CN110412838A - A kind of highly selective stripper, preparation method and application - Google Patents
A kind of highly selective stripper, preparation method and application Download PDFInfo
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- CN110412838A CN110412838A CN201910603572.1A CN201910603572A CN110412838A CN 110412838 A CN110412838 A CN 110412838A CN 201910603572 A CN201910603572 A CN 201910603572A CN 110412838 A CN110412838 A CN 110412838A
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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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Abstract
The invention discloses a kind of highly selective stripper, preparation method and applications.The stripper, its raw material includes the component of following mass fraction: the water of 0-30.00%, the linear class organic solvent of 5.00-20.00%, the sulfone class of 10.00-30.00% and/or sulfoxide type organic solvent, the alcohol ethers organic solvent of 21.00-79.00%, the alkane organic solvent of ketone of 5.00-20.00% and the surfactant of 0.01-5.00%, the sum of each component mass fraction is 100%, and the surfactant is the tetrasiloxane Gemini surface active agent containing sugared amide groups.Stripper of the invention does not constitute destruction corrosion in the case where the stripping performance having had, to other multiple materials, has high application value.
Description
Technical field
The present invention relates to a kind of highly selective stripper, preparation method and applications.
Background technique
In semiconductor integrated circuit manufacturing field and general semiconductors manufacture (such as photovoltaic, LED, mems chip, power core
Piece, storage chip) etc. related fieldss, lithography and etching technology is the general technology of these manufacturing fields, although there may be films
Layer property and line width difference, but technological principle communicates.With the progress of semiconductor field technology, chip line width gradually becomes
Small, chip layout shape becomes increasingly complex, and the film layer number of plies is also more and more.Suchlike variation, mentions semiconductor material
Increasingly higher demands out.In wet process technique especially in semiconductor fabrication process, wet chemical material is needed to meet each side
The requirement in face, such as highly selective corrosion, highly selective cleaning, removing etc..At present in photoresist lift off liquid material, market is urgently
Need the research and development of highly selective stripper.The present invention is a Gao Xuan of birth under this strong market demand
Selecting property stripper is not constituted other multiple materials in the case where cleaning photoetching glue residua and all good stripping photoresist performance
Destruction corrosion.Still without finding that the document of equivalent efficacy product discloses.
Summary of the invention
The technical problem to be solved by the present invention is to remove and clean light to exist for stripper in the prior art
While photoresist and its residue, it is difficult to realize the defect that various metals and nonmetallic materials are provided simultaneously with anticorrosion ability,
And provide a kind of highly selective stripper, preparation method and application.Stripper of the invention is in the removing having had and clearly
In the case where washing performance, destruction corrosion is not constituted to other multiple materials.
The present invention is mainly to solve above-mentioned technical problem by following technological means.
The present invention provides a kind of stripper, raw material includes the component of following mass fraction: the water of 0-30.00%,
The linear class organic solvent of 5.00-20.00%, the sulfone class of 10.00-30.00% and/or sulfoxide type organic solvent,
Alcohol ethers organic solvent, the alkane organic solvent of ketone of 5.00-20.00% and the surface of 0.01-5.00% of 21.00-79.00%
Activating agent, the sum of each component mass fraction are 100%, and the surfactant is the tetrasiloxane Shuangzi table containing sugared amide groups
Face activating agent.
The raw material components of the etching liquid are preferably free of quaternary ammonium compounds.
Wherein, the mass fraction of the water can be 3.00-23.00%, for example, 7.00-15.00%.The straight chain
The mass fraction of amide-type organic solvent can be 8.00-15.00%, for example, 10.00-12.00%.The sulfone class and/or Asia
The mass fraction of sulfone class organic solvent can be 15.00-25.00%, for example, 17.00.00-23.00%.The alcohol ethers have
The mass fraction of solvent can be 28.00-64.00%, for example, 51.00-60.00%.The matter of the alkane organic solvent of ketone
Measuring score can be 8.00-15.00%, for example, 10.00-12.00%.The tetrasiloxane Shuangzi surface containing sugared amide groups
The mass fraction of activating agent can be 0.05-1.50%, for example, 0.10-1.30%.
In some embodiments, the mass fraction of the water can for 4.00%, 29.00%, 0%, 27.00%,
15.00%, 12.00%, 3.00%, 10.00%, 4.00%, 23.00%, 7.00% or 24.00%.The linear
The mass fraction of class organic solvent can be 7.00%, 10.00%, 12.00%, 8.00%, 15.00%, 5.00%, 20.00%
Or 13.00%.The mass fraction of the sulfone class and/or sulfoxide type organic solvent can for 20.00%, 17.00%, 23.00%,
15.00%, 25.00%, 10.00% or 30.00%.The mass fraction of the alcohol ethers organic solvent can for 56.80%,
33.90%, 51.70%, 37.00%, 39.50%, 64.00%, 16.00%, 54.80%, 59.90%, 41.70%,
60.00%, 28.50%, 56.00% or 21.00%.The mass fraction of the alkane organic solvent of ketone can for 11.00%,
10.00%, 12.00%, 8.00%, 15.00%, 5.00% or 20.00%.The tetrasiloxane Shuangzi containing sugared amide groups
The mass fraction of surfactant can be 1.20%, 0.10%, 1.30%, 5.00%, 1.50%, 1.00% or 2.00%.
Wherein, the water can be the conventional water of this field, preferably in deionized water, distilled water, pure water and ultrapure water
One or more, such as deionized water.
The linear class organic solvent can be the conventional linear amide-type organic solvent of this field, preferably N- first
Base formamide, N- ethyl-formamide, N,N-dimethylformamide, N, N- diethylformamide, acetamide, N- methylacetamide,
DMAC N,N' dimethyl acetamide, N- (2- hydroxyethyl) acetamide, N, N- dimethylpropionamide, 3- methoxyl group-N, N- dimethyl propylene
Amide, 3- (2- ethylhexyl oxygroup)-N, one of N- dimethylpropionamide and 3- butoxy-N, N- dimethylpropionamide or
It is a variety of, for example, N-METHYLFORMAMIDE, N- ethyl-formamide, n,N-Dimethylformamide, N, N- diethylformamide, N, N- bis-
Methyl propanamide, 3- (2- ethylhexyl oxygroup)-N, N- dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide, N- first
Yl acetamide, or, N-METHYLFORMAMIDE and N- methylacetamide, more preferable N-METHYLFORMAMIDE.
When the linear class organic solvent is a variety of, described a variety of preferably two kinds, such as N- methyl formyl
The mixed solvent of amine and N- methylacetamide.When the linear class organic solvent is two kinds, the mass values of the two
It can be 0.5-2.0, for example, 1.0.For example, the mass values of N-METHYLFORMAMIDE and N- methylacetamide can be 0.5-2.0, example
Such as, 1.0.
The sulfone class organic solvent can be this field conventional sulfone class organic solvent, preferably methyl sulfone, sulfolane and
One of dipropyl sulfone is a variety of, more preferably sulfolane.The sulfoxide type organic solvent can be the conventional sulfoxide of this field
Class organic solvent, preferably dimethyl sulfoxide and first ethyl-sulfoxide, diphenyl sulfoxide, thionyl chloride, dipropyl sulfone and benzyl benzene sulfoxide
One of or it is a variety of.
When the sulfone class organic solvent is mixed with the sulfoxide type organic solvent, the sulfone class organic solvent with
The mass values of the sulfoxide type organic solvent can be 0.5-2.0, for example, 1.0.
The alcohol ethers organic solvent can be the conventional alcohol ethers organic solvent of this field, preferably ethylene glycol monomethyl
Ether, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol list
Ethylether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether,
Triethylene glycol monoisopropyl ether, triethylene glycol monobutyl base ether, polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, poly- second two
Alcohol single-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether,
One of dihydroxypropane single-ethyl ether, dipropylene glycol list propyl ether and dipropylene glycol mono butyl base ether are a variety of, such as ethylene glycol
Monomethyl ether and dipropylene glycol mono butyl base ether, more preferably ethylene glycol single methyl ether.
When the alcohol ethers organic solvent is a variety of, described a variety of preferably two kinds, such as ethylene glycol single methyl ether
With the mixed solvent of dipropylene glycol mono butyl base ether.When the alcohol ethers organic solvent is two kinds, the mass ratio of the two can be
0.5-2.0, for example, 1.0.For example, ethylene glycol single methyl ether and dipropylene glycol mono butyl base ether mass values can be 0.5-2.0, example
Such as, 1.0.
The alkane organic solvent of ketone can be the conventional alkane organic solvent of ketone of this field, preferably imidazolidine ketone
And/or pyrrolidinone compounds organic solvent, more preferably imidazolidine organic solvent of ketone.The imidazolidine organic solvent of ketone is excellent
It is selected as 2- imidazolidinone and/or 1,3- dimethyl -2- imidazolidinone, more preferably 2- imidazolidinone.The pyrrolidinone compounds
Organic solvent is preferably one of N- ethyl pyrrolidone, N-Methyl pyrrolidone and N- cyclohexyl pyrrolidone or a variety of.
When the alkane organic solvent of ketone is imidazolidine ketone and pyrrolidinone compounds organic solvent, the imidazolidine
Organic solvent of ketone is preferably 2- imidazolidinone, and the pyrrolidinone compounds organic solvent is preferably N- ethyl pyrrolidone.When
When the alkane organic solvent of ketone is imidazolidine ketone and pyrrolidinone compounds organic solvent, the mass ratio of the two can be 0.5-
2.0, for example, 1.0.For example, the mass values of the 2- imidazolidinone and the N- ethyl pyrrolidone can be 0.5-
2.0, for example, 1.0.
The tetrasiloxane Gemini surface active agent containing sugared amide groups be preferably as follows containing sugared amide groups
One of tetrasiloxane Gemini surface active agent is a variety of.When the tetrasiloxane Gemini surface active containing sugared amide groups
When agent is a variety of described tetrasiloxane Gemini surface active agents containing sugared amide groups, described a variety of preferably two kinds containing sugared amides
The mixed surfactant of the tetrasiloxane Gemini surface active agent of base.When the tetrasiloxane Shuangzi table containing sugared amide groups
When face activating agent is two kinds, the mass values of the two can be 0.5-2.0, for example, 1.0；
Wherein, R1For
N is the integer of 1-6, and s is the integer of 3-8；
R2For
R3ForX is the integer of 3-6；
R4For H or
The R1In, preferably n is 1, s 3；The R3In, preferably x is 3, the R4Preferably H.
The preparation method of the tetrasiloxane Gemini surface active agent containing sugared amide groups preferably includes following steps:
1. being 40-100 DEG C in reaction temperature, preferably by hexamethyldisiloxane, chloropropyl silane and acidic catalyst
It is reacted in the case where 50-80 DEG C；Wherein hexamethyldisiloxane and the mol ratio of chloropropyl silane are (1-20): 1, preferably
(2-10): 1, the mole dosage of acidic catalyst is the 0.30%- of the sum of hexamethyldisiloxane and chloropropyl silane mole
25.00%；After the reaction was completed, acidic catalyst is inactivated, filters off solid, vacuum distillation obtains chloropropyl tetrasiloxane；
2. alkyl diamine and chloropropyl tetrasiloxane, in the case where reaction temperature is 60-150 DEG C preferably 80-120 DEG C
Reaction；Wherein the mol ratio of alkyl diamine and chloropropyl tetrasiloxane is (1-20): 1, preferably (6-15): 1；Reaction is completed
Afterwards, mixture stratification, upper layer vacuum distillation, obtains N- β-aminoalkyl-γ-aminopropyl tetrasiloxane；
3.N- β-aminoalkyl-γ-aminopropyl tetrasiloxane and saccharic acid or saccharic acid lactone make solvent, reaction temperature in low-carbon alcohols
Degree is 60-150 DEG C, preferably 60-100 DEG C reaction；Wherein the mol ratio of alkyl diamine and saccharic acid or saccharic acid lactone is 1-2:1,
It is preferred that 1:1；After the reaction was completed, solvent is evaporated off, obtains the tetrasiloxane containing sugared amide groups；
4. tetrasiloxane and diglycidyl ether containing sugared amide groups make solvent, reaction temperature 60-150 in low-carbon alcohols
DEG C, preferably 60-100 DEG C reaction；The mol ratio of tetrasiloxane and diglycidyl ether wherein containing sugared amide groups is 2-3:1,
It is preferred that 2:1；After the reaction was completed, solvent is evaporated off, obtains the tetrasiloxane Gemini surface active agent containing sugared amide groups；
The chloropropyl silane may include: r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane etc..
The acidic catalyst may include: the concentrated sulfuric acid, Emathlite etc..
Described makes acidic catalyst inactivation be that alkali neutralization catalyst is added, is allowed to when the acidic catalyst concentrated sulfuric acid
Inactivation；When acidic catalyst is Emathlite, filtering is allowed to remove.
The alkyl diamine may include: 1,3- propane diamine, 1,4- butanediamine, 1,5- pentanediamine, 1,6- hexamethylene diamine etc..
The saccharic acid or saccharic acid lactone may include: in gluconic acid or glucolactone, lactobionic acid or lactobionic acid
Ester, mannonic acid or mannonic acid lactone etc..
The low-carbon alcohols may include: methanol, ethyl alcohol, normal propyl alcohol, isopropanol etc..
The diglycidyl ether may include: flexible hydrophilic compounds such as ethylene glycol diglycidylether, diethyl two
Alcohol diglycidyl ether, Triethylene Glycol Diglycidyl Ether, tetraethylene glycol diglycidyl ether, five Hexanediol diglycidyl ethers,
Six ethylene glycol diglycidylethers etc., flexible hydrophobic compound for example propylene glycol diglycidylether, butanediol diglycidyl ether,
Neopentyl glycol diglycidyl glycerin ether, hexanediol diglycidyl ether, heptandiol diglycidyl ether, ethohexadiol diglycidyl ether
Deng rigid compound such as resorcinol diglycidyl ether, benzene dimethanol diglycidyl ether etc..
The preparation method of the tetrasiloxane Gemini surface active agent containing sugared amide groups can refer to CN104069772B,
Specifically, it can refer to the embodiment 1- embodiment 8 of CN 104069772B specific embodiment part.
In a preferred embodiment of the invention, the raw material components of the stripper are by the water, the straight chain
Amide-type organic solvent, the sulfone class and/or sulfoxide type organic solvent, the alcohol ethers organic solvent, the imidazoles
Alkanone class and/or pyrrolidinone compounds organic solvent and surfactant composition, the sum of each component mass fraction are 100%.
The present invention also provides the preparation methods of the stripper described in one kind comprising the following steps: by the raw material
Mixing.Solid component in the raw material components is preferably added in liquid component by the mixing, and stirring is equal
It is even.The mixed temperature is room temperature.After the mixing, oscillation, the behaviour of filtering are preferably further comprised
Make.The purpose of oscillation is to be sufficiently mixed each raw material component, and hunting speed and time are unlimited.Filtering is insoluble in order to remove
Object.
The present invention also provides the removings of the photoresist and its residue of the stripper described in one kind in the semiconductor device
With the application in cleaning.Wherein the semiconductor devices is preferably logic chip, storage chip, mems chip (i.e. MEMS
Chip), one of photoelectric chip and power chip (such as IGBT) or a variety of.The application preferably includes the following steps:
It will be contacted with the remaining semiconductor devices of photoresist with stripper.The contact can be to pass through infusion process, spray
Method.
Preferred 55-85 DEG C of the temperature of the contact, more preferable 60-75 DEG C.
The time of the contact preferred 10-65min, more preferable 30-60min.
Room temperature refers to 10-30 DEG C in the present invention.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: stripper of the invention is right in the case where the stripping performance having had
Other multiple materials do not constitute destruction corrosion, have high application value.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiment and comparative examples, the preparation method of stripper includes the following steps: to mix corresponding raw material, i.e.,
It can.
In following embodiments, concrete operations temperature is not limited, is each meant and is carried out at room temperature.
I, the preparation method embodiment of stripper
One, the preparation of surfactant
The preparation embodiment of surfactant A 1-A6 is as follows, specifically refers to CN 104069772B, more specifically, A1
Preparation can refer to embodiment 1；The preparation of A2 can refer to embodiment 2；The preparation of A3 can refer to embodiment 3；The preparation of A4 can refer to
Embodiment 4；The preparation of A5 can refer to embodiment 5；The preparation of A6 can refer to embodiment 6.
The preparation of A1: hexamethyldisiloxane 1.62kg, r-chloropropyl trimethoxyl silane are added in reaction kettle 1
1.99kg, concentrated sulfuric acid 0.006kg react 4 hours at 40 DEG C of temperature, and adding sodium hydroxide makes catalyst inactivation, are filtered to remove solid
Body, vacuum distillation obtain chloropropyl tetrasiloxane.Chloropropyl tetrasiloxane 3.73kg, 1,3- propane diamine are added in reaction kettle 2
0.74kg is heated to 60 DEG C, reacts 4 hours, mixture stratification, and upper layer vacuum distillation obtains N- β-aminopropyl-γ-ammonia
Propyl tetrasiloxane.N- β-aminopropyl-γ-aminopropyl tetrasiloxane 4.10kg, glucolactone are added in reaction kettle 3
1.78kg is heated to 60 DEG C with methanol as solvent, reacts 8 hours.Ethylene glycol diglycidylether 0.87kg is added, is continued
Reaction 12 hours.Solvent methanol is evaporated off, obtains the tetrasiloxane Gemini surface active agent containing sugared amide groups.
The preparation of A2: hexamethyldisiloxane 8.12kg, r-chloropropyl trimethoxyl silane are added in reaction kettle 1
1.99kg, Emathlite 0.10kg react 4 hours, Filtration of catalyst under temperature 50 C, and vacuum distillation obtains chloropropyl
Tetrasiloxane.Chloropropyl tetrasiloxane 3.73kg, Putriscine 2.64kg are added in reaction kettle 2, is heated to 80 DEG C, reaction
3 hours, mixture stratification, upper layer vacuum distillation obtained N- β-ammonia butyl-γ-aminopropyl tetrasiloxane.In reaction kettle 3
Middle addition N- β-ammonia butyl-γ-aminopropyl tetrasiloxane 4.24kg, gluconic acid 1.96kg is heated to 70 with ethanol as solvent
DEG C, it reacts 8 hours.Propylene glycol diglycidylether 0.94kg is added, the reaction was continued 12 hours.Etoh solvent is evaporated off, obtains
Tetrasiloxane Gemini surface active agent containing sugared amide groups.
The preparation of A3: hexamethyldisiloxane 16.24kg, r-chloropropyl trimethoxyl silane are added in reaction kettle 1
1.99kg, concentrated sulfuric acid 0.54kg react 4 hours under temperature 60 C, and adding sodium hydroxide makes catalyst inactivation, are filtered to remove solid
Body, vacuum distillation obtain chloropropyl tetrasiloxane.Chloropropyl tetrasiloxane 3.73kg, 1,5- pentanediamine are added in reaction kettle 2
6.12kg is heated to 90 DEG C, reacts 2 hours, mixture stratification, and upper layer vacuum distillation obtains N- β-ammonia amyl-γ-ammonia
Propyl tetrasiloxane.N- β-ammonia amyl-γ-aminopropyl tetrasiloxane 4.38kg, mannonic acid lactone are added in reaction kettle 3
1.78kg is heated to 80 DEG C with methanol as solvent, reacts 10 hours.Butanediol diglycidyl ether 1.01kg is added, is continued
Reaction 12 hours.Solvent methanol is evaporated off, obtains the tetrasiloxane Gemini surface active agent containing sugared amide groups.
The preparation of A4: hexamethyldisiloxane 32.48kg, r-chloropropyl trimethoxyl silane are added in reaction kettle 1
1.99kg, Emathlite 5.59kg react 4 hours, Filtration of catalyst under temperature 70 C, and vacuum distillation obtains chloropropyl
Tetrasiloxane.Chloropropyl tetrasiloxane 3.73kg is added in reaction kettle 2,1,6- hexamethylene diamine 11.6kg is heated to 100 DEG C, instead
It answers 1 hour, mixture stratification, upper layer vacuum distillation obtains N- β-ammonia hexyl-γ-aminopropyl tetrasiloxane.In reaction kettle
N- β-ammonia hexyl-γ-aminopropyl tetrasiloxane 4.52kg is added in 3, mannonic acid 1.96kg is heated to ethanol as solvent
It 90 DEG C, reacts 10 hours.Neopentyl glycol diglycidyl glycerin ether 1.08kg is added, the reaction was continued 12 hours.Etoh solvent is evaporated off, obtains
To the tetrasiloxane Gemini surface active agent containing sugared amide groups.
The preparation of A5: hexamethyldisiloxane 1.62kg, chloropropyl triethoxysilane are added in reaction kettle 1
2.41kg, concentrated sulfuric acid 0.20kg react 3 hours at 80 DEG C of temperature, and adding sodium hydroxide makes catalyst inactivation, are filtered to remove solid
Body, vacuum distillation obtain chloropropyl tetrasiloxane.Chloropropyl tetrasiloxane 3.73kg, 1,3- propane diamine are added in reaction kettle 2
8.88kg is heated to 110 DEG C, reacts 4 hours, mixture stratification, and upper layer vacuum distillation obtains N- β-aminopropyl-γ-ammonia
Propyl tetrasiloxane.N- β-aminopropyl-γ-aminopropyl tetrasiloxane 4.10kg, lactobionolactone are added in reaction kettle 3
3.40kg is heated to 100 DEG C with methanol as solvent, reacts 8 hours.Diethylene glycol diglycidyl glycerin ether 1.09kg is added, after
Continuous reaction 12 hours.Solvent methanol is evaporated off, obtains the tetrasiloxane Gemini surface active agent containing sugared amide groups.
The preparation of A6: hexamethyldisiloxane 8.12kg, chloropropyl triethoxysilane are added in reaction kettle 1
2.41kg, Emathlite 3.19kg react 3 hours, Filtration of catalyst at 80 DEG C of temperature, and vacuum distillation obtains chloropropyl
Tetrasiloxane.Chloropropyl tetrasiloxane 3.73kg is added in reaction kettle 2, Putriscine 13.2kg is heated to 120 DEG C, instead
It answers 3 hours, mixture stratification, upper layer vacuum distillation obtains N- β-ammonia butyl-γ-aminopropyl tetrasiloxane.In reaction kettle
N- β-ammonia butyl-γ-aminopropyl tetrasiloxane 4.24kg, lactobionic acid 3.58kg is added in 3 and is heated to 120 with ethanol as solvent
DEG C, it reacts 8 hours.Triethylene Glycol Diglycidyl Ether 1.31kg is added, the reaction was continued 12 hours.Etoh solvent is evaporated off, obtains
To the tetrasiloxane Gemini surface active agent containing sugared amide groups.
The preparation embodiment and structural formula of surfactant B are as follows, and preparation embodiment specifically refers to CN102020672B
Embodiment 4.
Under nitrogen protection, by 212.5 grams (1.0mol) of chloromethyl triethoxysilane and 121.2 grams of (1.2mol) three
Ethamine, 136.2 grams of (1.0mol) N, N- dimethyl-p-phenylenediamines are placed on four mouthfuls with reflux unit and thermometer, dropping funel
In flask, strong mixer is started, revolving speed is 150 revs/min, is warming up to 120 DEG C, back flow reaction 6 hours；Reaction system is dropped
To room temperature, product is filtered removal amine salt and is precipitated, and filtrate purifies through vacuum distillation, obtains corresponding intermediate N, N- dimethyl pair
Phenylenediamine methyltriethoxysilane.
By intermediate N, N- dimethyl-p-phenylenediamine's methyltriethoxysilane 1.0mol is dissolved in 100 grams of toluene, in room
Temperature is lower to be added dropwise 1,3-propane sultone, and total dripping quantity is 1.0mol, and time for adding is 30 minutes；After being added dropwise, back flow reaction 4
Hour；After reaction, purification obtains surfactant B.Through nuclear-magnetism, infrared and mass spectral analysis, the structure of surfactant B is such as
Shown in lower:
Two, the preparation method embodiment of stripper
The raw material components of table 1 are uniformly mixed by the mass fraction in table 2.Wherein, the mixing generally will be described
Raw material components in solid component be added in liquid component, stir evenly.The mixing generally will be described
Solid component in raw material components is added in liquid component, is stirred evenly.The mixed temperature is room temperature.Institute
After the mixing stated, oscillation, the operation of filtering are generally further comprised.The purpose of oscillation is to keep each raw material component sufficiently mixed
It closes, hunting speed and time are unlimited.Filtering is to remove insoluble matter.
Constituent species in each embodiment of table 1
II, effect example
One, the remaining effect of photoresist after the ashing of removal dry etching
(1), the remaining effect of negative photoresist after the ashing of removal dry etching
1, silicon wafer rotary coating negative photoresist PMER N-HC600 (answering chemical industry (strain) to make in Tokyo), at 80 DEG C
It carries out 90 seconds pre- and bakes processing, the photoresist layer of 20 μm of film thickness of formation.
2, using FPA3000EX3 (Canon's (strain) system), after exposing the photoresist layer by mask pattern, at 110 DEG C
Processing is baked after carrying out 90 seconds, is developed with tetramethyl ammonium hydroxide (TMAH) aqueous solution of 2.38wt%, diameter is formed
The sectional hole patterns of 200nm.Then, dry etch process is carried out, then carries out plasma ashing processing.
3, the substrate Jing Guo above-mentioned processing is impregnated into the photoresist stripper of embodiment 1-15 and comparative example 1-12
(75 DEG C, 60 minutes) after carrying out lift-off processing, are handled with isopropyl alcohol, then with pure water rinsing.
4, it is observed with SEM (scanning electron microscope), evaluates the fissility of ashing treated residue at this time.
(2), the remaining effect of positive photoresist after the ashing of removal dry etching
1, silicon wafer rotary coating positive photoresist TDUR-P015PM (answering chemical industry (strain) to make in Tokyo), at 80 DEG C
It carries out 90 seconds pre- and bakes processing, the photoresist layer of 20 μm of film thickness of formation.
2, using FPA3000EX3 (Canon's (strain) system), after exposing the photoresist layer by mask pattern, at 110 DEG C
Processing is baked after carrying out 90 seconds, is developed with tetramethyl ammonium hydroxide (TMAH) aqueous solution of 2.38wt%, diameter is formed
The sectional hole patterns of 200nm.Then, dry etch process is carried out, then carries out plasma ashing processing.
3, the substrate Jing Guo above-mentioned processing is impregnated into the photoresist stripper of embodiment 1-15 and comparative example 1-12
(75 DEG C, 60 minutes) after carrying out lift-off processing, are handled with isopropyl alcohol, then with pure water rinsing.
4, it is observed with SEM (scanning electron microscope), evaluates the fissility of ashing treated residue at this time.
Fissility evaluation
A: residue is fully exfoliated, and can't see residue in liquid bath
B: residue is fully exfoliated, and residue can be seen in liquid bath
C: the removing of residue is incomplete, and can't see residue in liquid bath
D: the removing of residue is incomplete, and residue can be seen in liquid bath
Two, wet process is removed photoresist effect
(1), wet process goes negative photoresist effect
1, silicon wafer rotary coating negative photoresist PMER N-HC600 (answering chemical industry (strain) to make in Tokyo), at 80 DEG C
It carries out 90 seconds pre- and bakes processing, the photoresist layer of 20 μm of film thickness of formation.
2, using FPA3000EX3 (Canon's (strain) system), after exposing the photoresist layer by mask pattern, at 110 DEG C
Processing is baked after carrying out 90 seconds, is developed with tetramethyl ammonium hydroxide (TMAH) aqueous solution of 2.38wt%, diameter is formed
The sectional hole patterns of 200nm.
3, the substrate Jing Guo above-mentioned processing is impregnated into the photoresist stripper of embodiment 1-15 and comparative example 1-12
(75 DEG C, 30 minutes) carry out rinsing processing with pure water after carrying out lift-off processing.
4, it is observed with SEM (scanning electron microscope), evaluates the fissility of negative photoresist at this time.
(2), wet process goes positive photoresist effect
1, silicon wafer rotary coating positive photoresist TDUR-P015PM (answering chemical industry (strain) to make in Tokyo), at 80 DEG C
It carries out 90 seconds pre- and bakes processing, the photoresist layer of 20 μm of film thickness of formation.
2, using FPA3000EX3 (Canon's (strain) system), after exposing the photoresist layer by mask pattern, at 110 DEG C
Processing is baked after carrying out 90 seconds, is developed with tetramethyl ammonium hydroxide (TMAH) aqueous solution of 2.38wt%, diameter is formed
The sectional hole patterns of 200nm.
3, the substrate Jing Guo above-mentioned processing is impregnated into the photoresist stripper of embodiment 1-15 and comparative example 1-12
(75 DEG C, 30 minutes) carry out rinsing processing with pure water after carrying out lift-off processing.
4, it is observed with SEM (scanning electron microscope), evaluates the fissility of positive photoresist at this time.
Fissility evaluation
A: residue is fully exfoliated, and can't see residue in liquid bath
B: residue is fully exfoliated, and residue can be seen in liquid bath
C: the removing of residue is incomplete, and can't see residue in liquid bath
D: the removing of residue is incomplete, and residue can be seen in liquid bath
Three, sheet metal corrosion test
1, by the certain thickness Al-Cu piece that is deposited with of 6 cun of disk sizes, (thicknesses of layers 4700A, wherein Cu is adulterated
0.5wt% or less), Al-Si piece (thicknesses of layers 3800A, wherein Si adulterate 1.0wt% or less), Al piece (thicknesses of layers
3800A), copper sheet (thicknesses of layers 3800A), titanium sheet (thicknesses of layers 210A) are immersed in embodiment 1-15's and comparative example 1-12
In photoresist stripper (40L, 75 DEG C, 30 minutes), corrosion treatment is carried out, then first with after isopropyl alcohol, then uses pure water
Carry out rinsing processing.
2, the variation of the resistivity of corrosion front and back is surveyed with four-point probe instrument.
Four, dielectric layer corrosion test
1, certain thickness oxidized silicon chip (TEOS piece, thicknesses of layers 3800A), (the p-type nitridation of nitridation silicon wafer will be deposited with
Silicon, thicknesses of layers 1500A), nitridation titanium sheet (thicknesses of layers 1400A), vanadium oxide piece (thicknesses of layers 750A), polyimide piece
(thicknesses of layers 12000A), be immersed in the photoresist stripper of table 1 illustrated embodiment 1-15 and comparative example 1-12 (40L, 75
DEG C, 30 minutes), (flash speed: 20L/min) carries out corrosion treatment under overflow condition, then first with after isopropyl alcohol, then uses
Pure water carries out rinsing processing.
2, the variation of the thickness of dielectric layers of corrosion front and back is surveyed with film thickness gauge.
3 effect example of table
In table, I is the remaining effect of negative photoresist removed after dry etching ashing；II is that wet process removes negative photoresist
Residual effect；III is the remaining effect of positive photoresist removed after dry etching ashing；IV is that wet process goes positive photoresist residual
Stay effect.
From table 3 it can be seen that stripper of the invention, which passes through, adds specific surfactant, to photoresist and its residual
Object has stronger removal effect, and removing and cleaning performance are excellent while low to the corrosivity of multiple material, has high selection
Property.From embodiment 1-15 and comparative example 1-12 relatively from the point of view of, the tetrasiloxane Gemini surface active agent containing sugared amide groups is to negativity
Or the inhibition of removing, the corrosion of multiple material of positive photoresist and its residue plays certain effect, improves removing
Stripper removing and corrosion mitigating effect in the removing of liquid and corrosion resistance, especially embodiment 1 is best.
Claims (10)
1. a kind of stripper, which is characterized in that its raw material includes the component of following mass fraction: water, the 5.00- of 0-30.00%
The sulfone class and/or sulfoxide type organic solvent, 21.00- of 20.00% linear class organic solvent, 10.00-30.00%
79.00% alcohol ethers organic solvent, the alkane organic solvent of ketone of 5.00-20.00% and the surface-active of 0.01-5.00%
Agent, the sum of each component mass fraction are 100%, and the surfactant is that the tetrasiloxane Shuangzi surface containing sugared amide groups is living
Property agent.
2. stripper as described in claim 1, which is characterized in that its raw material components is free of quaternary ammonium compounds.
3. stripper as described in claim 1, which is characterized in that
The mass fraction of the water is 3.00-23.00%；
And/or the mass fraction of the linear class organic solvent is 8.00-15.00%；
And/or the mass fraction of the sulfone class and/or sulfoxide type organic solvent is 15.00-25.00%；
And/or the mass fraction of the alcohol ethers organic solvent is 28.00-64.00%；
And/or the mass fraction of the alkane organic solvent of ketone is 8.00-15.00%；
And/or the mass fraction of the surfactant is 0.05-1.50%.
4. stripper as claimed in claim 3, which is characterized in that
The mass fraction of the water is 7.00-15.00%；
And/or the mass fraction of the linear class organic solvent is 10.00-12.00%；
And/or the mass fraction of the sulfone class and/or sulfoxide type organic solvent is 17.00-23.00%；
And/or the mass fraction of the alcohol ethers organic solvent is 51.00-60.00%；
And/or the mass fraction of the alkane organic solvent of ketone is 10.00-12.00%；
And/or the mass fraction of the surfactant is 0.10-1.30.00%.
5. stripper as described in claim 1, which is characterized in that
The water is one of deionized water, distilled water, pure water and ultrapure water or a variety of；
And/or the linear class organic solvent is N-METHYLFORMAMIDE, N- ethyl-formamide, N, N- dimethyl formyl
Amine, N, N- diethylformamide, acetamide, N- methylacetamide, DMAC N,N' dimethyl acetamide, N- (2- hydroxyethyl) acetyl
Amine, N, N- dimethylpropionamide, 3- methoxyl group-N, N- dimethylpropionamide, 3- (2- ethylhexyl oxygroup)-N, N- dimethyl propylene
One of amide and 3- butoxy-N, N- dimethylpropionamide are a variety of；
And/or the sulfone class organic solvent is one of methyl sulfone, sulfolane and dipropyl sulfone or a variety of；
And/or the sulfoxide type organic solvent is dimethyl sulfoxide and first ethyl-sulfoxide, diphenyl sulfoxide, thionyl chloride, two
One of third sulfone and benzyl benzene sulfoxide are a variety of；
And/or the alcohol ethers organic solvent is ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list isopropyl
Ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethyl two
Alcohol single-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl
Base ether, polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol single-butyl ether, propylene glycol monomethyl ether, dipropyl
Glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dihydroxypropane single-ethyl ether, dipropylene glycol list third
One of base ether and dipropylene glycol mono butyl base ether are a variety of；
And/or the alkane organic solvent of ketone is imidazolidine ketone and/or pyrrolidinone compounds organic solvent；
And/or four containing sugared amide groups that the tetrasiloxane Gemini surface active agent containing sugared amide groups is as follows
One of siloxanes Gemini surface active agent is a variety of；
Wherein, R1ForN is
The integer of 1-6, s are the integer of 3-8；
R2For
R3ForX is the integer of 3-6；
R4For H or
6. stripper as claimed in claim 5, which is characterized in that
The water is deionized water；
And/or the linear class organic solvent is N-METHYLFORMAMIDE；
And/or the sulfone class organic solvent is sulfolane；
And/or the alcohol ethers organic solvent is ethylene glycol single methyl ether；
And/or the alkane organic solvent of ketone is imidazolidine organic solvent of ketone；
And/or the imidazolidine organic solvent of ketone is 2- imidazolidinone and/or 1,3- dimethyl -2- imidazolidinone；
And/or the pyrrolidinone compounds organic solvent is N- ethyl pyrrolidone, N-Methyl pyrrolidone and N- cyclohexyl pyrrole
One of pyrrolidone is a variety of；
And/or when the alkane organic solvent of ketone is imidazolidine ketone and pyrrolidinone compounds organic solvent, the alkanone
Class organic solvent is 2- imidazolidinone and N- ethyl pyrrolidone；
And/or in the surfactant, the R1In, n 1, s 3；The R3In, x 3, the R4For H.
7. stripper as claimed in any one of claims 1 to 6, which is characterized in that the raw material components of the stripper are by described
Water, the linear class organic solvent, the sulfone class and/or sulfoxide organic solvent, the alcohol ethers it is organic molten
Agent, the imidazolidine ketone and/or pyrrolidinone compounds organic solvent and surfactant composition, the sum of each component mass fraction
It is 100%.
8. a kind of preparation method of such as described in any item strippers of claim 1-7, which is characterized in that it includes following step
It is rapid: the raw material is mixed.
9. the preparation method of stripper as claimed in claim 8, which is characterized in that
Solid component in the raw material components is added in liquid component by described being mixed into, and is stirred evenly；
And/or the mixed temperature is room temperature；
And/or after the mixing, oscillation, the operation of filtering are further comprised.
10. a kind of photoresist and its residue in the semiconductor device of such as described in any item strippers of claim 1-7
Removing and cleaning in application；Wherein the semiconductor devices be preferably logic chip, storage chip, mems chip,
One of photoelectric chip and power chip are a variety of；The application preferably includes the following steps: will have photoetching glue residua
Semiconductor devices contacted with stripper；Preferred 55-85 DEG C of the temperature of the contact, more preferable 60-75 DEG C；It is described to connect
The time of touching preferred 10-65min, more preferable 30-60min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100330017A1 (en) * | 2009-06-29 | 2010-12-30 | L'oreal S.A. | Enhanced shine and moisture lip composition |
| CN102343235A (en) * | 2011-04-25 | 2012-02-08 | 烟台大学 | Dimeric organosilicon surfactant, preparation method thereof and purpose thereof |
| CN104069772A (en) * | 2014-07-15 | 2014-10-01 | 北京工商大学 | Tetrasiloxane dimeric surfactant containing sugar acylamino and preparation method |
| CN108211987A (en) * | 2017-12-25 | 2018-06-29 | 江南大学 | A kind of glucosyl group Gemini surface active agent coupled by oxalyl amine groups and preparation method thereof |
| CN109634071A (en) * | 2019-01-23 | 2019-04-16 | 福建省佑达环保材料有限公司 | A kind of aqua type photoresist lift off liquid for display panel and semiconductor field |
-
2019
- 2019-07-05 CN CN201910603572.1A patent/CN110412838B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100330017A1 (en) * | 2009-06-29 | 2010-12-30 | L'oreal S.A. | Enhanced shine and moisture lip composition |
| CN102343235A (en) * | 2011-04-25 | 2012-02-08 | 烟台大学 | Dimeric organosilicon surfactant, preparation method thereof and purpose thereof |
| CN104069772A (en) * | 2014-07-15 | 2014-10-01 | 北京工商大学 | Tetrasiloxane dimeric surfactant containing sugar acylamino and preparation method |
| CN108211987A (en) * | 2017-12-25 | 2018-06-29 | 江南大学 | A kind of glucosyl group Gemini surface active agent coupled by oxalyl amine groups and preparation method thereof |
| CN109634071A (en) * | 2019-01-23 | 2019-04-16 | 福建省佑达环保材料有限公司 | A kind of aqua type photoresist lift off liquid for display panel and semiconductor field |
Non-Patent Citations (2)
| Title |
|---|
| 王淑军: "含葡糖酰胺基四硅氧烷表面活性剂的合成与性能", 《硕士学位论文》 * |
| 王淑军等: "葡糖酰胺基四硅氧烷表面活性剂的合成及其表面活性", 《日用化学工业》 * |
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