layer 106 and complete.Processing comprises with 1-5 ℃/sec, preferably over heating rate to the temperature of approximately 200 ℃-Yue 600 ℃ of 5 ℃/sec, anneals.Temperature is remained on to plateau range and continue the approximately part second extremely time of approximately 60 minutes, subsequently cooling.Optionally, process and to be further included in Se steam time chien shih this annealed layer selenizing that continues approximately 60 seconds-Yue 10 minutes by 1-5 ℃/sec, heating rate to the temperature of approximately 225 ℃-Yue 575 ℃ that preferably surpasses 5 ℃/sec, wherein plateau temperature not necessarily keeps constant in time, thereby forms the film that comprises one or more chalcogenides that contain Cu, In, Ga and Se.Optionally, pack processing contains the selenizing without independent annealing steps in containing the atmosphere of hydrogen, but can contain H ₂se or H ₂with in the atmosphere of the mixture of Se steam with 1-5 ℃/sec, preferably surpass time densification and selenizing in a step that the heating rate of 5 ℃/sec continues approximately 120 seconds-Yue 20 minutes to the temperature of approximately 225 ℃-Yue 575 ℃.

As selection, can adjust annealing temperature to swing rather than to remain on specific plateau temperature in certain temperature range.This technology (being referred to herein as rapid thermal treatment or RTA) be particularly suitable for metal foil substrate for example but be not limited to form on aluminium foil photovoltaic active layer (being sometimes referred to as " absorber " layer).But other suitable substrate comprises and is not limited to other metal for example mixture, alloy and the blend of stainless steel, copper, titanium or molybdenum, metallized plastic foil, glass, ceramic membrane and these and similar or associated materials.Substrate can be flexible, for example paper tinsel form, or rigidity, the combination of for example plate form, or these forms.The other details of this technology are described in U.S. Patent application 10/943,685, by reference this application are incorporated to herein.

The atmosphere relevant with annealing steps also can change.In one embodiment, appropriate atmosphere comprises nitrogen atmosphere.Yet the oxygen content existing in described nano flake is very low or do not have in the other embodiments of oxygen, appropriate atmosphere can be blanket of nitrogen, argon atmospher, carbon monoxide atmosphere or have the atmosphere that is less than approximately 10% hydrogen.These other atmosphere can be favourable so that preparation during material processed become may be improved.

Referring now to Fig. 1 D, process precursor layer 106 to form dense film 110.In fact dense film 110 can have with the thickness of wet precursor layer 106 compares the thickness reducing, because removed carrier fluid and other material in processing procedure.In one embodiment, film 110 can have the thickness of approximately 0.5 μ m-approximately 2.5 μ m.In other embodiments, the thickness of film 110 can be approximately 1.5 μ m-approximately 2.25 μ m.In one embodiment, the dense film 110 producing can be substantially void-free.In some embodiments, dense film 110 has approximately 5% or less voidage.In other embodiments, voidage is approximately 10% or less.In another embodiment, voidage is approximately 20% or less.In another embodiment, voidage is approximately 24% or less.In another embodiment, voidage is approximately 30% or less.The thickness that the processing of precursor layer 106 can make nano flake fuse together and remove void space and reduce thus produced dense film under most of situations.

According to the type that is used for forming the material of film 110, film 110 can be suitable as absorbed layer or further process to become absorbed layer.More particularly, film 110 can be the film that a step process produces, or is used in the film in another step process subsequently that makes that it becomes two step process, or is used in the film in multistep technique.In a step process, form film 110 to comprise that IB-IIIA-VIA compounds of group and film 110 can be the absorber film being suitable in photovoltaic device.In two step process, film 110 can be the film of solid and/or densification, and it can have further processing to be suitable as the absorber film of using in photovoltaic device.As a kind of limiting examples, the film 110 in two step process can usually not serve as absorbed layer containing unit of VIA family any and/or q.s.Adding VIA family element or other material can be the second step of this two step process.Can use the mixture of two or more VIA elements, or as used another kind of VIA element to increase by the 3rd step for second step.The method of multiple this material of interpolation comprises printing, use VIA element steam and/or other technology of VIA family element.Be to be understood that in addition in two step process, processing atmosphere can be different.As limiting examples, a kind of atmosphere is ShiVIA family base atmosphere optionally.As another limiting examples, a kind of atmosphere can be inert atmosphere as described herein.For other treatment step of multistep technique can be wet-chemical surface treatment to improve IB-IIIA-VIA film surface, and/or other rapid thermal treatment is to improve volume and the surface property of IB-IIIA-VIA film.

Nano flake

Referring now to Fig. 2 A and 2B, will be described in more detail the embodiment of nano flake 108 of the present invention.Nano flake 108 can have various shape and size.In one embodiment, nano flake 108 can have the large aspect ratio with regard to grain thickness and particle length.Fig. 2 A shows packing density of particle.Fig. 2 A shows that some nano flakes have the thickness of the about 100nm of about 20-.Some can have about 500nm or less length.The aspect ratio of nano flake can be about 10:1 or larger (longest dimension of particle and the ratio of the shortest size) in some embodiments.Other embodiments can have about 30:1 or larger aspect ratio.Can there is in addition about 50:1 or larger aspect ratio.The increase of aspect ratio show that the relatively the shortest size of the size grown most increases or the shortest size with respect to the longest size reduction.Therefore, aspect ratio herein relates to the relatively normally the shortest size of sheet thickness of the longest lateral dimension (its length or width).Along edge or along major axis, measure these sizes to provide size to be for example still not limited to the measurement result of length, width, the degree of depth and/or diameter.When mentioning a plurality of nano flake with regulation aspect ratio, all nano flakes that refer to composition have the average aspect ratio of defined generally.Be to be understood that the particle distribution of aspect ratios that can exist around average aspect ratio.

As seen in Fig. 2 A, although the size and dimension of nano flake 108 can change, great majority comprise at least one smooth surface 120 substantially.This at least one flat surfaces 120 is allowed larger Surface Contact between adjacent nano flake 108.This larger Surface Contact provides multiple benefit.Larger contact allows that the atom improving between adjacent particle mixes.For the nano flake containing more than a kind of element, even may exist suitably atom to mix for particle, but the close contact in film allows to be easy to diffusion subsequently.Therefore,, as fruit granule is rich in a kind of element slightly, the contact of increase is conducive to element in the dense film producing and distributes more uniformly.In addition, larger grain boundary face area causes reaction rate faster.The flat shape of particle maximizes particle Contact area.Particle Contact area makes chemical reaction (for example reaction based on atom diffusion) be able to initiation, catalysis and/or carry out relatively rapidly and in large area simultaneously.Therefore, not only this shape improvement mixing, and larger interfacial area and particle Contact area also improve reaction rate.

Still with reference to Fig. 2 A, flat shape is also allowed the bulk density of raising.As seen in Fig. 2 A, nano flake 108 can be arranged essentially parallel to the surface orientation of substrate 102 and one and be stacked on another to form precursor layer 106.Inherently, the geometry of nano flake is allowed in precursor layer than spheric granules or the closer contact of nano particle.In fact, likely the flat surfaces of nano flake 100% contacts with another nano flake.Therefore, the prepared film of precursor layer of the spherical nanoparticle ink of the same composition substantially the same with using other side is compared, and the even shape of nano flake produces higher bulk density in dense film.In some embodiments, the flat shape of nano flake produces the bulk density at least about 70% in precursor layer.In other embodiments, this nano flake produces the bulk density at least about 80% in precursor layer.In other embodiments, this nano flake produces the bulk density at least about 90% in precursor layer.In other embodiments, this nano flake produces the bulk density at least about 95% in precursor layer.

As seen in Fig. 2 B, nano flake 108 can have various shapes.In some embodiments, the nano flake in ink can comprise those with comprise random sizes and/or random shape.On the contrary, particle size is of crucial importance for standard spherical nanoparticle, and those spherical nanoparticles of different size and composition have by generation the dispersion that unstable atom forms.The flat surfaces 120 of nano flake is allowed the particle that is easier to be suspended in carrier fluid.Therefore,, even if nano flake may not be monodispersed dimensionally, but make to form metal, there is sheet and provide a kind of and particle is suspended in carrier fluid and without the method for the quick and/or preferential sedimentation of any component.In addition, Fig. 2 C is according to the amplification plan view of the micron thin slice 121 of one embodiment of this invention.

Being to be understood that can form nano flake 108 of the present invention and/or it is carried out to size discrimination more has the size and dimension of control to distribute to provide.The distribution of sizes of nano flake can be to make a kind of standard deviation that departs from nano flake average length and/or width be less than about 250nm.In another embodiment, the distribution of sizes of nano flake can be to make a kind of standard deviation that departs from nano flake average length and/or width be less than about 200nm.In another embodiment, the distribution of sizes of nano flake can be to make a kind of standard deviation that departs from nano flake average length and/or width be less than about 150nm.In another embodiment, the distribution of sizes of nano flake can be to make a kind of standard deviation that departs from nano flake average length and/or width be less than about 100nm.In another embodiment, a kind of standard deviation that departs from nano flake average length is less than about 50nm.In another embodiment, a kind of standard deviation that departs from nano flake average thickness is less than about 10nm.In another embodiment of the present invention, a kind of standard deviation that departs from nano flake average thickness is less than about 5nm.Nano flake has the thickness that is less than about 250nm separately.In another embodiment, nano flake has the thickness that is less than about 100nm separately.In another embodiment, nano flake has the thickness that is less than about 50nm separately.In another embodiment, nano flake has the thickness that is less than about 20nm separately.With regard to its shape, nano flake can have at least about 10 or larger aspect ratio.In another embodiment, nano flake has at least about 15 or larger aspect ratio.Nano flake has random flat shape and/or random distribution of sizes.In other embodiments, nano flake has non-random flat shape and/or non-random distribution of sizes.

The stoichiometric proportion of element can change between single nano flake, as long as the total amount in the particle of all merging is under the expectation stoichiometric proportion of precursor layer and/or gained dense film or approaches this expectation stoichiometric proportion.According to a kind of preferred embodiment of this technique, the element total amount in the film producing has Cu/ (In+Ga) compositing range of about 0.7-approximately 1.0 and Ga/ (In+Ga) compositing range of about 0.05-approximately 0.30.Optionally, Se/ (In+Ga) compositing range can be about 0.00-approximately 4.00 to such an extent as to can need or can not need the step of using other Se source that relates to subsequently.

Nano flake forms

Referring now to Fig. 3, a kind of embodiment of the device that is used to form nano flake 108 will be described.Can by separately or the multiple technologies that the commercially available charging of simple substance, binary, ternary or the multicomponent material of expectation applied below with combination in any obtain nano flake 108, these technology include, but are not limited to crushing technology, and for example ball milling, pearl mill, little medium milling, blender ball milling, planetary grinding, horizontal ball milling, gravel grind, grind, the grinding of sledge mill, dry grinding, wet lapping, jet grinding or other type.Fig. 3 shows a kind of embodiment of grinding system 130, and its use contains ball or pearl or for the grinder 132 of other material of grinding technics.System 130 can be closed system to provide oxygen-free environment for the processing of feed material.Inert gas source 134 can be connected to keep oxygen-free environment with this closed system.Can also be by providing liquid nitrogen or other cooling source 136 (showing with diplopia) to configure grinding system 130 to allow cryogrinding.As selection, also can configure grinding system 130 so that heating to be provided during grinding technics.Can also during grinding technics, heat and/or cooling circulation.Optionally, grinding can also comprise carrier fluid and/or dispersant are mixed with the powder of processing or charging.In one embodiment of the present invention, but the nano flake 108 producing by grinding for example can have various sizes be not limited to the about 500nm of thick about 20nm-.In another embodiment, nano flake can thick about 75nm-100nm.

Be to be understood that grinding can be used harder than feed particles and/or have the made pearl of the material of high mass density more or microballon so that feed particles is transformed into suitable dimension and shape.In one embodiment, these pearls are glass, pottery, aluminium oxide, porcelain, carborundum or tungsten carbide pearl, have the stainless steel ball of ceramic case, have iron ball of ceramic case etc., thereby the pollution risk of nano flake is minimized.The parts of grinder itself or grinder also can have the liner of ceramic-lined or other inert material, or the parts of grinder can be pottery completely or become inertia so that the pollution of the slurry that contains nano flake minimizes with chemistry and mechanical means.Can also during technique, regularly sieve this pearl.

Ball milling can carry out in oxygen-free environment.This can relate to the grinder using with external environment condition sealing and removing air.So grind, can under inert atmosphere or other oxygen-free environment, carry out.Some embodiments can relate to grinder is placed on and is provided in the cover or chamber of sealing for oxygen-free environment.This technique can comprise carrier drying degassed or select anhydrous anaerobic solvent to start and feed in raw material and ingress of air not.Anaerobic is ground and can be produced anaerobic nano flake, itself so that reduce the needs to particle deoxygenation step.This can significantly reduce with nano flake precursor layer and become the relevant annealing time of dense film.In some embodiments, annealing time is within the scope of approximately 30 seconds.About manufacturing (pulverizing) without air nano flake, be to be understood that the present invention can also comprise airfree dispersion manufacture and airfree coating, storage and/or processing.

Grinding can be carried out under various temperature.In one embodiment of the present invention, grind and at room temperature carry out.In another embodiment, grind low temperature for example but be not limited to≤carry out at-175 ℃.This can make to grind to may be that liquid or crisp not particle work to pulverize under room temperature.Grind also and can under the grinding temperature of expectation, carry out, wherein all precursor granules are all that solid and precursor granules have enough ductility with the original shape formation flat shape from on-plane surface or plane under this grinding temperature.This preferred temperature can be room temperature, the circulation more than room temperature or below room temperature and/or between different temperatures.In one embodiment, grinding temperature can be lower than approximately 15 ℃.In another embodiment, this temperature is lower than approximately-175 ℃.In another embodiment, grinding can be passed through 80K, the cooled with liquid nitrogen of-193 ℃.Temperature during grinding is controlled can control possible chemical reaction between solvent, dispersant, feed material and/or grinder parts.Be to be understood that except above-mentioned, temperature can also change in the different times of grinding technics.As a kind of limiting examples, in process of lapping, grind and can in initial milling time section, at the first temperature, carry out and proceed to other temperature for time period subsequently.

Grinding can make substantially all precursor granules be transformed into nano flake.In some embodiments, grind and make to be transformed into nano flake at least about the precursor granules of 50% (with the weighing scale of all precursor granules).In other embodiments, at least 50 volume % of all precursor granules are transformed into nano flake.In addition, be to be understood that during grinding that temperature can be constant or change.This can be useful to adjusting the material character of feed material or part grinding-material to produce the particle of intended shape, size and/or composition.

Although the invention discloses " (top down) from top to bottom " method that forms nano flake, be to be understood that also and can use other technology.For example, on surface, for example liquid cools is bathed material from melt quenching.Indium (and possible gallium and selenium) nano flake can stir by the indium of emulsification melting simultaneously and form in cooling bath surface quenching.Be to be understood that any wet chemistry, dry chemical, dry-type and physical and/or wet type physical technique of preparing thin slice can be used (except dry type or case of wet attrition) together with the present invention.Therefore, the invention is not restricted to the method from top to bottom (grinding) of wet type physics, but can also comprise dry type/wet type method of (bottom-up) from bottom to top.Should be noted that in addition pulverizing can be optionally multistep technique.In a kind of limiting examples, first this can comprise the bulk/sheet that adopts mm size, and they are dry grinded to <100 μ m, then in one, two, three or more step, grinds, and reduce subsequently bead size to nano flake.

Be to be understood that for feed particles of the present invention and can prepare by several different methods.For example and without limitation, the people's such as B.M.Basol United States Patent (USP) 5,985,691 is described a kind of method based on particle and formed IB-IIIA-VIA compounds of group film.Eberspacher and Pauls be at United States Patent (USP) 6,821, describes a kind of technique of manufacturing the phase stable precursor of fine particulate form, for example sub-micron multi-element metal particle, and the heterogeneous mixed metal particles that comprises at least one metal oxide in 559.Bulent Basol publishes in patent application 20040219730 and describes a kind of technique that forms compound film in the U.S., and it comprises the nano-powder material that preparation has controlled total composition and has single solid solution pellet.Use solid solution method, can make in the form pick-up metal dispersion of gallium with non-oxidized substance---but approximately 18 relative atom percentage (Subramanian at the most only there is, P.R., Laughlin, D.E., Binary Alloy PhaseDiagrams. second edition, Massalski edits, T.B.1990.ASM international, Materials Park, OH, 1410-1412 page; Hansen, M., Constitutionof Binary Alloys.1958. second edition, McGraw Hill, 582-584 page).U.S. Patent application 11/081,163 is described a kind of technique that forms compound film by preparing the mixture of the simple substance nano particle consisting of IB, IIIA and optional VIA family element, and described mixture has controlled total composition.Discussion about chalcogenide powder also can be found in the following: [(1) Vervaet, A. etc., E.C.Photovoltaic Sol.Energy Conf., Proc.Int.Conf., 10th (1991), 900-3.; (2) Journal of ElectronicMaterials, Vol.27, No.5,1998, the 433 pages; Ginley etc.; (3) WO99,378,32; Ginley etc.; (4) US6,126,740].These methods can be used for making and need the charging of pulverizing.Other method can form the particle of the precursor submicron-scale of being ready for liquid deposition.All documents listed above are all for all objects are all incorporated to herein by reference.

Ink preparation

In order to prepare the dispersion for precursor layer 106, nano flake 108 is mixed and mix with one or more chemicals, this chemicals includes, but are not limited to dispersant, surfactant, polymer, binding agent, crosslinking agent, emulsifying agent, defoamer, drier, solvent, filler, replenishers, thickener, film adjusting agent, antioxidant, flowable, all flat agent and anticorrisive agent.

The ink made from the present invention can optionally comprise dispersant.Some embodiments can not comprise any dispersant.Dispersant (also referred to as wetting agent) is for preventing the surface reactive material of particle aggregation or flocculation, therefore promotes suspension and the stable dispersion thus made of solid material in liquid medium.If particle surface attracts each other, there is flocculation, it often causes assembles and reduction stability and/or uniformity.If particle surface repels mutually, there is static stabilization, wherein particle can not be assembled and not trend towards from solution, settling very soon.

Effectively dispersant can carry out pigment wetting, dispersion and stable conventionally.Dispersant is according to the character of ink/coating and difference.Polyphosphate, styrene-maleic acid salt and polyacrylate are often used for water-based preparaton, and derivative of fatty acid and low-molecular-weight modified alkyd resin and mylar are often used for organic preparaton.

Surfactant is to reduce them to be dissolved in the capillary surface-active agents of solvent wherein, and it serves as wetting agent, and the surface tension of (water-based) medium is remained on low-level so that ink and substrate surface interact.The surfactant of some type is also as dispersant.Surfactant contains hydrophobicity carbochain and hydrophily polar group conventionally.This polar group can be non-ionic.If polar group is ionic, electric charge can be plus or minus, produces cation or anion surfactant.Zwitterionic surfactant contains positive charge and negative electrical charge in same a part simultaneously; Example is N-dodecyl-N, N-dimethyl betaine.Some surfactant is often used as the dispersant of the aqueous solution.Representational kind comprises acetylenediol, derivative of fatty acid, phosphate, polyacrylic acid sodium salt, polyacrylic acid, soybean lecithin, tri octyl phosphine (TOP) and TOPO (TOPO).

Binding agent and resin are often used in dispersion nascent or that form, the particle being close to being kept together.The example of common binding agent comprises acrylic monomer (as monofunctional diluent and multifunctional reactive reagent), acrylic resin (acrylic compounds polyalcohol for example, amine synergist (amine synergists), propylene oxide acids, polyester acrylic class, polyoxyalkylene acrylate class, styrene/acrylic class, urethane acrylates class or vinylacrylic acid class), alkyd resins (long oil for example, middle oil, short oil or tall oil), adhesion promotor is for example still not limited to PVP (PVP), amide resin, amino resins (being for example still not limited to melamine-based or urea-based compound), pitch/pitch, butadiene acrylonitrile, celluosic resin (is for example still not limited to cellulose acetate-butyrate (CAB), cellulose-acetate propionate (CAP), ethyl cellulose (EC), NC Nitroncellulose (NC) or organic cellulose ester), chlorinated rubber, dimer aliphatic acid, epoxy resin (acrylate for example, bisphenol-A base resin, epoxy UV cured resin, ester, phenol and cresols (novolaks) or the compound based on phenoxy group), be total to-ter-polymers of ethene is ethylene acrylic/methacrylic acid for example, E/AA, E/M/AA or ethylene vinyl acetate (EVA), fluoropolymer, gelatin (for example, from Florham Park, the Pluronic F-68 of the BASF Corporation of NJ), dihydroxylic alcohols monomer, hydrocarbon resin is (for example aliphatic, aromatics or coumarone base be indenes for example), maleic resin, modified urea, natural rubber, natural resin and natural gum, rosin, phenol-formaldehyde resin modified, resol, polyamide, polybutadiene (liquid is hydroxy-end capped), polyester (saturated with undersaturated), polyolefin, polyurethane (PU) isocyanates (hexamethylene diisocyanate (HDI) for example, IPDI (IPDI), alicyclic compound, methyl diphenylene diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI) or trimethyl hexamethylene diisocyanate (TMDI)), polyurethane (PU) polyalcohol (caprolactone for example, dimer base polyester, polyester, or polyethers), polyurethane (PU) dispersion (PUDs) for example, based on those of polyester or polyethers, polyurethane prepolymer (caprolactone for example, dimer base polyester, polyester, polyethers and the compound based on urethane acrylate), polyurethane thermoplastic (TPU) is polyester or polyethers for example, silicate (for example alkyl silicate or waterglass based compound), organosilicon be (amine official energy, epoxy functionalized, ethyoxyl official energy, hydroxyl-functional, methoxy functional, silanol official energy, or vinyl (cinyl) sense), phenylethylene (styrene-butadiene emulsion for example, styrene/ethylene base toluene polymer and copolymer) or vinyl compound (for example polyolefin and polyolefin derivative thing, polystyrene and styrol copolymer, or polyvinyl acetate (PVAC)).

Emulsifying agent is make liquid and other liquid blend and so be stabilized in the dispersant of the suspension in solution by promoting aggregate material to be broken into droplet.For example, sorbitan ester as Water-In-Oil (w/o) emulsion prepare the emulsifying agent of use, for the preparation of oil suction substrate (w/o), for the preparation of w/o type brilliantine, as absorbent again and as nontoxic antifoaming agent.The example of emulsifying agent is for example NOFABLE SO-992 (Arlacel60), NOFABLE SO-992 (Arlacel83), sorbitan monolaurate (Span20), span 40 (Span40), sorbitan monostearate (Span60), sorbitan tristearate (Span65), dehydrated sorbitol mono-fatty acid ester (Span80) and sorbitan trioleate (Span85) of sorbitan ester, they all for example can be from New Castle, and the Uniqema of Delaware buys.Other polymer emulsifier comprises polyoxyl 40 stearate (Myrj45), polyoxyl 40 stearate (Myrj49), polyoxyethylene stearate (40) ester (Myrj52), Vinlub 73 (PEG400), the surfactant of Aceonon 300 MO (PEG400 monoleate) and polyoxyl 40 stearate (PEG400 monostearate) and Tween series, it includes, but are not limited to Tween 20 (Tween20), Tween 20 (Tween21), polyoxyethylene sorbitan monopalmitate (Tween40), polyoxyethylene sorbitan monostearate (Tween60), polyoxyethylene sorbitan tristearate (Tween61), Polysorbate 80 (Tween80), Polysorbate 80 (Tween81), with polyoxyethylene sorbitan trioleate (Tween85), they all for example can be from New Castle, and the Uniqema of Delaware buys.Arlacel, Myrj and Tween are Wilmington, the registered trade mark of the ICI Americans Inc. of Delaware.

During coating/typography, may by the release of various Ga-Ses, form foam, the words that especially typography is carried out at a high speed.Surfactant may adsorb and make it stable in liquid-air interface, promotes formation of foam.Antifoaming agent prevents from starting to spume, and defoamer makes the foam forming in advance minimize or be removed.Antifoaming agent comprises hydrophobic solid, fat oil and some surfactant, and they all infiltrate liquid-air interface so that formation of foam slows down.Antifoaming agent also comprises silicate, organosilicon and does not contain organosilyl material.Containing organosilyl material, do not comprise microwax, mineral oil, polymeric material and silicon-dioxide-substrate and surfactant sill.

Solvent can be water-based (water base) or nonaqueous (organic).Yet group water solution friendly on environment has than the relative higher capillary shortcoming of organic solvent, makes its more difficult wetting substrate, especially plastic.Substrate while using polymer substrate in order to improve is wetting, can add surfactant to reduce ink surface tension (making the stable foaming of surfactant minimize) simultaneously, simultaneously can (for example passing through corona treatment) to improve its surface by substrate surface modification.Common organic solvent comprises acetic acid esters, acrylate, alcohol (butanols, ethanol, isopropyl alcohol or methyl alcohol), aldehyde, benzene, methylene bromide, chloroform, carrene, dichloroethanes, trichloroethanes, cyclic compound (for example cyclopentanone or cyclohexanone), ester (for example butyl acetate or ethyl acetate), ether, glycol (for example ethylene glycol or propylene glycol), hexane, heptane, aliphatic hydrocarbon, aromatic hydrocarbons, ketone (acetone for example, methylethylketone or methyl iso-butyl ketone (MIBK)), natural oil, terpenes, terpinol, toluene.

Other component can comprise filler/extender, thickener, rheology modifier, surface conditioner (comprising adhesion promotor/bonding), antigelling agent, antiblocking agent, antistatic agent, chelating/compounding ingredient, corrosion inhibitor, flame proof agent/rust inhibitor, fire retardant, wetting agent, heat stabilizer, light stabilizer/UV absorbent, lubricant, pH stabilizer, slide and control material, antioxidant, mobile and all flat agent.Be to be understood that all components can add individually or with other combination of components.

Reel-to-reel is manufactured

Referring now to Fig. 4, will describe according to reel-to-reel manufacturing process of the present invention.Use the embodiment of the present invention of nano flake to be suitable for very much reel-to-reel manufacture.Particularly, in reel-to-reel manufacturing system 200, flexible substrate 201, for example aluminium foil march to winding volume 204 from supplying with volume 202.Supplying with volume and be wound around between volume, substrate 201 is through some spreader 206A, 206B, 206C, nick roller (microgravure rollers) and heater 208A, 208B, 208C.Different layers or the sublayer of each spreader precursors to deposit layer, example those layers described above.Heater is used for making different layer and/or sublayer to anneal to form dense film.In the example of describing at Fig. 4, spreader 206A and 206B can be coated with the different sublayers of precursor layer (for example precursor layer 106).Heater 208A and 208B can make each sublayer annealing before the next sublayer of deposition.As selection, two sublayers of can simultaneously annealing.Spreader 206C can optionally be coated with the extra material layer that contains as mentioned above chalcogen or alloy or simple substance particle.Heater 208C heats this optional layer and above-mentioned precursor layer.Note also can then depositing any extra layer and follow whole three layers IB-IIIA-chalcogenide compound film that heats to be together formed for photovoltaic absorption layer by precursors to deposit layer (or sublayer).Described reel-to-reel system can be the reel-to-reel system of continuous reel-to-reel and/or segmentation reel-to-reel and/or batch mode processing.

Photovoltaic device

Referring now to Fig. 5, the film of making as mentioned above can serve as the absorbed layer in photovoltaic device, module or solar panel.A kind of example of described photovoltaic device 300 is shown in Fig. 4.This device 300 comprises base substrate 302, optional adhesion layer 303, base stage or backplate 304, the p-type absorbed layer 306 that comprises the film of the above-mentioned type, N-shaped semiconductive thin film 308 and transparency electrode 310.For example, base substrate 302 can be by metal forming, polymer such as polyimides (PI), polyamide, polyether-ether-ketone (PEEK), polyether sulfone (PES), Polyetherimide (PEI), PEN (PEN), polyester (PET), relevant polymer, or metallized plastics are made.As nonrestrictive example, relevant polymer comprises those polymer with similar structures and/or functional character and/or material properties.Base stage 304 is made by electric conducting material.For example, base stage 304 can be the metal level that thickness can be selected from approximately 0.1 μ m-approximately 25 μ m.Optional intermediate layer 303 can be introduced between electrode 304 and substrate 302.Optionally, layer 303 can be that diffusion impervious layer is to prevent the material diffusion between substrate 302 and electrode 304.Diffusion impervious layer 303 can be that conductive layer or it can be nonconducting layers.As nonrestrictive example, layer 303 can be in multiple material anyly form, this material includes, but are not limited to chromium, vanadium, tungsten and glass, or the compound any single or Multiple Combination of nitride (comprising tantalum nitride, tungsten nitride, titanium nitride, silicon nitride, zirconium nitride and/or hafnium nitride), oxide, carbide and/or previous materials for example.Although be not limited to following content, the thickness of this layer can be 100nm-500nm.In some embodiments, this layer can be 100nm-300nm.Optionally, thickness can be the about 250nm of about 150nm-.Optionally, thickness can be about 200nm.In some embodiments, can use two barrier layers, one of the every side of substrate 302.Optionally, boundary layer can be arranged on electrode 304 and by forming such as including, but are not limited to following material: chromium, vanadium, tungsten and glass, or the compound any single or Multiple Combination of nitride (comprising tantalum nitride, tungsten nitride, titanium nitride, silicon nitride, zirconium nitride and/or hafnium nitride), oxide, carbide and/or previous materials for example.

Transparency electrode 310 can comprise that transparency conducting layer 309 and metal (for example Al, Ag, Cu or Ni) finger piece layer 311 are to reduce sheet resistance.

N-type semiconductive thin film 308 serves as knot pairing between compound film and transparency conducting layer 309.For example, n-type semiconductive thin film 308 (be sometimes referred to as knot pairing layer) can comprise for example two or more some combination of cadmium sulfide (CdS), zinc sulphide (ZnS), zinc hydroxide, zinc selenide (ZnSe), N-shaped organic material or these or similar material of inorganic material, or organic material for example N-shaped polymer and/or little molecule.The layer of these materials can for example be deposited into the thickness of the about 1000nm of about 2nm-, the more preferably from about about 500nm of 5nm-and the most preferably from about about 300nm of 10nm-by chemical bath deposition (CBD) and/or chemical surface deposition (and/or correlation technique).This can also be configured for use in continuous reel-to-reel and/or segmentation reel-to-reel and/or batch mode system.

Transparency conducting layer 309 can be inorganic, for example transparent conductive oxide (TCO) for example but be not limited to zinc oxide or the associated materials of tin indium oxide (ITO), the tin indium oxide of fluoridizing, zinc oxide (ZnO) or aluminium doping, it can be by any deposition including, but are not limited in following the whole bag of tricks: sputter, evaporation, CBD, plating, sol-gel based coating, spraying, chemical vapour deposition (CVD) (CVD), physical vapour deposition (PVD) (PVD), ald (ALD), etc.As selection, transparency conducting layer can comprise the transparent conductive polymer layer PEDOT (poly--3 that for example adulterates alone or in combination, 4-Ethylenedioxy Thiophene), the hyaline layer of carbon nano-tube or dependency structure or other transparent organic material, it can use spin coating, dip-coating or spraying etc. or by any deposition in various gas phase deposition technologies.Optionally, be to be understood that between CdS and the ZnO of Al doping and can use intrinsic (non-conductive) i-ZnO.Optionally, between layer 308 and transparency conducting layer 309, can comprise insulating barrier.Inorganic and combination organic material also can be used for forming heterozygosis transparency conducting layer.Therefore, layer 309 can be optionally organic (polymer or conjunct polymer molecules) or (organic and inorganic) of heterozygosis.The example of above-mentioned transparency conducting layer is for example being described in the common U.S. Patent Application Publication 20040187917 of transferring the possession of, and it is incorporated to herein by reference.

Those skilled in the art can design the modification in these teachings based on above-mentioned embodiment.For example, note in embodiments of the invention, part IB-IIIA precursor layer (or some sublayer of precursor layer or other layer in lamination) can be used the deposition techniques except nano flake base oil China ink.For example precursor layer or form sublayer can be by any deposition in multiple alternative deposition technique, these technology include, but are not limited to liquid deposition, for example ALD, evaporation, sputter, CVD, PVD, plating etc. of gas phase deposition technology of ball shaped nano powder base oil China ink.

Referring now to Fig. 6, the flow chart of a kind of embodiment that shows the inventive method will be described.Fig. 6 is presented at step 350, can manufacture nano flake 108 by one of technique as herein described.Optionally, can exist washing step 351 to remove any less desirable residue.Once make nano flake 108, step 352 shows and can for example still be not limited to carrier fluid preparation ink by nano flake and at least one other component.Optionally, be to be understood that embodiments more of the present invention can be merged into step 350 and 352 processing step, as shown in frame 353 (showing with diplopia) if manufacturing step produces the preparaton that can apply.As a kind of limiting examples, if between shaping period dispersant used and/or solvent also can be used for forming good coat can be this situation.In step 354, can be with ink coats substrate 102 to form precursor layer 106.Optionally, can exist by such as but the method that is not limited to heating, washing etc. is removed layers 106 dispersant of firm coating and/or the step 355 of other residue.Optionally, step 355 can comprise by using such as but the drying device that is not limited to drying tunnel/baker after ink deposition except the step of desolventizing.Step 356 Graphics Processing precursor layer is to form dense film, and this dense film can then further process to form absorbed layer in step 358.Optionally, be to be understood that, if dense film is absorbed layer and the further processing that does not need this film, embodiments more of the present invention can be merged into step 356 and 358 processing step.Step 360 shows can and/or be in contact with it formation N-type knot on absorbed layer.Step 362 shows and can on N-type knot layer, form transparency electrode to produce the lamination that can be used as solar cell.

Referring now to Fig. 7, be to be understood that in addition and a plurality of devices 300 can be incorporated in module 400 to form solar energy module, it comprises multiple packing, persistence and environmental protection feature so that device 300 can be arranged in outdoor environment.In one embodiment, module 400 can comprise the framework 402 of support substrates 404, can installing device 300 on substrate 404.This module 400 is simplified mounting process by allowing that a plurality of devices 300 are once installed.As selection, also can adopt form factor flexibly.Be to be understood that in addition encapsulated device and/or layer can be used for being protected from environmental impact.As a kind of limiting examples, encapsulated device and/or layer can stop that moisture and/or oxygen and/or acid rain enter device, especially during lasting environmental exposure.

Extra chalcogen source

Be to be understood that and use the present invention of nano flake can also be with the U.S. Patent application 11/290 of common pending trial, described in 633 (attorney docket NSL-045), the similar fashion of mode is used extra chalcogen source, wherein precursor material contains 1) chalcogenide for example but be not limited to copper selenide and/or indium selenide and/or gallium selenide and/or 2) source of extra chalcogen, for example still be not limited to, size is less than Se or the S nano particle of about 200nm.In a kind of limiting examples, chalcogenide and/or extra chalcogen can be nano flake and/or nano flake form, and extra chalcogen source can be thin slice and/or non-thin slice.This chalcogenide nano flake can be one or more bianry alloy chalcogenides for example but be not limited to IB family binary chalcogenide nano particle (IB family non-oxidized substance chalcogenide for example, for example Cu-Se, CuS or CuTe) and/or IIIA family chalcogenide nano particle (for example IIIA family non-oxidized substance chalcogenide, for example Ga (Se, S, Te), In (Se, S, Te) and Al (Se, S, Te)).In other embodiments, nano flake can be that non-chalcogenide is for example still not limited to IB and/or IIIA family material for example CuIn, CuGa and/or InGa.If chalcogen for example, in relatively low temperature (, being 220 ℃ for Se, is 120 ℃ for S) fusing, chalcogen produces good contact in liquid state and with nano flake.For example, if then fully heat (, at approximately 375 ℃) nano flake and chalcogen, chalcogen reacts to form the IB-IIIA-chalcogenide material of expectation with chalcogenide.Referring now to Fig. 8 A-8C, can on substrate 501, carry chalcogenide nano flake 502 and be for example the source 504 of the extra chalcogen of the powder type that contains chalcogen particle.As a kind of limiting examples, this chalcogen particle can be micron and/or non-oxygen chalcogen (for example Se, S or the Te) particle of submicron-scale, for example hundreds of nanometers of size or be less to several microns.The mixture of chalcogenide nano flake 502 and chalcogen particle 504 is placed on substrate 501 and is heated to and be enough to melt the temperature of extra chalcogen particle 504 to form liquid chalcogen 506 as shown in Figure 8 B.Liquid chalcogen 506 and chalcogenide 502 are heated to and are enough to make temperature that liquid chalcogen 506 reacts with chalcogenide 502 to form the dense film 508 of IB-IIIA family-chalcogenide compound as shown in Figure 1 C.Then make the dense film of IB-IIIA family-chalcogenide compound cooling.

Although be not limited to following content, chalcogenide particle 502 can be started to obtain by binary chalcogenide feed material, for example the particle of micron-scale or larger particle.In following table 1, shown out the example of commercially available chalcogenide material.

Table I

Chemical composition	Chemical formula	Typical case's purity %
			Aluminum selenide	Al ₂Se ₃	99.5
Aluminium sulfide	Al ₂S ₃	98
			Aluminium sulfide	Al ₂S ₃	99.9
Tellurium aluminium	Al ₂Te ₃	99.5
			Copper selenide	Cu-Se	99.5
Copper selenide	Cu ₂Se	99.5
			Gallium selenide	Ga ₂Se ₃	99.999
Copper sulfide	Cu ₂S (can be Cu1.8-2S)	99.5
			Copper sulfide	CuS	99.5
Copper sulfide	CuS	99.99
			Tellurium copper	CuTe (typical Cu _1.4Te)	99.5
Tellurium copper	Cu ₂Te	99.5
			Sulfuration gallium	Ga ₂S ₃	99.95
Sulfuration gallium	GaS	99.95
			Tellurium gallium	GaTe	99.999
Tellurium gallium	Ga ₂Te ₃	99.999
			Indium selenide	In ₂Se ₃	99.999
Indium selenide	In ₂Se ₃	99.99％
			Indium selenide	In ₂Se ₃	99.9
Indium selenide	In ₂Se ₃	99.9
			Indium sulfide	InS	99.999
Indium sulfide	In ₂S ₃	99.99
			Tellurium indium	In ₂Te ₃	99.999
Tellurium indium	In ₂Te ₃	99.999

The example of chalcogen powder and other commercially available charging is listed in lower Table II.

Table II

Chemical composition	Chemical formula	Typical case's purity %
			Selenium metal	Se	99.99
Selenium metal	Se	99.6
			Selenium metal	Se	99.6
Selenium metal	Se	99.999
			Selenium metal	Se	99.999
Sulphur	S	99.999
			Tellurium metal	Te	99.95
Tellurium metal	Te	99.5
			Tellurium metal	Te	99.5
Tellurium metal	Te	99.9999
			Tellurium metal	Te	99.99
Tellurium metal	Te	99.999
			Tellurium metal	Te	99.999
Tellurium metal	Te	99.95
			Tellurium metal	Te	99.5

Print the layer in extra chalcogen source

Referring now to Fig. 9 A-9E, another embodiment of the present invention of using nano flake will be described.Fig. 9 A shows the substrate 602 with the contact layer 604 that forms nano flake precursor layer 606 thereon.Extra chalcogen source can be provided on nano flake precursor layer 606, and it is for example still not limited to the discrete layers 608 of simple substance chalcogen particle 607 as containing extra chalcogen source.For example, and do not lose in general manner, this chalcogen particle can be the particle of selenium, sulphur or tellurium.As shown in Figure 9 B, nano flake precursor layer 606 and the layer 608 that contains chalcogen particle are applied to heat 609 they are heated to the temperature that is enough to melt this chalcogen particle 607 and makes the element reaction in chalcogen particle 607 and precursor layer 606.Be to be understood that nano flake can be made by the multiple material that includes, but are not limited to IB family element, IIIA family element and/or VIA family element.The element of chalcogen particle 607 and precursor layer 606 react the compound film 610 that forms IB-IIIA chalcogenide compound as shown in Figure 9 C.Preferably, this IB-IIIA-chalcogenide compound has CuIn _1-xga _xse _{2 (1-y)}s _2yform, wherein 0≤x≤1 and 0≤y≤1.Be to be understood that in some embodiments, can sintering precursor layer 106 before thering is layer 108 applies in extra chalcogen source.In other embodiments, do not heat in advance precursor layer 106 but layer 106 is heated together with 108.

In one embodiment of the present invention, precursor layer 606 can be that about 4.0-approximately 0.5 μ m is thick.The layer 608 that contains chalcogen particle 607 can have the thickness of approximately 4.0 μ m-approximately 0.5 μ m.Chalcogen particle 607 sizes in layer 608 can be about 1nm-approximately 25 μ m, and preferred size is the about 300nm of about 25nm-.Notice that chalcogen particle 607 can be greater than the final thickness of IB-IIIA-VIA compound film 610 at first.Thereby chalcogen particle 607 can be mixed to preparation with solvent, carrier, dispersant etc. and be adapted at wet deposition on precursor layer 606 to form ink or the thickener of layer 608.As selection, can prepare chalcogen particle 607 to deposit to form layer 608 on substrate by dry method.Be also noted that the heating of the layer 608 that can contain chalcogen particle 607 by example RTA technique described above.

Can form chalcogen particle 607 (for example Se or S) with some diverse ways.For example, can for example, with commercially available detailed catalogue powder (200 order/75 μ m) initial and powder is milled to desired size forms Se or S particle.Common ball-milling technology can be used the milled ceramic ball being filled with in liquid medium and can be the ceramic grinding tank of the feed material of powder type.When rotation or while shaking this tank, described ball vibrate also abrasive flour to reduce the particle size of feed material in liquid medium.Optionally, this technique can comprise that but dry type (in advance) for example grinds relatively large material be not limited to Se.Dry grinding can be used 2-6mm and less piece, but also can process larger piece.Notice that this is applicable to all pulverizing, wherein technique can be initial by larger feed material, and dry grinding starts wet-milling (being for example still not limited to ball milling) subsequently.Grinder itself can be from small-sized medium grinder to horizontal rotary ceramic pot.

Referring now to Fig. 9 D, be to be understood that in addition in some embodiments, can below precursor layer 606, form the layer 608 of chalcogen particle.Thereby the IBZu He IIIA family element complete reaction in chalcogen particle provides chalcogen from enough surpluses to precursor layer 606 and layer 606 is still allowed in layer 608 this position.In addition, because the chalcogen discharging in layer 608 can rise by layer 606, this position of layer 608 below layer 606 can be of value to the larger mixing of generation between element.The thickness of layer 608 can be approximately 4.0 μ m-approximately 0.5 μ m.In other embodiments, the thickness of layer 608 can be the about 50nm of about 500nm-.In a kind of limiting examples, about 100nm or larger independent Se layer can be enough.The coating of chalcogen can comprise that (being used alone or in combination) utilizes powder coated, Se to evaporate or other Se deposition process is for example still not limited to chemical vapour deposition (CVD) (CVD), physical vapour deposition (PVD) (PVD), ald (ALD), electroplates and/or similar or correlation technique.The deposition of material technology of other type can be used for obtaining the Se layer that thickness is less than 0.5 μ m or is less than 1.0 μ m.Be to be understood that in addition in some embodiments, extra chalcogen source is not limited to only simple substance chalcogen, but can be alloy and/or the solution of one or more chalcogens in some embodiments.

Optionally, be to be understood that extra chalcogen source can mix with precursor layer and/or be deposited on wherein, rather than as discrete layer.In one embodiment of the present invention, can use the anaerobic particle of chalcogen or the particle of anaerobic substantially.If chalcogen is used together with nano flake and/or sheet-like precursor material, densification may not can terminate by using the problem of the higher density that plane particle reaches, and precursor layer in print Se and/or other chalcogen source contrary to discrete layers therefore has no reason to get rid of.This may not relate to will be heated to previous treatment temperature by precursor layer.In some embodiments, this may relate to and not be used in approximately 400 ℃ and add above thermosetting film.In some embodiments, this may relate to and needn't heat above at approximately 300 ℃.

In other embodiments of the present invention, can print multiple material layer and react with chalcogen before lower one deck deposition.Limiting examples can be a deposition Cu-In-Ga layer, by its annealing, then deposits Se layer, then with RTA, processes, and deposition is rich in another precursor layer of Ga afterwards, and primary depositing Se, and the second last time RTA processes.More generally, this can comprise formation precursor layer (heat or do not heat), then apply extra chalcogen source layer (then heat or do not heat), then form more precursors (heat or do not heat) of another layer, then be the extra chalcogen source (then heat or do not heat) of another layer, and repeat the number of times of expectation so that form the crystalline size nucleation that gradually changes or make expectation.In a kind of limiting examples, this can be used for making gallium concentration gradually to change.In another embodiment, this can be used for making copper concentration gradually to change.In another embodiment, this can be used for making indium concentration gradually to change.In another embodiment, this can be used for selenium concentration is changed gradually.In another embodiment, this can be used for selenium concentration is changed gradually.Another reason is that then first the grow film of rich copper starts to add the layer of poor copper to recover stoichiometry to obtain large crystal.Certain this embodiment can combine to allow that chalcogen is deposited in the precursor layer about any related step.

Referring now to Fig. 9 E, for example utilize chalcogen but the alternative method that is not limited to the low melting point of Se and S is to form core-shell nano flake, its center is nano flake 607 and shell 620 is chalcogen coatings.Chalcogen 620 fusing and with the material fast reaction of core nano flake 607.As a kind of limiting examples, (for example, Cu) and/or the mixture of the simple substance particle of IIIA family (for example, Ga and In), it can be by obtaining simple substance charging ball milling to desired size to endorse Yi Shi IB family.The example of available simple substance feed material is listed in the table below in III.Described core can also be chalcogenide core or other material as herein described.

Table III

Chemical composition	Chemical formula	Typical case's purity %
			Copper metal	Cu	99.99
Copper metal	Cu	99
			Copper metal	Cu	99.5
Copper metal	Cu	99.5
			Copper metal	Cu	99
Copper metal	Cu	99.999
			Copper metal	Cu	99.999
Copper metal	Cu	99.9
			Copper metal	Cu	99.5
Copper metal	Cu	99.9 (O ₂Typical case 2-10%)
			Copper metal	Cu	99.99
Copper metal	Cu	99.997
			Copper metal	Cu	99.99
Gallium metal	Ga	99.999999
			Gallium metal	Ga	99.99999
Gallium metal	Ga	99.99
			Gallium metal	Ga	99.9999
Gallium metal	Ga	99.999
			Indium metal	In	99.9999
Indium metal	In	99.999
			Indium metal	In	99.999
Indium metal	In	99.99
			Indium metal	In	99.999
Indium metal	In	99.99
			Indium metal	In	99.99

The chalcogenide particle of rich chalcogen

Referring now to Figure 10 A-10C, be to be understood that another embodiment of the present invention comprises that nano flake particle wherein can be the embodiment of the chalcogenide particle (no matter their ShiIB family chalcogenides, IIIA family chalcogenide or other chalcogenide) of rich chalcogen.In these embodiments, because chalcogenide particle itself contains excessive chalcogen, therefore may not need to use independent chalcogen source.In a kind of limiting examples of IB family chalcogenide, this chalcogenide can be copper selenide, and wherein material comprises Cu _xse _y, x<y wherein.Therefore, this is the chalcogenide of rich chalcogen, and when processing the particle of precursor material, it can provide excessive selenium.

Provide the object in extra chalcogen source to be first to produce liquid to expand the contact area between initial solid particle (thin slice) and liquid.Secondly, when film cooperation with poor chalcogen, chalcogen is added to reach the chalcogen amount of stoichiometry expectation in this extra source.The 3rd, chalcogen for example Se is volatile and during processing, inevitably loses some.Therefore, main purpose is to produce liquid.Also there is multiple other route to increase the amount of liquid when processing precursor layer.These routes include, but are not limited to: 1) compare Cu _2-xthe Cu-Se of the richer Se of Se (>377 ℃, at >523 ℃ of more liquid above); 2) and Cu ₂se equates maybe when the extra Se of interpolation the Cu-Se (>220 ℃) than its richer Se; 3) form In ₄se ₃, or at In ₄se ₃with In ₁se ₁between In-Se (>550 ℃); 4) and In ₄se ₃equate maybe when the extra Se of interpolation the In-Se (>220 ℃) than its richer Se; 5) In and In ₄se ₃between In-Se (>156 ℃, owing to producing In preferably in oxygen-free environment); 6) Ga emulsion (>29 ℃, preferably oxygen-free); Be seldom (but may) Ga-Se.Even when with the cooperation of Se steam, it can be still also very favorable using one of said method or by suitable method, in precursor layer itself, produce extra liquid.

Referring now to Figure 10 A, be to be understood that ink can contain polytype particle.In Figure 10 A, particle 704 is first kind particles and particle 706 is Equations of The Second Kind particles.In a kind of limiting examples, ink can have polytype particle, and the particle that wherein only has a type is chalcogenide but also is rich chalcogen.In other embodiments, ink can have such particle, and wherein the chalcogenide in the ink of at least two types is rich chalcogen.As a kind of limiting examples, ink can have Cu _xse _y(wherein x<y) and In _ase _b(wherein a<b).In other embodiments, ink can have particle 704,706 and 708 (showing with diplopia), wherein at least the chalcogenide particle of three types in ink.As limiting examples, the chalcogenide particle of rich chalcogen can be Cu-Se, In-Se and/or Ga-Se.All three kinds of rich chalcogens all.Various combinations are possible excessive chalcogens with acquisition expectation.If ink has the particle of three types, be to be understood that it is chalcogenide or rich chalcogen that not every particle all needs.Even in only having the ink of particle, for example Cu-Se of one type, also can there is for example Cu of x<y wherein of rich chalcogen particle _xse _ythe particle of the rich chalcogen Cu of x>y wherein for example not _xse _ymixture.As a kind of limiting examples, mixture can contain copper selenide particle, and it can have following composition: Cu ₁se ₁and Cu ₁se ₂.

Still with reference to Figure 10 A, even if be to be understood that in addition in the situation that the particle of rich chalcogen, also can be in addition by extra play 710 (showing with diplopia) thus print or be coated to extra chalcogen source is provided on ink as previously mentioned.Material in this layer can be pure chalcogen, chalcogenide or the compound that contains chalcogen.As shown in Figure 10 C, if wish further to process with chalcogen, extra play 710 (showing with diplopia) can also be printed onto on produced film.

Referring now to Figure 10 B, can apply heat to start they transformations to particle 704 and 706.Due to the different fusion temperatures of the material in particle, some materials can start to present liquid form quickly than other material.In the present invention, if present the particle of liquid form, also discharge the excessive chalcogen as liquid 712, this liquid can be around other material in this layer and/or element for example 714 and 716, and this is particularly advantageous.Figure 10 B comprises the view of the enlarged drawing with liquid 712 and material and/or

element

714 and 716.

By the amount of the integrally provided extra chalcogen of whole particles be in process after the on level terms or level on it of the stoichiometry that exists in compound.In one embodiment of the present invention, chalcogen excessive comprises the amount larger than following sum: the stoichiometry and 2 1) existing in final IB-IIIA chalcogenide film) form during the processing of final IB-IIIA-chalcogenide of the stoichiometric proportion with expectation the minimum due to the necessary chalcogen of loss.Although be not limited to following content, excessive chalcogen can serve as flux, and it will liquefy under treatment temperature and the more thick atom of the particle that promotes to be provided by the excessive chalcogen liquefying mixes.The excessive chalcogen of liquefaction can also guarantee to exist enough chalcogen Yi YuIBHe IIIA family element reactions.Excessive chalcogen helps " digestion " or " dissolving " particle or thin slice.Excessive chalcogen will be deviate from before being completed into the film of expectation from layer.

Referring now to Figure 10 C, can continue to apply heat until form IB-IIIA family chalcogenide film 720.If wish specific feature, can apply another layer of 722 (showing with diplopia) so that the further processing of film 720.As a kind of limiting examples, can add extra gallium source and further react with film 720 to top layer.Other source can provide extra selenium to improve the selenizing on film 720 end faces.

Be to be understood that and multiple chalcogenide particle and non-chalcogenide particle can also be combined to reach the excessive supply of the chalcogen of expecting in precursor layer.Some nonrestrictive arrays that may combine between the non-chalcogenide particle of enumerating in the chalcogenide particle that following table (Table IV) has been enumerated in providing and being expert at and row.

Table IV

?

Cu

In

Ga

Cu-In

Cu-Ga

In-Ga

Cu-In-Ga

Se

Se+Cu

Se+In

Se+Ga

Se+Cu-In

Se+Cu-Ga

Se+In-Ga

Se+Cu-In-Ga

Cu-Se

Cu-Se+Cu

Cu-Se+In

Cu-Se+Ga

Cu-Se+Cu-In

Cu-Se+Cu-Ga

Cu-Se+In-Ga

Cu-Se+Cu-In-Ga

In-Se

In-Se+Cu

In-Se+In

In-Se+Ga

In-Se+Cu-In

In-Se+Cu-Ga

In-Se+In-Ga

In-Se+Cu-In-Ga

Ga-Se

Ga-Se+Cu

Ga-Se+In

Ga-Se+Ga

Ga-Se+Cu-In

Ga-Se+Cu-Ga

Ga-Se+In-Ga

Ga-Se+Cu-In-Ga

Cu-In-Se

Cu-In-Se+Cu

Cu-In-Se+In

Cu-In-Se+Ga

Cu-In-Se+Cu-In

Cu-In-Se+Cu-Ga

Cu-In-Se+In-Ga

Cu-In-Se+Cu-In-Ga

Cu-Ga-Se

Cu-Ga-Se+Cu

Cu-Ga-Se+In

Cu-Ga-Se+Ga

Cu-Ga-Se+Cu-In

Cu-Ga-Se+Cu-Ga

Cu-Ga-Se+In-Ga

Cu-Ga-Se+Cu-In-Ga

In-Ga-Se

In-Ga-Se+Cu

In-Ga-Se+In

In-Ga-Se+Ga

In-Ga-Se+CuIn

In-Ga-Se+Cu-Ga

In-Ga-Se+In-Ga

In-Ga-Se+Cu-In-Ga

Cu-In-Ga-Se

Cu-In-Ga-Se+Cu

Cu-In-Ga-Se+In

Cu-In-Ga-Se+Ga

Cu-In-Ga-Se+CuIn

Cu-In-Ga-Se+CuGa

Cu-In-Ga-Se+InGa

Cu-In-Ga-Se+Cu-In-Ga

In another embodiment, the present invention can be by multiple chalcogenide particle and the combination of other chalcogenide particle.Between the chalcogenide particle of enumerating in the chalcogenide particle that following table (Table V) is enumerated in providing and being expert at and row, some may combine nonrestrictive array.

Table V

?

Cu-Se

In-Se

Ga-Se

Cu-In-Se

Cu-Ga-Se

In-Ga-Se

Cu-In-Ga-Se

Se

Se+Cu-Se

Se+In-Se

Se+Ga-Se

Se+Cu-In-Se

Se+Cu-Ga-Se

Se+In-Ga-Se

Se+Cu-In-Ga-Se

Cu-Se

Cu-Se+In-Se

Cu-Se+Ga-Se

Cu-Se+Cu-In-Se

Cu-Se+Cu-Ga-Se

Cu-Se+In-Ga-Se

Cu-Se+Cu-In-Ga-Se

In-Se

In-Se+Cu-Se

In-Se

In-Se+Ga-Se

In-Se+Cu-In-Se

In-Se+Cu-Ga-Se

In-Se+In-Ga-Se

In-Se+Cu-In-Ga-Se

Ga-Se

Ga-Se+Cu-Se

Ga-Se+In-Se

Ga-Se

Ga-Se+Cu-In-Se

Ga-Se+Cu-Ga-Se

Ga-Se+In-Ga-Se

Ga-Se+Cu-In-Ga-Se

Cu-In-Se

Cu-In-Se+Cu-Se

Cu-In-Se+In-Se

Cu-In-Se+Ga-Se

Cu-In-Se

Cu-In-Se+Cu-Ga-Se

Cu-In-Se+In-Ga-Se

Cu-In-Se+Cu-In-Ga-Se

Cu-Ga-Se

Cu-Ga-Se+Cu-Se

Cu-Ga-Se+In-Se

Cu-Ga-Se+Ga-Se

Cu-Ga-Se+Cu-In-Se

Cu-Ga-Se

Cu-Ga-Se+In-Ga-Se

Cu-Ga-Se+Cu-In-Ga-Se

In-Ga-Se

In-Ga-Se+Cu-Se

In-Ga-Se+In-Se

In-Ga-Se+Ga-Se

In-Ga-Se+Cu-In-Se

In-Ga-Se+Cu-Ga-Se

In-Ga-Se

In-Ga-Se+Cu-In-Ga-Se

Cu-In-Ga-Se

Cu-In-Ga-Se+Cu-Se

Cu-In-Ga-Se+In-Se

Cu-In-Ga-Se+Ga-Se

Cu-In-Ga-Se+Cu-In-Se

Cu-In-Ga-Se+Cu-Ga-Se

Cu-In-Ga-Se+In-Ga-Se

Cu-In-Ga-Se

Nucleating layer

Referring now to Figure 11 A-11C, but another embodiment of the present invention of for example using thin slice being not limited to nano flake will be described.This embodiment provides a kind of method, and it is for growing with the crystal that serves as the nucleation plane of the precursor tunic growth forming on Gai IB-IIIA family chalcogenide thin layer and improve on substrate by deposit IB-IIIA family chalcogenide thin layer on substrate.Can before forming precursor layer, deposit, apply or form the nucleating layer of this IB-IIIA family chalcogenide.Can form this nucleating layer by vacuum or antivacuum technology.The precursor layer forming on nucleating layer can be by including, but are not limited to use the multiple technologies of the ink contain a plurality of nano flakes described in the application to form.

Figure 11 A shows can form absorbed layer on substrate 812, as shown in Figure 11 A.The surface of substrate 812 can be with contact layer 814 coated with promoting electrically contacting between substrate 812 and absorbed layer formed thereon.For example, aluminium substrate 812 can be coated with molybdenum contact layer 814.As discussed herein, if use contact layer, on substrate 812, formation or material arranged or material layer are included in and on contact layer 814, arrange or form such material or layer.

As shown in Figure 11 B, on substrate 812, be formed into stratum nucleare 816.This nucleating layer can comprise IB-IIIA family chalcogenide and can before forming precursor layer, deposit, applies or form.As a kind of limiting examples, this can be cigs layer, Ga-Se layer, any other high-melting-point IB-IIIA family chalcogenide layer or thin layer of gallium even.

Referring now to Figure 11 C, once form this nucleating layer, can on nucleating layer, form precursor layer 818.In some embodiments, nucleating layer and precursor layer can form simultaneously.Precursor layer 818 can contain one or more IB family elements and one or more IIIA family elements.Preferably, these one or more IB family elements comprise copper.These one or more IIIA family elements can comprise indium and/or gallium.Precursor layer can be formed by film, for example, by any technology in above-mentioned technology, form.

Still with reference to Figure 11 C, be to be understood that in addition and can in lamination, repeat nucleating layer alternately and the structure of precursor layer.Figure 11 C shows optionally can form another nucleating layer 820 (showing with diplopia) to continue nucleating layer alternately and the structure of precursor layer on precursor layer 818.Then can on nucleating layer 820, form another precursor layer 822 stacked to continue, this can carry out repetition as required.Although be not limited to following content, can exist the nucleating layer replacing of 2,3,4,5,6,7,8,9,10 or more groups and precursor layer to set up the characteristic of expectation.Each group is compared and can be had different materials or quantity of material from other group in lamination.Alternating layer can be liquid deposition, vacuum-deposited etc.Layer that can be different by different deposition techniques.In one embodiment, this can comprise liquid deposition (or vacuum moulding machine) precursor layer (optionally having the Cu of expectation and the ratio of In and Ga), add subsequently chalcogen (solution-based, vacuum-based or in addition for example but be not limited to steam or H ₂se etc.), this lamination of heat treatment (during introducing chalcogen source or afterwards) optionally, deposit subsequently other precursor layer (optionally thering is the Cu of expectation and the ratio of In and Ga), and last this final lamination of heat treatment (during introducing other chalcogen or afterwards).Target is to produce plane nucleation to do not exist substrate wherein not by film forms and/or crystal growth is covered hole or region subsequently.Optionally, also can before adding first precursor layer that contains Cu+In+Ga, introduce chalcogen source.Be to be understood that in addition in some of the other embodiments, layer 820 can be the layer containing chalcogen, for example, be still not limited to selenium layer, and (or finally after forming all precursor layers) heating together with each precursor layer.

Nucleating layer by means of thermal gradient

Referring now to Figure 12 A-12B, be to be understood that and can also form the nucleating layer using together with nano flake based precursor material by produce thermal gradient in precursor layer 850.As a kind of limiting examples, nucleating layer 852 can start from the top of precursor layer to form, or optionally by the bottom from precursor layer, is formed into stratum nucleare 854.In one embodiment of the present invention, nucleating layer can be regarded as wherein the layer of the crystal growth on the another location that the growth of initial IB-IIIA-VIA compound crystal has precedence over precursor layer and/or precursor layer lamination.By produce thermal gradient in precursor layer, make the part of this layer reach to be enough to the temperature that starts crystal growth to be formed into stratum nucleare 852 or 854.Nucleating layer can be to have the form of the nucleation plane of planar structure substantially to grow and make aperture and other irregular formation minimize simultaneously across the more uniform crystal of substrate with promotion.

From Figure 12 A, In one embodiment of the present invention, can produce for being formed into the thermal gradient of stratum nucleare 852 by coming with laser 856 only the top of precursor layer 850 to be brought up to treatment temperature.Thereby laser 856 can be pulse or in addition controlledly the whole thickness of precursor layer can be heated to treatment temperature.The back side 858 of precursor layer can contact with chill roll 862, cooling smooth contact surface or cooler drum with the substrate 860 that supports it, and they provide external refrigeration source to reach treatment temperature to prevent the bottom of described layer.Below treatment temperature when can provide refrigerating gas 864 on a side of substrate and precursor layer adjacent part in addition to the temperature of precursor layer being reduced to the nucleation of final IB-IIIA chalcogenide compound and starting.Be to be understood that and other device can be used for heating the top of precursor layer, for example, be still not limited to pulse heat processing, plasma heating or heat via IR lamp.

From Figure 12 B, in another embodiment of the present invention, can in the bottom of precursor layer 850, be formed into stratum nucleare 854 with being similar to above-mentioned those technology.Owing to can selecting for substrate 860 of the present invention, be heat conduction, so the heating of the downside of substrate also can cause the heating of precursor layer bottom.So nucleation plane can form along the bottom along bottom.The top of precursor layer can be cooling by multiple technologies, for example, be still not limited to refrigerating gas, chill roll or other cooling device.

After nucleating layer forms, it is preferably comprised of the material being equal to or approach final IB-IIIA chalcogenide compound, whole precursor layer or optionally only have precursor layer still more or less untreated those parts will be heated to treatment temperature, make remaining material to start to be converted into the final IB-IIIA chalcogenide compound contacting with nucleating layer.Nucleating layer guiding Crystallization and making because the possibility that inhomogeneous crystal growth forms aperture or has other irregular substrate region is reduced to minimum.

Be to be understood that except above-mentioned, in the different time sections that temperature can also be processed at precursor layer, change.As a kind of limiting examples, heating can be carried out and proceed to other temperature for processing time section subsequently in initial processing time section at the first temperature.Optionally, the method can comprise has a mind to produce that one or more temperature decline to such an extent as to as a kind of limiting examples, the method comprise heating, cooling, heat cooling subsequently.In one embodiment of the present invention, this can relate to temperature is reduced to approximately 50 ℃-Yue 200 ℃ from the temperature in the initial time period.

Nucleating layer by means of chemical gradient

Referring now to Figure 13 A-13F, will be described in more detail the another kind of method that is formed into stratum nucleare with nano flake precursor material of the present invention.In this embodiment of the present invention, can select the composition of precursor material layer to make in some layers Crystallization than starting sooner in other layer.Be to be understood that and the distinct methods that is formed into stratum nucleare can be combined with promoting layer and formed.As a kind of limiting examples, can combine thermal gradient and chemical gradient method to promote nucleating layer to form.The imagination draws the single or Multiple Combination that can be used in combination thermal gradient, chemical gradient and/or film nucleating layer.

Referring now to Figure 13 A, can on substrate 912, form absorbed layer, as shown in FIG. 13A.A surface of substrate 912 can be with contact layer 914 coated with promoting electrically contacting between substrate 912 and absorbed layer formed thereon.For example, aluminium substrate 912 can be coated with molybdenum contact layer 914.As discussed herein, if use contact layer, on substrate 912, formation or material arranged or material layer are included in and on contact layer 914, arrange or form such material or layer.Optionally, being to be understood that in addition can also be on contact layer 914 and/or directly on substrate 912, form layer 915.This layer can be that solution applies, evaporation and/or by vacuum-based deposition techniques.Although be not limited to following content, layer 915 can have the thickness that is less than precursor layer 916.In a kind of limiting examples, this layer can the about 100nm of thick about 1-.Layer 915 can form by including, but are not limited to following at least one multiple material: IB family element, IIIA family element, VIA family element, IA family element (new style: 1 family), the binary of any aforementioned elements and/or multicomponent alloy, the solid solution of any aforementioned elements, copper, indium, gallium, selenium, copper indium, copper gallium, indium gallium, sodium, sodium compound, sodium fluoride, indium sulfide sodium, copper selenide, copper sulfide, indium selenide, indium sulfide, gallium selenide, sulfuration gallium, copper indium diselenide, copper indium sulfide, gallium selenide copper, sulfuration gallium copper, selenizing gallium indium, sulfuration gallium indium, selenizing gallium indium copper and/or sulfuration gallium indium copper.

As shown in Figure 13 B, on substrate, form precursor layer 916.Precursor layer 916 contains one or more IB family elements and one or more IIIA family elements.Preferably, these one or more IB family elements comprise copper.These one or more IIIA family elements can comprise indium and/or gallium.Precursor layer can form by any technology in above-mentioned technology.In one embodiment, except inevitably existing as impurity or being accidentally present in outside those oxygen in the membrane component nano flake itself, precursor layer is oxygen-free.Although preferably form precursor layer 916 by antivacuum method, be to be understood that it can optionally form by other method, such as evaporation, sputter, ALD etc.For example, precursor layer 916 can be the non-oxygen compound that contains copper, indium and gallium.In one embodiment, under the pressure of antivacuum system more than about 3.2kPa (24 holder), work.Optionally, be to be understood that in addition and can also on precursor layer 916, form layer 917.Be to be understood that lamination can have layer 915 and 917 simultaneously, only have one of them or do not have this two-layer.Although be not limited to following content, layer 917 can have the thickness that is less than precursor layer 916.In a kind of limiting examples, this layer can the about 100nm of thick about 1-.Layer 917 can form by including, but are not limited to following at least one multiple material: IB family element, IIIA family element, VIA family element, IA family element (new style: 1 family), the binary of any aforementioned elements and/or multicomponent alloy, the solid solution of any aforementioned elements, copper, indium, gallium, selenium, copper indium, copper gallium, indium gallium, sodium, sodium compound, sodium fluoride, indium sulfide sodium, copper selenide, copper sulfide, indium selenide, indium sulfide, gallium selenide, sulfuration gallium, copper indium diselenide, copper indium sulfide, gallium selenide copper, sulfuration gallium copper, selenizing gallium indium, sulfuration gallium indium, selenizing gallium indium copper and/or sulfuration gallium indium copper.

Referring now to Figure 13 C, can optionally on precursor layer, apply the second precursor layer 918 of the second precursor material.The second precursor material can have total composition of comparing richer chalcogen with the first precursor material in precursor layer 916.As a kind of limiting examples, by producing two coatings (preferably after two precursor layer coatings of deposition lamination for once heating process), wherein the first coating contains the selenides of comparing and wherein have relative less selenium (but still enough) with the second coating, and this allows the gradient that produces available Se.For example, the precursor of the first coating can contain Cu _xse _y, wherein x is greater than in the second coating.Or it can contain Cu _xse _ythe mixture of particle, the wherein large selenides particle of x of the larger concentration of existence (by weight).In the current embodiment, every one deck preferably has target stoichiometry, because C/I/G ratio keeps identical to each precursor layer.Equally, although this second precursor layer 918 preferably forms by antivacuum method, be to be understood that it can optionally pass through for example evaporation of other method, sputter, ALD etc. formation.

Use chalcogen gradually to change or more generally from bottom to top the basic principle gradually changing of fusion temperature be, go deep into the relative speed of crystallization control and make crystallization for example at precursor layer laminated bottom than occurring sooner at precursor layer lamination top.Other basic principle is, general grain structure in conventionally effective liquid deposition CIGS unit still has considerable effciency of energy transfer, wherein this unit has large crystal grain and has overleaf little crystal grain at the top of Photoactive film, and this Photoactive film is a part for main photoactive Photoactive film.Be to be understood that in other embodiments, a plurality of chalcogen gradients that can be used for setting up expectation in many different precursor material layers, or more generally in fusion temperature and/or be frozen into subsequently the expectation gradient in final IB-IIIA-chalcogenide compound, or more generally owing to producing chemistry (compositions) gradient and/or thermal gradient in produced film, melting and/or be frozen into subsequently the expectation gradient in final IB-IIIA-chalcogenide compound.As limiting examples, the present invention can use particle and/or micron thin slice and/or the nano flake with different melting points, for example, be still not limited to and higher melt material In ₂se ₃, Cu ₂se compare compared with low melting material Se, In ₄se ₃, Ga and Cu ₁se ₁.

Referring now to Figure 13 C, apply heat 920 to sinter the first precursor layer 916 and the second precursor layer 918 into IB-IIIA compounds of group film 922.Can in example quick thermal annealing process described above, supply heat 920.Particularly, substrate 912 and precursor layer 916 and/or 918 can be heated to the plateau temperature range of approximately 200 ℃-Yue 600 ℃ from ambient temperature.Temperature is remained in this plateau range and continues the approximately time of part second to approximately 60 minutes, lower the temperature subsequently.

Optionally, as shown in Figure 13 D, be to be understood that and can before heating, the layer 924 that contains simple substance chalcogen particle be applied on precursor layer 916 and/or 918.Certainly, if material laminate does not comprise the second precursor layer, layer 924 is formed on precursor layer 916.For example, and do not lose in general manner, this chalcogen particle can be the particle of selenium, sulphur or tellurium.Can manufacture as mentioned above these particles.Chalcogen particle size in layer 924 can be about 1nm-approximately 25 μ m, preferably 50nm-500nm.Thereby chalcogen particle can be mixed to preparation with solvent, carrier, dispersant etc. and be adapted at wet deposition on precursor layer 916 and/or 918 to form ink or the thickener of layer 924.As selection, can prepare chalcogen particle for being deposited on by dry method on substrate to form layer 924.

Optionally, as shown in Figure 13 E, can optionally apply the layer 926 that contains extra chalcogen source and/or the atmosphere that contains chalcogen source to layer 922, if particularly there is no applied layer 924 in Figure 13 D.Thereby can be optionally to layer 922 and layer 926 and/or the atmosphere that contains chalcogen source apply heat 928 heat they to be enough to melt chalcogen element source and make chalcogen source and precursor layer 922 in IB family element and the temperature of IIIA family element reaction.Can in example quick thermal annealing process described above, apply heat 928.The reaction of chalcogen Yuan YuIBHe IIIA family element forms the compound film 930 of IB-IIIA family chalcogenide compound as shown in Figure 13 F.Preferably ，Gai IB-IIIA family chalcogenide compound has formula Cu _zin _1-xga _xse _{2 (1-y)}s _2y, wherein 0≤x≤1,0≤y≤1 and 0.5≤y≤1.5.

Still with reference to Figure 13 A-13F, be to be understood that and also can use sodium to improve the character of the film being produced together with precursor material.In first method, as just Figure 13 A and 13B, discuss like that, can above precursor layer 916 and/or below form one or more containing sodium material layer.This formation can apply and/or other technology is carried out by solution, for example but be not limited to sputter, evaporation, CBD, plating, sol-gel based coating, spraying, chemical vapour deposition (CVD) (CVD), physical vapour deposition (PVD) (PVD), ald (ALD) etc.

Optionally, in the second approach, the doping that also can be undertaken by the nano flake in precursor layer 916 and/or particle is introduced sodium in lamination.As a kind of limiting examples, nano flake in precursor layer 916 and/or other particle can be containing sodium material, for example, be still not limited to Cu-Na, In-Na, Ga-Na, Cu-In-Na, Cu-Ga-Na, In-Ga-Na, Na-Se, Cu-Se-Na, In-Se-Na, Ga-Se-Na, Cu-In-Se-Na, Cu-Ga-Se-Na, In-Ga-Se-Na, Cu-In-Ga-Se-Na, Na-S, Cu-S-Na, In-S-Na, Ga-S-Na, Cu-In-S-Na, Cu-Ga-S-Na, In-Ga-S-Na and/or Cu-In-Ga-S-Na.In one embodiment of the present invention, the sodium content in this nano flake and/or other particle can be to be less than approximately 1 atom % or still less.In another embodiment, sodium content can be approximately 0.5 atom % or still less.In another embodiment, sodium content can be approximately 0.1 atom % or still less.Be to be understood that and can make by several different methods particle and/or the thin slice of this doping, the method comprises grinds feed material together with containing sodium material and/or SODIUM METAL.

Optionally, in the third method, sodium can be introduced to ink itself, no matter the kind of the particle, nano particle that disperse in this ink, micron thin slice and/or nano flake how.As a kind of limiting examples, ink can comprise nano flake (Na doping or unadulterated) and have the sodium compound of means organic balance ion (but be for example not limited to sodium acetate) and/or have the sodium compound (but be for example not limited to vulcanized sodium) of inorganic counter ion counterionsl gegenions.Be to be understood that the sodium compound that joins (as independent compound) in ink may for example, exist or dissolve as particle (nano particle).Sodium can be " aggregation " form and " molecular level dissolving " form of sodium compound (for example discrete particles).

Thereby above-mentioned three kinds of methods none be mutually repel and also can be individually or to the lamination that contains precursor material, provide the sodium of desired amount with any single or Multiple Combination application.In addition, sodium and/or compounds containing sodium can also be added in substrate and (for example add in molybdenum target).In addition,, if use a plurality of precursor layers (adopting identical or different material), can between one or more precursor layers, form the layer containing sodium.Be to be understood that in addition those materials that sodium source is not limited to enumerate above.As a kind of limiting examples, substantially, the alcohol of any deprotonation that wherein proton is replaced by sodium, organic and the inorganic acid of any deprotonation, the sodium salt of (deprotonation) acid, NaOH, sodium acetate, and the sodium salt of following acid: butyric acid, caproic acid, sad, capric acid, dodecylic acid, tetradecanoic acid, hexadecanoic acid, palmitoleic acid, octadecanoid acid, 9-octadecenoic acid, vaccenic acid, 9,12-octadecadienoic acid, cis 9,12,15-oc-tadecatrienoic acid and/or 6,9,12-octatecatrienoic acid.

Optionally, as seen in Figure 13 F, being to be understood that in addition can at precursor layer, sintering or other joins sodium and/or sodium compound in the chalcogenide film of processing after processing.Therefore this embodiment of the present invention makes film modification after CIGS forms.When sodium exists, the carrier traps energy level relevant with crystal boundary reduces, and allows the electronic property of improvement in film.Can using multiple containing sodium material for example above-named those as layer 932, deposit on the film of processing then and anneal and process CIGS film.

In addition, can be by sodium material and other element combinations that Bandgap extension effect can be provided.Two kinds of elements can realizing this effect comprise gallium and sulphur.Except sodium, the use of one or more these elements can further improve the character of absorbed layer.Sodium compound is for example still not limited to Na ₂s, NaInS ₂thereby Deng use to film provide simultaneously Na and S and also can with annealing for example but be not limited to RTA step advance provide the band gap of band gap and unmodified cigs layer or film different layer.

Referring now to Figure 14, embodiment of the present invention can be manufactured compatible with reel-to-reel.Particularly, in reel-to-reel manufacturing system 1000, flexible substrate 1001, for example aluminium foil march to winding volume 1004 from supplying with volume 1002.In the middle of supplying with volume and being wound around volume, substrate 1001 for example, through some spreader 1006A, 1006B, 1006C, nick roller (microgravure rollers) and heater 1008A, 1008B, 1008C.Different layers or the sublayer of each spreader depositing photovoltaic device active layers, example those layers described above.Heater is used for making the annealing of different sublayers.In the example of describing at Figure 14, spreader 1006A and 1006B can be coated with the different sublayers of precursor layer (for example precursor layer 106, precursor layer 916 or precursor layer 918).Heater 1008A and 1008B can make each sublayer annealing before the next sublayer of deposition.As selection, two sublayers of can simultaneously annealing.Spreader 1006C can be coated with the material layer that contains as mentioned above chalcogen particle.Heater 1008C heats this chalcogen layer and above-mentioned precursor layer.Note also can then depositing containing the layer of chalcogen and then by whole three layers IB-IIIA-chalcogenide compound film that heats to be together formed for photovoltaic absorption layer by precursors to deposit layer (or sublayer).

The sum that can change print steps has the absorbed layer of different brackets band gap with structure.For example, can print (and optionally annealing between print steps) other layer (4 layers, 5 layers, 6 layers etc.) thus in absorbed layer, produce the more band gap of subfractionation.As selection, also can print less film (for example Double-layered printing) to produce the less band gap of subfractionation.For above-mentioned embodiment any, the chalcogens can also in every one deck with different amounts are grown with the crystal that changes the chalcogen amount that may be existed and affect.

In addition, be to be understood that in different layers and can use according to the present invention many combinations of thin slice and non-plane particle.As a kind of limiting examples, this combination can include, but are not limited to following:

Table VI

Combination 1	1) chalcogenide (thin slice)+non-chalcogenide (thin slice)
		Combination 2	2) chalcogenide (thin slice)+non-chalcogenide (non-thin slice)
Combination 3	3) chalcogenide (non-thin slice)+non-chalcogenide (thin slice)
		Combination 4	4) chalcogenide (non-thin slice)+non-chalcogenide (non-thin slice)
Combination 5	5) chalcogenide (thin slice)+chalcogenide (thin slice)
		Combination 6	6) chalcogenide (thin slice)+chalcogenide (non-thin slice)
Combination 7	7) chalcogenide (non-thin slice)+chalcogenide (non-thin slice)
		Combination 8	8) non-chalcogenide (thin slice)+non-chalcogenide (thin slice)
Combination 9	9) non-chalcogenide (thin slice)+non-chalcogenide (non-thin slice)
		Combination 10	10) non-chalcogenide (non-thin slice)+non-chalcogenide (non-thin slice)

Although be not limited to following content, these chalcogenides and non-chalcogenide material can be selected from any material in those that list in Table IV and V.

The fusion temperature reducing

In another embodiment of the present invention, can change the material character that the elemental ratio in particle or thin slice is more expected with generation.In a kind of limiting examples, this embodiment comprise use expectation stoichiometric proportion element so that in ink particle used there is the fusion temperature of reduction.As nonrestrictive example, for IB family chalcogenide, control the amount of IB family element and the amount of chalcogen so that the material producing moves to the part in phasor with the fusion temperature of reduction.Therefore for Cu _xse _y, select the value of x and y to produce the material of the fusion temperature with reduction, as measured with reference to the phasor of this material.The phasor of following material can, at the ASMHandbook that is all incorporated to by reference ASM International herein for all objects, find in Volume3Alloy Phase Diagrams (1992).Some instantiations can find at 2-168,2-170,2-176,2-178,2-208,2-214,2-257 and/or 2-259 page.

As a kind of limiting examples, copper selenide has multiple fusion temperature according to the ratio of copper in material and selenium.Solid solution Cu _2-xall of the richer Se of Se form (namely pure Cu on the left side and right side on pure Se binary phase diagraml on the right) can produce liquid selenium.According to composition, fusion temperature can be low to moderate 221 ℃ and (compare Cu ₁se ₂richer Se), be low to moderate 332 ℃ (for Cu ₁se ₁with Cu ₁se ₂between composition) and be low to moderate 377 ℃ (for Cu _2-xse and Cu ₁se ₁between composition).523 ℃ and more than, for than the Cu-Se of the richer Se of eutectic (～57.9wt%Se), this material is all liquid.For solid solution Cu _2-xcomposition between Se and eutectic (～57.9wt%Se), will and just produce solid-state solid solution Cu at 523 ℃ more than it _2-xse and liquid eutectic (～57.9wt%Se).

Another limiting examples comprises gallium selenide, and it can have multiple fusion temperature according to the ratio of gallium in material and selenium.Mainly the ratio Ga of pure Se ₂se ₃all of richer Se form (namely pure Ga on the left side and right side on pure Se binary phase diagraml on the right) can be at 220 ℃ of above liquid that produce.By preparation example as compound Ga ₂se ₃(or compare Ga ₁se ₁any compound of richer Se) can prepare and compare Ga ₁se ₁the Ga-Se of richer Se, but only have when interpolation is during other selenium source, and at Ga ₁se ₁and Ga ₂se ₃between or during composition (it be extra selenium source or the Cu-Se of the rich Se) cooperation identical with them, Ga-Se will liquefy under treatment temperature.Therefore, can provide extra Se source with promotion, to comprise the generation of the liquid of gallium selenide.

Another limiting examples comprises indium selenide, and it can have multiple fusion temperature according to the ratio of indium in material and selenium.Mainly the ratio In of pure Se ₂se ₃all of richer Se form (namely pure In on the left side and right side on pure Se binary phase diagraml on the right) can be at 220 ℃ of above liquid that produce.In is compared in preparation ₁se ₁the In-Se of richer Se can produce In ₂se ₃also has In ₆se ₇liquid (or at In ₁se ₁and the main assembly between Se), still when processing at In ₁se ₁and In ₂se ₃between or during the composition identical with them, only have by adding other Se source (its for extra selenium source or the Cu-Se of rich Se), this In-Se can liquefy under treatment temperature.Optionally for In-Se, exist another kind of by the method for carrying out in " another " direction and using the more liquid of composition generation of the less rich Se left side of binary phase diagraml (namely).By using pure In and In ₄se ₃between (or according to temperature at In and In ₁se ₁between or In and In ₆se ₇between) material form, can produce neat liquid In and (or the movement of carrying out richer Se when the eutectic point from～24.0wt%Se is until In at 520 ℃ at 156 ℃ ₁se ₁time under higher temperature) produce more liquid.Substantially, for than the main assembly of the less rich Se of In-Se eutectic (～24.0wt%Se), all In-Se can become liquid at 520 ℃.Certainly, for the poor Se material of these types, will need in other particle a kind of (for example but be not limited to Cu ₁se ₂and/or Se) or another Se source improve Se content.

Therefore, by producing liquid below under our treatment temperature: 1) add independently selenium source, 2) use and compare Cu _2-xthe Cu-Se of the richer Se of Se, 3) use Ga-emulsion (or In-Ga emulsion) or In (in without air ambient), or 4) use and compare In ₁se ₁the In-Se of less rich Se, although this also may require airfree environment.When using copper selenide, composition can be Cu _xse _y, wherein x is that about 2-approximately 1 and y are about 1-approximately 2.When using indium selenide, composition can be In _xse _y, wherein x is that about 1-approximately 6 and y are about 0-approximately 7.When using gallium selenide, composition can be Ga _xse _y, wherein x is that about 1-approximately 2 and y are about 1-approximately 3.

Be to be understood that adding independently selenium source can make composition on the interface of selenides particle and liquid selenium, show as at first richer Se under treatment temperature.

Chalcogen steam ambient

Referring now to Figure 15 A, another embodiment of the present invention will be described.In this embodiment of using, be to be understood that the superpressure from chalcogen steam is used to provide to chalcogen atmosphere to be processed and crystal growth to improve film together with nano flake precursor material.Figure 15 A has shown that chamber 1050 is together with the substrate 1052 with contact layer 1054 and precursor layer 1056.At this, indoorly comprise extra chalcogen source 1058 and make it reach the temperature that produces the chalcogen steam represented by lines 1060.In one embodiment of the present invention, provide chalcogen steam and be more than or equal to following vapour pressure so that be present in the dividing potential drop of the chalcogen in atmosphere: under treatment temperature and processing pressure, keep chalcogen dividing potential drop so that the loss of the chalcogen of precursor layer minimizes and the words of wishing provide the required chalcogen vapour pressure of precursor layer with extra chalcogen.Part determines this dividing potential drop based on chamber 1050 or the residing temperature of precursor layer 1056.Be to be understood that in addition and in chamber 1050, under antivacuum pressure, use chalcogen steam.In one embodiment, indoor pressure is about atmospheric pressure.According to perfect gas law PV=nRT, be to be understood that temperature affects vapour pressure.In one embodiment, can have therein or the partially or completely chamber of sealing in the chalcogen source 1062 that is connected with this chamber provides chalcogen steam by use.In using another embodiment of more unlimited chamber, the source that can produce chalcogen steam by supply provides chalcogen atmosphere.Chalcogen steam can be with helping to keep the chalcogen in film or providing chalcogen so that precursor layer transforms.Therefore, can with or can provide excessive chalcogen without chalcogen steam.In some embodiments, compare to film with more chalcogens are provided, this is the chalcogen for keeping film to exist more.Optionally, this can be as being incorporated in addition not containing chalcogen or not containing the chalcogen in the precursor layer of selenium.Being exposed to chalcogen steam can under atmospheric pressure occur.These conditions go for any embodiment as herein described.Can chalcogen be brought into indoor by carrier gas.Carrier gas can be inert gas such as nitrogen, argon gas etc.This chalcogen atmosphere system can be suitable for reel-to-reel system.

Referring now to Figure 15 B, demonstrate the present invention and can be applicable to using together with reel-to-reel system, with the substrate 1070 of precursor layer, can be wherein flexible and be configured to roll up 1072 and 1074.Chamber 1076 can be under vacuum or antivacuum pressure.Chamber 1076 can be designed to comprise different valve design so that the loss of the chamber inlet of reel-to-reel substrate 1070 and exit point place, chamber chalcogen steam minimizes.

Referring now to Figure 15 C, another embodiment of the present invention is used the chamber 1090 of sufficient size to hold whole substrate, comprises with using reel-to-reel and constructs relevant any

volume

1072 or 1074.

Referring now to Figure 16 A, be to be understood that in addition embodiment of the present invention can also be used in rigid substrate 1100.As limiting examples, rigid substrate 1100 can be glass, solar energy glass, low iron glass, green glass, soda-lime glass, steel, stainless steel, aluminium, polymer, pottery, coated polymer or be suitable as solar cell or other rigid material of solar energy module substrate.Can rigid substrate 1100 be moved to processing region from stacking or other storage area with high speed pick and place machine device people 1102.In Figure 16 A, substrate 1100 is placed on conveyer belt, then this conveyer belt makes them move through different process chambers.Optionally, substrate 1100 now may live through some processing and may on substrate 1100, comprise precursor layer.Other embodiment of the present invention can form precursor layer when substrate 1100 passes chamber 1106.

Figure 16 B shows another embodiment of native system, wherein with pick and place machine device people 1110, a plurality of rigid substrate is placed on conveying arrangement 1112, and this device can then move to processing region as shown in arrow 1114.This allows that loading a plurality of substrates 1100 then makes them all mobile with through being subject to processing together.

Referring now to Figure 17, another embodiment of the present invention will be described.In one embodiment, the particle that is used for forming precursor layer 1500 can comprise the particle as intermetallic particle 1502.In one embodiment, intermetallic material is the material that contains at least two kinds of elements, and wherein the amount of a kind of element in this intermetallic material is less than the approximately 50mol% of the integral molar quantity of that a kind of element in intermetallic material integral molar quantity and/or precursor material.The amount of the second element be variable and also can from this intermetallic material and/or precursor material that a kind of element integral molar quantity be less than about 50mol% to about 50mol% or larger.As selection, intermetallic phase material can be comprised of two or more metals, wherein with the ratio composite material between the upper limit of end border solid solution and the alloy that comprises one of element in approximately 50% intermetallic material.The distribution of particles showing in the enlarged drawing of Figure 10 is pure exemplary and is nonrestrictive.Be to be understood that some embodiments can have the particle of the mixture, metallic particles and intermetallic particle or its combination that all contain intermetallic material, metal material and intermetallic material.

Be to be understood that intermetallic phase material is compound and/or the intermediate solid solution that contains two or more metals, it has characteristic and the crystal structure different from simple metal or end border solid solution.Intermetallic phase material is that the diffusion that enters another kind of material via lattice vacancy by a kind of material causes, described lattice vacancy becomes available because of defect, pollution, impurity, crystal boundary and mechanical stress.After in two or more metals diffuse into each other, produce the intermetallic metal species as bi-material combination.The subclass of intermetallic compound comprises electron compound and interstitial compound.

If the metal of two or more mixing relative to each other has different crystal structures, valence state or electropositive, produce electron compound, example includes, but are not limited to copper selenide, gallium selenide, indium selenide, tellurium copper, tellurium gallium, tellurium indium and similar and/or relevant material and/or blend or the mixture of these materials.

Interstitial compound forms the metal of gap crystal structure or the generation of the mixture of metal and nonmetalloid, the space in this structure between the atom of the applicable another kind of material of a kind of atom of material from having the enough similar of atomic size to allow.The intermetallic material for every kind of material wherein with monocrystalline phase, bi-material demonstrates two diffraction maximums that are superimposed on same wave spectrum conventionally, represents separately every kind of independently material.Therefore intermetallic compound contains the crystal structure of the bi-material comprising in same volume conventionally.Example includes, but are not limited to Cu-Ga, Cu-In and similar and/or relevant material and/or blend or the mixture of these materials, and wherein the composition ratio of every kind of element and other element makes this material in its phasor in the region except the solid solution range of end border.

Intermetallic material can be used for the formation of the precursor material of CIGS photovoltaic device, wherein metal is with among highly all even consistent mode is dispersed in each other, and wherein every kind of material exists with substantially similar amount with respect to other material, allow thus kinetics fast, this is created in all three dimensions and uniform high-quality absorber film substantially on nanometer, micron and meso-scale.

While lacking the interpolation that is difficult to synthetic and indium nanometer particle that process, end border solid solution is difficult for allowing that enough precursor material for example, is incorporated in precursor film and makes to supply the light absorbing photolytic activity absorbed layer of height of formation with correct ratio (Cu/ (In+Ga)=0.85) on a large scale.In addition, end border solid solution can have the engineering properties different from intermetallic material and/or intermediate solid solution (solid solution between end border solid solution and/or simple substance).As a kind of limiting examples, the fragility of some end border solid solution is fewer than to be pulverized with grinding.Other embodiments may be too hard to such an extent as to can not grind.The use of intermetallic material and/or intermediate solid solution can solve some in these shortcomings.

The advantage with the particle 1502 of intermetallic phase is many-sided.As a kind of limiting examples, the precursor material being suitable in thin-film solar cells can contain IBZu He IIIA family element, and it is for example respectively copper and indium.If the intermetallic phase of use Cu-In is Cu for example ₁in ₂, indium be rich In Cu material a part and as pure indium, do not add.Owing to dividing in high yield, little and narrow nanoparticle size, plant the particle size that realizes the difficulty of In particle aspect synthetic and needs and increase more costs and judge, so to add pure indium be challenging as metallic particles.Use the Cu particle of the rich In of intermetallic to avoid pure simple substance In as precursor material.In addition, due to the poor Cu of this intermetallic material, thereby this also advantageously allows that independent interpolation Cu accurately reaches the Cu amount of expecting in precursor material.Cu does not rely on fixing ratio in the alloy that can be produced by Cu and In or solid solution.Between fine metal, material and Cu measure to reach the stoichiometric proportion of expectation as required.The ball milling of these particles causes not needing particle size to be judged, this reduces costs and improve the output of material preparation process.

In particular more of the present invention, having intermetallic material provides the more flexibility of wide region.Owing to manufacturing economically simple substance indium particle, be difficult, have and more cause that economically the indium source of concern can be favourable.In addition, if this indium source also allows that the Cu/ (In+Ga) and the Ga/ (In+Ga) that change in layer independently of one another can be favourable.As a kind of limiting examples, can be at Cu ₁₁in ₉and Cu ₁in ₂between by intermetallic phase, distinguish.If only use one deck precursor material particularly like this.For this particular instance, if only by Cu ₁₁in ₉indium is provided, and there are more restrictions in the stoichiometric proportion that can produce in final IB-IIIA-VIA compounds of group.Yet, at the Cu as unique indium source ₁in ₂under, in final IB-IIIA-VIA compounds of group, can produce much bigger ratio ranges.Cu ₁in ₂allow and in wide region, change independently Cu/ (In+Ga) and Ga/ (In+Ga), and Cu ₁₁in ₉can not.For example, Cu ₁₁in ₉only allow Ga/ (In+Ga)=0.25 under Cu/ (In+Ga) >0.92.As another example, Cu ₁₁in ₉only allow Ga/ (In+Ga)=0.20 under Cu/ (In+Ga) >0.98.As another example, Cu ₁₁in ₉only allow Ga/ (In+Ga)=0.15 under Cu/ (In+Ga) >1.04.Therefore for intermetallic material, particularly, when this intermetallic material is unique source of one of element in final compound, can produce final compound by stoichiometric proportion: this stoichiometric proportion is probed into the boundary of Cu/ (In+Ga) of the about 0.7-of compositing range approximately 1.0 and Ga/ (In+Ga) boundary of the about 0.05-of compositing range approximately 0.3 widelyr.In other embodiments, Cu/ (In+Ga) compositing range can be about 0.01-approximately 1.0.In other embodiments, Cu/ (In+Ga) compositing range can be about 0.01-approximately 1.1.In other embodiments, Cu/ (In+Ga) compositing range can be about 0.01-approximately 1.5.This produces extra Cu conventionally _xse _yif it may be removed on end face later.Be to be understood that these ratios go for any in above-mentioned embodiment herein.

In addition, be to be understood that during processing, intermetallic material can produce more liquid than other compound.As a kind of limiting examples, Cu ₁in ₂while heating, will form the more liquid than Cu11In9 during processing.More liquid promotes more atom to mix, because material is easier to mobile and mixes when liquid state.

In addition, the intermetallic particle of particular types is for example still not limited to Cu ₁in ₂there is special advantage.Cu ₁in ₂it is metastable material.This material is more prone to decompose, and this will advantageously improve reaction rate (in dynamics) for the present invention.In addition, less oxidation (for example comparing with pure In) and this of tending to of this material further simplified and processed.This material can also be single-phase, and this can make it more even as precursor material, produces better yield.

As seen in Figure 18 and 19, on substrate 1506, after sedimentary deposit 1500, can then under appropriate atmosphere, heat so that layer 1500 reaction in Figure 18 and the film 1510 shown in formation Figure 19.Be to be understood that layer 1500 can be combined with layer 915 and 917.1 family), the solid solution of the binary of any aforementioned elements and/or multicomponent alloy, any aforementioned elements layer 915 can form by including, but are not limited to following at least one various materials: IB family element, element ,IA family of element ,VIA family of IIIA family element (new style:.Be to be understood that also can by sodium or sodium sill for example but being not limited to sodium, sodium compound, sodium fluoride and/or indium sulfide sodium and precursor material one is used from layers 915 to improve the character of gained film.Figure 19 shows can also be as about using layer 932 described in Fig. 6 F.Any method of advising above about sodium content also can be applicable to using together with the embodiment shown in Figure 17-19.

Be to be understood that other embodiments of the present invention also openly comprise the material of at least two kinds of elements, wherein the amount of at least one element in this material is less than the approximately 50mol% of this element integral molar quantity in precursor material.This comprises that the amount of IB family element is wherein less than the embodiment of the IIIA family amount of element in intermetallic material.As a kind of limiting examples, this IB-IIIA family material that can comprise other PinIB family is the Cu of poor Cu for example _xin _yparticle (wherein x<y).The amount of IIIA family material can in officely be what is the need in the scope wanted (surpass the approximately 50mol% of this element in precursor material or be less than 50mol%).In another limiting examples, Cu ₁ga ₂can use together with simple substance In with simple substance Cu.Although this material is not intermetallic material, this material is intermediate solid solution and different from end border solid solution.All solids particle is all based on Cu ₁ga ₂precursor produces.In this embodiment, do not use emulsion.

In other embodiments of the present invention, IB-IIIA family material that can Yong Fu IB family forms other feasible precursor material.As a kind of limiting examples, can use multiple intermediate solid solution.Cu-Ga (38 atom %Ga) can be used from precursor layer 1500 with simple substance indium and elemental copper one.In another embodiment, Cu-Ga (30 atom %Ga) can be used from precursor layer 1500 with elemental copper and simple substance indium one.These two kinds of embodiments are all described the rich Cu material that IIIA family element is wherein less than the approximately 50mol% of this element in precursor material.In other embodiments, Cu-Ga (heterogeneous, 25 atom %Ga) can be used for together with indium forming the precursor layer of expectation with elemental copper.The nano particle that is to be understood that these materials can be manufactured by mechanical lapping or other breaking method.In other embodiments, these particles can be manufactured by electric detonation silk thread (EEW) processing, evaporative condenser (EC), pulsed plasma process or other method.Although be not limited to following content, particle size can be about 10nm-approximately 1 μ m.They can have any shape as herein described.

Referring now to Figure 19, in another embodiment of the present invention, can apply, print or form two-layer or multilayer material so that the precursor layer with expectation stoichiometric proportion to be provided in other mode.As a kind of limiting examples, layer 1530 can comprise and has Cu ₁₁in ₉with Ga source for example simple substance Ga and/or Ga _xse _yprecursor material.Can on layer 1530, print and contain Cu ₇₈in ₂₈(solid solution) and simple substance indium or In _xse _yrich copper precursors layer 1532.In such embodiments, the overall rate producing can have Cu/ (In+Ga)=0.85 and Ga/ (In+Ga) 0.19.In a kind of embodiment of gained film, this film has the stoichiometric proportion of Cu/ (In+Ga) stoichiometric proportion of the about 0.7-of compositing range approximately 1.0 and the Ga/ (In+Ga) of the about 0.05-of compositing range approximately 0.3.

Referring now to Figure 21, be to be understood that in some embodiments of the present invention, intermetallic material, as charging or raw material, can be formed to particle and/or nano particle by them.As a kind of limiting examples, Figure 21 shows a kind of intermetallic feed particles 1550 of processing to form other particle.For pulverizing and/or any method of change of shape can be applicable to, it includes, but are not limited to grinding, EEW, EC, pulsed plasma process or their combination.Can form particle 552,554,556 and 558.These particles can the vicissitudinous shape of tool and also some particles can only contain intermetallic phase and other particle can contain this phase and other material phase.

Referring now to Figure 22 A and 22B, thin slice 1600 (micron thin slice and/or nano flake) relatively other aspherical for example but being not limited to platelet (platelet) provides some advantage.Thin slice 1600 provides very effective stacking (due to uniform thickness on Z axis) and high surface area (in X and Y-axis).This causes reacting faster, better dynamics and more uniform product/film/compound (having less lateral bine prolongs).The platelet 1602 of seeing in Figure 23 A and 23B fails to possess all above-mentioned advantages.

Although the present invention is described and illustrates with reference to its some specific embodiments, but one of ordinary skill in the art would recognize that without departing from the spirit and scope of the present invention, can carry out various adjustment, change, improvement, replacement, the omission of technique and rules or increase.For example, for any above-mentioned embodiment, nano flake can be replaced by micron thin slice and/or mix with it, and wherein the length of this plane micron thin slice and/or maximum transverse size are about 500nm or larger.Micron thin slice can have the length that is less than approximately 5 μ m and is greater than about 500nm separately.Micron thin slice can have the length of the about 500nm of approximately 3 μ m-separately.Described particle can be the micron thin slice that length is greater than 500nm.This particle can be the micron thin slice that length is greater than 750nm.Micron thin slice can have about 100nm or less thickness separately.Described particle can be the about 75nm of thickness or less micron thin slice.This particle can be the about 50nm of thickness or less micron thin slice.Micron thin slice can have the thickness that is less than about 20nm separately.Micron thin slice can have the length that is less than approximately 2 μ m and the thickness that is less than 100nm.Micron thin slice can have the length that is less than approximately 1 μ m and the thickness that is less than 50nm.Micron thin slice can have at least about 10 or larger aspect ratio.Micron thin slice has at least about 15 or larger aspect ratio.

As mentioned, embodiments more of the present invention can comprise nano flake and micron thin slice simultaneously.Other embodiment can comprise special thin slice in nano flake size range or within the scope of micron lamina dimensions.For any above-mentioned embodiment, micron thin slice can be replaced by micron bar (microrods), and this micron bar is the slender bodies of substantial linear.For any above-mentioned embodiment, nano flake can be replaced by nanometer rods, and this nanometer rods is the material of the elongation of substantial linear.Other embodiments can be by nanometer rods and nano flake combination in precursor layer.Any above-mentioned embodiment can be used in rigid substrate, flexible substrate or both combinations, and this combination for example is still not limited to become during processing due to its material character the flexible substrate of rigidity.In one embodiment of the present invention, particle can be plate and/or dish and/or thin slice and/or line and/or the rod with micron-scale part.In another embodiment of the present invention, particle can be nano-plates and/or nanometer plate and/or nano flake and/or nano wire and/or the nanometer rods with nano-scale part.

Above-mentioned embodiment for any, is to be understood that except above-mentioned, in the different time sections that temperature can also be processed at precursor layer, changes.As a kind of limiting examples, heating can be carried out and proceed to other temperature for processing time section subsequently in initial processing time section at the first temperature.Optionally, the method can comprise has a mind to produce that one or more temperature decline to such an extent as to as a kind of limiting examples, the method comprise heating, cooling, heat and cooling subsequently.For any above-mentioned embodiment, can also in chalcogenide particle and/or the film producing, there is two or more IB elements.

In addition, can provide concentration, amount and other numeric data by range format herein.Be to be understood that this range format just used for convenience and simplicity, and should be interpreted as neatly not only comprising the numerical value of clearly enumerating as described range limit, but also comprise all indivedual numerical value or the subrange comprising within the scope of this, as each numerical value and subrange, be all clear and definite described.For example, about 1nm should be interpreted as not only comprising clear and definite described approximately 1nm and the boundary of about 200nm to the size range of about 200nm, but also comprises for example 2nm, 3nm, 4nm and subrange 10nm to 50nm for example of other size, 20nm to 100nm etc.

For example, other embodiments of the present invention can be used Cu-In precursor material, and wherein Cu-In contribution is less than approximately 50% the Cu existing in precursor material and In.Remaining amount is introduced by simple substance form or by non-IB-IIIA alloy.Therefore, Cu ₁₁in ₉can use to form with simple substance Cu, In the film of gained together with Ga.In another embodiment, for example Cu-Se, In-Se and/or Ga-Se can replace simple substance Cu, In and Ga as IBHuo IIIA family material source to other material.Optionally, in another embodiment, IB source can be any particle (Cu, Cu-Se) comprising less than the Cu with In and Ga alloying.IIIA source can be any particle (Ga, Ga-Se or In-Ga-Se) containing Ga that there is no any particle (In-Se, In-Ga-Se) containing In of Cu or there is no Cu.Other embodiments can have these combinations of the IB material of nitride or oxide form.Other embodiments can have these combinations of the IIIA material of nitride or oxide form.The present invention can use any combination of element and/or can use selenides (binary, ternary or polynary).Optionally, some of the other embodiments can be used for example In of oxide ₂o ₃to add the material of desired amount.Be to be understood that for any above-mentioned embodiment and can use more than a kind of solid solution, can also use heterogeneous alloy and/or alloy more generally.For any above-mentioned embodiment, annealing process can also comprise that compound film is exposed under gas, such as H ₂, CO, N ₂, Ar, H ₂combination or the blend of Se, Se steam or these gases.Be to be understood that in addition on the lamination that Se can be evaporated or be printed onto a plurality of layers to process.

Be to be understood that in addition some intermediate solid solution also can be applicable to using according to the present invention.As limiting examples, the composition (about 42.52-about 44.3wt%In) of the δ of Cu-In in mutually and/or δ phase and the Cu of Cu-In ₁₆in ₉between composition can be to be suitable for being used for together with the present invention forming material between the suitable metal of IB-IIIA-VIA compounds of group.Be to be understood that these intermetallic material can with simple substance or other material for example Cu-Se, In-Se and/or Ga-Se mix to provide IBHuo IIIA family material source, thereby reach the stoichiometric proportion of the expectation in final compound.Other limiting examples of intermetallic material comprises phase and the θ (the about 68.7wt%Ga of about 66.7-) between phase, end border solid solution and the γ 1 between the Cu-Ga composition that contains following phase: γ 1 (the about 39.8wt%Ga of about 31.8-), γ 2 (the about 39.9wt%Ga of about 36.0-), γ 3 (the about 44.9wt%Ga of about 39.7-), γ 2 and γ 3.For Cu-Ga, suitable composition is also present in end border solid solution and is only second in the scope between its intermediate solid solution.Advantageously, some in these intermetallic material can be heterogeneous, and they more may produce the fragile material that can carry out mechanical lapping.The phasor of following material can be at the ASM Handbook that is all incorporated to by reference ASM International herein for all objects, and Volume3AlloyPhase Diagrams finds in (1992).Some instantiations (being all incorporated to by reference herein) can find at 2-168,2-170,2-176,2-178,2-208,2-214,2-257 and/or 2-259 page.

The publication of discussing or quoting herein only provided before the submission date that is disclosed in the application due to them.Here should not be construed as and admit that the present invention does not have qualification to pass through formerly to invent prior to these publications.In addition, the publication date providing can be different with actual publication date, and this needs independent confirmation.By reference all publications of mentioning are herein incorporated to herein, so that disclosure and description structure and/or the method relevant with quoted publication.For all objects also will apply for being incorporated to herein by reference below: the U.S. Patent application 11/290 that on November 29th, 2005 submits to, 633, be entitled as " CHALCOGENIDE SOLAR CELLS ", the U.S. Patent application 10/782 that on February 19th, 2004 submits to, 017, be entitled as " SOLUTION-BASEDFABRICATION OF PHOTOVOLTAIC CELL ", the U.S. Patent application 10/943 that on September 18th, 2004 submits to, 657, be entitled as " COATED NANOPARTICLES AND QUANTUMDOTS FOR SOLUTION-BASED FABRICATION OF PHOTOVOLTAIC CELLS ", with the U.S. Patent application 11/081 of submitting on March 16th, 2005, 163, be entitled as " METALLICDISPERSION ", with the U.S. Patent application 10/943 of submitting on September 18th, 2004, 685, be entitled as " FORMATION OF CIGS ABSORBER LAYERS ON FOIL SUBSTRATES ", 11/361 of submission on February 23rd, 2006, 433, with 11/394 of submission on March 30th, 2006, 849, its whole disclosures are incorporated to herein by reference.

Although above-mentioned, be the complete description of the preferred embodiment of the invention, can use various alternative, modifications and equivalent.Therefore, should not determine scope of the present invention with reference to above-mentioned specification, phase reaction is determined scope of the present invention according to the full breadth of claims and their equivalent.Preferably whether no matter preferably whether no matter any feature,, all can be combined with any further feature.In the following claims, indefinite article " one ", or " a kind of "the quantity that refers to the project after described article is one or more, unless otherwise expressly stated.Claims should not be construed as and comprise that device adds the restriction of function, unless use phrase " for ... device " in given claim, explicitly point out this restriction.

Claims

1. a method that forms absorbed layer, it comprises:

The dispersion of preparation particle, wherein 50 % by weight or more particle are contain separately at least one from the element of IB, IIIA and/or VIA family and have the thin slice of aspheric flat shape, and the total amount of the element from IB, IIIA and/or VIA family comprising in wherein said dispersion makes this dispersion have the element chemistry metering ratio of expectation;

By this dispersion coated substrate to form precursor layer; With

In appropriate atmosphere, process this precursor layer to form dense film, described appropriate atmosphere is selected from nitrogen atmosphere, blanket of nitrogen, carbon monoxide atmosphere, selenium atmosphere, sulphur atmosphere, tellurium atmosphere, argon atmospher, H ₂s atmosphere, H ₂se atmosphere and their combination; And described dense film has 30% or less voidage;

Wherein at least one group of particle in this dispersion is the intermetallic plane particle that contains at least one IB-IIIA family intermetallic alloy phase.

2. the process of claim 1 wherein that at least one group of particle in dispersion is nanometer bead form.

3. the process of claim 1 wherein that at least one group of particle in dispersion is nanometer bead form and contains at least one IIIA family element.

4. the process of claim 1 wherein that at least one group of particle in dispersion is the nanometer bead form of the IIIA family element that comprises simple substance form.

5. the process of claim 1 wherein that intermetallic alloy is not end border solid solution phase mutually.

6. the process of claim 1 wherein that intermetallic alloy is not solid solution phase mutually.

7. the process of claim 1 wherein that the contribution of intermetallic plane particle is less than the IB family element existing in all particles of 50mol%.

8. the process of claim 1 wherein that the contribution of intermetallic plane particle is less than the IIIA family element existing in all particles of 50mol%.

9. the process of claim 1 wherein that contribution in the dispersion of intermetallic plane particle on being deposited on substrate is less than the IB family element of 50mol% and is less than the IIIA family element of 50mol%.

10. the process of claim 1 wherein that contribution in the dispersion of intermetallic plane particle on being deposited on substrate is less than the IB family element of 50mol% and more than the IIIA family element of 50mol%.

11.. the process of claim 1 wherein contribution in the dispersion of intermetallic plane particle on being deposited on substrate more than the IB family element of 50mol% and be less than the IIIA family element of 50mol%.

The method of 12. claims 9, the wherein integral molar quantity of the element in all particles of molar percentage based on existing in described dispersion.

13. to the process of claim 1 wherein that at least some particles have sheet crystalline.

14. to the process of claim 1 wherein that most of particle has sheet crystalline.

15. to the process of claim 1 wherein that all particles have sheet crystalline.

16. the process of claim 1 wherein that dispersion comprises emulsion.

17. the process of claim 1 wherein that intermetallic alloy is binary material mutually.

18. the process of claim 1 wherein that intermetallic alloy is ternary material mutually.

19. the process of claim 1 wherein that intermetallic alloy comprises Cu mutually ₁in ₂.

20. the process of claim 1 wherein that intermetallic alloy comprises Cu mutually ₁in ₂the composition of δ phase.

21. the process of claim 1 wherein that intermetallic alloy comprises Cu mutually ₁in ₂δ phase and Cu ₁₆in ₉composition between the phase limiting.

22. the process of claim 1 wherein that intermetallic alloy comprises Cu mutually ₁ga ₂.

23. the process of claim 1 wherein that intermetallic alloy comprises Cu mutually ₁ga ₂intermediate solid solution.

24. the process of claim 1 wherein that intermetallic alloy comprises Cu mutually ₆₈ga ₃₈.

25. the process of claim 1 wherein that intermetallic alloy comprises Cu mutually ₇₀ga ₃₀.

26. the process of claim 1 wherein that intermetallic alloy comprises Cu mutually ₇₅ga ₂₅.

27. the process of claim 1 wherein that intermetallic alloy comprises end border solid solution and the Cu-Ga composition that is only second to the phase between its intermediate solid solution mutually.

28. the process of claim 1 wherein that intermetallic alloy comprises γ mutually ₁the Cu-Ga of phase forms, 31.8-39.8wt%Ga.

29. the process of claim 1 wherein that intermetallic alloy comprises γ mutually ₂the Cu-Ga of phase forms, 36.0-39.9wt%Ga.

30. the process of claim 1 wherein that intermetallic alloy comprises γ mutually ₃the Cu-Ga of phase forms, 39.7-44.9wt%Ga.

31. the process of claim 1 wherein that intermetallic alloy comprises the Cu-Ga composition 66.7-68.7wt%Ga of θ phase mutually.

32. the process of claim 1 wherein that intermetallic alloy comprises γ mutually ₂with γ ₃between the Cu-Ga of phase form.

33. the process of claim 1 wherein that intermetallic alloy comprises end border solid solution and γ mutually ₁between the Cu-Ga of phase form.

34. the process of claim 1 wherein that intermetallic alloy comprises the Cu-Ga of rich Cu mutually.

35. the process of claim 1 wherein and with the form of suspension of nanometer bead, introduce gallium as IIIA family element.

The method of 36. claims 35, wherein forms gallium nanometer bead by produce the emulsion of liquid gallium in solution.

The method of 37. claims 35, it further comprises by stirring, mechanical device, calutron, Vltrasonic device and/or adds dispersant and/or emulsifying agent keeps or improves the dispersion of liquid gallium in solution.

The method of 38. claims 1, it further comprises interpolation, and one or more are selected from following simple substance particle: aluminium, tellurium or sulphur.

39. the process of claim 1 wherein that appropriate atmosphere contains following at least one: H ₂, CO, Ar and N ₂.

40. 1 kinds of methods that form absorbed layer, it comprises:

Preparation particle ink, wherein most of particles are contain separately at least one from the element of IB, IIIA and/or VIA family and have the nano flake of aspheric flat shape, and the total amount of the element from IB, IIIA and/or VIA family comprising in wherein said ink makes this ink have the element chemistry metering ratio of expectation;

With this ink coats substrate to form precursor layer; With

Process this precursor layer to be formed for the dense film of the semiconductor absorber growth of photovoltaic device, described dense film has 30% or less voidage;

Wherein at least one group of particle in this ink is the intermetallic nano flake particle that contains at least one IB-IIIA family intermetallic alloy phase.

The method of 41. claims 40, wherein by weight or be nano flake by the particle of number at least 80%.

The method of 42. claims 40, wherein by weight or be nano flake by the particle of number at least 90%.

43. 1 kinds of precursor materials that are used to form absorbed layer, it comprises:

A plurality of nano flakes, the material of described a plurality of nano flakes forms and contains at least one from the element of IB, IIIA and/or VIA family;

The precursor granules being wherein comprised of described material lap is prepared described nano flake, this material form provide enough ductility to form flat shape from nonplanar original shape when grinding, and the total amount of the IB, the IIIA that wherein comprise in the precursor granules merging and/or VIA family element is in the element chemistry metering ratio of expectation;

Wherein at least one group of nano flake contains at least one IB-IIIA family intermetallic alloy phase.

The material of 44. claims 43, wherein grinds and will be transformed into nano flake by weight or by the precursor granules of number at least 50%.

The material of 45. claims 43, wherein grinds and will be transformed into nano flake by weight or by the precursor granules of number at least 95%.

The material of 46. claims 43, wherein grinds all precursor granules is transformed into nano flake.

The material of 47. claims 43, wherein precursor granules is 10 μ m or larger when measuring along its longest dimension.

The material of 48. claims 43, wherein grinds and in oxygen-free atmosphere, carries out producing anaerobic nano flake.

The material of 49. claims 43, wherein grinds and in inert gas atmosphere, carries out producing anaerobic nano flake.

The material of 50. claims 43, wherein grinds and at room temperature carries out.

The material of 51. claims 43, wherein grinds and carries out at low temperatures, and described low temperature is≤-175 ℃.

The material of 52. claims 43, wherein grinds all elements in this precursor granules therein and be all under the grinding temperature of solid and carry out, and precursor granules has enough ductility to form flat shape from nonplanar original shape under this grinding temperature.

The material of 53. claims 43, wherein grinds at the temperature lower than 15 ℃ and carries out.

The material of 54. claims 43, wherein grinds at the temperature lower than-200 ℃ and carries out.

The material of 55. claims 43, wherein precursor granules is alloying pellet.

The material of 56. claims 43, wherein precursor granules is bianry alloy particle.

The material of 57. claims 43, wherein precursor granules is ternary alloy three-partalloy particle.

The material of 58. claims 43, wherein precursor granules is quaternary alloy particle.

The material of 59. claims 43, wherein precursor granules is solid solution pellet.

The material of 60. claims 43, wherein nano flake only comprises IBZu He IIIA family material.

The material of 61. claims 43, wherein the mol ratio of the IB family material in a plurality of nano flakes and IIIA family material is greater than 1.0.

The material of 62. claims 43, wherein precursor granules is simple substance particle and wherein from this simple substance particle, grinds and form alloy nano thin slice.

The material of 63. claims 43, wherein precursor granules is the particle of chalcogenide, and this particle is characterised in that following element chemistry metering ratio: this stoichiometric proportion provides enough ductility to form flat shape from nonplanar original shape to precursor granules.

The material of 64. claims 43, wherein precursor granules is selected from one of following: copper selenide, indium selenide or gallium selenide.

The material of 65. claims 43, wherein the metering of the element chemistry between nano flake is than changing, as long as the total amount in the nano flake of all merging is in the stoichiometric proportion of expectation.

The material of 66. claims 43, it further comprises nano flake is carried out to size discrimination to get rid of the nano flake be greater than desired length.

The material of 67. claims 43, it further comprises nano flake is carried out to size discrimination to get rid of the nano flake be greater than expectation thickness.

The material of 68. claims 43, its further comprise to nano flake carry out size discrimination with the change in size of controlling nano flake to as lower deviation: be less than average length 30% and average thickness 30%.

The material of 69. claims 43, a kind of standard deviation that wherein departs from nano flake average thickness is less than 10nm.

The material of 70. claims 43, a kind of standard deviation that wherein departs from nano flake average thickness is less than 5nm.

The material of 71. claims 43, it further comprises the material coated with nano thin slice with at least one deck contains VIA family element.

The material of 72. claims 43, it further comprises the material coated with nano thin slice with at least one deck contains selenium and/or selenides.

The material of 73. claims 43, wherein nano flake forms dried powder.

The material of 74. claims 43, wherein nano flake has at least 10 or larger aspect ratio.

The material of 75. claims 43, wherein nano flake has at least 15 or larger aspect ratio.

The material of 76. claims 43, wherein nano flake contains sodium.

The material of 77. claims 43, wherein nano flake contains at least one in following material: Cu-Na, In-Na, Ga-Na, Cu-In-Na, Cu-Ga-Na, In-Ga-Na, Na-Se, Cu-Se-Na, In-Se-Na, Ga-Se-Na, Cu-In-Se-Na, Cu-Ga-Se-Na, In-Ga-Se-Na, Cu-In-Ga-Se-Na, Na-S, Cu-S-Na, In-S-Na, Ga-S-Na, Cu-In-S-Na, Cu-Ga-S-Na, In-Ga-S-Na or Cu-In-Ga-S-Na.

The material of 78. claims 43, it further comprises ink, and this ink comprises the sodium compound with means organic balance ion or the sodium compound with inorganic counter ion counterionsl gegenions.

79. 1 kinds of rights to use require the method for 43 material, and it is included in non-oxygen chalcogen atmosphere and heats nano flake to form dense film, and described dense film has 30% or less voidage.

The method of the material of 80. 1 kinds of right to use requirements 43, it further comprises that then the material in heated substrate forms the layer containing sodium material to form film on this film.

81. 1 kinds of solar cells, it comprises:

Substrate;

The backplate forming on described substrate;

The p-type semiconductive thin film forming in described backplate;

Form to form the N-shaped semiconductive thin film of pn knot together with described p-type semiconductive thin film; And

The transparency electrode forming on described N-shaped semiconductive thin film;

Wherein said p-type semiconductive thin film is by being processed and produced by the formed dense film of a plurality of nano flakes, material that described a plurality of nano flake has forms and contains at least one from the element of IB, IIIA and/or VIA family, and wherein this dense film has 26% or less voidage;

And wherein at least one group of nano flake contains at least one IB-IIIA family intermetallic alloy phase.

The solar cell of 82. claims 81, wherein dense film is void-free film.

The solar cell of 83. claims 81, the mol ratio of the IB family material in wherein said a plurality of nano flakes and IIIA family material is greater than 1.0.

The solar cell of 84. claims 81, wherein nano flake is anaerobic nano flake.

The solar cell of 85. claims 81, wherein nano flake is alloying pellet.

The solar cell of 86. claims 81, wherein nano flake is bianry alloy particle.

The solar cell of 87. claims 81, wherein nano flake is ternary alloy three-partalloy particle.

The solar cell of 88. claims 81, wherein nano flake is quaternary alloy particle.

The solar cell of 89. claims 81, wherein nano flake is solid solution pellet.

The solar cell of 90. claims 81, wherein nano flake only comprises IBZu He IIIA family material.

The solar cell of 91. claims 81, a kind of standard deviation that wherein departs from nano flake average thickness is less than 10nm.

The solar cell of 92. claims 81, a kind of standard deviation that wherein departs from nano flake average thickness is less than 5nm.

The solar cell of 93. claims 81, wherein the metering of the element chemistry between nano flake is than changing, as long as the total amount in the particle of all merging is in the stoichiometric proportion of expectation.

The solar cell of 94. claims 81, wherein nano flake has at least 10 or larger aspect ratio.

The solar cell of 95. claims 81, wherein nano flake has at least 15 or larger aspect ratio.

The solar cell of 96. claims 81, wherein nano flake has the thickness that is less than 20nm separately.

The solar cell of 97. claims 81, wherein by the precursor layer of nano flake is heated to be greater than 375 ℃ but the temperature that is less than substrate fusion temperature continues 1 minute or time still less forms dense film.

The solar cell of 98. claims 81, wherein by the precursor layer of nano flake is heated to, annealing temperature is still less than lasting 1 minute of substrate fusion temperature or the time still less forms dense film, and described annealing temperature is 200-600 ℃.

The solar cell of 99. claims 81, wherein by promoting dense film to form by following at least one heat treatment technics: pulse heat processing, laser beam or heat by IR lamp.

The solar cell of 100. claims 81, wherein substrate is flexible substrate.

The solar cell of 101. claims 81, wherein substrate is rigid substrate.

The solar cell of 102. claims 81, wherein said dense film is formed by the precursor layer of nano flake and the layer containing sodium material contacting with this precursor layer.

The solar cell of 103. claims 81, wherein said dense film by the precursor layer of nano flake and contact with this precursor layer and contain at least one following material layer form: IB family element, element ,IA family of element ,VIA family of IIIA family element, the binary of any aforementioned elements and/or the solid solution of multicomponent alloy and/or any aforementioned elements.

The solar cell of 104. claims 81, wherein said dense film is by the precursor layer of nano flake and contact with this precursor layer and the layer that contains at least one following material forms: copper, indium, gallium, selenium, copper indium, copper gallium, indium gallium, sodium, sodium compound, copper selenide, copper sulfide, indium selenide, indium sulfide, gallium selenide, sulfuration gallium, copper indium diselenide, copper indium sulfide, gallium selenide copper, sulfuration gallium copper, selenizing gallium indium, sulfuration gallium indium, selenizing gallium indium copper and/or vulcanize gallium indium copper.

The solar cell of 105. claims 104, wherein said sodium compound is sodium fluoride and/or indium sulfide sodium.

The solar cell of 106. claims 81, wherein nano flake is containing sodium.

The solar cell of 107. claims 81, wherein nano flake contains at least one in following material: Cu-Na, In-Na, Ga-Na, Cu-In-Na, Cu-Ga-Na, In-Ga-Na, Na-Se, Cu-Se-Na, In-Se-Na, Ga-Se-Na, Cu-In-Se-Na, Cu-Ga-Se-Na, In-Ga-Se-Na, Cu-In-Ga-Se-Na, Na-S, Cu-S-Na, In-S-Na, Ga-S-Na, Cu-In-S-Na, Cu-Ga-S-Na, In-Ga-S-Na or Cu-In-Ga-S-Na.

The solar cell of 108. claims 81, wherein said dense film is by the precursor layer of nano flake and comprise the ink that has the sodium compound of means organic balance ion or have the sodium compound of inorganic counter ion counterionsl gegenions and form.

The solar cell of 109. claims 81, wherein said dense film is by forming below: the precursor layer of nano flake and the layer containing sodium material contacting with this precursor layer that contains at least one following material: Cu-Na, In-Na, Ga-Na, Cu-In-Na, Cu-Ga-Na, In-Ga-Na, Na-Se, Cu-Se-Na, In-Se-Na, Ga-Se-Na, Cu-In-Se-Na, Cu-Ga-Se-Na, In-Ga-Se-Na, Cu-In-Ga-Se-Na, Na-S, Cu-S-Na, In-S-Na, Ga-S-Na, Cu-In-S-Na, Cu-Ga-S-Na, In-Ga-S-Na or Cu-In-Ga-S-Na, and/or comprise nano flake and there is the sodium compound of means organic balance ion or there is the ink of the sodium compound of inorganic counter ion counterionsl gegenions.