WO2023093598A1 - 基于聚苯乙烯类硫鎓盐及其光刻胶组合物 - Google Patents

基于聚苯乙烯类硫鎓盐及其光刻胶组合物 Download PDF

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WO2023093598A1
WO2023093598A1 PCT/CN2022/132382 CN2022132382W WO2023093598A1 WO 2023093598 A1 WO2023093598 A1 WO 2023093598A1 CN 2022132382 W CN2022132382 W CN 2022132382W WO 2023093598 A1 WO2023093598 A1 WO 2023093598A1
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photoresist
polymer
alkyl
lithography
sulfonium salt
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PCT/CN2022/132382
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French (fr)
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陈金平
王志昊
李嫕
于天君
曾毅
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中国科学院理化技术研究所
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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
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—Styrene
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

  • the invention belongs to the technical field of materials, and in particular relates to a polystyrene-based sulfonium salt and a photoresist composition.
  • Photoresist is a key material for photolithographic pattern transfer in the process of semiconductor device processing.
  • the photoresist is coated on different substrates, and after being irradiated with energy such as beams, electron beams, ion beams or x-rays, the solubility changes, and then the corresponding pattern is transferred to the substrate through developing and etching processes.
  • the resolution achieved by the formed pattern has a decisive influence on the integration of the device, and the comprehensive performance of the photoresist needs to match the development of the current photolithography technology.
  • photoresist is a mixture composed of resin host material, PAG and various trace additives.
  • This simple physical mixing can easily cause the acid generator to form a small area with uneven distribution in the host material, which will affect the photolithographic pattern. edge roughness.
  • this physical mixing makes it difficult to control the diffusion rate of the generated acid in the host material and adversely affects the edge roughness of the pattern.
  • the non-chemically amplified photoresist does not have the process of acid diffusion, which can well overcome the problem of poor pattern quality caused by acid diffusion.
  • the photosensitive group After exposure of this type of photoresist, the photosensitive group directly generates The chemical reaction changes the solubility of the substance after exposure.
  • This single-component non-chemically amplified photoresist avoids the problems of uneven distribution of components and acid diffusion in the chemically amplified photoresist.
  • the present invention at first provides a polymer of sulfonium salt of styrene, the repeating unit of the polymer has the structure shown in the following formula (I):
  • R 1 is selected from sulfonium salt groups; the position of R 1 can be para-position, meta-position or ortho-position; R 2 is selected from H, OH, halogen (such as Cl, F, I), C 1-15 alkyl, C 1-15 alkoxyl group, aryl group; q is selected from the integer of 1-5, the integer of preferred 1-3;
  • X - is an anion, for example selected from halides, alkylsulfonates, haloalkylsulfonates (such as trifluoromethanesulfonate, perfluoropropylsulfonate, perfluorobutylsulfonate), p-toluenesulfonate, tetrafluoro Borate, hexafluorophosphate, bistrifluoromethanesulfonylimide ions.
  • halides alkylsulfonates, haloalkylsulfonates (such as trifluoromethanesulfonate, perfluoropropylsulfonate, perfluorobutylsulfonate), p-toluenesulfonate, tetrafluoro Borate, hexafluorophosphate, bistrifluoromethanesulfonylimide ions.
  • the R 1 is -S + R 3 R 4 , wherein R 3 and R 4 are the same or different, independently selected from C 1-15 alkyl, deuterated C 1-15 alkyl (such as deuterated methyl), aryl, or R 3 , R 4 and the S connected to it together form a 5-8 membered sulfur-containing heterocyclic group, and the sulfur-containing heterocyclic ring may optionally further contain 1-2 Oxygen or sulfur, said sulfur-containing heterocyclic ring is optionally fused with one or two benzene rings; said alkyl, aryl, sulfur-containing heterocyclic group can be replaced by one, two or more (such as 1 - 5) R 1 ' substitutions, each R 1 ' may be the same or different, independently selected from H, oxo, nitro, CN, C 1-15 alkyl, C 1-15 alkoxy.
  • said R 1 is selected from the following groups that are unsubstituted or optionally substituted by one, two or more R 1 ′:
  • R 1 may be selected from the following groups which are unsubstituted or optionally substituted by one, two or more R 1 ':
  • R 1a and R 1b may be the same or different, each independently selected from methyl, ethyl, propyl, isopropyl, butyl, deuterated methyl, R can be selected from H, nitro, ethoxy, ethyl, propyl, butyl, isopropyl, isobutyl; m can be 1 or 2; each R 1 ' can be the same or different, independently of each other is selected from H, nitro, ethoxy, ethyl, propyl, butyl, isopropyl, isobutyl.
  • the polymer has repeating units as shown below:
  • the polymer has a molecular weight of 500-200,000 Daltons, such as 1,000-100,000 Daltons, for example, 5,000-50,000 Daltons.
  • the present invention also provides a method for preparing the polymer as described above, comprising the steps of: the repeating unit is a polymer represented by formula (II):
  • R 3 , R 4 , R 1a , R 1b , Y, m, x, y have the above-mentioned definitions;
  • the reaction can be carried out under the action of a catalyst, and the catalyst can be trifluoromethanesulfonic anhydride or trifluoromethanesulfonic acid;
  • the molar ratio of polystyrene or its copolymer to the sulfoxide compound in the reaction may be 1:(0.3-2), such as 1:(0.5-1), and is exemplarily 1 :0.6.
  • the polymer with the structure represented by the formula (II) is prepared by the following method, comprising: polymerizing styrene and the compound of the formula (III) in a certain proportion to obtain a polymeric compound whose repeating unit is represented by the formula (II) things,
  • x, y, q, R2 are as defined above.
  • the present invention also provides the application of the above polymer as photoresist acid generator or host material.
  • the polymer when used as an acid generator, it can be mixed with other host materials; the other host materials can be any acid-sensitive host materials.
  • the present invention also provides a photoresist composition, comprising a polymer represented by formula (I) as a repeating unit.
  • the photoresist composition includes a repeating unit of a polymer represented by formula (I), a polymer with an acid-sensitive functional group, and a photoresist solvent.
  • the photoresist composition is a one-component photoresist
  • the one-component photoresist is composed of a polymer represented by the formula (I) as a repeating unit and a photoresist solvent.
  • the solubility of the host material changes significantly before and after exposure, and the photoresist performance is better.
  • the content of the polymer in the single-component photoresist is 1%-50% of the total mass of the photoresist, and the rest is photoresist solvent.
  • the photoresist solvent is selected from one or more of the following substances: cyclohexanone, ethyl n-pentanone, ethyl isoamyl ketone, ethanol, acetonitrile, isopropanol, acetone .
  • the present invention also provides a photoresist coating, which comprises a polymer represented by formula (I) as a repeating unit.
  • the present invention also provides a method for preparing the photoresist coating, comprising: spin-coating the photoresist composition on a substrate to form a film to obtain the photoresist coating.
  • the substrate may be a silicon wafer or the like.
  • the invention also provides the application of the photoresist coating in photolithography.
  • the photoresist coating is used in modern lithography techniques such as 365nm lithography, 248nm lithography, 193nm lithography, extreme ultraviolet lithography, nanoimprint lithography or electron beam lithography; especially It is suitable for high-resolution lithography technologies such as 193nm, electron beam lithography and extreme ultraviolet (EUV).
  • modern lithography techniques such as 365nm lithography, 248nm lithography, 193nm lithography, extreme ultraviolet lithography, nanoimprint lithography or electron beam lithography; especially It is suitable for high-resolution lithography technologies such as 193nm, electron beam lithography and extreme ultraviolet (EUV).
  • the polymer of the present invention contains a large amount of polar functional groups, it can be dissolved in polar solvents. When the polymer film is exposed to light, the polar sulfonium salt functional group decomposes, making the polymer less polar, resulting in a solubility difference. If a more polar solvent is selected for development, the polymer can be used as a negative photoresist; if a relatively less polar solvent is selected for development, the polymer can be used as a positive photoresist.
  • the invention provides a styrene sulfonium salt polymer represented by formula (I), which can be used as an acid generator or host material in a photoresist, which contains a photosensitive group sulfonium salt.
  • a styrene sulfonium salt polymer represented by formula (I)
  • the sulfonium salt in the polymer will decompose to produce acid, so it can be used as an acid generator.
  • the sulfonium salt in the polymer decomposes to form sulfide under light, which greatly changes its solubility, so it can also be directly used as the main material in the photoresist for development.
  • the photoresist When it is used as the host material, the photoresist does not need to add an additional acid generator, which can effectively avoid the problem of acid diffusion in the chemically amplified photoresist.
  • the pattern obtained by the photoresist prepared by it has very high resolution and low Line width roughness.
  • the polymer based on styrene sulfonium salt has a long absorption wavelength by changing the structure of sulfonium salt, so that the monomolecular resin can be used not only for deep ultraviolet lithography, but also for ultraviolet lithography (365nm).
  • Fig. 1 is a scanning electron microscope (SEM) image and an AFM image of a thin film of compound (1) in Example 2 of the present invention.
  • Fig. 2 is the thermal weight loss curve of compound (1) in Example 2 of the present invention.
  • Fig. 3 is the ultraviolet exposure pattern of the photoresist containing compound (1) in Example 6 of the present invention.
  • Fig. 4 is the electron beam exposure pattern (negative resist) of the photoresist containing compound (1) in Example 7 of the present invention.
  • Fig. 5 is the ultraviolet exposure pattern of the photoresist containing compound (1) in Example 8 of the present invention.
  • Fig. 6 is the electron beam exposure pattern (positive resist) of the photoresist containing compound (1) in Example 9 of the present invention.
  • halogen includes F, Cl, Br or I.
  • C 1-15 alkyl is understood to mean a linear or branched saturated monovalent hydrocarbon group having 1 to 15 carbon atoms.
  • C 1-6 alkyl refers to straight and branched chain alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms.
  • the alkyl group is for example methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl Base, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, etc. or their isomers.
  • C 1-15 alkoxy is to be understood as -OC 1-15 alkyl, wherein C 1-15 alkyl has the above definition.
  • aryl should be understood to mean an aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring with 6-20 carbon atoms, preferably “C 6-14 aryl”. For example, phenyl, naphthyl, fluorenyl, anthracenyl, and the like.
  • Example 2 The polymer (1) in Example 2 was dissolved in acetonitrile to obtain a 30 mg/ml solution, which was filtered through a microporous filter with a pore size of 0.22 ⁇ m to obtain a spin-coating solution, which was spin-coated on a silicon substrate to form a film.
  • the uniformity of the film was analyzed by scanning electron microscope SEM and AFM respectively, as shown in Figure 1. It can be seen from the figure that the obtained film is very uniform without crystallization.
  • a kind of photoresist formula and its negative development and ultraviolet lithography the polymer (1) of embodiment 2 is dissolved in acetonitrile, makes the solution of mass concentration 5%, filters with the microporous filter of aperture 0.22 ⁇ m , to obtain a spin-coating solution, spin-coat a film on a silicon substrate, bake at 100°C for 3 minutes, and perform an exposure experiment (254nm) on the prepared film.
  • the exposure time is 1min, and it is developed with deionized water to obtain a very Clear streaks, see Figure 3.
  • the width of the photolithographic stripes is 2 ⁇ m.
  • a kind of photoresist formula and its negative development and electron beam lithography the polymer (1) of embodiment 2 is dissolved in acetonitrile, makes the solution of mass concentration 5%, uses the microporous filter of aperture 0.22 ⁇ m Filtrate to obtain a spin-coating solution, spin-coat on a silicon substrate to form a film, bake at 100°C for 3 minutes, expose the prepared film to an electron beam, and develop it with a high-polarity developer to obtain very clear stripes (200nm), see Figure 4.
  • a kind of photoresist formula and its positive development and ultraviolet lithography the polymer (1) of embodiment 2 is dissolved in acetonitrile, makes the solution of mass concentration 5%, filters with the microporous filter of aperture 0.22 ⁇ m , to obtain a spin-coating solution, spin-coat a film on a silicon substrate, bake at 100°C for 3 minutes, and perform an exposure experiment (254nm) on the prepared film.
  • the exposure time is 1min, and it is developed with isopropanol to obtain a very Clear stripes, see Figure 5, the width of the photolithographic stripes is 2 microns.
  • a kind of photoresist formula and its positive development and electron beam lithography the polymer (1) of embodiment 2 is dissolved in acetonitrile, makes the solution of mass concentration 5%, uses the microporous filter of aperture 0.22 ⁇ m Filtrate to obtain a spin-coating solution, spin-coat on a silicon substrate to form a film, bake at 100°C for 3 minutes, expose the prepared film to an electron beam, and develop it with a low-polarity developer to obtain a very clear 60nm Stripes, see Figure 6.

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Abstract

本发明公开了一种包含下式(I)所示的重复单元的苯乙烯硫鎓盐聚合物作为产酸剂或光刻胶主体材料的应用。该类光刻胶材料在各种极性溶剂中都具有很好的溶解性，适于制成薄膜，该硫鎓盐聚合物本身包含酸敏感基团，无需添加额外产酸剂，能够有效避免化学放大光刻胶中酸扩散的问题，可以直接作为光刻胶主体材料，作为单一组分的光刻胶体系，用于不同类型的光刻。亦或者可以作为产酸剂与酸敏感主体材料混合作为光刻胶材料。通过改变硫鎓盐结构，使其具有长的吸收波长，也能够用于紫外光刻和深紫外光刻。

Description

基于聚苯乙烯类硫鎓盐及其光刻胶组合物
本发明要求享有于2021年11月24日向中国国家知识产权局提交的，专利申请号为202111407329.6，名称为“基于聚苯乙烯类硫鎓盐及其光刻胶组合物”的在先申请的优先权。该在先申请的全文通过引用的方式结合于本发明中。
技术领域
本发明属于材料技术领域，具体涉及一类基于聚苯乙烯类硫鎓盐以及光刻胶组合物。
背景技术
随着半导体工业的迅速发展，半导体器件的集成度越来越高，对光刻技术要求达到的分辨率也越来越高，高分辨光刻图形的质量也提出了更高的要求，尤其是图形的线宽粗糙度(LWR)和线边缘粗糙度(LER)要求越来越严苛。光刻胶是半导体器件加工过程中，光刻图形转移的关键材料。将光刻胶涂覆在不同基底上，通过光束、电子束、离子束或x射线等能量辐射后，溶解度发生变化，再通过显影、刻蚀工艺将对应的图案转移到基底上，光刻胶形成的图案所能达到的分辨率对器件的集成度具有决定影响，光刻胶的综合性能需要匹配当前光刻技术的发展。
目前，常规的高分辨光刻胶都采用化学放大胶，“化学放大”的概念是由IBM公司在1982年提出，其中光致产酸剂(Photo Acid Generator，PAG)是光刻胶组分中的关键组成部分。所谓“化学放大”是指PAG在光照后分解产生酸，酸引发一系列化学反应，使得光照区域和非光照区域的光刻胶材料溶解性发生显著变化，然后通过显影就可以实现图案转移，因此光致产酸剂的产酸效率、产酸剂在 材料中的分布均匀性对图案质量具有重要作用。通常光刻胶是由树脂主体材料、PAG以及各种微量添加剂组成的混合物，这种简单的物理混合很容易造成产酸剂在主体材料中形成不均匀分布的微小区域，从而会影响光刻图案的边缘粗糙度。另一方面，这种物理混合使得产生的酸在主体材料中的扩散速度很难控制，对图案的边缘粗糙度产生不利影响，这些原因限制了化学放大光刻胶的发展。
相比而言，非化学放大光刻胶不存在酸扩散的过程，可以很好的克服由于酸扩散导致的图形质量变差的问题，这类光刻胶在曝光后，光敏感基团直接发生化学反应，使曝光后的物质发生溶解度变化，这种单组份的非化学放大光刻胶避免了化学放大光刻胶中各组分分布不均、酸扩散等问题。
发明内容
为改善上述技术问题，本发明首先提供了一种苯乙烯的硫鎓盐的聚合物，所述聚合物的重复单元具有包含如下式(I)所示结构：
Figure PCTCN2022132382-appb-000001
其中：x和y表示聚合物中两种单体的含量百分比，x+y＝1，0.3＜x≤1，x例如为0.5、0.72；y例如为0.28、0.5；
R 1选自硫鎓盐基团；R 1的位置可以为对位、间位或邻位；R 2选自H、OH、卤素(如Cl、F、I)、C 1-15烷基、C 1-15烷氧基、芳基；q选自1-5的整数，优选1-3的整数；
X –为阴离子，例如选自卤离子、烷基磺酸根、卤代烷基磺酸根(如三氟甲磺酸根、全氟丙基磺酸根、全氟丁基磺酸根)、对甲苯磺酸根、四氟硼酸根、六氟磷酸根、双三氟甲烷磺酰亚氨离子。
根据本发明的实施方案，所述R 1为-S +R 3R 4，其中，R 3、R 4相同或不同，独立的选自C 1-15烷基、氘代C 1-15烷基(如氘代甲基)、芳基，或者R 3、R 4和与其相连的S一起形成5-8元含硫杂环基，所述含硫杂环任选的还可以再含有1-2个氧或硫，所述含硫杂环任选的与一个或两个苯环稠和；所述烷基、芳基、含硫杂环基可以被一个、两个或更多个(例如1-5个)R 1’取代，每个R 1’可以相同或不同，彼此独立地选自H、氧代、硝基、CN、C 1-15烷基、C 1-15烷氧基。
根据本发明的实施方案，所述R 1选自无取代或任选被一个、两个或更多个R 1’取代的以下基团：
Figure PCTCN2022132382-appb-000002
其中，
Figure PCTCN2022132382-appb-000003
表示取代基与主体结构中苯环的连接键；R 1a和R 1b可以相同或不同，各自独立地选自C 1-15烷基、氘代C 1-15烷基或被一个、两个或更多个R d取代的苯基；每个R d相同或不同，彼此独立地选自H、硝基、C 1-15烷基、C 1-15烷氧基；m可以选自0-5的整数；Y选自C、O、S、C(＝O)；
根据本发明的实施方案，R 1可以选自无取代或任选被一个、两个或更多个R 1’取代的以下基团：
Figure PCTCN2022132382-appb-000004
R 1a和R 1b可以相同或不同，各自独立地选自甲基、乙基、丙基、异丙基、丁基、氘代甲基、
Figure PCTCN2022132382-appb-000005
R d可以选自H、硝基、乙氧基、乙基、丙基、丁基、异丙基、异丁基；m可以为1或2；每个R 1’可以相同或不同，彼此独立地选自H、硝基、乙氧基、乙基、丙基、丁基、异丙基、异丁基。
作为实例，所述聚合物具有如下所示的重复单元：
Figure PCTCN2022132382-appb-000006
其中，x和y具有上文所述的定义。
根据本发明的实施方案，所述聚合物的分子量为500-200000道尔顿，例如1000-100000道尔顿，还例如为5000-50000道尔顿。
本发明还提供如上所述聚合物的制备方法，包括如下步骤：将重复单元为式(II)所示的聚合物：
Figure PCTCN2022132382-appb-000007
x、y、q、R 2如上所定义，
与亚砜类化合物反应得到重复单元为式(I)所示的聚合物；
任选的，将重复单元为式(I)所示的聚合物与相应的阴离子溶液进行离子交换，得到不同阴离子的聚苯乙烯类硫鎓盐。
所述亚砜类化合物可以为R 3-S(＝O)-R 4，例如选自：
Figure PCTCN2022132382-appb-000008
其中，R 3、R 4、R 1a、R 1b、Y、m、x、y具有上文所述的定义；
根据本发明的实施方案，所述反应可以在催化剂作用下进行，所述催化剂可以为三氟甲磺酸酐或三氟甲磺酸；
根据本发明的实施方案，所述反应中聚苯乙烯或其共聚物与亚砜类化合物的摩尔比可以为1:(0.3-2)，例如为1:(0.5-1)，示例性为1:0.6。
根据本发明，将聚苯乙烯与R 3-S(＝O)-R 4反应，得到重复单元为式(I)所示的聚合物；
根据本发明，所述式(II)所示结构的聚合物由如下方法制备，包括，将苯乙烯与式(III)化合物按一定比例进行聚合，得到重复单元为式(II)所示的聚 合物，
Figure PCTCN2022132382-appb-000009
x、y、q、R 2如上所定义。
本发明还提供上述聚合物用作光刻胶产酸剂或主体材料的应用。
根据本发明的实施方案，所述聚合物作为产酸剂时，可以与其他主体材料混合；所述其他主体材料可以为任意的酸敏感主体材料。
本发明还提供一种光刻胶组合物，包括重复单元为式(I)所示的聚合物。
根据本发明，所述光刻胶组合物包括重复单元为式(I)所示的聚合物、具有酸敏感官能团的聚合物和光刻胶溶剂。
根据本发明，所述光刻胶组合物为单组分光刻胶，所述单组分光刻胶由重复单元为式(I)所示的聚合物和光刻胶溶剂组成。
根据本发明的实施方案，所述单组分光刻胶中，所述聚合物中式(I)所示的重复单元的x值大于0.5时，曝光前后主体材料的溶解性变化明显，光刻胶的性能更好。
根据本发明的实施方案，所述单组分光刻胶中所述聚合物的含量是光刻胶总质量的1％-50％，其余均为光刻胶溶剂。
根据本发明的实施方案，所述光刻胶溶剂选自下列物质中的一种或多种：环己酮、乙基正戊酮、乙基异戊酮、乙醇、乙腈、异丙醇、丙酮。
本发明还提供一种光刻胶涂层，包括重复单元为式(I)所示的聚合物。
本发明还提供所述光刻胶涂层的制备方法，包括，将所述光刻胶组合物旋涂在基底上成膜，得到所述光刻胶涂层。
在一个实施方式中，所述基底可以为硅片等。
本发明还提供所述光刻胶涂层在光刻中的应用。
在一个实施方式中，所述光刻胶涂层用于365nm光刻、248nm光刻、193nm光刻、极紫外光刻、纳米压印光刻或电子束光刻等现代光刻技术中；尤其适用于193nm、电子束光刻和极紫外(EUV)等高分辨光刻技术中。
本发明的聚合物中由于含有大量的极性官能团，可以溶解在极性溶剂中。当聚合物薄膜被曝光后，极性的硫鎓盐官能团分解，使聚合物的极性减小，从而产生了溶解度差异。如果选择较大极性的溶剂进行显影，则该聚合物可作为负性光刻胶；如果选择相对小极性的溶剂进行显影，则该聚合物可作为正性光刻胶。
有益效果
本发明提供了一种式(I)所示的苯乙烯硫鎓盐聚合物，可作为光刻胶中的产酸剂或主体材料，其包含光敏感基团硫鎓盐。在光照下，聚合物中的硫鎓盐会分解产生酸，因此可以作为产酸剂。同时，聚合物中的硫鎓盐在光照下分解形成硫化物，从而使其溶解性发生较大的改变，因此也可以直接作为光刻胶中的主体材料用于显影。当其作为主体材料时，光刻胶无需添加额外产酸剂，能够有效避免化学放大光刻胶中酸扩散的问题，其制备的光刻胶所得到的图案具有非常高的分辨率和低的线宽粗糙度。基于苯乙烯硫鎓盐聚合物通过改变硫鎓盐结构，使其具有长的吸收波长，使得该单分子树脂不仅可以用于深紫外光刻，也可以用于紫外光刻(365nm)。
附图说明
图1为本发明实施例2中化合物(1)薄膜的扫描电子显微镜(SEM)图和AFM图。
图2为本发明实施例2中化合物(1)的热失重曲线图。
图3为本发明实施例6中含化合物(1)的光刻胶的紫外曝光图案。
图4为本发明实施例7中含化合物(1)的光刻胶的电子束曝光图案(负胶)。
图5为本发明实施例8中含化合物(1)的光刻胶的紫外曝光图案。
图6为本发明实施例9中含化合物(1)的光刻胶的电子束曝光图案(正胶)。术语定义与说明
除非另有定义，否则本文所有科技术语具有的含义与权利要求主题所属领域技术人员通常理解的含义相同。
“更多个”表示三个或三个以上。
术语“卤素”包括F、Cl、Br或I。
术语“C 1-15烷基”应理解为表示具有1～15个碳原子的直链或支链饱和一价烃基。例如，“C 1-6烷基”表示具有1、2、3、4、5、或6个碳原子的直链和支链烷基。所述烷基是例如甲基、乙基、丙基、丁基、戊基、己基、异丙基、异丁基、仲丁基、叔丁基、异戊基、2-甲基丁基、1-甲基丁基、1-乙基丙基、1,2-二甲基丙基、新戊基、1,1-二甲基丙基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、2-乙基丁基、1-乙基丁基、3,3-二甲基丁基、2,2-二甲基丁基、1,1-二甲基丁基、2,3-二甲基丁基、1,3-二甲基丁基或1,2-二甲基丁基等或它们的异构体。
术语“C 1-15烷氧基”应理解为-O-C 1-15烷基，其中C 1-15烷基具有上述定义。
术语“芳基”应理解为表示具有6～20个碳原子的芳香性单环、双环或三环烃环，优选“C 6-14芳基”。例如，苯基、萘基、芴基、蒽基等。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通 过已知方法制备。
实施例1.
制备聚苯乙烯，合成路线图如下：
Figure PCTCN2022132382-appb-000010
具体步骤：在500ml三口瓶中，加入苯乙烯(100ml)，AIBN(2g)，然后加入THF(200ml)。鼓泡30min。在70℃条件下反应24h，将反应液滴入甲醇中沉淀。所得产物真空干燥。使用GPC测试重均分子量约为2000道尔顿。不同分子量苯乙烯合成也可采用其它方法或直接购买。
实施例2.
制备聚合物(1)，合成路线图如下：
Figure PCTCN2022132382-appb-000011
具体步骤：在500ml Schlenk瓶中加入实施例1中制备的聚苯乙烯，然后加入溶剂DCM(200ml)，DMSO(1eq)。在-40℃，惰性气体条件下，滴加三氟甲烷磺酸酐(2eq)。室温搅拌过夜，将产物用二甲基亚砜溶解后，滴入正己烷和乙醚的混合液中沉淀，得聚合物(1)，x为0.72，y为0.28，真空干燥。 1H NMR(400MHz,DMSO)δ(ppm)7.67(s,2H),6.81(s,2H),3.16(s,4.3H),0.9-1.8(s,3H)。
实施例3.
制备聚合物(2)，合成路线图如下：
Figure PCTCN2022132382-appb-000012
具体步骤：在500ml Schlenk瓶中加入实施例1中制备的聚苯乙烯，然后加入溶剂DCM(200ml)，二苯基亚砜(0.6eq)。在-40℃，惰性气体条件下，滴加三氟甲烷磺酸酐。室温搅拌过夜，将产物用二氯甲烷溶解后，滴入正己烷中沉淀，得到聚合物(2)，x为0.5，y为0.5，真空干燥。 1H NMR(400MHz,DMSO)δ(ppm)6.7-7.8(m,9.5H),0.9-1.8(s,3H)。
实施例4
将实施例2中的聚合物(1)溶于乙腈中，制得30mg/ml的溶液，用孔径0.22μm的微孔过滤器过滤，得到旋涂液，在硅基底上进行旋涂制膜，分别用扫描电镜SEM和AFM对薄膜均匀度进行分析，见附图1，从图中可以看出所得到的薄膜非常均匀，无结晶现象。
实施例5
测定实施例2中制备得到的聚合物(1)热稳定性，结果显示其分解温度达到了200℃以上，具有很好的热稳定性，见附图2。
实施例6
一种光刻胶配方及其负性显影和紫外光刻：将实施例2的聚合物(1)溶于乙腈中，制得质量浓度5％的溶液，用孔径0.22μm的微孔过滤器过滤，得到旋涂液，在硅基底上进行旋涂制膜，在100℃下烘烤3分钟，将制备得到的薄膜进行曝光实验(254nm)，曝光时间为1min，使用去离子水显影，得到非常清晰的条纹， 见图3。光刻条纹的宽度为2微米。
实施例7
一种光刻胶配方及其负性显影和电子束光刻：将实施例2的聚合物(1)溶于乙腈中，制得质量浓度5％的溶液，用孔径0.22μm的微孔过滤器过滤，得到旋涂液，在硅基底上进行旋涂制膜，在100℃下烘烤3分钟，将制备得到的薄膜进行电子束曝光，使用大极性的显影液显影，得到非常清晰的条纹(200nm)，见图4。
实施例8
一种光刻胶配方及其正性显影和紫外光刻：将实施例2的聚合物(1)溶于乙腈中，制得质量浓度5％的溶液，用孔径0.22μm的微孔过滤器过滤，得到旋涂液，在硅基底上进行旋涂制膜，在100℃下烘烤3分钟，将制备得到的薄膜进行曝光实验(254nm)，曝光时间为1min，使用异丙醇显影，得到非常清晰的条纹，见图5，光刻条纹的宽度为2微米。
实施例9
一种光刻胶配方及其正性显影和电子束光刻：将实施例2的聚合物(1)溶于乙腈中，制得质量浓度5％的溶液，用孔径0.22μm的微孔过滤器过滤，得到旋涂液，在硅基底上进行旋涂制膜，在100℃下烘烤3分钟，将制备得到的薄膜进行电子束曝光，使用小极性的显影液显影，得到非常清晰的60nm条纹，见图6。
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种苯乙烯的硫鎓盐聚合物，所述聚合物的重复单元具有包含如下式(I)所示结构；
    Figure PCTCN2022132382-appb-100001
    其中：x和y表示聚合物中两种单体的含量百分比，x+y＝1，0.3＜x≤1；
    R 1选自硫鎓盐基团；R 1的位置可以为对位、间位或邻位；R 2选自H、OH、卤素(如Cl、F、I)、C 1-15烷基、C 1-15烷氧基、芳基；q选自1-5的整数，优选1-3的整数；
    X –为阴离子，例如选自卤离子、烷基磺酸根、卤代烷基磺酸根(如三氟甲磺酸根、全氟丙基磺酸根、全氟丁基磺酸根)、对甲苯磺酸根、四氟硼酸根、六氟磷酸根、双三氟甲烷磺酰亚氨离子。
  2. 根据权利要求1所述的聚合物，其特征在于，R 1为-S +R 3R 4，其中，R 3、R 4相同或不同，独立的选自C 1-15烷基、氘代C 1-15烷基、芳基，或者R 3、R 4和与其相连的S一起形成5-8元含硫杂环基，所述含硫杂环任选的还可以再含有1-2个氧或硫，所述含硫杂环任选的与一个或两个苯环稠和；所述烷基、芳基、含硫杂环基可以被一个、两个或更多个R 1’取代；每个R 1’可以相同或不同，彼此独立地选自H、氧代、硝基、CN、C 1-15烷基、C 1-15烷氧基。
  3. 根据权利要求1或2所述的聚合物，其特征在于，R 1选自无取代或任选被一个、两个或更多个R 1’取代的以下基团：
    Figure PCTCN2022132382-appb-100002
    其中，
    Figure PCTCN2022132382-appb-100003
    表示取代基与主体结构中苯环的连接键；R 1a和R 1b可以相同或不同，各自独立地选自C 1-15烷基、氘代C 1-15烷基或被一个、两个或更多个R d取代的苯基；每个R d相同或不同，彼此独立地选自H、硝基、C 1-15烷基、C 1-15烷氧基；m可以选自0-5的整数；Y选自C、O、S、C(＝O)。
  4. 根据权利要求1-3任一项所述的聚合物，其特征在于，R 1选自无取代或任选被一个、两个或更多个R 1’取代的以下基团：
    Figure PCTCN2022132382-appb-100004
    R 1a和R 1b可以相同或不同，各自独立地选自甲基、乙基、丙基、异丙基、丁 基、氘代甲基、
    Figure PCTCN2022132382-appb-100005
    R d选自H、硝基、乙氧基、乙基、丙基、丁基、异丙基、异丁基；m为1或2；每个R 1’可以相同或不同，彼此独立地选自H、硝基、乙氧基、乙基、丙基、丁基、异丙基、异丁基。
  5. 根据权利要求1-4任一项所述的聚合物，其特征在于，式(I)所示重复单元选自如下结构：
    Figure PCTCN2022132382-appb-100006
    其中，x和y具有权利要求1-4任一项所述的定义。
  6. 权利要求1-5任一项所述的聚合物的制备方法，其特征在于，所述方法包括如下步骤：
    将重复单元为式(II)所示的聚合物：
    Figure PCTCN2022132382-appb-100007
    x、y、q、R 2如权利要求1-5任一项所定义，
    与亚砜类化合物反应得到重复单元为式(I)所示的聚合物；
    任选的，将重复单元为式(I)所示的聚合物与相应的阴离子溶液进行离子交换，得到不同阴离子的聚苯乙烯类硫鎓盐；
    所述亚砜类化合物可为R 3-S(＝O)-R 4，例如选自：
    Figure PCTCN2022132382-appb-100008
    其中，R 3、R 4、R 1a、R 1b、Y、m、x、y具有权利要求1-5任一项所述的定义；
    优选地，所述反应在催化剂作用下进行，所述催化剂为三氟甲磺酸酐或三氟甲磺酸。
  7. 权利要求1-5任一项所述聚合物用作光刻胶产酸剂或主体材料的应用。
  8. 一种光刻胶组合物，包括权利要求1-5任一项所述的聚合物；
    优选的，所述光刻胶组合物包括权利要求1-5任一项所述的聚合物、具有酸敏感官能团的聚合物和光刻胶溶剂；
    优选的，所述光刻胶组合物为单组分光刻胶，所述单组分光刻胶由权利要求1-5任一项所述的聚合物和光刻胶溶剂组成；
    优选地，所述单组分光刻胶中，所述聚合物中式(I)所示重复单元的x值大于0.5；
    优选地，所述单组分光刻胶中所述聚合物的含量是光刻胶总质量的1％-50％，其余均为光刻胶溶剂；
    优选地，所述光刻胶溶剂选自下列物质中的一种或多种：环己酮、乙基正戊酮、乙基异戊酮、乙醇、乙腈、异丙醇、丙酮。
  9. 一种光刻胶涂层，包括权利要求1-5任一项所述的聚合物。
  10. 权利要求1-5任一项所述聚合物、权利要求7所述光刻胶组合物和/或权利要求8所述光刻胶涂层在光刻中的应用；
    优选地，所述聚合物、所述光刻胶组合物和/或光刻胶涂层用于365 nm光刻、248nm光刻、193nm光刻、极紫外光刻、纳米压印光刻或电子束光刻中。
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JP2006259508A (ja) * 2005-03-18 2006-09-28 Fuji Photo Film Co Ltd ポジ型レジスト組成物及びそれを用いたパターン形成方法
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JP2008065114A (ja) * 2006-09-08 2008-03-21 Fujifilm Corp ポジ型レジスト組成物及びそれを用いたパターン形成方法
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JPH06247925A (ja) * 1993-02-19 1994-09-06 Sanshin Chem Ind Co Ltd ビニル化合物およびその重合体
JP2006259508A (ja) * 2005-03-18 2006-09-28 Fuji Photo Film Co Ltd ポジ型レジスト組成物及びそれを用いたパターン形成方法
JP2008007743A (ja) * 2006-05-30 2008-01-17 Hyogo Prefecture 感光性樹脂及び感光性組成物
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