CN117111405A

CN117111405A - Preparation of linear polysiloxane low dielectric loss photosensitive resin and application of photoetching patterning

Info

Publication number: CN117111405A
Application number: CN202310978758.1A
Authority: CN
Inventors: 杨军校; 胡鑫雨; 马佳俊; 彭娟; 杜翰林
Original assignee: Southwest University of Science and Technology
Current assignee: Southwest University of Science and Technology
Priority date: 2023-08-04
Filing date: 2023-08-04
Publication date: 2023-11-24

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 of linear polysiloxane low dielectric loss photosensitive resin and application of photoetching patterning

Technical Field

The invention belongs to the technical field of preparation of photoetching patterning materials, and particularly relates to preparation of linear polysiloxane low-dielectric-loss photosensitive resin and application of photoetching patterning.

Background

Photolithography is a technique for transferring a pattern onto a substrate by an etching process, and photolithographic patterning is an efficient, convenient, and inexpensive method for improving chip performance, and after photoinitiation to form the pattern, rapid curing and high stability can be achieved.

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

It has been reported (U.S. Pat. No. 58888336, 1999) that tetramethyl divinyl siloxane bridged benzocyclobutene (DVSBCB for short) can be photo-cured and can be used as a passivation film, a photoresist, as an insulating layer in the manufacture of electrical devices, as a protective film for semiconductor elements, and as an interlayer dielectric in multi-chip modules and other multi-layer electronic circuits, and that a variety of azides are preferred as a photoinitiator (e.g., 2, 6-bis- (4-azidobenzeneyl) -4-methylcyclohexanone, 4' -diazidebenzacetophenone, etc.), a photosensitizer (3, 3' -carbonylbis (7-diethylaminocoumarin), 3' -carbonylbis (7-methoxycoumarin), etc.), an excellent adhesive, a preferred soft bake time (75 ℃), an exposure time, and an exposure energy (300-600 mJ/cm-1), among other process conditions.

Because of the defects of complex synthesis conditions, low molecular weight, complicated purification process, difficult control of a prepolymerization process and the like of DVSBCB resin, the inventor (publication No. CN202110125974.2,2021) introduces three organosilicon functional groups through Heck reaction on the basis of benzocyclobutene group to synthesize a new organosilicon structural monomer, and the technology is simple and easy to purify. Different amounts of hydrolyzable organic silicon functional groups are introduced into the BCB, and the structure of the organic silicon resin is regulated by regulating the types of silane monomers and the proportion of the hydrolyzable functional groups, so that the mechanical properties of the cured resin can be conveniently regulated and controlled, the molecular weight and viscosity are easy to control, the hydrolytic condensation condition is mild, the operation is simple, the cost is low, and the mass production is convenient.

Commercial DVSBCB resin materials exhibit higher brittleness after curing due to their high crosslink density, single monomer structure. Unlike the structural formula of DVSBCB, the linear benzocyclobutene polysiloxane is structurally one half more oxygen than DVSBCB, and the mechanical properties can be adjusted by regulating the proportion by cohydrolysis and the like. The brittleness of the DVSBCB material can be obviously improved, and compared with the pre-polymerization condition of the DVSBCB, the linear benzocyclobutene polysiloxane polymer is simple, convenient and controllable. The electrical and thermal properties of the two resins showed similar results.

The invention regulates and controls the co-hydrolysis proportion and the molecular weight or performs the prepolymerization based on the CN202110125974.2, and introduces different photoinitiators and photosensitizers to lead the hydrolytic condensation resin and the prepolymerization system thereof with different proportions to reach the technical requirement of photoetching patterning. With the rapid development of the semiconductor industry, the development and development of high-performance low-dielectric and low-loss materials have received high attention. Due to the development demands of high frequency and high speed, the size of very large scale integrated circuits is gradually reduced, and the link lines inside the chips are more and more compact, so that the transmission delay and the cross interference of signals are caused, and the demands on high-performance low-dielectric low-loss materials are also urgent.

The linear resin designed by the inventor (CN.Pat.202110125974.2, 2021) has a single structure, and can reduce the processability and the flexibility of the material due to the fact that the linear resin contains a large amount of benzocyclobutene groups. The invention designs several monomers to hydrolyze or cohydrolyze to obtain the final linear polysiloxane resin, and the resin is optimally designed by the monomers containing different groups to balance the relevant performance. Such as controlling the number of benzocyclobutene groups in the resin structure to regulate the processability of the resin, or using relatively inexpensive monomers to control costs, etc. But the polysiloxane resin obtained finally can realize ultraviolet crosslinking, thereby providing reference for the application of photoetching patterning.

Disclosure of Invention

The invention relates to a dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer, a compound light initiating system and a photosensitive resin system of solvent, wherein the photosensitive resin system can be used for the structural expansion of benzocyclobutene photosensitive resin, and the benzocyclobutene structure has stronger rigidity, so that the mechanical property and the thermal stability of the material are improved and enhanced; due to the introduction of double bonds, the synthesized polymer has a relatively large number of photocrosslinking sites and can be photocured under ultraviolet light irradiation. The polymer after photo/thermal curing has high crosslinking degree, excellent mechanical property, chemical stability and thermal stability, and relatively low dielectric constant and dielectric loss, can be applied to the field of microelectronics, and provides reference for cross-fusion of a plurality of patterning and microelectronics related fields.

It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.

To achieve these objects and other advantages and in accordance with the purpose of the invention, as embodied and broadly described herein, there is provided a method for preparing a linear polysiloxane low dielectric loss photosensitive resin for lithography patterning, which comprises preparing a photosensitive solution from a dimethoxy (methyl) (benzocyclobutenyl vinyl) silane-based linear polymer, a photoinitiating system and an organic solvent, and preparing a photosensitive film from the photosensitive solution, i.e., a linear polysiloxane low dielectric loss photosensitive resin for lithography patterning.

Preferably, the dimethoxy (methyl) (benzocyclobutenyl) silane-based linear polymer is a dimethoxy (methyl) (benzocyclobutenyl) linear polymer capped with methoxy (dimethyl) (benzocyclobutenyl) silane monomer, having the structural formula:

formula I:

wherein n=1 to 1000;

alternatively, the dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer is a copolymer of dimethoxy (methyl) (benzocyclobutenyl vinyl) 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) (benzocyclobutenyl) silane linear polymer is a copolymer of dimethoxy (methyl) (benzocyclobutenyl) silane and dimethoxy (methyl) (styryl) silane blocked by methoxy (dimethyl) (benzocyclobutenyl) silane monomer, and the structural formula is as follows:

formula II:

wherein n=1 to 1000, m=1 to 1000.

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

Formula III:wherein n=1 to 1000, m=1 to 1000;

alternatively, the dimethoxy (methyl) (benzocyclobutenyl) silane linear polymer is a copolymer of dimethoxy (methyl) (benzocyclobutenyl) silane and dimethoxy (methyl) (phenyl) silane blocked by methoxy (dimethyl) (benzocyclobutenyl) silane monomer, and the structural formula is:

formula IV:wherein the method comprises the steps of，n＝1～1000，m＝1～1000；

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

formula V:wherein n=1 to 1000, m=1 to 1000.

Preferably, the photoinitiating system is one or a combination of a plurality of polymers of azide, bismaleimide, acrylic ester, acetylene, isocyanate and conjugated aromatic ketone; the organic solvent is one or more of toluene, xylene, trimethylbenzene, trichloromethane, cyclopentanone, dichloromethane and N-methylpyrrolidone; more preferred are one or more of toluene, trimethylbenzene, chloroform, cyclopentanone, N-methylpyrrolidone (NMP); most preferred is a mixed solvent combination of toluene and cyclopentanone;

The mass ratio of the volume of the organic solvent to the dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer is 3-10 mL:1g; more preferred organic solvent dosage ratio is 3-7 mL:1g; the most preferable organic solvent dosage proportion is 3-5 mL:1g; carrying out ultrasonic dissolution in the process of preparing the photosensitive solution; the preparation process of the photosensitive solution is carried out in the dark.

Preferably, the azide is a highly conjugated aromatic bisazide comprising: any of 2, 6-bis (4-azidophenylene) -4-methylcyclohexanone, 2, 6-bis (4-azidophenylene) -4-tert-butylcyclohexanone, 2, 6-bis [3- (4-azidophenylene) -2-propenylidene ] -4-methylcyclohexanone, 2, 6-bis- (4-azidophenylene) -2-propenylidene ] cyclohexanone, 2, 6-bis [3- (4-azidophenyl) -2-propenylidene ] -4-methylcyclohexanone, 4 'or 3,3' diazidophenylsulfone, 4 'or 3,3' -diazidophenylsulfide, 4 'or 3,3' -diazidophenylether, 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-azidobenzene) cyclohexanone (BAC) is as follows:

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

the structural formula of the 2, 6-bis (4-azidobenzene) -4-tert-butylcyclohexanone is as follows:

the structural formula of the 3,3' -diazidophenylsulfone is as follows:

another consideration of 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 μm, the azide used is 2, 6-bis (4-azidobenzene) -4-methylcyclohexanone;

when the thickness of the photosensitive film is 5-10 micrometers, the azide is 2, 6-bis (4-azidophenylene) -4-methylcyclohexanone and one of 4,4 '-diazidophenylsulfone, 3' -diazidophenylsulfone, 4 '-diazidophenylether, 3' -diazidophenylether, 2-bis [4- (4-azidophenoxy) phenyl ] propane or 2, 2-bis [4- (3-azidophenoxy) phenyl ] propane;

when the thickness of the photosensitive film is more than 12 micrometers, the azide is one of 3,3' -diazidophenyl sulfone, 4' -diazidophenyl ether, 3' -diazidophenyl ether, 2-bis [4- (4-azidophenoxy) phenyl ] propane or 2, 2-bis [4- (3-azidophenoxy) phenyl ] propane.

Preferably, the photoinitiating system is used in an amount of 1-10% of the mass of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer; more preferably 1 to 5%; most preferably 1 to 3%.

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

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

The invention also provides an application of the linear polysiloxane low dielectric loss photosensitive resin for photoetching patterning, which is prepared by the preparation method, in photoetching patterning, wherein a 365nm UV-LED point light source is used for exposing the photosensitive film through a photomask, the exposed area is crosslinked and solidified to be indissolvable in a developing solution, and the unexposed area is soluble in the developing solution; developing by using a developing solution to obtain a pattern consistent with the photomask; finally, carrying out heat treatment on the film after photo-curing to obtain the film with high crosslinking density. The obtained film has higher thermal stability through the photo/thermal double cross-linking process. Meanwhile, in the heat treatment process, unreacted photoinitiator can be thermally decomposed, and the dielectric property of the film cannot be affected.

Preferably, the developing solution is cyclohexanone with the volume ratio of 2-8:1: and petroleum ether; more preferably, the developing solution is cyclohexanone with a volume ratio of 2-6:1: and petroleum ether; most preferably, the developing solution is cyclohexanone with the volume ratio of 4-6:1: and petroleum ether;

the heat treatment process comprises the steps of preserving heat at 150-170 ℃ for 0.5-1.5 hours, preserving heat at 175-190 ℃ for 0.5-1.5 hours, preserving heat at 195-205 ℃ for 1-3 hours, preserving heat at 210-220 ℃ for 1-3 hours, preserving heat at 225-235 ℃ for 1-3 hours, preserving heat at 210-220 ℃ for 0.5-1.5 hours, preserving heat at 195-205 ℃ for 0.5-1.5 hours, preserving heat at 175-190 ℃ for 0.5-1.5 hours, preserving heat at 150-170 ℃ for 0.5-1.5 hours, and naturally cooling;

The wavelength range of the UV-LED point light source used is 248 (KrF line) to 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 of the UV-LED point light source is 5-5000mW/cm ² The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the UV-LED point light source is used with an exposure energy ranging from 100 to 2000mW/cm ² The method comprises the steps of carrying out a first treatment on the surface of the Most preferably, the UV-LED point light source is used with an exposure energy in the range of 300-900mW/cm ² ；

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

The dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer is of a siloxane resin structure, and the molecular weight of the polymer is 1-20 thousands. Under the condition of an external electric field, the siloxane structure has the advantages of low chemical polarity and low polarizability, and is beneficial to reducing dielectric loss. The benzocyclobutene group is introduced, so that the benzocyclobutene can be crosslinked and solidified through heating, no small molecule is released, and the crosslinking density is high, so that the benzocyclobutene has good heat resistance and mechanical property. The monomer and polymer are blended into the photosensitive system so that the photosensitive system has good film forming property and photosensitive property, which is beneficial to the generation of photo patterning.

The invention at least comprises the following beneficial effects:

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.

The linear polysiloxane photosensitive resin can crosslink double bonds in a polymer chain through photo-curing and is insoluble in a developing solution, so that patterns with neat edges and high precision are obtained. The currently used polysiloxane photosensitive resin has the problem of insufficient thermal stability, so that the benzocyclobutene group is introduced, and the photo/thermal double-cross-linking structure is formed by thermal cross-linking and curing of the benzocyclobutene, so that the thermal stability of the polysiloxane photosensitive resin is improved, and meanwhile, the pattern cannot be deformed in the thermal treatment process.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Description of the drawings:

FIG. 1 is an infrared FTIR spectrum of the material prepared in example 1;

FIG. 2 is a thermogravimetric curve of the material prepared in example 1;

FIG. 3 is a thermogravimetric curve of the material prepared in example 1;

FIG. 4 shows the dielectric constants of the materials prepared in example 1;

FIG. 5 is the dielectric loss of the material prepared in example 1;

FIG. 6 is an SEM image of a UV cured film of the material of example 1;

FIG. 7 is an SEM image of the photo-cured material (UV/Thermally cured film) of example 1;

FIG. 8 is an optical microscope image of the material (UV cured film) after photo-curing of example 1;

FIG. 9 is an optical microscope image of the material (UV/Thermally cured film) after photo-curing of example 1.

The specific embodiment is as follows:

the present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.

It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.

Example 1:

into a 50ml dry flask was added dimethoxy (methyl) (benzocyclobutenyl vinyl) silane monomer BCB-VSilane (1 g,4.27 mmol), toluene (4 g) having a mass ratio of 1:4 to silane monomer was further added as a solvent, tetramethylammonium hydroxide (0.002 g,0.2 wt%) and water (0.23 g,12.81 mmol) were used as a catalyst, reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.20 g,0.85 mmol) was then added to terminate the end, and the temperature was raised to 100℃to continue the reaction for 2 hours; after the mixture was cooled to room temperature, it was washed several times with ultrapure water, the organic phase was dried with anhydrous magnesium sulfate, followed by filtration, the filtered organic phase was concentrated, and finally dried under vacuum to give a dimethoxy (methyl) (benzocyclobutenyl vinyl) silane-based linear polymer having a yield of 90%; the structural formula is as follows:

Formula I:

wherein n=100;

weighing 0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (M=1.7W) (BCB-LPS) into a 3mL brown sample bottle, weighing 0.005g of photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of solvent toluene and 0.3mL of cyclopentanone into the brown sample bottle, and dissolving by ultrasonic to obtain a photosensitive solution;

spin coating photosensitive solution drops on a glass sheet to obtain a photosensitive film (Uncured film), and putting the photosensitive film into an oven at 80 ℃ to be baked for 10 minutes; after the solvent is volatilized, a 365nm UV-LED point light source is used for exposing the photosensitive film through a photomask, the exposed area is crosslinked and solidified to be indissolvable in a developing solution, and the unexposed area is soluble in the developing solution; developing by using a developing solution to obtain a pattern (UV cured film) consistent with the photomask; finally, the light-cured film is subjected to a temperature programming process, wherein the temperature programming process is that the temperature is kept at 160 ℃ for 1 hour, 180 ℃ for 1 hour, 200 ℃ for 2 hours, 215 ℃ for 2 hours, 230 ℃ for 2 hours, 215 ℃ for 1 hour, 200 ℃ for 1 hour, 180 ℃ for 1 hour, 160 ℃ for 1 hour, and natural cooling is carried out, so that the film (UV/Thermal cured film) with high crosslinking density is obtained.

FIG. 1 is an infrared FTIR spectrum of the material prepared in example 1; determining a molecular structure and a photocuring reaction group through a vibration peak of a molecular absorption group; 960cm ^-1 An out-of-plane bending vibration absorption peak with = C-H bond, a vinyl group between phenyl groups having a trans-disubstituted structure; 1472cm ^-1 The C-H swing vibration absorption peak of the cyclobutene is positioned; 1489cm ^-1 The vibration absorption peak of cyclohexene is probably a cyclohexane structure generated by a coupling reaction between o-xylene and a cyclohexene structure generated by a Diels-Alder reaction between o-xylene and vinyl; 2110cm ^-1 There is a vibration absorption peak of azo group, and when azo is decomposed, the peak is lowered.

FIG. 2 is a thermogravimetric curve of the material prepared in example 1; it was found that the UV/heat curable polymer had a weight loss of 5% (T) ₅ The decomposition temperature is more than 450 ℃, and the heat stability is higher.

FIG. 3 is a thermogravimetric curve of the material prepared in example 1; the thermal curing process of the polymer film is estimated by measuring the thermal decomposition temperature of the polymer film; the thermal weight loss curve of the polymer film after different treatments, the sample after UV/thermal curing starts to decompose at 210 ℃ or above, the thermal weight loss stage appears at about 300 ℃, and the thermal weight loss curve shows a gradual decline curve on the TGA graph, because BAC starts to decompose at 120 ℃ and aziridine group starts to decompose at about 200 ℃.

FIG. 4 is an SEM image of a UV cured film of the material of example 1; the pattern is a saw-tooth pattern with a plurality of corner lines connected at 40 micrometers, and the picture can show that the obtained pattern has higher fineness and better patterning performance.

FIG. 5 is an SEM image of the material (UV/Thermal cured film) after photo-curing of example 1; the microscopic picture shows that the patterns of the photosensitive resin can not deform after heat treatment, and still maintain excellent patterning performance, and meanwhile, the obtained film has higher thermal stability through a photo/thermal double-crosslinking process.

Example 2:

BCB-VSilane (1 g,4.27 mmol) and dimethoxy (methyl) (styryl) silane monomer Ph-VSilane (0.89 g,4.27 mmol) were added into a 50ml dry flask, toluene (7.56 g) with a mass ratio of 1:4 to the silane monomer was added as a solvent, tetramethylammonium hydroxide (0.0038 g,0.2 wt%) and water (0.46 g,25.62 mmol) were used as a catalyst, and reacted at 80℃for 4 hours, after which methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.40 g,1.70 mmol) was added for end-capping, and the temperature was raised to 100℃for 2 hours; after the mixture is cooled to room temperature, washing the mixture with ultrapure water for a plurality of times, drying the organic phase with anhydrous magnesium sulfate, filtering, concentrating the filtered organic phase, and finally drying the organic phase in vacuum to obtain a copolymer of BCB-VSilane and Ph-VSilane with the yield of 90 percent; the structural formula is as follows:

Formula II:where n=50 and m=50.

Weighing 0.1g of a copolymer of BCB-VSilane and Ph-VSilane (M=1.6W) into a 3mL brown sample bottle, weighing 0.005g of a photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of toluene and 0.3mL of cyclopentanone into the brown sample bottle, and dissolving by ultrasonic to obtain a photosensitive solution;

spin-coating photosensitive solution drops on a glass sheet to obtain a photosensitive film, and putting the photosensitive film into an oven at 80 ℃ to be baked for 10 minutes; after the solvent is volatilized, a 365nm UV-LED point light source is used for exposing the photosensitive film through a photomask, the exposed area is crosslinked and solidified to be indissolvable in a developing solution, and the unexposed area is soluble in the developing solution; developing by using a developing solution to obtain a pattern consistent with the photomask; and finally, carrying out a temperature programming process on the film after photocuring, wherein the temperature programming process is that the temperature is kept at 160 ℃ for 1 hour, 180 ℃ for 1 hour, 200 ℃ for 2 hours, 215 ℃ for 2 hours, 230 ℃ for 2 hours, 215 ℃ for 1 hour, 200 ℃ for 1 hour, 180 ℃ for 1 hour, 160 ℃ for 1 hour, and naturally cooling to obtain the film with high crosslinking density.

Example 3:

BCB-VSilane (1 g,4.27 mmol) and dimethoxy (methyl) (styryl) silane monomer Ph-VSilane (2.07 g,9.96 mmol) were added into a 50ml dry flask, toluene (12.28 g) with a mass ratio of 1:4 to the silane monomer was added as a solvent, tetramethylammonium hydroxide (0.006g, 0.2 wt%) and water (0.77 g,42.69 mmol) were used as a catalyst, the mixture was reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.60 g,2.55 mmol) was added to carry out end-capping, and the temperature was raised to 100℃for 2 hours; after the mixture is cooled to room temperature, washing the mixture with ultrapure water for a plurality of times, drying the organic phase with anhydrous magnesium sulfate, filtering, concentrating the filtered organic phase, and finally drying the organic phase in vacuum to obtain a copolymer of BCB-VSilane and Ph-VSilane with the yield of 90 percent; the structural formula is as follows:

formula II:where n=30, m=70.

Weighing 0.1g of a copolymer of BCB-VSilane and Ph-VSilane (M=1.7W) into a 3mL brown sample bottle, weighing 0.005g of a photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of toluene and 0.3mL of cyclopentanone into the brown sample bottle, and dissolving by ultrasonic to obtain a photosensitive solution;

Example 4:

BCB-VSilane (1 g,4.27 mmol) and dimethoxy (methyl) (styryl) silane monomer Ph-VSilane (0.38 g,1.83 mmol) were added into a 50ml dry flask, toluene (5.52 g) with a mass ratio of 1:4 to the silane monomer was added as a solvent, tetramethylammonium hydroxide (0.0028 g,0.2 wt%) and water (0.33 g,18.30 mmol) were used as a catalyst, the mixture was reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.28 g,1.22 mmol) was added to carry out end-capping, and the temperature was raised to 100℃for 2 hours; after the mixture is cooled to room temperature, washing the mixture with ultrapure water for a plurality of times, drying the organic phase with anhydrous magnesium sulfate, filtering, concentrating the filtered organic phase, and finally drying the organic phase in vacuum to obtain a copolymer of BCB-VSilane and Ph-VSilane with the yield of 90 percent; the structural formula is as follows:

Formula II:where n=70, m=30.

Weighing 0.1g of a copolymer of BCB-VSilane and Ph-VSilane (M=1.8W) into a 3mL brown sample bottle, weighing 0.005g of a photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of toluene and 0.3mL of cyclopentanone into the brown sample bottle, and dissolving by ultrasonic to obtain a photosensitive solution;

Example 5:

BCB-VSilane (1 g,4.27 mmol) and dimethoxy (methyl) (benzocyclobutenyl) Silane monomer BCB-Silane (0.89 g,4.27 mmol) were added into a 50ml dry flask, toluene (7.56 g) with a mass ratio of 1:4 to Silane monomer was added as a solvent, tetramethylammonium hydroxide (0.0038 g,0.2 wt%) and water (0.46 g,25.62 mmol) were used as a catalyst, and reacted at 80℃for 4 hours, after which methoxy (dimethyl) (benzocyclobutenyl) Silane monomer (0.40 g,1.70 mmol) was added for capping, and the temperature was raised to 100℃for 2 hours; after the mixture is cooled to room temperature, washing the mixture with ultrapure water for a plurality of times, drying the organic phase with anhydrous magnesium sulfate, filtering, concentrating the filtered organic phase, and finally drying the organic phase in vacuum to obtain a copolymer of BCB-VSilane and BCB-Silane with the yield of 90 percent; the structural formula is as follows:

formula III:where n=50 and m=50.

Weighing 0.1g of a copolymer of BCB-VSilane and BCB-VSilane (M=1.6W) into a 3mL brown sample bottle, weighing 0.005g of a photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of toluene and 0.3mL of cyclopentanone into the brown sample bottle, and dissolving by ultrasonic to obtain a photosensitive solution;

Example 6:

BCB-VSilane (1 g,4.27 mmol) and dimethoxy (methyl) (benzocyclobutenyl) Silane monomer BCB-Silane (2.07 g,9.96 mmol) were added into a 50ml dry flask, toluene (12.28 g) with a mass ratio of 1:4 to Silane monomer was added as a solvent, tetramethylammonium hydroxide (0.006g, 0.2 wt%) and water (0.77 g,42.69 mmol) were used as a catalyst, reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) Silane monomer (0.60 g,2.55 mmol) was added to carry out end-capping, and the temperature was raised to 100℃for 2 hours; after the mixture is cooled to room temperature, washing the mixture with ultrapure water for a plurality of times, drying the organic phase with anhydrous magnesium sulfate, filtering, concentrating the filtered organic phase, and finally drying the organic phase in vacuum to obtain a copolymer of BCB-VSilane and BCB-Silane with the yield of 90 percent; the structural formula is as follows:

Formula III:wherein n=30，m＝70。

Weighing 0.1g of a copolymer of BCB-VSilane and BCB-VSilane (M=1.7W) into a 3mL brown sample bottle, weighing 0.005g of a photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of toluene and 0.3mL of cyclopentanone into the brown sample bottle, and dissolving by ultrasonic to obtain a photosensitive solution;

Example 7:

BCB-VSilane (1 g,4.27 mmol) and dimethoxy (methyl) (benzocyclobutenyl) Silane monomer BCB-Silane (0.38 g,1.83 mmol) were added into a 50ml dry flask, toluene (5.52 g) with a mass ratio of 1:4 to Silane monomer was added as a solvent, tetramethylammonium hydroxide (0.0028 g,0.2 wt%) and water (0.33 g,18.30 mmol) were used as a catalyst, reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) Silane monomer (0.28 g,1.22 mmol) was added for end-capping, and the temperature was raised to 100℃for 2 hours; after the mixture is cooled to room temperature, washing the mixture with ultrapure water for a plurality of times, drying the organic phase with anhydrous magnesium sulfate, filtering, concentrating the filtered organic phase, and finally drying the organic phase in vacuum to obtain a copolymer of BCB-VSilane and BCB-Silane with the yield of 90 percent; the structural formula is as follows:

formula III:where n=70, m=30.

Weighing 0.1g of a copolymer of BCB-VSilane and BCB-VSilane (M=1.8W) into a 3mL brown sample bottle, weighing 0.005g of a photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of toluene and 0.3mL of cyclopentanone into the brown sample bottle, and dissolving by ultrasonic to obtain a photosensitive solution;

Example 8:

into a 50ml dry flask were charged BCB-VSilane (1 g,4.27 mmol) and dimethoxy (methyl) (phenyl) silane monomer (0.78 g,4.27 mmol), toluene (7.12 g) having a mass ratio to silane monomer of 1:4 was further charged as a solvent, tetramethylammonium hydroxide (0.0036 g,0.2 wt%) and water (0.46 g,25.62 mmol) were used as a catalyst, reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.40 g,1.70 mmol) was then charged for blocking, and the temperature was raised to 100℃for further reaction for 2 hours; after the mixture was cooled to room temperature, it was washed several times with ultrapure water, the organic phase was dried with anhydrous magnesium sulfate, followed by filtration, the filtered organic phase was concentrated, and finally dried under vacuum to give a copolymer of BCB-VSilane and dimethoxy (methyl) (phenyl) silane in a yield of 90%; the structural formula is as follows:

Formula IV:where n=50 and m=50.

Weighing 0.1g of a copolymer of BCB-VSilane and dimethoxy (methyl) (phenyl) silane (M=1.5W) into a 3mL brown sample bottle, weighing 0.005g of a photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of toluene and 0.3mL of cyclopentanone into the brown sample bottle, and performing ultrasonic dissolution to obtain a photosensitive solution;

Example 9:

into a 50ml dry flask were charged BCB-VSilane (1 g,4.27 mmol) and dimethoxy (methyl) (phenyl) silane monomer (1.81 g,9.96 mmol), toluene (11.24 g) having a mass ratio to silane monomer of 1:4 was further charged as a solvent, tetramethylammonium hydroxide (0.0056 g,0.2 wt%) and water (0.77 g,42.69 mmol) were used as a catalyst, reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.60 g,2.55 mmol) was then charged for capping, and the temperature was raised to 100℃for 2 hours; after the mixture was cooled to room temperature, it was washed several times with ultrapure water, the organic phase was dried with anhydrous magnesium sulfate, followed by filtration, the filtered organic phase was concentrated, and finally dried under vacuum to give a copolymer of BCB-VSilane and dimethoxy (methyl) (phenyl) silane in a yield of 90%; the structural formula is as follows:

formula IV:where n=30, m=70.

Weighing 0.1g of a copolymer of BCB-VSilane and dimethoxy (methyl) (phenyl) silane (M=1.6W) into a 3mL brown sample bottle, weighing 0.005g of a photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of toluene and 0.3mL of cyclopentanone into the brown sample bottle, and performing ultrasonic dissolution to obtain a photosensitive solution;

Example 10:

into a 50ml dry flask were charged BCB-VSilane (1 g,4.27 mmol) and dimethoxy (methyl) (phenyl) silane monomer (0.33 g,1.83 mmol), toluene (5.32 g) having a mass ratio to silane monomer of 1:4 was further charged as a solvent, tetramethylammonium hydroxide (0.0027 g,0.2 wt%) and water (0.33 g,18.30 mmol) were used as a catalyst, reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.28 g,1.22 mmol) was then charged for blocking, and the temperature was raised to 100℃for further reaction for 2 hours; after the mixture was cooled to room temperature, it was washed several times with ultrapure water, the organic phase was dried with anhydrous magnesium sulfate, followed by filtration, the filtered organic phase was concentrated, and finally dried under vacuum to give a copolymer of BCB-VSilane and dimethoxy (methyl) (phenyl) silane in a yield of 90%; the structural formula is as follows:

Formula IV:where n=70, m=30.

Weighing 0.1g of a copolymer of BCB-VSilane and dimethoxy (methyl) (phenyl) silane (M=1.7W) into a 3mL brown sample bottle, weighing 0.005g of a photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC) and 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin), adding 0.3mL of toluene and 0.3mL of cyclopentanone into the brown sample bottle, and performing ultrasonic dissolution to obtain a photosensitive solution;

Example 11:

into a 50ml dry flask were charged BCB-VSilane (1 g,4.27 mmol) and dimethoxy (dimethyl) silane monomer (0.51 g,4.27 mmol), toluene (6.04 g) having a mass ratio to silane monomer of 1:4 was further charged as a solvent, tetramethylammonium hydroxide (0.003g, 0.2 wt%) and water (0.46 g,25.62 mmol) were used as a catalyst, reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.40 g,1.70 mmol) was then charged for capping, and the reaction was continued by raising the temperature to 100℃for 2 hours; after the mixture was cooled to room temperature, it was washed several times with ultrapure water, the organic phase was dried with anhydrous magnesium sulfate, followed by filtration, the filtered organic phase was concentrated, and finally dried under vacuum to obtain a copolymer of BCB-VSilane and dimethoxy (dimethyl) silane with a yield of 90%; the structural formula is as follows:

formula IV:where n=50 and m=50.

0.1g of a copolymer of BCB-VSilane and dimethoxy (dimethyl) silane (m=1.5W) was weighed into a 3mL brown sample bottle, 0.005g of 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC), 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin) as a photoinitiator were weighed into the brown sample bottle, and 0.3mL of toluene and 0.3mL of cyclopentanone as solvents were added into the brown sample bottle, and dissolved by ultrasonic to obtain a photosensitive solution;

Example 12:

into a 50ml dry flask were charged BCB-VSilane (1 g,4.27 mmol) and dimethoxy (dimethyl) silane monomer (1.20 g,9.96 mmol), toluene (8.8 g) was further charged in a mass ratio to silane monomer of 1:4 as a solvent, tetramethylammonium hydroxide (0.0044 g,0.2 wt%) and water (0.77 g,42.69 mmol) were used as a catalyst, reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.60 g,2.55 mmol) was then charged for capping, and the temperature was raised to 100℃for 2 hours; after the mixture was cooled to room temperature, it was washed several times with ultrapure water, the organic phase was dried with anhydrous magnesium sulfate, followed by filtration, the filtered organic phase was concentrated, and finally dried under vacuum to obtain a copolymer of BCB-VSilane and dimethoxy (dimethyl) silane with a yield of 90%; the structural formula is as follows:

Formula IV:where n=30, m=70.

0.1g of a copolymer of BCB-VSilane and dimethoxy (dimethyl) silane (m=1.3W) was weighed into a 3mL brown sample bottle, 0.005g of 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC), 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin) as a photoinitiator were weighed into the brown sample bottle, and 0.3mL of toluene and 0.3mL of cyclopentanone as solvents were added into the brown sample bottle, and dissolved by ultrasonic to obtain a photosensitive solution;

Example 13:

into a 50ml dry flask were charged BCB-VSilane (1 g,4.27 mmol) and dimethoxy (dimethyl) silane monomer (0.22 g,1.83 mmol), toluene (4.88 g) was further charged in a mass ratio to silane monomer of 1:4 as a solvent, tetramethylammonium hydroxide (0.0024 g,0.2 wt%) and water (0.33 g,18.30 mmol) were used as a catalyst, reacted at 80℃for 4 hours, methoxy (dimethyl) (benzocyclobutenyl) silane monomer (0.28 g,1.22 mmol) was then charged for capping, and the temperature was raised to 100℃for 2 hours; after the mixture was cooled to room temperature, it was washed several times with ultrapure water, the organic phase was dried with anhydrous magnesium sulfate, followed by filtration, the filtered organic phase was concentrated, and finally dried under vacuum to obtain a copolymer of BCB-VSilane and dimethoxy (dimethyl) silane with a yield of 90%; the structural formula is as follows:

formula IV:where n=70, m=30.

0.1g of a copolymer of BCB-VSilane and dimethoxy (dimethyl) silane (m=1.6w) was weighed into a 3mL brown sample bottle, 0.005g of 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC), 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin) as a photoinitiator were weighed into the brown sample bottle, and 0.3mL of toluene and 0.3mL of cyclopentanone as solvents were added into the brown sample bottle, and dissolved by ultrasonic to obtain a photosensitive solution;

Example 14:

weighing 0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (M=1.3W) into a 3mL brown sample bottle, weighing 0.004g of diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide and 0.002g of diphenyl ketone which are added with a photoinitiator, and then adding 0.3mL of solvent toluene and 0.3mL of cyclopentanone into the brown sample bottle, and performing ultrasonic dissolution to obtain a photosensitive solution;

Spin-coating photosensitive solution drops on a glass sheet or a silicon wafer to obtain a photosensitive film, and putting the photosensitive film into an oven at 80 ℃ to be baked for 10 minutes; after the solvent is volatilized, a 365nm UV-LED point light source is used for exposing the film through a photomask, the exposed area is crosslinked and solidified to be indissolvable in a developing solution, and the unexposed area is soluble in the developing solution; developing by using a developing solution (cyclohexanone: petroleum ether=4:1) to obtain a pattern consistent with the photomask; and finally, carrying out a temperature programming process on the film after photocuring, wherein the temperature programming process is that the temperature is kept at 160 ℃ for 1 hour, 180 ℃ for 1 hour, 200 ℃ for 2 hours, 215 ℃ for 2 hours, 230 ℃ for 2 hours, 215 ℃ for 1 hour, 200 ℃ for 1 hour, 180 ℃ for 1 hour, 160 ℃ for 1 hour, and naturally cooling to obtain the film with high crosslinking density.

Example 15:

weighing 0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (M=1.3W) into a 3mL brown sample bottle, weighing 0.005g of photoinitiator 2, 6-bis- (4-azidophenone) cyclohexanone (BAC) and 0.001g of benzophenone, adding 0.3mL of solvent toluene and 0.3mL of cyclopentanone into the brown sample bottle, and performing ultrasonic dissolution to obtain a photosensitive solution;

Example 16:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) was weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone (BAC), 0.001g of diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide was weighed into the mixture, and then 0.3mL of toluene and 0.3mL of cyclopentanone were added into the brown sample bottle, and the mixture was dissolved by ultrasonic to obtain a photosensitive solution;

Example 17:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) was weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 2, 6-bis [3- (4-azidophenyl) -2-propenylidene ] cyclohexanone were weighed into the photoinitiator, and then 0.3mL of toluene and 0.3mL of cyclopentanone were added into the brown sample bottle, and the mixture was dissolved by ultrasonic to obtain a photosensitive solution;

Example 18:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) was weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 2, 6-bis [3- (4-azidophenyl) -2-propenylidene ] -4-methylcyclohexanone was weighed into the same, and then 0.3mL of solvent toluene and 0.3mL of cyclopentanone were added into the same, and the mixture was dissolved by ultrasonic to obtain a photosensitive solution;

Example 19:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3w) was weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone was weighed into the same, and then 0.3mL of solvent toluene and 0.3mL of cyclopentanone were added into the same, and the mixture was dissolved by ultrasonic to obtain a photosensitive solution;

Example 20:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3w) was weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 2, 6-bis (4-azidobenzylidene) -4-tert-butylcyclohexanone were weighed into the same, and then 0.3mL of solvent toluene and 0.3mL of cyclopentanone were added into the same bottle, and the mixture was dissolved by ultrasonic to obtain a photosensitive solution;

Example 21:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) was weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 4,4' diazidophenyl sulfone were weighed into the photoinitiator, and then 0.3mL of toluene and 0.3mL of cyclopentanone were added into the brown sample bottle, and dissolved by ultrasonic to obtain a photosensitive solution;

Example 22:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) is weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 3,3' diazidophenyl sulfone are weighed into the photoinitiator, 0.3mL of toluene and 0.3mL of cyclopentanone are added into the brown sample bottle, and the mixture is dissolved by ultrasonic to obtain a photosensitive solution;

Example 23:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) is weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 4,4' -diazidophenyl sulfide are weighed into the photoinitiator, 0.3mL of toluene and 0.3mL of cyclopentanone are added into the brown sample bottle, and the mixture is dissolved by ultrasonic to obtain a photosensitive solution;

Example 24:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) is weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 3,3' -diazidophenyl sulfide are weighed into the photoinitiator, 0.3mL of toluene and 0.3mL of cyclopentanone are added into the brown sample bottle, and the mixture is dissolved by ultrasonic to obtain a photosensitive solution;

Example 25:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) was weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 4,4' -diazidophenyl ether was weighed into the mixture, and then 0.3mL of toluene and 0.3mL of cyclopentanone were added into the brown sample bottle, and the mixture was dissolved by ultrasonic to obtain a photosensitive solution;

Example 26:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) was weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 3,3' -diazidophenyl ether was weighed into the same, and then 0.3mL of toluene and 0.3mL of cyclopentanone were added into the same, and dissolved by ultrasonic to obtain a photosensitive solution;

Example 27:

weighing 0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (M=1.3W) into a 3mL brown sample bottle, weighing 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M) and 0.001g of 2, 2-bis [4- (4-azidophenoxy) phenyl ] propane, adding 0.3mL of solvent toluene and 0.3mL of cyclopentanone into the brown sample bottle, and performing ultrasonic dissolution to obtain a photosensitive solution;

Example 28:

weighing 0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (M=1.3W) into a 3mL brown sample bottle, weighing 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M) and 0.001g of 2, 2-bis [4- (3-azidophenoxy) phenyl ] propane, adding 0.3mL of solvent toluene and 0.3mL of cyclopentanone into the brown sample bottle, and performing ultrasonic dissolution to obtain a photosensitive solution;

Example 29:

weighing 0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (M=1.3W) into a 3mL brown sample bottle, weighing 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M) and 0.001g of diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, adding 0.3mL of solvent toluene and 0.3mL of cyclopentanone into the brown sample bottle, and performing ultrasonic dissolution to obtain a photosensitive solution;

Example 30:

Example 31:

0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (m=1.3W) is weighed into a 3mL brown sample bottle, 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M), 0.001g of 3,3' -carbonylbis (7-diethylaminocoumarin) is weighed into the mixture, and then 0.3mL of solvent toluene and 0.3mL of cyclopentanone are added into the brown sample bottle, and the mixture is dissolved by ultrasonic to obtain a photosensitive solution;

Example 32:

weighing 0.1g of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer (M=1.3W) into a 3mL brown sample bottle, weighing 0.005g of photoinitiator 2, 6-bis (4-azidobenzylidene) -4-methylcyclohexanone (BAC-M) and 0.001g of benzophenone, adding 0.3mL of solvent toluene and 0.3mL of cyclopentanone into the brown sample bottle, and performing ultrasonic dissolution to obtain a photosensitive solution;

In examples 2 to 13 described above, the photoinitiator may be replaced by a system of complexing 2, 6-bis- (4-azidobenzene) cyclohexanone with diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, a system of complexing 2, 6-bis- (4-azidobenzene) cyclohexanone with benzophenone, a system of complexing diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide with benzophenone, a system of complexing 2, 6-bis (4-azidobenzene) -4-methylcyclohexanone (BAC-M) with benzophenone, 2, 6-bis [3- (4-azidophenyl) -2-propenylidene ] cyclohexanone, 2, 6-bis [3- (4-azidobenzenyl) -2-propenylidene ] -4-methylcyclohexanone, 2, 6-bis (4-azidobenzenyl) -4-tert-butylcyclohexanone, 4' or 3,3' diazidophenylsulfone, 4' or 3,3' -diazidophenylsulfide, 4' -diazidophenylsulfide, 3, 4' -diazidophenylpropane, or 3, 4' -diazidophenylpropane, 2, 6-bis [3- (4-azidophenyl) -2-methylpropanene.

In examples 14-32 above, dimethoxy (methyl) (benzocyclobutenyl vinyl) silane-based linear polymers may be replaced with copolymers of BCB-VSilane and Ph-VSilane and copolymers of BCB-VSilane and BCB-VSilane.

The reaction mechanism of the invention is as follows:

the photoinitiator 2, 6-bis- (4-azidobenzene) cyclohexanone forms an azene free radical under the irradiation of ultraviolet light, and the azene free radical reacts with a double bond to form a ternary nitrogen heterocyclic structure for crosslinking. In the heat curing process, the four-membered ring of benzocyclobutene is opened at high temperature to form an o-dimethylenequinone intermediate, and the o-dimethylenequinones mutually undergo Diels-Alder reaction to form an eight-membered ring structure or undergo Diels-Alder reaction with a double bond to form a six-membered ring structure for crosslinking. The functional group conversion rate, the photosensitive dynamics and the like of the photoinitiator are researched by adjusting and optimizing the quantity, the exposure energy, the exposure time and the like of the photoinitiator, so that the resin photosensitive system is optimized.

Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.

Claims

1. A preparation method of a linear polysiloxane low dielectric loss photosensitive resin for photoetching patterning is characterized in that a photosensitive solution is prepared from dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer, a photoinitiation system and an organic solvent, and a photosensitive film is prepared through the photosensitive solution, namely the linear polysiloxane low dielectric loss photosensitive resin for photoetching patterning.

2. The method for preparing a linear polysiloxane low dielectric loss photosensitive resin for photolithographic patterning of claim 1, wherein the dimethoxy (methyl) (benzocyclobutenyl) silane-based linear polymer is a dimethoxy (methyl) (benzocyclobutenyl) vinyl-based linear polymer capped with methoxy (dimethyl) (benzocyclobutenyl) silane monomer, having the structural formula:

formula I:

wherein n=1 to 1000;

formula II:

wherein n=1 to 1000, m=1 to 1000.

3. The method of preparing a linear polysiloxane low dielectric loss photosensitive resin for photolithographic patterning of claim 1, wherein the dimethoxy (methyl) (benzocyclobutenyl) silane-based linear polymer is a copolymer of dimethoxy (methyl) (benzocyclobutenyl) silane and dimethoxy (methyl) (benzocyclobutenyl) silane capped with methoxy (dimethyl) (benzocyclobutenyl) silane monomer, having the structural formula:

formula III:

wherein n=1 to 1000, m=1 to 1000;

Formula IV:

wherein n=1 to 1000, m=1 to 1000;

formula V:

wherein n=1 to 1000, m=1 to 1000.

4. The method of preparing a linear polysiloxane low dielectric loss photosensitive resin for photolithographic patterning of claim 1, wherein the photoinitiating system is one or a combination of several of azide, bismaleimide, acrylate, acetylene, isocyanate, conjugated aromatic ketone polymers; the organic solvent is one or more of toluene, xylene, trimethylbenzene, trichloromethane, cyclopentanone, dichloromethane and N-methylpyrrolidone; the mass ratio of the volume of the organic solvent to the dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer is 3-10 mL:1g; carrying out ultrasonic dissolution in the process of preparing the photosensitive solution; the preparation process of the photosensitive solution is carried out in the dark.

5. The method of preparing a linear polysiloxane low dielectric loss photosensitive resin for photolithographic patterning of claim 1, wherein the azide is a highly conjugated aromatic bisazide comprising: any of 2, 6-bis (4-azidophenylene) -4-methylcyclohexanone, 2, 6-bis (4-azidophenylene) -4-tert-butylcyclohexanone, 2, 6-bis [3- (4-azidophenylene) -2-propenylidene ] -4-methylcyclohexanone, 2, 6-bis- (4-azidophenylene) -2-propenylidene ] cyclohexanone, 2, 6-bis [3- (4-azidophenyl) -2-propenylidene ] -4-methylcyclohexanone, 4 'or 3,3' diazidophenylsulfone, 4 'or 3,3' -diazidophenylsulfide, 4 'or 3,3' -diazidophenylether, 2-bis [4- (4-azidophenoxy) phenyl ] propane or 2, 2-bis [4- (3-azidophenoxy) phenyl ] propane.

6. The method for preparing a linear polysiloxane low dielectric loss photosensitive resin for photolithographic patterning of claim 1, wherein,

when the thickness of the photosensitive film is less than 5 micrometers, the azide is 2, 6-bis (4-azidobenzene) -4-methylcyclohexanone;

7. The method for preparing a linear polysiloxane low dielectric loss photosensitive resin for lithography patterning as set forth in claim 1, wherein the photoinitiating system is 1-10% of the mass of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer; the mass fraction of the dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer in the photosensitive solution is 90-99.9%.

8. The method for preparing a linear polysiloxane low dielectric loss photosensitive resin for lithography patterning as claimed in claim 1, wherein when the photoinitiating system used is an azide photosensitizer, other photosensitizers having a maximum absorption wavelength close to the absorption wavelength of the photosensitizer used are added to increase photosensitivity of the photosensitizers, the other photosensitizers being any one of 3,3 '-carbonylbis (7-diethylaminocoumarin), 3' -carbonylbis (7-methoxycoumarin), benzophenone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide; the photoinitiation system is 1-10% of the mass of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer; the mass fraction of the dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer in the photosensitive solution is 90-99.9%; the dosage of the other photosensitizer is 0.001-5% of the mass of dimethoxy (methyl) (benzocyclobutenyl vinyl) silane linear polymer.

9. Use of the linear polysiloxane low dielectric loss photosensitive resin for lithography patterning prepared by the preparation method according to any one of claims 1 to 8 in lithography patterning, wherein a 365nm UV-LED point light source is used to expose the photosensitive film through a photomask, the exposed area is crosslinked and cured to be insoluble in a developing solution, and the unexposed area is soluble in the developing solution; developing by using a developing solution to obtain a pattern consistent with the photomask; finally, carrying out heat treatment on the film after photo-curing to obtain the film with high crosslinking density.

10. The use of a linear polysiloxane low dielectric loss photosensitive resin for lithographic patterning prepared by the preparation method as claimed in claim 9, wherein,

the developing solution is cyclohexanone with the volume ratio of 2-8:1: and petroleum ether;

The wavelength range of the used UV-LED point light source is 248-436nm; the exposure energy of the UV-LED point light source is 5-5000mW/cm ² The method comprises the steps of carrying out a first treatment on the surface of the The exposure time of the UV-LED point light source used is in the range of 1-1000s.