WO2018205896A1 - Résine d'oxétane à base de poly (p-hydroxystyrène), et synthèse et utilisation de celle-ci - Google Patents

Résine d'oxétane à base de poly (p-hydroxystyrène), et synthèse et utilisation de celle-ci Download PDF

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WO2018205896A1
WO2018205896A1 PCT/CN2018/085810 CN2018085810W WO2018205896A1 WO 2018205896 A1 WO2018205896 A1 WO 2018205896A1 CN 2018085810 W CN2018085810 W CN 2018085810W WO 2018205896 A1 WO2018205896 A1 WO 2018205896A1
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formula
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polymer
alkyl
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邹应全
郭晔嘉
王政
庞玉莲
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湖北固润科技股份有限公司
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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
    • 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
    • C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • 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
    • C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F112/22—Oxygen
    • 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
    • C08F112/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J137/00—Adhesives based on homopolymers or 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 a heterocyclic ring containing oxygen; Adhesives based on derivatives of such polymers
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur

Definitions

  • This invention relates to poly(p-hydroxystyrene) oxetane resins.
  • This resin can be used as a film-forming resin for a photoresist system.
  • the invention also relates to the preparation of poly(p-hydroxystyrene) oxetane resins and their use as film-forming resins in photoresist systems.
  • the photoresist is an etch-resistant film material whose solubility changes under irradiation or irradiation of a light source such as an ultraviolet light, an excimer laser, an electron beam, an ion beam, or an X-ray. Since its invention in the 1950s, photoresist has become the core process material in the semiconductor industry and is widely used in the manufacture of integrated circuits and printed circuit boards. In the early 1990s, photoresist was applied to the processing of LCD devices, which played an important role in promoting the large size, high definition and colorization of LCD panels. Photoresist also plays a pivotal role in the fine processing of microelectronics manufacturing from micron, submicron, deep submicron to nanoscale.
  • solubility of the photoresist before and after exposure it can be divided into a positive photoresist and a negative photoresist.
  • the solubility of the positive photoresist increases after exposure and development, and the solubility of the negative photoresist decreases after exposure and development.
  • positive photoresists have the advantages of high resolution, strong resistance to dry etching, good heat resistance, easy gel removal, good contrast, etc., but poor adhesion and mechanical strength, and high cost.
  • the negative photoresist has good adhesion to the substrate, acid and alkali resistance, and fast speed. However, due to cross-linking in the exposed area, the solubility is weakened, which causes deformation and swelling during development, thereby limiting its Resolution.
  • Lithography has gone from g-line (436 nm) lithography, i-line (365 nm) lithography, to KrF (deep ultraviolet 248 nm) lithography, ArF (deep ultraviolet 193 nm) lithography, and next-generation extreme ultraviolet (EUV, 13.5).
  • Nm The development of lithography, corresponding to the photoresist of each exposure wavelength also came into being.
  • the key formulation components in the photoresist such as film-forming resins, photoinitiators, and additives, also change, making the overall performance of the photoresist better meet the process requirements.
  • Micro-Electro-Mechanical System is a miniaturized mechatronics intelligent system consisting of three main components: micro-sensor, micro-actuator and micro-energy.
  • the system size is generally micron or even smaller, and the internal structure size is even micron. nanoscale.
  • Micro-electromechanical systems have the advantages of miniaturization, intelligence, integration, multi-function and suitable for mass production. They have broad development prospects in the fields of military, aerospace, information and communication, biomedicine, automatic control, and automobile industry.
  • MEMS fabrication is achieved by a photolithography process. Unlike the pursuit of higher resolution in lithography processes in general integrated circuit fabrication, MEMS fabrication pursues higher aspect ratios, which require photoresists for MEMS to have a certain thickness. In order to meet the needs of the development of MEMS products, thick film photoresist came into being. In general, thick film photoresists require good photosensitivity and aspect ratio, and coating thicknesses typically range to at least 10 microns.
  • thick glue can be directly used as a working part of MEMS devices, or as a sacrificial layer material to fabricate MEMS devices with film structures and cantilever structures, or as a mask layer for wet etching, or as an electroplated Model for making 3D MEMS devices with non-silicon materials. Therefore, with the continuous development of MEMS, it is very important to develop thick film photoresist suitable for MEMS manufacturing.
  • the commercially available thick film lithography positive adhesives mainly include AZ series positive glue, SJR3000 series positive glue, Ma-p100 positive glue and SPR 220-7 positive glue, etc.
  • the negative glue is negative by SU-8 series produced by American MicroChem Company. Glue-based.
  • diazonaphthoquinone positive photoresists mainly composed of phenolic resin, photosensitive compound diazonaphthoquinone and organic solvent.
  • the diazonaphthoquinone compound in the exposed area undergoes photolysis reaction, loses a molecule of nitrogen, and the Wolff rearrangement is converted into hydrazine carboxylic acid, so that the film can be dissolved in the alkaline developing solution.
  • SU-8 series photoresist is an epoxy resin photoresist. Due to its good chemical, optical and mechanical properties, it has become the most widely used and widely used lithographic thick adhesive in MEMS.
  • the main components of the SU-8 photoresist include a bisphenol A type novolac epoxy resin, an organic solvent ( ⁇ -butyrolactone or cyclopentanone), and a small amount of a photoacid generator triarylsulfonium salt. When exposed, the triarylsulfonium salt absorbs photons and releases a strong acid.
  • the epoxy group in the acid-catalyzed epoxy resin undergoes cationic polymerization cross-linking, and the cross-linking reaction grows in chains, which can be formed quickly.
  • the photoacid generator cannot produce acid, and thus cannot catalyze the polymerization and crosslinking of the epoxy group, and the resin is soluble in the developer during development.
  • the sensitization principle of the SU-8 series photoresist is based on cationic photocuring of epoxy resin.
  • Cationic photocuring system is rapidly developing as an important system in UV curing technology. Compared with free radical photocuring system, its most significant advantage is that it is not inhibited by oxygen, the volume shrinkage rate is small, the curing reaction is not easy to terminate, and the light stops. After that, the curing reaction can continue and the toxicity is low. Due to these advantages, cationic photocurable materials are very suitable for use as a major component of thick film photoresists.
  • cationic photocuring systems mainly include vinyl ether systems, epoxy systems, and oxetane systems.
  • the main advantage of the vinyl ether cationic photocuring system is that the curing rate is very fast, there is no induction period, it can be cured at normal temperature, but there are disadvantages such as poor stability, and the viscosity is low, and it is difficult to form a thick film.
  • Epoxy system is the most commonly used cationic photocuring system. It has a wide variety of monomers, low price, good adhesion after curing, high strength and high viscosity. Although curing is affected by environmental temperature and humidity, the curing reaction rate is slow. However, it can be reduced by appropriate process conditions, and is more suitable for thick film photoresist film-forming resins.
  • an epoxy system mainly including novolac epoxy resin, its main performance characteristics are as described for the film-forming resin of SU-8 photoresist described above, which has the disadvantage that the phenolic resin is synthesized by polycondensation reaction.
  • the degree of polycondensation reaction is not easy to control, and the obtained product has a wide molecular weight distribution, and the product needs to be classified and screened, the process flow is complicated, the operation is difficult, and the cost is high. If the molecular weight of the resin is not uniform, the dissolution in the developer is not uniform, which may affect the resolution of the photoresist.
  • the oxetane photocuring system is a relatively new type of cationic photocuring system, and currently has a small number of monomers and is relatively expensive. Compared with the epoxy system, the significant advantage is that the curing is less affected by the ambient temperature, it can be cured at normal temperature, and the curing is thorough. When used for photoresist film-forming resin, this advantage is beneficial to the resin in the exposed area. The light cures the reaction to achieve higher resolution.
  • poly-p-hydroxystyrene In addition to phenolic resins, another type of film-forming resin for photoresists is poly-p-hydroxystyrene and its derivatives.
  • the group has a butyl carbonate, an acetal, a ketal, a silane group and the like.
  • the remarkable advantage of poly(p-hydroxystyrene) is that it is synthesized by polyaddition reaction, so that a resin having a high molecular weight and a narrow molecular weight distribution can be obtained by a cationically controlled living polymerization method, and polyparaxyl styrene is very Good UV light transmission, high molecular weight, narrow molecular weight distribution, good UV light transmission and other characteristics are conducive to improve the resolution of the photoresist.
  • This type of photoresist is a positive photoresist.
  • the imaging principle is: in the exposed area, the acid generated by the acid generator catalyzes the decomposition of the film-forming resin, removes the protective group, and dissolves in the alkaline developer instead of the exposed area.
  • the resin is insoluble in the alkaline developer due to the presence of the protecting group.
  • the imaging principle of the poly-p-hydroxystyrene-based lithographic negative adhesive is: in the exposed region, the acid-catalyzed crosslinking agent reacts with the film-forming resin to cause the exposed resin to be insoluble in the developer, and the non-exposed area is dissolved in the developer. .
  • poly(p-hydroxystyrene) lithographic negative adhesives which are currently developed, and the obtained photoresist is not a thick film photoresist, and is a common photoresist.
  • the inventors of the present invention conducted extensive and intensive research on the film-forming resin of photoresist, in order to find a new film-forming resin for cationic photocurable photoresist.
  • the film-forming resin has the advantages of good ultraviolet light transmittance, large viscosity, thick film formation, complete photocuring, and high resolution.
  • the present inventors have found that the introduction of an oxetane moiety on a polyparaxylene molecule can achieve the aforementioned object.
  • polypara-hydroxystyrene is used as the main structure, and polyparaxyl styrene itself is synthesized by polyaddition reaction, and a resin having a high molecular weight and a narrow molecular weight distribution can be obtained by a cation-controlled living polymerization method, and a poly-p-hydroxy group is obtained.
  • Styrene has good UV light transmission, and high molecular weight, narrow molecular weight distribution, good UV light transmission and other characteristics are beneficial to improve the resolution of the photoresist; a large amount of benzene ring, benzene exists in the resin structure
  • the rigidity of the ring makes the resin have good etching resistance; the oxetane group is introduced into the resin, and the oxetane group can undergo cationic photopolymerization, complete photocuring, no oxygen inhibition, and thus polymerization.
  • the resin When used as a film-forming resin for a photoresist, the resin has the advantages of good ultraviolet light transmittance, large viscosity, thick film formation, complete photocuring, and high resolution.
  • Another object of the present invention is to provide a process for preparing a modified polyparaxyl styrene resin containing an oxetane moiety of the present invention.
  • Still another object of the present invention is to provide a use of the modified polyparaxyl styrene resin containing an oxetane moiety of the present invention as a film-forming resin in a photoresist.
  • Still another object of the present invention is to provide a photoresist comprising the modified polyparaxyl styrene resin containing the oxetane moiety of the present invention.
  • R a -R d are each independently selected from H, halogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkane a group of an oxy group, a C 3 -C 12 cycloalkyl group and a halogenated C 3 -C 12 cycloalkyl group;
  • R is selected from H, halo, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy and halogeno C 1 -C a group of 6 alkoxy groups;
  • n is a number of 20-40.
  • R a -R d are each independently selected from the group consisting of H, chlorine, bromine, C 1 -C 4 alkyl, chloro C 1 -C 4 alkyl, bromo C 1 -C 4 alkyl, C 1 -C 4 a group of alkoxy, chloro C 1 -C 4 alkoxy, bromo C 1 -C 4 alkoxy and C 3 -C 6 cycloalkyl, preferably R a -R d are each independently selected from a group of H, C 1 -C 4 alkyl, halo C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyclopropyl, cyclobutyl and cyclopentyl; and/or
  • R is selected from the group consisting of H, chlorine, bromine, C 1 -C 4 alkyl, chloro C 1 -C 4 alkyl, bromo C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, C 1 - a group of a C 4 alkoxy group, a chloro C 1 -C 4 alkoxy group, a brominated C 1 -C 4 alkoxy group and a C 3 -C 6 cycloalkyl group, preferably R is H, chlorine, C 1 - C 4 alkyl, chloro C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyclopropyl, cyclobutyl or cyclopentyl; and/or
  • n is a number from 24 to 36, preferably a number from 25 to 30.
  • the compound of formula (III) is first reacted with p-toluenesulfonyl chloride to give a compound of formula (IV), which is then reacted with a polymer of formula (II).
  • R a -R d , R and n are each as defined in the first or second term, and X is a halogen, preferably chlorine or bromine, or X is a hydroxyl group.
  • the molar ratio of the catalyst is from 1:0.1 to 1:1:1, preferably from 1:0.6 to 1:1; when X is a hydroxyl group, the polymer of the formula (II) and the basic catalyst are used in an amount such that the polymer of the formula (II)
  • the molar ratio of the monomer unit to the basic catalyst is from 1:0.1 to 1:1, preferably from 1:0.5 to 1:1.
  • phase transfer catalyst preferably a phase transfer catalyst
  • a tetraalkylammonium halide such as a tetra C 1 -C 4 alkylammonium halide such as tetrabutylammonium bromide.
  • a photoresist comprising the polymer of formula (I) according to item 1 or 2 as a film-forming resin.
  • the photoresist according to item 10 which comprises the polymer of the formula (I) according to the item 1 or 2 as a film-forming resin, a photoacid generator, a photopolymerizable monomer, a basic additive, a sensitizer And a photoresist solvent; preferably, the mass ratio of the film-forming resin, photoacid generator, photopolymerizable monomer, basic additive, sensitizer, and photoresist solvent is (30-40): (1 4): (20-25): (1-2): (0-2): (40-50); more preferably the film-forming resin, photoacid generator, photopolymerizable monomer, alkaline additive, The mass ratio of the sensitizer to the photoresist solvent was 35:3.0:25:1.5:1.5:50.
  • the acid agent, the sulfonium salt acid generator and the heterocyclic acid generator have the following general formulae (V), (VI) and (VII):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently phenyl, halophenyl, nitrophenyl, C 6 -C 10 aryl or C a 1- C 10 alkyl substituted benzoyl;
  • Y, Z are non-nucleophilic anions such as triflate, BF 4 - , ClO 4 - , PF 6 - , AsF 6 - or SbF 6 - .
  • the photopolymerizable monomer is N-vinylpyrrolidone, hydroxyethyl methacrylate or a mixture thereof; and/or
  • the basic additive is a tertiary amine and/or a quaternary amine, more preferably any one or more of triethanolamine, trioctylamine and tributylamine; and/or
  • the sensitizer is any one or more of 2,4-diethylthiaxanthone, 9-fluorenyl methanol and 1-[(2,4-dimethylphenyl)azo]-2-naphthol Kind; and/or
  • the photoresist solvent is any one or more of cyclopentanone, ⁇ -butyrolactone, and ethyl acetate.
  • Example 1 is a lithographic image of four photoresists obtained in Example 9;
  • Example 2 is a lithographic image of four photoresists obtained in Example 10.
  • R a -R d are each independently selected from H, halogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkane a group of an oxy group, a C 3 -C 12 cycloalkyl group and a halogenated C 3 -C 12 cycloalkyl group;
  • R is selected from the group consisting of H, halogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy, and halogenated C 1 -C a group of 6 alkoxy groups;
  • n is a number of 20-40.
  • R a - R d is a group on the benzene ring.
  • R a -R d are the same or different from each other, and are each independently selected from the group consisting of H, halogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated a group of a C 1 -C 6 alkoxy group, a C 3 -C 12 cycloalkyl group, and a halogenated C 3 -C 12 cycloalkyl group.
  • R a -R d are each independently selected from the group consisting of H, chlorine, bromine, C 1 -C 4 alkyl, chloro C 1 -C 4 alkyl, bromo C 1 -C 4 alkyl, C a group of 1 -C 4 alkoxy, chloro C 1 -C 4 alkoxy, bromo C 1 -C 4 alkoxy and C 3 -C 6 cycloalkyl.
  • R a -R d are each independently selected from the group consisting of H, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyclopropyl, ring a group of a butyl group and a cyclopentyl group.
  • R is a group on the oxetane ring.
  • R is selected from the group consisting of H, halogen, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy, and halogenated C 1 -C a group of 6 alkoxy groups.
  • R is selected from the group consisting of H, chlorine, bromine, C 1 -C 4 alkyl, chloro C 1 -C 4 alkyl, bromo C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl a group of a C 1 -C 4 alkoxy group, a chloro C 1 -C 4 alkoxy group, a brominated C 1 -C 4 alkoxy group, and a C 3 -C 6 cycloalkyl group.
  • R is H, chlorine, C 1 -C 4 alkyl, chloro C 1 -C 4 alkyl, C 1 -C 4 alkoxy, cyclopropyl, cyclobutyl or cyclopentyl.
  • n represents the number of structural units of the polypara-hydroxystyrene epoxy resin, and is usually a number of from 20 to 40, preferably from 24 to 36, more preferably from 25 to 30.
  • a process for the preparation of a polymer of the formula (I) according to the invention wherein, when X is a halogen, the polymer of the formula (II) is reacted with a compound of the formula (III); When X is a hydroxyl group, the compound of the formula (III) is first reacted with p-toluenesulfonyl chloride to give a compound of the formula (IV), and the compound of the formula (IV) is further reacted with the polymer of the formula (II).
  • R a -R d , R and n are each as defined for the polymer of formula (I), and X is a halogen, preferably chlorine or bromine, or X is a hydroxyl group.
  • the reaction of the polymer of the formula (II) with the compound of the formula (III) is usually carried out in the presence of a basic catalyst.
  • a basic catalyst is one or more of NaOH, KOH, Na 2 CO 3 , K 2 CO 3 . It is particularly preferred that the basic catalyst is K 2 CO 3 and/or KOH.
  • the reaction of the polymer of the formula (II) with the compound of the formula (III) is not particularly limited with respect to the amount of the basic catalyst.
  • the polymer of formula (II) and the basic catalyst are used in an amount such that the molar ratio of monomer units to basic catalyst contained in the polymer of formula (II) is from 1:0.1 to 1:1. It is particularly preferred that the polymer of formula (II) and the basic catalyst are used in an amount such that the molar ratio of monomer units to basic catalyst contained in the polymer of formula (II) is from 1:0.6 to 1:1.
  • the reaction of the polymer of the formula (II) with the compound of the formula (III) generally ensures that the polymer of the formula (II) is sufficiently reacted.
  • the polymer of formula (II) and the compound of formula (III) are used in an amount such that the molar ratio of monomer units contained in the polymer of formula (II) to the compound of formula (III) is generally from 1:1 to 1:3.
  • the polymer of formula (II) and the compound of formula (III) are used in an amount such that the molar ratio of monomer units of formula (II) to compound of formula (III) is from 1:1.8 to 1:2.
  • the reaction of the polymer of the formula (II) with the compound of the formula (III) is usually carried out in a solution.
  • the solvent is one or more selected from the group consisting of ethanol, acetone, ethyl acetate, dichloromethane, and chloroform. It is particularly preferred that the organic solvent is one selected from the group consisting of ethanol and acetone.
  • the reaction of the polymer of the formula (II) with the compound of the formula (III) is required for the reaction conditions such as temperature and pressure.
  • the reaction is carried out at 50-80 °C. It is particularly preferred that the reaction be carried out at 50-70 °C.
  • the reaction time is advantageously from 12 to 15 hours.
  • the reaction pressure is advantageously atmospheric.
  • the reaction of the compound of the formula (III) with p-toluenesulfonyl chloride is usually carried out in a solution.
  • the solvent is one or more selected from the group consisting of pyridine, dichloromethane, and chloroform. It is particularly preferred that the organic solvent is one selected from the group consisting of pyridine and dichloromethane.
  • the molar ratio of the compound of the formula (III) to p-toluenesulfonyl chloride is usually from 1:1 to 1:1.5, preferably from 1:1.2 to 1:1.5.
  • the reaction of the compound of the formula (III) with p-toluenesulfonyl chloride is conventional for the reaction conditions such as temperature and pressure. Preferably, the reaction is carried out at -10 to 10 °C. It is particularly preferred that the reaction be carried out at -5 to 5 °C.
  • the reaction time is advantageously 2-3 hours.
  • the reaction pressure is advantageously atmospheric.
  • the reaction of the polymer of the formula (II) with the compound of the formula (IV) is usually carried out in the presence of a basic catalyst.
  • a basic catalyst is one or more of NaOH, KOH, Na 2 CO 3 , K 2 CO 3 . It is particularly preferred that the basic catalyst is K 2 CO 3 and/or KOH.
  • the reaction of the polymer of the formula (II) with the compound of the formula (IV) is not particularly limited with respect to the amount of the basic catalyst.
  • the polymer of formula (II) and the basic catalyst are used in an amount such that the molar ratio of monomer units to basic catalyst contained in the polymer of formula (II) is from 1:0.1 to 1:1. It is particularly preferred that the polymer of formula (II) and the basic catalyst are used in an amount such that the molar ratio of monomer units to basic catalyst contained in the polymer of formula (II) is from 1:0.5 to 1:1.
  • the reaction of the polymer of the formula (II) with the compound of the formula (IV) is usually carried out in the presence of a phase transfer catalyst.
  • a phase transfer catalyst is a tetraalkylammonium halide such as a tetra C 1 -C 4 alkyl ammonium halide such as tetrabutylammonium bromide.
  • the reaction of the polymer of the formula (II) with the compound of the formula (IV) is not particularly limited with respect to the amount of the phase transfer catalyst.
  • the polymer of formula (II) and the phase transfer catalyst are used in an amount such that the molar ratio of monomer units to phase transfer catalyst in the polymer of formula (II) is from 1:0.01 to 1:0.05. It is particularly preferred that the polymer of formula (II) and the phase transfer catalyst are used in an amount such that the molar ratio of monomer units to phase transfer catalyst contained in the polymer of formula (II) is from 1:0.01 to 1:0.02.
  • the reaction of the polymer of the formula (II) with the compound of the formula (IV) generally ensures that the polymer of the formula (II) is sufficiently reacted.
  • the polymer of formula (II) and the compound of formula (IV) are used in an amount such that the molar ratio of the monomer unit of the polymer of formula (II) to the compound of formula (IV) is generally from 1:1 to 1:2.
  • the polymer of formula (II) and the compound of formula (IV) are used in an amount such that the molar ratio of monomer units of formula (II) to compound of formula (IV) is from 1:1.5 to 1:2.
  • the reaction of the polymer of the formula (II) with the compound of the formula (IV) is usually carried out in a solution.
  • the solvent is one or more selected from the group consisting of ethanol, acetone, ethyl acetate, dichloromethane, and chloroform. It is particularly preferred that the organic solvent is one selected from the group consisting of ethanol and acetone.
  • the reaction of the polymer of the formula (II) with the compound of the formula (IV) is required for the reaction conditions such as temperature and pressure.
  • the reaction is carried out at 60-80 °C. It is especially preferred that the reaction be carried out at 60-70 °C.
  • the reaction time is advantageously from 12 to 15 hours.
  • the reaction pressure is advantageously atmospheric.
  • Step 1) mixing the polymer of formula (II) and a basic catalyst in a solvent to obtain a mixture;
  • Step 2) gradually adding a compound of the formula (III) to the mixture obtained in the step 1) to carry out a reaction;
  • Step 3 After completion of the reaction, the mixture is extracted, dried, and the solvent is evaporated under reduced pressure to give a solid, which is washed, filtered, and dried to give a polymer of the formula (I).
  • the operation of the step 1) can be carried out by first adding a polymer of the formula (II), stirring, introducing nitrogen gas, and then adding a basic catalyst to obtain a mixture.
  • the operation of the step 2) can be carried out by slowly dropwise adding the compound of the formula (III) at 50 to 70 ° C in the mixture obtained in the step 1), and carrying out the reaction for 12 to 15 hours.
  • step 3 The operation of the step 3) can be carried out as follows: after completion of the reaction, the mixture is separated by adding water and dichloromethane, and the organic phase is dried over MgSO 4 , and the solvent is evaporated under reduced pressure to give a solid, washed, filtered and dried to give the formula (I) polymer.
  • the preparation of the polymer of formula (I) can generally be carried out as follows:
  • Step 1 ' in solvent A, p-toluenesulfonyl chloride is added to obtain a mixture;
  • Step 2' gradually adding a compound of the formula (III) to the mixture obtained in the step 1') to carry out a reaction;
  • Step 3' After completion of the reaction, the solid is precipitated by adding water, filtered, washed and dried to obtain a compound of the formula (IV);
  • Step 4' mixing the polymer of the formula (II) with a basic catalyst and a phase transfer catalyst in a solvent B to obtain a mixture;
  • Step 5' gradually adding a compound of the formula (IV) to the mixture obtained in the step 4') to carry out a reaction;
  • Step 6' After completion of the reaction, extraction, drying, and distillation under reduced pressure to give a solid, which is washed, filtered, and dried to give a polymer of formula (I).
  • the operation of the step 1') can be carried out by adding p-toluenesulfonyl chloride in a solvent A, stirring and dissolving, and introducing nitrogen gas to obtain a mixture.
  • the operation of the step 2') can be carried out by gradually adding the compound of the formula (III) to the mixture obtained in the step 1') and reacting in an ice water bath for 2-3 hours.
  • step 3' The operation of the step 3') can be carried out as follows: after completion of the reaction, stirring with ice water to precipitate a solid, filtering, washing, and vacuum drying to obtain a compound of the formula (IV).
  • the operation of the step 4') can be carried out by first adding a polymer of the formula (II) in a solvent B, stirring, introducing nitrogen gas, and further adding a basic catalyst and a phase transfer catalyst to obtain a mixture.
  • step 5' The operation of the step 5') can be carried out by gradually adding the compound of the formula (IV) obtained in the step 3') to the mixture obtained in the step 4'), and reacting at 60 to 70 ° C for 12 to 15 hours.
  • step 6' The operation of the step 6') can be carried out as follows: after completion of the reaction, water and dichloromethane are separated and the organic phase is dried over MgSO 4 , and the solvent is evaporated under reduced pressure to give a solid, which is washed, filtered and dried to give the formula (I) )polymer.
  • a polymer of the formula (I) according to the invention as a film-forming resin in a photoresist.
  • polypara-hydroxystyrene is used as a main structure, and polypara-hydroxystyrene itself is synthesized by addition polymerization, and can be controlled by a cation.
  • the living polymerization method obtains a resin having a high molecular weight and a narrow molecular weight distribution, and the poly-p-hydroxystyrene has excellent ultraviolet light transmittance, and the high molecular weight, narrow molecular weight distribution, and good ultraviolet light transmittance are all characterized. It is beneficial to improve the resolution of the photoresist; there are a large number of benzene rings in the resin structure, and the rigidity of the benzene ring makes the resin have good etching resistance; the oxetane group and the oxetane group are introduced into the resin.
  • the group can undergo cationic photopolymerization, complete photocuring, no oxygen inhibition, so the polymerization reaction is not easy to terminate, and the polymerization can be continued in the dark, and a crosslinked network is easily formed in the exposed area, thereby obtaining a high-resolution lithographic pattern;
  • Another advantage of the heterocyclic butane resin is its high viscosity, so that the resulting film adheres well to the substrate and a thicker photoresist film can be obtained.
  • a photoresist comprising the polymer of formula (I) of the invention as a film-forming resin.
  • the photoresist of the present invention consists essentially of the following components: a polymer of formula (I) as a film-forming resin, a photoacid generator, a photopolymerizable monomer, a basic additive, a sensitizer, and light.
  • Glue solvent Preferably, the mass ratio of the film-forming resin, photoacid generator, photopolymerizable monomer, basic additive, sensitizer, and photoresist solvent is (30-40):(1-4): (20-25): (1-2): (0-2): (40-50).
  • the mass ratio of the film-forming resin, photoacid generator, photopolymerizable monomer, basic additive, sensitizer and photoresist solvent is 35:3.0:25:1.5:1.5:50 .
  • substantially herein is meant that at least 90% by weight, more preferably at least 95% by weight, especially at least 98% by weight, in particular at least 99% by weight, of the total weight of the photoresist is from the formula (I) as a film-forming resin.
  • the photoresist film-forming resin is any one or more of the polymers of the formula (I).
  • the photoacid generator is any one or more of an iodonium salt, a sulfonium salt and a heterocyclic acid generator. More preferably, the iodonium salt acid generator, the sulfonium salt acid generator and the heterocyclic acid generator have the following general formulae (V), (VI) and (VII):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently phenyl, halophenyl, nitrophenyl, C 6 -C 10 aryl or C 1 -C 10 alkyl substituted benzoyl;
  • Y, Z are non-nucleophilic anions such as triflate, BF 4 - , ClO 4 - , PF 6 - , AsF 6 - or SbF 6 - .
  • the photopolymerizable monomer is N-vinylpyrrolidone, hydroxyethyl methacrylate or a mixture thereof.
  • the basic additive is a tertiary amine and/or a quaternary amine, and more preferably any one or more of triethanolamine, trioctylamine and tributylamine.
  • the sensitizer is a sensitizer sensitive to a specific wavelength, such as 2,4-diethylthiazinone, 9-oxime methanol and 1-[(2,4-xylene) Any one or more of azo]-2-naphthol.
  • the photoresist solvent is any one or more of cyclopentanone, ⁇ -butyrolactone and ethyl acetate.
  • the beneficial effect of the polymer of the formula (I) of the invention as a film-forming resin of a photoresist is that polypara-hydroxystyrene is used as a main structure, and polypara-hydroxystyrene itself is synthesized by polyaddition reaction, and a cation can be used.
  • the method of controlled living polymerization obtains a resin having a high molecular weight and a narrow molecular weight distribution, and the poly(p-hydroxystyrene) has excellent ultraviolet light transmittance, and high molecular weight, narrow molecular weight distribution, and good ultraviolet light transmittance are all characterized.
  • the group can undergo cationic photopolymerization, complete photocuring, no oxygen inhibition, so the polymerization reaction is not easy to terminate, and the polymerization can be continued in the dark, and a crosslinked network is easily formed in the exposed area, thereby obtaining a high-resolution lithographic pattern;
  • Another advantage of the oxetane resin is its high viscosity, so that the resulting film adheres well to the substrate and a thicker photoresist film can be obtained.
  • the infrared spectrum was measured by Shimadzu IRAffinity Fourier Transform Infrared Spectrometer, the scanning range was 4000-400 cm -1 , and the samples were processed by KBr tableting.
  • the sample was formulated into a solution having a concentration of 30 ppm using acetonitrile as a solvent, and the ultraviolet absorption spectrum was measured by a Shimadzu UV-2450 ultraviolet-visible spectrophotometer.
  • the measurement range was 200-400 nm, the resolution was 0.1 nm, and the band width was 0.1-5 nm. , stray light is 0.015% or less.
  • the nuclear magnetic data of the obtained product is as follows (d-CDCl 3 ): ⁇ 1.87 methylene chloride in the polystyrene chain; ⁇ 2.76 methine in the polystyrene chain; ⁇ 6.57, 6.82, 6.84 on the benzene ring; ⁇ 2.35 phenyl ring-linked methyl group; ⁇ 3.86 linked to methylene group of phenoxy group and oxetane; methylene group in ⁇ 4.65 oxetane ring; ⁇ 1.25 oxetane a methylene group in an ethyl group of an alkyl group; a methyl group in an ethyl group of ⁇ 0.96 oxetane.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 223 nm, there is no ultraviolet absorption peak above 223 nm, and there is good light transmission in the ultraviolet light region above 223 nm.
  • the nuclear magnetic data of the obtained product is as follows (d-CDCl 3 ): ⁇ 1.87 methylene chloride in the polystyrene chain; ⁇ 2.76 methine in the polystyrene chain; ⁇ 6.53, 6.58, 6.60 H on the benzene ring; ⁇ 3.98 methylene group in the ethoxy group of the benzene ring; ⁇ 1.33 methyl group in the ethoxy group of the benzene ring; ⁇ 4.03 to the methylene group of the phenoxy group and the oxetane; ⁇ 4 a methylene group in a .82 oxetane ring; a methyl group in a methoxy group of ⁇ 3.24 oxetane.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 227 nm, there is no ultraviolet absorption peak above 227 nm, and there is good light transmission in the ultraviolet light region above 227 nm.
  • the nuclear magnetic data of the obtained product is as follows (d-CDCl 3 ): methylene group in the polystyrene chain of ⁇ 1.87; methine in the ⁇ 2.76 polystyrene chain; ⁇ 6.64, H on the 6.88 benzene ring; ⁇ 2. 59 methylene group in the phenyl ring of ethyl; ⁇ 1.24 benzyl ring in the ethyl group; ⁇ 4.64 benzene ring chloromethyl; ⁇ 3.86 linked phenoxy and oxetane Methylene of alkane; methylene group in ⁇ 4.65 oxetane ring; methyl group of ⁇ 1.16 oxetane.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 221 nm, there is no ultraviolet absorption peak above 221 nm, and there is good light transmission in the ultraviolet light region above 221 nm.
  • the nuclear magnetic data of the obtained product is as follows (d-CDCl 3 ): ⁇ 1.87 methylene group in the polystyrene chain; ⁇ 2.76 methine in the polystyrene chain; ⁇ 6.61, 6.84, 6.89 on the benzene ring; a methylene group in a cyclopropyl group of ⁇ 0.51 benzene ring; a methine group in a cyclopropyl group of ⁇ 1.50 benzene ring; a methylene group of ⁇ 3.86 linking a phenoxy group and an oxetane; a methylene group in the ⁇ 4.65 oxetane ring; a methylene group in the ethyl group of ⁇ 1.25 oxetane; and a methyl group in the ethyl group of ⁇ 0.96 oxetane.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 225 nm, there is no ultraviolet absorption peak above 225 nm, and there is good light transmission in the ultraviolet light region above 225 nm.
  • the oxetane-3-ylmethyl ester (0.15 mol) was added dropwise over 0.5 h, after which the resulting reaction mixture was reacted at 60 ° C for 12 h. After reaction completion, 100mL of methylene chloride was added, extracted with water, the organic layer was dried with MgSO 4, the solvent was distilled off under reduced pressure, to give the solid product was washed three times with water, filtered and dried to give the product, was analyzed to be the title compound.
  • the nuclear magnetic data of the obtained product are as follows (d-CDCl 3 ): methylene group in ⁇ 1.87 polystyrene chain; methine in ⁇ 2.76 polystyrene chain; H on ⁇ 7.02 benzene ring; ⁇ 4.64 benzene Cyclomethylmethyl; ⁇ 3.86 methylene group linking phenoxy and oxetane; methylene group in ⁇ 4.65 oxetane ring; methylene group in ⁇ 0.18 cyclopropyl group Base; ⁇ 0.21 methine in cyclopropyl.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 223 nm, there is no ultraviolet absorption peak above 223 nm, and there is good light transmission in the ultraviolet light region above 223 nm.
  • the nuclear magnetic data of the obtained product is as follows (d-CDCl 3 ): methylene group in ⁇ 1.87 polystyrene chain; methine in ⁇ 2.76 polystyrene chain; ⁇ 6.41, 6.77 on the benzene ring; ⁇ 2.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 220 nm, there is no ultraviolet absorption peak above 220 nm, and there is good light transmission in the ultraviolet region above 220 nm.
  • the nuclear magnetic data of the obtained product is as follows (d-CDCl 3 ): methylene group in ⁇ 1.87 polystyrene chain; methine in ⁇ 2.76 polystyrene chain; ⁇ 6.53, 6.58 on benzene ring; ⁇ 3.
  • a methylene group adjacent to oxygen in a phenyl ring-linked propoxy group a methylene group adjacent to a methyl group in a propyl 1.75 benzene ring-linked propoxy group; a ⁇ 0.96 phenyl ring-linked propoxy group Methyl group; ⁇ 3.86 linking methylene group of phenoxy group and oxetane; methylene group in ⁇ 4.65 oxetane ring; methyl group of ⁇ 1.16 oxetane.
  • Ultraviolet absorption spectrum results: the maximum absorption wavelength is 226 nm, there is no ultraviolet absorption peak above 226 nm, and there is good light transmission in the ultraviolet light region above 226 nm.
  • the oxetane-3-ylmethyl ester (0.15 mol) was added dropwise over 0.5 h, after which the resulting reaction mixture was reacted at 60 ° C for 12 h. After reaction completion, 100mL of methylene chloride was added, extracted with water, the organic layer was dried with MgSO 4, the solvent was distilled off under reduced pressure, to give the solid product was washed three times with water, filtered and dried to give the product, was analyzed to be the title compound.
  • the nuclear magnetic data of the obtained product are as follows (d-CDCl 3 ): methylene group in the polystyrene chain of ⁇ 1.87; methine in the ⁇ 2.76 polystyrene chain; ⁇ 6.38, H on the 6.41 benzene ring; ⁇ 2.
  • Ultraviolet absorption spectroscopy results the maximum absorption wavelength is 228 nm, there is no ultraviolet absorption peak above 228 nm, and there is good light transmission in the ultraviolet light region above 228 nm.
  • photoresists were prepared as follows: 30 g of each of the polymers prepared in Examples 1-4, 2 g of 3-nitrophenyl. diphenylthio hexafluorophosphate, 25 g of N were prepared. -vinylpyrrolidone, 1.8 g of trioctylamine, 1 g of 9-oxime methanol and 50 g of ethyl acetate, the above materials are mixed and thoroughly stirred to completely dissolve, and filtered through a 0.45 ⁇ m polytetrafluoroethylene microporous membrane to obtain Four new negative chemical amplification photoresists.
  • photoresists were prepared as follows: 40 g of each of the polymers prepared in Examples 5-8, 3 g of bis(4-tert-butylphenyl)iodotrifluoromethanesulfonate, 20 g of hydroxyethyl methacrylate, 1.5 g of triethanolamine, 1.5 g of 2,4-diethylthiaxanone and 50 g of cyclopentanone, the above materials were mixed and thoroughly stirred to completely dissolve, and passed through 0.45 ⁇ m of polytetrafluoroethylene.
  • Four kinds of new negative chemical amplification photoresists can be obtained by filtering the ethylene microporous membrane.
  • the four negative chemically amplified photoresists obtained in the above Example 9 were respectively coated on a 6-inch single crystal silicon wafer by spin coating (rotation speed: 4000 rpm), baked at 90 ° C for 2 minutes, and cooled to room temperature, and then coated.
  • a good silicon wafer was exposed to an exposure machine having a wavelength of 365 nm, and after baking, it was baked at 110 ° C for 2 minutes, and developed with a propylene glycol methyl ether acetate aqueous solution as a developing solution for 60 s to obtain a lithographic image.
  • the lithographic images of the photoresists obtained in the polymers obtained in Examples 1-4 are shown in Figures 1(a)-(d), respectively.
  • the four negative chemically amplified photoresists obtained in the above Example 10 were respectively coated on a 6-inch single crystal silicon wafer by spin coating (rotation speed: 4000 rpm), baked at 100 ° C for 2 minutes, and cooled to room temperature, and then coated.
  • a good silicon wafer was exposed to an exposure machine having a wavelength of 248 nm, and after baking, it was baked at 100 ° C for 2 minutes, and developed with a propylene glycol methyl ether acetate aqueous solution as a developing solution for 50 s to obtain a lithographic image.
  • the lithographic images of the photoresists obtained in Examples 5-8 were as shown in Figures 2(a)-(d), respectively.
  • Fig. 1 the polymer obtained in the examples 1-4 is used as a film-forming resin, and the obtained photoresist is prepared, and after exposure, development and the like, a clear pattern with a diameter of about 30 ⁇ m can be obtained, and the resolution is high.
  • the graphics are arranged neatly, the edges are complete, and there is no glue or residue.
  • the polymer obtained in the examples 5-8 is used as a film-forming resin, and the obtained photoresist is prepared, and after exposure, development and the like, a film having a relatively large thickness can be obtained, and the obtained lithographic pattern can be obtained. It has a three-dimensional structure with a thickness of up to about 70 ⁇ m and an aspect ratio of up to 1:1.
  • the polymer prepared in the above examples is used for the negative chemical amplification of the photoresist, based on the cationic photocuring of the oxetane group, using a chemical amplification technique, with the poly(p-hydroxystyrene) structure as the main body. Its high molecular weight, narrow molecular weight distribution, and good UV light transmission make the photoresist have good resolution.
  • the introduction of the oxetane structure makes the resin easily form a crosslinked network in the exposed region, thereby obtaining a high-resolution lithographic pattern; in addition, the viscosity of the oxetane resin is large, so that the obtained film is on the substrate.

Abstract

L'invention concerne un polymère de formule (I), un procédé de préparation du polymère de formule (I), l'utilisation du polymère de formule (I) en tant que résine filmogène dans une résine photosensible, et une résine photosensible comprenant le polymère de formule (I) en tant que résine filmogène.
PCT/CN2018/085810 2017-05-12 2018-05-07 Résine d'oxétane à base de poly (p-hydroxystyrène), et synthèse et utilisation de celle-ci WO2018205896A1 (fr)

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