Photoresist composition as well as preparation method and application thereof

Abstract

The invention relates to the technical field of photoresist compositions, in particular to a photoresist composition as well as a preparation method and application thereof. The photoresist composition is prepared from the following raw materials: (A) a photo-initiation multifunctional group resin polymer, (B) a cationic photoinitiator, (C) a film-forming agent, (D) a silicon-containing auxiliary agent and (E) a fluorine-containing compound, the photo-initiated multifunctional group resin polymer comprises a multifunctional group epoxy resin and a hydroxyl-containing oligomer. The photoresist composition is applied to the technical field of photoetching, and is applied to a soft / hard substrate to prepare a permanent photoresist pattern. And the ultraviolet light exposure energy can be reduced, and better resolution and attachment effect can be obtained.

Description

Technical Field

[0001] The invention relates to the technical field of photoresist compositions, and in particular to a photoresist composition and a preparation method and application thereof. Background Art

[0002] Photoresists can achieve optical imaging and are currently used in the field of semiconductor and micro-electromechanical systems technology. Optical imaging is achieved by exposing the photoresist coating on the substrate to patterned radiation, but such an operation will cause the solubility of the material in the photoresist coating to change, so that the exposed and unexposed areas can be selectively removed by treatment with a suitable developer composition. Positive or negative photoimageable coatings can be obtained by increasing or decreasing the solubility of the photoresist material in the developer according to the degree of exposure to radiation. It has been applied in the fields of micromechanical components, electronic circuits (including radio frequency components), optical component inkjet printing heads, DNA sequencing chips, chip laboratory technology, micro-propulsion, adaptive lenses, pixelated optical filters and various types of sensors. In recent years, it has also been applied and valued in display technology for computer and mobile device applications, but it is usually required that the photoimageable coating can produce uniform spin-coated films in films with a thickness greater than ten microns and high aspect ratio images with vertical sidewall distribution (the height-width ratio that defines the imaging feature).

[0003] The Chinese patent application number 202211583173.1 discloses a photoresist composition, a method for photoresist patterning, and a method for film layer patterning. The photoresist layer formed by the photoresist composition has good corrosion resistance to the etching liquid used in the etching process after heating and exposure treatment; however, there is no disclosed solution to the technical problems of uniformity of the spin-coated film and high aspect ratio images with vertical sidewall distribution.

[0004] Therefore, providing a photoresist composition that can form a uniform spin-coated film and has a high aspect ratio image with a vertical sidewall distribution is a major technical problem that needs to be solved at present. Summary of the invention

[0005] In order to solve the above problems, the first aspect of the present invention provides a photoresist composition, the preparation raw materials of which include: components A, B, C, D, and E, wherein component A includes a photoinitiator multifunctional group resin polymer, component B includes a cationic photoinitiator, component C includes a film-forming agent, component D includes a silicon-containing auxiliary agent, and component E includes a fluorine-containing compound; the photoinitiator multifunctional group resin polymer contains a multifunctional epoxy resin and a hydroxyl-containing oligomer.

[0006] In one embodiment, the photoinitiated multifunctional resin polymer comprises a multifunctional epoxy resin A1 and a hydroxyl-containing oligomer A2.

[0007] In one embodiment, the weight portion of the multifunctional epoxy resin in the photoresist composition is 25-75 parts; the weight portion of the hydroxyl-containing oligomer in the photoresist composition is 0.2-12 parts.

[0008] In a preferred embodiment, the weight portion of the multifunctional epoxy resin in the photoresist composition is 50-75 parts; the weight portion of the hydroxyl-containing oligomer in the photoresist composition is 0.5-8 parts.

[0009] In order to make the photoresist composition have an excellent high aspect ratio, a vertical sidewall structure, reduce the resolution and adhesion of the negative permanent photoresist pattern on the silicon wafer, make it have good processing performance in an aqueous developer, and have the easy removability and flexibility required by the micro-electromechanical system (MEMS), the inventors found in the experimental process that by selecting a multifunctional epoxy resin and a hydroxyl-containing oligomer to form a photo-initiated multifunctional resin polymer, the resolution and adhesion of the negative permanent photoresist pattern on the silicon wafer can be reduced. In addition, the toughness of the photoresist composite film can be improved to avoid the state where the edge of the photoresist composite film is easily broken during hot pressing.

[0010] In one embodiment, the multifunctional epoxy resin comprises one or more epoxy resins according to Formula I to Formula XII:

[0011]

[0012] The multifunctional epoxy resin in Formula I is selected from EPON SU-8 of HEXION USA, and has an epoxy equivalent of 195-230 g / eq.

[0013]

[0014] The multifunctional epoxy resin in Formula II is selected from EPON 1031 of HEXION USA, and has an epoxy equivalent of 195-230 g / eq.

[0015]

[0016] The multifunctional epoxy resin in Formula III is selected from HEXION EPON 828 of the United States, and has an epoxy equivalent of 185-192 g / eq.

[0017]

[0018] The multifunctional epoxy resin in Formula IV is selected from bisphenol A jER of Mitsubishi Chemical TM 157S70, epoxy equivalent is 200-220g / eq.

[0019]

[0020] The multifunctional epoxy resin in Formula V is selected from bisphenol A jER of Mitsubishi Chemical TM YX7110s, epoxy equivalent is 1100g / eq.

[0021]

[0022] The multifunctional epoxy resin in Formula VI is selected from Nippon Kayaku Co., Ltd. Tokyo NC-3000H, and has an epoxy equivalent of 270-300 g / eq.

[0023]

[0024] The multifunctional epoxy resin in Formula VII is NER-7403 selected from Nippon Kayaku Co., Ltd. Tokyo, and has an epoxy equivalent of 200-500 g / eq.

[0025]

[0026] The multifunctional epoxy resin in Formula VIII is selected from BPA phenolic epoxy resin SQAN-205, epoxy equivalent weight is 190-230g / eq.

[0027]

[0028] The multifunctional epoxy resin in Formula IX is selected from Trifunctional phenolic epoxy resin SQSN-331, epoxy equivalent weight is 158-178g / eq.

[0029]

[0030] The multifunctional epoxy resin in the formula X is pentaerythritol tetraglycidyl ether, and the epoxy equivalent is 58-80 g / eq.

[0031]

[0032] The multifunctional epoxy resin in the formula XI is a hydrogenated bisphenol A epoxy resin selected from Tohto Kasei Co., Ltd. of Japan or Jiangsu Tailter, with a model of Tailuck-ST3000 and an epoxy equivalent of 220-240 g / eq.

[0033]

[0034] The multifunctional epoxy resin in Formula XII is a 4,4'-diaminodiphenylmethane epoxy resin selected from Shanghai Haodeng Materials, and has an epoxy equivalent of 117-134 g / eq.

[0035] In one embodiment, the hydroxyl-containing oligomer comprises one or more polyols, wherein the hydroxyl number of the hydroxyl-containing oligomer is greater than or equal to 20 mg KOH / g; the hydroxyl-containing oligomer may be selected from the following models: BASF Lupranol 3402, which has a hydroxyl number of 470 mg KOH / g; BASF Lupranol 4003 / 1, which has a hydroxyl number of 20 mg KOH / g; Covestro Polyol 4200, hydroxyl number is 28mg KOH / g; Covestro Polyol F-3022, containing 52 mg KOH / g of hydroxyl group; DOW TONE 301POLYOL, containing 561.1 mg KOH / g of hydroxyl group; DOW TONE305POLYOL, containing 311.7 mg KOH / g of hydroxyl group; Shell CARADOL SC48-08, containing 48 mg KOH / g of hydroxyl group; Shell CARADOL SA250-06, containing 250 mg KOH / g of hydroxyl group.

[0036] In order to reduce the resolution and adhesion of negative permanent photoresist patterns on silicon wafers, the inventors found during the experiment that the resolution and adhesion cannot be reduced by simply using a multifunctional epoxy resin and a hydroxyl-containing oligomer. The inventors further found that a photoinitiated multifunctional resin polymer combination containing BPA novolac epoxy resin SQAN-205 can reduce the resolution and adhesion of negative permanent photoresist patterns on silicon wafers when combined with a hydroxyl-containing oligomer.

[0037] In the following embodiments, different types of multifunctional epoxy resins and hydroxyl-containing oligomers are coordinated in the photoinitiated multifunctional resin polymer of component A; the multifunctional epoxy resins described by formulas I to XII can be used alone or in combination of two or more.

[0038] In one embodiment, the photoinitiated multifunctional group resin polymer of component A can be a multifunctional epoxy resin selected from formula I and a hydroxyl-containing oligomer of model BASF Lupranol 3402; the multifunctional epoxy resin of formula I is HEXION EPON SU-8 of the United States, and the epoxy equivalent is 195-230g / eq; the hydroxyl number of the hydroxyl-containing oligomer of model BASF Lupranol3402 is 470mg KOH / g.

[0039] In one embodiment, the component A photoinitiated multifunctional resin polymer can be a multifunctional epoxy resin selected from formula II and III and a hydroxyl-containing oligomer of model BASF Lupranol 4003 / 1; the formula II and III are compositions of HEXION EPON 1031 and 828, respectively, with epoxy equivalents of 195-230 g / eq and 182-192 g / eq, respectively; the hydroxyl-containing oligomer of model BASF Lupranol 4003 / 1 has a hydroxyl number of 20 mg KOH / g.

[0040] In one embodiment, the photoinitiated multifunctional resin polymer of component A can be a multifunctional epoxy resin selected from formula IV and a Covestro The hydroxyl-containing oligomer of Polyol 4200; the formula IV is Mitsubishi Chemical bisphenol A jER TM 157S70, epoxy equivalent is 200-220g / eq,; the model is Covestro The hydroxyl number of the hydroxyl-containing oligomer of Polyol 4200 is 28 mg KOH / g.

[0041] In one embodiment, the photoinitiated multifunctional resin polymer of component A can be a multifunctional epoxy resin selected from formula V and a Covestro The hydroxyl-containing oligomers of Polyol F-3022 and DOW TONE 301POLYOL; the formula V is Mitsubishi Chemical bisphenol A jER TM YX7110s, epoxy equivalent is 1100g / eq; the model is Covestro The hydroxyl numbers of the hydroxyl-containing oligomers of Polyol F-3022 and DOW TONE 301 POLYOL are 52 mg KOH / g and 561.1 mg KOH / g, respectively.

[0042] In one embodiment, the photoinitiated multifunctional resin polymer of component A can be a multifunctional epoxy resin selected from the group consisting of Formula VI and Covestro The hydroxyl-containing oligomer of Polyol 4200; the formula VI is Nippon Kayaku Co., Ltd. Tokyo NC-3000H, with an epoxy equivalent of 270-300g / eq; the model is Covestro The hydroxyl-containing oligomer of Polyol 4200 has a hydroxyl number of 28 mg KOH / g.

[0043] In one embodiment, the photoinitiated multifunctional group resin polymer of component A can be a multifunctional epoxy resin selected from formula VII and a hydroxyl-containing oligomer with model number DOW TONE 305POLYOL; the formula VII is Nippon Kayaku Co., Ltd. Tokyo NER-7403, with an epoxy equivalent of 200-500 g / eq; the hydroxyl-containing oligomer with model number DOW TONE305POLYOL has a hydroxyl number of 311.7 mg KOH / g.

[0044] In one embodiment, the photoinitiated multifunctional resin polymer of component A can be a multifunctional epoxy resin selected from the group consisting of formula VIII and a hydroxyl-containing oligomer of model DOW TONE 301 POLYOL; the formula VIII is The BPA novolac epoxy resin SQAN-205 has an epoxy equivalent of 190-230 g / eq; the hydroxyl-containing oligomer of model DOW TONE 301 POLYOL has a hydroxyl number of 561.1 mg KOH / g.

[0045] In one embodiment, the photoinitiated multifunctional resin polymer of component A can be a multifunctional epoxy resin selected from the group consisting of Formula IX and X and a hydroxyl-containing oligomer of model DOW TONE 305POLYOL; the Formula IX and X are respectively Trifunctional phenolic epoxy resin SQSN-331 and pentaerythritol tetraglycidyl ether; the hydroxyl-containing oligomer with the model number of DOW TONE305POLYOL has a hydroxyl number of 311.7 mg KOH / g.

[0046] In one embodiment, the photoinitiated multifunctional group resin polymer of component A can be a hydroxyl-containing oligomer formed by combining a multifunctional epoxy resin selected from formula XI and models DOW TONE 305POLYOL and Shell CARADOL SC48-08; the formula XI is a hydrogenated bisphenol A epoxy resin; the hydroxyl number of the hydroxyl-containing oligomer of model DOW TONE 305POLYOL is 311.7 mg KOH / g; the hydroxyl number of the hydroxyl-containing oligomer of model Shell CARADOL SC48-08 is 48 mg KOH / g.

[0047] In one embodiment, the photoinitiated multifunctional group resin polymer of component A can be a hydroxyl-containing oligomer formed by combining a multifunctional epoxy resin selected from formula XII and models DOW TONE 301POLYOL and DOW TONE 305POLYOL; the formula XII is 4,4'-diaminodiphenylmethane epoxy resin; the hydroxyl number of the hydroxyl-containing oligomer of model DOW TONE 305POLYOL is 311.7 mg KOH / g; the hydroxyl number of the hydroxyl-containing oligomer of model DOW TONE 301POLYOL is 561.1 mg KOH / g.

[0048] In one embodiment, the component B cationic photoinitiator may be selected from aromatic iodonium complex salts and / or aromatic sulfonium complex salts.

[0049] In one embodiment, the specific examples of the aromatic iodonium complex salt can be selected from one or more of (perfluoro-n-octyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrakis(pentafluorophenyl)borate, and bis(4-substituted benzene)iodonium hexafluorophosphate.

[0050] In one embodiment, the specific examples of the aromatic sulfonium complex salt can be selected from triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4'-bis [diphenylsulfonium] diphenyl sulfide bis hexafluorophosphate, 4,4'-bis [bis (B-hydroxyethoxy) phenylsulfonium] diphenyl sulfide bis hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonium diphenyl sulfide One or more of tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, 4,4'-bis[bis(B-hydroxyethoxy)(phenylsulfonium)diphenyl sulfide-bishexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonium diphenyl sulfide hexafluorophosphate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonium diphenyl sulfide hexafluorophosphate, and 4-tert-butylphenylcarbonyl-4'-diphenylsulfonium diphenyl sulfide hexafluoroantimonate.

[0051] In one embodiment, the cationic photoinitiator of component B may be selected from the following brands: WPI-116 from FUJIFILM Wako, WPI-124 from FUJIFILM Wako, 7MP, Dow's UVI-6976, SpeedCure 939, SpeedCure 992 from Double Bond Chemical (DBC), DOUBLECURE 1176 from Double Bond Chemical (DBC), DOUBLECURE 1190 from Double Bond Chemical (DBC), OMNICAT 250 from IGM, OMNICAT 432 from IGM.

[0052] In one embodiment, the FUJIFILM Wako's WPI-116 and FUJIFILM Wako's WPI-124 are useful photoacid generators capable of generating hexafluoroantimonic acid.

[0053] In one embodiment, the 7MP is a useful hexafluorophosphate photoacid generator compound that does not contain antimony.

[0054] In one embodiment, the Dow's UVI-6976 is a mixed aromatic sulfonium hexafluoroantimonate photoacid generator.

[0055] In one embodiment, the SpeedCure 939, SpeedCure 992 is an aromatic iodonium borate and an aromatic sulfonium phosphate.

[0056] In one embodiment, the DOUBLECURE 1176 of Double Bond Chemical (DBC) and the DOUBLECURE 1190 of Double Bond Chemical (DBC) are aromatic antimony-containing hexafluoroantimonate and antimony-free hexafluorophosphate, respectively.

[0057] In one embodiment, the IGM's OMNICAT 250 and the IGM's OMNICAT 432 are aromatic iodonium and aromatic sulfonium hexafluorophosphates, respectively.

[0058] In one embodiment, the film-forming agent of component C is selected from one or more of low-boiling point or high-boiling point ketone solvents, ester solvents, and ether solvents.

[0059] In the present application, the component C film-forming agent is capable of dissolving other components to form a flowable composition and forming a coating on a substrate, and the film-forming agent can be evaporated by heating; it can be used alone or in combination of two or more solvents according to special applications and needs to further improve the drying characteristics and viscosity of the photoresist composition.

[0060] In one embodiment, examples of usable ketone solvents may include one or more selected from the group consisting of butanone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, methyl ethyl ketone, and cyclopentanone.

[0061] In one embodiment, examples of usable ester solvents may include one or more selected from ethyl acetate, propylene carbonate, dimethyl carbonate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol dibenzoate and γ-butyrolactone.

[0062] In one embodiment, examples of the ether solvent that can be used may include one or more of dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,3-dioxolane, and 1,4-dioxane.

[0063] In one embodiment, the silicon-containing auxiliary agent of component D contains epoxy functional groups.

[0064] In one embodiment, the silicon-containing auxiliary agent containing epoxy functional groups can be selected from CoatOsil 1770 and Wetlink 78 of MOMENTIVE, KBM-303, KBM-403 and KBE-402 of ShinEtsu, and one or more of Z-6043 and Z-6044 of DOW CORNING as usable examples.

[0065] In one embodiment, the fluorine-containing compound of component E can be selected from CYTONIX FluorN 561 and 562 with ethylene glycol as the main structure, selected from 3M The series includes 7100, 7200 with alkanes as the main structure, 7300 with trifluoromethyl functional group, and 2,3-dihydroperfluoropentane. The fluorine-containing compound may include a combination of one or more types of raw materials.

[0066] In one embodiment, the component A photoinitiated multifunctional resin polymer comprises the above-mentioned multifunctional epoxy resin formulas I to VII, and its weight part in the photoresist composition is 25-75 parts, preferably 50-75 parts by weight; the weight part of the hydroxyl-containing oligomer contained in the photoresist composition is 0.2-12 parts, preferably 0.5-8 parts by weight.

[0067] In one embodiment, the cationic photoinitiator component B is present in the photoresist composition in an amount of 0.2-6 parts by weight, preferably 0.4-4 parts by weight.

[0068] In one embodiment, the component C film former is present in the photoresist composition in an amount of 25-75 parts by weight, preferably 25-50 parts by weight. The actual amount of the film former that can be used depends on the expected coating thickness; the (C) film former may comprise a mixture of one or more; the mixture may be used to modify the viscosity and drying characteristics of the photoresist composition.

[0069] In a preferred embodiment, the film-forming agent of component C is selected from one or more of cyclopentanone, 2-pentanone, 1,3-dioxolane and propylene carbonate.

[0070] In one embodiment, the silicon-containing auxiliary agent of component D is present in the photoresist composition in an amount of 1-10 parts by weight, preferably 1.5-4 parts by weight.

[0071] In one embodiment, the fluorine-containing compound of component E is present in the photoresist composition in an amount of 1-5 parts by weight, preferably 1.5-3 parts by weight.

[0072] In one embodiment, the photoresist composition, calculated by weight, comprises the following raw materials: component A, photoinitiator multifunctional group resin polymer 25-87 parts, component B, cationic photoinitiator 0.2-6 parts, component C, film former 25-75 parts, component D, silicon-containing auxiliary agent 1-10 parts, component E, fluorine-containing compound 1-5 parts.

[0073] In one embodiment, the photoresist composition for soft / hard substrates comprises the following raw materials: a multifunctional epoxy resin is a composition of pentaerythritol tetraglycidyl ether and a BPA phenolic epoxy resin SQAN-205, a hydroxyl-containing oligomer is DOW TONE 305POLYOL, a cationic photoinitiator is a composition of DOW UVI-6976 and Double Bond Chemical's DOUBLECURE 1176; a film former is one or a combination of two of 2-pentanone, 1,3-dioxolane and propylene carbonate; a silicon-containing additive is ShinEtsu KBM-403; a fluorine-containing compound is CYTONIX FluorN 561 or 3M One or a combination of the 7100.

[0074] In order to form a uniform spin-coated film, reduce the ultraviolet light exposure energy, and obtain better resolution and adhesion effects, the inventors found in the experimental process that a limited combination of raw materials can obtain better resolution and adhesion effects, especially the preparation raw materials include: a multifunctional epoxy resin is a composition of pentaerythritol tetraglycidyl ether and a BPA phenolic epoxy resin SQAN-205, a hydroxyl-containing oligomer is DOW TONE 305POLYOL, a cationic photoinitiator is a composition of a model DOWUVI-6976 and a Double Bond Chemical DOUBLECURE 1176; a film-forming agent is a combination of one or two of 2-pentanone, 1,3-dioxolane and propylene carbonate; a silicon-containing auxiliary agent is ShinEtsu KBM-403; a fluorine-containing compound is CYTONIX FluorN 561 or 3M 7100; The photoresist composition for soft / hard substrates formed by the combination of the above raw materials can form a uniform spin-coated film when used, can effectively reduce the ultraviolet light exposure energy to 300mJ, and obtain better resolution and adhesion effects.

[0075] In order to reduce the ultraviolet light exposure energy to 200mJ and further improve the resolution and adhesion effect of the photoresist composition used on soft / hard substrates during application, the inventors found during the experiment that when the mass ratio of BPA novolac epoxy resin SQAN-205 and pentaerythritol tetraglycidyl ether is (4-4.2):1, they are combined with a hydroxyl-containing oligomer of model DOW TONE 305POLYOL and a cationic photoinitiator of model DOUBLECURE 1176 of Double Bond Chemical to reduce the ultraviolet light exposure energy to 200mJ, thereby further improving the resolution and adhesion effect of the photoresist composition used on soft / hard substrates during application.

[0076] A second aspect of the present invention provides a method for preparing a photoresist composition for a soft / hard substrate, comprising the following steps:

[0077] S1. The component A photoinitiated multifunctional group resin polymer and 85wt% of the component C film-forming agent are added to a stirring device and mixed to obtain a mixture F;

[0078] S2. The cationic photoinitiator of component B, the silicon-containing additive of component D, and the fluorine-containing compound of component E are added to 15 wt % of the film-forming agent of component C and mixed to obtain a mixture G;

[0079] S3. Mixing mixture F and mixture G to obtain a photoresist composition.

[0080] In one embodiment, the method for preparing the photoresist composition for soft / hard substrate comprises the following steps:

[0081] S1. The photoinitiator multifunctional group resin polymer of component A and 85 wt % of the film-forming agent of component C are added to a high shear stirring device at 25-40 ℃ to obtain a mixture F;

[0082] S2. The cationic photoinitiator of component B, the silicon-containing additive of component D, and the fluorine-containing compound of component E are added to 15 wt % of the film-forming agent of component C and mixed to obtain a mixture G;

[0083] S3. Mix the mixture F and the mixture G at 25° C. to obtain a photoresist composition for a soft / hard substrate.

[0084] A third aspect of the present invention provides an application of a photoresist composition, wherein the photoresist composition is applied in the field of photolithography technology and is applied to a soft / hard substrate to prepare a permanent photoresist pattern.

[0085] In one embodiment, the application of the photoresist composition on the soft / hard substrate comprises the following steps:

[0086] A1. The photoresist composition is coated on a PET substrate;

[0087] A2. Heating the PET substrate to obtain a photoresist composite film;

[0088] A3. Attaching the photoresist composite film to the soft / rigid substrate by hot pressing;

[0089] A4. irradiating the photoresist composite film with ultraviolet rays through a mask;

[0090] A5. Heating the photoresist composite film;

[0091] A6. Cool the mixture to 25°C and develop it with a solvent to form a negative permanent photoresist pattern.

[0092] In one embodiment, the application of the photoresist composition on the soft / hard substrate comprises the following steps:

[0093] A1. The photoresist composition is coated on a PET substrate;

[0094] A2. by heating the coated PET substrate so that most of the solvent evaporates from the photoresist composition layer to form a photoresist combination film on the soft / hard substrate;

[0095] A3. Attaching the photoresist composite film to the soft / rigid substrate by hot pressing;

[0096] A4. irradiating the photoresist composite film with ultraviolet rays through a mask;

[0097] A5. The irradiated photoresist film is cross-linked and cured by two-stage heating;

[0098] A6. Cool the mixture to 25°C and develop it with a solvent to form a negative permanent photoresist pattern.

[0099] In one embodiment, the coating method of coating the photoresist composition on the PET substrate in A1 includes blade coating, roller coating, dip coating, spin coating and screen printing to uniformly coat the composition on the PET substrate with low surface energy.

[0100] In one embodiment, a photomask with opaque and transparent area patterns can be used to expose it in contact, proximity or projection exposure mode using an exposure tool of actinic radiation in the form of ultraviolet rays, electron beams or X-ray radiation. After exposure, post-exposure baking is performed, and two-stage heating is used to accelerate the cationic polymerization reaction in the exposed area of ​​the coating to form a cross-linked cure. After standing and cooling to room temperature, the negative photolithographic relief image of the photomask in the coating is formed by solvent development. The coating substrate is immersed in an organic solvent developer to dissolve the non-cross-linked polymerization area of ​​the coating. The basic development condition is to immerse the coating in an organic solvent developer and shake it for 1 to 2 minutes at 25°C; finally, the developed image is washed with a washing solvent to remove the residual developer to prevent the residual developer and the dissolved photoresist components from forming deposits in the negative permanent photoresist pattern.

[0101] In one embodiment, the organic solvent used for the solvent development can be selected from one or more of propylene glycol monomethyl ether acetate, acetone, cyclopentanone, diacetone alcohol, N-methylpyrrolidone, ethyl lactate and γ-butyrolactone; preferably propylene glycol monomethyl ether acetate.

[0102] In order to improve the solubility of unexposed photoresist components, the inventors found in the experimental process that using propylene glycol monomethyl ether acetate as the developing organic solvent can have good solubility for unexposed photoresist components and the cost is relatively low.

[0103] In one embodiment, the post-development washing solvent comprises the above-mentioned developer solvent and any one of methanol, ethanol, isopropanol and n-butyl acetate. A washing solvent that can dry quickly is the main consideration, preferably acetone, methanol, ethanol, isopropanol.

[0104] In one embodiment, the application of the photoresist composition for soft / hard substrates for preparing a negative permanent photoresist pattern comprises the following steps:

[0105] A1. The photoresist composition was scraped onto the PET substrate using a 50 μm spacing scraper. The film layer formed by the photoresist composition on the PET substrate had a thickness of about 20-25 μm.

[0106] A2. The coated PET substrate was heated at 90°C for 10 min to evaporate the solvent from the photoresist composition layer to form a photoresist composite film on the PET substrate;

[0107] A3. Preheat the soft / hard substrate by controlling the hot stage temperature to 50°C, and attach the photoresist composite film to the soft / hard substrate (copper foil / silicon wafer) by hot pressing;

[0108] A4. irradiating the photoresist composite film with ultraviolet rays through a mask;

[0109] A5. The irradiated photoresist film is cross-linked and cured by two-stage heating;

[0110] A6. Cool the mixture to 25°C and develop it with a solvent to form a negative permanent photoresist pattern.

[0111] The hot pressing conditions in A3 are as follows: the laminating roller temperature is 75°C / 50°C, the pressure is 2.5kg, and the speed is 0.6M / min.

[0112] The A4 is placed at 25° C. for 15 minutes and then exposed, and the photoresist composite film is irradiated with ultraviolet rays through a mask with an exposure energy of 400 mJ; and the film is baked after being placed for 15 minutes, and the PET is peeled off before baking.

[0113] In the A5, two-stage heating is performed at 55° C. / 5 min+95° C. / 3 min to crosslink and solidify the irradiated photoresist film.

[0114] After the A6 was placed at 25° C. for 15 minutes, it was developed with propylene glycol monomethyl ether acetate for 1-2 minutes to further form a mask negative type permanent photoresist pattern.

[0115] In one embodiment, the thickness of the negative permanent photoresist pattern is measured using an optical film thickness meter.

[0116] In one embodiment, the resolution and adhesion of the negative permanent photoresist pattern are measured using an electron microscope. The test results are shown in Figure 1 , Figure 2 .

[0117] The photoresist composition formed by using a multifunctional epoxy resin A1 and a hydroxyl-containing oligomer A2 in the present invention can be applied to manufacturing a mask negative permanent photoresist pattern on a soft / hard substrate. The photoresist composition provided by the present invention can be used to manufacture micro-electromechanical system (MEMS) components, micro-mechanical components, optical element inkjet printing heads, DNA sequencing chips and dielectric layers, etc., which can be patterned using ultraviolet exposure combined with spin coating or screen printing methods, wherein the photo-induced negative permanent photoresist pattern can be formed on a soft / hard substrate.

[0118] Beneficial Effects

[0119] 1. Through the technical solution provided by the present invention, a uniform spin-coated film can be formed, with a high aspect ratio image having a vertical sidewall distribution.

[0120] 2. The photoresist composition for soft / hard substrates provided by the present invention can reduce the resolution and adhesion of negative permanent photoresist patterns on silicon wafers; it can have good processing performance in aqueous developers and have the easy release and flexibility required by microelectromechanical systems (MEMS).

[0121] 3. The photoresist composition for use on a soft / hard substrate provided by the present invention can improve the toughness of the photoresist composite film, thereby preventing the photoresist composite film from being easily broken at the edge during hot pressing.

[0122] 4. The photoresist composition for soft / hard substrates provided by the present invention can reduce the ultraviolet light exposure energy and obtain better resolution and adhesion effects.

[0123] 5. The technical solution provided by the present invention can prevent residual developer and dissolved photoresist components from forming deposits in the negative permanent photoresist pattern. BRIEF DESCRIPTION OF THE DRAWINGS

[0124] Figure 1 This is an analytical image of the negative permanent photoresist pattern obtained in the example measured using an electron microscope.

[0125] Figure 2 The adhesion map of the negative permanent photoresist pattern obtained in the example was measured using an electron microscope.

[0126] Figure 3 This is a state diagram of the negative type permanent photoresist pattern obtained in Comparative Example 1 measured using an electron microscope. DETAILED DESCRIPTION

[0127] The types, sources, functions and component types of the raw materials used in the following examples and comparative examples are shown in Table 1.

[0128] Table 1

[0129]

[0130]

[0131]

[0132] Example 1

[0133] The first aspect of the present embodiment provides a photoresist composition, the preparation raw materials of which include: (A) a photoinitiator multifunctional group resin polymer, (B) a cationic photoinitiator, (C) a film-forming agent, (D) a silicon-containing auxiliary agent, and (E) a fluorine-containing compound; the photoinitiator multifunctional group resin polymer comprises a multifunctional epoxy resin A1 and a hydroxyl-containing oligomer A2; in parts by weight, the preparation raw materials include: 60.5 parts of a multifunctional epoxy resin A1 of model EPON SU-8, 4.56 parts of a hydroxyl-containing oligomer A2 of model Lupranol 3402, 0.25 parts of (B) a cationic photoinitiator of model WPI-116, 0.25 parts of (B) a cationic photoinitiator of model WPI-124, 30 parts of butanone as (C) a film-forming agent, 2 parts of (D) a silicon-containing auxiliary agent of model CoatOsil 1770, and 2.44 parts of (E) a fluorine-containing compound of model FluorN 561.

[0134] A second aspect of the present embodiment provides a method for preparing a photoresist composition, comprising the following steps:

[0135] S1. At 25°C, the component (A) photoinitiator multifunctional group resin polymer and 85 wt% of the component (C) film-forming agent were added to a high shear stirring device and mixed to obtain a mixture F;

[0136] S2. The component (B) cationic photoinitiator, the component (D) silicon-containing auxiliary agent, and the component (E) fluorine-containing compound are added to 15 wt % of the component (C) film-forming agent and mixed to obtain a mixture G;

[0137] S3. Mix the mixture F and the mixture G at 25° C. to obtain a photoresist composition for a soft / hard substrate.

[0138] A third aspect of the present embodiment provides an application of a photoresist composition, comprising the following steps:

[0139] A1. The photoresist composition is scraped onto the PET substrate using a 50 μm spacing scraper. The thickness of the film formed by the photoresist composition on the PET substrate is 25 μm.

[0140] A2. The coated PET substrate was heated at 90°C for 10 min to evaporate the solvent from the photoresist composition layer to form a photoresist composite film on the PET substrate;

[0141] A3. Preheat the soft / rigid substrate to 50°C on a hot plate, and attach the photoresist composite film to the soft / rigid substrate (copper foil / silicon wafer) by hot pressing;

[0142] A4. irradiating the photoresist composite film with ultraviolet rays through a mask;

[0143] A5. The irradiated photoresist film is cross-linked and cured by two-stage heating;

[0144] A6. Cool the mixture to 25°C and develop it with a solvent to form a negative permanent photoresist pattern.

[0145] The hot pressing conditions in A3 are as follows: the laminating roller temperature is 75°C / 50°C, the pressure is 2.5kg, and the speed is 0.6M / min.

[0146] The A4 was placed at 25° C. for 15 minutes and then exposed, and the photoresist composite film was irradiated with ultraviolet rays through a mask with an exposure energy of 400 mJ. After being placed for 15 minutes, it was baked, and the PET was peeled off before baking.

[0147] In the A5, the irradiated photoresist film is cross-linked and cured by two-stage heating, in which the first stage heating condition is 55° C. and 5 minutes, and the second stage heating condition is 95° C. and 3 minutes.

[0148] After the A6 was placed at 25° C. for 15 minutes, it was developed with propylene glycol monomethyl ether acetate (PGMEA) solvent for 2 minutes to further form the mask negative permanent photoresist pattern.

[0149] The width (um) of the negative permanent photoresist pattern of the mask was tested using an electron microscope to determine the resolution and adhesion performance of the pattern.

[0150] Example 2

[0151] Example 2 provides a photoresist composition, the preparation raw materials of which include, by weight: 40.5 parts of multifunctional epoxy resin A1 with model number EPON1031, 22 parts of multifunctional epoxy resin A1 with model number EPON 828, 2.3 parts of hydroxyl-containing oligomer A2 with model number Lupranol 4003 / 1, 0.5 parts of (B) cationic photoinitiator with model number 7MP, 30 parts of cyclopentanone as (C) film-forming agent, 2 parts of (D) silicon-containing auxiliary agent with model number Wetlink78, and 2.7 parts of (E) fluorine-containing compound with model number FluorN 562.

[0152] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 2.

[0153] Example 3

[0154] Example 3 provides a photoresist composition, which is prepared by raw materials including, by weight: bisphenol AjER TM 157S70 multifunctional epoxy resin A1 61.5 parts, model 2.5 parts of hydroxyl-containing oligomer A2 of Polyol 4200, 0.25 parts of (B) cationic photoinitiator of model UVI-6976, 0.25 parts of (B) cationic photoinitiator of model WPI-124, 30 parts of propylene glycol methyl ether acetate as (C) film-forming agent, 2.5 parts of (D) silicon-containing additive of model KBM-303, 7100 (E) 2.5 parts of fluorine-containing compound.

[0155] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 2.

[0156] Example 4

[0157] Example 4 provides a photoresist composition, which comprises, by weight, bisphenol AjER TM YX7110s multifunctional epoxy resin A1 62 parts, model 23 parts of hydroxyl-containing oligomer A of Polyol F-3022, 0.5 parts of (B) cationic photoinitiator of model SpeedCure 939, 15 parts of γ-butyrolactone as (C) film-forming agent, 15 parts of ethylene glycol butyl ether acetate as (C) film-forming agent, 1.5 parts of (D) silicon-containing additive of model KBM-403, 1.5 parts of (D) silicon-containing additive of model KBE-402, 7200 (E) 2.5 parts of fluorine-containing compound.

[0158] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 2.

[0159] Example 5

[0160] Example 5 provides a photoresist composition, the preparation raw materials of which include, by weight: 61.5 parts of multifunctional epoxy resin A1, 3 parts of hydroxyl-containing oligomer A2, (B) 0.5 parts of cationic photoinitiator, (C) 30 parts of film-forming agent, (D) 3 parts of silicon-containing auxiliary agent, and (E) 3 parts of fluorine-containing compound; the (D) silicon-containing auxiliary agent includes 1.5 parts of silicon-containing auxiliary agent with model number Z-6043 and 1.5 parts of silicon-containing auxiliary agent with model number Z-6044; 2 parts of (D) silicon-containing auxiliary agent with model number FluorN 561 and 1 part of (D) silicon-containing auxiliary agent with model number FluorN 562.

[0161] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 2.

[0162] Example 6

[0163] Example 6 provides a photoresist composition, the preparation raw materials of which include, by weight: 62 parts of multifunctional epoxy resin A1, 3 parts of hydroxyl-containing oligomer A2, (B) 0.5 parts of cationic photoinitiator, (C) 30 parts of film-forming agent, (D) 2.5 parts of silicon-containing auxiliary agent, and (E) 2.5 parts of fluorine-containing compound; the (B) cationic photoinitiator is composed of 0.25 parts of cationic photoinitiator with model number UVI-6976 and 0.25 parts of cationic photoinitiator with model number WPI-124, and the (C) film-forming agent is composed of 15 parts of propylene glycol methyl ether acetate and 15 parts of diethylene glycol dibenzoate.

[0164] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 2.

[0165] Table 2

[0166]

[0167] Example 7

[0168] Example 7 provides a photoresist composition, wherein the raw materials for its preparation include, by weight: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 3 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the (C) film former is composed of 15 parts of 2-pentanone and 15 parts of propylene carbonate. The (D) silicon-containing auxiliary agent is composed of 1.5 parts of KBM-303 and 1.5 parts of KBE-402.

[0169] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 3.

[0170] Example 8

[0171] Example 8 provides a photoresist composition, wherein the raw materials for its preparation include, by weight: 62.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 2 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 40.5 parts of trifunctional phenolic epoxy resin SQSN-331 and 22 parts of pentaerythritol tetraglycidyl ether; the (B) cationic photoinitiator is composed of 0.3 parts of SpeedCure 939 and 0.2 parts of SpeedCure 992. The (C) film former is composed of 20 parts of γ-butyrolactone and 10 parts of 1,3-dioxolane.

[0172] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 3.

[0173] Example 9

[0174] Example 9 provides a photoresist composition, and its preparation raw materials include, by weight: 60.5 parts of multifunctional epoxy resin A1, 4 parts of hydroxyl-containing oligomer A2, 1 part of (B) cationic photoinitiator, 30 parts of (C) film-forming agent, 1.5 parts of (D) silicon-containing auxiliary agent, and 3 parts of (E) fluorine-containing compound; the hydroxyl-containing oligomer A2 is composed of 3 parts of hydroxyl-containing oligomer with model number TONE 305POLYOL and 1 part of SC48-08. The (B) cationic photoinitiator is composed of 0.5 parts of DOUBLECURE 1176 and 0.5 parts of DOUBLECURE 1190. The (C) film-forming agent is composed of 15 parts of 2-pentanone and 15 parts of 1,3-dioxolane. The (E) fluorine-containing compound is composed of 2 parts of FluorN 561 and 1 part of 7100 of fluorine-containing compounds.

[0175] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 3.

[0176] Example 10

[0177] Example 10 provides a photoresist composition, wherein the raw materials for its preparation include, by weight: 62 parts of multifunctional epoxy resin A1, 3 parts of hydroxyl-containing oligomer A2, (B) 1 part of cationic photoinitiator, (C) 30 parts of film-forming agent, (D) 1.5 parts of silicon-containing auxiliary agent, and (E) 2.5 parts of fluorine-containing compound;

[0178] The hydroxyl-containing oligomer A2 is composed of 1.5 parts of hydroxyl-containing oligomers with the model number TONE 301POLYOL and 1.5 parts of hydroxyl-containing oligomers with the model number TONE305POLYOL. The (B) cationic photoinitiator is composed of 0.5 parts of OMNICAT 250 and 0.5 parts of OMNICAT 432. The (C) film-forming agent is composed of 20 parts of methyl isobutyl ketone and 10 parts of dimethyl carbonate. The (E) fluorine-containing compound is composed of 1.5 parts of The fluorinated compound is composed of 7300 and 1 part of 2,3-dihydroperfluoropentane.

[0179] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 3.

[0180] Embodiment 11

[0181] Example 11 provides a photoresist composition, wherein the raw materials for its preparation include, by weight: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film-forming agent, 3 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the hydroxyl-containing oligomer A2 is prepared by 1.25 parts of The (C) film former is composed of 15 parts of 2-pentanone and 15 parts of propylene carbonate. The (D) silicon-containing additive is composed of 1.5 parts of KBM-303 and 1.5 parts of KBE-402.

[0182] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 3.

[0183] Example 12

[0184] Example 12 provides a photoresist composition, wherein the raw materials for its preparation include, by weight: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film-forming agent, 3 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the hydroxyl-containing oligomer A2 is prepared by 1.25 parts of The (C) film former is composed of 15 parts of 2-pentanone and 15 parts of propylene carbonate. The (D) silicon-containing additive is composed of 1.5 parts of KBM-303 and 1.5 parts of KBE-402.

[0185] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 3.

[0186] Embodiment 13

[0187] Example 13 provides a photoresist composition, wherein the raw materials for its preparation include, by weight: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film-forming agent, 3 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the multifunctional epoxy resin A1 is prepared by 40 parts of bisphenol AjER TM YX7110s and 21.5 parts of a multifunctional epoxy resin of the type BPA phenolic epoxy resin SQAN-205. The hydroxyl-containing oligomer A2 is composed of 1.25 parts of The (C) film former is composed of 15 parts of 2-pentanone and 15 parts of propylene carbonate. The (D) silicon-containing additive is composed of 1.5 parts of KBM-303 and 1.5 parts of KBE-402.

[0188] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 3.

[0189] Table 3

[0190]

[0191] Embodiment 14

[0192] Example 14 provides a photoresist composition, and its raw materials include: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 3 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 40 parts of BPA phenolic epoxy resin SQAN-205 and 21.5 parts of trifunctional phenolic epoxy resin SQSN-331. The (C) film former is composed of 15 parts of 2-pentanone and 15 parts of propylene carbonate. The (D) silicon-containing auxiliary agent is composed of 1.5 parts of KBM-303 and 1.5 parts of KBE-402.

[0193] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 4.

[0194] Embodiment 15

[0195] Example 15 provides a photoresist composition, the raw materials for its preparation include: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 3 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 40 parts of multifunctional epoxy resin with the model of BPA phenolic epoxy resin SQAN-205 and 21.5 parts of trifunctional phenolic epoxy resin SQSN-331. The (C) film former is composed of 15 parts of 2-pentanone and 15 parts of propylene carbonate. The (D) silicon-containing auxiliary agent is composed of 1.5 parts of silicon-containing auxiliary agent with the model of KBM-303 and 1.5 parts of KBE-402.

[0196] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 4.

[0197] Example 16

[0198] Example 16 provides a photoresist composition, the raw materials for its preparation include: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 3 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 40 parts of BPA phenolic epoxy resin SQAN-205 and 21.5 parts of trifunctional phenolic epoxy resin SQSN-331. The (B) cationic photoinitiator is composed of 0.25 parts of UVI-6976 and 0.25 parts of DOUBLECURE 1176; the (C) film former is composed of 15 parts of 2-pentanone and 15 parts of propylene carbonate. The (D) silicon-containing auxiliary agent is composed of 1.5 parts of silicon-containing auxiliary agents with a model number of KBM-303 and 1.5 parts of silicon-containing auxiliary agents with a model number of KBE-402.

[0199] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 4.

[0200] Embodiment 17

[0201] Example 17 provides a photoresist composition, the raw materials for its preparation include: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 3 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 40 parts of multifunctional epoxy resin with the model of BPA phenolic epoxy resin SQAN-205 and 21.5 parts of pentaerythritol tetraglycidyl ether. The (B) cationic photoinitiator is composed of 0.25 parts of UVI-6976 and 0.25 parts of DOUBLECURE 1176; the (C) film former is composed of 15 parts of 2-pentanone and 15 parts of propylene carbonate. The (D) silicon-containing auxiliary agent is composed of 1.5 parts of silicon-containing auxiliary agents with the model number KBM-303 and 1.5 parts of silicon-containing auxiliary agents with the model number KBE-402.

[0202] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 4.

[0203] Embodiment 18

[0204] Example 18 provides a photoresist composition, the raw materials for its preparation include: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 3 parts of (D) silicon-containing auxiliary agent, and 2.5 parts of (E) fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 40 parts of multifunctional epoxy resin with the model of BPA phenolic epoxy resin SQAN-205 and 21.5 parts of pentaerythritol tetraglycidyl ether. The (B) cationic photoinitiator is composed of 0.25 parts of UVI-6976 and 0.25 parts of DOUBLECURE 1176; the (C) film former is composed of 15 parts of 2-pentanone and 15 parts of 1,3-dioxolane.

[0205] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 4.

[0206] Embodiment 19

[0207] Example 19 provides a photoresist composition, the raw materials for its preparation include: 61.5 parts of multifunctional epoxy resin A1, 2.5 parts of hydroxyl-containing oligomer A2, (B) 0.5 parts of cationic photoinitiator, (C) 30 parts of film-forming agent, (D) 3 parts of silicon-containing auxiliary agent, and (E) 3 parts of fluorine-containing compound;

[0208] The multifunctional epoxy resin A1 is composed of 40 parts of a multifunctional epoxy resin of the model number BPA novolac epoxy resin SQAN-205 and 21.5 parts of pentaerythritol tetraglycidyl ether.

[0209] The (B) cationic photoinitiator is composed of 0.25 parts of a cationic photoinitiator with a model number of UVI-6976 and 0.25 parts of a cationic photoinitiator with a model number of DOUBLECURE1176;

[0210] The (C) film-forming agent consists of 15 parts of 2-pentanone and 15 parts of 1,3-dioxolane.

[0211] The (E) fluorine-containing compound is composed of 2 parts of FluorN 561 and 1 part of 7100 of fluorine-containing compounds.

[0212] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 4.

[0213] Table 4

[0214]

[0215]

[0216] Embodiment 20

[0217] Example 20 provides a photoresist composition, the raw materials for its preparation include: 63 parts of multifunctional epoxy resin A1, 1 part of hydroxyl-containing oligomer A2, (B) 0.5 parts of cationic photoinitiator, (C) 30 parts of film-forming agent, (D) 3 parts of silicon-containing auxiliary agent, (E) 3 parts of fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 41 parts of multifunctional epoxy resin with the model of BPA phenolic epoxy resin SQAN-205 and 22 parts of pentaerythritol tetraglycidyl ether. The (B) cationic photoinitiator is composed of 0.25 parts of UVI-6976 and 0.25 parts of DOUBLECURE 1176; the (C) film-forming agent is composed of 15 parts of 2-pentanone and 15 parts of 1,3-dioxolane. The (E) fluorine-containing compound is composed of 2 parts of FluorN 561 and 1 part of 7100 of fluorine-containing compounds.

[0218] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 5.

[0219] Embodiment 21

[0220] Example 21 provides a photoresist composition, the raw materials for its preparation include: 63 parts of multifunctional epoxy resin A1, 1 part of hydroxyl-containing oligomer A2, (B) 0.5 parts of cationic photoinitiator, (C) 30 parts of film-forming agent, (D) 3 parts of silicon-containing auxiliary agent, (E) 3 parts of fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 51 parts of multifunctional epoxy resin with the model of BPA phenolic epoxy resin SQAN-205 and 12 parts of pentaerythritol tetraglycidyl ether. The (B) cationic photoinitiator is composed of 0.25 parts of UVI-6976 and 0.25 parts of DOUBLECURE 1176; the (C) film-forming agent is composed of 15 parts of 2-pentanone and 15 parts of 1,3-dioxolane. The (E) fluorine-containing compound is composed of 2 parts of FluorN 561 and 1 part of 7100 of fluorine-containing compounds.

[0221] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 5.

[0222] Embodiment 22

[0223] Example 22 provides a photoresist composition, the raw materials for its preparation include: 63 parts of multifunctional epoxy resin A1, 1 part of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 3 parts of (D) silicon-containing auxiliary agent, and 3 parts of (E) fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 51 parts of multifunctional epoxy resin with the model of BPA phenolic epoxy resin SQAN-205 and 12 parts of pentaerythritol tetraglycidyl ether. The (C) film former is composed of 15 parts of 2-pentanone and 15 parts of 1,3-dioxolane. The (E) fluorine-containing compound is composed of 2 parts of FluorN 561 and 1 part of 7100 of fluorine-containing compounds.

[0224] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 5.

[0225] Embodiment 23

[0226] Example 23 provides a photoresist composition, the raw materials for its preparation include: 64.5 parts of multifunctional epoxy resin A1, 1 part of hydroxyl-containing oligomer A2, (B) 0.5 parts of cationic photoinitiator, (C) 30 parts of film former, (D) 1.5 parts of silicon-containing auxiliary agent, (E) 3 parts of fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 52 parts of multifunctional epoxy resin with the model of BPA phenolic epoxy resin SQAN-205 and 12.5 parts of pentaerythritol tetraglycidyl ether. The (C) film former is composed of 15 parts of 2-pentanone and 15 parts of 1,3-dioxolane. The (E) fluorine-containing compound is composed of 2 parts of FluorN 561 and 1 part of 7100 of fluorine-containing compounds.

[0227] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 5.

[0228] Comparative Example 1

[0229] Comparative Example 1 provides a photoresist composition, the raw materials for its preparation include: 64.5 parts of multifunctional epoxy resin A1, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 1.5 parts of (D) silicon-containing auxiliary agent, and 3 parts of (E) fluorine-containing compound; the multifunctional epoxy resin A1 is composed of 52 parts of multifunctional epoxy resin with the model of BPA phenolic epoxy resin SQAN-205 and 12.5 parts of pentaerythritol tetraglycidyl ether. The (C) film former is composed of 15 parts of 2-pentanone and 15 parts of 1,3-dioxolane. The (E) fluorine-containing compound is composed of 2 parts of FluorN 561 and 1 part of 7100 of fluorine-containing compounds.

[0230] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 5.

[0231] Comparative Example 2

[0232] Comparative Example 2 provides a photoresist composition, the raw materials for its preparation include: 64.5 parts of multifunctional epoxy resin A1, 1 part of hydroxyl-containing oligomer A2, 0.5 parts of (B) cationic photoinitiator, 30 parts of (C) film former, 1.5 parts of (D) silicon-containing auxiliary agent, and 3 parts of (E) fluorine-containing compound; the (C) film former is composed of 15 parts of 2-pentanone and 15 parts of 1,3-dioxolane. The (E) fluorine-containing compound is composed of 2 parts of FluorN 561 and 1 part of 7100 of fluorine-containing compounds.

[0233] The preparation method and application method of the photoresist composition are the same as those in Example 1. The types and amounts of the raw materials used in its preparation are shown in Table 5.

[0234] Table 5

[0235]

[0236]

[0237] The ultraviolet radiation exposure energy used in the above examples is shown in Table 6.

[0238] Table 6

[0239]

[0240]

[0241] Performance Testing

[0242] 1. Analytical test:

[0243] The photoresist compositions obtained in Examples 1-23 and Comparative Examples 1-2 were applied to form negative permanent photoresist patterns on silicon wafers. The width (um) of the negative permanent photoresist pattern of the mask was tested using an electron microscope to determine the analytical performance of the pattern. The test results are shown in Table 10.

[0244] 2. Adhesion test

[0245] The photoresist compositions obtained in Examples 1-23 and Comparative Examples 1-2 were applied to form negative permanent photoresist patterns on silicon wafers. The width (um) of the negative permanent photoresist pattern of the mask was tested using an electron microscope to determine the adhesion performance of the pattern. The test results are shown in Table 10.

[0246] Figure 1 This is an analytical image of the negative permanent photoresist pattern obtained in the example measured using an electron microscope.

[0247] Figure 2 The adhesion map of the negative permanent photoresist pattern obtained in the example was measured using an electron microscope.

[0248] Table 7

[0249]

[0250]

[0251] It can be seen from the test data in Table 7 that the photoresist compositions using different proportions of components (A)-(E) in Examples 1-10 show different differences in resolution and adhesion of negative permanent photoresist patterns on silicon wafers. Compared with the results of Examples 1-10, the resolution and adhesion test results obtained in Examples 4, 7, 8 and 9 are in the numerical range of 25-30μm and 20-30μm respectively. It can be seen from the test results that the resolution and adhesion test results are affected by the combination of raw materials in the photoresist composition. Compared with Examples 4, 7, 8 and 9, Examples 11-19 have better resolution and adhesion; and it can be seen from Examples 20 and 21 that increasing the mass ratio of BPA novolac epoxy resin SQAN-205 in the photoinitiator multifunctional group resin polymer can improve the adhesion of the photoresist composition on the silicon wafer. Compared with Example 23, in Comparative Example 1, the hydroxyl-containing oligomer A2 of model TONE 305POLYOL in the photoinitiator multifunctional group resin polymer combination was removed, and the addition ratio of other components was fixed, showing a decrease in resolution and adhesion, which decreased by 10 and 14 μm respectively. The importance of using the hydroxyl-containing oligomer polyol A2 for the resolution and adhesion of the negative permanent photoresist pattern on the silicon wafer was confirmed. It was also found that the photoresist combination film formed in Comparative Example 1 was relatively brittle and was prone to edge cracking during hot pressing. The edge cracking state was seen Figure 3 .

[0252] It can be seen from the test data in Table 7 that, compared with Example 23, in Comparative Example 2, the multifunctional epoxy resin A1 of model BPA phenolic epoxy resin SQAN-205 in the photoinitiated multifunctional group resin polymer combination was removed, pentaerythritol tetraglycidyl ether was used alone, and the addition ratio of other components was fixed, and the resolution and adhesion were significantly reduced by 26 and 29 μm.

Claims

1. A photoresist composition, characterized in that The preparation raw materials include: components A, B, C, D, and E, wherein component A includes a photoinitiator multifunctional group resin polymer, component B includes a cationic photoinitiator, component C includes a film former, component D includes a silicon-containing auxiliary agent, and component E includes a fluorine-containing compound; the photoinitiator multifunctional group resin polymer includes a multifunctional epoxy resin and a hydroxyl-containing oligomer.

2. The photoresist composition according to claim 1, characterized in that The weight portion of the multifunctional epoxy resin in the photoresist composition is 25-75 parts; the weight portion of the hydroxyl-containing oligomer in the photoresist composition is 0.2-12 parts.

3. The photoresist composition according to claim 2, characterized in that The weight portion of the multifunctional epoxy resin in the photoresist composition is 50-75 parts; the weight portion of the hydroxyl-containing oligomer in the photoresist composition is 0.5-8 parts.

4. The photoresist composition according to claim 1, wherein The component B cationic photoinitiator is selected from aromatic iodonium complex salts and / or aromatic sulfonium complex salts.

5. The photoresist composition according to claim 1, wherein The film-forming agent of component C is selected from one or more of ketone solvents, ester solvents and ether solvents.

6. The photoresist composition according to claim 1, wherein The silicon-containing auxiliary agent of component D contains epoxy functional groups.

7. The photoresist composition according to any one of claims 1 to 6, characterized in that: The raw materials for its preparation include, by weight: component A, 25-87 parts of photoinitiator multifunctional group resin polymer, component B, 0.2-6 parts of cationic photoinitiator, component C, 25-75 parts of film former, component D, 1-10 parts of silicon-containing auxiliary agent, and component E, 1-5 parts of fluorine-containing compound.

8. A method for preparing a photoresist composition according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1. The component A photoinitiated multifunctional group resin polymer and 85wt% of the component C film-forming agent are added to a stirring device and mixed to obtain a mixture F; S2. The cationic photoinitiator of component B, the silicon-containing additive of component D, and the fluorine-containing compound of component E are added to 15 wt % of the film-forming agent of component C and mixed to obtain a mixture G; S3. Mixing mixture F and mixture G to obtain a photoresist composition.

9. Use of the photoresist composition according to any one of claims 1 to 7, characterized in that: The photoresist composition is used in the field of photolithography and is applied to a soft / hard substrate to prepare a permanent photoresist pattern.

10. Use of the photoresist composition according to claim 9, characterized in that: The following steps are involved: A1. The photoresist composition is coated on a PET substrate; A2. Heating the PET substrate to obtain a photoresist composite film; A3. Attaching the photoresist composite film to the soft / rigid substrate by hot pressing; A4. Irradiating the photoresist composite film with ultraviolet rays through the mask; A5. Heating the photoresist composite film; A6. Cool the mixture to 25°C and develop it with a solvent to form a negative permanent photoresist pattern.

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