CN109991811A - A kind of acid dispersion inhibitor and preparation method thereof and photoetching compositions - Google Patents
A kind of acid dispersion inhibitor and preparation method thereof and photoetching compositions Download PDFInfo
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- CN109991811A CN109991811A CN201910145917.3A CN201910145917A CN109991811A CN 109991811 A CN109991811 A CN 109991811A CN 201910145917 A CN201910145917 A CN 201910145917A CN 109991811 A CN109991811 A CN 109991811A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
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Abstract
The invention discloses a kind of sour dispersion inhibitor and preparation method thereof and photoetching compositions, sour dispersion inhibitor is using (methyl) acrylate as structural unit, in the fluoropolymer resin for wherein introducing basic group formation.By (methyl) acrylate monomer with basic group, under the conditions of existing for the radical initiator, copolyreaction is carried out by heating and is prepared, can be used for preparing photoetching compositions.The present invention provides one kind with acid dispersion inhibitor existing for polymer form, it can control the light acid diffusion of non-exposed area；Distribution in photoresist itself can more effectively be improved simultaneously, photoresist resolution ratio and line width roughness is improved, improve the film forming ability of photoresist.
Description
Technical field
The present invention relates to a kind of high molecular polymers and preparation method thereof, and in particular to it is a kind of acid dispersion inhibitor resin and
Preparation method, and the purposes of sour dispersion inhibitor resin.
Background technique
Three important parameters of photoresist include resolution ratio, sensitivity, line width roughness, they determine photoresist in core
Process window when piece manufactures.As semiconductor core piece performance is constantly promoted, exponentially type increases the integrated level of integrated circuit, collection
It is constantly reduced at the figure in circuit.In order to make smaller size of figure, it is necessary to which the above three performance for improving photoresist refers to
Mark.According to Rayleigh equation formula, the resolution ratio of photoresist can be improved using the light source of short wavelength in a lithographic process.Photoetching process
Optical source wavelength from 365nm(I- line) develop to 248nm(KrF), 193nm(ArF), 13nm(EUV).For the spirit for improving photoresist
Sensitivity, KrF, ArF of mainstream, EUV lithography glue use chemical amplification type photosensitive resin at present.
Studies have shown that control light acid diffusion is to improve resolution ratio and reduce line after chemical amplification photo etching glue exposure
The important means of broad and rough rugosity.Improve control light acid diffusivity approach first is that using acid-base neutralization principle, use alkali
Property compound lower light acid range of scatter, this kind of alkali compounds is referred to as sour dispersion inhibitor.
Acid activity resin, photosensitizer, sour dispersion inhibitor are the main components in photoetching glue formula.In the prior art, amine
Class molecule is one of the key component of control acid diffusion.However amine molecule and photoetching gum resin have biggish difference in structure
It is different, cause amine molecule that cannot be distributed evenly in photoresist film very much, reduces the resolution ratio and line width roughness of photoresist.
On the other hand, in order to reach preferable etch resistance energy, it will use the non-aromatic of a large amount of phenyl ring or large volume in photoetching gum resin
Caged scaffold.These structures are easy to cause the intersolubility between high-molecular compound to mismatch, and film forming ability is poor, photoresist occur
The problems such as film embrittlement, peeling.Simultaneously there is pollution photoetching when being applied to immersion lithography process with filtered air in the alkali compounds of small molecule
The possibility of glue camera lens causes serious consequence.
Therefore, develop that a kind of sour dispersion inhibitor distribution is fixed, acid diffusion rejection ability is high and with acid activity resinousness
The good sour dispersion inhibitor of matter matching, film forming ability is imperative, this will provide necessity for the exploitation of subsequent liquid immersion lithography glue
Basis.
Summary of the invention
Goal of the invention of the invention is to provide a kind of sour dispersion inhibitor, has it when being applied to photoetching compositions
Distribution is fixed, acid diffusion rejection ability is high and matches with acid activity resin properties, the feature that film forming ability is good；Of the invention is another
One goal of the invention is to provide the preparation method of this sour dispersion inhibitor；Another goal of the invention of the invention is to provide acid diffusion
The photoetching compositions of inhibitor preparation.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: it is a kind of acid dispersion inhibitor, it is with (first
Base) acrylate be structural unit, wherein introduce basic group formed fluoropolymer resin, general structure be (I) or
(II):
(I),(II)
In formula, the integer that n is 2~30, the selection of n so that weight average molecular weight between 100~30000g/mol；naIt is alkylidene
Carbon atom number, naIt is 1~20；R1、R2It is hydrogen, carbon atom number is that alkyl, aryl or sulfur-bearing, oxygen, azepine between 1~20 are former
One of substituent group of son is a variety of.
In above-mentioned technical proposal, on the basis of (methyl) acrylate, introduces the monomer containing basic group and form sour expansion
Dissipate inhibitor film-forming resin.Since basic group is fixed on high molecular resin structure, and structure and acid activity resin
Structure proximate, this enables acid inhibitor to be evenly distributed in photoresist film.The resinoid shows outstanding light acid diffusion
Rejection ability improves photoresist resolution ratio and line width roughness；The water solubility for reducing photoresist component, improves the film forming of photoresist
Ability avoids photoetching machine lens from staiing.
In above-mentioned technical proposal, R1、R2It is carbon atom number is straight chained alkyl between 1~20, one in naphthenic base or aryl
Kind is a variety of.
Specifically, R1、R2Nitrogen-containing functional group with N atomic building is n-butylamine-based, tert-butylamine base, dimethylamino, diethylamine
Base, diη-propyl, diisopropylamino, di-n-butylamine base, di-iso-butylmanice base, two tert-butylamine bases, cyclopenta amido, cyclo-hexylamine
Base, phenylmethanamine base, phenylethylamine base, phenyl n-propylamine base, phenyl n-butylamine-based, Phenyl-tertiary-butylamine base, diphenyl amido, two
One of (p-methoxyphenyl) amido, two (to tertiary butoxyphenyl) amidos are a variety of.
R1、R2It is as follows with the preferred structure of nitrogen-containing functional group of N atomic building:
、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、。
Another goal of the invention to realize the present invention provides a kind of preparation method of sour dispersion inhibitor, by with alkali
Property group (methyl) acrylate monomer, under the conditions of existing for the radical initiator, pass through heating and carry out copolyreaction system
Standby to form, the general structure of described (methyl) acrylate with basic group is (III) or (IV):
(III) or(IV)
In formula, nbIt is the chain length for the alkyl that carbon atom number is between 1~20.
In above-mentioned technical proposal, R1、R2It is carbon atom number is straight chained alkyl between 1~20, one in naphthenic base or aryl
Kind is a variety of.
Preferably, R1、R2Nitrogen-containing functional group with N atomic building is n-butylamine-based, tert-butylamine base, dimethylamino, diethylamine
Base, diη-propyl, diisopropylamino, di-n-butylamine base, di-iso-butylmanice base, two tert-butylamine bases, cyclopenta amido, cyclo-hexylamine
Base, phenylmethanamine base, phenylethylamine base, phenyl n-propylamine base, phenyl n-butylamine-based, Phenyl-tertiary-butylamine base, diphenyl amido, two
One of (p-methoxyphenyl) amido, two (to tertiary butoxyphenyl) amidos are a variety of.
Preferably, the structure of (methyl) acrylate monomer of basic group may be, but not limited to:
Above-mentioned (methyl) acrylate monomer with basic group the preparation method is as follows: by the long-chain chemical combination containing basic group
Object is under the action of acid binding agent, and the reaction of (methyl) acryloyl chloride is prepared, comprising the following steps:
(1) long-chain compound, acid binding agent and solvent containing basic group are configured to solution, mixed liquor to temperature is controlled -20
~80 DEG C, the molar ratio of long-chain compound, acid binding agent and solvent containing basic group is 1:(1 ~ 1.5): (4 ~ 16)；
(2) at -20~80 DEG C, agitation and dropping (methyl) acryloyl chloride, time for adding is 1 ~ 5h, the long-chain containing basic group
The molar ratio of compound and (methyl) acryloyl chloride is 1:(1 ~ 1.2)
(3) after being added dropwise, continue to react 2 ~ 20h at -20~80 DEG C；
(4) after the reaction was completed to room temperature, reaction solution is washed 2 times with aqueous sodium carbonate, and pure water 2 times, saturated common salt washing
It washs 1 time, anhydrous sodium sulfate is dry, concentration, distills (methyl) acrylate for obtaining and having basic group.
In above-mentioned technical proposal, the solvent is ethyl acetate, butyl acetate, butyl acetate, acetic acid peopentyl ester, lactic acid second
Ester, propylene glycol methyl ether acetate, propylene glycol list Acetic Ester, dihydroxypropane single-ether, propylene glycol methyl ether acetate, tirethylene glycol first
Ether, tirethylene glycol ether, tetrahydrofuran, methyltetrahydrofuran, chloroform, methylene chloride, 1,2- dichloroethanes, just oneself
Alkane, pentane, normal heptane, acetone, cyclohexanone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, paraxylene or connection
One of benzene is a variety of.
Above-mentioned acid dispersion inhibitor film-forming resin the preparation method is as follows: (methyl) acrylate list with basic group
In body dissolution solvent, under the conditions of existing for the initiator, carries out polymerization reaction and is prepared, comprising the following steps:
(1) (methyl) acrylate monomer of basic group is dissolved in solvent, heating mixed liquor to temperature is 40~90
DEG C, the molar ratio of monomer and solvent is 1:(4-16)；
(2) by quality be comonomer quality 0.3%~15% initiator dissolution solvent in, obtain it is prefabricated, initiator with it is molten
The molar ratio of agent is 1:(4-16)
(3) initiator solution that step (2) obtain is added drop-wise to it is preheated containing in the mixed liquor containing monomer in step (1), 40
~90 DEG C constant temperature back flow reaction 2~30 hours；
(4) it is cooled to room temperature after the reaction was completed, with nonpolar solvent precipitated resin, filtering drying obtains sour dispersion inhibitor.
In above-mentioned technical proposal, initiator is the radical initiator of azo initiator, peroxide, and preferred azo draws
Sending out agent is azodiisobutyronitrile or azobisisoheptonitrile, and the radical initiator of preferred peroxide is that tert-butyl hydroperoxide is special
Valerate, tertiary fourth oxygen hydrogen peroxide, benzoic acid hydrogen peroxide or benzoyl peroxide etc.；The initiator amount is comonomer
The 0.3% ~ 15% of gross mass；The adding manner of initiator is that monomer and partial solvent is first added, and is then heated to polymerization temperature, then
Initiator solution is added dropwise.The temperature of polymerization reaction controls between 40 ~ 90 DEG C according to the solvent used and initiator difference, gathers
The time is closed also according to the solvent used and initiator difference, is controlled between 2 ~ 30 hours.
The copolyreaction of sour dispersion inhibitor film-forming resin can be carried out in various solvents or multi-solvents mixing species, these
Solvent includes methanol, ethyl alcohol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyltetrahydrofuran, benzene, toluene, diformazan
Benzene, chloroform, dichloroethanes, trichloroethanes etc..
It, can be in pure water, methanol, methanol/water mixture, second after the copolyreaction of sour dispersion inhibitor film-forming resin
Alcohol, ethanol/water mixture, isopropanol, iso-propanol/water mixture, normal heptane, n-hexane, hexamethylene, pentane, petroleum ether, second
The organic or inorganic solvents kind precipitation and separation such as ether, methyl tertiary butyl ether(MTBE), the yield for being dried in vacuo rear copolymer is 60% ~ 90%.
Sour dispersion inhibitor of the invention can be used for preparing photoetching compositions, and the photoetching compositions are at least by one kind
Sour dispersion inhibitor, a kind of film-forming resin with acid activity, a kind of photosensitizer and organic solvent are constituted, and the acid diffusion inhibits
Agent be it is above-mentioned using (methyl) acrylate as structural unit, wherein introduce basic group formation fluoropolymer resin；To improve
Effect can be added other acid inhibitors and be used in combination.
It is calculated in mass percent, the content of sour dispersion inhibitor is 0.001 ~ 10%, the film forming with acid activity in composition
The content of resin is that the content of 1 ~ 20%, photosensitizer is 0.01 ~ 10%, remaining is organic solvent.
The configuration method of photoetching compositions is: at room temperature, in a clean vial, according to formula rate elder generation
Acid activity resin, photosensitizer, acid inhibitor resin and solvent, mixture are added afterwards to be protected from light concussion in bottle 16~96 hours, make
It is sufficiently dissolved；Then photoresist solution successively is filtered with 0.5 micron and nylon material below and the filter of UPE material；
Filtrate is collected in a clean vial, and required photoetching compositions are obtained.Lithography experiments are carried out after the completion.
Above-mentioned acid activity resin is polymerized by multiple functional groups, includes acid activity group and polar group.Acid is living
The general structure of property resin is as follows:
The molecular weight of acid activity film-forming resin is 3000 ~ 100000, and molecular weight distribution is between 1.0-3.0.Wherein acid activity base
The content of the monomer of group is between 30%-70%, and the content of monomer of polar group is between 70-30%.Preferably 50:50.
Containing the acid-labile group of different substituents, specially acid activity (methyl) acrylate, structure in acid activity resin
To meet at least one of chemical general formula monomer, specific acid activity monomer structure general formula is as follows:
R1The carbochain of=H or carbon atom number in 1-20.R2=acid-sensitive level Four carbon.
Specifically, R2It is a kind of level Four ester of carbon atom number between 6-30, the carbon atom being connected with ester bond oxygen atom
Hydrogen atom all replaced by other groups, possible structure be tertiary butyl ester, substituted tert-butyl ester, alkyl-substituted Buddha's warrior attendant
Alkyl ester, alkyl-substituted adamantane derivative ester, alkyl-substituted norbornyl ester, alkyl-substituted norborneol derivative ester, alkane
Cyclic alkyl ester, alkyl-substituted cyclic alkyl derivative ester that base replaces etc. are one such or a variety of.
Contain one or more polar groups, specially (methyl) acrylate of polar functionalities, knot in acid activity resin
Structure is to meet at least one of chemical general formula monomer, and specific polar monomer general structure is as follows:
R3The carbochain of=H or carbon atom number in 1-20.R4(methyl) acrylate of=polar functionalities.
Specifically, R4For carbon atom number between 6 ~ 30 the ring-type, caged of hydroxyl or straight chain type containing carbon structure and all kinds of
Lactone structure, possible structure are the Buddha's warrior attendant alkyl ester containing one or more independent hydroxyls, the ring containing one or more independent hydroxyls
Own ester, the ring pentyl ester containing one or more independent hydroxyls, the polycyclic ester type compound containing one or more independent hydroxyls, containing 1 or
The caged ester type compound of multiple independent hydroxyls, valerolactone, replaces valerolactone, caprolactone, replaces caprolactone, containing gold butyrolactone
Lactone, the lactone containing multiring structure, the lactone containing cage structure of rigid alkyl structure etc. are one such or a variety of.
Acid activity film-forming resin the preparation method is as follows: under the conditions of comonomer is existing for the radical initiator, molten
Polymerization reaction is carried out in agent to be prepared.In the polymerization reaction of acid activity film-forming resin, initiator is azo initiator, peroxidating
The radical initiator of object, preferred azo initiator are azodiisobutyronitrile or azobisisoheptonitrile, preferred peroxide
Radical initiator be tert-butyl hydroperoxide pivalate, tertiary fourth oxygen hydrogen peroxide, benzoic acid hydrogen peroxide or peroxide benzene
Formyl etc.；The initiator amount is the 0.3% ~ 15% of comonomer gross mass；The adding manner of initiator is that monomer is first added
And partial solvent, it is then heated to polymerization temperature, then initiator solution is added dropwise.The temperature of polymerization reaction according to the solvent that uses and
Initiator is different, controls between 40~90 DEG C, and polymerization time is different also according to the solvent used and initiator, control 4 ~
Between 32 hours.
The copolyreaction of acid activity film-forming resin can be carried out in various solvents or multi-solvents mixing species, these solvent packets
Include methanol, ethyl alcohol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyltetrahydrofuran, benzene,toluene,xylene, chlorine
Imitative, dichloroethanes, trichloroethanes etc..
After the copolyreaction of acid activity film-forming resin, can pure water, methanol, methanol/water mixture, ethyl alcohol, ethyl alcohol/
Aqueous mixtures, isopropanol, iso-propanol/water mixture, normal heptane, n-hexane, hexamethylene, pentane, petroleum ether, ether, methyl
The organic or inorganic solvents kind precipitation and separation such as tertbutyl ether, the yield for being dried in vacuo rear copolymer is 50% ~ 80%.
The sour dispersion inhibitor used is a kind of nitrogenous compound, including primary amine, secondary amine and tertiary amine compound, is especially had
There are the amine compounds of hydroxyl, ehter bond, ester bond, amido bond, lactonic ring, cyano or sulfonic acid ester bond, may be structure diethylamine, three second
One of the fatty amines or aromatic amine such as amine, ethanol amine, triethanolamine, aniline, phenyl ethylamine are a variety of.
The more sulfosalt photo-acid generators of above-mentioned acid activity resin, long flexible chain and acid diffusion suppression can be dissolved comprising one kind
The organic solvent of preparation is propylene glycol methyl ether acetate, propylene glycol list Acetic Ester, dihydroxypropane single-ether, propylene glycol monomethyl ether acetic acid
Ester, tirethylene glycol methyl ether, tirethylene glycol ether, butyl acetate, acetic acid peopentyl ester, ethyl lactate, methyl ethyl ketone and first
One of base isobutyl ketone is a variety of.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1, the present invention provides one kind with acid dispersion inhibitor existing for polymer form.The sour dispersion inhibitor one of it and routine
Sample equally can control the light acid diffusion of non-exposed area；Other small molecule organic bases are different from simultaneously, can more effectively improve itself
Distribution in photoresist improves photoresist resolution ratio and line width roughness, improves the film forming ability of photoresist.
2, compared to organic bases inhibitor, dissolubility is lower in water for acid dispersion inhibitor existing for polymer form,
Such resinoic acid dispersion inhibitor can reduce photoresist leaching rate, photoetching machine lens is avoided to stain in liquid immersion lithography.
Specific embodiment
The present invention will be further described below with reference to examples:
Embodiment one: a kind of (methyl) acrylate with basic group
The preparation method is as follows: being equipped at one in cooling round-bottomed flask, N, N- dimethylethanolamine, triethylamine 34g is added
With 150g methylene chloride, mixed liquor is cooled to 0 DEG C.Then 28g(methyl is added dropwise under stiring) acryloyl chloride, it is precipitated a large amount of solid
Body.After adding, continue to stir 2h.Then reaction solution is made to be slowly increased to room temperature, using saturated aqueous sodium carbonate washing 2 times, often
Secondary 200mL；Then 150mL pure water 2 times；Last 150mL saturated salt solution washed once.Organic phase anhydrous sodium sulfate is dry
Dry, concentration, distillation obtain 27gN, N- dimethyl ethanol base (methyl) acrylate, yield 76%.Nuclear-magnetism result:1H NMR
(CDCl3, δ) and 2.11, s, 3H；2.96, s, 6H;3.44, t, 2H;4.43, t, 2H;5.5, s, 1H；6.5, s, 1H.
Embodiment two: a kind of sour dispersion inhibitor film-forming resin containing basic group, by copolymerized monomers, in free radical
Under the conditions of initiator is existing, copolyreaction is carried out by heating and is prepared:
The preparation method is as follows: adding in the 500mL four-hole bottle for being equipped with the magnetic stirrer with heating, condenser pipe, thermometer at one
Enter 50g N, N- dimethyl amine methyl acrylate and methyl ethyl ketone 300g.Mixture stirs 10 minutes under a nitrogen, then
It is heated to 65 ~ 70 DEG C.Then the methyl ethyl ketone of 2.5g azodiisobutyronitrile (AIBN) and 50g is added dropwise to reaction system in 10 minutes
Solution.The reaction was continued after adding 8 ~ 12h of reflux, is then cooled to room temperature.Mixture is precipitated in electron level n-hexane, is filtered.
Polymer solids 200g electronic grade acetone dissolves, and precipitates in electron level n-hexane again, and it is solid that polymer is obtained after filtration drying
Body, yield 70%, molecular weight 2465, molecular weight distribution 1.45.
Embodiment three: the present embodiment be Application Example of the invention, modulate it is a kind of containing sour dispersion inhibitor resin just
Property chemical amplification photoresist, formula composition are as follows:
Sour dispersion inhibitor resin is the resin in embodiment two.
Acid activity resin is to include 2 kinds of acid activity groups and 2 kinds of polar groups, ratio 50:50.
Photosensitizer is perfluoro butyl sulfonic acid triphenyl sulfosalt.
Solvent is PGMEA:PGME=6:4.
Specific formula modulator approach:
In a new clean 100mL vial, 8.5g acid activity resin, 0.21g perfluoro butyl sulfonic acid triphenyl is added
Sulfosalt, 0.06g acid dispersion inhibitor resin, 54gPGMEA, 36gPGME.At room temperature, mixture shakes 24 hours in bottle,
Dissolve it sufficiently.Then photoresist solution successively is filtered with 0.22 micron and 0.02 micron of filter.Light is carried out after the completion
Carve experiment.
Lithography experiments method: the photoresist of above-mentioned preparation is rotated on 8 " silicon wafers with 2000 ~ 3000 revs/min of speed
Film is toasted 90 seconds on 120 DEG C of hot plates, is then exposed on exposure machine, exposure intensity 10-50mJ/cm2.In 110 DEG C of heat after exposure
It is toasted on plate 90 seconds, finally develops 60 seconds in 2.38%TMAH developer solution, then dry in Electron microscopy photoetching knot
Fruit.
Acid dispersion inhibitor provided by the invention resin is a kind of acid inhibitor of polymer electrolyte, can control non-exposure very well
The light acid in light area is spread；Distribution is good in the photoresist simultaneously, and is not easy to be precipitated in camera lens liquid, matches in ArF photoresist
It has a good application prospect in side.
Claims (10)
1. a kind of acid dispersion inhibitor, it is characterised in that: it is introduced wherein using (methyl) acrylate as structural unit
The fluoropolymer resin that basic group is formed, general structure are (I) or (II):
(I),(II)
In formula, the integer that n is 2~30, the selection of n so that weight average molecular weight between 100~30000g/mol；naIt is alkylidene
Carbon atom number, naIt is 1~20；R1、R2It is hydrogen, carbon atom number is that alkyl, aryl or sulfur-bearing, oxygen, azepine between 1~20 are former
One of substituent group of son is a variety of.
2. acid dispersion inhibitor according to claim 1, it is characterised in that: R1、R2Be carbon atom number be 1~20 between
One of straight chained alkyl, naphthenic base or aryl are a variety of.
3. acid dispersion inhibitor according to claim 1 or 2, it is characterised in that: R1、R2With the nitrogenous function of N atomic building
The structure of group is selected from:
、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、。
4. in claim 1-3 it is any acid dispersion inhibitor preparation method, it is characterised in that: it is described acid dispersion inhibitor be by
(methyl) acrylate monomer with basic group is dissolved in solvent, under the conditions of existing for the initiator, polymerize anti-
It should be prepared, comprising the following steps:
(1) (methyl) acrylate monomer of basic group is dissolved in solvent, heating mixed liquor to temperature is 40~90
DEG C, the molar ratio of monomer and solvent is 1:(4~16)；
(2) 0.3%~15% initiator that quality is comonomer quality is dissolved in solvent, obtains initiator solution, draws
The molar ratio for sending out agent and solvent is 1:(4~16)；
(3) initiator solution that step (2) obtain is added drop-wise in step (1) in the preheated mixed liquor containing monomer, 40~
90 DEG C constant temperature back flow reaction 2~30 hours；
(4) it is cooled to room temperature after the reaction was completed, with nonpolar solvent precipitated resin, filtering drying obtains sour dispersion inhibitor.
5. the preparation method of acid dispersion inhibitor according to claim 4, it is characterised in that: the initiator is azo two
Isobutyronitrile, azobisisoheptonitrile, tert-butyl hydroperoxide pivalate, tertiary fourth oxygen hydrogen peroxide, benzoic acid hydrogen peroxide or peroxide
One of benzoyl is a variety of；
The solvent is ethyl acetate, butyl acetate, butyl acetate, acetic acid peopentyl ester, ethyl lactate, propylene glycol monomethyl ether acetic acid
Ester, propylene glycol list Acetic Ester, dihydroxypropane single-ether, propylene glycol methyl ether acetate, tirethylene glycol methyl ether, tirethylene glycol second
Ether, tetrahydrofuran, methyltetrahydrofuran, chloroform, methylene chloride, 1,2- dichloroethanes, n-hexane, pentane, normal heptane,
One of acetone, cyclohexanone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene, paraxylene or biphenyl are a variety of；
The general structure of described (methyl) acrylate with basic group is (III) or (IV):
(III),(IV)
In formula, nbIt is the carbon atom number of alkylidene, nbIt is 1~20；R1、R2Be hydrogen, carbon atom number be 1~20 between alkyl, virtue
Base or sulfur-bearing, oxygen, nitrogen heteroatom one of substituent group or a variety of.
6. the preparation method of acid dispersion inhibitor according to claim 5, it is characterised in that: R1、R2Be carbon atom number be 1
One of straight chained alkyl, naphthenic base or aryl between~20 are a variety of.
7. the preparation method of acid dispersion inhibitor according to claim 5 or 6, it is characterised in that: with basic group
Contain long-chain and basic functionality in its structure of (methyl) acrylate, structure is as follows:
。
8. the preparation method of acid dispersion inhibitor according to claim 7, it is characterised in that: described with basic group
(methyl) acrylate be by the long-chain compound containing basic group under the action of acid binding agent, and (methyl) acryloyl chloride reaction
It is prepared, comprising the following steps:
(1) long-chain compound, acid binding agent and solvent containing basic group are configured to solution, mixed liquor to temperature is controlled -20
~80 DEG C, the molar ratio of long-chain compound, acid binding agent and solvent containing basic group is 1:(1 ~ 1.5): (4 ~ 16)；
(2) at -20~80 DEG C, agitation and dropping (methyl) acryloyl chloride, time for adding is 1 ~ 5h, the long-chain containing basic group
The molar ratio of compound and (methyl) acryloyl chloride is 1:(1 ~ 1.2)；
(3) after being added dropwise, continue to react 2 ~ 20h at -20~80 DEG C；
(4) after the reaction was completed to room temperature, reaction solution is washed 2 times with aqueous sodium carbonate, and pure water 2 times, saturated common salt washing
It washs 1 time, anhydrous sodium sulfate is dry, concentration, distills (methyl) acrylate for obtaining and having basic group；
Wherein, the solvent is ethyl acetate, butyl acetate, butyl acetate, acetic acid peopentyl ester, ethyl lactate, propylene glycol monomethyl ether
Acetate, propylene glycol list Acetic Ester, dihydroxypropane single-ether, propylene glycol methyl ether acetate, tirethylene glycol methyl ether, tirethylene glycol
Ether, tetrahydrofuran, methyltetrahydrofuran, methanol, ethyl alcohol, the tert-butyl alcohol, isopropanol, acetone, cyclohexanone, methyl ethyl ketone, first
One of base isobutyl ketone, toluene, dimethylbenzene, paraxylene or biphenyl are a variety of.
9. a kind of photoetching compositions, it is characterised in that: in the photoetching compositions, include at least a kind of claims 1 to 3
In any sour dispersion inhibitor, a kind of film-forming resin with acid activity, a kind of photosensitizer and organic solvent.
10. photoetching compositions according to claim 9, it is characterised in that: the photoetching compositions also include other
Acid inhibitor is selected from n-butylamine, tert-butylamine, dimethyl amine, diethylamide, di-n-propylamine, diisopropylamine, di-n-butyl
Amine, diisobutyl amine, di-t-butyl amine, Trimethylamine, triethylamine, Tri-n-Propylamine, triisopropylamine, tri-n-butyl amine, three
Isobutylamine, tri-tert amine, ethanol amine, diethanol amine, triethanolamine, cyclopentamine, cyclohexylamine, morpholine, N- methyl ring penta
Amine, methylaniline, ethyl aniline, n-butyl aniline, tert-butyl aniline, dimethylaniline, diethylaniline, dibutyl benzene, two
One of phenylaniline is a variety of.
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| CN112521529A (en) * | 2020-11-24 | 2021-03-19 | 同济大学 | LED sensitive distyryl oxime ester photoinitiator and preparation and application thereof |
| CN112925166A (en) * | 2021-01-22 | 2021-06-08 | 宁波南大光电材料有限公司 | High-resolution photoresist |
| CN112898170A (en) * | 2021-01-22 | 2021-06-04 | 宁波南大光电材料有限公司 | Preparation method of acid diffusion inhibitor and photoresist composition |
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