Aqueous developing negative photosensitive polyimide coating adhesive as well as preparation method and application thereof

Abstract

The invention discloses a water-based developing negative photosensitive polyimide coating adhesive as well as a preparation method and application thereof. The polyimide coating adhesive is prepared from the following raw materials in parts by weight: hydroxyl-containing polyamide acid ester resin, a photoinitiator, a cross-linking agent, a copper color change inhibitor, a photosensitive accelerator, an adhesion promoter, a thermal polymerization inhibitor and an organic solvent A, the preparation method of the hydroxyl-containing polyamic acid ester resin comprises the following steps: S1, in the presence of organic alkali, carrying out esterification reaction on raw materials including aromatic tetracid dianhydride and hydroxyl-containing methacrylate in an organic solvent B to form an aromatic diacid diester solution; s2, adding thionyl chloride into the aromatic diacid diester solution for reaction to obtain an aromatic diacyl chloride diester solution; and S3, adding the aromatic diacyl chloride diester solution into the aromatic diamine solution shown in the formula I for reaction. The coating adhesive disclosed by the invention has the characteristics of high depth-to-width ratio of a photoetching pattern, low dielectric constant, high heat resistance of cured resin, good adhesion with different metal interfaces and the like.

Description

Technical Field

[0001] The present invention relates to an aqueous-developable negative photosensitive polyimide coating adhesive and its preparation method and application, belonging to the technical field of polymer material preparation. Background Art

[0002] Photosensitive polyimide coating (PSPI) can be coated on the surface of substrates such as single-crystalline silicon to form a liquid film. After processes such as pre-baking, exposure, development, and rinsing, a three-dimensional precursor resin pattern can be formed on the substrate surface. The polyimide resin formed after high-temperature curing has advantages such as high temperature resistance, high strength and toughness, high electrical insulation, and high chemical corrosion resistance, and is widely used in the manufacturing and packaging of ultra-large-scale integrated circuits (ULSI), mainly including interlayer insulating dielectric films for multi-layer metal interconnect circuits and multi-layer wiring (RDL), α-particle barrier layers, stress relief and buffer coating films, etc. At the same time, it also has wide application value in the preparation of optoelectronic displays such as OLED, PLED, and LCD, mainly including cathode isolation columns, insulating layers, pixel division layers, planarization layers, etc.

[0003] Positive PSPI has obvious advantages in environmental friendliness due to the use of an aqueous development system, but it is difficult to prepare thick films due to limitations in chemical implementation methods. Negative PSPI not only has the potential to fabricate high aspect ratio patterns on thick films, but also its higher mechanical properties, adhesion, and chemical resistance make it more reliable in extreme environments. In recent years, in response to the semiconductor industry's demand for sustainable development, considering the improvement of production safety and reduction of environmental hazards, the industry is trying to convert the organic development system used in traditional negative photoresists into the same aqueous development system as positive photoresists.

[0004] On the other hand, as the chip integration density becomes higher and higher, the devices become smaller and smaller, and the distance between conductive interconnects becomes shorter and shorter. As a result, the parasitic resistance effect and parasitic capacitance effect in the circuit become more and more serious, and the resistance and capacitance delay of metal interconnects increase nearly quadratically, leading to signal transmission delay and crosstalk, directly affecting device performance. In order to minimize the signal delay time in the interconnect circuit, reducing the dielectric constant of the interlayer dielectric material can effectively reduce the RC delay.

[0005] Chen Xing et al. (CN110028670A) disclosed a low dielectric loss negative photosensitive polyamic acid ester resin, a resin composition, and a preparation method thereof. In the composition, a fluorine-containing diester diacyl chloride and a non-fluorine-containing diester diacyl chloride are mixed and then polycondensed with a fluorine-containing diamine and a non-fluorine-containing diamine to form a polyamic acid ester. The formed polyamic acid ester is mixed with a photosensitizer, a crosslinking agent, an adhesion promoter, an inhibitor, and an organic solvent to form a negative photosensitive polyamic acid ester resin composition. After pre-baking and exposure, it is developed with an organic solvent, and the dielectric constant can reach 2.7 after curing.

[0006] Zhang Guoping et al. (CN109824833B) disclosed a composition of a negative photosensitive polyimide and an application method thereof. The photosensitive composition is composed of a glycerol methacrylate esterified polyamic acid ester resin, an oxime ester photosensitizer with a low esterification degree, a crosslinking agent, an organic solvent, and other additives. After pre-baking and exposure, it is developed with an organic solvent, and the dielectric constant can reach about 2.5 or even lower after curing.

[0007] Min Yonggang et al. (CN114907567B) disclosed a negative photosensitive polyimide composition that can be developed with an alkaline solution. The composition is composed of an alkynyl-containing polyamic acid, a thiol crosslinking agent, an initiator, and an organic solvent. After pre-baking and exposure, it is developed with a 2.38% TMAH aqueous solution, and the dielectric constant can reach 2.8 after curing.

[0008] Although the above compositions of negative photosensitive polyimides also have a low dielectric constant after curing, their development with organic solvents is not environmentally friendly, or the performances such as the dielectric constant, the aspect ratio of the lithographic pattern, the heat resistance of the cured resin, and the adhesion to different metal interfaces need to be further improved. Therefore, it is still an urgent technical problem to be solved at present to develop an aqueous-developable negative photosensitive polyimide coating adhesive with high aspect ratio of lithographic pattern, low dielectric constant, high heat resistance of the cured resin, and good adhesion to different metal interfaces. Summary of the Invention

[0009] The object of the present invention is to provide an aqueous-developable negative photosensitive polyimide coating adhesive, a preparation method thereof, and an application thereof. The aqueous-developable negative polyimide coating adhesive is developed in an alkaline aqueous solution, which meets the current environmental protection requirements of the semiconductor industry. At the same time, it has the characteristics of high aspect ratio of lithographic pattern, low dielectric constant, high heat resistance of the cured resin, and good adhesion to different metal interfaces, and is suitable for applications in fields such as optoelectronic flat panel display and semiconductor chip packaging.

[0010] In the first aspect, the present invention provides an aqueous-developable negative polyimide coating adhesive, which is made from raw materials including the following parts by weight:

[0011] 100 parts of a hydroxyl-containing polyamic acid ester resin, 0.1 - 10 parts of a photoinitiator, 1 - 30 parts of a crosslinking agent, 0.5 - 5 parts of a copper discoloration inhibitor, 0.1 - 25 parts of a photosensitization promoter, 0.5 - 25 parts of an adhesion promoter, 0.005 - 12 parts of a thermal polymerization inhibitor, and 100 - 250 parts of an organic solvent A;

[0012] The preparation method of the hydroxyl-containing polyamic acid ester resin comprises the following steps:

[0013] S1. In the presence of an organic base, an aromatic tetracarboxylic dianhydride and a hydroxyl-containing methacrylate are subjected to an esterification reaction in an organic solvent B to obtain an aromatic diacid diester solution;

[0014] S2. Thionyl chloride is added to the aromatic diacid diester solution for reaction to obtain an aromatic diacyl chloride diester solution;

[0015] S3. The aromatic diacyl chloride diester solution is added to a solution of the aromatic diamine shown in Formula I for reaction to obtain the hydroxyl-containing polyamic acid ester resin;

[0016]

[0017] In Formula I, R1, R2, R3, and R4 each independently selected from any one of NH2 and OH; X1, X2, X3, X4, and X5 each independently selected from any one of H, F, OH, CF3, CH3, C(CH3), and CH(CH3)2.

[0018] Further, in Formula I, R1 and R2 are NH2, R3 and R4 are OH; X1 and X2 are H, and X3, X4, and X5 are each independently OH, CF3, CH3, CH(CH3)2, or H.

[0019] In the embodiments of the present invention, the aromatic diamine shown in Formula I is any one of the following compounds of Formula 1 - Formula 4:

[0020]

[0021]

[0022] In the above-mentioned aqueous developing negative polyimide coating adhesive, the aromatic tetracarboxylic dianhydride is selected from at least one of 4,4'-oxybisphthalic anhydride (ODPA), pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylether tetracarboxylic dianhydride (OPDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (BFDA), 2,2-bis(3,4-phthalic anhydride) propane (BAPPA), and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA);

[0023] The hydroxy group-containing methacrylate is selected from at least one of 2-hydroxyethyl methacrylate (HEMA), 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate;

[0024] The molar ratio of the aromatic tetracarboxylic dianhydride to the hydroxy group-containing methacrylate is 1:(1 - 2.5), preferably 1:(1.3 - 2), such as 1:1.3, 1:1.5, or 1:2.0;

[0025] In step S1, the raw materials further include lower aliphatic alcohols;

[0026] The lower aliphatic alcohol is selected from at least one of methanol, ethanol, propanol, isopropanol, n-butanol, and tert-butanol;

[0027] The molar ratio of the hydroxy group-containing methacrylate to the lower aliphatic alcohol is 1:(0 - 99), such as 1:(0.01 - 99), preferably 1:(0 - 10), such as 1:(0.01 - 10), 1:0.15;

[0028] The temperature of the esterification reaction is 20 - 150°C, preferably 25 - 100°C (such as 25°C), and the time is 0.5 - 96 h, preferably 0.5 - 24 h (such as 6 h);

[0029] The organic solvent B is selected from at least one of N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, tetrahydrofuran, dioxane, ethyl lactate, ethylene glycol monomethyl ether, and ethylene glycol dimethyl ether;

[0030] The weight ratio of the aromatic tetracarboxylic dianhydride to the organic solvent B is (5 to 100):100, preferably (10 to 40):100, such as 24:100;

[0031] The organic base is selected from at least one of triethylamine, pyridine, isoquinoline, 4-dimethylaminopyridine, 2,6-dimethylpyridine, imidazole, piperazine, N,N-diisopropylethylamine, and N,N-dimethylformamide;

[0032] The mass ratio of the organic base to the organic solvent B is (1 to 20):100, such as 12:100.

[0033] In the above aqueous-developable negative polyimide coating adhesive, the molar ratio of the aromatic diacid diester to the thionyl chloride is 1:(1.5 to 3), preferably 1:(1.8 to 2.2);

[0034] In step S2, the temperature of the reaction is -30 to 50 °C, preferably -20 to 25 °C, and the time is 1 to 48 h, preferably 2 to 12 h, such as reacting at (such as 0 - 10 °C for 2 h and at room temperature for 4 h).

[0035] In the above aqueous-developable negative polyimide coating adhesive, the molar ratio of the aromatic tetracarboxylic dianhydride to the aromatic diamine is 1:(0.8 to 1.2), preferably 1:(0.9 to 1.1), such as 1:0.95;

[0036] The solvent in the solution of the aromatic diamine is at least one of N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), ethyl acetate, tetrahydrofuran, dioxane, and ethyl lactate;

[0037] The molar ratio of the aromatic diacyl chloride diester to the aromatic diamine is 1:(0.8 to 1.2);

[0038] The aromatic diacyl chloride diester solution is added dropwise to the solution of the aromatic diamine shown in formula I, and the dropping temperature is -30 to 10 °C, preferably -10 to 10 °C;

[0039] In step S3, the reaction temperature of the aromatic diamine and the aromatic diacyl chloride diester is -15 to 30 °C, and the time is 0.5 to 96 h, preferably 1 to 24 h;

[0040] In step S3, after the reaction, there is also a step of adding a capping agent and continuing the reaction;

[0041] The capping agent is selected from at least one of phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, acetic anhydride, propionic anhydride, aniline, 3-methylaniline, 4-methylaniline, 3-aminophenylacetylene, 4-ethynylaniline, 3-aminophenol, 4-aminophenol, methylamine, ethylamine, and propylamine;

[0042] The molar ratio of the capping agent to the aromatic diamine is (0 - 70):100, preferably (0 - 50):100, such as 10.5:100, to achieve the said molecular weight range;

[0043] The temperature for the continued reaction is -15 to 40 °C (such as 25 °C), and the time is 1 to 12 h (such as 1 h);

[0044] The weight-average molecular weight of the hydroxyl-containing polyimide resin is 5000 - 100000 g / mol.

[0045] After the reaction is completed in step S3, the said method further includes the following post-treatment steps: pouring the reaction solution into deionized water, precipitating solids, filtering, and vacuum drying.

[0046] In the above aqueous-developable negative polyimide coating adhesive, the photoinitiator is selected from at least one of benzophenone, dibenzyl ketone, 4-benzoyl-4'-methyldiphenyl ketone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzil, benzil dimethyl ketal, benzil-β-methoxyethyl ketal, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime)), 1-phenyl-1,2-butanedione-2-(0-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(0-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2-(0-benzoyl) oxime, 1,3-diphenylpropane trione-2-(0-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropane trione-2-(0-benzoyl) oxime, N-phenylglycine, benzoyl peroxide, and α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyl oxime).

[0047] In the above-mentioned aqueous developing negative polyimide coating adhesive, the crosslinking agent is selected from at least one of diethylene glycol dimethacrylate (2EM), tetraethylene glycol dimethacrylate (4EM), tricyclodecane dimethanol diacrylate, pentaerythritol tetraacrylate, tris(2-hydroxyethyl) isocyanurate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, cyclohexane dimethacrylate, and 1,4-butanediol dimethacrylate.

[0048] The copper discoloration inhibitor is selected from azole compounds such as tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, bulky-effect phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 4,4'-methylenebis(2,6-di-tert-butylphenol), or a mixture thereof in any proportion.

[0049] In the above-mentioned aqueous developing negative polyimide coating adhesive, the photosensitizing promoter is selected from at least one of 4-morpholinobenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 4,4′-bis(dimethylamino)benzophenone, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, p-dimethylaminocinnamylindanone, p-dimethylaminobenzylideneindenone, 2-(p-dimethylaminophenylazophenyl)-benzothiazole, 2-(p-dimethylaminostyryl)-benzoxazole, 2-(p-dimethylaminophenylvinylidene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)isoindolothiazole, N-phenyldiethanolamine, N,N-dihydroxyethyl-p-toluidine, N-p-tolyldiethanolamine, N-phenylethanolamine, N-phenyl-N'-ethylethanolamine, 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 1-phenyl-5-mercaptotetrazole;

[0050] The adhesion promoter is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(triethoxysilyl)propyl succinic anhydride, N-(3-diethoxymethylsilylpropyl)succinimide, N-(3-diethoxymethylsilylpropyl)phthalic acid amide, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid and benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid;

[0051] The thermal polymerization inhibitor is selected from at least one of hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-cresol, 2,6-dimethoxymethyl-4-tert-butylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, ammonium salt of N-nitroso-N-phenylhydroxylamine and ammonium salt of N-nitroso-N(1-naphthyl)hydroxylamine;

[0052] In the above aqueous-developable negative polyimide coating adhesive, the organic solvent A is selected from at least one of N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), γ-butyrolactone (GBL), acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, tetrahydrofuran, dioxane, ethyl lactate, pyruvic acid, isobutyric acid, citraconic acid, mandelic acid, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol;

[0053] In at least one embodiment of the present invention, the aqueous-developable negative polyimide coating adhesive is made from the following raw materials in parts by weight: 100 parts of a hydroxyl-containing polyamic acid ester resin, 10 parts of a photoinitiator, 30 parts of a crosslinking agent, 1 part of a copper discoloration inhibitor, 2 parts of a photosensitization promoter, 4 parts of an adhesion promoter, 6 parts of a thermal polymerization inhibitor and 200 parts of an organic solvent A.

[0054] In a second aspect, the present invention provides an interlayer dielectric insulating film, a stress absorption-buffer protective film, a passivation protective film or an α-particle shielding layer film for fabricating a multilayer interconnect circuit on the surface of a chip, which is made of the aqueous-developable negative polyimide coating adhesive described in any one of the above.

[0055] In a third aspect, the present invention provides an application of the aqueous-developable negative polyimide coating adhesive described in any one of the above in optoelectronic flat panel display, semiconductor chip manufacturing or advanced electronic packaging, especially in the preparation of an interlayer dielectric insulating film, a stress absorption-buffer protective film, a passivation protective film or an α-particle shielding layer film for fabricating a multilayer interconnect circuit on the surface of a chip.

[0056] As an example, the aqueous-developable negative polyimide coating adhesive is used to fabricate a multilayer interconnect circuit on the surface of copper. The method for fabricating a multilayer interconnect circuit on the surface of copper includes the following steps:

[0057] 1) Coating: Coating the aqueous-developable negative photosensitive polyimide resin photoresist described in any one of the above on the surface of a wafer by spin coating and / or spraying;

[0058] 2) Pre-baking: Performing pre-baking treatment at 90 - 130 °C to form a resin film with a thickness of 5 - 40 μm;

[0059] 3) Exposure: Performing exposure using an ultraviolet light source through a photomask or a reticle;

[0060] 4) Post-baking: Performing post-baking for film hardening at 100 - 140 °C;

[0061] 5) Development + rinsing: Dissolving and removing the exposed resin layer using an alkaline developer, leaving the unexposed resin layer; after rinsing with deionized water, forming a three-dimensional pattern of polyimide resin;

[0062] 6) Heating and curing: Heating and curing the three-dimensional pattern of polyimide resin on the surface of the silicon wafer.

[0063] Specifically, the alkaline developer is an aqueous solution of 2.38 wt% tetramethylammonium hydroxide.

[0064] Using the above process, a multilayer interconnect circuit can be formed on the surface of copper.

[0065] The present invention has the following beneficial effects:

[0066] The chemically amplified negative polyimide coating adhesive of the present invention has advantages such as a high aspect ratio (≥0.7), a dielectric constant ≤ 2.8, high heat resistance (Tg > 280 °C), and good adhesion to the metal interface (peel strength ≥ 70 MPa), and is suitable for applications in fields such as flat panel display, semiconductor chip manufacturing, and advanced packaging. Detailed implementation mode

[0067] The present invention will be further described in detail below in conjunction with specific embodiments. The provided embodiments are only for clarifying the present invention and not for limiting the scope of the present invention. The following embodiments can be used as a guide for those of ordinary skill in the art to make further improvements, and do not constitute any limitation to the present invention in any way.

[0068] The methods used in the following embodiments are all conventional methods unless otherwise specified, and are carried out according to the techniques or conditions described in the literature in the field or according to the product specifications. The materials, reagents, etc. used in the following embodiments can be obtained from commercial sources unless otherwise specified.

[0069] Synthesis Example of Diamine Monomer Containing Phenolic Hydroxyl

[0070] The diamine monomers containing phenolic hydroxyl used in the following synthesis examples were obtained by referring to the preparation method disclosed in CN101362700B. The specific steps for synthesizing each diamine monomer containing phenolic hydroxyl are as follows:

[0071] Diamine Synthesis Example 1: Add 94.11 g (1.00 mol) of phenol and 60.53 g (0.25 mol) of 3′-trifluoromethyl-2,2,2-trifluoroacetophenone into a three-necked flask and stir evenly with mechanical stirring. Heat the three-necked flask to 50 °C to 100 °C and react for more than 1 hour until the raw materials are completely dissolved. Dropwise add 10 g of trifluoromethanesulfonic acid and keep the temperature at 50 °C to 100 °C and react for 10 hours. After cooling to room temperature, wash the product with boiling deionized water until it is pure white, and place it in a vacuum oven at 80 °C to dry to obtain 1,1-bis(4′-hydroxyphenyl)-1-(3′-trifluoromethylphenyl)-2,2,2-trifluoroethane (D-1). Take 51.54 g (0.125 mol) of D-1 and dissolve it in 300 mL to 500 mL of glacial acetic acid. Circulatingly cool the reaction vessel to -20 °C to -30 °C, and slowly dropwise add 100 mL of concentrated nitric acid at this temperature. After the dropping is completed, react for 10 to 24 hours and then pour it into crushed ice. Filter and collect the yellow reaction product, wash it with deionized water until it is neutral, and then dry it in a vacuum oven at 80 °C to obtain 1,1-bis(4′-hydroxy-3′-nitrophenyl)-1-(3′-trifluoromethylphenyl)-2,2,2-trifluoroethane (E-1). Take 62.79 g (0.125 mol) of E-1 and completely dissolve it in 700 ml of ethanol. Add 1.8 g of 5% palladium / carbon and 120 ml of hydrazine hydrate and heat to reflux for 12 hours. Filter to remove palladium carbon at a temperature above 60 °C, then rotary evaporate and concentrate the filtrate. After cooling, filter to obtain the precipitated white powder, and dry it in a vacuum oven at 80 °C to obtain the diamine monomer containing phenolic hydroxyl 1,1-bis(4′-hydroxy-3′-aminophenyl)-1-(3′-trifluoromethylphenyl)-2,2,2-trifluoroethane (DA-1), and the structure is as

[0072] shown in Formula 1.

[0073]

[0074] Synthesis Example 2 of diamine: Replace 60.53 g (0.25 mol) of 3'-trifluoromethyl-2,2,2-trifluoroacetophenone in Synthesis Example 1 of diamine with 140.96 g (0.45 mol) of 3',5'-bis(trifluoromethyl)-2,2,2-trifluoroacetophenone; replace 10 g of trifluoromethanesulfonic acid with 18 g of p-toluenesulfonic acid to obtain 1,1-bis(4'-hydroxyphenyl)-1-[3',5'-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane (D-2). Then replace 51.54 g (0.125 mol) of D-1 with 60.04 g (0.125 mol) of D-2; replace 100 mL of concentrated nitric acid with 80 ml of a 1:1 (v / v) mixed solution of concentrated nitric acid / sulfuric acid to obtain 1,1-bis(4'-hydroxy-3'-nitrophenyl)-1-[3',5'-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane (E-2). Finally, replace 62.79 g (0.125 mol) of E-1 with 71.3 g (0.125 mol) of E-2. Other operations are the same as those in Synthesis Example 1 of diamine to obtain 1,1-bis(4'-hydroxy-3'-aminophenyl)-1-[3',5'-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane (DA-2), and its structure is shown in Formula 2.

[0075]

[0076] Synthesis Example 3 of diamine: Replace 60.53 g (0.25 mol) of 3'-trifluoromethyl-2,2,2-trifluoroacetophenone in Synthesis Example 1 of diamine with 60.53 g (0.25 mol) of 4'-trifluoromethyl-2,2,2-trifluoroacetophenone to obtain 1,1-bis(4'-hydroxyphenyl)-1-(4'-trifluoromethylphenyl)-2,2,2-trifluoroethane (D-3). Then replace 51.54 g (0.125 mol) of D-1 with 51.54 g (0.125 mol) of D-3; replace 100 mL of concentrated nitric acid with 120 ml of a 2:1 (v / v) mixed solution of concentrated nitric acid / methanesulfonic acid. Obtain 1,1-bis(4'-hydroxy-3'-nitrophenyl)-1-(4'-trifluoromethylphenyl)-2,2,2-trifluoroethane (E-3). Finally, replace 62.79 g (0.125 mol) of E-1 with 62.80 g (0.125 mol) of E-3. Other operations are the same as those in Synthesis Example 1 of diamine to obtain 1,1-bis(4'-hydroxy-3'-aminophenyl)-1-(4'-trifluoromethylphenyl)-2,2,2-trifluoroethane DA-3, and its structure is shown in Formula 3.

[0077]

[0078] Synthesis Example 4 of diamine: Replace 60.53 g (0.25 mol) of 3'-trifluoromethyl-2,2,2-trifluoroacetophenone in Synthesis Example 1 of diamine with 86.5 g (0.4 mol) of 4-isopropyl-2,2,2-trifluoroethane to obtain 1,1-bis(1'-hydroxyphenyl)-1-(4'-isopropylphenyl)-2,2,2-trifluoroethane (D-4). Then replace 51.54 g (0.125 mol) of D-1 with 48.3 g (0.125 mol) of D-4; change the circulating cooling temperature from -20 to -30 °C to -10 to 10 °C to obtain 1,1-bis(4'-hydroxy-3'-nitrophenyl)-1-(4'-isopropylphenyl)-2,2,2-trifluoroethane (E-4). Finally, replace 62.79 g (0.125 mol) of E-1 with 59.55 g (0.125 mol) of E-4. The rest is the same as in Synthesis Example 1 of diamine to obtain 1,1-bis(4'-hydroxy-3'-aminophenyl)-1-(4'-isopropylphenyl)-2,2,2-trifluoroethane DA-4, and its structure is as shown in Formula 4.

[0079]

[0080] Synthesis Example of Hydroxyl-Containing Polyimide Precursor Solid Resin

[0081] The hydroxyl-containing polyimide precursor solid resins used in the following examples were obtained through the following synthesis examples respectively:

[0082] Synthesis Example 1 In a 500 ml three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 0.10 mol (31.02 g) of 4,4'-oxybisphthalic anhydride (ODPA), 0.13 mol (16.92 g) of 2-hydroxyethyl methacrylate (HEMA), 15.82 g of pyridine and 129 g of N-methylpyrrolidone (NMP), stir at room temperature for 6 h to generate the corresponding aromatic diacid dimethacrylate. React the above product with 23.79 g of SOCl2 at 0-10 °C for 2 h and at room temperature for 4 h to generate the corresponding ODPA diacyl chloride dimethacrylate.

[0083] In a 1 L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 0.095 mol (41.64 g) of DA-1 prepared in Synthesis Example 1 of diamine and 150 NMP were added, and stirred to dissolve to form a homogeneous transparent solution; the temperature of the reaction solution was cooled to below 10 °C using an ice bath, and the ODPA diacyl chloride dimethacrylate prepared above was added dropwise to the NMP solution of DA-1, and the dropping time was 0.5 h; then, the reaction was carried out at room temperature for 10 h; then 0.01 mol (0.11 g) of 4-aminophenol was added, and stirring was continued for 1 h; the reaction solution was poured into 5 L of deionized water, the solid was precipitated, filtered, and vacuum dried to obtain a 65% esterified polyimide precursor resin solid (also known as Polymer A1). Mw: 23197 g / mol

[0084] Synthesis Example 2 The addition amount of HEMA in Synthesis Example 1 was increased to 0.15 mol (19.52 g), and the method in Synthesis Example 1 was followed otherwise to obtain a 75% esterified polyimide precursor resin solid (also known as Polymer A2). Mw: 24323 g / mol

[0085] Synthesis Example 3 The addition amount of HEMA in Synthesis Example 1 was increased to 0.2 mol (26.03 g), and the method in Synthesis Example 1 was followed otherwise to obtain a 100% esterified polyimide precursor resin solid (also known as Polymer A3). Mw: 23947 g / mol

[0086] Synthesis Example 4 0.095 mol (47.33 g) of DA-2 was used to replace 0.095 mol (41.64 g) of DA-1 in Synthesis Example 2 of the resin of the present invention, and the reaction was carried out according to the method in Synthesis Example 2 of the resin of the present invention otherwise to obtain a polyimide precursor resin solid (also known as Polymer A4). Mw: 21347 g / mol

[0087] Synthesis Example 5 0.095 mol (41.64 g) of DA-3 was used to replace 0.095 mol (41.64 g) of DA-1 in Synthesis Example 2 of the resin of the present invention, and the reaction was carried out according to the method in Synthesis Example 2 of the resin of the present invention otherwise to obtain a polyimide precursor resin solid (also known as Polymer A5). Mw: 22047 g / mol

[0088] Synthesis Example 6 0.095 mol (42.13 g) of DA-4 was used to replace 0.095 mol (41.64 g) of DA-1 in Synthesis Example 2 of the resin of the present invention, and the reaction was carried out according to the method in Synthesis Example 2 of the resin of the present invention otherwise to obtain a polyimide precursor resin solid (also known as Polymer A6). Mw: 23841 g / mol

[0089] Synthesis Example 7 0.1 mol (32.22 g) of 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) was used to replace 0.1 mol (31.02 g) of 3,3',4,4'-oxydiphthalic dianhydride (ODPA) in Synthesis Example 2 of the resin of the present invention. Except for this, the reaction was carried out according to the method in Synthesis Example 2 of the resin of the present invention to obtain a polyimide precursor resin solid (also known as Polymer A7). Mw: 21038 g / mol

[0090] Synthesis Example 8 0.05 mol (15.51 g) of 3,3',4,4'-oxydiphthalic dianhydride (ODPA) and 0.05 mol (22.21 g) of 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA) were used to replace 0.1 mol (31.02 g) of 3,3',4,4'-oxydiphthalic dianhydride (ODPA) in Synthesis Example 2 of the resin of the present invention. Except for this, the reaction was carried out according to the method in Synthesis Example 2 of the resin of the present invention to obtain a polyimide precursor resin solid (also known as Polymer A8). Mw: 22025 g / mol

[0091] Synthesis Example 9 0.02 mol of ethanol (9.21 g) and 0.13 mol of 2-hydroxyethyl methacrylate (HEMA) (16.92 g) were used to replace 0.15 mol (19.52 g) of 2-hydroxyethyl methacrylate (HEMA) in Synthesis Example 2 of the resin of the present invention. Except for this, the reaction was carried out according to the method in Synthesis Example 2 of the resin of the present invention to obtain a polyimide precursor resin solid (also known as Polymer A9). Mw: 21341 g / mol

[0092] Synthesis Example 10 0.95 mol (34.79 g) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was used to replace 0.095 mol (41.64 g) of DA-1 in Synthesis Example 3 of the resin of the present invention. Except for this, the reaction was carried out according to the method in Synthesis Example 3 of the resin of the present invention to obtain a polyimide precursor resin solid (also known as Polymer B1). Mw: 20462 g / mol

[0093] Synthesis Example 11 0.95 mol (20.54 g) of 3,3'-dihydroxybenzidine was used to replace 0.095 mol (41.64 g) of DA-1 in Synthesis Example 3 of the resin of the present invention. Except for this, the reaction was carried out according to the method in Synthesis Example 3 of the resin of the present invention to obtain a polyimide precursor resin solid (also known as Polymer B2). Mw: 20117 g / mol

[0094] Synthesis Example 12 In a 1 L three-necked round-bottom flask equipped with a mechanical stirrer, a thermometer, and a nitrogen protection device, 0.1 mol (32.02 g) of 2,2'-bis(trifluoromethyl)benzidine (TFDB) and 150 g of NMP were added, and stirred to dissolve to form a homogeneous transparent solution. The temperature of the reaction solution was cooled to below 10 °C using an ice bath, and 0.05 mol (22.21 g) of 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane (6FDA) and 0.05 mol (15.91 g) of 4,4'-(ethyne-1,2-diyl)diphthalic anhydride were added to the NMP solution of TFDB. Then, the reaction was carried out at room temperature for 10 h. The reaction solution was poured into 5 L of deionized water, and the solid was precipitated, filtered, and dried in vacuo to obtain a polyamic acid resin (also known as Polymer B3). Mw: 22656 g / mol

[0095] Preparation Example of Aqueous Developable Negative Photosensitive Polyimide Coating Adhesive

[0096] The following evaluation method was used to evaluate the performance of the prepared aqueous developable negative PSPI photoresist:

[0097] 1) Resolution: The negative PSPI photoresist solution was spin-coated on the surface of a silicon wafer; pre-baked at 90 - 130 °C to form a film, obtaining a polyimide layer film with a thickness of about 10 μm. A mask was placed on its surface, and exposed using i-line or ultraviolet light (i and g lines), then post-baked at 100 - 140 °C; developed using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide developer, rinsed with deionized water, and then heat-cured in a nitrogen-protected forced-air oven (140 °C / 1 h, 350 °C / 1 h) to obtain a three-dimensional photolithography pattern of polyimide resin. The cross-section of the pattern was cut by focused ion beam to observe the development of the pattern, and the minimum resolution of the complete and clean pattern was measured.

[0098] 2) Aspect ratio: The negative PSPI photoresist solution was spin-coated on the surface of a silicon wafer; pre-baked at 90 - 130 °C to form a film, obtaining a polyimide layer film with a thickness of about 10 μm. A mask was placed on its surface, and exposed using i-line or ultraviolet light (i and g lines), then post-baked at 100 - 140 °C; developed using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide developer, rinsed with deionized water, and then heat-cured in a nitrogen-protected forced-air oven (140 °C / 1 h, 350 °C / 1 h) to obtain a three-dimensional photolithography pattern of polyimide resin. The cross-section of the pattern was cut by focused ion beam to measure the thickness of the cured film, and the ratio of the thickness of the cured film to the minimum resolution was calculated.

[0099] 3) Heat resistance: Spin-coat the negative PSPI photoresist solution on the surface of a silicon wafer; perform pre-baking at 90 - 130 °C to form a film, obtaining a polyimide layer film with a thickness of about 10 μm. Expose it using i-line or ultraviolet light (i and g lines), then perform post-baking at 100 - 140 °C; develop it using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as the developer, rinse it with deionized water, and then heat and cure it in a blast oven under nitrogen protection (140 °C / 1 h, 350 °C / 1 h). Immerse the silicon wafer with the film in 47% HF for 5 - 10 minutes, then rinse it with water to obtain a polyimide film with a thickness of 5 - 7 μm; cut the polyimide film into strip-shaped samples, and use a dynamic thermomechanical analyzer (DMA) to measure the glass transition temperature (tanδ peak) of the film. The DMA test frequency is 1 Hz, and the heating rate is 5 °C / min.

[0100] 4) Adhesion to copper surface: Spin-coat the negative PSPI photoresist solution on the surface of a silicon wafer that has been sputtered with Ti (thickness: 200 nm) and Cu (thickness: 400 nm) in sequence; spin-coat the negative PSPI photoresist solution on the surface of a silicon wafer; perform pre-baking at 90 - 130 °C to form a film, obtaining a polyimide layer film with a thickness of about 10 μm. Expose it using i-line or ultraviolet light (i and g lines), then perform post-baking at 100 - 140 °C; develop it using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as the developer, rinse it with deionized water, and then heat and cure it in a blast oven under nitrogen protection (140 °C / 1 h, 350 °C / 1 h) to obtain a polyimide layer film with a thickness of 5 - 7 μm. Use the stud pull die bond strength test of Quad Group to measure the chip bond strength and test the adhesion of the film to copper.

[0101] 5) Dielectric properties: Spin-coat the negative PSPI photoresist solution on the surface of a silicon wafer; perform pre-baking at 90 - 130 °C to form a film, obtaining a polyimide layer film with a thickness of about 10 μm. Expose it using i-line or ultraviolet light (i and g lines), then perform post-baking at 100 - 140 °C; develop it using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as the developer, rinse it with deionized water, and then heat and cure it in a blast oven under nitrogen protection (140 °C / 1 h, 350 °C / 1 h). Immerse the silicon wafer with the film in 47% HF for 5 - 10 minutes, then rinse it with water to obtain a polyimide film with a thickness of 5 - 7 μm; use a network analyzer to measure the dielectric constant of the film at 10 GHz.

[0102] Example 1: In a clean room equipped with yellow lights, 50 g of polymer A1 was weighed and dissolved in 100 g of NMP solvent to form a homogeneous solution. Then, 5 g of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (OXE01), 1 g of 4,4′-bis(dimethylamino)benzophenone, 15 g of tetraethylene glycol dimethacrylate (4EM), 0.5 g of 5-methyl-1H-benzotriazole, 2 g of γ-glycidoxypropyltrimethoxysilane, 2.5 g of 2,6-dimethoxymethyl-4-tert-butylphenol, and 0.5 g of N-nitrosodiphenylamine were successively added and stirred at room temperature for 1 h to form a negative PSPI photoresist solution with a solid content of 33 ± 1% and a viscosity of 3500 mPa·s at room temperature.

[0103] The above negative PSPI photoresist solution was spin-coated on the surface of the wafer to form a liquid film. After baking at 90 - 130 °C for 2 - 5 min, a solid film with a thickness of about 10 μm was formed. A mask plate was placed on its surface and exposed using i-line or ultraviolet light (i and g lines). Then, it was baked at 100 - 140 °C for 0 min - 6 min. Development was carried out using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide developer. After rinsing with deionized water, a stereolithographic pattern was formed. It was heated and cured in a nitrogen-protected forced-air oven (140 °C / 1 h + 350 °C / 1 h) to obtain a stereolithographic pattern formed by a cured polyimide film on the surface of the wafer.

[0104] The photolithographic pattern resolution of this negative PSPI photoresist was 6 μm, the aspect ratio of the cured PI pattern was 0.7, the Tg was 303 °C, the copper surface peel strength was >70 MPa, and the dielectric constant was 2.6.

[0105] Example 2: 50 g of polymer A2 was used instead of 50 g of polymer A1, and otherwise, the same method as described in Example 1 of the present invention was carried out.

[0106] The photolithographic pattern resolution of this negative PSPI photoresist was 6 μm, the aspect ratio of the cured PI pattern was 1.2, the Tg was 303 °C, the copper surface peel strength was >70 MPa, and the dielectric constant was 2.6.

[0107] Example 3: 50 g of polymer A3 was used instead of 50 g of polymer A1, and otherwise, the same method as described in Example 1 of the present invention was carried out.

[0108] The photolithographic pattern resolution of this negative PSPI photoresist was 7 μm, the aspect ratio of the cured PI pattern was 0.8, the Tg was 303 °C, the copper surface peel strength was >70 MPa, and the dielectric constant was 2.6.

[0109] Example 4: Replace 15 g of tetraethylene glycol dimethacrylate in Example 1 with 15 g of pentaerythritol tetraacrylate, and perform the same method as described in Example 1 of the present invention.

[0110] The lithography pattern resolution of this negative PSPI photoresist is 6 μm, the aspect ratio of the cured PI pattern is 1.2, the Tg is 303 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.6.

[0111] Example 5: Replace 15 g of tetraethylene glycol dimethacrylate in Example 1 with 15 g of ethoxylated trimethylolpropane triacrylate, and perform the same method as described in Example 1 of the present invention.

[0112] The lithography pattern resolution of this negative PSPI photoresist is 7 μm, the aspect ratio of the cured PI pattern is 1.0, the Tg is 303 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.6.

[0113] Example 6: Replace 1 g of 4,4′-bis(dimethylamino)benzophenone in Example 4 with 1 g of N,N-di(hydroxyethyl)-p-toluidine, and perform the same method as described in Example 4 of the present invention.

[0114] The lithography pattern resolution of this negative PSPI photoresist is 5 μm, the aspect ratio of the cured PI pattern is 1.0, the Tg is 303 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.6.

[0115] Example 7: Replace 1 g of 4,4′-bis(dimethylamino)benzophenone in Example 4 with 1 g of 2-mercaptobenzoxazole, and perform the same method as described in Example 4 of the present invention.

[0116] The lithography pattern resolution of this negative PSPI photoresist is 6 μm, the aspect ratio of the cured PI pattern is 1.2, the Tg is 303 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.6.

[0117] Example 8: Replace 5 g of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) (OXE01) in Example 7 with 5 g of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyl oxime) (OXE-02), and perform the same method as described in Example 7 of the present invention.

[0118] The lithography pattern resolution of this negative PSPI photoresist is 6 μm, the aspect ratio of the cured PI pattern is 1.2, the Tg is 303 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.6.

[0119] Example 9: 50 g of polymer A4 was used to replace 50 g of polymer A1, and the same method as described in Example 8 of the present invention was carried out otherwise.

[0120] The lithographic pattern resolution of this negative PSPI photoresist is 5 μm, the aspect ratio of the cured PI pattern is 1.2, the Tg is 287 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.5.

[0121] Example 10: 50 g of polymer A5 was used to replace 50 g of polymer A1, and the same method as described in Example 8 of the present invention was carried out otherwise.

[0122] The lithographic pattern resolution of this negative PSPI photoresist is 6 μm, the aspect ratio of the cured PI pattern is 1.2, the Tg is 301 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.6.

[0123] Example 11: 50 g of polymer A6 was used to replace 50 g of polymer A1, and the same method as described in Example 8 of the present invention was carried out otherwise.

[0124] The lithographic pattern resolution of this negative PSPI photoresist is 8 μm, the aspect ratio of the cured PI pattern is 0.9, the Tg is 310 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.8.

[0125] Example 12: 50 g of polymer A7 was used to replace 50 g of polymer A1, and the same method as described in Example 8 of the present invention was carried out otherwise.

[0126] The lithographic pattern resolution of this negative PSPI photoresist is 7 μm, the aspect ratio of the cured PI pattern is 1, the Tg is 318 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.7.

[0127] Example 13: 50 g of polymer A8 was used to replace 50 g of polymer A1, and the same method as described in Example 8 of the present invention was carried out otherwise.

[0128] The lithographic pattern resolution of this negative PSPI photoresist is 5 μm, the aspect ratio of the cured PI pattern is 1.2, the Tg is 312 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.5.

[0129] Example 14: 50 g of polymer A9 was used to replace 50 g of polymer A1, and the same method as described in Example 8 of the present invention was carried out otherwise.

[0130] The lithography pattern resolution of this negative PSPI photoresist is 5 μm, the aspect ratio of the cured PI pattern is 0.7, the Tg is 302 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.6.

[0131] Comparative Example 1: Use 50 g of Polymer B1 to replace 50 g of Polymer A1, and perform in the same manner as described in Example 8 of the present invention otherwise.

[0132] The lithography pattern resolution of this negative PSPI photoresist is 20 μm, the aspect ratio of the cured PI pattern is 0.2, the Tg is 297 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.9.

[0133] Comparative Example 2: Use 50 g of Polymer B2 to replace 50 g of Polymer A1, and perform in the same manner as described in Example 8 of the present invention otherwise.

[0134] The lithography pattern resolution of this negative PSPI photoresist is 6 μm, the aspect ratio of the cured PI pattern is 1, the Tg is 313 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 3.3.

[0135] Comparative Example 3: In a clean room equipped with a yellow light, 50 g of Resin B3 prepared in Synthesis Example 11 of the present invention was dissolved in 100 g of NMP to form a homogeneous solution; then, 2.5 g of Michler's ketone and 5 g of 3,6-dioxaoctane-1,8-dithiol were added successively and stirred at room temperature for 1 h to form a negative PSPI photoresist solution.

[0136] The lithography pattern resolution of this negative PSPI photoresist is 20 μm, the aspect ratio of the cured PI pattern is 0.4, the Tg is 339 °C, the copper surface peel strength > 70 MPa, and the dielectric constant is 2.9.

[0137] The performance comparison data of the photoresists prepared in the above examples and comparative examples are shown in Table 1.

[0138] Table 1. Performance of Photoresists in Examples and Comparative Examples

[0139]

[0140]

[0141] Compared with the negative PSPI photoresist shown in Comparative Example 1, in Example 8, Polymer A1 is used instead of Polymer B1. The difference between Polymer A1 and Polymer B1 is that the diamine monomer used in Polymer A1 is DA-1 (1,1-bis(4'-hydroxy-3'-aminophenyl)-1-(3'-trifluoromethylphenyl)-2,2,2-trifluoroethane), while the diamine monomer used in Polymer B1 is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (commonly used fluorine-containing o-hydroxy diamine). From the comparison data of Comparative Example 1 and Example 8 in Table 1, it can be seen that the photoresist made of the polymer prepared with the diamine monomer of the present invention has a lower dielectric constant and a higher aspect ratio.

[0142] Similarly, compared with the negative PSPI photoresist shown in Comparative Example 2, in Example 8, Polymer A1 is used instead of Polymer B2. The difference between Polymer A1 and Polymer B2 is that the diamine monomer used in Polymer A1 is DA-1 (1,1-bis(4'-hydroxy-3'-aminophenyl)-1-(3'-trifluoromethylphenyl)-2,2,2-trifluoroethane), while the diamine monomer used in Polymer B2 is 3,3'-dihydroxybenzidine (commonly used o-hydroxy diamine without fluorine). From the comparison data of Comparative Example 2 and Example 8 in Table 1, it can be seen that the photoresist made of the polymer prepared with the diamine monomer of the present invention has a lower dielectric constant and a higher aspect ratio.

[0143] Compared with the negative PSPI photoresist shown in Comparative Example 3, in Example 8, Polymer A1 is used instead of Polymer B3. The main difference in the glue solution is that phenolic hydroxyl groups are used as water-soluble groups in all examples, while carboxyl hydroxyl groups are used as water-soluble groups in Comparative Example 3. The resolution and adhesion of the present invention are significantly better than those of Comparative Example 3.

[0144] Compared with Example 8, in Example 14, Polymer A9 is used to replace Polymer A1. Polymer A9 uses ethanol and 2-hydroxyethyl methacrylate (HEMA) to replace 2-hydroxyethyl methacrylate (HEMA) in Synthesis Example 2. It is found that the negative PSPI photoresist shown in Example 14 has a higher resolution, but the aspect ratio of the pattern decreases.

[0145] In summary, the negative PSPI photoresist of the present invention can be developed in a water-soluble alkaline developer and has better comprehensive properties, including high resolution, high aspect ratio, high heat resistance, high adhesion, and low dielectric constant. Compared with the PSPI prepared using common fluorine-containing o-hydroxy diamine, the PSPI of the present invention has both a lower dielectric constant and a higher aspect ratio; compared with the PSPI prepared using common o-hydroxy diamine without fluorine, the PSPI of the present invention has a lower dielectric constant. Compared with the PSPI prepared using a crosslinkable polyamic acid resin, the PSPI of the present invention has a lower dielectric constant and a higher aspect ratio. The aqueous-developable negative PSPI photoresist of the present invention has excellent properties in all aspects and can be applied to semiconductor manufacturing and packaging and related application scenarios in flat panel display manufacturing and packaging, and an alkaline aqueous solution that is more beneficial to the environment and production safety can be used for development.

[0146] The present invention has been described in detail above. For those skilled in the art, the present invention can be implemented within a relatively wide range under equivalent parameters, concentrations, and conditions without departing from the purpose and scope of the present invention. Although specific embodiments of the present invention are given, it should be understood that the present invention can be further improved. In short, according to the principle of the present invention, this application intends to cover any modifications, uses, or improvements to the present invention, including changes made using conventional techniques known in the art that depart from the scope disclosed in this application.

Claims

1. A water-developable negative photosensitive polyimide coating adhesive, which is made from raw materials comprising the following parts by weight: 100 parts of a hydroxyl-containing polyamic acid ester resin, 0.1 to 10 parts of a photoinitiator, 1 to 30 parts of a crosslinking agent, 0.5 to 5 parts of a copper discoloration inhibitor, 0.1 to 25 parts of a photosensitization promoter, 0.5 to 25 parts of an adhesion promoter, 0.005 to 12 parts of a thermal polymerization inhibitor, and 100 to 250 parts of an organic solvent A; The preparation method of the hydroxyl-containing polyamic acid ester resin comprises the following steps: S1. In the presence of an organic base, raw materials including an aromatic tetracarboxylic dianhydride and a hydroxyl-containing methacrylate are subjected to an esterification reaction in an organic solvent B to obtain an aromatic diacid diester solution; S2. Thionyl chloride is added to the aromatic diacid diester solution for reaction to obtain an aromatic diacyl chloride diester solution; S3. The aromatic diacyl chloride diester solution is added to a solution of the aromatic diamine shown in Formula I for reaction to obtain the hydroxyl-containing polyamic acid ester resin; In Formula I, R1, R2, R3, and R4 each independently selected from any one of NH2 and OH; X1, X2, X3, X4, and X5 each independently selected from any one of H, F, OH, CF3, CH3, C(CH3), and CH(CH3)2.

2. The aqueous developing negative polyimide coating adhesive according to claim 1, wherein: The aromatic tetracarboxylic dianhydride is selected from at least one of 4,4'-oxybisphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylether tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride) propane, and 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane; The hydroxyl-containing methacrylate is selected from at least one of 2-hydroxyethyl methacrylate, 2-methacryloyloxyethanol, 1-methacryloyloxy-3-propanol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-tert-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate; The molar ratio of the aromatic tetracarboxylic dianhydride to the hydroxyl-containing methacrylate is 1:(1 to 2.5); In step S1, the raw materials further include a lower aliphatic alcohol; The lower aliphatic alcohol is selected from at least one of methanol, ethanol, propanol, isopropanol, n-butanol, and tert-butanol; The molar ratio of the hydroxyl-containing methacrylate to the lower aliphatic alcohol is 1:(0 to 99); The temperature of the esterification reaction is 20 to 150 °C, and the time is 0.5 to 96 h; The organic solvent B is selected from at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, tetrahydrofuran, dioxane, ethyl lactate, ethylene glycol monomethyl ether, and ethylene glycol dimethyl ether; The weight ratio of the aromatic tetracarboxylic dianhydride to the organic solvent B is (5 to 100):100; The organic base is selected from at least one of triethylamine, pyridine, isoquinoline, 4-dimethylaminopyridine, 2,6-dimethylpyridine, imidazole, piperazine, N,N-diisopropylethylamine, and N,N-dimethylformamide; The mass ratio of the organic base to the organic solvent B is (1 to 20):

100.

3. The aqueous-developable negative polyimide coating adhesive according to any one of claims 1-2, characterized in that: The molar ratio of the aromatic diacid diester to the thionyl chloride is 1:(1.5 to 3); In step S2, the temperature of the reaction is -30 to 50 °C, and the time is 1 to 48 h.

4. The aqueous developing negative polyimide coating adhesive according to any one of claims 1-3, characterized in that: The molar ratio of the aromatic tetracarboxylic dianhydride to the aromatic diamine is 1:(0.8 to 1.2); The solvent in the solution of the aromatic diamine is at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, tetrahydrofuran, dioxane, and ethyl lactate; The molar ratio of the aromatic diacyl chloride diester to the aromatic diamine is 1:(0.8 to 1.2); The solution of the aromatic diacyl chloride diester is added dropwise to the solution of the aromatic diamine shown in formula I, and the dropping temperature is -30 to 10 °C; In step S3, the reaction temperature of the aromatic diamine and the aromatic diacyl chloride diester is -15 to 30 °C, and the time is 0.5 to 96 h; In step S3, after the reaction, there is also a step of adding a capping agent and continuing the reaction; The capping agent is selected from at least one of phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, acetic anhydride, propionic anhydride, aniline, 3-methylaniline, 4-methylaniline, 3-aminophenylacetylene, 4-ethynylaniline, 3-aminophenol, 4-aminophenol, methylamine, ethylamine, and propylamine; The molar ratio of the capping agent to the aromatic diamine is (0 to 70):100; The temperature of the continued reaction is -15 to 40 °C, and the time is 1 to 12 h; The weight average molecular weight of the hydroxyl-containing polyimide resin is 5000 to 100000 g / mol.

5. The aqueous developable negative polyimide coating adhesive according to any one of claims 1-4, characterized in that: The photoinitiator is selected from at least one of benzophenone, dibenzyl ketone, 4-benzoyl-4'-methyldibenzyl ketone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzil, benzil dimethyl ketal, benzil-β-methoxyethyl ketal, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime)), 1-phenyl-1,2-butanedione-2-(0-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(0-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(0-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(0-benzoyl)oxime, 1,3-diphenylpropane trione-2-(0-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropane trione-2-(0-benzoyl)oxime, N-phenylglycine, benzoyl peroxide and α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyl oxime).

6. The aqueous developable negative polyimide coating adhesive according to any one of claims 1-5, characterized in that: The crosslinking agent is selected from at least one of diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol tetraacrylate, tris(2-hydroxyethyl)isocyanurate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, cyclohexane dimethacrylate and 1,4-butanediol dimethacrylate; The copper discoloration inhibitor is selected from at least one of tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 4,4'-methylenebis(2,6-di-tert-butylphenol).

7. The aqueous developing negative polyimide coating adhesive according to any one of claims 1-6, characterized in that: The photosensitive promoter is selected from at least one of 4-morpholinobenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 4,4′-bis(dimethylamino)benzophenone, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, p-dimethylaminocinnamylindanone, p-dimethylaminobenzylideneindenone, 2-(p-dimethylaminodiphenyl)-benzothiazole, 2-(p-dimethylaminostyryl)-benzoxazole, 2-(p-dimethylaminovinylidene)-benzothiazole, 2-(p-dimethylaminovinylidene)isoindeno[1,2-b]thiazole, N-phenyldiethanolamine, N,N-dihydroxyethyl-p-toluidine, N-p-tolyldiethanolamine, N-phenylethanolamine, N-phenyl-N'-ethylethanolamine, 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole and 1-phenyl-5-mercaptotetrazole; The tackifier is selected from at least one of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-methacryloxypropyl dimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-(triethoxysilyl)propyl succinic anhydride, N-(3-diethoxymethylsilylpropyl)succinimide, N-(3-diethoxymethylsilylpropyl)phthalimide acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid and benzene-1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid; The thermal polymerization inhibitor is selected from at least one of hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-cresol, 2,6-dimethoxymethyl-4-tert-butylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, ammonium salt of N-nitroso-N-phenylhydroxylamine and ammonium salt of N-nitroso-N(1-naphthyl)hydroxylamine.

8. The aqueous developing negative polyimide coating adhesive according to any one of claims 1-7, characterized in that: The organic solvent A is selected from at least one of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, tetrahydrofuran, dioxane, ethyl lactate, pyruvic acid, isobutyric acid, citraconic acid, mandelic acid, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol.

9. An interlayer dielectric insulating film, stress absorption-buffer protection film, passivation protection film or α-particle shielding layer film for fabricating a multi-layer interconnect circuit on the surface of a chip, characterized in that, It is made of the aqueous-developable negative polyimide coating adhesive according to any one of claims 1-8.

10. Application of the aqueous-developable negative polyimide coating adhesive according to any one of claims 1-8 in optoelectronic flat panel display, semiconductor chip manufacturing or advanced electronic packaging, especially in the application of preparing an interlayer dielectric insulating film, a stress absorption-buffer protective film, a passivation protective film or an α-particle shielding layer film for fabricating a multilayer interconnect circuit on the surface of a chip.

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