CN112592303B - Photoacid generator containing double onium salt structure, preparation method and photoresist composition - Google Patents
Photoacid generator containing double onium salt structure, preparation method and photoresist composition Download PDFInfo
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- CN112592303B CN112592303B CN202011526905.4A CN202011526905A CN112592303B CN 112592303 B CN112592303 B CN 112592303B CN 202011526905 A CN202011526905 A CN 202011526905A CN 112592303 B CN112592303 B CN 112592303B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/30—Sulfides having the sulfur atom of at least one thio group bound to two carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/04—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
- C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
The invention discloses a photo-induced acid generator containing a double onium salt structure, which has the following structural general formula (I):
wherein n=0 or 1 or 2, r 1 ‑R 6 Is one or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen hetero atoms; m is M ‑ Anions and Q ‑ The anion is a sulfonic acid anion. The photoacid generator containing the double-onium salt structure has higher acid generating efficiency than that of the photoacid generator containing the single-onium salt structure, and can be suitable for light sources with various wavelengths.
Description
Technical Field
The invention belongs to the technical field of photoresist, and particularly relates to a photo-induced acid generator containing a double onium salt structure, a preparation method and a photoresist composition.
Background
The photoresist composition is one of key materials in the field of integrated circuit manufacturing, and the main components of the photoresist composition are light-sensitive mixed liquid composed of film forming resin, photosensitizer, acid inhibitor, solvent and the like. Under the irradiation of ultraviolet light, deep ultraviolet light, electron beam, ion beam and other light or radiation, the solubility of the components is changed, and the soluble part is dissolved out through the treatment of proper developing solution to obtain the final required photoresist image.
As a photosensitive component in a photoresist, photoacid generators play an important role in photochemical reactions. Therefore, the acid production efficiency of the photoacid generator is improved, and the performances such as photoresist sensitivity, contrast and the like are directly affected.
However, in the related art, the photoacid generator in the photoresist composition is generally a single structure sulfonium salt or iodonium salt structure, and has only one acid generating point, so that the acid generating efficiency is low.
Disclosure of Invention
In view of the above, it is necessary to provide a photoacid generator containing a bis-onium salt structure to solve the technical problem of low acid production efficiency of the existing photoacid generator.
A photoacid generator comprising a bis-onium salt structure, characterized in that: the structural general formula is shown as (I):
（I）
wherein n=0 or 1 or 2;
R 1 -R 6 is one or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen hetero atoms; the method comprises the steps of carrying out a first treatment on the surface of the
M - Anions and Q - The anion is a sulfonic acid anion.
Still further, the sulfonic acid anion is a fluoroalkyl sulfonic acid anion, an aryl sulfonic acid anion, or a camphorsulfonic acid anion, and derivatives thereof.
Still further, the sulfonic acid anion is a perfluorobutyl sulfonic acid anion, a perfluorooctyl sulfonic acid anion, a p-toluene sulfonic acid anion, or a camphorsulfonic acid anion.
The embodiment of the invention also provides a preparation method of the photoinduced acid generator containing the double onium salt structure, which comprises the following steps:
s11: dissolving diaryl sulfoxide and diaryl thioether in a certain proportion in a first organic solvent in a reaction kettle in protective gas to obtain a mixed solution, and cooling the reaction kettle to a certain temperature;
s12: dropwise adding sulfonic anhydride into the reaction kettle, reacting for a period of time, adding water to stop the reaction, extracting an organic phase, and desolventizing to constant weight to obtain a compound A;
s13: and dissolving the compound A and the sulfonate in a second organic solvent, mixing, stirring, adding water, continuously stirring, desolventizing to obtain a turbid water phase, extracting, and desolventizing to obtain the photoinduced acid generator containing the double onium salt structure.
Further, the ratio of the diaryl sulfoxide to the diaryl sulfide to the sulfonic anhydride is (1.5-2.5): 0.5-1.5): 1-2.
Further, the sulfonic anhydride is trifluoromethanesulfonic anhydride (Tf 2 O), p-toluenesulfonic anhydride, perfluorobutylsulfonic anhydride or methylsulfonic anhydride.
Still further, the sulfonate is perfluorobutyl sulfonate, perfluorooctyl sulfonate, p-toluene sulfonate, or camphorsulfonate.
Still further, the temperature is-30-30 ℃.
The embodiment of the invention also provides a photoresist, which comprises a photoacid generator, film-forming resin, an acid diffusion inhibitor and an organic solvent, wherein the photoacid generator is the photoacid generator.
Further, the content of the photoacid generator is 0.1% -5%, the mass content of the film-forming resin is 1% -30%, the mass content of the acid diffusion inhibitor is 0.001% -1%, and the mass content of the organic solvent is 64% -98.899%.
Compared with the prior art, the invention has the following advantages: the photoinduced acid generator provided by the embodiment of the invention comprises two sulfonium salt structures, has two acid generating points, can generate two parts of photoacid through photolysis under the action of light, and has high acid generating efficiency.
In addition, the photoacid generator containing the double onium salt structure of the present embodiment is also useful for widening absorption wavelength, and can be applied to 248nm (KrF), 193nm (ArF) and 13nm (EUV) light sources.
Drawings
FIG. 1 is a flow chart of a method for preparing photoacid generator according to a preferred embodiment of the present invention.
Fig. 2 is an electron micrograph of a photoresist composition according to the second embodiment of the present invention after photolithography.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In a first aspect, an embodiment of the present invention provides a photoacid generator (hereinafter, abbreviated as photoacid generator) having a bis-onium salt structure, for preparing a photoresist composition, which has a general structural formula as follows:
wherein n=0 or 1 or 2; R1-R6 are one or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen hetero atoms;
the M-anions and Q-anions are sulfonic acid anions, specifically fluoroalkyl sulfonic acid anions, aryl sulfonic acid anions, camphorsulfonic acid anions, and derivatives thereof.
In a particular embodiment of the invention, the sulfonic acid anion may be one or both of perfluorobutyl sulfonic acid anion, perfluorooctyl sulfonic acid anion, p-toluene sulfonic acid anion, or camphorsulfonic acid anion.
In this embodiment, the double onium salt structures are all sulfonium salt structures, and in other embodiments, other onium salts such as iodonium salts may be used.
Therefore, the photoacid generator provided by the embodiment of the invention comprises two sulfonium salt structures, has two acid generating points, can generate two parts of photoacid by photolysis under the action of light, and has high acid generating efficiency. And can widen the absorption wavelength, and can be applied to 248nm (KrF), 193nm (ArF) and 13nm (EUV) light sources.
In a second aspect, the invention also provides a preparation method of the photoacid generator. The method comprises the following steps:
s11: in protective gas, diaryl sulfoxide and diaryl thioether are dissolved in a first organic solvent in a certain proportion in a reaction kettle to obtain a mixed solution, and the reaction kettle is cooled to a certain temperature.
Wherein the cooling temperature is in the range of-30 to 30 ℃.
In a specific embodiment of the present invention, the diaryl sulfoxide is diphenyl sulfoxide, the diaryl sulfide is diphenyl sulfide, and the first organic solvent is one or more selected from dichloromethane, chloroform and dichloroethane. Dissolving diphenyl sulfoxide and diphenyl sulfide in dichloromethane under nitrogen, and cooling to-30 deg.C o C。
S12: and (3) dropwise adding sulfonic anhydride into the reaction kettle, reacting for a period of time, adding water to stop the reaction, extracting an organic phase, and desolventizing to constant weight to obtain the compound A.
The chemical reaction formula is as follows:
wherein in the above chemical reaction formula
Is of the general structural formula of diaryl sulfoxide, wherein +.>
Is of the general structural formula of diaryl sulfide, wherein R 1 R4 is one or more of H, alkyl with 1-20 carbon atoms, aryl or substituent containing sulfur/oxygen/nitrogen hetero atoms.
Wherein the mass ratio of the diaryl sulfoxide to the diaryl sulfide to the sulfonic anhydride is (1.5-2.5) (0.5-1.5) (1-2).
In a specific embodiment of the present invention, the mass ratio of the diaryl sulfoxide, the diaryl sulfide, and the sulfonic anhydride is 2:1:2.
The structural general formula of the sulfonic anhydride is shown in the chemical reaction formula
Wherein R is 5 、R 6 Including but not limited to trifluoromethyl (-CF) 3 ) P-tolyl, perfluorobutyl (-C) 4 F 9 ) Or methyl (-CH) 3 ) I.e., the sulfonic anhydride may include, but is not limited to, trifluoromethanesulfonic anhydride, p-toluenesulfonic anhydride, perfluorobutylsulfonic anhydride, or methylsulfonic anhydride, etc.
In a specific embodiment of the present invention, the sulfonic anhydride is trifluoromethanesulfonic anhydride (Tf 2 O）。
The reaction time may be 1 to 6 hours, preferably 3 hours in this step.
In addition, after the organic phase is extracted, the organic phase is concentrated and washed with diethyl ether, the washing times can be one or more times, a crude product is obtained after the washing is completed, and the crude product can be recrystallized by a methanol/n-hexane system to improve the purity.
S13: and dissolving the compound A and the sulfonate in a second organic solvent, mixing, stirring, adding pure water, continuously stirring, desolventizing to obtain a turbid water phase, extracting, and desolventizing to obtain a compound B, wherein the compound B is the photoinduced acid generator with the double onium salt structure.
The chemical reaction formula is as follows:
wherein the sulfonate includes, but is not limited to, fluoroalkyl sulfonate, aryl sulfonate, or camphorsulfonate, and derivatives thereof.
Specifically, in one embodiment of the present invention, the sulfonate salts are sodium perfluorobutyl sulfonate and sodium p-toluene sulfonate.
Wherein the mass ratio of the compound A to the sodium perfluorobutyl sulfonate to the sodium paratoluenesulfonate is (0.8-1.6): 1.
the second organic solvent can be one or more of methanol, ethyl acetate, dichloromethane, ethanol, acetone, methyl ethyl ketone and tetrahydrofuran, wherein the second organic solvent can be the same or different from the first organic solvent.
In one embodiment of the present invention, the solvent used in the above extraction process may be one or more of dichloromethane, chloroform, ethyl acetate, dichloroethane and trichloroethane.
In still another aspect, based on the photoacid generator and the preparation method thereof, the embodiment of the invention further provides a photoresist composition, which comprises the photoacid generator, a film-forming resin, an acid diffusion inhibitor and an organic solvent, wherein the photoacid generator is prepared by adopting the method.
In one embodiment, the photoresist composition is composed of at least one film-forming resin, one photosensitizer, one additive and an organic solvent, and the components can be formulated according to the component ratios of conventional photoresist compositions.
In a preferred embodiment, the photoacid generator is present in an amount ranging from 0.1% to 5%, the film-forming resin is present in an amount ranging from 1% to 30%, the acid diffusion inhibitor is present in an amount ranging from 0.001% to 1%, and the organic solvent is present in an amount ranging from 64% to 98.899%. Of course, reasonable adjustment of the content ratio of the components according to practical application is also within the scope of the disclosure of the specification.
In specific embodiments, the acid diffusion inhibitor includes, but is not limited to, one or at least two of N-butylamine, t-butylamine, dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, diisobutylamine, di-t-butylamine, trimethylamine, triethylamine, tri-N-propylamine, triisopropylamine, tri-N-butylamine, triisobutylamine, tri-t-butylamine, ethanolamine, diethanolamine, triethanolamine, cyclopentylamine, cyclohexylamine, morphine, N-methylcyclopentylamine, methylaniline, ethylaniline, N-butylaniline, t-butylaniline, dimethylaniline, diethylaniline, dibutylbenzene, diphenylaniline.
Wherein the acid diffusion inhibitor can inhibit acid diffusion in the photoresist.
Preferably, the acid diffusion inhibitor in the photoresist composition is a mixed acid diffusion inhibitor of t-butylamine and diisobutylamine.
The organic solvent includes, but is not limited to, one or more of propylene glycol methyl ether acetate, propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, ethylene glycol methyl ether diacetate, ethylene glycol diethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone.
The organic solvent can effectively dissolve other components contained in the photoresist composition, and the content of the organic solvent is adjusted, so that the photoresist composition can be adjusted to a certain viscosity, and the photoresist composition can be uniformly coated on the surface of a substrate.
In the photoresist composition, the photoacid generator with the double onium salt structure can generate two parts of photoacid under illumination, so that the acid-sensitive groups in the catalytic film-forming resin are accelerated to react, the solubility of the resin in the exposed area and the resin in the non-exposed area in a developing solution (TMAH) are different, and corresponding patterns are generated on the substrate after exposure and development.
In addition, in one embodiment of the present invention, the preparation method of the film-forming resin specifically comprises the following steps:
s21, adding the monomer 1, the monomer 2 and the monomer 3 into a reaction kettle in a protective atmosphere, adding a first solvent, mixing, stirring, heating the stirring kettle to a reaction temperature T, adding a mixed solution of a second solvent and an initiator into the stirring kettle, reacting for a period of time T at a polymerization temperature T, stopping the reaction, and cooling the reaction kettle to room temperature.
Wherein, the structural formulas of the monomer 1, the monomer 2 and the monomer 3 are respectively 1, 2 and 3 as follows:
wherein 1 is cyclopentylmethacrylate, 2 is 3-methacrylate-4-butyrolactone, and 3 is adamantylmethacrylate. The mass ratio range of the three is (65-70): (25-29.9): (0.1 to 10).
Wherein the polymerization reaction can be carried out in various solvents or various solvent mixture species, and the first solvent and the second solvent comprise one or more of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane and trichloroethane.
Preferably, the first solvent and the second solvent in this embodiment are the same, and ethyl acetate is used.
Wherein the initiator may be azo initiator and peroxide free radical initiator.
Specifically, the azo initiator includes, but is not limited to, one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, and the peroxide radical initiator includes, but is not limited to, one or more of tert-butyl pivalate peroxide, tert-butoxyhydroperoxide, hydrogen benzoate, or benzoyl peroxide.
The polymerization temperature T is controlled between 40 and 90 ℃ according to the difference of the first solvent, the second solvent and the initiator, and the polymerization time T is controlled between 4 and 32 hours according to the difference of the first solvent, the second solvent and the initiator.
S22, adding a third solvent into the reaction kettle cooled to room temperature in the step S21, leading out liquid in the reaction kettle after generating a precipitate, and then adding a fourth solvent into the precipitate in the reaction kettle until the precipitate is dissolved.
Wherein the third solvent includes, but is not limited to, water, methanol/water mixtures, ethanol/water mixtures, isopropanol/water mixtures, n-heptane, n-hexane, cyclohexane, n-pentane, petroleum ether, diethyl ether, methyl tertiary butyl ether, and the like.
The fourth solvent includes, but is not limited to, one or more of methanol, ethanol, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, benzene, toluene, xylene, chloroform, dichloroethane, trichloroethane.
S23, adding the third solvent into the reaction kettle in the step S22, leading out liquid in the reaction kettle to obtain a second precipitate, and drying the second precipitate in vacuum to obtain the film-forming resin.
In addition, the above step S23 is repeated a plurality of times in order to increase the purity of the product. In a specific embodiment, the repetition is 3 times.
The present invention will now be described in more detail by way of the following examples, which are given by way of illustration only and not limitation.
Embodiment one: preparation of photoacid generator containing bis-onium salt structure
S11: 21g of diphenyl sulfoxide and 19g of diphenyl sulfide are dissolved in 300ml of dichloromethane, added into a reaction kettle filled with nitrogen, and the temperature of the reaction kettle is reduced to minus 15 DEG C
S12, dropwise adding 29g of trifluoromethanesulfonic anhydride into the reaction kettle for 30min, reacting for 3h, adding 200ml of pure water to stop the reaction, cooling the reaction kettle to room temperature, separating liquid to obtain an organic phase, desolventizing to constant weight, and washing with 50ml of diethyl ether twice to obtain 22g of a compound A.
The reaction formula is as follows:
s13, 86g of compound A is dissolved in 50g of methanol, 33g of sodium perfluor butyl sulfonate is dissolved in 50g of methanol, 20g of sodium p-toluenesulfonate is dissolved in 50g of methanol, stirring is carried out for 12 hours, 50ml of pure water is added, stirring is carried out for 3 hours, a turbid water phase is obtained after desolventizing, 50g of dichloromethane is used for extracting an organic phase, and the desolventizing is carried out to obtain a compound B.
The specific reaction formula is as follows:
wherein the yield of the compound a in this example was 26%, and the yield of the compound B was 38%.
Embodiment two: preparation of film-forming resins
S21, adding 45g of monomer 1, 50g of monomer 2 and 20g of monomer 3 into a reaction kettle filled with nitrogen, adding 60g of ethyl acetate into the reaction kettle, stirring uniformly to obtain a mixed solution of the monomers, heating the reaction kettle to 77 ℃, mixing 10g of ethyl acetate and 12g of benzoyl peroxide to obtain a mixed solution of initiator substances, dripping the mixed solution of the initiator substances into the reaction kettle of the mixed solution of the monomers, reacting for 7 hours at 77 ℃, stopping the reaction, and cooling the reaction kettle to room temperature.
S22, adding 600g of methanol into the reaction kettle cooled to room temperature, generating a first precipitate for 1h, discharging liquid in the reaction kettle, and then adding 70g of ethyl acetate into the reaction kettle until the first precipitate is dissolved.
S23, adding 600g of methanol into the reaction kettle to generate a second precipitate, then leading out liquid in the reaction kettle to obtain the second precipitate, and placing the second precipitate in vacuum for drying to obtain 76g of film-forming resin.
The yield of the film-forming resin obtained in this example was 66%.
The molecular weight mw=8655 and pdi=1.46 of the film-forming resin obtained in this example were measured by the GPC apparatus.
Embodiment III: preparation of photoresist composition
In a clean 100mL glass bottle, 8.5g of film-forming resin, 0.25g of the photo-acid generator containing the double onium salt structure prepared in the first embodiment, 0.06g of mixed acid diffusion inhibitor with the mass ratio of tertiary butyl amine to diisobutyl amine being 2:8, 32g of methyl ether acetate and 48g of propylene glycol monoethyl ether are sequentially added, and the mixture is vibrated in the bottle for 24 hours at room temperature to fully dissolve the mixture to obtain a mixed solution. Then, the solution was filtered through a 0.22 μm filter and then a 0.02 μm filter, and the filtrate was collected to obtain a photoresist composition solution.
Photolithography experiments were performed on the photoresist prepared in the third embodiment. The method of the lithography experiment is as follows:
the prepared photoresist composition solution is coated on a 12' silicon wafer at 2000-3000 rpmIs rotated into a film at a speed of 120 ℃ for 90 seconds, and then is subjected to an exposure intensity of 10-50mJ/cm on an exposure machine 2 Is a light exposure of the above. After exposure, the resist was baked on a hot plate at 110℃for 90 seconds, developed in a 2.38% TMAH developer for 60 seconds, and then baked and the result of lithography was examined by electron microscopy.
The photoacid generator containing the double-onium salt structure of the embodiment has a double-onium salt structure, and compared with the photoacid generator containing a single-onium salt structure, the polymeric photoacid generator containing the double-onium salt structure has higher acid generating efficiency and can be suitable for light sources with various wavelengths.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (3)
1. A preparation method of a photo-acid generator containing a double onium salt structure is characterized by comprising the following steps: comprising the following steps:
s11: dissolving diaryl sulfoxide and diaryl thioether in a first organic solvent in a reaction kettle according to a certain proportion in protective gas to obtain a mixed solution, and cooling the reaction kettle to a certain temperature;
s12: dropwise adding sulfonic anhydride into the reaction kettle, reacting for a period of time, adding water to stop the reaction, extracting an organic phase, and desolventizing to constant weight to obtain a compound A;
s13: dissolving the compound A and sulfonate in a second organic solvent, mixing, stirring, adding water, continuously stirring, desolventizing to obtain a turbid water phase, extracting, and desolventizing to obtain a photoinduced acid generator containing a double onium salt structure;
the mass ratio of the diaryl sulfoxide to the diaryl sulfide to the sulfonic anhydride is (1.5-2.5) (0.5-1.5) (1-2);
the structural general formula of the photo-acid generator containing the double onium salt structure is shown as the following formula (I):
formula (I);
wherein n=0 or 1 or 2,
R 1 -R 6 is H;
M - anions and Q - The anions are sulfonic acid anions; the sulfonic acid anion is perfluoro butyl sulfonic acid anion, perfluoro octyl sulfonic acid anion, p-toluenesulfonic acid anion or camphorsulfonic acid anion;
the sulfonic anhydride is trifluoromethanesulfonic anhydride.
2. The method of claim 1, wherein: the sulfonate is perfluorobutyl sulfonate, perfluorooctyl sulfonate, p-toluene sulfonate or camphorsulfonate.
3. The method of claim 1, wherein: the temperature is-30-30 ℃.
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| KR20010040187A (en) * | 1999-10-28 | 2001-05-15 | 무네유키 가코우 | Positive photoresist composition |
| JP2002303981A (en) * | 2001-04-06 | 2002-10-18 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
| US7678528B2 (en) * | 2005-11-16 | 2010-03-16 | Az Electronic Materials Usa Corp. | Photoactive compounds |
| JP2013235258A (en) * | 2012-04-13 | 2013-11-21 | Fujifilm Corp | Photoacid generator-containing composition, photosensitive composition using the same, cured film, and pattern alignment film |
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