Photosensitive benzocyclobutene-based polycarbosilane based on intramolecular sila-hydrido polymerization and preparation and use in advanced packaging

Abstract

The application discloses a photosensitive benzocyclobutene-based polycarbosilane based on internal alkyne silicon hydride polymerization, preparation and application in advanced packaging, and relates to polycarbosilane obtained by a silicon hydride polymerization reaction of benzocyclobutene-based internal alkyne monomers and 1,4-di(dimethylsilyl)benzene; the polycarbosilane, a photo-crosslinking agent, a photo-initiator and an organic solvent are compounded to obtain a photoresist. The photoresist is further used as a high-performance dielectric material, realizes high-density and high-performance re-routed layers in advanced packaging, and is one of key materials supporting the development of advanced packaging technology, and therefore plays an indispensable role in frontiers such as high-performance computing and artificial intelligence, high-end communication and radio frequency, heterogeneous integration and chip grain design, image sensor and micro-electro-mechanical system.

Description

Technical Field

[0001] This invention belongs to the field of advanced packaging material preparation technology for integrated circuits, specifically relating to photosensitive benzocyclobutene-based polycarbosilane based on endoyne silane-hydropolymerization, its preparation, and its application in advanced packaging. Background Technology

[0002] Advanced packaging, as a crucial sector for surpassing Moore's Law, has become a key link in improving chip performance and a strategic battleground for global semiconductor companies. With the continuous iteration of advanced packaging technologies and the increasing number of process steps, the upstream advanced packaging materials market is also experiencing rapid growth. The global advanced packaging materials market is projected to grow from US$25.2 billion in 2023 to over US$26 billion in 2025, with a CAGR of approximately 5.6% until 2028. Advanced packaging materials encompass seven core categories: chip carriers, electroplating materials, encapsulation and protection materials, electronic adhesives, photolithography materials, chemical mechanical polishing (CMP) materials, and temporary bonding materials. Among these, advanced packaging photoresists, as a vital component of photolithography materials, are widely used in advanced packaging processes (such as wafer-level packaging, 2.5D / 3D packaging, etc.) through the patterning process of interconnect structures. Advanced packaging photoresists mainly consist of film-forming resins, photosensitive compounds (such as diazonaphthoquinone, diazid compounds, etc.), solvents, and other additives. Their thickness ranges from several micrometers to hundreds of micrometers. They typically possess advantages such as high aspect ratio (vertical sidewalls), excellent adhesion, and low stress, meeting the demands of advanced packaging with micrometer-level resolution. Currently, the domestic production rate of advanced packaging photoresists is estimated to be less than 10%, primarily limited by technological barriers related to core raw materials (such as resins and photosensitive compounds), material formulation, purity control, and compatibility with equipment.

[0003] Benzocyclobutene (BCB) resins, as a class of high-performance advanced encapsulation photoresists, include hydrocarbon (CHO) structures, hydrocarbon (CHON) structures, all-hydrogen (CH) structures, siloxane (Si-O-Si) structures, carbosilane (Si-C) structures, and carbosilane / siloxane (Si-C and Si-O-Si) structures. Their unique molecular structures endow them with excellent properties: superior thermal stability, excellent dielectric properties, excellent processability (curing process requires no catalyst and produces no small molecule byproducts), low water / moisture absorption, good mechanical properties, and compatibility. However, BCB resins also have some inherent defects, which limit their application in certain scenarios. Although DuPont's commercial BCB resins (Si-C and Si-O-Si frameworks) have high crosslinking density after curing, resulting in insufficient material toughness and brittleness, these resins have long maintained a monopoly in the international advanced encapsulation photoresist market. To improve the overall material properties of BCB resins, domestic researchers have conducted extensive research. Patent CN101463042B reports a high-performance BCB resin monomer with a Si-O-Si main chain structure, but does not report its photosensitive or patterning properties, limiting its application in advanced packaging. Patent CN117111405B reports a BCB resin with a Si-O-Si main chain structure and excellent photosensitive properties, but its thermal stability has certain defects (short chain segments may decompose at low temperatures), and the Si-O-Si structure causes a large coefficient of thermal expansion. Patents CN106916312A and CN106957433B report photosensitive hyperbranched polycarbosilane BCB resins, but the synthesis process is relatively complex, and halide ions may be present due to incomplete reactions. Patents CN107298764B and CN106866719B report silane heterocyclic butane derivatives and their photosensitive resins with excellent thermal stability, but such materials require the use of platinum photocatalysts during photocuring / patterning, which are expensive and the residual platinum at the ppm level will seriously reduce the encapsulation performance of the photoresist. Summary of the Invention

[0004] One object of the present invention is to solve at least the above-mentioned problems and / or defects, and to provide at least the advantages described below.

[0005] This invention relates to the preparation of various benzocyclobutenyl polycarbosilanes with linear macromolecular chain structures through endoyne-based benzocyclobutenyl monomers and disilane compounds undergoing endoyne-based silane-hydropolymerization in the presence of a metal catalyst. This invention also relates to the composition of benzocyclobutenyl polycarbosilane photosensitive resins, the preparation of photoresists, and the application of these photoresists in advanced packaging.

[0006] To achieve these objectives and other advantages according to the present invention, a method for preparing photosensitive benzocyclobutenyl polycarbosilane based on endoyne silane polymerization is provided, wherein the polycarbosilane is obtained by hydropolymerization of benzocyclobutenyl endoyne monomer and 1,4-di(dimethylsilyl)benzene. The benzocyclobutenyl endyne monomer is any one of monobenzocyclobutenyl endyne monomer, dibenzocyclobutenyl endyne monomer, and tribenzocyclobutenyl endyne monomer. The structural formula of the monobenzocyclobutenyl endyne monomer is chemical formula 1 or chemical formula 2: Chemical Formula 1: Chemical formula 2: Among them, R1 to R in chemical formula 1 or chemical formula 2 14 Hydrogen, substituted C1 to C 16 Aliphatic hydrocarbon groups, substituted C6 to C 16 aryl and substituted C7 to C 16 One or more of the aryl alkyl groups; The structural formula of the bisbenzocyclobutenyl endyne monomer is chemical formula 3 or chemical formula 4: Chemical formula 3: Chemical formula 4: Among them, R1 to R in chemical formula 3 or chemical formula 4 14 Hydrogen, substituted C1 to C 16 Aliphatic hydrocarbon groups, substituted C6 to C 16 aryl and substituted C7 to C 16 One or more of the aryl alkyl groups; The structural formula of the tribenzocyclobutenyl endyne monomer is chemical formula 5: Chemical formula 5: Among them, R1 to R in chemical formula 5 14 Hydrogen, substituted C1 to C 16 Aliphatic hydrocarbon groups, substituted C6 to C 16 aryl and substituted C7 to C 16 One or more of the aryl alkyl groups.

[0007] Preferably, under anaerobic conditions, benzocyclobutenyl endyne monomer and 1,4-di(dimethylsilyl)benzene in a molar ratio of 1~3:1~3 are added to a solvent, degassed, heated and Karstedt catalyst is added, and the reaction is carried out at 85~120℃ for 12~36 hours. The crude product is passed through a chromatography column, precipitated, and vacuum dried to obtain polycarbosilane.

[0008] Preferably, the polycarbosilane has a structural formula of any one of chemical formulas 6, 7, 8, 9, and 10. Chemical formula 6: Chemical Formula 7: Chemical formula 8: Chemical formula 9: Chemical Formula 10: Among them, R1 to R in chemical formulas 6, 7, 8, 9, and 10 14 Hydrogen, substituted C1 to C 16 Aliphatic hydrocarbon groups, substituted C6 to C 16 aryl and substituted C7 to C 16 One or more of the aryl alkyl groups, where n is an integer in the range of 5-1000.

[0009] The present invention also provides a photosensitive benzocyclobutene-based polycarbosilane prepared by the preparation method described above.

[0010] This invention also provides a method for preparing photoresist based on endoyne silane-hydropolymerization of photosensitive benzocyclobutene polycarbosilane using the preparation method described above. The method involves compounding polycarbosilane, a photocrosslinking agent, a photoinitiator, and an organic solvent to obtain the photoresist. The polycarbosilane accounts for 20%-60% of the photoresist by weight, the photocrosslinking agent accounts for 0.5%-7.5% by weight, the photoinitiator accounts for 1%-5% by weight, and the organic solvent accounts for 30%-70% by weight. During the compounding process, ultrasonic or stirring-assisted dissolution is performed. The photoresist is prepared under yellow light and at a temperature below 25°C. o Perform under C.

[0011] Preferably, the photocrosslinking agent is an azide compound; its structural formula is: In Formula 15, R is any one of a substituted C1 to C12 aliphatic hydrocarbon group, a substituted C1 to C12 aliphatic hydrocarbon oxygen group, a substituted C6 to C12 aryl group, and a substituted C7 to C12 arylalkyl group, wherein the substituted substituent group includes at least one of halogen, hydroxyl, hydroxyalkyl, carboxyl, carboxylalkyl, alkyl, ester, and acyl groups. The photoinitiators are coumarin-based, oxazole-based, pyrazoline-based, hexaaryl biimidazole compounds, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, thioxanthone, benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, benzo[a]anthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, 9-phenylacrimidine, 1,7-di(9,9) One or more of (-acridyl)heptane; the organic solvent is one or more of toluene, xylene, 1,3,5-trimethylbenzene, cyclopentanone, chloroform, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and N-methylpyrrolidone.

[0012] The present invention also provides an application of photoresist prepared by the above-described preparation method in advanced packaging processes, comprising: cleaning and surface activation of a substrate; then coating the photoresist on the substrate to obtain a dry film, followed by heat treatment, exposure of the dry film, and treatment with a developer to obtain a patterned morphology; finally, heat treatment, and after partial or complete cross-linking, a photolithographically patterned dielectric layer is obtained.

[0013] Preferably, the substrate is any one of glass, quartz, sapphire, silicon, smooth copper foil / copper sheet, and SiC; The cleaning treatment methods include using piranha solution, concentrated sulfuric acid, concentrated nitric acid wet process, or any one of photochemical treatment, high temperature flame treatment, corona discharge treatment, and surface plasma treatment; The surface activation treatment includes the use of any one of silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, and organochromium coupling agents; The coating method includes any one of spin coating, ultrasonic spraying, slot coating, gravure coating, bar coating, and ultrasonic spraying.

[0014] Preferably, the exposure method includes any one of mercury lamp / photomask, LED / photomask, laser direct writing without mask, and EB without mask; The developing solution is one or more of cyclohexanone, petroleum ether, toluene, xylene, and 1,3,5-trimethylbenzene; wherein the developing method includes one or more of vertical developing, rinsing developing, and immersion developing. Preferably, the heat treatment includes one or more of the following: resistance heating, infrared heating, electromagnetic induction heating, laser and electron beam heating, and plasma heating.

[0015] The present invention has at least the following beneficial effects: (1) The main chain contains carbon-carbon double bonds, that is, it contains one σ bond and one π bond. The carbon atoms are sp² hybridized, which gives the polymer chain a planar rigid structure, which can improve the glass transition temperature (Tg) and heat distortion temperature of the material, thereby improving the heat resistance and electrical properties. (2) The carbon-carbon double bonds in the main chain can undergo cross-linking reactions under the action of light and heat to form a three-dimensional network structure, which significantly improves the hardness, strength and solvent resistance of the material; (3) The main chain is composed of alternating silicon-carbon (Si-C) bonds, which has excellent high temperature resistance, can be ceramicized with high ceramicization yield, has a dense structure and excellent mechanical properties. (4) In particular, such advanced packaging photoresist further serves as a high-performance dielectric material, enabling high-density, high-performance redistribution layers in advanced packaging. It is one of the key materials supporting the development of advanced packaging technology, and therefore plays an indispensable role in cutting-edge fields such as high-performance computing and artificial intelligence, high-end communication and radio frequency, heterogeneous integration and chip design, image sensors and microelectromechanical systems.

[0016] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached image description: Figure 1 Example 1: 1H NMR spectrum of chemical formula 16; Figure 2 Example 1: Carbon NMR spectrum of chemical formula 16; Figure 3 Example 1: High-resolution mass spectrum of chemical formula 16; Figure 4 Example 1: The 1H NMR spectrum, 1C NMR spectrum, and 1S NMR spectrum of chemical formula 17; Figure 5 Example 1: GPC spectrum of chemical formula 17; Figure 6 Example 4: 1H NMR spectrum of chemical formula 22; Figure 7 Example 4: Carbon NMR spectrum of chemical formula 22; Figure 8 Example 4: High-resolution mass spectrum of chemical formula 22; Figure 9 Example 4: The 1H NMR spectrum, 1C NMR spectrum, and 1H NMR spectrum of chemical formula 23; Figure 10Example 4: GPC spectrum of chemical formula 23; Figure 11 Thermosetting DSC curves of Chemical Formula 17 in Example 1 and Chemical Formula 23 in Example 4; Figure 12 Thermogravimetric curves of photothermal curing films of chemical formula 17 in Example 1 and chemical formula 23 in Example 4; Figure 13 Dielectric constant-frequency curves of photothermal curable films of chemical formula 17 in Example 1 and chemical formula 23 in Example 4; Figure 14 Contact angle curves of photothermal curable films of chemical formula 17 in Example 1 and chemical formula 23 in Example 4; Figure 15 Photolithographic patterned microstructures of Chemical Formula 17 in Example 1 and Chemical Formula 23 in Example 4; Figure 16 Example 1: FIB-SEM morphology of a photothermal curable film of chemical formula 17; Figure 17 Example 1: Schematic diagram of photothermal curing film / interdigital electrode encapsulation of chemical formula 17; Figure 18 Example 1: Microstructure and device appearance after reliability testing of photothermal curable film / interdigital electrode package of chemical formula 17; Figure 19 Microstructure of the photothermal curing films in Examples 1-8. Detailed implementation method: The present invention will now be described in further detail with reference to the accompanying drawings, so that those skilled in the art can implement it based on the description.

[0017] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not imply the presence or addition of one or more other elements or combinations thereof.

[0018] Example 1: (1) Synthesis of monobenzocyclobutene endyne monomer (Chemical Formula 16): 3,6-dibromobenzocyclobutene (1.0 g, 3.9 mmol), phenylacetylene (1.8 g, 17.6 mmol), cuprous iodide (15.0 mg, 80.0 μmol), and bis(triphenylphosphine)palladium dichloride (105.0 mg, 150.0 μmol) were added to a 250 mL dry flask. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycles) three times to remove dissolved oxygen and moisture. A suitable amount of dry tetrahydrofuran was added as a solvent, and a suitable amount of triethylamine was added as an acid-binding agent. The reaction was carried out in a metal bath at 70 °C for 15 h. After the reaction was completed, the reaction system was cooled to room temperature. The organic phase was first removed by rotary evaporation concentration. The residue was then dissolved in toluene, washed three times with deionized water, dried with anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The sample was purified by column chromatography using petroleum ether as the eluent and 200-300 mesh silica gel. The final product was a white solid obtained by recrystallization with anhydrous ethanol.

[0019] Chemical Formula 16 (2) Synthesis of monobenzocyclobutenyl endyne monomeric polycarbosilane (Chemical Formula 17): Monomer (Chemical Formula 16, 0.91 g, 3.0 mmol) and 1,4-di(dimethylsilyl)benzene (0.58 g, 3.0 mmol) were added to a 25 mL dry anaerobic flask. 12 mL of dry toluene was added as solvent. The reaction system was deeply degassed using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) three times to remove dissolved oxygen and moisture. Then, 60 µL of catalyst Pt (DVS) was added when the temperature was raised to 100 °C. o The reaction was stopped after 24 hours at temperature C. The crude product was passed through a chromatography column (200-300 mesh silica gel) to remove impurities such as metal ions, then precipitated 1-2 times with ice-cold methanol, and finally dried under vacuum to obtain a solid powder.

[0020] Chemical Formula 17 Where n=44 (calculated based on GPC test Mw).

[0021] (3) Under yellow light, weigh 0.1 g of the polymer (chemical formula 17) and add it to a 3 mL brown sample bottle. Then add 4 mg of photocrosslinking agent (chemical formula 15), 3 mg of photoinitiator 9-phenylacridine, and 0.4 g of toluene. After ultrasonic dissolution, a photosensitive solution is obtained. The photosensitive solution is dropped onto a silicon wafer (treated with piranha solution and modified with silane coupling agent) and spin-coated (1000 rpm, 60 s) to obtain a photosensitive film. Place it on a 70℃ heating stage and bake for 5 minutes. After the solvent evaporates, expose the photosensitive film through a photomask using a 365nm UV light source. The exposed areas are cross-linked and cured, making them difficult to dissolve in the developer, while the unexposed areas are soluble in the developer. After development with the developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, specifically starting from 30℃ and rising to 150℃ within 20 minutes, holding for 15 minutes, then rising to 250℃ within 30 minutes, holding for 60 minutes, and then cooling down to 150℃ within 60 minutes, allowing it to cool naturally to room temperature, resulting in a film with a high cross-linking density.

[0022] Example 2: (1) Synthesis of monobenzocyclobutene endyne monomer (Chemical Formula 18): 3,6-dibromobenzocyclobutene (1.0 g, 3.9 mmol), 4-methylphenylacetylene (1.68 g, 14.52 mmol), cuprous iodide (CuI, 15.0 mg, 80.0 μmol), and bis(triphenylphosphine)palladium dichloride (105.0 mg, 150.0 μmol) were added to a 250 mL dry flask. The reaction system was then subjected to deep degassing using a liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) method, repeated three times to remove dissolved oxygen and moisture. A suitable amount of dry tetrahydrofuran was added as a solvent, and a suitable amount of triethylamine was added as an acid-binding agent. The reaction was carried out in a metal bath at 70 °C for 15 h. After the reaction was completed, the reaction system was cooled to room temperature. The organic phase was first removed by rotary evaporation concentration. The residue was then dissolved in toluene, washed three times with deionized water, dried with anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The sample was purified by column chromatography using petroleum ether as the eluent and 200-300 mesh silica gel. The final product was a white solid obtained by recrystallization with anhydrous ethanol.

[0023] Chemical Formula 18 (2) Synthesis of monobenzocyclobutenyl endyne monomeric polycarbosilane (Chemical Formula 19): Monomer (Chemical Formula 18, 1.0 g, 3.0 mmol), 1,4-di(dimethylsilyl)benzene (0.58 g, 3.0 mmol), and 12 mL of dry toluene were added as solvent. The reaction system was subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) three times to remove dissolved oxygen and moisture. Then, 60 µL of catalyst Pt (DVS) was added when the temperature was raised to 100 °C. o The reaction was stopped after 24 hours at temperature C. The crude product was passed through a chromatography column (200-300 mesh silica gel) to remove impurities such as metal ions, then precipitated 1-2 times with ice-cold methanol, and finally dried under vacuum to obtain a solid powder.

[0024] Chemical formula 19 Where n=25 (calculated based on GPC test Mw).

[0025] (3) Under yellow light, weigh 0.1 g of the polymer (chemical formula 19) and add it to a 3 mL brown sample bottle. Add 4 mg of photocrosslinking agent (chemical formula 15), 3 mg of photoinitiator 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone and 0.4 g of toluene. After ultrasonic dissolution, a photosensitive solution is obtained. A photosensitive solution was dropped onto a silicon wafer (treated with piranha solution and modified with silane coupling agent) and spin-coated (1000 rpm, 60 s) to obtain a photosensitive film. The film was then placed on a 70°C heating stage and baked for 5 min. After the solvent evaporated, the photosensitive film was exposed to a photomask using a 365 nm UV light source. The exposed areas were cross-linked and cured, making them difficult to dissolve in the developer, while the unexposed areas were soluble in the developer. After development, a pattern consistent with the photomask was obtained. Finally, the photocured film was subjected to a programmed temperature rise process, specifically starting from 30°C and rising to 150°C within 20 min, holding for 15 min, then rising to 250°C within 30 min, holding for 60 min, and then cooling down to 150°C within 60 min, allowing it to cool naturally to room temperature, resulting in a film with a high cross-linking density.

[0026] Example 3: (1) Synthesis of monobenzocyclobutene endyne monomer (Chemical Formula 20): 3,6-dibromobenzocyclobutene (1.0 g, 3.9 mmol), 2-naphthylacetylene (1.52 g, 10 mmol), cuprous iodide (CuI, 15.0 mg, 80.0 μmol), and bis(triphenylphosphine)palladium dichloride (105.0 mg, 150.0 μmol) were added to a 250 mL dry flask. The reaction system was then subjected to deep degassing using a liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) method, repeated three times to remove dissolved oxygen and moisture. A suitable amount of dry tetrahydrofuran was added as a solvent, and a suitable amount of triethylamine was added as an acid-binding agent. The reaction was carried out in a metal bath at 70 °C for 15 h. After the reaction was completed, the reaction system was cooled to room temperature. The organic phase was first removed by rotary evaporation concentration. The residue was then dissolved in toluene, washed three times with deionized water, dried with anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The sample was purified by column chromatography using petroleum ether as the eluent and 200-300 mesh silica gel. The final product was a white solid obtained by recrystallization with anhydrous ethanol.

[0027] Chemical formula 20 (2) Synthesis of monobenzocyclobutenyl endyne monomeric polycarbosilane (Chemical Formula 21): Monomer (Chemical Formula 20, 1.21 g, 3.0 mmol), 1,4-di(dimethylsilyl)benzene (0.58 g, 3.0 mmol) were added to a 25 mL dry anaerobic flask. 12 mL of dry toluene was added as solvent. The reaction system was deeply degassed using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) and repeated three times to remove dissolved oxygen and moisture. Then, 60 µL of catalyst Pt (DVS) was added when the temperature was raised to 100 °C. o The reaction was stopped after 24 hours at temperature C. The crude product was passed through a chromatography column (200-300 mesh silica gel) to remove impurities such as metal ions, then precipitated 1-2 times with ice-cold methanol, and finally dried under vacuum to obtain a solid powder.

[0028] Chemical Formula 21 Where n=18 (calculated based on GPC test Mw).

[0029] (3) Under yellow light, weigh 0.1 g of the polymer (chemical formula 21) and add it to a 3 mL brown sample bottle. Add 3 mg of photocrosslinking agent (chemical formula 15), 3 mg of photoinitiator 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, and 0.5 g of 1,3,5-meta-toluene. After ultrasonic dissolution, a photosensitive solution is obtained. A photosensitive solution was dropped onto a silicon wafer (treated with piranha solution and modified with silane coupling agent) and spin-coated (1000 rpm, 60 s) to obtain a photosensitive film. The film was then placed on a 70°C heating stage and baked for 5 min. After the solvent evaporated, the photosensitive film was exposed to a photomask using a 365 nm UV light source. The exposed areas were cross-linked and cured, making them difficult to dissolve in the developer, while the unexposed areas were soluble in the developer. After development, a pattern consistent with the photomask was obtained. Finally, the photocured film was subjected to a programmed temperature rise process, specifically starting from 30°C and rising to 150°C within 20 min, holding for 15 min, then rising to 250°C within 30 min, holding for 60 min, and then cooling down to 150°C within 60 min, allowing it to cool naturally to room temperature, resulting in a film with a high cross-linking density.

[0030] Example 4: (1) Synthesis of bisbenzocyclobutene endyne monomer (Chemical Formula 22): 1,4-Diethynylbenzene (0.98 g, 7.8 mmol), 4-bromobenzocyclobutene (3.15 g, 17.2 mmol), cuprous iodide (CuI, 65.0 mg, 340.0 μmol), and bis(triphenylphosphine)palladium dichloride (481.0 mg, 680.0 μmol) were added to a 250 mL dry flask. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) three times to remove dissolved oxygen and moisture. A suitable amount of dry tetrahydrofuran was added as a solvent, and a suitable amount of triethylamine was added as an acid-binding agent. The reaction was carried out in a metal bath at 70 °C for 15 h. After the reaction was completed, the reaction system was cooled to room temperature. The organic phase was first removed by rotary evaporation concentration. The residue was then dissolved in toluene, washed three times with deionized water, dried with anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The sample was purified by column chromatography using petroleum ether as the eluent and 200-300 mesh silica gel. The final product was a white solid obtained by recrystallization from ethyl acetate.

[0031] Chemical formula 22 (2) Synthesis of bisbenzocyclobutenyl endyne monomeric polycarbosilane (Chemical Formula 23): Monomer (Chemical Formula 22, 0.99 g, 3.0 mmol) and 1,4-di(dimethylsilyl)benzene (0.58 g, 3.0 mmol) were added to a 25 mL dry anaerobic flask. 12 mL of dry toluene was added as a solvent. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycles) three times to remove dissolved oxygen and moisture. 60 µL of catalyst Pt (DVS) was added when the temperature was raised to 100 °C. o The reaction was stopped after 24 hours at temperature C. The crude product was passed through a chromatography column (200-300 mesh silica gel) to remove impurities such as metal ions, then precipitated 1-2 times with ice-cold methanol, and finally dried under vacuum to obtain a solid powder.

[0032] Chemical formula 23 Where n=6 (calculated based on GPC test Mw).

[0033] (3) Under yellow light, weigh 0.1 g of the polymer (chemical formula 23) and add it to a 3 mL brown sample bottle. Add 4 mg of photocrosslinking agent (chemical formula 15), 3 mg of photoinitiator 9-phenylacridine, and 0.5 g of toluene. After ultrasonic dissolution, a photosensitive solution is obtained. A photosensitive solution was dropped onto a silicon wafer (treated with piranha solution and modified with silane coupling agent) and spin-coated (1000 rpm, 60 s) to obtain a photosensitive film. The film was then placed on a 70°C heating stage and baked for 5 min. After the solvent evaporated, the photosensitive film was exposed to a photomask using a 365 nm UV light source. The exposed areas were cross-linked and cured, making them difficult to dissolve in the developer, while the unexposed areas were soluble in the developer. After development, a pattern consistent with the photomask was obtained. Finally, the photocured film was subjected to a programmed temperature rise process, specifically starting from 30°C and rising to 150°C within 20 min, holding for 15 min, then rising to 250°C within 30 min, holding for 60 min, and then cooling down to 150°C within 60 min, allowing it to cool naturally to room temperature, resulting in a film with a high cross-linking density.

[0034] Example 5: (1) Synthesis of bisbenzocyclobutene endyne monomer (Chemical Formula 24): 1,3-Diethynylbenzene (0.98 g, 7.8 mmol), 4-bromobenzocyclobutene (3.15 g, 17.2 mmol), cuprous iodide (CuI, 65.0 mg, 340.0 μmol), and bis(triphenylphosphine)palladium dichloride (481.0 mg, 680.0 μmol) were added to a 250 mL dry flask. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) three times to remove dissolved oxygen and moisture. A suitable amount of dry tetrahydrofuran was added as a solvent, and a suitable amount of triethylamine was added as an acid-binding agent. The reaction was carried out in a metal bath at 70 °C for 15 h. After the reaction was completed, the reaction system was cooled to room temperature. The organic phase was first removed by rotary evaporation concentration. The residue was then dissolved in toluene, washed three times with deionized water, dried with anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The sample was purified by column chromatography using petroleum ether as the eluent and 200-300 mesh silica gel. The final product was a white solid obtained by recrystallization from ethyl acetate.

[0035] Chemical formula 24 (2) Synthesis of bisbenzocyclobutenyl endyne monomeric polycarbosilane (Chemical Formula 25): Monomer (Chemical Formula 24, 0.99 g, 3.0 mmol) and 1,4-di(dimethylsilyl)benzene (0.58 g, 3.0 mmol) were added to a 25 mL dry anaerobic flask. 12 mL of dry toluene was added as a solvent. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) three times to remove dissolved oxygen and moisture. 60 µL of catalyst Pt (DVS) was added when the temperature was raised to 100 °C. o The reaction was stopped after 24 hours at temperature C. The crude product was passed through a chromatography column (200-300 mesh silica gel) to remove impurities such as metal ions, then precipitated 1-2 times with ice-cold methanol, and finally dried under vacuum to obtain a solid powder.

[0036] Chemical Formula 25 Where n=13 (calculated based on GPC test Mw).

[0037] (3) Under yellow light, weigh 0.1 g of the polymer (chemical formula 25) and add it to a 3 mL brown sample bottle. Add 4 mg of photocrosslinking agent (chemical formula 15), 3 mg of photoinitiator 9-phenylacridine, and 0.63 g of toluene. After ultrasonic dissolution, a photosensitive solution is obtained. A photosensitive solution was dropped onto a silicon wafer (treated with piranha solution and modified with silane coupling agent) and spin-coated (800 rpm, 60 s) to obtain a photosensitive film. The film was then placed on a 70°C heating stage and baked for 5 min. After the solvent evaporated, the photosensitive film was exposed to a photomask using a 365 nm UV light source. The exposed areas were cross-linked and cured, making them difficult to dissolve in the developer, while the unexposed areas were soluble in the developer. After development, a pattern consistent with the photomask was obtained. Finally, the photocured film was subjected to a programmed temperature rise process, specifically starting from 30°C and rising to 150°C within 20 min, holding for 15 min, then rising to 250°C within 30 min, holding for 60 min, and then cooling to 150°C within 60 min, allowing it to cool naturally to room temperature, resulting in a film with a high cross-linking density.

[0038] Example 6: (1) Synthesis of bisbenzocyclobutene endyne monomer (Chemical Formula 26): 4,4'-diethynylbiphenyl (1.58 g, 7.8 mmol), 4-bromobenzocyclobutene (3.15 g, 17.2 mmol), cuprous iodide (CuI, 65.0 mg, 340.0 μmol), and bis(triphenylphosphine) palladium dichloride (481.0 mg, 680.0 μmol) were added to a 250 mL dry flask. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) three times to remove dissolved oxygen and moisture. A suitable amount of dry tetrahydrofuran was added as a solvent, and a suitable amount of triethylamine was added as an acid-binding agent. The reaction was carried out in a metal bath at 70 °C for 15 h. After the reaction was completed, the reaction system was cooled to room temperature. The organic phase was first removed by rotary evaporation concentration, and the residue was dissolved in toluene. After washing three times with deionized water, the residue was dried with anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The sample was purified by column chromatography using petroleum ether as the eluent and 200-300 mesh silica gel. The final product was a white solid obtained by recrystallization from ethyl acetate.

[0039] Chemical formula 26 (2) Synthesis of bisbenzocyclobutenyl endyne monomeric polycarbosilane (Chemical Formula 27): Monomer (Chemical Formula 26, 1.22 g, 3.0 mmol) and 1,4-di(dimethylsilyl)benzene (0.58 g, 3.0 mmol) were added to a 25 mL dry anaerobic flask. 15 mL of dry toluene was added as a solvent. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) three times to remove dissolved oxygen and moisture. 60 µL of catalyst Pt (DVS) was added when the temperature was raised to 100 °C. o The reaction was stopped after 24 hours at temperature C. The crude product was passed through a chromatography column (200-300 mesh silica gel) to remove impurities such as metal ions, then precipitated 1-2 times with ice-cold methanol, and finally dried under vacuum to obtain a solid powder.

[0040] Chemical formula 27 Where n=16 (calculated based on GPC test Mw).

[0041] (3) Under yellow light, weigh 0.1 g of the polymer (chemical formula 27) and add it to a 3 mL brown sample bottle. Add 5 mg of photocrosslinking agent (chemical formula 15), 4 mg of photoinitiator 9-phenylacridine, and 0.75 g of toluene. After ultrasonic dissolution, a photosensitive solution is obtained. A photosensitive solution was dropped onto a silicon wafer (treated with piranha solution and modified with silane coupling agent) and spin-coated (800 rpm, 60 s) to obtain a photosensitive film. The film was then placed on a 70°C heating stage and baked for 5 min. After the solvent evaporated, the photosensitive film was exposed to a photomask using a 365 nm UV light source. The exposed areas were cross-linked and cured, making them difficult to dissolve in the developer, while the unexposed areas were soluble in the developer. After development, a pattern consistent with the photomask was obtained. Finally, the photocured film was subjected to a programmed temperature rise process, specifically starting from 30°C and rising to 150°C within 20 min, holding for 15 min, then rising to 250°C within 30 min, holding for 60 min, and then cooling to 150°C within 60 min, allowing it to cool naturally to room temperature, resulting in a film with a high cross-linking density.

[0042] Example 7: (1) Synthesis of bisbenzocyclobutene endyne monomer (Chemical Formula 28): 2,6-Diethynylnaphthalene (1.34 g, 7.8 mmol), 4-bromobenzocyclobutene (3.15 g, 17.2 mmol), cuprous iodide (CuI, 65.0 mg, 340.0 μmol), and bistriphenylphosphine palladium dichloride (481.0 mg, 680.0 μmol) were added to a 250 mL dry flask. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycles) three times to remove dissolved oxygen and moisture. A suitable amount of dry tetrahydrofuran was added as a solvent, and a suitable amount of triethylamine was added as an acid-binding agent. The reaction was carried out in a metal bath at 70 °C for 15 h. After the reaction was completed, the reaction system was cooled to room temperature. The organic phase was first removed by rotary evaporation concentration, and the residue was dissolved in toluene. After washing three times with deionized water, the residue was dried with anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The sample was purified by column chromatography using petroleum ether as the eluent and 200-300 mesh silica gel. The final product was a white solid obtained by recrystallization from ethyl acetate.

[0043] Chemical formula 28 (2) Synthesis of bisbenzocyclobutenyl endyne monomeric polycarbosilane (Chemical Formula 29): Monomer (Chemical Formula 28, 1.14 g, 3.0 mmol) and 1,4-di(dimethylsilyl)benzene (0.58 g, 3.0 mmol) were added to a 25 mL dry anaerobic flask. 20 mL of dry toluene was added as a solvent. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) three times to remove dissolved oxygen and moisture. 60 µL of catalyst Pt (DVS) was added when the temperature was raised to 100 °C. o The reaction was stopped after 24 hours at temperature C. The crude product was passed through a chromatography column (200-300 mesh silica gel) to remove impurities such as metal ions, then precipitated 1-2 times with ice-cold methanol, and finally dried under vacuum to obtain a solid powder.

[0044] Chemical formula 29 Where n=25 (calculated based on GPC test Mw).

[0045] (3) Under yellow light, weigh 0.1 g of the polymer (chemical formula 28) and add it to a 3 mL brown sample bottle. Add 5 mg of photocrosslinking agent (chemical formula 29), 4 mg of photoinitiator 9-phenylacridine, and 0.5 g of toluene. After ultrasonic dissolution, a photosensitive solution is obtained. A photosensitive solution was dropped onto a silicon wafer (treated with piranha solution and modified with silane coupling agent) and spin-coated (800 rpm, 60 s) to obtain a photosensitive film. The film was then placed on a 70°C heating stage and baked for 5 min. After the solvent evaporated, the photosensitive film was exposed to a photomask using a 365 nm UV light source. The exposed areas were cross-linked and cured, making them difficult to dissolve in the developer, while the unexposed areas were soluble in the developer. After development, a pattern consistent with the photomask was obtained. Finally, the photocured film was subjected to a programmed temperature rise process, specifically starting from 30°C and rising to 150°C within 20 min, holding for 15 min, then rising to 250°C within 30 min, holding for 60 min, and then cooling to 150°C within 60 min, allowing it to cool naturally to room temperature, resulting in a film with a high cross-linking density.

[0046] Example 8: (1) Synthesis of tribenzocyclobutene endyne monomer (Chemical Formula 30): 3,6-dibromobenzocyclobutene (1.0 g, 3.9 mmol), 4-ethynylbenzocyclobutene (1.92 g, 15 mmol), cuprous iodide (CuI, 15.0 mg, 80.0 μmol), and bis(triphenylphosphine)palladium dichloride (105.0 mg, 150.0 μmol) were added to a 250 mL dry flask. The reaction system was then subjected to deep degassing using a liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) method, repeated three times to remove dissolved oxygen and moisture. A suitable amount of dry tetrahydrofuran was added as a solvent, and a suitable amount of triethylamine was added as an acid-binding agent. The reaction was carried out in a metal bath at 70 °C for 15 h. After the reaction was completed, the reaction system was cooled to room temperature. The organic phase was first removed by rotary evaporation concentration. The residue was then dissolved in toluene, washed three times with deionized water, dried with anhydrous sodium sulfate, filtered, and concentrated to obtain the crude product. The sample was purified by column chromatography using petroleum ether as the eluent and 200-300 mesh silica gel. The final product was a white solid obtained by recrystallization with anhydrous ethanol.

[0047] Chemical formula 30 (2) Synthesis of tribenzocyclobutenyl endyne monomeric polycarbosilane (Chemical Formula 31): Monomer (Chemical Formula 30, 1.07 g, 3.0 mmol) and 1,4-di(dimethylsilyl)benzene (0.58 g, 3.0 mmol) were added to a 25 mL dry anaerobic flask. 20 mL of dry toluene was added as a solvent. The reaction system was then subjected to deep degassing using liquid nitrogen freezing-vacuuming-thawing (i.e., freeze-thaw cycle) three times to remove dissolved oxygen and moisture. 60 µL of catalyst Pt(DVS) was added when the temperature was raised to 100 °C. o The reaction was stopped after 24 hours at temperature C. The crude product was passed through a chromatography column (200-300 mesh silica gel) to remove impurities such as metal ions, then precipitated 1-2 times with ice-cold methanol, and finally dried under vacuum to obtain a solid powder.

[0048] Chemical Formula 31 Where n=18 (M=2.2W) (3) Under yellow light, weigh 0.1 g of the polymer and add it to a 3 mL brown sample bottle. Weigh and add 0.004 g of photoinitiator (BAC-E), 0.003 g of 9-phenylacridine (9PA), and 0.4 g of toluene. Dissolve by sonication to obtain a photosensitive solution. A photosensitive solution was dropped onto a glass slide and spin-coated to obtain a photosensitive film. The film was then placed on a 70°C heating stage and baked for 5 minutes. After the solvent evaporated, the photosensitive film was exposed through a photomask using a 365nm UV-LED point light source. The exposed areas were cross-linked and cured, making them difficult to dissolve in the developer, while the unexposed areas were soluble in the developer. After development, a pattern consistent with the photomask was obtained. Finally, the photocured film was subjected to a programmed temperature rise process: the temperature was increased from 30°C to 150°C within 20 minutes, held for 15 minutes, increased to 250°C within 30 minutes, held for 60 minutes, and then cooled to 150°C within 60 minutes, allowing it to cool naturally to room temperature, resulting in a film with a high cross-linking density.

[0049] Application example: The specific sample preparation process is as follows Figure 17As shown, the specific steps are as follows: 1) Electrode preparation: Clean the interdigital electrode with ethanol using ultrasound, and then dry it with nitrogen gas to ensure that the surface of the interdigital electrode is clean and free of contamination. 2) Coating and curing: (a) Adhere polyimide tape to both sides of the interdigital electrode; (b) Apply chemical formula 17 from Example 1 (or chemical formula 19, chemical formula 21, chemical formula 23, chemical formula 25, chemical formula 27, chemical formula 29, chemical formula 31 corresponding to Examples 2-8) to the area of ​​the interdigital electrode where no tape is applied, and evaporate the solvent; (c) Expose the resin sample to a 365 nm LED light source first, and then heat and cure it according to the heating procedure in Example 1 (3) (or Examples 2-8 (3)); (d) Remove the polyimide tape. (3) Fix the interdigital electrode on the probe stage, connect its two electrode pins with the probe, and connect the measurement end (HI) and the high voltage end (LO), and turn on the instrument to preheat for at least 15-30 minutes. Refer to the standard such as ASTM D257, set the voltage to 3.5 V, select the resistance measurement mode, and apply the test voltage under a stable initial environment (such as room temperature and dry air). After the reading stabilizes (usually taking tens of seconds to several minutes), record the stable resistance value R0, which is the initial resistance. (4) Use the HAST high-pressure steam aging tester, select the test conditions as 130℃ / 85%RH / 96 hours, and complete the resistance Rt test within 2 hours after the test. The reliability performance test conclusion is as follows: Figure 18 Or as shown in Table 1.

[0050] Table 1 compares the performance parameters of the photothermal curing films in Examples 1-8. Table 1 In Table 1, Dk / 10 MHz represents the dielectric constant at a frequency of 10 MHz, which is a key factor in optimizing the electrical performance of the RDL. The lower the dielectric constant, the more the material can reduce capacitance and delay by lowering the dielectric constant of the insulating layer, thereby improving the overall signal transmission speed and reliability of the package. 5% T is the temperature at which the material loses 5% of its initial mass during the heating process. 5% It is an important indicator for measuring the thermal stability and initial decomposition temperature of a material. 5% A higher L / S ratio generally indicates that the material is more stable before reaching that temperature and has better heat resistance. L / S, or linewidth / line spacing, is the core indicator for measuring the capability and precision of photolithography technology. A smaller L / S value results in finer patterns, higher chip integration, stronger performance, and potentially lower power consumption.

[0051] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. A method for preparing photosensitive benzocyclobutenyl polycarbosilane based on endoyne silane hydropolymerization, characterized in that, Polycarbosilane was obtained by hydrosilyl polymerization of benzocyclobutenyl endyne monomer and 1,4-di(dimethylsilyl)benzene. The benzocyclobutenyl endyne monomer is any one of monobenzocyclobutenyl endyne monomer, dibenzocyclobutenyl endyne monomer, and tribenzocyclobutenyl endyne monomer. The structural formula of the monobenzocyclobutenyl endyne monomer is chemical formula 1 or chemical formula 2: Chemical Formula 1: Chemical formula 2: Among them, R1 to R in chemical formula 1 or chemical formula 2 14 Hydrogen, substituted C1 to C 16 Aliphatic hydrocarbon groups, substituted C6 to C 16 aryl and substituted C7 to C 16 One or more of the aryl alkyl groups; The structural formula of the bisbenzocyclobutenyl endyne monomer is chemical formula 3 or chemical formula 4: Chemical formula 3: Chemical formula 4: Among them, R1 to R in chemical formula 3 or chemical formula 4 14 Hydrogen, substituted C1 to C 16 Aliphatic hydrocarbon groups, substituted C6 to C 16 aryl and substituted C7 to C 16 One or more of the aryl alkyl groups; The structural formula of the tribenzocyclobutenyl endyne monomer is chemical formula 5: Chemical formula 5: Among them, R1 to R in chemical formula 5 14 Hydrogen, substituted C1 to C 16 Aliphatic hydrocarbon groups, substituted C6 to C 16 aryl and substituted C7 to C 16 One or more of the aryl alkyl groups.

2. The method for preparing photosensitive benzocyclobutenyl polycarbosilane based on endoyne silane polymerization as described in claim 1, characterized in that, Under anaerobic conditions, benzocyclobutenyl endyne monomer and 1,4-di(dimethylsilyl)benzene in a molar ratio of 1~3:1~3 were added to a solvent, degassed, heated and Karstedt catalyst was added, and the reaction was carried out at 85~120℃ for 12~36 hours. The crude product was passed through a chromatography column, precipitated, and dried under vacuum to obtain polycarbosilane.

3. The method for preparing photosensitive benzocyclobutenyl polycarbosilane based on endoyne silane polymerization as described in claim 1, characterized in that, The polycarbosilane has the structural formula of any one of chemical formulas 6, 7, 8, 9, and 10. Chemical formula 6: Chemical Formula 7: Chemical formula 8: Chemical formula 9: Chemical Formula 10: Among them, R1 to R in chemical formulas 6, 7, 8, 9, and 10 14 Hydrogen, substituted C1 to C 16 Aliphatic hydrocarbon groups, substituted C6 to C 16 aryl and substituted C7 to C 16 One or more of the aryl alkyl groups, where n is an integer in the range of 5-1000.

4. A photosensitive benzocyclobutene-based polycarbosilane prepared by the preparation method according to any one of claims 1 to 3.

5. A method for preparing photoresist based on endoyne silane-hydropolymerization using the preparation method described in any one of claims 1 to 3, characterized in that, A photoresist is prepared by compounding polycarbosilane, a photocrosslinking agent, a photoinitiator, and an organic solvent; wherein the polycarbosilane accounts for 20%-60% of the photoresist by weight, the photocrosslinking agent accounts for 0.5%-7.5% of the photoresist by weight, the photoinitiator accounts for 1%-5% of the photoresist by weight, and the organic solvent accounts for 30%-70% of the photoresist by weight.

6. The method as described in claim 5, characterized in that, The photocrosslinking agent is an azide compound; the photoinitiator is a coumarin-based, oxazole-based, pyrazoline-based, hexaarylbiimidazole compound, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, thioxanthone, benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, benzo[a]anthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, 9-phenylacrimidine, 1,7-di(9,9) One or more of (-acridyl)heptane; the organic solvent is one or more of toluene, xylene, 1,3,5-trimethylbenzene, cyclopentanone, chloroform, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and N-methylpyrrolidone.

7. The application of a photoresist prepared by the method described in claim 5 in advanced packaging processes, characterized in that, include: The substrate is cleaned and surface activated. The photoresist is then coated onto the substrate to obtain a dry film, followed by heat treatment, exposure of the dry film, and treatment with a developer to obtain a patterned morphology; finally, heat treatment is performed, and after partial or complete cross-linking, a photolithographically patterned dielectric layer is obtained.

8. The application as described in claim 7, characterized in that, The substrate can be any one of glass, quartz, sapphire, silicon, smooth copper foil / copper sheet, or SiC. The cleaning treatment methods include using piranha solution, concentrated sulfuric acid, concentrated nitric acid wet process, or any one of photochemical treatment, high temperature flame treatment, corona discharge treatment, and surface plasma treatment; The surface activation treatment includes the use of any one of silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, and organochromium coupling agents; The coating method includes any one of spin coating, ultrasonic spraying, slot coating, gravure coating, bar coating, and ultrasonic spraying.

9. The application as described in claim 7, characterized in that, The exposure method includes any one of mercury lamp / photomask, LED / photomask, laser direct writing without mask, and EB without mask; The developing solution is one or more of cyclohexanone, petroleum ether, toluene, xylene, and 1,3,5-trimethylbenzene; wherein the developing method includes one or more of vertical developing, rinsing developing, and immersion developing.

10. The application as described in claim 7, characterized in that, The heat treatment includes one or more of the following: resistance heating, infrared heating, electromagnetic induction heating, laser and electron beam heating, and plasma heating.

Images