CN117111405B - Preparation of linear polysiloxane low dielectric loss photosensitive resin and application of photoetching patterning - Google Patents

Abstract

The invention discloses a preparation method of linear polysiloxane low dielectric loss photosensitive resin and application of photoetching patterning, which is characterized in that dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer, a photoinitiation system and an organic solvent are prepared to form a photosensitive solution, and a photosensitive film is prepared through the photosensitive solution, namely the linear polysiloxane low dielectric loss photosensitive resin for photoetching patterning. The pattern obtained after the photo-curing of the photosensitive system has higher definition, and the obtained film has higher thermal stability through the photo/thermal double-crosslinking process; meanwhile, in the heat treatment process, unreacted photoinitiator can be thermally decomposed, so that the dielectric property of the film is not affected; the linear polysiloxane photosensitive resin provided by the invention has relatively excellent dielectric properties (10 GHz, dk:2.7, df: 0.002-0.003), heat resistance (T5%: 450 ℃) and chemical stability, and is expected to be applied to the field of microelectronics.

Description

Preparation and photolithography patterning application of linear polysiloxane low dielectric loss photosensitive resin

Technical Field

The invention belongs to the technical field of photolithography patterning material preparation, and specifically relates to the preparation of a linear polysiloxane low dielectric loss photosensitive resin and its photolithography patterning application.

Background Art

Photolithography is a technology that transfers patterns onto a substrate through an etching process. Photolithography patterning is an efficient, convenient and low-cost method to improve chip performance. After light-induced patterning, fast curing and high stability can be obtained.

Linear polymers can be considered as a potential precursor due to their unique structure and favorable properties, such as lower viscosity, good solubility, and a large number of terminal functional groups. In particular, photopolymerization involves UV irradiation on polysiloxane, and if photocrosslinking groups are added, patterning with complex structures and shapes can be fabricated with fewer processing steps or free-mold processing. However, it has poor film-forming properties and has limitations in the practical application of low-dielectric materials.

It has been reported (U.S.Pat.5882836, 1999) that tetramethyl divinylsiloxane-bridged benzocyclobutene (DVSBCB for short) can be photocured and can be used for passivation films, photoresists, as insulating layers in the manufacture of electrical devices, as protective films for semiconductor elements, and as interlayer dielectrics in multi-chip modules and other multi-layer electronic circuits. The report preferably selects a series of process conditions such as a variety of azides as photoinitiators (such as 2,6-bis-(4-azidobenzylidene)-4-methylcyclohexanone, 4,4'-diazidebenzoylacetophenone, etc.), photosensitizers with absorption maxima near the wavelength of the photon source used (3,3'-carbonylbis(7-diethylaminocoumarin), 3,3'-carbonylbis(7-methoxycoumarin), etc.), adhesives with excellent adhesion, preferred soft baking time (75°C), exposure time, and exposure energy (300-600mJ/cm-1).

Due to the shortcomings of DVSBCB resin, such as complex synthesis conditions, low molecular weight, cumbersome purification process, and difficult to control prepolymerization process, the inventors (publication number CN202110125974.2, 2021) have introduced three organosilicon functional groups through Heck reaction on the basis of benzocyclobutene to synthesize new organosilicon structural monomers, which are not only simple in process and easy to purify. Different numbers of hydrolyzable organosilicon functional groups are introduced into BCB, and the structure of the organosilicon resin is adjusted by adjusting the type of silane monomer and the proportion of the contained hydrolyzed functional groups, so as to conveniently regulate the mechanical properties of the cured resin, and it is easy to control the molecular weight and viscosity, and the hydrolysis and condensation conditions are mild, the operation is simple, the cost is low, and it is convenient for large-scale production.

Commercial DVSBCB resin materials have high crosslinking density and single monomer structure, which makes the cured resin show high brittleness. Different from the structural formula of DVSBCB, linear benzocyclobutene polysiloxane has one-half more oxygen in structure than DVSBCB, and the ratio can be adjusted by co-hydrolysis to achieve adjustable mechanical properties. The brittleness of DVSBCB materials can be significantly improved, and the prepolymerization conditions of linear benzocyclobutene polysiloxane polymers are simpler and more controllable than those of DVSBCB. The electrical and thermal properties of the two resins show similar results.

The present invention regulates the co-hydrolysis ratio and molecular weight or performs prepolymerization on the basis of the above-mentioned CN202110125974.2, and introduces different photoinitiators and photosensitizers to make different proportions of hydrolysis condensation resins and their prepolymerization systems meet the technical requirements of photolithographic patterning. With the rapid development of the semiconductor industry, the research and development of high-performance, low-dielectric, and low-loss materials have received great attention. Due to the development needs of high frequency and high speed, the size of ultra-large-scale integrated circuits has gradually decreased, and the link lines inside the chip have become increasingly close, resulting in signal transmission delays and cross-interference, and the demand for high-performance, low-dielectric, and low-loss materials has become increasingly urgent.

The linear resin structure designed by the inventor (CN.Pat.202110125974.2, 2021) is single, and due to the presence of a large number of benzocyclobutene groups, the processing performance of the material may be reduced and the flexibility is weakened. The present invention designs several monomers that are hydrolyzed or co-hydrolyzed to obtain the final linear polysiloxane resin, and optimizes the design of the resin by containing monomers of different groups, weighing the relevant properties. Such as controlling the number of benzocyclobutene groups in the resin structure to regulate the processing performance of the resin, or using relatively cheap monomers to control costs. However, the polysiloxane resins finally obtained can all be cross-linked by ultraviolet light, providing a reference for the application of photolithographic patterning.

Summary of the invention

The present invention relates to the preparation of a photosensitive resin system of a dimethoxy (methyl) (benzocyclobutene vinyl) silane linear polymer, a composite photoinitiator system and a solvent. The photosensitive resin system can be used for the structural expansion of a benzocyclobutene photosensitive resin. The benzocyclobutene structure has relatively strong rigidity, so that the mechanical properties and thermal stability of the material are improved and enhanced. Due to the introduction of double bonds, the synthesized polymer has relatively more photocrosslinking sites and can be photocured under ultraviolet light. The polymer after photo/thermal curing has a high degree of crosslinking, excellent mechanical properties, chemical stability and thermal stability, and relatively low dielectric constant and dielectric loss, and can be applied to the field of microelectronics, and provides a reference for the cross-integration of multiple patterning and microelectronics related fields.

An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages which will be described hereinafter.

In order to achieve these purposes and other advantages according to the present invention, a method for preparing a linear polysiloxane low dielectric loss photosensitive resin for photolithographic patterning is provided, wherein a photosensitive solution is formed by preparing a dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer, a photoinitiator system and an organic solvent, and a photosensitive film is prepared by the photosensitive solution, i.e., a linear polysiloxane low dielectric loss photosensitive resin for photolithographic patterning.

Preferably, the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a dimethoxy(methyl)(benzocyclobutenylvinyl) linear polymer terminated with a methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer, and its structural formula is:

Formula I:

Wherein, n=1 to 1000;

Alternatively, the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a copolymer of dimethoxy(methyl)(benzocyclobutenylvinyl)silane and siloxane; the siloxane is any one of dimethoxy(methyl)(styryl)silane, dimethoxy(methyl)(benzocyclobutenyl)silane, dimethoxy(methyl)(phenyl)silane and dimethoxy(dimethyl)silane;

Alternatively, the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a copolymer of dimethoxy(methyl)(benzocyclobutenylvinyl)silane and dimethoxy(methyl)(styryl)silane terminated with a methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer, and has the structural formula:

Formula II:

Among them, n=1～1000, m=1～1000.

Preferably, the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a copolymer of dimethoxy(methyl)(benzocyclobutenylvinyl)silane and dimethoxy(methyl)(benzocyclobutenyl)silane terminated with methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer, and has the structural formula:

Formula III: Wherein, n=1～1000, m=1～1000;

Alternatively, the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a copolymer of dimethoxy(methyl)(benzocyclobutenylvinyl)silane and dimethoxy(methyl)(phenyl)silane terminated with a methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer, and has the structural formula:

Formula IV: Wherein, n=1～1000, m=1～1000;

Alternatively, the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a copolymer of dimethoxy(methyl)(benzocyclobutenylvinyl)silane and dimethoxy(dimethyl)silane terminated with a methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer, and has the structural formula:

Formula V: Among them, n=1～1000, m=1～1000.

Preferably, the photoinitiator system is one or a combination of azide, bismaleimide, acrylate, acetylene, isocyanate, and a polymer of conjugated aromatic ketone; the organic solvent is one or more of toluene, xylene, trimethylbenzene, chloroform, cyclopentanone, dichloromethane, and N-methylpyrrolidone; more preferably, it is one or more of toluene, trimethylbenzene, chloroform, cyclopentanone, and N-methylpyrrolidone (NMP); most preferably, it is a mixed solvent combination of toluene and cyclopentanone;

The volume ratio of the organic solvent to the mass ratio of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is in the range of 3 to 10 mL:1 g; the more preferred organic solvent usage ratio is 3 to 7 mL:1 g; the most preferred organic solvent usage ratio is 3 to 5 mL:1 g; ultrasonic dissolution is performed during the preparation of the photosensitizing solution; the preparation of the photosensitizing solution is performed under light protection.

Preferably, the azide is a highly conjugated aromatic bisazide oxide, including: 2,6-bis(4-azidophenylene)-4-methylcyclohexanone, 2,6-bis(4-azidophenylene)-4-tert-butylcyclohexanone, 2,6-bis[3-(4-azido)-2-propenylene]-4-methylcyclohexanone, 2,6-bis-(4-azidophenylene)cyclohexanone, 2,6-bis[3-(4-azidophenylene)-2-propenylene]-4-methylcyclohexanone, Any one of: 2,6-bis[3-(4-azidophenyl)-2-propenylene]-4-methylcyclohexanone, 4,4' or 3,3'diazidephenyl sulfone, 4,4' or 3,3'-diazidephenyl sulfide, 4,4' or 3,3'-diazidephenyl ether, 2,2-bis[4-(4-azidophenoxy)phenyl]propane or 2,2-bis[4-(3-azidophenoxy)phenyl]propane;

Wherein, the structural formula of the 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) is:

The structural formula of the 2,6-bis(4-azidophenylene)-4-methylcyclohexanone (BAC-M) is:

The structural formula of the 2,6-bis(4-azidophenylene)-4-tert-butylcyclohexanone is:

The structural formula of the 3,3'-diazide phenyl sulfone is:

Another consideration for the azide in the system used is the film thickness of the BCB-LPS resin. BAC-M is suitable for film thicknesses of 5 microns or less;

Preferably, when the thickness of the photosensitive film is less than 5 microns, the azide used is 2,6-bis(4-azidophenylene)-4-methylcyclohexanone;

When the thickness of the photosensitive film is 5 to 10 microns, the azide used is a compound of 2,6-bis(4-azidophenylene)-4-methylcyclohexanone and 4,4'diazidephenyl sulfone, 3,3'diazidephenyl sulfone, 4,4'-diazidephenyl ether, 3,3'-diazidephenyl ether, 2,2-bis[4-(4-azidophenoxy)phenyl]propane, or 2,2-bis[4-(3-azidophenoxy)phenyl]propane;

When the thickness of the photosensitive film is greater than 12 microns, the azide used is one of 3,3'-diazidephenyl sulfone, 4,4'-diazidephenyl ether, 3,3'-diazidephenyl ether, 2,2-bis[4-(4-azidophenoxy)phenyl]propane or 2,2-bis[4-(3-azidophenoxy)phenyl]propane.

Preferably, the amount of the photoinitiator system is 1 to 10% of the mass of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer; more preferably 1 to 5%; most preferably 1 to 3%.

The mass fraction of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer in the photosensitive solution is 90-99.9%.

Preferably, when the photoinitiator system used is an azide photosensitizer, other photosensitizers with a maximum absorption wavelength close to the absorption wavelength of the photosensitizer used are added to increase the photosensitivity of the photosensitizer, and the other photosensitizers are any one of 3,3'-carbonylbis(7-diethylaminocoumarin), 3,3'-carbonylbis(7-methoxycoumarin), benzophenone, and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; more preferably, 3,3'-carbonylbis(7-diethylaminocoumarin), 3,3'-carbonylbis(7-methoxycoumarin); most preferably, 3,3 '-carbonylbis(7-diethylaminocoumarin); the amount of the photoinitiator system is 1 to 10% of the mass of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer; the mass fraction of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer in the photosensitive solution is 90 to 99.9%; the amount of the other photosensitizers is 0.001 to 5% of the mass of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer; more preferably 0.001 to 3%; most preferably 0.001 to 2%.

The present invention also provides an application of a linear polysiloxane low dielectric loss photosensitive resin for photolithography patterning prepared by the preparation method as described above in photolithography patterning, wherein a 365nm UV-LED point light source is used to expose a photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer; and finally, the photocured film is heat-treated to obtain a film with a high cross-linking density. Through the light/heat double cross-linking process, the obtained film has a high thermal stability. At the same time, during the heat treatment process, the unreacted photoinitiator will be thermally decomposed, which will not affect the dielectric properties of the film.

Preferably, the developer is cyclohexanone and petroleum ether in a volume ratio of 2 to 8:1; more preferably, the developer is cyclohexanone and petroleum ether in a volume ratio of 2 to 6:1; most preferably, the developer is cyclohexanone and petroleum ether in a volume ratio of 4 to 6:1;

The heat treatment process is: keeping warm at 150-170°C for 0.5-1.5 hours, keeping warm at 175-190°C for 0.5-1.5 hours, keeping warm at 195-205°C for 1-3 hours, keeping warm at 210-220°C for 1-3 hours, keeping warm at 225-235°C for 1-3 hours, keeping warm at 210-220°C for 0.5-1.5 hours, keeping warm at 195-205°C for 0.5-1.5 hours, keeping warm at 175-190°C for 0.5-1.5 hours, keeping warm at 150-170°C for 0.5-1.5 hours, and cooling naturally;

The wavelength range of the UV-LED point light source used is 248 (KrF line)-436nm (g line); more preferably, the wavelength range of the UV-LED point light source used is 365-405nm; most preferably, the wavelength of the UV-LED point light source used is 365nm;

The exposure energy range of the UV-LED point light source used is 5-5000 mW/cm ² ; more preferably, the exposure energy range of the UV-LED point light source used is 100-2000 mW/cm ² ; most preferably, the exposure energy range of the UV-LED point light source used is 300-900 mW/cm ² ;

The exposure time range of the UV-LED point light source used is 1-1000s; more preferably, the exposure time range of the UV-LED point light source used is 10-240s; most preferably, the exposure time range of the UV-LED point light source used is 30-180s.

The dimethoxy (methyl) (benzocyclobutene vinyl) silane linear polymer of the present invention is a siloxane resin structure, and the molecular weight of the polymer is 1,000 to 200,000. Under the condition of an applied electric field, the siloxane structure has the advantages of low chemical polarity and low polarizability, which is conducive to reducing dielectric loss. Due to the introduction of benzocyclobutene groups, cross-linking and curing can be carried out by heating, without small molecule release, and the cross-linking density is large, so it has good heat resistance and mechanical properties. The monomer and polymer are blended and added to the photosensitive system, so that the photosensitive system has good film-forming properties and photosensitivity, which is beneficial to the generation of light patterning.

The present invention has at least the following beneficial effects:

The pattern obtained after photocuring of the photosensitive system of the present invention has high clarity, and the obtained film has high thermal stability through the light/heat double crosslinking process; at the same time, during the heat treatment process, the unreacted photoinitiator will be thermally decomposed and will not affect the dielectric properties of the film; the linear polysiloxane photosensitive resin provided by the present invention has relatively excellent dielectric properties (10GHz, Dk: 2.7, Df: 0.002-0.003), heat resistance (T5%: 450°C) and chemical stability, and is expected to be applied to the field of microelectronics.

The linear polysiloxane photosensitive resin of the present invention can crosslink the double bonds in the polymer chain through photocuring and become insoluble in the developing solution, thereby obtaining a pattern with neat edges and high precision. However, the polysiloxane photosensitive resin currently used faces the problem of insufficient thermal stability, so a benzocyclobutene group is introduced to form a light/heat double crosslinking structure through thermal crosslinking curing of benzocyclobutene, thereby improving the thermal stability of the polysiloxane photosensitive resin, and at the same time, the pattern will not be deformed during the heat treatment process.

Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is an infrared FTIR spectrum of the material prepared in Example 1;

FIG2 is a thermogravimetric curve of the material prepared in Example 1;

FIG3 is a thermogravimetric curve of the material prepared in Example 1;

FIG4 is a dielectric constant of the material prepared in Example 1;

FIG5 is a diagram showing the dielectric loss of the material prepared in Example 1;

FIG6 is a SEM image of the light-cured material (UV cured film) of Example 1;

FIG7 is a SEM image of the UV/Thermally cured film of Example 1;

FIG8 is an optical microscope image of the light-cured material (UV cured film) of Example 1;

FIG. 9 is an optical microscope image of the photocured material (UV/Thermally cured film) of Example 1. FIG.

DETAILED DESCRIPTION

The present invention will be further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

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

Embodiment 1:

In a 50 ml dry flask, dimethoxy (methyl) (benzocyclobutenyl vinyl) silane monomer BCB-VSilane (1 g, 4.27 mmol) was added, and then toluene (4 g) was added as a solvent in a mass ratio of 1:4 to the silane monomer, and tetramethylammonium hydroxide (0.002 g, 0.2 wt%) and water (0.23 g, 12.81 mmol) were used as catalysts. The reaction was carried out at 80° C. for 4 h, and then methoxy (dimethyl) (benzocyclobutenyl vinyl) silane monomer (0.20 g, 0.85 mmol) was added for end-capping, and the temperature was raised to 100° C. and the reaction was continued for 2 h; after the mixture was cooled to room temperature, it was washed several times with ultrapure water, and then the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer with a yield of 90%; its structural formula is:

Formula I:

Where n = 100;

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.7W) (BCB-LPS) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

The photosensitive solution is dropped on a glass sheet and spin-coated to obtain a photosensitive film (Uncured film), which is placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, the photosensitive film is exposed through a photomask using a 365nm UV-LED point light source, the exposed area is cross-linked and cured and difficult to dissolve in a developer, and the unexposed area is soluble in a developer; after development with a developer, a pattern consistent with the photomask is obtained (UV cured film); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density (UV/Thermal cured film).

Fig. 1 is the infrared FTIR spectrum of the material prepared in Example 1; the molecular structure and the photocuring reaction group are determined by the vibration peaks of the molecular absorption groups; there is an out-of-plane bending vibration absorption peak of the =CH bond at 960cm ^-1 , and the vinyl groups between the phenyl groups have a trans-disubstituted structure; there is a CH swing vibration absorption peak of cyclobutene at 1472cm ^-1 ; there is a vibration absorption peak of cyclohexene at 1489cm ^-1 , which may be due to the cyclohexane structure generated by the coupling reaction between o-xylene and the cyclohexene structure generated by the Diels-Alder reaction between o-xylene and vinyl groups; there is a vibration absorption peak of the azo group at 2110cm ^-1 , and the peak will decrease when the azo group decomposes.

FIG. 2 is a thermogravimetric curve of the material prepared in Example 1; it can be seen that the decomposition temperature of the UV/heat-cured polymer at a weight loss of 5% (T ₅ %) is above 450° C., and has high thermal stability.

Figure 3 is the thermogravimetric curve of the material prepared in Example 1; the thermal curing process of the polymer film was inferred by measuring the thermal decomposition temperature of the polymer film; the thermogravimetric curves of the polymer films after different treatments, the sample after UV/heat curing began to decompose above 210°C, and a thermogravimetric stage appeared at around 300°C, showing a gradually decreasing curve on the TGA graph. This is because BAC began to decompose at 120°C and the aziridine group began to decompose at around 200°C.

FIG4 is a SEM image of the UV cured film of Example 1; the pattern therein is a 40-micron sawtooth pattern with multiple corner lines connected. The image shows that the obtained pattern has a high degree of fineness and the patterning performance of this photosensitive resin is good.

FIG5 is a SEM image of the photocured material (UV/Thermal cured film) of Example 1; the micrograph shows that the pattern of the photosensitive resin does not deform after heat treatment and still retains excellent patterning performance. At the same time, through the light/heat double cross-linking process, the obtained film has higher thermal stability.

Embodiment 2:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(methyl)(styryl)silane monomer Ph-VSilane (0.89 g, 4.27 mmol) were added to a 50 ml dry flask, and then toluene (7.56 g) was added as a solvent at a mass ratio of 1:4 to the silane monomer, and tetramethylammonium hydroxide (0.0038 g, 0.2 wt%) and water (0.46 g, 25.62 mmol) were used as catalysts. The mixture was reacted at 80° C. for 4 h, and then methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.40 g, 1.70 mmol) was added for end-capping. The temperature was raised to 100° C. and the reaction was continued for 2 h. After the mixture was cooled to room temperature, it was washed several times with ultrapure water, and the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a copolymer of BCB-VSilane and Ph-VSilane with a yield of 90%; its structural formula is:

Formula II: Among them, n=50, m=50.

Weigh 0.1 g of a copolymer of BCB-VSilane and Ph-VSilane (M=1.6W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, which is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 3:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(methyl)(styryl)silane monomer Ph-VSilane (2.07 g, 9.96 mmol) were added to a 50 ml dry flask, and then toluene (12.28 g) was added as a solvent at a mass ratio of 1:4 to the silane monomer, and tetramethylammonium hydroxide (0.006 g, 0.2 wt%) and water (0.77 g, 42.69 mmol) were used as catalysts. The mixture was reacted at 80° C. for 4 h, and then methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.60 g, 2.55 mmol) was added for end-capping. The temperature was raised to 100° C. and the reaction was continued for 2 h. After the mixture was cooled to room temperature, it was washed with ultrapure water several times, and the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a copolymer of BCB-VSilane and Ph-VSilane with a yield of 90%; its structural formula is:

Formula II: Among them, n=30, m=70.

Weigh 0.1 g of a copolymer of BCB-VSilane and Ph-VSilane (M=1.7W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, which is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 4:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(methyl)(styryl)silane monomer Ph-VSilane (0.38 g, 1.83 mmol) were added to a 50 ml dry flask, and then toluene (5.52 g) was added as a solvent at a mass ratio of 1:4 to the silane monomer, tetramethylammonium hydroxide (0.0028 g, 0.2 wt%) and water (0.33 g, 18.30 mmol) were used as catalysts, and the mixture was reacted at 80° C. for 4 h, and then methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.28 g, 1.22 mmol) was added for end-capping, and the temperature was raised to 100° C. and the reaction was continued for 2 h; after the mixture was cooled to room temperature, it was washed several times with ultrapure water, and the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a copolymer of BCB-VSilane and Ph-VSilane with a yield of 90%; its structural formula is:

Formula II: Among them, n=70, m=30.

Weigh 0.1 g of a copolymer of BCB-VSilane and Ph-VSilane (M=1.8W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, which is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 5:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(methyl)(benzocyclobutenyl)silane monomer BCB-Silane (0.89 g, 4.27 mmol) were added to a 50 ml dry flask, and toluene (7.56 g) was added as solvent at a mass ratio of 1:4 to silane monomer. Tetramethylammonium hydroxide (0.0038 g, 0.2 wt%) and water (0.46 g, 25.62 mmol) were used as catalysts. The mixture was stirred at 80 °C for 2 h. ℃ for 4h, then add methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.40g, 1.70mmol) for end-capping, raise the temperature to 100℃ and continue to react for 2h; after the mixture is cooled to room temperature, wash with ultrapure water several times, and then dry the organic phase with anhydrous magnesium sulfate, then filter, concentrate the filtered organic phase, and finally vacuum dry to obtain a copolymer of BCB-VSilane and BCB-Silane with a yield of 90%; its structural formula is:

Formula III: Among them, n=50, m=50.

Weigh 0.1 g of a copolymer of BCB-VSilane and BCB-VSilane (M=1.6W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet and spin-coated to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 6:

In a 50 ml dry flask, BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(methyl)(benzocyclobutenyl)silane monomer BCB-Silane (2.07 g, 9.96 mmol) were added, and toluene (12.28 g) with a mass ratio of 1:4 to silane monomer was added as solvent, tetramethylammonium hydroxide (0.006 g, 0.2 wt%) and water (0.77 g, 42.69 mmol) were used as catalysts, and the mixture was stirred at 80 °C for 2 h. ℃ for 4h, then add methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.60g, 2.55mmol) for end-capping, raise the temperature to 100℃ and continue to react for 2h; after the mixture is cooled to room temperature, wash with ultrapure water several times, and then dry the organic phase with anhydrous magnesium sulfate, then filter, concentrate the filtered organic phase, and finally vacuum dry to obtain a copolymer of BCB-VSilane and BCB-Silane with a yield of 90%; its structural formula is:

Formula III: Among them, n=30, m=70.

Weigh 0.1 g of a copolymer of BCB-VSilane and BCB-VSilane (M=1.7W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet and spin-coated to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 7:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(methyl)(benzocyclobutenyl)silane monomer BCB-Silane (0.38 g, 1.83 mmol) were added to a 50 ml dry flask, and toluene (5.52 g) was added as solvent at a mass ratio of 1:4 to silane monomer. Tetramethylammonium hydroxide (0.0028 g, 0.2 wt%) and water (0.33 g, 18.30 mmol) were used as catalysts. The mixture was stirred at 80 °C for 2 h. ℃ for 4h, then add methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.28g, 1.22mmol) for end-capping, raise the temperature to 100℃ and continue to react for 2h; after the mixture is cooled to room temperature, wash with ultrapure water several times, and then dry the organic phase with anhydrous magnesium sulfate, then filter, concentrate the filtered organic phase, and finally vacuum dry to obtain a copolymer of BCB-VSilane and BCB-Silane with a yield of 90%; its structural formula is:

Formula III: Among them, n=70, m=30.

Weigh 0.1 g of a copolymer of BCB-VSilane and BCB-VSilane (M=1.8W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet and spin-coated to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 8:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(methyl)(phenyl)silane monomer (0.78 g, 4.27 mmol) were added to a 50 ml dry flask, and toluene (7.12 g) was added as a solvent at a mass ratio of 1:4 to the silane monomer. Tetramethylammonium hydroxide (0.0036 g, 0.2 wt%) and water (0.46 g, 25.62 mmol) were used as catalysts. The mixture was reacted at 80° C. for 4 h, and then methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.40 g, 1.70 mmol) was added for end-capping. The temperature was raised to 100° C. and the reaction was continued for 2 h. After the mixture was cooled to room temperature, it was washed with ultrapure water several times, and the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a copolymer of BCB-VSilane and dimethoxy(methyl)(phenyl)silane with a yield of 90%; its structural formula is:

Formula IV: Among them, n=50, m=50.

Weigh 0.1 g of a copolymer of BCB-VSilane and dimethoxy(methyl)(phenyl)silane (M=1.5W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet and spin-coated to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 9:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(methyl)(phenyl)silane monomer (1.81 g, 9.96 mmol) were added to a 50 ml dry flask, and toluene (11.24 g) was added as a solvent at a mass ratio of 1:4 to the silane monomer. Tetramethylammonium hydroxide (0.0056 g, 0.2 wt%) and water (0.77 g, 42.69 mmol) were used as catalysts. The mixture was reacted at 80° C. for 4 h, and then methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.60 g, 2.55 mmol) was added for end-capping. The temperature was raised to 100° C. and the reaction was continued for 2 h. After the mixture was cooled to room temperature, it was washed several times with ultrapure water, and the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a copolymer of BCB-VSilane and dimethoxy(methyl)(phenyl)silane with a yield of 90%; its structural formula is:

Formula IV: Among them, n=30, m=70.

Weigh 0.1 g of a copolymer of BCB-VSilane and dimethoxy(methyl)(phenyl)silane (M=1.6W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet and spin-coated to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 10:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(methyl)(phenyl)silane monomer (0.33 g, 1.83 mmol) were added to a 50 ml dry flask, and toluene (5.32 g) was added as a solvent at a mass ratio of 1:4 to the silane monomer. Tetramethylammonium hydroxide (0.0027 g, 0.2 wt%) and water (0.33 g, 18.30 mmol) were used as catalysts. The mixture was reacted at 80° C. for 4 h, and then methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.28 g, 1.22 mmol) was added for end-capping. The temperature was raised to 100° C. and the reaction was continued for 2 h. After the mixture was cooled to room temperature, it was washed several times with ultrapure water, and the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a copolymer of BCB-VSilane and dimethoxy(methyl)(phenyl)silane with a yield of 90%; its structural formula is:

Formula IV: Among them, n=70, m=30.

Weigh 0.1 g of a copolymer of BCB-VSilane and dimethoxy(methyl)(phenyl)silane (M=1.7W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet and spin-coated to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 11:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(dimethyl)silane monomer (0.51 g, 4.27 mmol) were added to a 50 ml dry flask, and toluene (6.04 g) was added as a solvent at a mass ratio of 1:4 to the silane monomer. Tetramethylammonium hydroxide (0.003 g, 0.2 wt%) and water (0.46 g, 25.62 mmol) were used as catalysts. The mixture was reacted at 80° C. for 4 h, and then methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.40 g, 1.70 mmol) was added for end-capping. The temperature was raised to 100° C. and the reaction was continued for 2 h. After the mixture was cooled to room temperature, it was washed several times with ultrapure water, and the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a copolymer of BCB-VSilane and dimethoxy(dimethyl)silane with a yield of 90%; its structural formula is:

Formula IV: Among them, n=50, m=50.

Weigh 0.1 g of a copolymer of BCB-VSilane and dimethoxy(dimethyl)silane (M=1.5W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet and spin-coated to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 12:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(dimethyl)silane monomer (1.20 g, 9.96 mmol) were added to a 50 ml dry flask, and then toluene (8.8 g) was added as a solvent at a mass ratio of 1:4 to the silane monomer. Tetramethylammonium hydroxide (0.0044 g, 0.2 wt%) and water (0.77 g, 42.69 mmol) were used as catalysts. The mixture was reacted at 80° C. for 4 h, and then methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.60 g, 2.55 mmol) was added for end-capping. The temperature was raised to 100° C. and the reaction was continued for 2 h. After the mixture was cooled to room temperature, it was washed several times with ultrapure water, and the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a copolymer of BCB-VSilane and dimethoxy(dimethyl)silane with a yield of 90%; its structural formula is:

Formula IV: Among them, n=30, m=70.

Weigh 0.1 g of a copolymer of BCB-VSilane and dimethoxy(dimethyl)silane (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet and spin-coated to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 13:

BCB-VSilane (1 g, 4.27 mmol) and dimethoxy(dimethyl)silane monomer (0.22 g, 1.83 mmol) were added to a 50 ml dry flask, and toluene (4.88 g) was added as a solvent at a mass ratio of 1:4 to the silane monomer. Tetramethylammonium hydroxide (0.0024 g, 0.2 wt%) and water (0.33 g, 18.30 mmol) were used as catalysts. The mixture was reacted at 80° C. for 4 h, and then methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer (0.28 g, 1.22 mmol) was added for end-capping. The temperature was raised to 100° C. and the reaction was continued for 2 h. After the mixture was cooled to room temperature, it was washed several times with ultrapure water, and the organic phase was dried with anhydrous magnesium sulfate, then filtered, the filtered organic phase was concentrated, and finally vacuum dried to obtain a copolymer of BCB-VSilane and dimethoxy(dimethyl)silane with a yield of 90%; its structural formula is:

Formula IV: Among them, n=70, m=30.

Weigh 0.1 g of a copolymer of BCB-VSilane and dimethoxy(dimethyl)silane (M=1.6W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of a photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet and spin-coated to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes. After the solvent is evaporated, a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, and the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer. After development with a developer, a pattern consistent with the photomask is obtained. Finally, the photocured film is subjected to a programmed temperature rise process, and the temperature rise process is 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 14:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add a photoinitiator of 0.004 g of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 0.002 g of benzophenone, then add 0.3 mL of toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 15:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of benzophenone, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 16:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis-(4-azidobenzylidene)cyclohexanone (BAC) and 0.001 g of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 17:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 2,6-bis[3-(4-azidophenyl)-2-propenylidene]cyclohexanone, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 18:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 2,6-bis[3-(4-azidophenyl)-2-propenylidene]-4-methylcyclohexanone, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 19:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 20:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 2,6-bis(4-azidobenzylidene)-4-tert-butylcyclohexanone, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 21:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 4,4'diazidephenylsulfone, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 22:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 3,3'diazidephenylsulfone, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 23:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 4,4'-diazidephenyl sulfide, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 24:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 3,3'-diazidephenyl sulfide, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 25:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 4,4'-diazidephenyl ether, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 26:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 3,3'-diazidephenyl ether, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 27:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 2,2-bis[4-(4-azidophenoxy)phenyl]propane, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 28:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 2,2-bis[4-(3-azidophenoxy)phenyl]propane, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 29:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 30:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 31:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of 3,3'-carbonylbis(7-diethylaminocoumarin), then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

Embodiment 32:

Weigh 0.1 g of dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer (M=1.3W) and add it to a 3 mL brown sample bottle, weigh and add 0.005 g of photoinitiator 2,6-bis(4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and 0.001 g of benzophenone, then add 0.3 mL of solvent toluene and 0.3 mL of cyclopentanone to the brown sample bottle, and dissolve by ultrasonication to obtain a photosensitive solution;

A photosensitive solution is dropped onto a glass sheet or a silicon wafer for spin coating to obtain a photosensitive film, which is then placed in an oven at 80°C for 10 minutes; after the solvent is evaporated, a 365nm UV-LED point light source is used to expose the film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, while the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained after development with a developer (cyclohexanone: petroleum ether = 4:1); finally, the photocured film is subjected to a programmed temperature rise process, the temperature rise process being 160°C for 1 hour, 180°C for 1 hour, 200°C for 2 hours, 215°C for 2 hours, 230°C for 2 hours, 215°C for 1 hour, 200°C for 1 hour, 180°C for 1 hour, 160°C for 1 hour, and natural cooling to obtain a film with a high cross-linking density.

In the above embodiments 2 to 13, the photoinitiator can be replaced by a composite system of 2,6-bis-(4-azidobenzylidene)cyclohexanone and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, a composite system of 2,6-bis-(4-azidobenzylidene)cyclohexanone and benzophenone, a composite system of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and benzophenone, and a composite system of 2,6-bis (4-azidobenzylidene)-4-methylcyclohexanone (BAC-M) and benzophenone, 2,6-bis [3- (4-azidophenyl) -2-propenylene ] cyclohexanone, 2,6-bis[3-(4-azidophenyl)-2-propenyl]-4-methylcyclohexanone, 2,6-bis(4-azidobenzylidene)-4-tert-butylcyclohexanone, 4,4' or 3,3'diazidephenyl sulfone, 4,4' or 3,3'-diazidephenyl sulfide, 4,4' or 3,3'-diazidephenyl ether, 2,2-bis[4-(4-azidophenoxy)phenyl]propane, 2,2-bis[4-(3-azidophenoxy)phenyl]propane, and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

In the above Examples 14-32, the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer can be replaced by a copolymer of BCB-VSilane and Ph-VSilane and a copolymer of BCB-VSilane and BCB-VSilane.

The reaction mechanism of the present invention is:

The photoinitiator 2,6-bis-(4-azidobenzylidene) cyclohexanone forms nitrene radicals under ultraviolet light, and the nitrene radicals react with double bonds to form a three-membered nitrogen heterocyclic structure for cross-linking. During the thermal curing process, the benzocyclobutene four-membered ring opens at high temperature to form an o-dimethylenquinone intermediate, and o-dimethylenquinone undergoes a Diels-Alder reaction with each other to form an eight-membered ring structure or a Diels-Alder reaction with a double bond to form a six-membered ring structure for cross-linking. By adjusting and optimizing the amount of photoinitiator, exposure energy, exposure time, etc., the functional group conversion rate, photosensitive kinetics, etc. are studied to optimize the resin photosensitive system.

Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.

Claims (6)

1. An application of a linear polysiloxane low dielectric loss photosensitive resin for photolithography patterning in photolithography patterning, characterized in that a 365nm UV-LED point light source is used to expose a photosensitive film through a photomask, the exposed area is cross-linked and cured and difficult to dissolve in a developer, and the unexposed area is soluble in a developer; a pattern consistent with the photomask is obtained by developing with a developer; and finally the photocured film is heat-treated to obtain a film with a high cross-linking density; The developer is cyclohexanone and petroleum ether in a volume ratio of 2 to 8:1; The heat treatment process is as follows: keeping warm at 150-170°C for 0.5-1.5 hours, keeping warm at 175-190°C for 0.5-1.5 hours, keeping warm at 195-205°C for 1-3 hours, keeping warm at 210-220°C for 1-3 hours, keeping warm at 225-235°C for 1-3 hours, keeping warm at 210-220°C for 0.5-1.5 hours, keeping warm at 195-205°C for 0.5-1.5 hours, keeping warm at 175-190°C for 0.5-1.5 hours, keeping warm at 150-170°C for 0.5-1.5 hours, and cooling naturally; The wavelength range of the UV-LED point light source used is 248-436nm; the exposure energy range of the UV-LED point light source used is 5-5000mW/ ^cm2 ; the exposure time range of the UV-LED point light source used is 1-1000s; The method for preparing the linear polysiloxane low dielectric loss photosensitive resin for photolithography patterning is as follows: a photosensitive solution is prepared from a dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer, a photoinitiator system and an organic solvent, and a photosensitive film is prepared from the photosensitive solution, i.e., the linear polysiloxane low dielectric loss photosensitive resin for photolithography patterning; The dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a copolymer of dimethoxy(methyl)(benzocyclobutenylvinyl)silane and dimethoxy(methyl)(styryl)silane terminated with methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer, and its structural formula is: Formula II: ; Among them, n=1~1000, m=1~1000; The photoinitiator system is one or more of azide, bismaleimide, acrylate, acetylene, isocyanate, and a combination of conjugated aromatic ketone polymers; the organic solvent is one or more of toluene, xylene, trimethylbenzene, chloroform, cyclopentanone, dichloromethane, and N-methylpyrrolidone; the volume ratio of the organic solvent to the mass ratio of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is in the range of 3 to 10 mL: 1 g; ultrasonic dissolution is performed during the preparation of the photosensitive solution; and the preparation of the photosensitive solution is performed under light protection. 2. The use of a linear polysiloxane low dielectric loss photosensitive resin for photolithography patterning according to claim 1, characterized in that the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a copolymer of dimethoxy(methyl)(benzocyclobutenylvinyl)silane and dimethoxy(methyl)(benzocyclobutenyl)silane terminated with a methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer, and the structural formula thereof is: Formula III: ; Among them, n=1~1000, m=1~1000; Alternatively, the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a copolymer of dimethoxy(methyl)(benzocyclobutenylvinyl)silane and dimethoxy(methyl)(phenyl)silane terminated with a methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer, and has the structural formula: Formula IV: ; Among them, n=1~1000, m=1~1000; Alternatively, the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer is a copolymer of dimethoxy(methyl)(benzocyclobutenylvinyl)silane and dimethoxy(dimethyl)silane terminated with a methoxy(dimethyl)(benzocyclobutenylvinyl)silane monomer, and has the structural formula: Formula V: ; Among them, n=1~1000, m=1~1000. 3. The use of the linear polysiloxane low dielectric loss photosensitive resin for photolithography patterning according to claim 1 in photolithography patterning, characterized in that the azide is a highly conjugated aromatic bisazide oxide, including: 2,6-bis(4-azidophenylene)-4-methylcyclohexanone, 2,6-bis(4-azidophenylene)-4-tert-butylcyclohexanone, 2,6-bis[3-(4-azido)-2-propenyl]-4-methylcyclohexanone, 2,6-bis-(4-azidophenylene)-4-tert-butylcyclohexanone Any one of cyclohexanone, 2,6-bis[3-(4-azidophenyl)-2-propenylidene]cyclohexanone, 2,6-bis[3-(4-azidophenyl)-2-propenylidene]-4-methylcyclohexanone, 4,4' or 3,3'diazidephenyl sulfone, 4,4' or 3,3'-diazidephenyl sulfide, 4,4' or 3,3'-diazidephenyl ether, 2,2-bis[4-(4-azidophenoxy)phenyl]propane or 2,2-bis[4-(3-azidophenoxy)phenyl]propane. 4. Use of the linear polysiloxane low dielectric loss photosensitive resin for photolithography patterning according to claim 1 in photolithography patterning, characterized in that: When the thickness of the photosensitive film is less than 5 microns, the azide used is 2,6-bis(4-azidophenylene)-4-methylcyclohexanone; When the thickness of the photosensitive film is 5 to 10 microns, the azide used is a compound of 2,6-bis(4-azidophenylene)-4-methylcyclohexanone and 4,4'diazidephenyl sulfone, 3,3'diazidephenyl sulfone, 4,4'-diazidephenyl ether, 3,3'-diazidephenyl ether, 2,2-bis[4-(4-azidophenoxy)phenyl]propane, or 2,2-bis[4-(3-azidophenoxy)phenyl]propane; When the thickness of the photosensitive film is greater than 12 microns, the azide used is one of 3,3'-diazidephenyl sulfone, 4,4'-diazidephenyl ether, 3,3'-diazidephenyl ether, 2,2-bis[4-(4-azidophenoxy)phenyl]propane or 2,2-bis[4-(3-azidophenoxy)phenyl]propane. 5. The use of the linear polysiloxane low dielectric loss photosensitive resin for photolithography patterning as claimed in claim 1 is characterized in that the amount of the photoinitiator system is 1-10% of the mass of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer; the mass fraction of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer in the photosensitive solution is 90-99.9%. 6. The use of the linear polysiloxane low dielectric loss photosensitive resin for photolithography patterning as claimed in claim 1, characterized in that when the photoinitiator system used is an azide photosensitizer, other photosensitizers with a maximum absorption wavelength close to the absorption wavelength of the photosensitizer used are added to increase the photosensitivity of the photosensitizer, and the other photosensitizers are 3,3'-carbonylbis(7-diethylaminocoumarin), 3,3'-carbonylbis(7-methoxycoumarin), benzophenone, diphenyl(2,4,6 -trimethylbenzoyl)phosphine oxide; the amount of the photoinitiator system is 1-10% of the mass of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer; the mass fraction of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer in the photosensitive solution is 90-99.9%; the amount of the other photosensitizer is 0.001-5% of the mass of the dimethoxy(methyl)(benzocyclobutenylvinyl)silane linear polymer.