CN101454872A - Stripper composition for photoresist - Google Patents
Stripper composition for photoresist Download PDFInfo
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- CN101454872A CN101454872A CNA2007800191632A CN200780019163A CN101454872A CN 101454872 A CN101454872 A CN 101454872A CN A2007800191632 A CNA2007800191632 A CN A2007800191632A CN 200780019163 A CN200780019163 A CN 200780019163A CN 101454872 A CN101454872 A CN 101454872A
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0272—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers for lift-off processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
- H01L21/30608—Anisotropic liquid etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
- H01L21/30612—Etching of AIIIBV compounds
- H01L21/30617—Anisotropic liquid etching
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- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The present invention relates to a photoresist stripper composition. During a lift-off process as well as a known process of stripping a photoresist, the photoresist stripper composition is capable of completely stripping a photoresist film denatured due to an excessive photolithography process at low temperatures within a short period, does not damage a conductive film or an insulating film at a lower part of the photoresist even if rinsing is performed by only using water and not isopropanol, which is an intermediate rinsing solution, and has an excellent corrosion inhibiting ability to the conductive metal film or the insulating film at the lower part of the photoresist.
Description
Technical field
The present invention relates to a kind of light carving rubber stripper composition.
The application requires the priority at the 10-2006-0047668 korean patent application of KIPO submission on May 26th, 2006, incorporates its full content into the application with way of reference.
Background technology
The method of the fine circuitry of preparation semiconductor integrated circuit or LCD comprises: be formed on the substrate by aluminium, aluminium alloy, apply photoresist equably on the conductive metal film that copper or copper alloy are made or on as the dielectric film of silicon dioxide film or silicon nitride film, optionally to resist exposure and it is developed to form the photoresist pattern, photoresist film by adopting patterning carries out wet etching or dry etching with the lower floor of fine circuitry design transfer to photoresist as mask to conductive metal film or dielectric film, and adopts remover to remove unwanted photoresist layer.
When using remover to remove to be used to prepare the photoresist of semiconductor device and LCD, need to consider following performance.
Need can be at short notice stripping photoresist at low temperatures, thereby and need splendid stripping ability prevent that the surplus materials that washes the back photoresist from remaining on the substrate.In addition, need low corrosivity to prevent destruction to the metal film or the dielectric film of photoresist lower floor.If interact between the solvent of formation remover, the storage stability of this remover may descend and its physical property may change according to the order by merging in the preparation remover process.Therefore, even nonreactive to each other solvent is at high temperature also guaranteed stability simultaneously need be mixed with each other the time.In addition, with regard to toxicity, when considering waste disposal, remover is should be to the operator harmless and be environmental protection.When at high temperature carrying out the peeling off of photoresist, if a large amount of volatilizations, then the ratio of component changes rapidly, has reduced the stability of remover and the repeatability of operation.Therefore, the volatility of remover is minimized.In addition, should adopt a spot of remover to handle multiple substrate, should easily supply with the component that constitutes remover with low cost, and should reuse excessive remover to guarantee business efficiency.
In order to satisfy above-mentioned requirements, developed polytype remover combination that is used for photoresist, the example is as described below.
Disclose the example of the light carving rubber stripper composition that begins to develop most in JP-A-51-72503, wherein, it is 150 ℃ or higher non-halogenated aromatic hydrocarbon that this remover combination contains alkyl benzene sulphonate and boiling point with 10～20 carbon atoms.JP-A-57-84456 discloses the remover combination that contains methyl-sulfoxide or diethyl sulfoxide and organic sulfoxide compound.In addition, the 4th, 256, No. 294 U.S. Patent Publications contain alkyl aryl sulphonic acid, have the remover combination that the hydrophilic aromatic sulphonic acid of 6～9 carbon atoms and boiling point are 150 ℃ or higher non-halogenated aromatic hydrocarbon.Yet above-mentioned composition is owing to the severe corrosive of the conductive metal film made by aluminium, aluminium alloy, copper or copper alloy, strong toxicity and environmental pollution are difficult to use.
For fear of the problems referred to above, considered the remover combination that comprises polytype organic solvent, this organic solvent contains the essential component of water-soluble alkanolamine conduct that is mixed with each other, and the example of this remover combination is as described below.
The 4th, 617, No. 251 U.S. Patent Publications based on the remover combination of two kinds of components, it comprises as the organic amine compound of monoethanolamine (MEA) and 2-(2-amino ethoxy)-1-ethanol (AEE) and as the polar solvent of dimethyl formamide (DMF), dimethylacetylamide (DMAc), N-crassitude diketone (NMP), methyl-sulfoxide (DMSO), diethylene glycol monoethyl ether acetate and propylene glycol methyl ether acetate (PGMEA).The 4th, 770, No. 713 U.S. Patent Publications based on the remover combination of two kinds of components, it comprises organic amine compound and as N-methylacetamide, dimethyl formamide (DMF), dimethylacetylamide (DMAc), N-methyl-N-ethyl propionamide, diethyl acetamide (DEAc), Valpromide (DPAc), N, N-dimethyl propylene acid amides and N, the amide solvent of N-amide dimethyl butyrate.JP-A-62-49355 discloses the remover combination that contains alkylidene polyamine sulphones (alkylene polyamine sulfone compound), and the oxirane for alkanolamine and ethylenediamine and ethylene glycol one alkyl ether (glycol monoalkyl ether) wherein is provided.JP-A-63-208043 discloses and has contained water-soluble alkanolamine and 1, the remover combination of 3-dimethyl-2-imidazolone (DMI).JP-A-63-231343 discloses the eurymeric light carving rubber stripper composition, and it contains amines, polar solvent and surfactant.JP-A-64-42653 discloses a kind of remover combination, it contains 50wt% or more methyl-sulfoxide (DMSO), 1～50wt% is selected from diethylene glycol (DEG) one alkyl ether, diethylene glycol (DEG) dialkyl ether, gamma-butyrolacton and 1, one or more solvents in 3-dimethyl-2-imidazolone (DMI), and as the nitrogenous organic hydroxy compounds of monoethanolamine (MEA).JP-A-4-124668 discloses a kind of remover combination, and it contains the organic amine of 20～90wt%, the phosphate ester surfactants of 0.1～20wt%, the 2-butine-1 of 0.1～20wt%, 4-glycol, diethylene glycol (DEG) dialkyl ether and proton-less polarity solvent.Thus, add 2-butine-1,4-two pure and mild phosphate ester surfactants are in order to prevent that when not reducing stripping ability metal level is corroded.Yet because this composition that is used for stripping photoresist has poor inhibition intensity to aluminium and aluminium alloy film, its problem is to occur obvious corrosion and forms defective part in the process of deposition gate insulating film that is reprocessing in strip step.
In addition, JP-A-4-350660 discloses a kind of remover combination, it contains 1,3-dimethyl-2-imidazolone (DMI), methyl-sulfoxide (DMSO) and water-soluble organic amine, and JP-A-5-281753 discloses a kind of remover combination, and it contains alkanolamine, sulphones or sulfoxide compound and (C
6H
6)
n(OH)
nThe hydroxy compounds of (n is 1,2 or 3 integer).JP-A-8-87118 discloses a kind of remover combination, and it contains the N-alkyl alkanolamine of 50～90wt% and methyl-sulfoxide (DMSO) or the dimethyl formamide (DMF) of 50～10wt%.Yet, in the method recently of preparation LCD and semiconductor device,, for example under 120 ℃ or higher high temperature, handle glass substrate and silicon wafer substrate because processing conditions is extreme, photoresist often will at high temperature stand back baking (postbake).Therefore, its problem is: owing to significantly solidify, unsatisfactory by adopting above-mentioned remover combination to remove.
Proposed to contain the light carving rubber stripper composition of water and/or hydroxylamine compounds as the composition that is used for thoroughly removing by the photoresist that adopts high-temperature step curing.For example, JP-A-4-289866 discloses the remover combination that contains hydroxylamine, alkanolamine and water.JP-A-6-266119 discloses the remover combination that contains hydroxylamine, alkanolamine, water and corrosion inhibiter.In addition, JP-A-7-69618 discloses a kind of remover combination, the polar aprotic solvents as gamma-butyrolacton (GBL), dimethyl formamide (DMF), dimethylacetylamide (DMAc) and N-crassitude diketone (NMP) that it comprises by predetermined ratio contains the amino alcohol and the water of 2-methylamino ethanol (N-MAE).In addition, JP-A-8-123043 discloses and has contained amino alcohol, water and as the remover combination of the ethylene glycol alkyl ether of DEGMBE (BDG).JP-A-8-262746 discloses the remover combination that contains alkanolamine, alkoxyalkyl amine, ethylene glycol one alkyl ether, sugar compounds, quaternary ammonium base and water, and JP-A-9-152721 disclose contain alkanolamine, hydroxylamine, diethylene glycol (DEG) one alkyl ether, as corrosion inhibiter as the sugar compounds of D-sorbite and the remover combination of water.JP-A-9-96911 discloses a kind of remover combination, and it contains hydroxylamine, water, acid ionization constant (pKa) is 7.5～13 amine, water-soluble polar organic solvent and corrosion inhibiter.Yet, owing to superhigh temperature processing, dry etching, ashing and ion implantation step make above-mentioned remover combination deterioration.Just to crosslinked photoresist film and in etching step the stripping ability by the photoresist etch residues that forms with metal byproducts reaction, and for the corrosion inhibiting ability for the aluminum or aluminum alloy film of the lower guide electrolemma of photoresist, above-mentioned remover combination is unfavorable.In addition, there is the at high temperature unstable problem of decomposing after through a section time of hydroxylamine compounds.
Above-mentioned remover combination is according to component and with the stripping performance of photoresist, to the ratio of the relevant component of repeatability, storage stability and the business efficiency of corrosion of metal, the type of peeling off the afterflush step, operation and obviously different each other, and still needs to develop a kind of remover combination that has optimum performance cheaply under polytype processing conditions.
Simultaneously, the size of LCD has increased, and LCD is large-scale production.Therefore, adopt the single-wafer processing device to carry out peeling off of photoresist usually, wherein, wafer of single treatment rather than use the infusion process of a large amount of removers, and use the remover combination useful to this device.
For example, publication number is that the Korean Patent special permission of 2000-8103 discloses a kind of remover combination, and it contains the alkanolamine of 5～15wt%, the glycol ether of the sulfoxide of 35～55wt% or sulphones and 35～55wt%.Publication number is that the Korean Patent special permission of 2000-8553 discloses a kind of remover combination, and it contains the water-soluble amine compound of 10～30wt% and diethylene glycol (DEG) one alkyl ether and N-alkyl pyrrolidine diketone or the hydroxy alkyl pyrrolidine-diones of 70～90wt%.Yet the shortcoming of above-mentioned composition is: although poor to the low stripping ability at low temperatures of corrosion of metal.
And in strip step, after photoresist was coated in whole surface and forms required pattern, depositing metallic films or as the dielectric film of silicon dioxide film or silicon nitride film was then removed photoresist thereon.Therefore, its advantage is to have saved and is used for film is carried out the patterned etch step.Yet,, therefore need carry out strip step for a long time to photoresist owing to be not to whole resist exposures.
In addition, the shortcoming of above-mentioned all compositions is: be 10 minutes or longer and corrosion occurs at aluminium that applies said composition or copper wire place to the splitting time of photoresist in stripping process.
Summary of the invention
Technical problem
The inventor studies stripping photoresist at short notice and the light carving rubber stripper composition that in the known steps of strip step and stripping photoresist metal film or dielectric film had a low-corrosiveness, found that: contain the water-soluble organic amine compound of predetermined ratio and the light carving rubber stripper composition of corrosion inhibiter and in the strip step process, can thoroughly peel off at low temperatures at short notice because the photoresist film of the sex change that excessive photoetching treatment causes, even only adopt water but not isopropyl alcohol is middle rinse solution cleans the conducting film and the dielectric film that also can not destroy the photoresist bottom, and have at the conductive metal film of photoresist bottom or the splendid corrosion inhibiting ability of dielectric film, thereby finished the present invention.
Therefore, one object of the present invention is for providing a kind of light carving rubber stripper composition, and it has to the splendid stripping ability of photoresist and to the anti-damage ability or the corrosion inhibiting ability of conducting film and dielectric film height.
Another object of the present invention is for providing a kind of method by adopting light carving rubber stripper composition to come stripping photoresist.
Another object of the present invention is for providing a kind of method for preparing LCD or semiconductor device, and this method comprises the method for stripping photoresist.
Technical scheme
The invention provides a kind of light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper.This light carving rubber stripper composition comprises: 1) corrosion inhibiter, and it comprises and is selected from least a by in the group formed of compounds of Chemical formula 1,2 and 3 expressions; 2) water-soluble organic amine compound, its weight are 2～50 times of described corrosion inhibiter weight; And 3) polar solvent:
[Chemical formula 1]
Wherein, R1 and R2 are same to each other or different to each other, and are hydrogen or hydroxyl independently of one another, and
R3 is hydrogen, the tert-butyl group, carboxylic acid group (COOH), carbomethoxy (COOCH
3), ethoxycarbonyl (COOC
2H
5) or propyl ester base (COOC
3H
7),
[Chemical formula 2]
Wherein, R4 is hydrogen or the alkyl that contains 1～4 carbon atom, and
R5 and R6 are same to each other or different to each other, and are the hydroxyalkyl that contains 1～4 carbon atom independently of one another,
[chemical formula 3]
In addition, can further comprise water soluble nonionic surfactant according to remover combination of the present invention.
And, can further comprise non-polar solven according to light carving rubber stripper composition of the present invention.
Beneficial effect
In the step of strip step and known stripping photoresist, can thoroughly peel off at low temperatures at short notice because the photoresist film of the sex change that excessive photoetching treatment causes according to light carving rubber stripper composition of the present invention, even do not use isopropyl alcohol for middle rinse solution can not destroy the conducting film and the dielectric film made by aluminum or aluminum alloy of photoresist bottom yet, it has splendid corrosion inhibiting ability to conductive metal film or the dielectric film as copper or tin-copper alloy film in the photoresist bottom, and the type handled of photoresist all can be coated in it and contains aluminium, on the substrate of copper or aluminium and copper.
Description of drawings
Fig. 1 is the cutaway view of the step of the photoresist of demonstration stripper crystal display.
Fig. 2 is for showing the cutaway view of the step that adopts the stripping technology stripping photoresist.
Embodiment
Hereinafter will describe the component that constitutes according to light carving rubber stripper composition of the present invention in detail.
In light carving rubber stripper composition according to the present invention, preferably will not destroy the conductive metal film of photoresist lower floor or the compound of dielectric film and be used as corrosion inhibiter 1).Even only adopt water but not isopropyl alcohol is middle rinse solution washes, corrosion inhibiter of the present invention has also prevented to be corroded as the conducting film of aluminum or aluminum alloy film or dielectric film.
Usually, when only adopting water but not isopropyl alcohol is middle rinse solution when washing, the amine component in the remover mixes the hydroxyl ion that produces the alkali with severe corrosive with water, therefore impel metal to be corroded.Yet in the present invention, even corrosion inhibiter also is used to and aluminium forms complex in alkaline environment, this complex surface of being adsorbed on aluminium forms diaphragm like this, thereby prevents the corrosion that caused by hydroxyl ion.
In light carving rubber stripper composition according to the present invention, compare with tolyl-triazole with the BTA of the corrosion inhibiter that is widely used as known copper film, have the corrosion inhibiting ability that significantly improves by Chemical formula 1,2 or 3 corrosion inhibiter of representing.Therefore, even only add a spot of corrosion inhibiter, the conducting film as copper or tin-copper alloy film of photoresist lower floor also can not corrode and as described in corrosion inhibiter very effective for the surplus materials of the photoresist of removing curing.
Inhibition mechanism by Chemical formula 1,2 or 3 corrosion inhibiter of representing is as described below.For the corrosion inhibiter of representing by Chemical formula 1, be attached together by the hydroxyl that adopts alkaline solution to make directly to be added on the phenyl ring and aluminium and control corrosion of metal.For the corrosion inhibiter by Chemical formula 2 or 3 expressions, the unshared electron pair of the nitrogen-atoms that triazole ring is rich in combines (electronically bonded) and controls corrosion of metal with the copper electronics.
In light carving rubber stripper composition according to the present invention, described corrosion inhibiter can be the compound represented by Chemical formula 1 and mixture by the compounds of Chemical formula 2 or 3 expressions.
In light carving rubber stripper composition according to the present invention, based on the total weight of described composition, the content of described corrosion inhibiter is preferably 0.01～5wt% and 0.1～1wt% more preferably.If the content of corrosion inhibiter is lower than 0.01wt%, after the substrate that will peel off and remover Long contact time, metallic circuit may be by partial corrosion.When its content during greater than 5wt%, viscosity can increase and reduce stripping ability, and because the price of composition increases, its cost performance is just unsatisfactory.
In light carving rubber stripper composition according to the present invention, water-soluble organic amine compound 2) is preferably and is selected from least a in the group of forming by primary amino alcohols compound, secondary amino group alcoholic compound and uncle's alkamine compound.
Described alkamine compound is preferably and is selected from least a in the group of being made up of the amino isopropyl alcohol (AIP) of monoethanolamine (MEA), 1-, 2-amino-1-propyl alcohol, N-methylamino ethanol (N-MAE), 3-amino-1-propyl alcohol, 4-amino-1-butanols, 2-(2-amino ethoxy)-1-ethanol (AEE), 2-(2-aminoethylamino)-1-ethanol, diethanol amine (DEA), triethanolamine (TEA) and hydroxyethyl piperazine (HEP).Consider stripping ability, corrosion inhibiting ability and business efficiency, more preferably use 2-(2-amino ethoxy)-1-ethanol (AEE).
The content of water-soluble organic amine compound can be 2～50 times of corrosion inhibiter content, and based on the total weight of described composition, is preferably 1～60wt% and 3～30wt% more preferably.If it is the content of water-soluble organic amine compound is lower than 1wt%, undesirable to the stripping ability of the photoresist of sex change.If its content surpasses 60wt%,, therefore increased splitting time because the viscosity increase has reduced the amount that penetrates in the stripping technology in the photoresist.In addition, increased the corrosion of not wishing to occur to the conductive metal film of photoresist lower floor.
In light carving rubber stripper composition according to the present invention, when corrosion inhibiter 1) when being the mixture of two or more components, water-soluble organic amine compound 2) be preferably the primary amino alcohols compound, and 2-(2-amino ethoxy)-1-ethanol (AEE) more preferably.
In light carving rubber stripper composition according to the present invention, polar solvent 3) very compatible and be organic compound and the effect of playing the solvent of dissolving photoresist to water.In addition, thus polar solvent has reduced the surface tension of remover has improved wet performance to photoresist film.
Described polar solvent preferably has 1cP or lower viscosity and 150 ℃ or higher boiling point.The instantiation of described polar solvent comprises: N-methyl pyrrolidone (NMP), 1,3-dimethyl-2-imidazolone (DMI), methyl-sulfoxide (DMSO), dimethylacetylamide (DMAc), dimethyl formamide (DMF), N-methylformamide (NMF), sulfolane or its mixture.
Based on the total weight of described composition, the content of described polar solvent is preferably 1～95wt%, 35～95wt% more preferably, and most preferably be 50～95wt%.If the content of polar aprotic solvents is 1wt% or lower, then the viscosity of remover increases, and this has reduced the stripping ability of remover.Therefore, preferably increase the weight of polar solvent as much as possible.
In addition, can further comprise water soluble nonionic surfactant according to light carving rubber stripper composition of the present invention.
And, can further comprise non-polar solven according to light carving rubber stripper composition of the present invention.
The example of described non-polar solven can comprise: BDG (butyldiglycol), EDG (ethyl diethylene glycol (DEG)), MDG (methyl diethylene glycol (DEG)), TEG (triethylene glycol) and DEM (carbitol).
Based on the total weight of described composition, the content of described non-polar solven is preferably 0～40wt%.The content of non-polar solven is set in preferred lowland as far as possible.When the amount of non-polar solven increased, stripping ability reduced generation impurity, and along with the increase productive rate of the photoresist of handling reduces unfriendly.
Do not destroy the conducting film of photoresist bottom and dielectric film and have conductive metal film or the splendid corrosion inhibiting ability of dielectric film according to light carving rubber stripper composition of the present invention the photoresist bottom.
Described conductive metal film or dielectric film can be the monofilm that contains aluminium, copper or its alloy or have two-layer or more multi-layered multilayer film, perhaps for to contain the monofilm of aluminium, copper or its alloy and neodymium, molybdenum or its alloy or to have two-layer or more multi-layered multilayer film.
Usually, in the process of preparation semiconductor device and LCD, carry out the one or many photoresist and handle.In addition, conductive metal film that forms on substrate or dielectric film can be the monofilm that contains aluminium and/or copper or have two-layer or more multi-layered multilayer film.In correlation technique, in the photoresist processing procedure with different light carving rubber stripper with on the substrate that forms the conductive metal film that contains aluminium or dielectric film thereon and in the photoresist processing procedure, use it on the substrate of the conductive metal film that forms cupric on it or dielectric film.
Yet formation on it is contained the conductive metal film of aluminium, copper or aluminium and copper to light carving rubber stripper composition according to the present invention or the substrate of dielectric film has splendid peeling off and corrosion inhibiting ability.In other words, multipurpose light carving rubber stripper composition according to the present invention contains the water-soluble organic amine compound and the corrosion inhibiter of predetermined ratio, thereby can use it on any substrate that contains aluminium and/or copper.
In addition, the invention provides a kind of from the substrate that contains aluminium, copper or aluminium and copper the method for stripping photoresist.Described method comprises: 1) photoresist is coated on the conductive metal film or dielectric film that is formed on the substrate, 2) on this substrate, form the photoresist pattern, 3) adopt the photoresist film of patterning to come etching conductive metal film or dielectric film as mask, and 4) adopt according to light carving rubber stripper composition stripping photolithography glue-line of the present invention.
In addition, the invention provides a kind of from the substrate that contains aluminium, copper or aluminium and copper the method for stripping photoresist.Described method comprises: 1) in whole base plate surface-coated photoresist, 2) formation photoresist pattern on substrate, 3) conductive metal deposition film or dielectric film on the substrate of patterning, and 4) adopt according to light carving rubber stripper composition stripping photoresist of the present invention.
In the method for stripping photoresist, conductive metal film or dielectric film can be the monofilm that contains aluminium, copper or its alloy or have two-layer or more multi-layered multilayer film, perhaps for to contain the monofilm of aluminium, copper or its alloy and neodymium, molybdenum or its alloy or to have two-layer or more multi-layered multilayer film.Particularly, preferred Al-Nd/Mo duplicature or Cu/MoX.
On adopting the substrate that forms the fine circuitry pattern according to light carving rubber stripper composition of the present invention from it in the method for stripping photoresist, both can use infusion process also can use the single-wafer processing method, the substrate that will peel off in infusion process immerses in a large amount of removers simultaneously, and in the single-wafer processing method remover is sprayed on the substrate one by one to remove photoresist.
Employing comprises according to the example of the photoresist that light carving rubber stripper composition of the present invention can be peeled off: the photoresist of eurymeric photoresist, negative photoresist and just/negative dimorphism.Can with the example of photoresist comprise the photoresist that contains light-sensitive compound, this light-sensitive compound contains phenol resin (novolac based phenol resin) and the diazo naphthoquinone (diazonaphthoquinone) based on novolaks, but does not limit its component.
In addition, the invention provides a kind of method for preparing LCD or semiconductor device.This method comprises the method for stripping photoresist.
When adopting preparation in accordance with the present invention to prepare LCD and semiconductor device, when photoresist was stripped from, the substrate with fine pattern both be not corroded not destroyed yet, and the amount of residual photoresist is few.
The invention provides a kind of light carving rubber stripper composition, it can easily remove the photoresist film of sex change in photo-etching technological process at short notice under high temperature and low temperature, even only adopt water but not isopropyl alcohol is middle rinse solution washes, it does not corrode the conducting film and the dielectric film made by aluminium, aluminium alloy, copper or copper alloy of photoresist bottom yet.
Especially, in the present invention, in the stripping technology of stripping photoresist, can thoroughly peel off at low temperatures at short notice because the photoresist film of the sex change that excessive photoetching process causes.
Embodiment
The present invention may be better understood with reference to the following embodiment that lists for explaining, but these embodiment are not in order to limit the present invention.In the following example and comparing embodiment, unless specialize, the component ratio of composition is a weight ratio.
＜embodiment 1～33 〉
Component and composition that use is described in following table 1 stirred 2 hours and filtered the material obtain at normal temperatures to obtain the particle that size is 0.1 μ m.Thereby, make stripper solution.
＜comparing embodiment 1～6 〉
The component that adopts as describe in the following table 1 and composition use and embodiment 1 identical step prepares stripper solution.
Table 1
※ AEE:2-(2-amino ethoxy)-1-ethanol,
The NMF:N-methylformamide,
The NMP:N-methyl pyrrolidone,
DMAc: dimethylacetylamide,
MEA: monoethanolamine,
NMAE:N-methylamino ethanol,
BDG: DEGMBE,
EDG: carbitol,
MDG: the methyl diethylene glycol (DEG),
C1: the compound of following chemical formula 5:
[chemical formula 5]
C2: the compound of following chemical formula 6:
[chemical formula 6]
＜experimental example〉estimate stripping ability and the corrosivity be used to peel off
Adopt the stripping ability and the corrosivity of the remover combination that following method evaluation prepares in embodiment 1～33 and comparing embodiment 1～6.
With regard to the sample that is used to test, following two kinds of samples have been used.Adopt stripping technology to prepare pixel layer glass, in the formation of handling through grid on glass
The Al-Nd layer, and in the process of TFT circuit of preparation LCD, form thereon
The Mo layer, apply and to contain the eurymeric photoresist of novolac resin (novolac resin) and PAC and be dried, adopt photoetching process formation pattern, and carry out wet etching and prepare a kind of sample.On the glass substrate of handling through grid, form
Molybdenum alloy after form thereon
The Cu layer, apply and to contain the eurymeric photoresist of novolac resin and PAC and be dried, adopt photoetching process to form pattern, and carry out wet etching and prepare another kind of sample.
1. evaluation stripping ability
Sample is immersed in the stripper solution to descend to keep 1 minute at 70 ℃ and 50 ℃, use deionized water rinsing 30 seconds, and use nitrogen drying.After drying is finished, adopt light microscope with 1,000 * enlargement ratio and electron microscope (FE-SEM) with 5,000～10,000 * the enlargement ratio observation sample to estimate peeling off to photoresist.Adopt following standard evaluation stripping performance.
※ ◎: splendid stripping performance,
Zero: acceptable stripping performance,
△: unacceptable stripping performance,
*: the stripping performance of difference.
2. estimate first etch state
Carry out the evaluation of first etch state and peel off the etch state of back in the step that adopts deionized water to wash with evaluation.The sample that will estimate immerse in the acetone soln 40 ℃ keep down 10 minutes then with isopropyl alcohol flushing 30 seconds and with deionized water rinsing 30 seconds with to be evaluated.The solution mixture that the sample that will be used for estimating immerses 50g stripper solution and 950g water continues 3 minutes at normal temperatures, uses deionized water rinsing 30 seconds, and uses nitrogen drying.Utilize electron microscope (FE-SEM) with 50,000～10,000 * surface, side and the cross section of enlargement ratio observation sample estimate etch state.
Adopt following standard evaluation etch state.
The surface and the side of ※ ◎: Al-Nd and Mo circuit are not corroded,
Zero: the surface of Al-Nd and Mo circuit and side be by mild corrosion,
The surface of △: Al-Nd and Mo circuit and side be by partial corrosion,
*: the surface of Al-Nd and Mo circuit and side are by heavy corrosion.
3. estimate second etch state
Sample is immersed in the stripper solution to descend to keep 10 minutes at 70 ℃, use deionized water rinsing 30 seconds, use nitrogen drying then.After continuously repeating 3 disbonded tests, utilize electron microscope (FE-SEM) with 50,000～10,000 * surface, side and the cross section of enlargement ratio observation sample to estimate etch state.
Adopt following standard evaluation etch state.
※ ◎: the surface and the side of Cu circuit are not corroded,
Zero: the surface of Cu circuit and side be by mild corrosion,
△: the surface of Cu circuit and side be by partial corrosion,
*: the surface of Cu circuit and side are by heavy corrosion.
Estimate stripping ability and etch state, and in following table 2, describe the result.
Table 2
As shown in table 2, with good grounds remover combination of the present invention have splendid peeling off and corrosion inhibiting ability.
Claims (22)
1, a kind of light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper, it comprises:
1) corrosion inhibiter, it comprises and is selected from least a by in the group formed of compounds of Chemical formula 1,2 and 3 expressions;
2) water-soluble organic amine compound, its weight are 2～50 times of described corrosion inhibiter weight; And
3) polar solvent:
[Chemical formula 1]
Wherein, R1 and R2 are same to each other or different to each other, and are hydrogen or hydroxyl independently of one another, and
R3 is hydrogen, the tert-butyl group, carboxylic acid group (COOH), carbomethoxy (COOCH
3), ethoxycarbonyl (COOC
2H
5) or propyl ester base (COOC
3H
7),
[Chemical formula 2]
Wherein, R4 is hydrogen or the alkyl that contains 1～4 carbon atom, and
R5 and R6 are same to each other or different to each other, and are the hydroxyalkyl that contains 1～4 carbon atom independently of one another,
[chemical formula 3]
2, the light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, wherein, described corrosion inhibiter 1) be the compound represented by Chemical formula 1 and mixture by the compounds of Chemical formula 2 or 3 expressions.
3, the content light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, wherein, based on the total weight of described composition, described corrosion inhibiter 1) is 0.01～5wt%.
4, the light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, wherein, described water-soluble organic amine compound 2) comprise and be selected from least a in the group of forming by primary amino alcohols compound, secondary amino group alcoholic compound and uncle's alkamine compound.
5, the light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, wherein, described water-soluble organic amine compound 2) comprise and be selected from least a in the group of forming by the amino isopropyl alcohol (AIP) of monoethanolamine (MEA), 1-, 2-amino-1-propyl alcohol, N-methylamino ethanol (N-MAE), 3-amino-1-propyl alcohol, 4-amino-1-butanols, 2-(2-amino ethoxy)-1-ethanol (AEE), 2-(2-aminoethylamino)-1-ethanol, diethanol amine (DEA), triethanolamine (TEA) and hydroxyethyl piperazine (HEP).
6, the content light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, wherein, based on the total weight of described composition, described water-soluble organic amine compound 2) is 1～60wt%.
7, the light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, wherein, described corrosion inhibiter 1) be the compound represented by Chemical formula 1 and mixture by the compounds of Chemical formula 2 or 3 expressions, and described water-soluble organic amine compound 2) be 2-(2-amino ethoxy)-1-ethanol (AEE).
8, the light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, wherein, described polar solvent 3) comprises and being selected from, at least a in the group that 3-dimethyl-2-imidazolone (DMI), methyl-sulfoxide (DMSO), dimethylacetylamide (DMAc), dimethyl formamide (DMF), N-methylformamide (NMF) and sulfolane are formed by N-methyl pyrrolidone (NMP), 1.
9, the content light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, wherein, based on the total weight of described composition, described polar solvent 3) is 1～95wt%.
10, the content light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, wherein, based on the total weight of described composition, described polar solvent 3) is 50～95wt%.
11, the light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, it contains water soluble nonionic surfactant in addition.
12, the light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 1, it contains non-polar solven in addition.
13, the light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 12, wherein, described non-polar solven comprises and is selected from least a in the group of being made up of BDG (butyldiglycol), EDG (ethyl diethylene glycol (DEG)), MDG (methyl diethylene glycol (DEG)), TEG (triethylene glycol) and DEM (carbitol).
14, the light carving rubber stripper composition that is used to contain the substrate of aluminium, copper or aluminium and copper according to claim 12, wherein, based on the total weight of described composition, the content of described non-polar solven is greater than 0wt% and less than 40wt%.
15, a kind of from the substrate that contains aluminium, copper or aluminium and copper the method for stripping photoresist, it comprises the following steps:
1) applies photoresist being formed on conductive metal film on the substrate or the dielectric film;
2) on this substrate, form the photoresist pattern;
3) come above-mentioned conductive metal film of etching or dielectric film by the photoresist film that adopts patterning as mask; And
4) come the stripping photolithography glue-line by adopting according to each described light carving rubber stripper composition in the claim 1～14.
16, according to claim 15 from the substrate that contains aluminium, copper or aluminium and copper the method for stripping photoresist, wherein, described conducting film or dielectric film are to contain the monofilm of aluminium, copper or aluminium copper or have two-layer or more multi-layered multilayer film, perhaps for to contain the monofilm of aluminium, copper, aluminium copper and neodymium, molybdenum or neodymium molybdenum alloy or to have two-layer or more multi-layered multilayer film.
17, a kind of method for preparing LCD, it comprises the described method of claim 15.
18, a kind of method for preparing semiconductor device, it comprises the described method of claim 15.
19, a kind of from the substrate that contains aluminium, copper or aluminium and copper the method for stripping photoresist, it comprises the following steps:
1) at the whole surface-coated photoresist of substrate;
2) on this substrate, form the photoresist pattern;
3) conductive metal deposition film or dielectric film on the substrate of patterning; And
4) by adopting according to each described light carving rubber stripper composition stripping photolithography glue-line in the claim 1～14.
20, according to claim 19 described from the substrate that contains aluminium, copper or aluminium and copper the method for stripping photoresist, wherein, described conducting film or dielectric film are to contain the monofilm of aluminium, copper or aluminium copper or have two-layer or more multi-layered multilayer film, perhaps for to contain the monofilm of aluminium, copper, aluminium copper and neodymium, molybdenum or neodymium molybdenum alloy or to have two-layer or more multi-layered multilayer film.
21, a kind of method for preparing LCD, it comprises the described method of claim 19.
22, a kind of method for preparing semiconductor device, it comprises the described method of claim 19.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2006-0047668 | 2006-05-26 | ||
| KR20060047668 | 2006-05-26 | ||
| KR1020060047668 | 2006-05-26 | ||
| PCT/KR2007/002542 WO2007139315A1 (en) | 2006-05-26 | 2007-05-25 | Stripper composition for photoresist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101454872A true CN101454872A (en) | 2009-06-10 |
| CN101454872B CN101454872B (en) | 2011-04-06 |
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|---|---|---|---|
| CN2007800191632A Active CN101454872B (en) | 2006-05-26 | 2007-05-25 | Stripper composition for photoresist and method for stripping photoresist stripping composition using the composition |
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| Country | Link |
|---|---|
| JP (1) | JP4773562B2 (en) |
| KR (2) | KR20070114038A (en) |
| CN (1) | CN101454872B (en) |
| TW (1) | TWI362571B (en) |
| WO (1) | WO2007139315A1 (en) |
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-
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- 2007-05-25 KR KR1020070050852A patent/KR20070114038A/en not_active Ceased
- 2007-05-25 KR KR20070050844A patent/KR100913048B1/en active Active
- 2007-05-25 CN CN2007800191632A patent/CN101454872B/en active Active
- 2007-05-25 WO PCT/KR2007/002542 patent/WO2007139315A1/en active Application Filing
- 2007-05-25 TW TW96118832A patent/TWI362571B/en active
- 2007-05-25 JP JP2009513051A patent/JP4773562B2/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100913048B1 (en) | 2009-08-25 |
| TW200801855A (en) | 2008-01-01 |
| JP4773562B2 (en) | 2011-09-14 |
| KR20070114038A (en) | 2007-11-29 |
| WO2007139315A1 (en) | 2007-12-06 |
| KR20070114037A (en) | 2007-11-29 |
| CN101454872B (en) | 2011-04-06 |
| JP2009538456A (en) | 2009-11-05 |
| TWI362571B (en) | 2012-04-21 |
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