CN103594555B - A kind of preparation method with the black silicon material of self-cleaning function - Google Patents
A kind of preparation method with the black silicon material of self-cleaning function Download PDFInfo
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- CN103594555B CN103594555B CN201310553963.XA CN201310553963A CN103594555B CN 103594555 B CN103594555 B CN 103594555B CN 201310553963 A CN201310553963 A CN 201310553963A CN 103594555 B CN103594555 B CN 103594555B
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- 229910021418 black silicon Inorganic materials 0.000 title claims abstract description 36
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 30
- 238000004140 cleaning Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000003292 glue Substances 0.000 claims abstract description 16
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims abstract description 6
- 238000001020 plasma etching Methods 0.000 claims abstract description 6
- 238000005530 etching Methods 0.000 claims abstract description 5
- 239000002086 nanomaterial Substances 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000004381 surface treatment Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 238000000992 sputter etching Methods 0.000 claims description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 239000004945 silicone rubber Substances 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004049 embossing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/12—Gaseous compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a kind of preparation method with the black silicon material of self-cleaning function.Concrete steps: (1) silicon nano-array preparation technology: utilize sol evenning machine evenly to apply polymethyl methacrylate layers and ultraviolet nanometer impression glue-line on a silicon substrate successively; Utilize ultraviolet nanometer impression compound soft template to carry out impression and obtain impression glue nano array structure; Utilize reactive ion etching, expose silicon substrate; Sample surfaces after etching plates one deck chromium, and obtains chromium nano array structure with lifting off technique; With chromium nano array structure for mask, reactive ion etching is utilized to obtain wedge silicon nanostructure and black silicon material; (2) black silicon material etched is carried out to the process of oxygen plasma, and then carry out chemical surface treatment with silicon fluoride reagent.Preparation method of the present invention can obtain the black silicon material of the periodicity nano array structure with self-cleaning function on a silicon substrate, can be widely used in the preparation of high performance solar cells and photoelectric effect device.
Description
Technical field
The invention belongs to area of solar cell, be specifically related to a kind of preparation method with the black silicon material of self-cleaning function.
Background technology
Solar cell, as a kind of renewable and clean energy resource, receives the concern of a lot of country.Wherein, the market share of silica-based solar cell reaches more than 90%.Black silicon material has the characteristic that wide spectral absorbs, and therefore has very large application prospect on the solar cell.
Black silicon is that a kind of surface has silicon materials that are in order accurate or periodic micro structure.Black silicon has very low reflectivity and very high absorptivity to sunlight, and it almost all absorbs near infrared light near ultraviolet.Utilize solar cell prepared by black silicon, greatly can improve the absorption rate of sunlight.
Nineteen ninety-five, professor S.Y.Chou of Princeton University first proposed nanometer embossing.Nanometer embossing has high-resolution, high yield, large area, advantages such as low cost and be widely used in biomedicine, and information stores, subwavelength optical element, the preparation of surface micro-structure in the numerous areas such as nanoelectronics.In numerous nanometer embossing, soft template nanometer embossing more receives publicity because it can prepare high-resolution nano pattern fast on curved surface and Non-planar substrates.
Self-cleaning function refers to that sample surfaces has super-hydrophobicity and very low water droplet adhesiveness, and water droplet very easily tumbles on this surface thus takes away the pollutants such as dust on the surface thus the clean effect of teaching display stand.The surface with self-cleaning function has very large meaning for the outside work performance of solar cell.
Summary of the invention
The object of this invention is to provide a kind of preparation method with the black silicon material of self-cleaning function, can area of solar cell be applied in.
For achieving the above object, technical scheme of the present invention is:
Have a preparation method for the black silicon material of self-cleaning function, it is characterized in that, the method comprises the following steps:
(1) sol evenning machine is utilized evenly to apply one deck polymethyl methacrylate on a silicon substrate;
(2) utilize sol evenning machine in polymethyl methacrylate layers, evenly apply one deck ultraviolet nanometer impression glue;
(3) utilize ultraviolet nanometer to impress compound soft template and carry out the ultraviolet nanometer impression glue nano array structure that ultraviolet nanometer impression obtains solidification;
(4) polymethyl methacrylate recycling the remnant layer and lower floor that reactive ion etching wears ultraviolet nanometer impression glue nano array structure exposes silicon substrate;
(5) utilize electron beam evaporation deposition instrument sample surfaces plating layer of metal chromium after etching, and obtain crome metal nano array structure with lifting off technique;
(6) again with crome metal nano array structure for mask, utilize the mixed gas reaction ion etching of fluoroform, carbon tetrafluoride and oxygen to obtain wedge silicon nanostructure and black silicon material;
(7) black silicon material etched is carried out to the process of oxygen plasma, and then carry out chemical surface treatment with silicon fluoride reagent, namely obtain the black silicon material with self-cleaning function.
The polished silicon slice that described silicon substrate is (100), the thickness in (110) or (111) direction is not limit, or be the smooth omnidirectional silicon or amorphous silicon surfaces that grow on other substrates.
Described ultraviolet nanometer impression compound soft template is that flexible substrate and high durometer polymeric material are formed as rigid structural layer by flexible silicone rubber material.
The invention provides a kind of preparation method with the black silicon material of self-cleaning function, the beneficial effect compared with prior art had is:
(1) on black silicon of the present invention, nano array structure preparation adopts soft template nanometer embossing, do not need complicated Embosser, the impact of the pollutants such as dust in Conventional nano imprint process on impression can also be reduced, and the high-resolution top wedge nanostructure of Large-Area-Uniform can be obtained, this is very large for high-quality solar cell meaning.
(2) black silicon material with self-cleaning function that prepared by the present invention has very low reflectivity (comparing smooth silicon face) at sunlight wave band, and this can improve the light absorption utilance of black silicon solar cell greatly.
(3) black silicon material with self-cleaning function that prepared by the present invention has excellent ultra-hydrophobicity, can realize self-cleaning function, can improve the outside work performance of black silicon solar cell.
Accompanying drawing explanation
Fig. 1 is the black silicon material preparation flow schematic diagram that the present invention has self-cleaning function; 1-ultraviolet nanometer impression glue-line; 2-polymethyl methacrylate layers; 3-silicon substrate; 4-compound soft template flexible substrate; 5-compound soft template rigid structural layer; The ultraviolet nanometer impression glue nano array structure of 6-solidification; The crome metal of 7-electron beam evaporation deposition.
Fig. 2 is the electron scanning micrograph of black silicon material surface nano array structure prepared by embodiment, a () is 200 nanometer cycle nanometer dark silicon trench arrays and black silicon face water drop static contact angle digital photograph, (b) is that water drop static contact angle 158.3 ° of roll angles are less than 5 °.
Fig. 3 is that the present invention has the black silicon material of self-cleaning function and the reflectance spectrum of the smooth silicon face of non-structure.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail:
The concrete making step of the black silicon material with self-cleaning function of the present embodiment:
(1) utilize sol evenning machine with 3000 revs/min on silicon substrate 3, within 60 seconds, evenly apply one deck polymethyl methacrylate 2.
(2) utilize sol evenning machine with 1600 revs/min in polymethyl methacrylate layers, within 40 seconds, evenly apply one deck ultraviolet nanometer impression glue 1.
(3) ultraviolet nanometer being impressed compound soft template is laid on substrate with structural plane facing to the mode of ultraviolet glue, forms stamped combo.Ultraviolet stamping glue is known from experience due to capillary force automatic filling template rigid structural layer 5, and the flexible substrate 4 of compound soft template can fit tightly with silicon substrate 3.Expose 1 minutes with ultraviolet mercury lamp again, ultraviolet stamping glue 1 is fully solidified; Be separated the ultraviolet nanometer impression glue nano array structure 6 that template obtains solidifying again.
(4) remnant layer that ultraviolet nanometer is impressed glue nano array structure 6 by the reactive ion etching recycling the mist of fluoroform and oxygen has etched and has exposed the polymethyl methacrylate 2 of lower floor.
(5) again with ultraviolet nanometer impression glue nano array structure 6 for mask, utilize the reactive ion etching of oxygen by polymethyl methacrylate 2 etching of lower floor wear until expose silicon substrate.
(6) electron beam evaporation deposition instrument plated surface a layer thickness 30 nano metal chromium 7 after etching again.
(7) supersonic cleaning machine ultrasonic sample in chlorobenzene is used again, remove the crome metal on polymer and polymeric material top, complete and lift off technique and obtain impressing the contrary crome metal nano array structure of glue nano array structure 6 pattern with ultraviolet nanometer in surface of silicon.
(8) again with crome metal nano array structure for mask, utilize fluoroform, carbon tetrafluoride, crome metal nano array structure is delivered to next silicon substrate by the mixed gas reaction ion etching of oxygen.
(9) on the basis of 8, extend etch period, until crome metal mask has been consumed, go out wedge nanostructure and black silicon material at the top etch of silicon nano array structure.
(10) black silicon material etched is carried out to the process of oxygen plasma, and then carry out chemical surface treatment with silicon fluoride reagent, there is described in namely obtaining the black silicon material of self-cleaning function.
Claims (3)
1. have a preparation method for the black silicon material of self-cleaning function, it is characterized in that, the method comprises the following steps:
(1) sol evenning machine is utilized evenly to apply one deck polymethyl methacrylate on a silicon substrate;
(2) utilize sol evenning machine in polymethyl methacrylate layers, evenly apply one deck ultraviolet nanometer impression glue;
(3) utilize ultraviolet nanometer to impress compound soft template and carry out the ultraviolet nanometer impression glue nano array structure that ultraviolet nanometer impression obtains solidification;
(4) polymethyl methacrylate recycling the remnant layer and lower floor that reactive ion etching wears ultraviolet nanometer impression glue nano array structure exposes silicon substrate;
(5) utilize electron beam evaporation deposition instrument sample surfaces plating layer of metal chromium after etching, and obtain crome metal nano array structure with lifting off technique;
(6) again with crome metal nano array structure for mask, utilize the mixed gas reaction ion etching of fluoroform, carbon tetrafluoride and oxygen to obtain wedge silicon nanostructure and black silicon material;
(7) black silicon material etched is carried out to the process of oxygen plasma, and then carry out chemical surface treatment with silicon fluoride reagent, namely obtain the black silicon material with self-cleaning function.
2. a kind of preparation method with the black silicon material of self-cleaning function according to claim 1, it is characterized in that, the polished silicon slice that described silicon substrate is (100), the thickness in (110) or (111) direction is not limit, or be the smooth amorphous silicon surfaces at Grown.
3. a kind of preparation method with the black silicon material of self-cleaning function according to claim 1 and 2, it is characterized in that, described ultraviolet nanometer impression compound soft template is that flexible substrate and high durometer polymeric material are formed as rigid structural layer by flexible silicone rubber material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310553963.XA CN103594555B (en) | 2013-11-08 | 2013-11-08 | A kind of preparation method with the black silicon material of self-cleaning function |
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| CN201310553963.XA CN103594555B (en) | 2013-11-08 | 2013-11-08 | A kind of preparation method with the black silicon material of self-cleaning function |
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| CN103594555A CN103594555A (en) | 2014-02-19 |
| CN103594555B true CN103594555B (en) | 2016-03-23 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3320399A1 (en) | 2015-07-07 | 2018-05-16 | Illumina, Inc. | Selective surface patterning via nanoimprinting |
| CN106006544B (en) * | 2016-05-24 | 2018-04-13 | 中国人民解放军国防科学技术大学 | A kind of anti-icing method of surface hydrophobicity |
| CN106653952B (en) * | 2017-01-17 | 2018-05-08 | 南京大学 | A kind of preparation method of the middle infrared antireflective micro-structure of silicon |
| CN107403787B (en) * | 2017-08-02 | 2020-02-21 | 武汉新芯集成电路制造有限公司 | Method for forming metal isolation gate |
| CN109609907B (en) * | 2019-01-31 | 2020-01-21 | 中国科学院半导体研究所 | Method for preparing metal nanostructure by self-absorption nanoimprint lithography |
| CN109950335A (en) * | 2019-04-08 | 2019-06-28 | 西安工业大学 | A kind of photovoltaic conversion structure and production method of visible light |
| CN114296168B (en) * | 2021-12-08 | 2023-03-10 | 中国科学技术大学 | Method for manufacturing variable-period narrow grating by using wide-grating nano-imprinting template |
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