CN100595670C - Mask pattern and its forming method, method for manufacturing coating composition, and method for manufacturing semiconductor device - Google Patents

Mask pattern and its forming method, method for manufacturing coating composition, and method for manufacturing semiconductor device Download PDF

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CN100595670C
CN100595670C CN200510064902A CN200510064902A CN100595670C CN 100595670 C CN100595670 C CN 100595670C CN 200510064902 A CN200510064902 A CN 200510064902A CN 200510064902 A CN200510064902 A CN 200510064902A CN 100595670 C CN100595670 C CN 100595670C
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coating composition
corrosion
repetitive
resisting pattern
proton
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CN1721986A (en
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畑光宏
夏政焕
金贤友
禹相均
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Samsung Electronics Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds

Abstract

A mask pattern for semiconductor device fabrication is dislosed. A mask pattern for semiconductor device fabrication comprises a resist pattern formed on a semiconductor substrate, and an interpolymercomplex film formd on the resist pattern, wherein the interpolymer complex film includes a network formed by a hydrogen bond between a proton donor polymer and a proton acceptor polymer.

Description

The method of the preparation method of mask pattern and forming method thereof, coating composition and manufacturing semiconductor devices
The cross reference of related application
The application requires the korean patent application 10-2004-0024021 that submits on April 8th, 2004 in Korea S Department of Intellectual Property and the right of priority of the 10-2004-0057163 that submits on July 22nd, 2004, and this paper introduces it, and content is as a reference in full.
Background
1. technical field
The present invention relates to be used for coating composition, the method for formation mask pattern and the method for manufacturing semiconductor devices that semiconductor devices is made; More specifically, relate to and be used for the mask pattern that semiconductor devices is made, it has the coating composition of the fine pattern that surmounts the restriction of photoetching process wavelength, the method that forms mask pattern, fine pattern formation usefulness and uses the coating composition manufacturing that the method for the semiconductor devices of fine pattern is arranged.
2. correlation technique discussion
Be used for the conventional patterning process that semiconductor devices is made, be used for pattern and form wanting to form on etched some film the photoresist pattern.Use the photoresist pattern to come some film of etching such as silicon thin film, dielectric film or conductive film, thereby form pattern as etching mask.Along with the raising of semiconductor devices integrated level, the photoetching technique of the design rule of littler critical dimension (CD) and formation fine pattern becomes most important.Fine pattern comprises contact hole with littler bore size or the spacing with littler width.
In the conventional photoetching technique that forms the reduced size contact hole, use short wave length exposure instrument such as beamwriter lithography method or halftone phase shift mask.Photoetching based on the short wave length exposure instrument is relevant with material and uneconomical.Photoetching process based on the halftone phase shift mask is difficult to form the contact hole of size less than 150nm.
The various technology of fine pattern have been proposed to form.Japanese patent publication 1989-307228 discloses the technology that forms corrosion-resisting pattern.Thermal treatment is passed through the corrosion-resisting pattern of the film exposure against corrosion and the formation of developing so that change the contour shape of corrosion-resisting pattern.According to this technology, the resist flow of the upper area of corrosion-resisting pattern and central region is different.When because hot-fluid makes the CD amount of contraction of corrosion-resisting pattern is 100nm or more for a long time, the profile of corrosion-resisting pattern is owing to the quick flow performance of film against corrosion is out of shape.Therefore, near central region, obtain crooked outline.This technology is restricted on adjustment corrosion-resisting pattern flow, and this makes it be difficult to reduce the CD of corrosion-resisting pattern when keeping the vertically profiling shape.
Japanese patent publication 1993-241348,1994-250379,1998-73927,1999-204399,1999-283905,1999-283910,2000-58506,2000-298356,2001-66782,2001-228616,2001-19860 and 2001-109165 disclose the method that forms corrosion-resisting pattern by chemical treatment.Japanese patent publication 2001-228616 discloses the technology that reduces the bore dia and the insulation width of corrosion-resisting pattern by the thickness that increases corrosion-resisting pattern.According to this technology, the corrosion-resisting pattern that can be used as acid donors scribbles and will cooperate (framing) material with the crosslinked picture frame of acid.When by heating with acid when corrosion-resisting pattern is transferred to the layer that the picture frame compounding ingredient makes, cross-linked layer just forming at the interface between corrosion-resisting pattern and picture frame compounding ingredient layer cover corrosion-resisting pattern layer.But chemical crosslink reaction also may take place in unwanted zone, thereby causes pattern defect.Utilize routine techniques, the accurate temperature control that causes required chemical crosslink reaction may be difficult.
Japanese patent publication 2003-107752,2003-84448,2003-84459,2003-84460,2003-142381,2003-195527,2003-202679,2003-303757 and 2003-316026 disclose pattern and have formed with composition and pattern formation method.Japanese patent publication 2003-202679 discloses the use coating agent and has formed method of patterning.Coating agent is applied on the substrate with photoresist pattern, utilizes the thermal pinch of coating agent to reduce spacing between the photoresist pattern.Distribute because the thermal shrinking quantity of coating agent generally depends on substrate temperature, therefore may be difficult on the whole surface of substrate, form uniform corrosion-resisting pattern.In addition, need to use the low anticorrosive additive material of glass transition temperature.In addition, in order accurately to obtain specific characteristic dimension, need carry out complicated computation process and proofread and correct isodensity deviation (iso-dense bias).
As mentioned above, reduce in the technology, utilize heat treated resist stream technology that good side wall profile can not be provided at the CD that has proposed so far.For example, on corrosion-resisting pattern, apply independent material may cause in the corrosion-resisting pattern unwanted crosslinked, thereby cause pattern defect.In addition, the material that is retained on the non-required zone may cause various pattern defects after development.When the size of hole that the exposure tool that uses wavelength for about 157nm or about 193nm maybe will form or groove reduced, pattern defect may increase.
In double-deck resist of routine (BLR) or multilayer resist (MLR) method, use siliceous resist to carry out composition by photoetching process as the top layer resist.Utilize O 2It (is SiO that reactive ion etching (RIE) technology is transformed into glass by dry-etching method with the silicon atom in the siliceous resist X), on the resist layer surface, to form cured layer.The cured layer that forms is used as etching mask in dry etch process subsequently.Because cured layer has improved the corrosion stability to dry ecthing, therefore can form pattern, and can prevent pattern sinking (pattern falling) phenomenon with high aspect ratio.Therefore, the patterning process based on MLR can provide the high resolution design with high aspect ratio.But along with the increase of silicone content in the anticorrosive additive material of top, the top resist layer has poor thermal stability and to the wettability of developer.
In addition, when the corrosion-resisting pattern that will utilize heat treated resist stream technology to be applied to make by the top anticorrosive additive material when forming fine pattern, the thickness of corrosion-resisting pattern reduces, this makes pattern be difficult to transfer to the bottom resist layer.When the technology that will use cross-linked layer as the layer formation fine pattern that covers corrosion-resisting pattern is applied to the MLR method, is used for the material crosslinked and may has not enough silicone content on the corrosion-resisting pattern surface.Therefore, cross-linked layer can not be as utilizing O 2Hard mask in the dry etch process of RIE technology.Japanese patent publication 1999-283910 discloses siliceous anticorrosive additive material.But this technology comprises that the mixed solution with organic solvent replaces rinsed with deionized water, and this is difficult to produce in a large number.
Summary of the invention
In exemplary of the present invention, on the corrosion-resisting pattern surface, form the interpolymer composite membrane, to reduce the size of mask pattern perforate.The interpolymer composite membrane is the water-insoluble film, has the network that forms by the hydrogen bond between proton donor polymkeric substance and proton accepting polymer.The interpolymer composite membrane that forms on the corrosion-resisting pattern surface can form the mask pattern with small size perforate that surmounts the restriction of photoetching technique wavelength.In addition, can keep the vertical sidewall profile of mask constant.In addition, when reducing, aperture widths can minimize the isodensity deviation.
According to exemplary of the present invention, the mask pattern that is used for the semiconductor devices manufacturing comprises and is formed at the corrosion-resisting pattern on the Semiconductor substrate and is formed at interpolymer composite membrane on the corrosion-resisting pattern that wherein the interpolymer composite membrane comprises the network that forms by the hydrogen bond between proton donor polymkeric substance and proton accepting polymer.
According to another exemplary of the present invention, the method that is formed for the mask pattern of semiconductor devices manufacturing is included in and forms corrosion-resisting pattern on the substrate and form the interpolymer composite membrane with network on the corrosion-resisting pattern surface, and described network forms by the hydrogen bond between proton donor polymkeric substance and proton accepting polymer.
According to another exemplary of the present invention, the method that is formed for the mask pattern of semiconductor devices manufacturing is included in and forms corrosion-resisting pattern on the Semiconductor substrate, make the coating composition that comprises proton donor polymkeric substance and proton accepting polymer contact and on the corrosion-resisting pattern surface, form water-insoluble interpolymer composite membrane with the corrosion-resisting pattern surface.
According to another exemplary of the present invention, preparing fine pattern forms method with coating composition and comprises and prepare first solution that comprises the proton accepting polymer and first solvent, preparation comprises second solution of the proton donor polymkeric substance and second solvent and prepares first solution and the mixed solution of second solution.
According to another exemplary of the present invention, the method of making semiconductor devices is included in and forms bottom on the Semiconductor substrate, formation has the corrosion-resisting pattern that is exposed to the perforate of first width for bottom, on the corrosion-resisting pattern surface, form water-insoluble interpolymer composite membrane by heating Semiconductor substrate under coating composition that comprises proton donor polymkeric substance and proton accepting polymer and corrosion-resisting pattern surface state of contact, to expose bottom by perforate to than little second width of first width with use corrosion-resisting pattern and interpolymer composite membrane to come etching bottom as etching mask.These and other exemplary of the present invention, feature and advantage will be described its exemplary in conjunction with the drawings in detail and become more apparent.
The accompanying drawing summary
Fig. 1 is a schematic flow diagram of making the method for semiconductor devices according to exemplary of the present invention.
Fig. 2 prepares the schematic flow diagram that fine pattern forms the method for using coating composition for exemplary according to the present invention.
Fig. 3 A to 3F is a sectional view of making the method for semiconductor devices according to exemplary of the present invention.
Fig. 4 A to 4H is the sectional view that another exemplary according to the present invention is made the method for semiconductor devices.
Fig. 5 forms the sectional view of mechanism for explanation interpolymer composite membrane in according to the mask pattern formation method of illustrative embodiments of the invention.
Fig. 6 is the exemplary plot according to the interpolymer composite membrane forming process of Fig. 5 mechanism.
Fig. 7 is another exemplary plot according to the interpolymer composite membrane forming process of Fig. 5 mechanism.
Fig. 8 is the sectional view that the interpolymer composite membrane forms mechanism in the mask pattern formation method of another exemplary according to the present invention.
Fig. 9 is the interpolymer composite membrane forming process figure according to Fig. 8 mechanism.
Exemplary describes in detail
Now exemplary of the present invention will be described more fully in conjunction with the accompanying drawings.But the present invention can implement with multiple different form, should not think that the present invention is limited to the embodiment that this paper proposes.Certainly, provide these embodiments, and can fully principle of the present invention be conveyed to those skilled in the art so that the disclosure is more complete.Now will be in conjunction with flow chart description shown in Figure 1 method, semi-conductor device manufacturing method according to illustrative embodiments of the invention.
Step 10
In step 10, on Semiconductor substrate, form and want etched bottom.Bottom can be dielectric film, as silicon thin film, sull, nitride film or oxide-nitride thing film.Bottom can be conductive film.For in bottom, forming contact hole, can use dielectric film.On bottom, form film against corrosion.Can be by the conventional photoetching process exposure and the film against corrosion that develops.Can form and have the corrosion-resisting pattern that is exposed to the perforate of certain width for bottom.
Step 20
In step 20, preparation comprises the coating composition of proton donor polymkeric substance and proton accepting polymer.The proton donor polymkeric substance and the proton accepting polymer that are included in the coating composition can all be water miscible.
In the general assembly (TW) of coating composition, proton donor polymkeric substance and proton accepting polymer use amount separately is about 0.1 to about 5.0wt%, and preferred about 0.1 to about 2.0wt%.Proton donor polymkeric substance and proton accepting polymer can be with about 1: 9 to about 9: 1 weight ratio mixing.
Coating composition also comprises solvent.Coating composition also can comprise alkali, acid, surfactant or thermic acid producing agent.Coating composition also can comprise material such as silicon alkoxide monomer, silicon alkoxide oligomer or their partial hydrolysate.
(1) The proton donor polymkeric substance
The proton donor polymkeric substance comprises the monomeric repeating unit with carboxyl or sulfo group.Preferably, the proton donor polymkeric substance comprises first repetitive of being made up of the maleic acid monomer unit of representing with following formula 1:
[formula 1]
Figure C20051006490200171
The proton donor polymkeric substance also can comprise by comonomer unit Z 1Second repetitive of forming.Comonomer unit Z 1With the copolymerization of maleic acid monomer unit, represent as shown in the formula 2:
[formula 2]
By comonomer unit Z 1Second repetitive of forming can be acrylic monomers unit, vinyl monomer unit, alkylene glycol monomeric unit, ethylene imine monomeric unit, the monomeric unit that contains oxazoline group, acrylonitrile monemer unit, acrylyl amine monomers unit, 3,4-dihydropyrane monomer unit or 2,3-dihydrofuran monomeric unit.According to second repetitive, the proton donor polymkeric substance can be multipolymer, terpolymer, quadripolymer or higher.That is to say that second repetitive of proton donor polymkeric substance can comprise the monomeric unit that two or more are different.
The example that constitutes the acrylic monomers unit of second repetitive comprises acrylate, methacrylate, acrylamide, anhydrous maleic acid, N, the N-DMAA, Methacrylamide, N, the N-dimethylmethacryl amide, the N-N-isopropylacrylamide, the aminopropyl acrylamide, the aminopropyl Methacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl Methacrylamide, the N-acryloyl morpholine, N methacrylamide, diacetone acrylamide, N, the N-dimethyl amino ethyl methacrylate, N, N-diethylamino ethyl-methyl acrylate and N, the N-dimethyl amino ethyl acrylate.
The example that constitutes the vinyl monomer unit of second repetitive comprises vinyl alcohol, vinylacetate, vinyl acetal (vinylacetal), methyl vinyl ether, ethyl vinyl ether, N-vinyl pyrrolidone, N-caprolactam, vinyl imidazole alkane ketone and vinyl sulfonic acid.
The example that constitutes the alkylene glycol monomeric unit of second repetitive comprises ethylene glycol and propylene glycol.
Second repetitive can be made up of separately hydrophilic monomeric units, or is made up of hydrophilic monomeric units associating hydrophobic monomer unit.When second repetitive comprises a small amount of hydrophobic monomer unit, can help the formation of interpolymer composite membrane in the subsequent step (step 40 of Fig. 1).In the sum of repetitive, the use amount of first repetitive is about 3 to about 90%, preferred about 5 to about 50% in the proton donor polymkeric substance.The proton donor polymkeric substance can have about 1000 to 100000 daltonian mean molecular weight, and preferred about 2000 to about 50000 dalton.
(2) Proton accepting polymer
Proton accepting polymer comprises the monomeric repeating unit with acylamino-.
Preferably, proton accepting polymer can comprise first repetitive of being made up of the vinyl monomer unit of following formula 3 expressions:
[formula 3]
Figure C20051006490200191
R 1Be hydrogen atom or methyl.R 2And R 3Be hydrogen atom or C 1To C 5Alkyl.Can be with-R 2-R 3-form connect R 2And R 3
Proton accepting polymer also can comprise by comonomer unit Z 2Second repetitive of forming.Comonomer unit Z 2With the vinyl monomer unit copolymerization, represent as shown in the formula 4:
[formula 4]
Figure C20051006490200192
R 1, R 2And R 3Identical with above-mentioned qualification.
By comonomer unit Z 2Second repetitive of forming can be acrylic monomers unit, vinyl monomer unit, alkylene glycol monomeric unit, ethylene imine monomeric unit, the monomeric unit that contains oxazoline group, acrylonitrile monemer unit, acrylyl amine monomers unit, 3,4-dihydropyrane monomeric unit or 2,3-dihydrofuran monomeric unit.According to second repetitive, proton accepting polymer can be multipolymer, terpolymer, quadripolymer or higher.That is to say that second repetitive of proton accepting polymer can comprise the monomeric unit that two or more are different.
The example that constitutes the acrylic monomers unit of second repetitive comprises acrylate, methacrylate, maleic acid, anhydrous maleic acid, N, the N-DMAA, Methacrylamide, N, the N-dimethylmethacryl amide, the N-N-isopropylacrylamide, the aminopropyl acrylamide, the aminopropyl Methacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl Methacrylamide, the N-acryloyl morpholine, N methacrylamide, diacetone acrylamide, N, the N-dimethyl amino ethyl methacrylate, N, N-diethylamino ethyl-methyl acrylate and N, the N-dimethyl amino ethyl acrylate.
The example that constitutes the vinyl monomer unit of second repetitive comprises vinyl alcohol, vinylacetate, vinyl acetal, methyl vinyl ether, ethyl vinyl ether, N-vinyl pyrrolidone, N-caprolactam, vinyl imidazole alkane ketone and vinyl sulfonic acid.
The example that constitutes the alkylene glycol monomeric unit of second repetitive comprises ethylene glycol and propylene glycol.
Second repetitive can be made up of separately hydrophilic monomeric units, or is made up of hydrophilic monomeric units associating hydrophobic monomer unit.When second repetitive comprises a small amount of hydrophobic monomer unit, can help the formation of interpolymer composite membrane in the subsequent step (step 40 of Fig. 1).
When with-R 2-R 3-form connect R 2And R 3The time, formula 3 can replace with following formula 5:
[formula 5]
Figure C20051006490200211
N is 1 to 5 integer.
The example of proton accepting polymer with repetitive of formula 5 is the compound that comprises first repetitive of being made up of the vinylpyrrolidone monomer unit, as 6 expressions of following formula:
[formula 6]
Figure C20051006490200212
Another example of proton accepting polymer with repetitive of formula 5 is the compound that comprises first repetitive of being made up of the caprolactam monomeric unit, as 7 expressions of following formula:
[formula 7]
Figure C20051006490200213
Preferably, proton accepting polymer can comprise first repetitive of being made up of the vinyl monomer unit of following formula 8 expressions:
[formula 8]
R 4Be hydrogen atom or methyl.R 5And R 6Be hydrogen atom, methyl, n-pro-pyl, isopropyl, aminopropyl or N, the N-dimethylaminopropyl.
Proton accepting polymer also can comprise by comonomer unit Z 3Second repetitive of forming.Comonomer unit Z 3With the vinyl monomer unit copolymerization of formula 8, represent as shown in the formula 9:
[formula 9]
Wherein, R 4, R 5And R 6Identical with above-mentioned qualification.
By comonomer unit Z 2The foregoing description of second repetitive of forming is also applicable to by comonomer unit Z 3Second repetitive of forming.
In the sum of repetitive, the use amount of first repetitive is about 3 to about 100%, preferred about 50 to about 100% in the proton accepting polymer.Preferably, proton accepting polymer has about 1000 to about 100000 daltonian mean molecular weight, and preferred about 2000 to about 50000 dalton.
(3) Alkali
Alkali can prevent that sediment forms in the coating composition.In the general assembly (TW) of coating composition, the use amount of alkali can be about 0.1 to about 5.0wt%, and preferred about 0.2 to about 1.0wt%.Preferably, alkali can be that boiling point is about 140 ℃ or higher material.Alkali in the coating composition can be monoethanolamine, triethanolamine or tetramethylammonium hydroxide (TMAH).
(4) Acid
Coating composition also can comprise Bronsted acid.Bronsted acid can use separately or unite use with alkali.When uniting the use Bronsted acid with alkali, the proton bronsted lowry acids and bases bronsted lowry can form salt.In the general assembly (TW) of coating composition, the use amount of Bronsted acid is about 0.1 to about 10wt%, and preferred about 0.2 to about 1.0wt%.Bronsted acid can be selected from various materials.Acidic compound replaced when Bronsted acid can be used on heating.Acid in the coating composition can be p-toluenesulfonic acid, trifluoroacetic acid or dodecylbenzene sulfonic acid.
(5) Surfactant
During the corrosion-resisting pattern that forms in coating composition coating step 10, surfactant can provide good deposited lid feature.In the general assembly (TW) of coating composition, the use amount of surfactant can be about 0.01 to about 0.5wt%.Surfactant can be commercially available " Zonyl-FSN " (DuPont), " PolyFox (TM) " (OMNOVA Solution Inc.), " Fluorad TM" (3M), " NONIPORU TM" (SANYOKASEI), " MEGAFACE TM" (Dainippon Ink﹠amp; Or their potpourri Chemicals).
(6) thermic acid producing agent
The thermic acid producing agent can be " CYCAT4040 " (Cymel Co.), can obtain from commercial.
(7) material
Coating composition used herein can comprise material.Material can be silicon alkoxide monomer, silicon alkoxide oligomer or their partial hydrolysate.Material can be water miscible and non-hydrolysable.Preferably, can use boiling point to be about 140 ℃ or higher material.In the general assembly (TW) of coating composition, the use amount of material can be about 0.1 to about 5.0wt%, and preferred about 1.0 to about 3.0wt%.
The example of silicon alkoxide monomer can comprise tetraethyl orthosilicate (TEOS) in the coating composition; tetramethoxy-silicane (TMOS); propyl group silicate; butyl silicate; methyltrimethoxy silane; methyl triethoxysilane; dimethyldimethoxysil,ne; dimethyldiethoxysilane; vinyltrimethoxy silane; vinyltriethoxysilane; vinyl three (2-methoxy ethoxy) silane; N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane; N-(2-amino-ethyl)-3-aminopropyl methyl triethoxysilane; N-(2-amino-ethyl)-3-aminopropyl methyltrimethoxy silane; diethylene triamido propyl trimethoxy silicane; diethylene triamido propyl-triethoxysilicane; diethylene triamido propyl group methyl dimethoxysilane; diethylene triamido propyl group methyldiethoxysilane; the cyclohexyl TSL 8330; hexane diamido methyltrimethoxy silane; the anilino-methyltrimethoxy silane; the anilino-methyl triethoxysilane; diethylamino methyltriethoxy silane alkane; (diethylamino methyl) methyl dimethoxysilane; the 3-aminopropyltriethoxywerene werene; 3-aminopropyl methyldiethoxysilane; the 3-TSL 8330; 3-aminopropyl methyl dimethoxysilane; the 3-glycidoxypropyltrime,hoxysilane; 3-glycidoxy propyl-triethoxysilicane; 3-glycidoxy propyl group methyldiethoxysilane; 3-glycidoxy propyl group methyl dimethoxysilane; 2-(3; the 4-epoxycyclohexyl) ethyl trimethoxy silane; 3-methacryl propyl trimethoxy silicane; 3-methacryl propyl-triethoxysilicane; 3-methacryl propyl group methyl dimethoxysilane; 3-sulfydryl propyl trimethoxy silicane; 3-sulfydryl propyl group methyl dimethoxysilane; 3-sulfydryl propyl-triethoxysilicane; two (triethoxysilylpropyltetrasulfide) tetrasulfide; two (triethoxysilylpropyltetrasulfide) disulfide; 3-sulfo-cyano group propyl-triethoxysilicane; N-(1; 3-dimethyl butylidene)-3-(triethoxysilyl)-1-propylamine; N-[2-(vinyl benzyl amino) ethyl]-3-TSL 8330 hydrochloric acid and N, N '-two [3-(trimethoxysilyl) propyl group] ethylenediamine.
The example of silicon alkoxide oligomer comprises that (Tama Chemicals Co., Ltd.), each in them all has Si for " Silicate40 ", " Silicate45 " and " Silicate48 " in the coating composition nO N-1(OC 2H 5) 2n+2Composition, consist of Si nO N-1(OCH 3) 2n+2" MSilicate51 " (Tama Chemicals Co., Ltd.), poly-(dimethoxysiloxane) and consist of Si nO N-1(OH) 2(OCH 3) 2nHydroxy-end capped oligomer.
The partial hydrolysate that also can comprise above-mentioned silicon alkoxide monomer or oligomer in the coating composition.The example of the partial hydrolysate of silicon alkoxide monomer or oligomer comprises partial hydrolysis " Silicate40 ", " Silicate45 " and " Silicate48 " (Si nO N-1(OH) x(OC 2H 5) 2n+2-x), " MSilicate51 " (Si of partial hydrolysis nO N-1(OH) x(OCH 3) 2n+2-x), poly-(dimethoxysiloxane) and the hydroxy-end capped Si of partial hydrolysis nO N-1(OH) 2+x(OCH 3) 2n-x
Usually, to compare with its parent compound be chemically unstable to the partial hydrolysate of Si oxide.Because the high-dissolvability in water can use partial hydrolysate as silicon-containing compound in according to the coating composition of illustrative embodiments of the invention.The example of the partial hydrolysate of the Si oxide that can use in illustrative embodiments of the invention is for existing the tetraethyl orthosilicate (TEOS) of lower part hydrolysis at about 5ppm TMAH.
(8) Solvent
The solvent that uses in the coating composition can be deionized water.Perhaps, solvent can be the potpourri of deionized water and organic solvent.When solvent was the potpourri of deionized water and organic solvent, in the general assembly (TW) of coating composition, the use amount of organic solvent can be about 0 to about 20wt%.Organic solvent can be alcohol, nitrile, ketone, ester, lactate, aromatic hydrocarbon or acid amides.
Preferably, the content of adjustment bronsted lowry acids and bases bronsted lowry makes the lower critical solution temperature (LCST) of coating composition be about 30 to about 70 ℃.
(9) Coating composition
Can use the proton donor polymkeric substance as first polymkeric substance.Can use proton accepting polymer as second polymkeric substance.Coating composition also can comprise neither as proton donor also not as the terpolymer of proton acceptor.Terpolymer is as the binder polymer between proton donor polymkeric substance and the proton accepting polymer.For example, terpolymer is a polyvinyl alcohol (PVA).
Because the carrying out of step 10 and 20 order is not had particular restriction, therefore can carry out in these two steps one according to technological design, carry out another again.
Step 30
In step 30, the surface of the corrosion-resisting pattern that forms in the coating polymer that comprises proton donor polymkeric substance and proton accepting polymer and the step 10 is contacted.Can use spin coating, puddling, dip-coating or spraying to be used for this process.
For example, can be about 30 to about 90 seconds duration of contact.Coating composition can be maintained at about 10 to about 30 ℃.In a kind of exemplary of the present invention, can use room temperature.Contact process also can be carried out in identical temperature range is 10 to about 30 ℃.
When coating composition is contacted with the surface of corrosion-resisting pattern, can be according to contact method rotation or fixing Semiconductor substrate.For example, utilizing under the situation of spin coating, Semiconductor substrate 500 to about 3000rpm is rotated with certain speed according to appointment around its center.Do not have pattern defect for realizing evenly applying, in exemplary of the present invention, use about rotational speed of 1500 to about 2000rpm.When utilizing puddling or when spraying, fixedly Semiconductor substrate.
Step 40
In step 40, can make coating composition and corrosion-resisting pattern surface heat Semiconductor substrate under the state of contact, on the surface of corrosion-resisting pattern, to form the interpolymer composite membrane.In exemplary of the present invention, semiconductor substrate is heated to about 80 to about 160 ℃ temperature.The time that heating needs can be about 60 to about 90 seconds.The interpolymer composite membrane has the network that forms by the hydrogen bond between proton donor polymkeric substance and the proton accepting polymer.The interpolymer composite membrane is water-insoluble.In the network that constitutes the interpolymer composite membrane, can comprise acid.
According to exemplary of the present invention, the acid in the corrosion-resisting pattern is towards the coating composition diffusion of contact corrosion-resisting pattern, and with coating composition in combine the proton donor polymkeric substance alkali reaction form salt.Hydrogen bond in coating composition the proton donor polymkeric substance and proton accepting polymer between form.According to another exemplary of the present invention, the alkali in the coating composition is diffused into the hydrogen bond that brings out in the corrosion-resisting pattern between proton donor polymkeric substance and the proton accepting polymer.
Step 50
In step 50, to remove and be retained in interpolymer composite membrane water-soluble coating composition on every side, this interpolymer composite membrane forms on the corrosion-resisting pattern surface.In a kind of exemplary of the present invention, can be by removing coating composition with rinsed with deionized water.For example, can carry out rinsing to about 90 seconds by rotation Semiconductor substrate about 30 under about speed of 500 to about 4000rpm.
When removing water-soluble coating composition, water-insoluble interpolymer composite membrane is retained on the surface of corrosion-resisting pattern.The interpolymer composite membrane can reduce the bottom width by the perforate exposure of corrosion-resisting pattern.
Step 60
In step 60, be etched in the bottom that forms on the Semiconductor substrate as etching mask by using corrosion-resisting pattern and interpolymer composite membrane.Can obtain surmounting the fine pattern of photoetching process wavelength restriction.
Fig. 2 prepares the schematic flow diagram that fine pattern forms the method for using coating composition for exemplary according to the present invention.The step 21 of Fig. 2 is to the step 20 of 26 pie graphs 1.
Step 21
In step 21, preparation comprises the solution of the proton accepting polymer and first solvent.
First solvent can be the potpourri of deionized water or deionized water and organic solvent.
First solution also can comprise alkali, surfactant, material or their potpourri.Proton accepting polymer, first solvent, alkali, surfactant and material are described in the step 20 of Fig. 1.First solution also can comprise neither as proton donor also not as the binder polymer of proton acceptor.For example, can use polyvinyl alcohol (PVA) as binder polymer.
Step 22
In step 22, preparation comprises second solution of the proton donor polymkeric substance and second solvent.
Second solvent can be the potpourri of deionized water or deionized water and organic solvent.
The proton donor polymkeric substance and second solvent are described in the step 20 of Fig. 1.
Because the carrying out of step 21 and 22 order is not had particular restriction, therefore can carry out in two steps one according to technological design, carry out another again.
Step 23
In step 23, mix first solution and second solution with the preparation mixed solution.Process drips second solution in first solution hereto.Preferably, under agitation in first solution, drip second solution, to prevent the formation of interpolymer complex in the mixed solution.
Step 24
In step 24, but the mixed solution of sonicated first solution and second solution, to disperse to be present in sediment or the hydrogel in the mixed solution fully.Sonicated can be omitted.
Step 25
In step 25, in mixed solution, add acid, become muddy up to mixed solution.Acid is described in the step 20 of Fig. 1.
Step 26
In step 26, filter mixed solution and obtain clean coating composition.
Coating composition can have about 30 to about 70 ℃ LCST according to its component.For example, when coating composition comprises proton donor polymkeric substance, proton accepting polymer and alkali, when promptly not comprising acid in the coating composition, the low LCST that coating composition has.Therefore, even when the temperature of coating composition is improved a little, it is muddy that coating composition also becomes.Proton donor polymkeric substance in the coating composition and proton accepting polymer interact with each other being higher than under the temperature of room temperature, thereby form water-insoluble interpolymer complex.It at high temperature may be not preferred keeping coating composition, because the dispersion of sediment or hydrogel may difficulty in the coating composition.LCST by the content may command coating composition of acid or alkali in the adjustment mixed solution.
Fig. 3 A to 3F uses individual layer resist (SLR) to make the method sectional view of semiconductor devices according to exemplary of the present invention.
With reference to figure 3A, on Semiconductor substrate 100, form the bottom 110 of wanting etched formation specific pattern such as contact hole or groove.Bottom 110 can be dielectric film, conductive film or semiconductive film.
On bottom 110, form corrosion-resisting pattern 120.The corrosion-resisting pattern 120 that forms has the perforate that exposes the first width d1 for the upper surface of bottom 110.The corrosion-resisting pattern 120 that forms can have a plurality of perforates of limiting hole pattern or limit many lines of line and pitch pattern.When the corrosion-resisting pattern 120 that forms had many lines, the first width d1 was corresponding to the width of each spacing between the line.
Corrosion-resisting pattern 120 can be made by the anticorrosive additive material that comprises novolac resin and diazo naphthoquinone (DNQ) based compound.Also can use the chemistry that comprises photic acid producing agent (PAG) to amplify the resist composition and form corrosion-resisting pattern 120.Can use g line resist composition, i line resist composition, KrF excimer laser (248nm wavelength) resist composition, ArF excimer laser (193nm wavelength) resist composition, F 2Excimer laser (157nm wavelength) forms corrosion-resisting pattern 120 with resist composition or electron beam with the resist composition.Also can use positive type resist composition or negative type resist composition to form corrosion-resisting pattern 120.
With reference to figure 3B, in conjunction with as described in the step 30 of Fig. 1, coating composition 130 contacts with the surface of corrosion-resisting pattern 120 as top.In a kind of exemplary of the present invention, rotating Semiconductor substrate 100 about 30 in about 90 seconds with about speed of 500 to about 3000rpm, applying coatings composition 130 on corrosion-resisting pattern 120.Preferably, with about 1500 to about 2000rpm speed rotation Semiconductor substrate 100, there is not pattern defect on Semiconductor substrate 100, evenly to apply coating composition 130.
With reference to figure 3C, heating Semiconductor substrate 100 under the state on coating composition 130 contact corrosion-resisting patterns 120 surfaces is to form interpolymer composite membrane 132 on the surface of corrosion-resisting pattern 120.Can under about 160 ℃, heat about 80.The interpolymer composite membrane of Xing Chenging is water-insoluble like this.Corrosion-resisting pattern 120 and interpolymer composite membrane 132 are used as the mask pattern of etching mask when constituting etching bottom 110.
With reference to figure 3D, remove and be retained in interpolymer composite membrane 132 coating composition 130 on every side.Because coating composition 130 is water miscible, therefore can be by removing with rinsed with deionized water.Bottom 110 is exposed to the second width d2 littler than the first width d1 by the perforate of corrosion-resisting pattern 120.Be formed on the exposed region that corrosion-resisting pattern 120 lip-deep interpolymer composite membranes 132 define bottom 110.With reference to figure 3E, use corrosion-resisting pattern 120 and interpolymer composite membrane 132 to come dry ecthing bottom 110, thereby form bottom pattern 110a as etching mask.
With reference to figure 3F, remove the etching mask that comprises corrosion-resisting pattern 120 and interpolymer composite membrane 132.
Fig. 4 A to 4F uses double-deck resist (BLR) for another exemplary according to the present invention and makes the sectional view of the method for semiconductor devices.
With reference to figure 4A, on Semiconductor substrate 200, form and want etched bottom 210 to be used to form contact hole or groove.Bottom 210 can be dielectric film, conductive film or semiconductive film.
On bottom 210, form bottom film 222 against corrosion.Bottom film 222 against corrosion organic hard mask or the agraphitic carbon that poly-(arylene ether) made of can serving as reasons.
Can be on bottom film 222 against corrosion the spin-coating erosion resistant agent composition, to form top layer film 224 against corrosion.The resist composition that is used to form top layer film 224 against corrosion can be siliceous resist composition or not siliceous resist composition.
With reference to figure 4B, exposure and development top layer film 224 against corrosion are to form top corrosion-resisting pattern 224a.With reference to figure 4C, as top in conjunction with as described in Fig. 3 B, applying coatings composition 230 on the corrosion-resisting pattern 224a of top.Coating composition 230 comprises material, described in the step 20 of Fig. 1.
With reference to figure 4D, in conjunction with as described in Fig. 3 C, heating Semiconductor substrate 200 under the state on coating composition 230 contact corrosion-resisting pattern 224a surfaces, top is to form interpolymer composite membrane 232 on the surface of top corrosion-resisting pattern 224a as top.
With reference to figure 4E, in conjunction with as described in Fig. 3 D, remove the coating composition 230 that is retained in around the interpolymer composite membrane 232 as top.
With reference to figure 4F, use the mask pattern of forming by top corrosion-resisting pattern 224a and interpolymer composite membrane 232 to come dry ecthing bottom film 222 against corrosion, thereby form bottom corrosion-resisting pattern 222a as etching mask.The part of top corrosion-resisting pattern 224a and interpolymer composite membrane 232 can be worn.
With reference to figure 4G, use the mask pattern comprise top corrosion-resisting pattern 224a and interpolymer composite membrane 232 and following bottom corrosion-resisting pattern 222a to come dry ecthing bottom 210, thereby form bottom pattern 210a as etching mask.
With reference to figure 4H, remove the mask pattern that comprises top corrosion-resisting pattern 224a and interpolymer composite membrane 232 and bottom corrosion-resisting pattern 222a.
According to as described in another embodiment of the present invention, in the composition process of using BLR, use the coating composition 230 that comprises material to form interpolymer composite membranes 232 as top.When etching bottom film 222 against corrosion, material has increased the silicone content in the etching mask, thereby has guaranteed the resistibility to bottom film 222 dry ecthings against corrosion.
In another exemplary of the present invention, can use multilayer resist (MLR) method, wherein after forming the interlayer sull between bottom film 222 against corrosion and the top layer film 224 against corrosion, bottom 210 is carried out composition.
Fig. 5 and 6 is the top figure that forms mechanism in conjunction with interpolymer composite membrane 132 in Fig. 3 C and the described heating process of 4D and 232.The formation mechanism of interpolymer composite membrane 232 is substantially similar to the formation mechanism of interpolymer composite membrane 132.
In the time of will being described in coating composition 130 and contacting in conjunction with Fig. 5 and 6 with the surface of corrosion-resisting pattern 120 by adding the mechanism of thermosetting interpolymer composite membrane 132 (referring to Fig. 3 C).The acid 122 that exists in the corrosion-resisting pattern 120 is towards coating composition 130 diffusions that contacts with corrosion-resisting pattern 120, and with coating composition 130 in be attached to the alkali 134 reaction formation salt of proton donor polymkeric substance 136.Hydrogen bond 150 in coating composition 130 proton donor polymkeric substance 136 and proton accepting polymer 138 between form.Therefore, form water-insoluble interpolymer complex.
When comprising proton donor polymkeric substance 136, proton accepting polymer 138, alkali and deionized water, coating composition 130 can use above-mentioned mechanism.
Fig. 7 is that top in conjunction with interpolymer composite membrane 132 in the described heating process of Fig. 3 C another forms the figure of mechanism.
Mechanism shown in Figure 7 is similar to the mechanism shown in Fig. 5 and 6, because the acid 122 in the corrosion-resisting pattern 120 is towards coating composition 130 diffusions that contact with corrosion-resisting pattern 120.When not using alkali, can use mechanism shown in Figure 7.Therefore, coating composition 130 comprises proton donor polymkeric substance 136, proton accepting polymer 138, acid 122 and deionized water.
When heating under the state on coating composition 130 contact corrosion-resisting patterns 120 surfaces, acid 122 has promoted the hydrogen bonding between the proton donor polymkeric substance 136 and proton accepting polymer 138 in the coating composition 130, thereby forms the interpolymer complex.Acid 122 130 diffusions from corrosion-resisting pattern 120 towards coating composition.Perhaps, acid 122 is present in the coating composition.Therefore, help the formation of water-insoluble interpolymer complex.The network that forms by hydrogen bond 150 in the interpolymer composite membrane 132 (referring to Fig. 3 C) can comprise acid 122.
Fig. 8 and 9 is the figure that forms another mechanism of interpolymer composite membrane according to exemplary of the present invention.
With reference to figure 8 and 9, when heating under the state on coating composition 130 contact corrosion-resisting patterns 120 surfaces, the alkali 134 in the coating composition 130 is diffused in the corrosion-resisting pattern 120.Therefore, hydrogen bond 150 in coating composition 130 proton donor polymkeric substance 136 and proton accepting polymer 138 between form, thereby form water-insoluble interpolymer complex.
But the mechanism shown in the application drawing 8 and 9 when coating composition 130 comprises proton donor polymkeric substance 136, proton accepting polymer 138, alkali 134 and deionized water.
Hereinafter, will the illustrative embodiment of the mask pattern that forms according to the mask pattern formation method according to the semiconductor devices manufacturing usefulness of illustrative embodiments of the invention be described.
Embodiment 1
Step 1-1: the formation of corrosion-resisting pattern
On 8 inches naked silicon chips, form anti-reflection film (for example, DUV-30, NissanChemical Industries is Ltd.) to about 360 ℃ thickness.Then, spin coating ArF cured under about 105 ℃ about 60 seconds then with photoresist (for example, SAIL-G24c, ShinEtsu Chemical Co.Ltd) on anti-reflection film, and formation thickness is about 3000 film against corrosion.Make film against corrosion be exposed to the light of ArF (wavelength is 193nm) stepper, about 60 seconds then at about 105 ℃ of following post exposure bakes (PEB).Then, use 2.38wt% tetramethylammonium hydroxide (TMAH) solution development wafer, on wafer, to form corrosion-resisting pattern with a plurality of perforates.Corrosion-resisting pattern has the isolated sectional hole patterns (hereinafter, be called " i-sectional hole patterns ") of diameter for about 129.7nm.Corrosion-resisting pattern also has in hole array center partly locates the intensive sectional hole patterns (hereinafter, be called " d-sectional hole patterns ") of diameter for about 138.0nm, wherein forms the pattern in a plurality of holes with about 240nm spacing.
Step 1-2: the preparation of coating composition
Gather (vinyl pyrrolidone) at about 450mg H to about 50mg 2Add about 6.0mg triethanolamine in the solution among the O at about 594mg H 2Solution among the O (deionized water) obtains mixed solution.Again to wherein adding about 400mg H 2The mixed solution that O obtains diluting.Under agitation the about 50mg of mixed solution and dripping to dilution gathers (acrylic acid-be total to-maleic acid) at about 450mg H 2Solution among the O.Can be dispersed in partly precipitated thing and the hydrogel that produces in the dropping process by sonicated.Drip the aqueous solution of about 1% p-toluenesulfonic acid monohydrate, muddy up to the mixed solution change of gained.Filter the gains that obtain like this, obtain clean coating composition.
Step 1-3: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 1-2 on the corrosion-resisting pattern that forms in step 1-1 forms homogeneous film.Under about 155 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.Therefore, on the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 92.3nm and about 118.7nm respectively.
Embodiment 2
Step 2-1: the preparation of coating composition
Gather (vinyl pyrrolidone) at about 1800mg H to about 200mg 2Add about 20.0mg TMAH in the solution among the O at about 2480mg H 2Solution among the O obtains mixed solution.Add about 1500mg H again 2The mixed solution that O obtains diluting.Under agitation gather (acrylic acid) at about 1800mg H to the about 200mg of mixed solution and dripping of dilution 2Solution among the O.Can be dispersed in partly precipitated thing and the hydrogel that produces in the dropping process by sonicated.Drip the aqueous solution of about 1% p-toluenesulfonic acid monohydrate, become muddy up to the gained mixed solution.Filter the gains that obtain like this and obtain clean coating composition.
Step 2-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 2-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 155 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.Therefore, on the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 113.8nm and about 129.5nm respectively.
Embodiment 3
Step 3-1: the preparation of coating composition
Gather (vinyl pyrrolidone) at about 1800mg H to about 200mg 2Add about 32.0mg TMAH in the solution among the O at about 3968mg H 2Solution among the O and about 32mg thermic acid producing agent (for example commodity CYCAT4040, the Cymel Co.) solution in about 47mg isopropyl alcohol obtains mixed solution.Under agitation gather (acrylic acid) at about 1800mg H to the about 200mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained obtains clean coating composition.
Step 3-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 3-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 155 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.Therefore, on the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 111.6nm and about 138.4nm respectively.
Embodiment 4
Carry out this embodiment by mode similar to Example 1, except coating composition comprises surfactant, rather than acid.
Step 4-1: the preparation of coating composition
Gather (vinyl pyrrolidone) at about 900mg H to about 100mg 2Add about 30mg triethanolamine in the solution among the O at about 2970mg H 2(commodity Zonyl-FSN for example is DuPont) at about 396mg H for solution among the O, about 4.0mg surfactant 2Solution among the O and about 600mg H 2O obtains mixed solution.Under agitation gather (acrylic acid-be total to-maleic acid) at about 900mg H to the about 100mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained obtains clean coating composition.The LCST of the coating composition that obtains is about 36 ℃.
Step 4-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 4-1 on by the corrosion-resisting pattern that forms with the essentially identical mode of embodiment 1 step 1-1 forms homogeneous film.The homogeneous film of Xing Chenging can be divided into four sample sets like this.Four sample sets were cured under about 140 ℃, 145 ℃, 150 ℃ or 153 ℃ about 60 seconds respectively, and used rinsed with deionized water.On each surface of four sample sets, all be formed uniformly water-insoluble interpolymer composite membrane.For in about 140 ℃ of sample sets of curing, i-sectional hole patterns and d-sectional hole patterns have the diameter of about 99.0nm and about 114.5nm respectively, for in about 145 ℃ of sample sets of curing, the diameter that has about 105.1nm and about 118.3nm respectively, for in about 150 ℃ of sample sets of curing, the diameter that has about 72.1nm and about 117.2nm respectively in about 153 ℃ of sample sets of curing, has the diameter of about 61.3nm and about 100.5nm respectively.
Embodiment 5
Step 5-1: the preparation of coating composition
Gather (vinyl pyrrolidone) at about 900mg H to about 100mg 2Add about 30mg triethanolamine in the solution among the O at about 2970mg H 2Solution among the O and about 4.0mg surfactant (commodity PolyFox, OMNOVA Solutions Inc.) are at about 396mg H 2Solution among the O obtains mixed solution.Under agitation gather (acrylic acid-be total to-maleic acid) at about 900mg H to the about 100mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained obtains clean coating composition.
Step 5-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 5-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 153 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.The i-sectional hole patterns is in " not perforate " state, and the d-sectional hole patterns has the diameter of about 74.2nm.
Embodiment 6
Step 6-1: the preparation of coating composition
Gather (vinyl pyrrolidone) at about 900mg H to about 100mg 2Add about 35.0mg triethanolamine in the solution among the O at about 3465mg H 2(commodity Zonyl-FSN for example is DuPont) at about 396mg H for solution among the O, about 4.0mg surfactant 2Solution among the O and about 100mgH 2O obtains mixed solution.Under agitation gather (acrylic acid-be total to-maleic acid) at about 900mg H to the about 100mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained is to obtain clean coating composition.
Step 6-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 6-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 145 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 73.8nm and about 115.3nm respectively.
Embodiment 7
Step 7-1: the preparation of coating composition
Gather (vinyl pyrrolidone) at about 900mg H to about 100mg 2Add about 16.0mg monoethanolamine in the solution among the O at about 1584mg H 2(commodity Zonyl-FSN is DuPont) at about 396mg H for solution among the O, about 4.0mg surfactant 2Solution among the O and about 2.0g H 2O obtains mixed solution.Under agitation gather (acrylic acid-be total to-maleic acid) at about 900mg H to the about 100mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained obtains clean coating composition.
Step 7-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 7-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 145 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 89.7nm and about 113.5nm respectively.
Embodiment 8
Step 8-1: the preparation of coating composition
To about 150mg poly-(vinyl pyrrolidone-be total to-caprolactam) (vinyl pyrrolidone: caprolactam=50: 50) at about 1350mg H 2Add about 32.0mg triethanolamine in the solution among the O at about 3168mg H 2(commodity Zonyl-FSN is DuPont) at about 396mg H for solution among the O, about 4.0mg surfactant 2Solution among the O and about 6.4g H 2O obtains mixed solution.Under agitation gather (acrylic acid-be total to-maleic acid) at about 450mg H to the about 50mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained obtains clean coating composition.In the coating composition of gained, the weight ratio of proton donor polymkeric substance and proton accepting polymer is about 1: 3.
Step 8-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 8-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 145 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 91.4nm and about 98.4nm respectively.
Embodiment 9
Zhi Bei coating composition also comprises the polyvinyl alcohol (PVA) as binder polymer except comprising proton donor polymkeric substance and proton accepting polymer in this embodiment.
Step 9-1: the preparation of coating composition
To about 190mg polyvinyl alcohol (PVA) at about 3610mgH 2Add about 4mg triethanolamine in the solution among the O at about 396mg H 2(commodity Zonyl-FSN is DuPont) at about 396mg H for solution among the O, about 4.0mg surfactant 2Solution among the O, about 5mg poly-(vinyl pyrrolidone-be total to-caprolactam) (vinyl pyrrolidone: caprolactam=50: 50) at about 45mgH 2Solution among the O and about 7.3g H 2O obtains mixed solution.Under agitation gather (acrylic acid-be total to-maleic acid) at about 45mg H to the about 5.0mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained is to obtain clean coating composition.
The formation of step 9-2. interpolymer composite membrane
The coating composition that obtains among the spin coating step 9-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 145 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 83.9nm and about 124.4nm respectively.
Embodiment 10
Step 10-1: the preparation of coating composition
To about 400mg poly-(vinyl pyrrolidone-be total to-caprolactam) (vinyl pyrrolidone: caprolactam=50: 50) at about 3.6g H 2Add about 157mg triethanolamine in the solution among the O at about 156mg H 2(commodity Zonyl-FSN is DuPont) at about 1584mg H for solution among the O, about 16mg surfactant 2Solution among the O and about 14.1g H 2O obtains mixed solution.Under agitation gather (acrylic acid-be total to-maleic acid) at about 3.9g H to the about 400mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained is to obtain clean coating composition.
Step 10-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 10-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 145 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 88.0nm and about 115.8nm respectively.
Embodiment 11
Zhi Bei coating composition comprises acid rather than alkali in this embodiment.Use has the polyacrylamide of structure shown in the formula 9 as proton accepting polymer.
Step 11-1: the preparation of coating composition
To about 50mg polyacrylamide at about 450mg H 2Add about 10mg p-toluenesulfonic acid-hydrate in the solution among the O at about 990mg H 2Solution among the O obtains mixed solution.Under agitation gather (acrylic acid-be total to-maleic acid) at about 450mg H to the about 50mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained is to obtain clean coating composition.
Step 11-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 11-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 155 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 113.9nm and about 136.4nm respectively.
Embodiment 12
Zhi Bei coating composition comprises acid rather than alkali in this embodiment.
Step 12-1: the preparation of coating composition
To about 100mg polyvinyl pyrrolidone at about 900mg H 2Add about 17mg p-toluenesulfonic acid monohydrate in the solution among the O at about 693mg H 2Solution among the O and about 3.3g H 2O obtains mixed solution.Under agitation gather (methyl ethylene ester-friendship (alt)-maleic acid) at about 900mg H to the about 100mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained is to obtain clean coating composition.
Step 12-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 12-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 153 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 99.0nm and about 126.4nm respectively.
Embodiment 13
Zhi Bei coating composition comprises acid rather than alkali in this embodiment.
Step 13-1: the preparation of coating composition
To about 100mg poly-(vinyl pyrrolidone-be total to-caprolactam) (vinyl pyrrolidone: caprolactam=50: 50) at about 900mg H 2Add about 40mg p-toluenesulfonic acid monohydrate in the solution among the O at about 3690mg H 2Solution among the O obtains mixed solution.Under agitation gather (2,3-dihydrofuran-friendship-maleic acid) at about 900mg H to the about 100mg of mixed solution and dripping 2Solution among the O.The mixed solution that filters gained is to obtain clean coating composition.
Step 13-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 13-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 153 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 96.6nm and about 125.7nm respectively.
Embodiment 14
Carry out this embodiment by mode similar to Example 4, except the tetraethyl orthosilicate (TEOS) that uses partial hydrolysis as material.
Step 14-1: the preparation of coating composition
To about 180mg poly-(vinyl pyrrolidone-be total to-caprolactam) (vinyl pyrrolidone: caprolactam=50: 50) at about 1.62g H 2Add about 100mg triethanolamine in the solution among the O at about 100mg H 2The TEOS of the solution among the O, about 320mg partial hydrolysis is at about 7.68g H 2(commodity Zonyl-FSN is DuPont) at about 396mg H for solution among the O and about 4.0mg surfactant 2Solution among the O obtains mixed solution.Add about 3.4g H again 2The mixed solution that O obtains diluting.Under agitation the about 20mg of mixed solution and dripping to dilution gathers (acrylic acid-be total to-maleic acid) at about 180mg H 2Solution among the O.Be dispersed in some water and sediment gels that produce in the dropping process by sonicated, filter then and obtain clean coating composition.
Step 14-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 14-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 120 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 81.0nm and about 95.1nm respectively.
Embodiment 15
Carry out this embodiment by mode similar to Example 14, except using TEOS as material.
Step 15-1: the preparation of coating composition
To about 190mg poly-(vinyl pyrrolidone-be total to-caprolactam) (vinyl pyrrolidone: caprolactam=50: 50) at about 1.71g H 2Add about 50mg triethanolamine in the solution among the O at about 50mg H 2Solution among the O, about 320mg TEOS are at about 7.68g H 2(commodity Zonyl-FSN is DuPont) at about 396mgH with about 4.0mg surfactant for solution among the O 2Solution among the O obtains mixed solution.Add about 3.5g H again 2The mixed solution that O obtains diluting.The about 10mg of mixed solution and dripping to dilution poly-(acrylic acid-be total to-maleic acid) is at about 90mgH 2Solution among the O.Be dispersed in some water and sediment gels that produce in the dropping process by sonicated, filter then and obtain clean coating composition.
Step 15-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 15-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 110 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.The i-sectional hole patterns is " not perforate " state, is also referred to as " closed pore pattern ", and the d-sectional hole patterns has the diameter of about 89.8nm.
Embodiment 16
Carry out this embodiment by mode similar to Example 14, except using TEOS as material.
Step 16-1: the preparation of coating composition
To about 90mg poly-(vinyl pyrrolidone-be total to-caprolactam) (vinyl pyrrolidone: caprolactam=50: 50) at about 810mg H 2Add about 25mg triethanolamine in the solution among the O at about 25mg H 2Solution among the O, about 120mg TEOS are at about 2.88gH 2(commodity Zonyl-FSN is DuPont) at about 198mg H with about 2.0mg surfactant for solution among the O 2Solution among the O obtains mixed solution.Add about 2.75g H again 2The mixed solution that O obtains diluting.The about 10mg of mixed solution and dripping to dilution poly-(acrylic acid-be total to-maleic acid) is at about 90mg H 2Solution among the O.Be dispersed in some water and sediment gels that produce in the dropping process by sonicated, filter then and obtain clean coating composition.
Step 16-2: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 16-1 on by the corrosion-resisting pattern that forms with the basic similarly mode of embodiment 1 step 1-1 forms homogeneous film.Under about 120 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 70.3nm and about 109.9nm respectively.
Embodiment 17
Step 17-1: the formation of corrosion-resisting pattern
(DUV-30, Nissan ChemicalIndustries is Ltd.) to about 360 ℃ thickness to form anti-reflection film on 8 inches naked silicon chips.Spin coating ArF cured under about 110 ℃ about 60 seconds then with photoresist (SAIL-G24c, ShinEtsu Chemical Co.Ltd) on anti-reflection film, and formation thickness is about 2500 film against corrosion.Make film against corrosion be exposed to the light of ArF (193nm) stepper, about 60 seconds then at about 105 ℃ of following post exposure bakes (PEB).Use 2.38wt%TMAH solution development wafer, on wafer, to form corrosion-resisting pattern with a plurality of perforates.Corrosion-resisting pattern has diameter and partly locates the d-sectional hole patterns of diameter for about 134.7nm for the i-sectional hole patterns of about 196.3nm with in hole array center, wherein forms the pattern in a plurality of holes with the spacing of about 210nm * about 260nm.
Step 17-2: the preparation of coating composition
To about 180mg poly-(vinyl pyrrolidone-be total to-caprolactam) (vinyl pyrrolidone: caprolactam=50: 50) at about 1.62g H 2Add about 20mg triethanolamine in the solution among the O at about 1980mg H 2Solution among the O, about 320mg 3-glycidoxypropyltrime,hoxysilane are at about 7.68g H 2(commodity Zonyl-FSN is DuPont) at about 396mg H with about 4.0mg surfactant for solution among the O 2Solution among the O obtains mixed solution.Again to wherein adding about 1.6g H 2The mixed solution that O obtains diluting.Under agitation the about 20mg of mixed solution and dripping to dilution gathers (acrylic acid-be total to-maleic acid) at about 180mg H 2Solution among the O.Be dispersed in some water and sediment gels that produce in the dropping process by sonicated, filter then and obtain clean coating composition.
Step 17-3: the formation of interpolymer composite membrane
The coating composition that obtains among the spin coating step 17-2 on the corrosion-resisting pattern that forms in step 17-1 forms homogeneous film.Under about 85 ℃, cure homogeneous film about 60 seconds, and use rinsed with deionized water.On the corrosion-resisting pattern surface, be formed uniformly water-insoluble interpolymer composite membrane.I-sectional hole patterns and d-sectional hole patterns have the diameter of about 147.7nm and about 126.7nm respectively.
According to exemplary of the present invention, can on the surface of corrosion-resisting pattern, form the interpolymer composite membrane to obtain mask pattern.The mask pattern that forms has the small size perforate that surmounts the restriction of photoetching technique wavelength.The interpolymer composite membrane can be the water-insoluble film that comprises network, and described network forms by the hydrogen bond between proton donor polymkeric substance and the proton accepting polymer.The mask pattern of the interpolymer composite membrane that comprises corrosion-resisting pattern and form on corrosion-resisting pattern can keep the vertical sidewall profile.In addition, energy minimization isodensity deviation when reducing aperture widths.In addition, when use comprises that the coating composition of material carries out BLR or MLR method, just on the corrosion-resisting pattern of top, form the interpolymer composite membrane, thereby improved the silicone content in the corrosion-resisting pattern of top.Therefore, to the resistibility raising of dry ecthing, thereby guaranteed high pattern duty ratio (duty ratio).
Although this paper has described exemplary in conjunction with the accompanying drawings, but should understand the present invention and be not restricted to these accurate embodiments, only otherwise depart from the scope of the present invention or spirit, a those of ordinary skill in described field can be realized various other variations and change.All this variations and change are all planned to be included in the scope of the present invention that limits as accessory claim.

Claims (72)

1. one kind is used for the mask pattern that semiconductor devices is made, and it comprises:
The corrosion-resisting pattern that on Semiconductor substrate, forms; With
The interpolymer composite membrane that on corrosion-resisting pattern, forms, wherein this interpolymer composite membrane comprises the network that forms by the hydrogen bond between proton donor polymkeric substance and proton accepting polymer,
Wherein said proton accepting polymer comprises first repetitive, and wherein this first repetitive comprises the monomeric unit with acylamino-,
And wherein said proton donor polymkeric substance comprises first repetitive, and wherein this first repetitive is the maleic acid monomer unit with carboxyl or sulfo group.
2. mask pattern as claimed in claim 1, wherein the interpolymer composite membrane is water-insoluble.
3. mask pattern as claimed in claim 1, wherein the network of interpolymer composite membrane comprises acid.
4. mask pattern as claimed in claim 1, wherein the interpolymer composite membrane comprises silicon.
5. mask pattern as claimed in claim 1, first repetitive of wherein said proton donor polymkeric substance comprises the maleic acid monomer unit of representing with following formula:
6. mask pattern as claimed in claim 5, wherein the proton donor polymkeric substance also comprises second repetitive, this second repetitive comprises acrylic monomers unit, vinyl monomer unit, alkylene glycol monomeric unit, ethylene imine monomeric unit, the monomeric unit that contains oxazoline group, acrylonitrile monemer unit, acrylyl amine monomers unit, 3,4-dihydropyrane monomeric unit and 2, at least a in the 3-dihydrofuran monomeric unit.
7. mask pattern as claimed in claim 6, wherein in the sum of repetitive, the amount of first repetitive of proton donor polymkeric substance is 3 to 90%.
8. mask pattern as claimed in claim 1, wherein the proton donor polymkeric substance has 1000 to 100000 daltonian weight-average molecular weight.
9. mask pattern as claimed in claim 1, wherein proton accepting polymer comprises first repetitive, wherein first repetitive comprises the vinyl monomer unit of representing with following formula:
Figure C2005100649020003C1
R wherein 1Be hydrogen atom or methyl, R 2And R 3Be hydrogen atom or C 1To C 5Alkyl, R 2And R 3With-R 2-R 3-form connect.
10. mask pattern as claimed in claim 9, wherein proton accepting polymer comprises first repetitive of representing with following formula:
Figure C2005100649020003C2
Wherein n is 1 to 5 integer.
11. mask pattern as claimed in claim 10, wherein proton accepting polymer comprises first repetitive, and wherein this first repetitive comprises the vinylpyrrolidone monomer unit.
12. mask pattern as claimed in claim 10, wherein proton accepting polymer comprises first repetitive, and wherein this first repetitive comprises the caprolactam monomeric unit.
13. mask pattern as claimed in claim 1, wherein proton accepting polymer comprises first repetitive, and wherein this first repetitive comprises the vinyl monomer unit of representing with following formula:
R wherein 4Be hydrogen atom or methyl, R 5And R 6Be hydrogen atom, methyl, n-pro-pyl, isopropyl, aminopropyl or N, the N-dimethylaminopropyl.
14. mask pattern as claimed in claim 1, wherein proton accepting polymer also comprises second repetitive, wherein this second repetitive comprises acrylic monomers unit, vinyl monomer unit, alkylene glycol monomeric unit, ethylene imine monomeric unit, the monomeric unit that contains oxazoline group, acrylonitrile monemer unit, acrylyl amine monomers unit, 3,4-dihydropyrane monomeric unit and 2, at least a in the 3-dihydrofuran monomeric unit.
15. mask pattern as claimed in claim 9, wherein in the sum of repetitive, the use amount of first repetitive of proton accepting polymer is 3 to 100%.
16. mask pattern as claimed in claim 1, wherein proton accepting polymer has 1000 to 100000 daltonian weight-average molecular weight.
17. mask pattern as claimed in claim 1, wherein the interpolymer composite membrane be included as first polymkeric substance of proton donor polymkeric substance, for second polymkeric substance of proton accepting polymer with not as the terpolymer of proton donor polymkeric substance or proton accepting polymer.
18. mask pattern as claimed in claim 17, wherein terpolymer is a polyvinyl alcohol (PVA).
19. mask pattern as claimed in claim 1, wherein corrosion-resisting pattern is made by the anticorrosive additive material that comprises novolac resin and diazo naphthoquinone based compound.
20. mask pattern as claimed in claim 1, wherein corrosion-resisting pattern uses the chemistry that comprises photic acid producing agent to amplify the formation of resist composition.
21. mask pattern as claimed in claim 1, wherein corrosion-resisting pattern uses g line resist composition, i line resist composition, KrF excimer laser resist composition, ArF excimer laser resist composition, F 2Excimer laser forms with the resist composition with resist composition or electron beam.
22. mask pattern as claimed in claim 1, wherein corrosion-resisting pattern uses positive type resist composition or negative type resist composition to form.
23. mask pattern as claimed in claim 1, wherein the corrosion-resisting pattern of Xing Chenging has a plurality of perforates of limiting hole pattern.
24. mask pattern as claimed in claim 1, wherein the corrosion-resisting pattern of Xing Chenging has many lines that limit line and pitch pattern.
25. a method that is formed for the mask pattern of semiconductor devices manufacturing, this method comprises:
On substrate, form film against corrosion;
The exposure and the described film against corrosion that develops are to form corrosion-resisting pattern on substrate;
Preparation comprises the coating composition of proton donor polymkeric substance and proton accepting polymer; And
Coating composition is contacted with the surface of corrosion-resisting pattern to form the interpolymer composite membrane on the corrosion-resisting pattern surface, and described interpolymer composite membrane has the network that forms by the hydrogen bond between proton donor polymkeric substance and the proton accepting polymer,
Wherein said proton accepting polymer comprises first repetitive, and wherein this first repetitive comprises the monomeric unit with acylamino-,
And wherein said proton donor polymkeric substance comprises first repetitive, and wherein this first repetitive is the maleic acid monomer unit with carboxyl or sulfo group.
26. method as claimed in claim 25, wherein coating composition has 30 to 70 ℃ lower critical solution temperature.
27. method as claimed in claim 25, wherein proton donor polymkeric substance and proton accepting polymer have 1: 9 to 9: 1 weight ratio in the coating composition.
28. method as claimed in claim 25, wherein coating composition comprises proton donor polymkeric substance, proton accepting polymer, alkali and solvent.
29. method as claimed in claim 28, wherein in the general assembly (TW) of coating composition, the use amount of alkali is 0.1 to 5.0wt%.
30. method as claimed in claim 28, wherein alkali is that boiling point is 140 ℃ or higher material.
31. method as claimed in claim 28, wherein alkali is monoethanolamine, triethanolamine or tetramethylammonium hydroxide.
32. method as claimed in claim 28, wherein coating composition also comprises Bronsted acid.
33. method as claimed in claim 25, wherein coating composition comprises proton donor polymkeric substance, proton accepting polymer, Bronsted acid and solvent.
34. method as claimed in claim 25, wherein coating composition comprises material.
35. method as claimed in claim 34, wherein material is silicon alkoxide monomer, silicon alkoxide oligomer or their partial hydrolysate.
36. method as claimed in claim 25, wherein in the general assembly (TW) of coating composition, the use amount of proton donor polymkeric substance is 0.1 to 5.0wt%.
37. method as claimed in claim 25, wherein in the general assembly (TW) of coating composition, the use amount of proton accepting polymer is 0.1 to 5.0wt%.
38. method as claimed in claim 25, wherein the proton donor polymkeric substance also comprises:
Comprise acrylic monomers unit, vinyl monomer unit, alkylene glycol monomeric unit, ethylene imine monomeric unit, the monomeric unit that contains oxazoline group, acrylonitrile monemer unit, acrylyl amine monomers unit, 3,4-dihydropyrane monomeric unit and 2, at least a second repetitive in the 3-dihydrofuran monomeric unit.
39. method as claimed in claim 25, wherein proton accepting polymer also comprises:
Comprise acrylic monomers unit, vinyl monomer unit, alkylene glycol monomeric unit, ethylene imine monomeric unit, the monomeric unit that contains oxazoline group, acrylonitrile monemer unit, acrylyl amine monomers unit, 3,4-dihydropyrane monomeric unit and 2, at least a second repetitive in the 3-dihydrofuran monomeric unit.
40. method as claimed in claim 25, wherein coating composition also comprises binder polymer.
41. method as claimed in claim 40, wherein binder polymer is a polyvinyl alcohol (PVA).
42. method as claimed in claim 33, wherein in the general assembly (TW) of coating composition, the use amount of Bronsted acid is 0.1 to 10wt%.
43. method as claimed in claim 33, wherein Bronsted acid is p-toluenesulfonic acid, trifluoroacetic acid or dodecylbenzene sulfonic acid.
44. method as claimed in claim 25, wherein coating composition also comprises the solvent in the potpourri that is selected from deionized water and deionized water and organic solvent.
45. method as claimed in claim 44, wherein in the general assembly (TW) of coating composition, the use amount of organic solvent is 0 to 20wt%.
46. method as claimed in claim 25, wherein coating composition also comprises at least a in surfactant and the thermic acid producing agent.
47. method as claimed in claim 46, wherein in the general assembly (TW) of coating composition, the use amount of each is 0.01 to 0.5wt% in surfactant and the thermic acid producing agent.
48. method as claimed in claim 25 wherein prepares coating composition and comprises:
Preparation comprises first solution of proton accepting polymer;
In first solution, add second solution that comprises the proton donor polymkeric substance, obtain mixed solution; With
Filter mixed solution.
49. method as claimed in claim 48 wherein prepares coating composition and also is included in adding acid in the filtration forward direction mixed solution.
50. method as claimed in claim 48, wherein first solution also comprises alkali, surfactant, thermic acid producing agent or their potpourri.
51. method as claimed in claim 48, wherein first solution also comprises material.
52. method as claimed in claim 51, wherein material is silicon alkoxide monomer, silicon alkoxide oligomer or their partial hydrolysate.
53. method as claimed in claim 48 wherein drips second solution to obtain mixed solution in first solution.
54. method as claimed in claim 53 wherein under agitation drips second solution in first solution.
55. method as claimed in claim 48 wherein prepares coating composition and also comprises the sonicated mixed solution.
56. method as claimed in claim 28, wherein the alkali in the coating composition is diffused in the corrosion-resisting pattern under the state on coating composition contact corrosion-resisting pattern surface.
57. method as claimed in claim 25, wherein the acid in the corrosion-resisting pattern is diffused in the coating composition under the state on coating composition contact corrosion-resisting pattern surface.
58. method as claimed in claim 25 also is included under the state on coating composition contact corrosion-resisting pattern surface heated substrate under 80 to 160 ℃ temperature.
59. method as claimed in claim 58 also is included in and removes the coating composition that is retained in around the interpolymer composite membrane after the heating.
60. method as claimed in claim 25 is wherein carried out contacting of coating composition and corrosion-resisting pattern surface by spin coating, puddling, dip-coating or spraying.
61. a method of making semiconductor devices, this method comprises:
On Semiconductor substrate, form bottom;
Formation has the corrosion-resisting pattern that is exposed to the perforate of first width for bottom;
Under coating composition that comprises proton donor polymkeric substance and proton accepting polymer and corrosion-resisting pattern surface state of contact, on the corrosion-resisting pattern surface, form water-insoluble interpolymer composite membrane by the heating Semiconductor substrate, to expose bottom to second width littler than first width by perforate; With
Use corrosion-resisting pattern and interpolymer composite membrane to come etching bottom as etching mask,
Wherein said proton accepting polymer comprises first repetitive, and wherein this first repetitive comprises the monomeric unit with acylamino-,
And wherein said proton donor polymkeric substance comprises first repetitive, and wherein this first repetitive is the maleic acid monomer unit with carboxyl or sulfo group.
62. method as claimed in claim 61 wherein heats under 80 to 160 ℃ temperature.
63. method as claimed in claim 61 also comprises by spin coating, puddling, dip-coating or spraying coating composition is contacted with the corrosion-resisting pattern surface.
64. method as claimed in claim 61 also comprises removing being retained in interpolymer composite membrane coating composition on every side.
65. as the described method of claim 64, wherein when removing the coating composition that is retained in around the interpolymer composite membrane, with the surface of rinsed with deionized water interpolymer composite membrane.
66. method as claimed in claim 61, wherein coating composition also comprises at least a in the bronsted lowry acids and bases bronsted lowry.
67. method as claimed in claim 61, wherein coating composition also comprises material.
68. method as claimed in claim 61, wherein coating composition also comprises at least a in surfactant and the thermic acid producing agent.
69. method as claimed in claim 61, wherein coating composition has 30 to 70 ℃ LCST.
70. method as claimed in claim 61, wherein corrosion-resisting pattern uses the chemistry that contains PAG to amplify the formation of resist composition.
71. method as claimed in claim 61, wherein corrosion-resisting pattern uses g line resist composition, i line resist composition, KrF excimer laser resist composition, ArF excimer laser resist composition, F 2Excimer laser forms with the resist composition with resist composition or electron beam.
72. method as claimed in claim 61, wherein corrosion-resisting pattern uses siliceous resist composition to form.
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