阅读说明：本技术 含立方烷基的光敏成膜树脂、光刻胶组合物及其制备方法 (Photosensitive film-forming resin containing cubic alkyl, photoresist composition and preparation method thereof ) 是由 聂俊 李三保 朱晓群 孙芳 于 2021-08-26 设计创作，主要内容包括：本发明提供一种含立方烷基的光敏成膜树脂、光刻胶组合物及其制备方法,所述光敏成膜树脂按照质量份数计,由30～70份的立方烷基不饱和酯单体与30～70份的(甲基)丙烯酸酯单体共聚而成；所述立方烷基不饱和酯单体选自立方烷基丁烯酸酯单体和含杂环的立方烷基丁烯酸酯单体中的至少一种。本发明提供的含立方烷基的光敏成膜树脂,通过引入立方烷基不饱和酯单体与(甲基)丙烯酸酯单体共聚,提高了光敏成膜树脂中碳的致密度,从而有助于提高光敏成膜树脂的刚度、感光度以及耐刻蚀性,进而能够提供一种具有优异耐刻蚀性能、优异耐热性能的光刻胶用光敏成膜树脂。(The invention provides photosensitive film-forming resin containing cubic alkyl, a photoresist composition and a preparation method thereof, wherein the photosensitive film-forming resin is prepared by copolymerizing 30-70 parts by mass of a cubic alkyl unsaturated ester monomer and 30-70 parts by mass of a (methyl) acrylate monomer; the cubic alkyl unsaturated ester monomer is at least one of a cubic alkyl butenoate monomer and a heterocycle-containing cubic alkyl butenoate monomer. According to the photosensitive film-forming resin containing the cubic alkyl, the density of carbon in the photosensitive film-forming resin is improved by introducing the copolymerization of the cubic alkyl unsaturated ester monomer and the (methyl) acrylate monomer, so that the rigidity, the light sensitivity and the etching resistance of the photosensitive film-forming resin are improved, and the photosensitive film-forming resin for the photoresist with excellent etching resistance and excellent heat resistance can be provided.)

1. The photosensitive film-forming resin containing the cubic alkyl is characterized by being prepared by copolymerizing 30-70 parts by mass of a cubic alkyl unsaturated ester monomer and 30-70 parts by mass of a (methyl) acrylate monomer;

the cubic alkyl unsaturated ester monomer is selected from at least one of a cubic alkyl butenoate monomer and a heterocycle-containing cubic alkyl butenoate monomer; wherein the content of the first and second substances,

the cubic alkyl butenoate monomer has a structural formula shown in a formula (1):

the cubic alkyl butenoate monomer containing the heterocycle has a structural formula shown in a formula (2):

in the formula, R₁At least one selected from the group consisting of a linear/branched hydrocarbon group having 15 or less carbons, a cyclic hydrocarbon group, and an ether group;

r2 has the structural formula shown in formula (3):

in the formula (I), the compound is shown in the specification,represents a linkage to a cubane methoxy group; l is₁And L₂Respectively represent-O-and-S-; s₁Is an integer of 1 to 3; s₂Is an integer of 0 to 3.

2. A photosensitive cubic alkyl group-containing film-forming resin as claimed in claim 1, wherein the (meth) acrylate ester monomer has a structural formula represented by formula (4):

in the formula, R₃Is a hydrogen atom or a methyl group, R₄Is any one of a chain/branched chain hydrocarbon group, a cyclic hydrocarbon group and an ether group having 15 or less carbon atoms.

3. A photosensitive film-forming resin containing cubic alkyl groups according to claim 1 or 2, wherein the photosensitive film-forming resin containing cubic alkyl groups is at least one of a copolymer, terpolymer or tetrapolymer; the photosensitive film-forming resin containing cubic alkyl has a weight average molecular weight of 15000-50000 and a molecular weight distribution of 1.5-3.0.

4. A photoresist composition is characterized by comprising 15-40 parts by weight of the photosensitive film-forming resin containing cubic alkyl as claimed in any one of claims 1-3, 0.5-5 parts by weight of a photoacid generator, 55-80 parts by weight of a solvent and 2 parts by weight of an auxiliary agent.

5. The photoresist composition of claim 4, wherein the photoacid generator is at least one selected from the group consisting of sulfonium salt derivatives, iodonium salt derivatives, triazine derivatives, sulfonate derivatives, p-toluenesulfonic acid derivatives, diazonium salt derivatives, and diazomethane derivatives.

6. The photoresist composition of claim 4, wherein the auxiliary agent is selected from at least one of a leveling agent, a plasticizer, a dissolution rate enhancer, and a photosensitizer.

7. The photoresist composition of claim 4, wherein the solvent is at least one selected from the group consisting of propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, γ -butyrolactone, ethyl acetate, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether acetate.

8. A method for preparing the photoresist composition according to any one of claims 4 to 7, comprising the steps of:

s1: preparing a cubic alkyl unsaturated ester monomer;

s2: under the protection of nitrogen, the cubic alkyl unsaturated ester monomer and the (methyl) acrylate monomer are used as raw materials to react at the temperature of 60-120 ℃ to prepare the photosensitive film-forming resin containing cubic alkyl;

s3: according to the mass parts, 15-40 parts of the photosensitive film-forming resin containing the cubic alkyl, 0.5-5 parts of a photoacid generator, 55-80 parts of a solvent and 6 parts of an auxiliary agent are mixed at room temperature to obtain the photoresist composition.

Technical Field

The invention relates to the technical field of photoresist, in particular to a photosensitive film-forming resin containing cubic alkyl, a photoresist composition and a preparation method thereof.

Background

A semiconductor is a material whose conductivity can be controlled, ranging from an insulator to a conductor. At present, most electronic products, such as computers, mobile phones or digital audio recorders, have a core unit in close contact with semiconductors. In the production of semiconductor devices, it is necessary to transfer a circuit pattern to a substrate by photolithography using a photosensitive resin. With the higher and higher requirements for the refinement of semiconductor devices, the higher and higher requirements for the refinement of patterns in the lithography technology are met; at present, the etching resistance of the photosensitive film-forming resin for the photoresist is a key factor for restricting the refinement degree of an etched pattern; therefore, it is an urgent technical problem to provide a photosensitive film-forming resin for photoresist with high etching resistance.

Disclosure of Invention

The problem to be solved by the present invention is to provide a photosensitive film-forming resin having high etching resistance.

In order to solve the problems, the invention provides a photosensitive film-forming resin containing cubic alkyl, which is prepared by copolymerizing 30-70 parts by mass of a cubic alkyl unsaturated ester monomer and 30-70 parts by mass of a (methyl) acrylate monomer;

the cubic alkyl unsaturated ester monomer is selected from at least one of a cubic alkyl butenoate monomer and a heterocycle-containing cubic alkyl butenoate monomer; wherein the content of the first and second substances,

the cubic alkyl butenoate monomer has a structural formula shown in a formula (1):

the cubic alkyl butenoate monomer containing the heterocycle has a structural formula shown in a formula (2):

in the formula, R₁At least one selected from the group consisting of a linear/branched hydrocarbon group having 15 or less carbons, a cyclic hydrocarbon group, and an ether group;

R₂has the advantages ofA structural formula represented by formula (3):

in the formula (I), the compound is shown in the specification,represents a linkage to a cubane methoxy group; l is₁And L₂Respectively represent-O-and-S-; s₁Is an integer of 1 to 3; s₂Is an integer of 0 to 3.

The photosensitive film-forming resin is introduced into the photosensitive film-forming resin through the cubic alkyl unsaturated ester which has good stability, certain rigidity and high structural symmetry, so that the photosensitive film-forming resin is provided with the cubic alkyl, and the photosensitive film-forming resin is modified through the cubic alkyl unsaturated ester, so that the photosensitive film-forming resin containing the cubic alkyl has higher etching resistance.

Specifically, the cubic alkyl unsaturated ester can be cubic alkyl butenoate, and can also be cubic alkyl butenoate containing heterocycle.

Wherein the structural formula of the cubic alkyl butenoate is shown as a formula (1), and in the structural formula, R₁Any one of the following structural formulas can be selected:

in the structural formulaRepresents a bond to a cubane methoxy group in the structure.

R is as defined above₁In the structural formula (II), when R is₁Preferably, the cyclic hydrocarbon group or ether group having 15 or less carbons, contributes to increase of the carbon-to-hydrogen ratio in the photosensitive film-forming resin, thereby contributing to increase of the etching resistance of the cubic alkyl group-containing photosensitive film-forming resin.

In order to further improve the carbon-hydrogen ratio in the photosensitive film-forming resin containing cubic alkyl and further improve the etching resistance of the photosensitive film-forming resin containing cubic alkyl, the cubic alkyl unsaturated ester in the application can also be cubic alkyl crotonate containing heterocycle, and the structural formula of the cubic alkyl crotonate containing heterocycle is preferably shown as a formula (2); as shown in the formula (3), the heterocycle introduced by the heterocycle-containing cubic alkyl butenoate is a polymer rigid chain, is difficult to dissolve and refractory, has the characteristics of high glass transition temperature, high temperature resistance, high strength, high modulus and the like, and has excellent electrical insulation, radiation resistance and chemical medium corrosion resistance, and the heterocycle structure in the formula (3) is grafted to the cubic alkyl butenoate, so that the carbon-hydrogen ratio is improved, the carbon density is improved, the etching resistance of the photosensitive film-forming resin is improved, and the curing speed and the heat resistance of the photosensitive film-forming resin are improved.

According to the photosensitive film-forming resin containing cubic alkyl, the degree of density of carbon in the photosensitive film-forming resin is improved by introducing the copolymerization of the cubic alkyl unsaturated ester monomer and the (methyl) acrylate monomer, so that the rigidity, the light sensitivity and the etching resistance of the photosensitive film-forming resin are improved, and the photosensitive film-forming resin containing cubic alkyl for the photoresist with excellent etching resistance and excellent heat resistance can be provided.

Alternatively, the (meth) acrylate monomer has a structural formula shown in formula (4):

in the formula, R₃Is a hydrogen atom or a methyl group, R₄Is any one of a chain/branched chain hydrocarbon group, a cyclic hydrocarbon group and an ether group having 15 or less carbon atoms.

Specifically, the structure of R4 is preferably selected from any one of the following structural formulas:

wherein, X₁Is methyl or ethylThe base group is a group of a compound,represents a bond to an ester group in the host structure.

The reaction of the copolymerization process of the square alkyl crotonate monomer and the (meth) acrylate monomer in the present application is as follows:

also, the copolymerization of the heterocycle-containing cubic alkyl crotonate monomer with the (meth) acrylate monomer in this application is carried out as follows:

the cubic alkyl-containing photosensitive film-forming resin provided by the application improves the etching resistance of the photosensitive film-forming resin by introducing the cubic alkyl, and further passes through R in a (methyl) acrylate monomer₄Any one of chain/branched chain hydrocarbon group, cyclic hydrocarbon group and ether group with less than 15 carbon atoms is introduced into the copolymer, particularly the cyclic hydrocarbon group and the ether group are adopted, so that the carbon-hydrogen ratio in the copolymer can be further improved, the carbon density is increased, the etching resistance and the heat resistance of the photosensitive film-forming resin containing the cubic alkyl group are further improved, and the curing speed is increased.

Optionally, the cubic alkyl-containing photosensitive film-forming resin is at least one of a copolymer, a terpolymer or a tetrapolymer; the photosensitive film-forming resin containing cubic alkyl has a weight average molecular weight of 15000-50000 and a molecular weight distribution of 1.5-3.0.

The invention also aims to provide a photoresist composition, which comprises 15-40 parts by weight of the photosensitive film-forming resin containing the cubic alkyl, 0.5-5 parts by weight of a photoacid generator, 55-80 parts by weight of a solvent and 2 parts by weight of an auxiliary agent.

According to the photoresist composition provided by the invention, the cubic alkyl unsaturated ester monomer and the (methyl) acrylate monomer are introduced for copolymerization, so that the density of carbon in the photosensitive film-forming resin is improved, the rigidity, the light sensitivity and the etching resistance of the photosensitive film-forming resin are improved, and the photoresist composition with excellent etching resistance and excellent heat resistance can be provided.

Optionally, the photoacid generator is selected from at least one of sulfonium salt derivatives, iodonium salt derivatives, triazine derivatives, sulfonate derivatives, p-toluenesulfonic acid derivatives, diazonium salt derivatives, and diazomethane derivatives.

Optionally, the auxiliary agent is selected from at least one of a leveling agent, a plasticizer, a dissolution rate enhancer, and a photosensitizer.

Optionally, the solvent is at least one selected from propylene glycol monoacetate, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, gamma-butyrolactone, ethyl acetate, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether acetate.

It is still another object of the present invention to provide a method for preparing the photoresist composition as described above, comprising the steps of:

s1: preparing a cubic alkyl unsaturated ester monomer;

s2: under the protection of nitrogen, the cubic alkyl unsaturated ester monomer and the (methyl) acrylate monomer are used as raw materials to react at the temperature of 60-120 ℃ to prepare the photosensitive film-forming resin containing cubic alkyl;

s3: according to the mass parts, 15-40 parts of the photosensitive film-forming resin containing the cubic alkyl, 0.5-5 parts of a photoacid generator, 55-80 parts of a solvent and 2 parts of an auxiliary agent are mixed at room temperature to obtain the photoresist composition.

Wherein the preparation method of the squarely alkyl unsaturated ester monomer in the step S1 comprises a preparation method of a cubic alkyl butenoate monomer and a preparation method of a heterocycle-containing cubic alkyl butenoate monomer; moreover, the preparation method of the cubic alkyl butenoate monomer and the preparation method of the heterocycle-containing cubic alkyl butenoate monomer can be the preparation methods provided in the embodiments of the present application, and any existing preparation method in the prior art can also be used.

In order to achieve both the yield and the economic efficiency of the reaction, the reaction time in step S2 is preferably 15 to 20 hours in step S2 and 15 to 25 hours in step S3.

Compared with the prior art, the photosensitive film-forming resin containing cubic alkyl provided by the invention has the following advantages:

according to the photosensitive film-forming resin containing the cubic alkyl, the density of carbon in the photosensitive film-forming resin is improved by introducing the copolymerization of the cubic alkyl unsaturated ester monomer and the (methyl) acrylate monomer, so that the rigidity, the light sensitivity and the etching resistance of the photosensitive film-forming resin are improved, and the photosensitive film-forming resin for the photoresist with excellent etching resistance and excellent heat resistance can be provided.

Detailed Description

The following describes embodiments of the present invention in detail. The embodiments described below are exemplary and are intended to be illustrative of the present invention and should not be construed as limiting the present invention, and all other embodiments that can be obtained by one of ordinary skill in the art based on the embodiments of the present invention without inventive step fall within the scope of the present invention.

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments thereof are described in detail below.

Example 1

S1: preparing a cubic alkyl butenoate monomer: synthesizing 4-methoxymethyl-cubane-1-methyl butenoate.

50mL of CCl was added to a four-necked round-bottomed flask equipped with a magnetic stirrer, a thermometer, a reflux condenser and a drying tube₄4.1g (0.05mol) of cyclopentenone, 8.9g (0.05mol) of cyclopentenoneN-bromosuccinimide (NBS) was heated to reflux with stirring. After reacting for 2h, filtering, taking filtrate to obtain solution A, and refrigerating at low temperature for later use.

Into a 100mL four-necked round-bottomed flask equipped with a magnetic stirrer, a thermometer, a reflux condenser and a drying tube, solution A was charged, and 4.5g (0.028mol) of Br was added₂Dissolved in 10mL of CCl₄Then, the mixture is placed in a constant pressure funnel, and slowly dropped into the solution A under the cooling and stirring. After the dropwise addition, stirring was continued for 30 min. And distilling under reduced pressure to remove the solvent to obtain a crude product B, and refrigerating at low temperature for later use.

50mL of diethyl ether and the crude product B are respectively added into a 250mL four-neck round-bottom flask with a magnetic stirring device, a thermometer and a drying tube, stirred and dissolved, and cooled to-30 ℃. Dissolving 0.318mol of diethylamine in 50mL of diethyl ether, placing the solution in a constant pressure funnel, cooling and stirring the solution, slowly dripping the solution into the solution, and controlling the dripping speed so that the temperature of the mixture is not higher than-25 ℃. After the dropwise addition, stirring was continued for 30 min. Filtering, washing, decoloring by active carbon, and recrystallizing to obtain a white solid, wherein the white solid is 2-bromocyclopentadienone dimer.

50mL of methanol as a solvent, 1.0mL of dilute hydrochloric acid and 1.5g of 2-bromocyclopentadienone dimer were put in a three-necked quartz flask equipped with a thermometer and a reflux condenser, and then irradiated with ultraviolet light while cooling and stirring. TLC is adopted for detection in the experimental process, methanol is recovered by rotary evaporation after the reaction is finished, and then the residue is dissolved in 30mL of distilled water, heated and refluxed for 4h, and cooled to obtain an aqueous solution of an intermediate product C. Putting the aqueous solution into a single-neck flask, adding a certain amount of solid NaOH, adjusting the pH value of the solution to 9-10, and heating and refluxing for 4 hours. Slowly adding into 40mL concentrated hydrochloric acid/ice mixture, keeping the temperature not higher than 10 deg.C, separating out solid, filtering, washing filter cake with ice water 10mL × 3 times, and air drying to obtain crude product D.

2g of lithium aluminum hydride was dissolved in 100mL of anhydrous tetrahydrofuran, and a solution of the crude solid product D in 80mL of anhydrous tetrahydrofuran was added dropwise in a cold salt bath (-5 ℃ C.), and the reaction was continued at the same temperature for 0.5h after the completion of the dropwise addition. 3mL of water and 6.5 mol. L of water were sequentially added to the reaction system^-13mL of sodium hydroxide solution and 10mL of water were stirred at room temperature for 1 hour. AddingAnd (4) adding magnesium sulfate into the mixture, continuously stirring the mixture for 0.5h, and filtering the mixture to obtain the cubane-1, 4-dimethanol.

0.07mol of cubane-1, 4-dimethyl alcohol and 50mL of a 1% aqueous solution of sodium hydroxide were put into a three-necked quartz flask equipped with a thermometer and a reflux condenser, and dissolved by stirring. Then, methyl chloride (0.07mol) was added dropwise thereto to react at 50 ℃ for 3 hours. Neutralizing, washing and filtering to obtain the 4-methoxy methyl-cubane-1-methanol.

Dissolving 4-methoxymethyl-cubane-1-methanol in 50mL of anhydrous tetrahydrofuran, then dropwise adding the solution into an anhydrous tetrahydrofuran solution of sodium hydride at normal temperature, heating to 65 ℃ after dropwise adding, stirring for 3h, cooling to room temperature, carrying out suction filtration, and removing the sodium hydride. The reaction mixture was added dropwise to 20mL of an anhydrous tetrahydrofuran solution containing 0.07mol of butenoyl chloride at 3 ℃. After the dripping is finished, the temperature is raised to 50 ℃ and the reaction lasts for 3 hours. The solvent was removed by rotary evaporation, the resulting solid was dissolved in cyclohexane and washed with clear water to pH 6-7, the organic layer was separated and dried over anhydrous magnesium sulfate for 5 h. And (5) carrying out suction filtration and reduced pressure rotary evaporation to obtain a crude product. The crude product is passed through a silica gel column (petroleum ether: ethyl acetate: 100: 1) by a dry method, solvent is removed by rotary evaporation, and the crude product is dried in vacuum to obtain 4-methoxymethyl-cubane-1-methyl butenoate, wherein the yield is 10%.

¹H NMR(400MHz,DMSO)(δ,ppm)6.98(dt,J＝15.1,6.4Hz,1H),5.85(q,J＝15.1,1.0Hz,1H),4.01(s,2H),3.79(s,2H),3.71(t,J＝7.0Hz,6H),3.23(s,3H),1.88(dd,J＝6.4,1.0Hz,3H).¹³C NMR(100MHz,DMSO)(δ,ppm)166.5,146.2,144.4,83.4,73.3,59.9,55.6,54.9,33.9,33.7,18.6.IR(KBr)cm^-1:1722(C＝O),1637(C＝C),1199(C-O-C).

S2: 25g of 4-methoxymethyl-cubane-1-methyl butenoate, 35g of tert-butyl methacrylate, 2.0g of Azobisisobutyronitrile (AIBN), which is a free radical polymerization initiator, and 100g of 1, 4-dioxane, are sequentially added into a 500mL three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, and then the mixture is heated to 60 ℃ under the protection of nitrogen to react for 20 hours. And (3) drying the obtained crude product in an oven to obtain the photosensitive film-forming resin 1 containing the cubic alkyl. GPC measurement showed that the weight average molecular weight of the resulting photosensitive film-forming resin was 18500 and the molecular weight distribution was 1.71.

The polymerization reaction formula is as follows:

s3: 15 parts by weight of the cubic alkyl group-containing photosensitive film-forming resin synthesized in step S2, 3 parts by weight of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts by weight of an auxiliary agent (polydimethylsiloxane), and 77 parts by weight of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 25 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain an ArF photoresist composition J1.

The prepared photoresist composition J1 was subjected to a photoresist hardness test: the prepared ArF photoresist composition was placed on a silicon wafer, spin-coated at 1000 rpm, baked on a hot plate at 110 ℃ for 90 seconds, and then exposed to light using a 193nm exposure machine. And baking the substrate on a hot plate at 120 ℃ for 120s after exposure, finally developing the substrate for 60s in a tetramethylammonium hydroxide developing solution with the mass percent of 2.38%, and drying to obtain a photoetching pattern. Then, surface hardness measurement was performed: the test rating is carried out according to the detection method of the national standard GB/T6739-1996, the higher the rating number is, the better the performance is, the pencil hardness is 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, HB, B, 2B, 3B, 4B, 5B and 6B in sequence, wherein 9H is the hardest and 6B is the softest. According to the pencil hardness sequence, the hardness is tested from hard to soft in sequence until the pen point can not scratch the surface of the photoresist film completely, the hardness of the photoresist is obtained, and the test result is shown in table 1.

The prepared photoresist composition J1 was subjected to a photoresist heat resistance test: the prepared ArF photoresist composition was placed on a silicon wafer, spin-coated at 1000 rpm, baked on a hot plate at 110 ℃ for 90 seconds, and then exposed to light using a 193nm exposure machine. After exposure, baking the silicon wafer on a hot plate at 120 ℃ for 120s respectively, finally developing the silicon wafer in a tetramethylammonium hydroxide developing solution with the mass percent of 2.38% for 60s, and baking the silicon wafer with the initial morphology at 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃ and 140 ℃ for 180s respectively after developing. The line morphology was observed with a Scanning Electron Microscope (SEM), the softening temperature of the photoresist morphology was monitored, the heat resistance of the photoresist was analyzed, and the test results are shown in table 1.

The prepared photoresist composition J1 was subjected to photoresist resolution and edge roughness tests: the prepared ArF photoresist composition was placed on a silicon wafer, spin-coated at 1000 rpm, baked on a hot plate at 110 ℃ for 90 seconds, and then exposed to light using a 193nm exposure machine. And baking the substrate on a hot plate at 120 ℃ for 120s after exposure, finally developing the substrate for 60s in a tetramethylammonium hydroxide developing solution with the mass percent of 2.38%, and drying to obtain a photoetching pattern. The pattern was tested for resolution and edge roughness (LER) using a Scanning Electron Microscope (SEM) and the results are shown in table 1.

The prepared photoresist composition J1 was subjected to a photoresist sensitivity test: the photoresist composition thus obtained was placed on a silicon wafer, spin-coated at 1000 rpm, baked on a hot plate at 110 ℃ for 90 seconds, and then exposed to light using a 193nm exposure machine. And baking the substrate on a hot plate at 120 ℃ for 120s after exposure, finally developing the substrate for 60s in a tetramethylammonium hydroxide developing solution with the mass percent of 2.38%, and drying to obtain a photoetching pattern. Then, the thickness of the photoresist film is measured by a film thickness meter. Respectively placing more than one test piece into an etching machine under the process conditions of 60Mt/1000W/500W/45CF₄/180Ar/1000₂Etch for 20 seconds. The thickness of the residual photoresist film layer was measured and the etching rate and the residual film rate of the film layer were calculated, and the test results are shown in table 2.

Example 2

S1: 4-methoxymethyl-cubane-1-methylbutenoate is prepared as provided in example 1;

s2: 35g of 4-methoxymethyl-cubane-1-methyl butenoate, 35g of tert-butyl methacrylate, 2.0g of Azobisisobutyronitrile (AIBN), which is a free radical polymerization initiator, and 100g of 1, 4-dioxane, are sequentially added into a 500mL three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, and then the mixture is heated to 80 ℃ under the protection of nitrogen to react for 18 hours. And (3) putting the crude product into an oven to be dried to obtain the photosensitive film-forming resin 2 containing the cubic alkyl. GPC measurement showed that the weight average molecular weight of the resulting photosensitive film-forming resin was 19400 and the molecular weight distribution was 1.77.

S3: in parts by weight, 20 parts by weight of the cubic alkyl group-containing photosensitive film-forming resin synthesized in step S2, 3 parts by weight of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts by weight of an auxiliary agent (polydimethylsiloxane), and 71 parts by weight of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain ArF photoresist composition J2.

The resulting photoresist composition J2 was tested according to the test method provided in example 1; the test results are detailed in tables 1 and 2.

Example 3

S1: 4-methoxymethyl-cubane-1-methylbutenoate is prepared as provided in example 1;

s2: 54g of 4-methoxymethyl-cubane-1-methyl butenoate, 35g of tert-butyl methacrylate, 2.0g of Azobisisobutyronitrile (AIBN), which is a free radical polymerization initiator, and 100g of 1, 4-dioxane, are sequentially added into a 500mL three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, and then the mixture is heated to 100 ℃ under the protection of nitrogen to react for 15 hours. And (3) putting the crude product into an oven to be dried to obtain the photosensitive film-forming resin 3 containing the cubic alkyl. GPC measurement showed that the weight average molecular weight of the resulting photosensitive film-forming resin was 20500 and the molecular weight distribution was 1.83.

S3: 25 parts by weight of the cubic alkyl group-containing photosensitive film-forming resin synthesized in step S2, 3 parts by weight of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts by weight of an auxiliary agent (polydimethylsiloxane), and 66 parts by weight of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 15 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain an ArF photoresist composition J3.

The resulting photoresist composition J3 was tested according to the test method provided in example 1; the test results are detailed in tables 1 and 2.

Example 4

S1: 4-methoxymethyl-cubane-1-methylbutenoate is prepared as provided in example 1;

s2: 54g of 4-methoxymethyl-cubane-1-methyl butenoate, 42g of cyclopentyl methacrylate, 2.0g of Azobisisobutyronitrile (AIBN) which is a free radical polymerization initiator and 100g of 1, 4-dioxane which is a solvent are sequentially added into a 500mL three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, and then the mixture is heated to 70 ℃ under the protection of nitrogen to react for 18 hours. And (3) putting the crude product into an oven to be dried to obtain the photosensitive film-forming resin 4 containing the cubic alkyl. GPC measurement showed that the weight average molecular weight of the resulting photosensitive film-forming resin was 20400 and the molecular weight distribution was 1.89.

The polymerization reaction formula is as follows:

s3: 25 parts by weight of the cubic alkyl group-containing photosensitive film-forming resin synthesized in step S2, 3 parts by weight of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts by weight of an auxiliary agent (polydimethylsiloxane), and 66 parts by weight of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain an ArF photoresist composition J4.

The resulting photoresist composition J4 was tested according to the test method provided in example 1; the test results are detailed in tables 1 and 2.

Example 5

S1: preparing a cubic alkyl butenoate monomer: 4-ethoxymethyl-cubane-1-methyl butenoate.

The method of example 1 is followed to synthesize cubane-1, 4-dimethanol, 0.07mol of cubane-1, 4-dimethanol and 50mL of 1% by mass aqueous solution of sodium hydroxide are added into a three-neck quartz flask equipped with a thermometer and a reflux condenser, and the mixture is stirred under nitrogen atmosphere, ethylene oxide is introduced at 160-180 ℃, and the reaction is carried out for 4 hours. Neutralizing and washing to obtain 4-ethoxy methyl-cubane-1-methanol.

Dissolving 4-ethoxymethyl-cubane-1-methanol in 50mL of anhydrous tetrahydrofuran, then dropwise adding the solution into an anhydrous tetrahydrofuran solution of sodium hydride at normal temperature, heating to 65 ℃ after dropwise adding, stirring for 3h, cooling to room temperature, carrying out suction filtration, and removing the sodium hydride. The reaction mixture was added dropwise to 20mL of an anhydrous tetrahydrofuran solution containing 0.07mol of butenoyl chloride at 3 ℃. After the dripping is finished, the temperature is raised to 50 ℃ and the reaction lasts for 3 hours. The solvent was removed by rotary evaporation, the resulting solid was dissolved in cyclohexane and washed with clear water to pH 6-7, the organic layer was separated and dried over anhydrous magnesium sulfate for 5 h. And (5) carrying out suction filtration and reduced pressure rotary evaporation to obtain a crude product. The crude product is passed through a silica gel column (petroleum ether: ethyl acetate: 100: 1) by a dry method, solvent is removed by rotary evaporation, and the crude product is dried in vacuum to obtain 4-ethoxymethyl-cubane-1-methoxyl butenoate, wherein the yield is 9%.

¹H NMR(400MHz,DMSO)(δ,ppm)6.98(dt,J＝15.1,6.4Hz,1H),5.85(q,J＝15.1,1.0Hz，1H),4.01(s,2H),3.79(s,2H),3.71(t,J＝7.0Hz,6H),3.46(q,J＝8.0Hz,2H),1.88(dd,J＝6.4,1.0Hz,3H),1.05(t,J＝8.0Hz,3H).¹³C NMR(100MHz,DMSO)(δ,ppm)166.5,146.2,144.4,80.9,73.3,67.2,55.9,54.9,33.9,33.7,18.6,15.2.IR(KBr)cm^-1:1719(C＝O),1640(C＝C),1195(C-O-C).

S2: 57g of 4-ethoxymethyl-cubane-1-methoxycrotonate, 35g of tert-butyl methacrylate, 2.0g of Azobisisobutyronitrile (AIBN), which is a free radical polymerization initiator, and 100g of 1, 4-dioxane, are sequentially added into a 500mL three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, and then the mixture is heated to 80 ℃ under the protection of nitrogen to react for 18 hours. And (3) putting the crude product into an oven to be dried to obtain the photosensitive film-forming resin 5 containing the cubic alkyl. GPC measurement showed that the weight average molecular weight of the resulting photosensitive film-forming resin was 21500, and the molecular weight distribution was 1.97.

The polymerization reaction formula is as follows:

s3: 25 parts by weight of the cubic alkyl group-containing photosensitive film-forming resin synthesized in step S2, 3 parts by weight of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts by weight of an auxiliary agent (polydimethylsiloxane), and 66 parts by weight of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain an ArF photoresist composition J5.

The resulting photoresist composition J5 was tested according to the test method provided in example 1; the test results are detailed in tables 1 and 2.

Example 6

S1: preparation of heterocycle-containing cubic alkyl butenoate monomer cubic alkane-1, 4-dimethanol was synthesized as in example 1.

A three-neck quartz flask equipped with a thermometer and a reflux condenser was charged with 0.07mol of cubane-1, 4-dimethyl alcohol and 50mL of a 1% aqueous solution of sodium hydroxide by mass fraction, and the mixture was dissolved by stirring. Then 2-chloro-1, 4-dioxane (0.07mol) is added to react for 3h at 50 ℃. And neutralizing, washing and filtering to obtain an intermediate product E.

And dissolving the intermediate product E in 50mL of anhydrous tetrahydrofuran, dropwise adding the intermediate product E into an anhydrous tetrahydrofuran solution of sodium hydride at normal temperature, heating to 65 ℃ after dropwise adding, stirring for 3h, cooling to room temperature, carrying out suction filtration, and removing the sodium hydride. The reaction mixture was added dropwise to 20mL of an anhydrous tetrahydrofuran solution containing 0.07mol of butenoyl chloride at 3 ℃. After the dripping is finished, the temperature is raised to 50 ℃ and the reaction lasts for 3 hours. The solvent was removed by rotary evaporation, the resulting solid was dissolved in cyclohexane and washed with clear water to pH 6-7, the organic layer was separated and dried over anhydrous magnesium sulfate for 5 h. And (5) carrying out suction filtration and reduced pressure rotary evaporation to obtain a crude product. The crude product is passed through a silica gel column (petroleum ether: ethyl acetate: 100: 1) by a dry method, solvent is removed by rotary evaporation, and the crude product is dried in vacuum to obtain the heterocycle-containing cubic alkyl butenoate 1, the yield is 10 percent, and the structural formula of the heterocycle-containing cubic alkyl butenoate 1 is as follows:

¹H NMR(400MHz,DMSO)(δ,ppm)6.98(dt,J＝15.1,6.4Hz,1H),5.85(q,J＝15.1,1.0Hz，1H),5.80(s,2H),5.51(t,J＝7.0Hz,1H),4.01(s,2H),3.60-4.00(m,12H),1.88(dd,J＝6.4,1.0Hz，3H).¹³C NMR(100MHz,DMSO)(δ,ppm)166.5,146.2,144.4,111.0,78.2,75.3,73.3,67.5,63.5,56.2,54.9,33.9,33.7,18.6.IR(KBr)cm^-1:1719(C＝O),1638(C＝C),1197(C-O-C).

s2: adding 16g of cubic alkyl butenoate 1 containing a heterocycle, 16g of tert-butyl methacrylate, 2.0g of a free radical polymerization initiator (AIBN) and 100g of solvent toluene in a 500mL three-neck flask in sequence, introducing nitrogen for 10 minutes under the stirring condition, heating to 70 ℃ under the protection of nitrogen for reacting for 18 hours, and putting the crude product into an oven for drying to obtain the photosensitive film-forming resin 6. GPC measurement showed that the weight average molecular weight of the resulting film-forming resin was 23000 and the molecular weight distribution was 1.81.

The polymerization reaction formula is as follows:

s3: 15 parts by weight of the cubic alkyl group-containing photosensitive film-forming resin synthesized in step S2, 3 parts by weight of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts by weight of an auxiliary agent (polydimethylsiloxane), and 77 parts by weight of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain an ArF photoresist composition J6.

The resulting photoresist composition J6 was tested according to the test method provided in example 1; the test results are detailed in tables 1 and 2.

Example 7

S1: the heterocycle-containing cubic alkyl crotonate 1 was synthesized according to the procedure in example 6.

S2: 30g of cubic alkyl butenoate 1 containing a heterocycle, 16g of tert-butyl methacrylate, 2.0g of a free radical polymerization initiator (AIBN) and 100g of solvent toluene are sequentially added into a 500mL three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, then the mixture is heated to 70 ℃ under the protection of nitrogen for reaction for 18 hours, and the crude product is placed into an oven to be dried to obtain the photosensitive film-forming resin 7. GPC measurement showed that the resulting film-forming resin had a weight average molecular weight of 25600 and a molecular weight distribution of 1.88.

S3: according to the weight parts, 20 parts of the cubic alkyl group-containing photosensitive film-forming resin synthesized in the step S2, 3 parts of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts of an auxiliary agent (polydimethylsiloxane) and 71 parts of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain an ArF photoresist composition J7.

The resulting photoresist composition J7 was tested according to the test method provided in example 1; the test results are detailed in tables 1 and 2.

Example 8

S1: the heterocycle-containing cubic alkyl crotonate 1 was synthesized according to the procedure in example 6.

S2: adding 55g of cubic alkyl butenoate 1 containing a heterocycle, 16g of tert-butyl methacrylate, 2.0g of a free radical polymerization initiator (AIBN) and 100g of solvent toluene in a 500mL three-neck flask in sequence, introducing nitrogen for 10 minutes under the stirring condition, heating to 70 ℃ under the protection of nitrogen for reacting for 18 hours, and putting the crude product into an oven for drying to obtain the photosensitive film-forming resin 8. GPC measurement showed that the weight average molecular weight of the resulting film-forming resin was 27700, and the molecular weight distribution was 1.95.

S3: 25 parts by weight of the cubic alkyl group-containing photosensitive film-forming resin synthesized in step S2, 3 parts by weight of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts by weight of an auxiliary agent (polydimethylsiloxane), and 66 parts by weight of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain an ArF photoresist composition J8.

The resulting photoresist composition J8 was tested according to the test method provided in example 1; the test results are detailed in tables 1 and 2.

Example 9

S1: the heterocycle-containing cubic alkyl crotonate 1 was synthesized according to the procedure in example 6.

S2: adding 55g of cubic alkyl butenoate 1 containing a heterocycle, 17g of cyclopentyl methacrylate, 2.0g of a free radical polymerization initiator (AIBN) and 100g of solvent toluene in turn into a 500mL three-neck flask, introducing nitrogen for 10 minutes under the stirring condition, heating to 70 ℃ under the protection of nitrogen for reacting for 18 hours, and putting the crude product into an oven for drying to obtain the photosensitive film-forming resin 9. GPC measurement showed that the weight average molecular weight of the resulting film-forming resin was 27800, and the molecular weight distribution was 2.01.

The polymerization reaction formula is as follows:

s3: 25 parts by weight of the cubic alkyl group-containing photosensitive film-forming resin synthesized in step S2, 3 parts by weight of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts by weight of an auxiliary agent (polydimethylsiloxane), and 66 parts by weight of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain an ArF photoresist composition J9.

The resulting photoresist composition J9 was tested according to the test method provided in example 1; the test results are detailed in tables 1 and 2.

Example 10

S1: preparation of heterocycle-containing cubic alkyl butenoate monomer cubic alkane-1, 4-dimethanol was synthesized as in example 1.

A three-neck quartz flask equipped with a thermometer and a reflux condenser was charged with 0.07mol of cubane-1, 4-dimethyl alcohol and 50mL of a 1% aqueous solution of sodium hydroxide by mass fraction, and the mixture was dissolved by stirring. Then 2-chloro-1, 4-thioxane (0.07mol) was added to react at 50 ℃ for 3 h. Neutralizing, washing and filtering to obtain an intermediate product F.

And dissolving the intermediate product F in 50mL of anhydrous tetrahydrofuran, dropwise adding the intermediate product F into an anhydrous tetrahydrofuran solution of sodium hydride at normal temperature, heating to 65 ℃ after dropwise adding, stirring for 3h, cooling to room temperature, carrying out suction filtration, and removing the sodium hydride. The reaction mixture was added dropwise to 20mL of an anhydrous tetrahydrofuran solution containing 0.07mol of butenoyl chloride at 3 ℃. After the dripping is finished, the temperature is raised to 50 ℃ and the reaction lasts for 3 hours. The solvent was removed by rotary evaporation, the resulting solid was dissolved in cyclohexane and washed with clear water to pH 6-7, the organic layer was separated and dried over anhydrous magnesium sulfate for 5 h. And (5) carrying out suction filtration and reduced pressure rotary evaporation to obtain a crude product. The crude product is passed through a silica gel column (petroleum ether: ethyl acetate: 100: 1) by a dry method, solvent is removed by rotary evaporation, and the product of the cubic alkyl butenoate 2 containing the heterocycle is obtained by vacuum drying, the yield is 9 percent, and the structural formula of the cubic alkyl butenoate 2 containing the heterocycle is as follows:

s2: 50g of cubic alkyl butenoate containing a heterocycle, 16g of tert-butyl methacrylate, 2.0g of a free radical polymerization initiator (AIBN) and 100g of solvent toluene are sequentially added into a 500mL three-neck flask, nitrogen is introduced for 10 minutes under the stirring condition, then the mixture is heated to 70 ℃ under the protection of nitrogen for reaction for 18 hours, and the crude product is placed into an oven to be dried, so that the photosensitive film-forming resin 10 is obtained. GPC measurement showed that the resulting film-forming resin had a weight average molecular weight of 27500 and a molecular weight distribution of 2.09.

The polymerization reaction formula is as follows:

s3: 25 parts by weight of the cubic alkyl group-containing photosensitive film-forming resin synthesized in step S2, 3 parts by weight of a photoacid generator (4,4' -dimethyldiphenyliodohexafluorophosphate), 6 parts by weight of an auxiliary agent (polydimethylsiloxane), and 66 parts by weight of a solvent (cyclohexanone) were added to a clean plastic container (250mL polypropylene plastic bottle), and the plastic container was fixed on a mechanical shaker, shaken at room temperature for 20 hours to sufficiently dissolve the components, and then filtered sequentially with a first filter having a pore size of 50nm and a second filter having a pore size of 10nm to obtain an ArF photoresist composition J10.

The resulting photoresist composition J10 was tested according to the test method provided in example 1; the test results are detailed in tables 1 and 2.

TABLE 1

TABLE 2

As can be seen from the test data in table 1, the photoresist composition provided by the present application increases the molecular weight of the photosensitive film-forming resin and increases the hardness of the prepared photoresist composition as the content of the squarylium unsaturated ester monomer in the photosensitive film-forming resin increases; furthermore, as the number of heterocycles incorporated into the photosensitive film-forming resin increases, the hardness of the prepared photoresist composition increases, the pattern resolution increases, the edge roughness decreases, and the curing rate increases.

As can be seen from the data in table 2, the photoresist composition provided by the present application has strong etching resistance, and as the content of the squarylium unsaturated ester monomer in the photosensitive film-forming resin increases, the molecular weight of the photosensitive film-forming resin increases, and the etching resistance of the prepared photoresist composition increases; and, as the number of heterocyclic rings incorporated into the photosensitive film-forming resin increases, the etch resistance of the photoresist composition produced increases.

In addition, other monomers and film-forming resins of the present invention can be synthesized according to the methods in the examples, which are not described again. It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.