CN108178807B - Photoacid generator and preparation method and application thereof - Google Patents
Photoacid generator and preparation method and application thereof Download PDFInfo
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- CN108178807B CN108178807B CN201611122773.2A CN201611122773A CN108178807B CN 108178807 B CN108178807 B CN 108178807B CN 201611122773 A CN201611122773 A CN 201611122773A CN 108178807 B CN108178807 B CN 108178807B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing 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
Abstract
The invention relates to a photoacid generator, a preparation method and application thereof. Specifically, the invention discloses a photoacid generator which comprises a polymer skeleton and acid-generating active groups bonded to the polymer skeleton, wherein 50-100 wt% of the acid-generating active groups are positioned at the tail end of the polymer skeleton. The invention also discloses a preparation method and application of the photoacid generator. The photoacid generator adopts a polymer framework, and the acid-generating active group is basically positioned at the tail end of the polymer framework, so the photoacid generator has the advantages of high quantum efficiency, high acid-generating efficiency, low diffusion and low volatility of decomposition products.
Description
Technical Field
The invention relates to the field of materials, in particular to a photoacid generator and a preparation method and application thereof.
Background
Photoresists are multi-component mixtures that undergo solubility changes upon exposure to light of a particular wavelength, with one of the exposed and unexposed portions being readily removed by a developer, exposing the surface to be further etched or modified. Chemically amplified photoresists (CARs) contain a photoacid generator (PAG), a substance that photolytically generates an acid. An important class of these are onium salts. After illumination, iodonium or sulfonium ions are degraded, and the anion part obtains protons to form acid to catalyze the decomposition of an alkenyl ester structure in the photoresist.
The photoacid generator is the most important component in the photoresist, other than the photosensitive resin. The design of the photoresist is not independent of the design and synthesis of the photoacid generator. Therefore, when designing a photoresist, it is necessary to consider the light transmittance of a photoacid generator, quantum efficiency, diffusion distance of itself, diffusion distance of generated acid, and the like. These properties directly affect the resolution, Line Width Roughness (LWR), profile, etc. of the photoresist.
The active unit positions of the traditional polymeric PAG are randomly distributed on a high molecular main chain, so that the traditional polymeric PAG is easily wrapped by a high molecular chain, and the quantum efficiency and the diffusion efficiency of generated acid are low.
In order to meet the increasing demands of the market, the development of a photoacid generator with better performance is urgently needed in the field.
Disclosure of Invention
The invention aims to provide a photoacid generator with a novel structure and better performance, and a preparation method and application thereof.
In a first aspect of the present invention, there is provided a photoacid generator comprising a polymer skeleton and an acid-generating active group bonded to the polymer skeleton, wherein 50 to 100 wt% of the acid-generating active groups are located at a terminal of the polymer skeleton.
In another preferred embodiment, in the photoacid generator, 60 to 99 wt% of the acid-generating active groups are located at the terminal of the polymer backbone, preferably 70 to 95 wt%, more preferably 80 to 90 wt%.
In another preferred example, 10 to 100 mol% of the terminals of the photoacid generator are the acid-generating active groups.
In another preferred embodiment, 20 to 90 mol% of the terminals of the photoacid generator are the acid generating active groups, preferably 30 to 80 mol%, more preferably 40 to 60 mol%.
In another preferred embodiment, the acid-producing reactive group is covalently bonded to the polymeric backbone, and the covalently bonded precursor of the acid-producing reactive group has a bonding site selected from the group consisting of: halogen, hydroxyl, amino, imino, or combinations thereof.
In another preferred embodiment, the covalently bonded precursor of the acid generating active group is an onium salt type structural unit selected from the group consisting of: sulfonium, iodonium, or combinations thereof.
In another preferred embodiment, the onium salt type structural unit has a structure represented by formula I:
X-Y+formula I
In the formula, Y+Has a structure selected from the group consisting of: r1R2R3S+、R5R6I+Or a combination thereof;
R1、R2、R3may be the same or different and are each independently selected from the group consisting of: substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 RingAlkyl, substituted or unsubstituted C6-C18 aryl, -R4(C ═ O) -substituted or unsubstituted C6-C18 aryl, 5-10 membered heteroaromatic ring containing 1-2 heteroatoms selected from S, O, N, -R4-a substituted or unsubstituted C6-C18 aryl, or a combination thereof;
R4is a substituted or unsubstituted C1-C6 alkylene group;
the substitution means substitution with 1 or more groups selected from the group consisting of: C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, halogen, hydroxy, amino, imino, -O- (C1-C6 alkyl-O)n- (C1-C6 alkyl), -O- (C1-C6 alkyl) - (fully fluorinated C1-C6 alkyl), or combinations thereof; n is a positive integer selected from the group consisting of: 0. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10;
and R is1、R2And R3At least 1 of which is substituted with a group selected from: halogen, hydroxy, amino, imino, or combinations thereof;
optionally, R1、R2And R3Wherein two groups are formed as an S-containing 5-10 membered heterocyclic ring, said S-containing 5-10 membered heterocyclic ring optionally containing one or more heteroatoms O;
optionally, R1、R2And R3Wherein two groups are directly linked and form a 5-membered ring with S or a 6-membered ring containing 1 or 2S by a linkage selected from the group consisting of: -S-, -O-;
R5、R6each independently, which may be the same or different, is a substituted or unsubstituted C6-C18 aryl group; the substitution means substitution with 1 or more groups selected from the group consisting of: substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C6-C18 aryl, halogen, hydroxy, amino, imino, or combinations thereof; and R is5、R6At least 1 of which is substituted with a group selected from: halogen, hydroxy, amino, imino, or combinations thereof;
X-has a structure selected from the group consisting of: (R)7(SO2))(R8(SO2))N-、(R7(SO2))(R8(SO2))(R9(SO2))C-、R10(SO3)-Or a combination thereof;
R7、R8、R9may be the same or different and are each independently selected from the group consisting of: a fully fluorinated C1-C6 alkyl group, a fully fluorinated phenyl group, -phenyl- (fully fluorinated or unsubstituted C1-C6 alkyl), - (fully fluorinated C1-C5 alkylene) -O-fully fluorinated C1-C6 alkyl, - (fully fluorinated C1-C5 alkylene) -fully fluorinated 6-membered heterocycle containing 1 oxygen atom, - (C1-C3 alkylene) - (7-10 membered bridged ring containing a C ═ O group), or a combination thereof;
optionally, R7、R8Is connected to contain- (SO)2)N-(SO2) -a fully fluorinated 5-10 membered heterocyclic ring;
R10has a structure selected from the group consisting of: fluoro or unsubstituted C6-C10 aryl, fluoro or unsubstituted C1-C10 alkyl, R11((C＝O)O)R12(C6-C12 bridged ring);
R11and R12Is a substituted or unsubstituted C1-C6 alkyl, said substitution being by halogen.
In another preferred embodiment, the C3-C10 cycloalkyl is a cycloalkyl selected from the group consisting of: a C3-C10 monocyclic ring, a C3-C10 bridged ring, or a combination thereof.
In another preferred embodiment, the C6-C18 aryl group is selected from the group consisting of: phenyl, naphthyl, anthracenyl, phenanthryl, pyrenyl, or combinations thereof.
In another preferred embodiment, the halogen is selected from the group consisting of: F. cl, Br, I, or a combination thereof.
In another preferred embodiment, Y+Has a structure selected from the group consisting of:
wherein n is a positive integer selected from the group consisting of: 0. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.
In another preferred embodiment, X-Has a structure selected from the group consisting of:
in another preferred embodiment, the covalently bonded precursor of the macromolecular scaffold has a bonding site selected from the group consisting of: halogen, hydroxyl, amino, imino, or combinations thereof.
In another preferred embodiment, the molecular weight of the polymeric backbone is from 500 to 10000 dalton, preferably from 1000 to 7000 dalton, more preferably from 2000 to 4000 dalton.
In another preferred embodiment, the polymer skeleton has a structure selected from the group consisting of: chain, star, tree, comb, or combinations thereof.
In another preferred embodiment, the covalently bonded precursor of the macromolecular skeleton is selected from the group consisting of: substituted polymethyl methacrylate, substituted polyacrylate, substituted C1-C50 alkyl, substituted (C1-C10 alkyl) - [ O- (C1-C10 alkyl)]m-O- (C1-C10 alkyl), or a combination thereof; the substitution means substitution with at least one group selected from the group consisting of: halogen, hydroxy, amino, imino, or combinations thereof; m is a positive integer selected from the group consisting of: 1. 2, 3, 4, 5, 6 and 7.
In another preferred embodiment, the acid production efficiency of the photoacid generator is increased by at least 20%, preferably 30%, and more preferably 50% compared to the photoacid generator in which the acid-producing active groups are randomly distributed and bound to the polymer backbone, under the same illumination intensity and the same illumination time.
In another preferred embodiment, when the photoacid generator is in a solvent having a polarity similar to that of the photoacid generator, the skeleton of the photoacid generator is in an extended state.
In another preferred example, when the photoacid generator is located in a solvent having a polarity dissimilar to that of the photoacid generator, the skeleton of the photoacid generator is in a contracted state.
In another preferred embodiment, when the photo-acid generator is used for photoetching, the roughness of the obtained lines is less than or equal to 6 percent, preferably less than or equal to 5 percent, and more preferably less than or equal to 4 percent.
In another preferred embodiment, the photoacid generator has one or more characteristics selected from the group consisting of:
1) the diffusion distance of the photoacid generator is less than or equal to 5nm (preferably less than or equal to 4nm, and more preferably less than or equal to 3 nm);
2)1g of the photo-acid generator has a volatility of less than or equal to 20% (preferably less than or equal to 15%, more preferably less than or equal to 10%) after being exposed to light with a wavelength of 193 nm.
In a second aspect of the present invention, there is provided a method for producing the photoacid generator of the first aspect of the present invention, comprising the steps of:
reacting a polymer backbone compound a with a covalently bonded precursor of an acid generating active group in an inert solvent to form a photoacid generator according to the first aspect of the present invention:
polymer backbone compound a + covalently bonded precursor of acid-producing active group → photoacid generator.
In another preferred embodiment, the polymer skeleton compound a is selected from the group consisting of: substituted polymethyl methacrylate, substituted polyacrylate, substituted C2-C40 alkyl, substituted (C1-C10 alkyl) - [ O- (C1-C10 alkyl)]m-O- (C1-C10 alkyl), or a combination thereof; the substitution means substitution with at least one group selected from the group consisting of: halogen, hydroxy, amino, imino, or combinations thereof; m is a positive integer selected from the group consisting of: 1. 2, 3, 4, 5, 6 and 7.
In another preferred embodiment, the covalently bonded precursor of the acid generating reactive group and the photoacid generator are as defined in the first aspect of the invention.
In a third aspect of the present invention there is provided a composite material comprising or consisting of a photoacid generator according to the first aspect of the present invention.
In another preferred example, the composite material is photoresist.
In another preferred embodiment, the photoacid generator of the first aspect of the present invention is present in an amount of 5 to 40 wt%, preferably 10 to 30 wt%, more preferably 15 to 25 wt%, based on the total weight of the composite material.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a schematic view of solvent-controlled stretching morphology of polymeric PAG.
Detailed Description
The present inventors have conducted extensive and intensive studies for a long time and have unexpectedly prepared a novel photoacid generator through a large number of screenings. Specifically, in the photoacid generator, the skeleton is a polymer, and the active unit for generating acid is basically located at the terminal of the polymer skeleton, so that the photoacid generator has the advantages of high quantum efficiency, high acid generation efficiency, low diffusion and low volatility of decomposition products, and lines obtained by photoetching with the photoacid generator have very low roughness. On this basis, the inventors have completed the present invention.
Photoacid generators
The invention provides a photoacid generator which comprises a polymer skeleton and an acid-generating active group bonded to the polymer skeleton, wherein 40-100 wt% of the acid-generating active group is positioned at the tail end of the polymer skeleton.
In another preferred embodiment, in the photoacid generator, the lower limit of the content of the acid-generating active group located at the terminal of the polymer skeleton is selected from the group consisting of: 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%.
In another preferred embodiment, in the photoacid generator, the upper limit of the content of the acid-generating active group located at the terminal of the polymer skeleton is selected from the group consisting of: 80 wt%, 85 wt%, 90 wt%, 95 wt%, 99 wt%.
In another preferred embodiment, in the terminal of the photoacid generator, the lower limit of the content of the acid-generating active group in the terminal is selected from the group consisting of: 5% mole, 10% mole, 15% mole, 20% mole, 25% mole, 30% mole, 35% mole, 40% mole.
In another preferred embodiment, in the terminal of the photoacid generator, the upper limit of the content of the acid-generating active group in the terminal is selected from the group consisting of: 60% mole, 65% mole, 70% mole, 75% mole, 80% mole, 85% mole, 90% mole, 95% mole, 100% mole.
In the present invention, the acid-generating reactive group is covalently bonded to the polymer backbone, and the covalently bonded precursor of the acid-generating reactive group has a bonding site including (but not limited to) the following group: halogen, hydroxyl, amino, imino, or combinations thereof.
In the present invention, the covalently bonded precursor of the acid generating active group is an onium salt type structural unit including (but not limited to) the following group: sulfonium, iodonium, or combinations thereof.
In another preferred embodiment, the onium salt type structural unit has a structure represented by formula I:
X-Y+formula I
In the formula, Y+Has a structure selected from the group consisting of: r1R2R3S+、R5R6I+Or a combination thereof;
R1、R2、R3may be the same or different and are each independently selected from the group consisting of: substituted or unsubstituted C3-C8 alkyl, substituted or unsubstituted C5-C8 cycloalkyl, substituted or unsubstituted C10-C16 aryl, -R4(C ═ O) -substituted or unsubstituted C8-C14 aryl, 6-8 membered heteroaromatic ring containing 1-2 heteroatoms selected from S, O, N, -R4-a substituted or unsubstituted C8-C14 aryl, or a combination thereof;
R4is a substituted or unsubstituted C2-C4 alkylene group;
the substitution means substitution with 1 or more groups selected from the group consisting of: C2-C4 alkyl, substituted or unsubstituted C2-C4 alkoxy, halogen, hydroxy, amino, imino, -O- (C2-C4 alkyl-O)n- (C2-C4 alkyl), -O- (C2-C4 alkyl) - (fully fluorinated C2-C4 alkyl), or combinations thereof; n is a positive integer selected from the group consisting of: 0. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10;
and R is1、R2And R3At least 1 of which is substituted with a group selected from: halogen, hydroxy, amino, imino, or combinations thereof;
optionally, R1、R2And R3Wherein two groups are formed as an S-containing 6-8 membered heterocyclic ring, said S-containing 6-8 membered heterocyclic ring optionally containing one or more heteroatoms O;
optionally, R1、R2And R3In which two radicals are directly connected to each otherAnd joined to form a 5-membered ring with S or a 6-membered ring containing 1 or 2S by a linkage selected from the group consisting of: -S-, -O-;
R5、R6each independently, which may be the same or different, is a substituted or unsubstituted C6-C14 aryl group; the substitution means substitution with 1 or more groups selected from the group consisting of: substituted or unsubstituted C2-C4 alkyl, substituted or unsubstituted C2-C4 alkoxy, substituted or unsubstituted C6-C14 aryl, halogen, hydroxy, amino, imino, or combinations thereof; and R is5、R6At least 1 of which is substituted with a group selected from: halogen, hydroxy, amino, imino, or combinations thereof;
X-has a structure selected from the group consisting of: (R)7(SO2))(R8(SO2))N-、(R7(SO2))(R8(SO2))(R9(SO2))C-、R10(SO3)-Or a combination thereof;
R7、R8、R9may be the same or different and are each independently selected from the group consisting of: a fully fluorinated C2-C4 alkyl group, a fully fluorinated phenyl group, -phenyl- (fully fluorinated or unsubstituted C2-C46 alkyl), - (fully fluorinated C2-C4 alkylene) -O-fully fluorinated C2-C4 alkyl, - (fully fluorinated C2-C4 alkylene) -fully fluorinated 6-membered heterocycle containing 1 oxygen atom, - (C1-C3 alkylene) - (7-10 membered bridged ring containing a C ═ O group), or a combination thereof;
optionally, R7、R8Is connected to contain- (SO)2)N-(SO2) -a fully fluorinated 6-8 membered heterocyclic ring;
R10has a structure selected from the group consisting of: fluoro or unsubstituted C6-C10 aryl, fluoro or unsubstituted C2-C8 alkyl, R11((C＝O)O)R12(C6-C12 bridged ring);
R11and R12Is a substituted or unsubstituted C2-C4 alkyl, said substitution being by halogen.
In another preferred embodiment, the cycloalkyl group is a cycloalkyl group selected from the group consisting of: a monocyclic ring, a bridged ring, or a combination thereof.
Specifically, since the acid-generating active group of the photoacid generator of the present invention is substantially located at the terminal of the backbone polymer chain (or polymer backbone), the photoacid generator is a polymer PAG whose terminal is very active. Compared with small molecular PAG, the high molecular PAG has the advantages of short diffusion distance and small volatility of decomposition products after exposure, and can improve the contrast of the photoresist, thereby improving the resolution of the photoresist.
Compared with the traditional high molecular PAG, the acid-producing active group of the photo-acid generator is basically positioned at the tail end of the skeleton high molecular chain (or a high molecular skeleton), so that the photo-acid generator can be prevented from being wrapped by the high molecular chain, the quantum efficiency and the diffusion of the generated acid of the photo-acid generator are superior to those of the common high molecular PAG, the performance of the low molecular PAG can be achieved or approached, and the photo-acid generator has the advantage of low diffusion of the high molecular PAG.
In addition, when the macromolecular PAG structure is designed, the structure of the PAG unit and the hydrophilicity (hydrophobicity) and lipophilicity (lipophilicity) of the macromolecular framework unit are changed, so that the solvent can be adjusted to change the stretching morphology of the macromolecular PAG in subsequent application, and the solubility, the dispersion uniformity, the acid production efficiency and the diffusion rate of the macromolecular PAG in an acid-sensitive matrix can be regulated and controlled.
FIG. 1 is a schematic diagram of solvent-controlled polymeric PAG stretching morphology, wherein P represents an acid-generating active group, A represents a linking group, and Core represents a polymeric backbone.
It is understood that, because the acid-producing active groups in the photoacid generator are positioned at the terminal ends of the backbone polymer, the acid-producing center of the photoacid generator is less affected by the microenvironment of the backbone polymer, and is closer to the acid-producing performance of the small-molecule PAG.
Typically, the photoacid generator has a structure selected from the group consisting of:
P-A is ｃA single-side end-capped chain type of formulｃA I,
P1-A-P2formula II, a double-sided end-capped chain,
It is understood that, since the acid-generating active group is substantially located at the terminal of the polymer skeleton in the photoacid generator of the present invention, the photoacid generator has very high acid-generating efficiency when irradiated with light. In addition, because the microenvironment (such as chemical environment) of the acid-generating active groups in the photoacid generator is more consistent when the photoacid generator is irradiated with light, the diffusion of the generated acid is more uniform, and the roughness of the lines generated by final photoetching is significantly lower.
It should be understood that the above principle analysis is only used for explaining the present invention, but not to limit the scope of the present invention in any way.
Preparation method
The invention also provides a preparation method of the photoacid generator, which comprises the following steps:
reacting a polymeric backbone compound a with a covalently bonded precursor of an acid generating active group in an inert solvent to form the photoacid generator:
polymer backbone compound a + covalently bonded precursor of acid-producing active group → photoacid generator.
In the invention, a structure and a molecular weight controllable high molecular skeleton are prepared by a living polymerization method, and the terminal reaction site is connected with various photo-acid generators containing bonding sites, thereby obtaining the high molecular photo-acid generator with the terminal end capped by the photo-acid generator.
Applications of
The invention also provides a composite material comprising or consisting of the photoacid generator.
In another preferred example, the composite material is photoresist.
In another preferred embodiment, the photoacid generator of claim 1 is contained in an amount of 5 to 40 wt%, preferably 10 to 30 wt%, more preferably 15 to 25 wt%, based on the total weight of the composite material.
In the present invention, the polymeric photoacid generators would be expected to be useful in deep ultraviolet lithography, including dry and immersion.
Compared with the prior art, the invention has the following main advantages:
(1) the photoacid generator has the advantages of high quantum efficiency, low diffusion, and low volatility of decomposition products;
(2) the photo-acid generator has high acid generation efficiency, and lines obtained by photoetching with the photo-acid generator have very low roughness;
(3) the preparation method has the advantage of simple process.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Universal test method
It is to be understood that the acid generation efficiency and roughness as described herein are measured using test methods common in the art.
EXAMPLE 1 preparation of photoacid Generator 1
Preparation of PMMA-Br:
a25 ml test tube was charged with 0.08 mmol of methyl bromobenzoate and 0.04 mmol of CuBr, and freeze-thaw degassed for 3 cycles, and finally blanketed with argon. Then 24 mmol MMA and 0.04 mmol pentamethyldiethylenetriamine were added to another test tube, and after two cycles of freeze-thaw and degassing, the mixture was transferred to the above argon-protected test tube. The reaction was warmed to 90 ℃ and held for 4 hours. After the reaction was complete, the plug was opened and the system was cooled to room temperature. The reaction solution was diluted with tetrahydrofuran and passed through a neutral alumina column. The obtained polymer was repeatedly dissolved and precipitated with tetrahydrofuran and n-hexane three times. Filtering and drying to obtain white powdery PMMA-Br polymer.
Preparation of end-capped intermediate 1:
to the eaton reagent (1.3 ml) was added phenol (4.0 mmol). After the mixture was stirred for 30 minutes, diphenylsulfoxide 2.0 mmol was added. The reaction was stirred at room temperature overnight and the resulting mixture was poured into aqueous potassium perfluorobutylsulfonate (810 mg, 2.4 mmol, 20 ml deionized water). After stirring vigorously for 30 minutes, methylene chloride was added to the system to extract intermediate 1. The organic phase was washed five times with distilled water, concentrated and dried. Purification of the crude product by column chromatography (gradient eluent dichloromethane and dichloromethane/methanol 19:1 mixed solvent) afforded intermediate 1 in 38% yield.
Preparation of photoacid generator 1:
to a supported tube was added 1.0 g of PMMA-Br polymer and 200 mg of intermediate 1, 300 mg of cesium carbonate and a catalytic amount of potassium iodide. After the gas was pumped out three times, the system was in a nitrogen atmosphere. 3 ml of N, N-dimethylformamide was added and the system was heated to 60 ℃ and left at this temperature for 8 hours. After the reaction was complete, the N, N-dimethylformamide was removed under high vacuum. The crude product was purified by column chromatography (eluent dichloromethane and dichloromethane/methanol 19:1 mixed solvent) to afford photoacid generator 1.
According to the determination, at least 60% of the acid-producing active groups converted from the intermediate 1 in the photoacid generator 1 are located at the terminal of the polymer backbone polymethyl methacrylate, and at least 50% of the terminals in the photoacid generator 1 are the acid-producing active groups converted from the intermediate 1, and the acid-producing efficiency of the photoacid generator 1 is very high, which is much higher than that of a conventional photoacid generator in which the acid-producing active groups are uniformly distributed (increased by about 65%).
Example 2 preparation of Photoresist 1
A photoresist 1 is prepared by using the photoacid generator 1 obtained in example 1 according to a conventional method, wherein the weight content of the photoacid generator 1 in the photoresist 1 is 20 wt%.
Through determination: the roughness of the lines obtained by photoetching the photoresist 1 is less than or equal to 4 percent.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. A photoacid generator comprising a polymer skeleton and an acid-generating active group bonded to the polymer skeleton, wherein 50 to 100 wt% of the acid-generating active groups in the photoacid generator are located at a terminal of the polymer skeleton; compared with a photoacid generator with acid-producing active groups randomly distributed and combined on the macromolecular skeleton, the acid-producing efficiency of the photoacid generator is improved by at least 20% under the same illumination intensity and the same illumination time; and the photoacid generator has a structure selected from the group consisting of:
wherein P represents an acid-producing active group, A represents a linking group, and Core represents a polymer skeleton.
2. The photoacid generator according to claim 1, wherein 10 to 100 mol% of the terminals of the photoacid generator are the acid-generating active groups.
3. The photoacid generator of claim 1 wherein said acid-generating reactive group is covalently bonded to said polymeric backbone and the covalently bonded precursor of said acid-generating reactive group has a bonding site selected from the group consisting of: halogen, hydroxyl, amino, imino, or combinations thereof.
4. A photoacid generator as claimed in claim 3, characterized in that the covalently bonded precursor of the acid generating active group is an onium salt type structural unit selected from the group of: sulfonium, iodonium, or combinations thereof.
5. The photoacid generator of claim 3 wherein the covalently bonded precursor of the polymeric backbone has a bonding site selected from the group consisting of: halogen, hydroxyl, amino, imino, or combinations thereof.
6. The photoacid generator of claim 3, wherein the acid generation efficiency of the photoacid generator is increased by at least 30% compared to a photoacid generator in which the acid generating active groups are randomly distributed and bound to the polymer backbone under the same illumination intensity and the same illumination time.
7. The photoacid generator according to claim 6, wherein the roughness of the resulting line is 6% or less when the photoacid generator is used for photolithography.
8. The photoacid generator of claim 1 wherein the photoacid generator has one or more characteristics selected from the group consisting of:
1) the diffusion distance of the photoacid generator is less than or equal to 5 nm;
2)1g of the photoacid generator has a volatility of less than or equal to 20% after being exposed by light with a wavelength of 193 nm.
9. A method for producing the photoacid generator according to claim 1, comprising the steps of:
reacting a polymeric backbone compound with a covalently bonded precursor of an acid generating active group in an inert solvent to form the photoacid generator:
polymer backbone compound + covalently bonded precursor of acid-producing active group → photoacid generator.
10. A composite material comprising or consisting of the photoacid generator of claim 1.
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| CN1727998A (en) * | 2005-04-06 | 2006-02-01 | 常州华钛化学有限公司 | Photosensitive agent for producing acid containing fluorin-aether structured multi functional groups |
| CN101080673A (en) * | 2004-12-20 | 2007-11-28 | 东京应化工业株式会社 | Resist composition for liquid immersion exposure and method for resist pattern formation |
| CN102718902A (en) * | 2012-03-09 | 2012-10-10 | 北京师范大学 | Poly p-hydroxystyrene based chemically amplified one-component photoresist material, and synthetic method and application thereof |
| CN105669889A (en) * | 2016-01-28 | 2016-06-15 | 北京师范大学 | Styrene derivative-methacrylate copolymer containing photo-acid generation groups as well as preparation and application of styrene derivative-methacrylate copolymer |
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| CN101080673A (en) * | 2004-12-20 | 2007-11-28 | 东京应化工业株式会社 | Resist composition for liquid immersion exposure and method for resist pattern formation |
| CN1727998A (en) * | 2005-04-06 | 2006-02-01 | 常州华钛化学有限公司 | Photosensitive agent for producing acid containing fluorin-aether structured multi functional groups |
| CN102718902A (en) * | 2012-03-09 | 2012-10-10 | 北京师范大学 | Poly p-hydroxystyrene based chemically amplified one-component photoresist material, and synthetic method and application thereof |
| CN105669889A (en) * | 2016-01-28 | 2016-06-15 | 北京师范大学 | Styrene derivative-methacrylate copolymer containing photo-acid generation groups as well as preparation and application of styrene derivative-methacrylate copolymer |
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