CN113698329A - Photoacid generator for 193nm immersion lithography and intermediate thereof - Google Patents

Photoacid generator for 193nm immersion lithography and intermediate thereof Download PDF

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CN113698329A
CN113698329A CN202110979288.1A CN202110979288A CN113698329A CN 113698329 A CN113698329 A CN 113698329A CN 202110979288 A CN202110979288 A CN 202110979288A CN 113698329 A CN113698329 A CN 113698329A
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CN113698329B (en
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王溯
方书农
徐森
林逸鸣
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Shanghai Xinke Micro Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • 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
    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes
    • 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 aPhotoacid generators for 193nm immersion lithography and intermediates therefor. The photoacid generator of the present invention is represented by formula I. The photoresist containing the photoacid generator has the advantages of high resolution, high sensitivity and low line width roughness, and has good application prospect.

Description

Photoacid generator for 193nm immersion lithography and intermediate thereof
Technical Field
The invention relates to a photoacid generator for 193nm immersion lithography and an intermediate thereof.
Background
The photolithography technique is a fine processing technique for transferring a pattern designed on a mask plate to a pattern on a substrate by using the chemical sensitivity of a photolithography material (particularly a photoresist) under the action of visible light, ultraviolet rays, electron beams and the like through the processes of exposure, development, etching and the like. The photoresist material (specifically referred to as photoresist), also called photoresist, is the most critical functional chemical material involved in the photolithography technology, and its main components are resin, Photo Acid Generator (PAG), and corresponding additives and solvents. The photo-acid generator is a light-sensitive compound, which is decomposed under illumination to generate acid, and the generated acid can make acid-sensitive resin generate decomposition or cross-linking reaction, so that the dissolution contrast of the illuminated part and the non-illuminated part in a developing solution is increased, and the photo-acid generator can be used in the technical field of pattern micro-machining.
Three important parameters of the photoresist include resolution, sensitivity, line width roughness, which determine the process window of the photoresist during chip fabrication. With the increasing performance of semiconductor chips, the integration level of integrated circuits is increased exponentially, and the patterns in the integrated circuits are continuously reduced. In order to make patterns with smaller dimensions, the performance indexes of the three photoresists must be improved. The use of a short wavelength light source in a photolithography process can improve the resolution of the photoresist according to the rayleigh equation. The light source wavelength for the lithographic process has evolved from 365nm (I-line) to 248nm (KrF), 193nm (ArF), 13nm (EUV). In order to improve the sensitivity of the photoresist, the current KrF, ArF and EUV photoresists are mainly made of chemically amplified photosensitive resin. Thus, photosensitizers (photoacid generators) compatible with chemically amplified photosensitive resins are widely used in high-end photoresists.
With the gradual development of the photoetching process, the process complexity is increased to 193nm immersion process, and higher requirements are put on the photo-acid generator. The development of a photoacid generator capable of improving the resolution, sensitivity and line width roughness of photoresist becomes a problem to be solved urgently in the industry.
Disclosure of Invention
The invention aims to overcome the defect that the variety of photoacid generators matched with chemically amplified photosensitive resin is few in the prior art, and provides a photoacid generator for 193nm immersion lithography and an intermediate thereof so as to improve the performances of the photoresist in various aspects such as resolution, sensitivity and line width roughness.
The invention solves the technical problems through the following technical scheme.
The invention provides a compound as shown in a formula I:
Figure BDA0003228407810000021
a is I or S;
n is 2 or 3;
r is H, halogen, C1-6Alkyl or C1-6One or more of alkoxy, wherein the number of substituents of R on a benzene ring is 1-5;
y is
Figure BDA0003228407810000022
Quilt Y1Substituted by
Figure BDA0003228407810000023
Or by Y2Substituted by
Figure BDA0003228407810000024
Wherein, Y1And Y2Independently 1, 2, 3 or 4; m is1、m2、n1And n2Independently 0, 1, 2 or 3; y is1And Y2Independently of one another is amino, C1-6Alkylamino, carboxyl, C1-6Alkyl carboxyl or C1-6An alkyl group.
In some embodiments, in R, the halogen is F, Cl, Br, or I.
In some embodiments, R is C1-6Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
In some embodiments, R is C1-6Alkoxy is methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy.
In some embodiments, Y is1In (b), the C1-6Alkyl, said C1-6Alkylamino and said C1-6C in alkylcarboxy1-6Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
In some embodiments, Y is2In (b), the C1-6Alkyl, said C1-6Alkylamino and said C1-6C in alkylcarboxy1-6Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
In some embodiments, Y is1And Y2Independently 1 or 2.
In some aspects, m1、m2、n1And n2Independently 0 or 1.
In some embodiments, R is H.
In some embodiments, n is 3.
In some embodiments, a is S.
In some embodiments, Y is1And Y2Independently is amino, carboxyl or C1-6An alkyl group.
In some embodiments, R is H;
a is S;
n is 3;
y is
Figure BDA0003228407810000031
Quilt Y1Substituted by
Figure BDA0003228407810000032
Or by Y2Substituted by
Figure BDA0003228407810000033
Y1And Y2Independently 1 or 2;
m1、m2、n1and n2Independently 0 or 1;
Y1and Y2Independently amino, carboxyl or methyl.
In some of the embodiments described herein, the first and second,
Figure BDA0003228407810000034
is composed of
Figure BDA0003228407810000035
In some embodiments, Y is
Figure BDA0003228407810000041
Figure BDA0003228407810000042
In some embodiments, the compound of formula I is any one of the following:
Figure BDA0003228407810000043
Figure BDA0003228407810000051
the invention also provides a preparation method of the compound shown in the formula I, which comprises the following steps:
in a solvent, carrying out a salt forming reaction shown in the specification on a compound II and a compound III to obtain a compound shown in the formula I;
Figure BDA0003228407810000052
wherein A, R, Y, N is as defined above, X is a halogen and N is an alkali metal.
In X, the halogen is preferably F, Cl, Br or I, for example Cl.
In N, the alkali metal is preferably Li, Na or K, for example Na.
The salt-forming reaction can be a conventional reaction of the salt-forming reaction in the field, and the following conditions and operations are particularly preferred in the invention:
in the salt forming reaction, the solvent can be an alcohol solvent and water. The alcohol solvent may be methanol, ethanol, n-propanol or isopropanol, and further may be methanol. The volume ratio of the alcohol solvent to the water is 0.8:1-1.5:1, such as 1.0: 1. The amount of the alcohol solvent is 60-80ml, for example 70 ml.
In the salt formation reaction, the molar ratio of the compound III to the compound II may be 1.5:1 to 2.5:1, for example, 2.0: 1.
In the salt-forming reaction, the compound III is preferably added in the form of an aqueous solution to a solution containing the compound II.
The salt-forming reaction can be carried out under the condition of keeping out light.
The temperature of the salt formation reaction may be 5 to 40 ℃, for example, room temperature.
The progress of the salt-forming reaction can be monitored by methods conventional in the art (e.g., TLC) with the end point of the reaction being that compound III is no longer reacted. The time for the salt-forming reaction may be 8 to 24 hours, for example 16 hours.
The work-up step of the salt-forming reaction may be a work-up step conventional in the art for such salt-forming reactions, preferably extraction. The solvent for the extraction may be a halogenated hydrocarbon solvent (e.g., chloroform). The number of extractions may be 2-3, for example 3.
The preparation method of the compound shown in the formula I can further comprise the following steps:
step 1, reacting a compound V and a compound IV in a solvent in the presence of an alkaline reagent to obtain a mixture;
step 2, in the presence of hydrogen peroxide, reacting the mixture obtained in the step 1 in water to obtain a compound II;
Figure BDA0003228407810000061
in step 1, the alkaline agent may be an alkaline agent conventional in the art, preferably an alkali metal carbonate and/or an alkali metal bicarbonate (e.g., sodium bicarbonate).
In step 1, the molar ratio of the basic agent to the compound V may be a molar ratio conventional in the art, preferably 1.5:1 to 4.0:1, for example 3.0: 1.
In step 1, the molar ratio of said compound IV to said compound V may be a molar ratio as conventional in the art, preferably 1.5:1 to 2.5:1, e.g. 2.0: 1.
In step 1, the solvent may be a solvent conventional in such reactions in the art, preferably a nitrile solvent (e.g., acetonitrile) and water. The volume ratio of said nitrile solvent to said water is from 0.8:1 to 1.2:1, for example 1.0: 1. The nitrile solvent is used in an amount of 70-90ml, for example 80 ml.
In step 1, the temperature of the reaction may be 50 to 90 ℃, for example 70 ℃.
In step 1, the reaction time may be 8 to 24 hours, for example, 16 hours.
In step 2, the molar ratio of the compound hydrogen peroxide to the compound V may be a molar ratio conventional in the art, and is preferably 1.5:1 to 3.0:1, for example, 2.0: 1.
In step 2, the temperature of the oxidation reaction may be 5 to 40 ℃, for example, room temperature.
In step 2, the time of the oxidation reaction may be 8 to 24 hours, for example, 16 hours.
The preparation method of the compound shown in the formula I can further comprise the following steps: carrying out esterification reaction on a compound VII and a compound VI in a solvent in the presence of p-toluenesulfonic acid to obtain a compound V;
Figure BDA0003228407810000071
the esterification reaction may be an esterification reaction which is conventional in the art, and the following conditions and operations are particularly preferred in the present invention:
in the esterification reaction, the molar ratio of the p-toluenesulfonic acid to the compound VI may be 0.1:1 to 0.3:1, for example 0.22: 1.
In the esterification reaction, the molar ratio of the compound VI to the compound VII may be 2.0:1 to 4.0:1, for example, 3.0: 1.
In the esterification reaction, the solvent may be an aromatic hydrocarbon solvent (e.g., toluene). The aromatic hydrocarbon solvent is used in an amount of 70 to 90ml, for example 80 ml.
The esterification reaction temperature may be 110-130 deg.C, such as 120 deg.C.
The progress of the esterification reaction can be monitored by methods conventional in the art (e.g., TLC) with the end point of the reaction being the point at which the compound VI is no longer reacted. The esterification reaction time may be 5 to 10 hours, for example 8 hours.
The post-treatment step of the esterification reaction may be a post-treatment step conventional in the art for such esterification reactions, and is preferably alkali-washed (e.g., 3 times), washed with saturated brine (e.g., 1 time), and dried (e.g., dried over anhydrous sodium sulfate).
The present invention also provides a compound II as described above:
Figure BDA0003228407810000081
wherein Y and N are as defined above.
The compound II is any one of the following compounds:
Figure BDA0003228407810000082
Figure BDA0003228407810000091
the invention also provides an application of the compound of the formula I as a photoacid generator in photoresist.
The invention also provides a photoresist composition, which comprises the following raw materials: the compound of formula I, resin, basic additive and solvent described above;
the resin is
Figure BDA0003228407810000092
In the photoresist composition, the compound shown in the formula I preferably accounts for 2-10 parts by weight, for example 4 parts by weight.
In the photoresist composition, the resin is preferably 20 to 120 parts by weight, for example, 100 parts by weight.
In the photoresist composition, the alkaline additive is preferably present in an amount of 0.1 to 1 part by weight, for example 0.5 part by weight.
In the photoresist composition, the alkaline additive is preferably C1-4Alkyl quaternary ammonium bases such as tetramethyl ammonium hydroxide.
In the photoresist composition, the solvent is preferably 500-2000 parts by weight, such as 1000 parts by weight.
In the photoresist composition, the solvent is preferably an ester solvent, such as propylene glycol methyl ether acetate.
The photoresist composition comprises the following raw materials in parts by weight: 4 parts of the compound shown in the formula I, 100 parts of resin, 0.5 part of alkaline additive and 1000 parts of solvent.
The photoresist composition is prepared from the following raw materials: the compound of formula I, the resin, the basic additive, and the solvent.
The invention also provides a preparation method of the photoresist composition, which comprises the following steps: mixing the above components uniformly.
In the preparation method, the mixing mode can be a mixing mode conventional in the field, and shaking is preferred.
In the preparation method, the mixing step preferably further comprises membrane filtration, for example, filtration with a 0.2 μm membrane.
The invention also provides an application of the photoresist composition in a photoetching process.
Wherein, the photoetching process preferably comprises the following steps: the photoresist composition is coated on a pretreated substrate, dried (e.g., at 110 ℃ for 90 seconds), exposed, and developed (e.g., using a developer solution that is an aqueous solution of tetramethylammonium hydroxide).
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and part of the raw materials used in the invention are available on the market, and part of the raw materials are self-made.
The positive progress effects of the invention are as follows: the photoresist composition prepared by the photoacid generator has the advantages of high resolution, high sensitivity and low line width roughness, and compared with a comparative photoresist composition, the sensitivity is improved by 25-49%, the resolution is improved by 4-44%, and the line width roughness is reduced by 40-74%.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Preparation of the resin
In the examples of the invention or comparative examples, the resins were prepared as follows:
3-bicyclo [2.2.1] hept-5-en-2-yl-3-hydroxy-propionic acid tert-butyl ester (hereinafter referred to as BHP), 1-methyladamantane acrylate and gamma-butyrolactone acrylate were added in a molar ratio of 1: 1. 1, 4-dioxane as a polymerization solvent was added in an amount of 300 parts by weight relative to 100 parts by weight of the total amount of the reactive monomers, azobisisobutyronitrile as an initiator was added in an amount of 4 parts by mole relative to 100 parts by mole of the total amount of the reactive monomers, and the mixture was reacted at 65 ℃ for 16 hours.
After the reaction, the reaction solution was precipitated with n-hexane, and the precipitate was removed and dried in vacuo. Thereby obtaining
Figure BDA0003228407810000111
The weight average molecular weight was about 8500 g/mol.
Example 1
Figure BDA0003228407810000112
Step 1: synthesis of Compound V-1
2-bromo-2, 2-difluoroethanol (76.94g, 0.48mol, 3.0eq), compound VII-1(38g, 0.16mol, 1.0eq), p-toluenesulfonic acid (5.53g, 0.03mol, 0.22eq), and 80mL of toluene were charged in a 250mL glass bottle equipped with an oil-water separator and a condenser, and the mixture was heated under reflux for 8h with stirring. After the reaction, the reaction mixture was cooled, washed 3 times with 50mL of an aqueous sodium carbonate solution, 1 time with 50mL of a saturated saline solution, and the organic phase was dried over anhydrous sodium sulfate and concentrated to obtain 55.0g of an intermediate in total, with a yield of 66.0%.
1HNMR(300MHz,DMSO)：δppm：8.52,2H；1.50,2H；2.01,4H；1.67,2H；2.15,2H；1.79,4H；4.90,4H.
Step 2: synthesis of Compound II-1
In a 500mL round-bottomed flask, compound V-1(78.0g, 0.15mol, 1.0eq) and 80mL acetonitrile were added and dissolved with stirring. Under nitrogen protection, 80mL of an aqueous solution containing sodium dithionite (51.98g, 0.30mol, 2.0eq) and sodium bicarbonate (37.56g, 0.45mol, 3.0eq) was added dropwise, and after completion of addition, the reaction mixture was heated at 70 ℃ and stirred for 16 hours. After the reaction was complete, it was cooled and an appropriate amount of sodium chloride solid was added until the solution was saturated. The reaction solution was separated into layers, and the aqueous phase was extracted 2 times with 30mL of acetonitrile. The organic phase was combined and transferred to a 500mL round-bottomed flask, to which 100mL of purified water was added. The mixture was added dropwise to 30% hydrogen peroxide (10.1g, 0.30mol, 2.0eq) under nitrogen, and then stirred at room temperature for 16 h. After the reaction, the layers were separated, the aqueous phase was extracted 2 times with 50mL acetonitrile, the organic phases were combined and dried over anhydrous sodium sulfate, and after concentration, Compound II-147.36 g was obtained with a yield of 55.8%.
1HNMR(300MHz,DMSO)：δppm：8.52,2H；1.50,2H；2.01,4H；1.67,2H；2.15,2H；1.79,4H；4.96,2H；4.4,2H.
And step 3: synthesis of Compound I-1
Synthesis of triphenyl sulfonium chloride salt
Under nitrogen protection, diphenyl sulfoxide (7.56g, 0.037mol, 1.0eq) and 60mL of anhydrous dichloromethane were charged into a 250mL three-necked flask, and trimethylchlorosilane (12.18g, 0.112mol, 3.0eq) was added dropwise at a temperature below 0 ℃. After the dropwise addition, the temperature was slowly raised to room temperature, and stirring was continued for 1 hour. The reaction mixture was then cooled to 0 ℃ or lower again, and at this temperature, a tetrahydrofuran solution of phenylmagnesium chloride (45ml/2M, 0.113mol, 3.01eq) was added dropwise. After the dropwise addition, the temperature is slowly raised to the room temperature, and the stirring is continued for 2 hours. The reaction was quenched with a small amount of water and 75mL of 0.2N aqueous hydrochloric acid was added. The mixed solution is washed twice by 30mL of ether, and the water phase is the aqueous solution of the triphenyl sulfonium chloride salt and is placed in a dark place for standby.
Synthesis of Compound I-1
Compound II-1(13.1g, 0.023mol, 1.0eq) and 70mL of methanol were added to a 250mL round-bottomed flask and dissolved with stirring. Then, an aqueous solution (0.045mmol, 2.0eq) of the triphenylsulfonium chloride salt prepared in advance was added dropwise while keeping out of the light. And after the dropwise addition, stirring for 16 hours in a dark place. After completion, the mixture was extracted 3 times with 30mL of chloroform, and the organic phases were combined and washed 2 times with 30mL of pure water. The layers were separated, the aqueous phase was removed and the organic phase was concentrated to give compound I-110.55 g, 43.6% yield.
1HNMR(300MHz,DMSO)：δppm：8.52,2H；7.33,12H；7.35,12H；7.36,6H；1.50，2H；2.01，4H；1.67，2H；2.15，2H；1.79，4H；4.96，2H；4.4，2H.
Examples 2 to 6
Examples 2-6 were prepared according to example 1. The starting materials, intermediate compounds II and compounds I used are shown in tables 1 and 2, respectively.
TABLE 1
Figure BDA0003228407810000131
Figure BDA0003228407810000141
TABLE 2
Figure BDA0003228407810000142
Figure BDA0003228407810000151
EXAMPLE 7 preparation of Photoresist composition
The photoresist compositions of the invention and the comparative photoresist compositions were prepared as follows:
100 parts by weight of the resin prepared as above, 4 parts by weight of the photoacid generator prepared as above, and 0.5 parts by weight of tetramethylammonium hydroxide (as a basic additive) were dissolved in 1000 parts by weight of propylene glycol methyl ether acetate, and then the solution was filtered through a 0.2- μm membrane filter, thereby preparing a photoresist composition. The photoacid generators in the photoresist compositions of examples 1 to 7 and comparative example 1 are shown in table 3.
TABLE 3
Photoresist composition numbering Kind of photo-acid generator
Photoresist composition 1 Compound I-1
Photoresist composition 2 Compound I-2
Photoresist composition 3 Compound I-3
Photoresist composition 4 Compound I-4
Photoresist composition 5 Compound I-5
Photoresist composition 6 Compound I-6
Comparative example 1 Photoresist composition Comparative Compound 1
Comparative example 2 Photoresist composition Comparative Compound 2
Comparative example 3 Photoresist composition Comparative Compound 3
Comparative example 4 resist setCompound (I) Comparative Compound 4
Comparative example 5 Photoresist composition Comparative Compound 5
Comparative example 6 Photoresist composition Comparative Compound 6
Comparative example 7 resist composition Comparative Compound 7
Comparative example 8 Photoresist composition Comparative Compound 8
Comparative example 9 Photoresist composition Comparative Compound 9
Comparative example 10 Photoresist composition Comparative Compound 10
Comparative example 11 resist composition Comparative Compound 11
Comparative example Compound 1 bis Triphenylsulfonium salt bis (2-sulfonic acid-2, 2-difluoroethoxy) succinate
Figure BDA0003228407810000161
The procedure for the preparation of bis (triphenylsulfonium salt, bis (2-sulfonic acid-2, 2-difluoroethoxy) succinate is as in example 1.
1HNMR(300MHz,DMSO)：δppm:2.73,4H；4.96,2H；4.4,2H；7.33,12H；7.35,12H；7.36,6H；
Comparative Compounds 2 to 11
Figure BDA0003228407810000171
Comparative compounds 2-9 were prepared according to step 2 and step 3 of example 1.
Comparative compounds 10-11 were prepared according to example 1.
Effect examples and comparative effect examples
The silicon wafer (12 inches) was coated with an anti-reflective coating ARC-29(Nissan Chemical Industries, Ltd.) using a spin coater, then baked at 205 ℃ for 60 seconds to form a 70nm thick organic anti-reflective coating, and then coated with the prepared photoresist composition and dried at 110 ℃ for 90 seconds to form a film having a thickness of 0.20 μm. The resulting structure was exposed to light using an immersion exposure apparatus (1700i, manufactured by ASML co.) and baked at a temperature of 105 ℃ for 60 seconds. Thereafter, the film was developed with a 2.38 wt% aqueous tetramethylammonium hydroxide solution for 40 seconds, and washed and dried. Thereby forming a photoresist pattern using ultrapure water as an immersion medium.
The exposure amount used when a line-and-space (L/S) pattern of 0.10- μm was formed with a reticle width of 1:1 after development was designated as the optimum exposure amount, and the optimum exposure amount was designated as the sensitivity (unit: mJ/cm)2). The minimum pattern size resolved at this time was designated as resolution (unit: nm).
Further, in the case of the Line Edge Roughness (LER), the pattern roughness in a line pitch (L/S) pattern of 0.10- μm formed after development was observed, and the LER (smaller numerical value indicates better LER) (unit: nm) was measured.
The effects of the photoresist compositions of examples 1-6 and comparative examples 1-11 are shown in Table 4.
TABLE 4
Figure BDA0003228407810000181
Figure BDA0003228407810000191
Therefore, the photoresist composition prepared by the photoacid generator has the advantages of high resolution, high sensitivity and low line width roughness, and compared with the comparative photoresist composition, the sensitivity is improved by 25-49%, the resolution is improved by 4-44% and the line width roughness is reduced by 40-74%.

Claims (9)

1. A compound according to formula I:
Figure FDA0003228407800000011
wherein A is I or S;
n is 2 or 3;
r is H, halogen, C1-6Alkyl or C1-6One or more of alkoxy, wherein the number of substituents of R on a benzene ring is 1-5;
y is
Figure FDA0003228407800000012
Quilt Y1Substituted by
Figure FDA0003228407800000013
Or by Y2Substituted by
Figure FDA0003228407800000014
Y1And Y2Independently 1, 2, 3 or 4;
m1、m2、n1and n2Independently 0, 1, 2 or 3;
Y1and Y2Independently of one another is amino, C1-6Alkylamino, carboxyl, C1-6Alkyl carboxyl or C1-6An alkyl group.
2. The compound of formula I according to claim 1, wherein the compound of formula I satisfies one or more of the following conditions:
in R, the halogen is F, Cl, Br or I;
(II) in R, the C1-6Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl;
③ R, C1-6Alkoxy is methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy;
④Y1in (b), the C1-6Alkyl, said C1-6Alkylamino and said C1-6C in alkylcarboxy1-6Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl;
⑤Y2in (b), the C1-6Alkyl, said C1-6Alkylamino and said C1-6C in alkylcarboxy1-6Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
3. The compound of formula I according to claim 1, wherein the compound of formula I satisfies one or more of the following conditions:
r is H;
②Y1and Y2Independently 1 or 2;
③m1、m2、n1and n2Independently 0 or 1;
fourthly, A is S;
n is 3;
⑥Y1and Y2Independently is amino, carboxyl or C1-6An alkyl group.
4. The compound of formula I according to claim 1, wherein R is H;
a is S;
n is 3;
y is
Figure FDA0003228407800000021
Quilt Y1Substituted by
Figure FDA0003228407800000022
Or by Y2Substituted by
Figure FDA0003228407800000023
Y1And Y2Independently 1 or 2;
m1、m2、n1and n2Independently 0 or 1;
Y1and Y2Independently amino, carboxyl or methyl.
5. The compound of formula I according to claim 1, wherein the compound of formula I satisfies one or more of the following conditions:
①
Figure FDA0003228407800000024
is composed of
Figure FDA0003228407800000025
Y is
Figure FDA0003228407800000031
Figure FDA0003228407800000032
6. The compound of formula I according to claim 1, wherein the compound of formula I is any one of the following compounds:
Figure FDA0003228407800000033
Figure FDA0003228407800000041
7. a compound II:
Figure FDA0003228407800000042
wherein Y is as defined in any one of claims 1 to 5; n is an alkali metal.
8. The compound of claim 7, wherein in N, the alkali metal is Li, Na or K.
9. The compound II according to claim 7, wherein said compound II is any one of the following compounds:
Figure FDA0003228407800000043
Figure FDA0003228407800000051
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