阅读说明：本技术 硝基苯甲醇磺酸酯化合物作为增速剂在光刻胶中的应用、用于制备光刻胶的组合物 (Application of nitrobenzyl alcohol sulfonate compound as accelerator in photoresist and composition for preparing photoresist ) 是由 孙嘉 李冰 马洁 陈昕 王文芳 董栋 张宁 于 2020-12-31 设计创作，主要内容包括：本申请提供硝基苯甲醇磺酸酯化合物作为增速剂在光刻胶中的应用、用于制备光刻胶的组合物,属于半导体材料技术领域。硝基苯甲醇磺酸酯化合物在受热后会分解产生路易斯质子酸,使其能够作为增速剂添加到酚醛树脂-重氮奈醌型光刻胶和化学放大光刻胶中,提升光刻胶的感光速度,光刻胶的感光能力提升20％以上。在酚醛树脂-重氮奈醌型光刻胶中,增速剂能够在胶膜底部释放的相对浓度更高的路易斯质子酸,从而弥补了胶膜底部生成的茚酸不足的缺陷,帮助树脂在胶膜底部快速溶解。在化学放大光刻胶中,增速剂和产酸剂协同作用在曝光区域沿着胶膜厚度纵向方向产生良好的路易斯质子酸环境,从而提升光刻胶感光速度和消除图形不垂直等形貌缺陷。(The application provides an application of a nitrobenzyl alcohol sulfonate compound as a speed increaser in a photoresist and a composition for preparing the photoresist, belonging to the technical field of semiconductor materials. The nitrobenzol sulfonate compound can be decomposed to generate Lewis protonic acid after being heated, so that the Lewis protonic acid can be used as a speed increasing agent to be added into phenolic resin-diazonaphthoquinone type photoresist and chemical amplification photoresist, the photosensitive speed of the photoresist is increased, and the photosensitive capacity of the photoresist is increased by more than 20%. In the phenolic resin-diazonaphthoquinone type photoresist, the accelerator can release Lewis protonic acid with higher relative concentration at the bottom of an adhesive film, so that the defect of insufficient indene acid generated at the bottom of the adhesive film is overcome, and the resin is helped to be quickly dissolved at the bottom of the adhesive film. In the chemically amplified photoresist, the accelerator and the acid generator act synergistically to generate a good Lewis protonic acid environment in an exposure area along the longitudinal direction of the thickness of a photoresist film, so that the photosensitive speed of the photoresist is improved, and the shape defects of non-perpendicularity of a pattern and the like are eliminated.)

1. The application of the nitrobenzyl sulfonate compound as a speed accelerator in photoresist is characterized in that the structural formula of the nitrobenzyl sulfonate compound is as follows:

wherein R is₁Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a);

R₂selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a);

R₃selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Cycloalkyl radical, C_1～20Alkoxy group of (C)_1～20Halogenoalkyl of, C_1～20Rare radicals or C_1～20A ketone group;

the photoresist comprises phenolic resin-diazonaphthoquinone type photoresist and chemical amplification photoresist.

2. Use of nitrobenzenesulfonate compounds as accelerators in photoresists according to claim 1, characterized in that R is₁Selected from hydrogen, halogen, C_1～10Alkyl radical, C_1～10Alkoxy or C_1～10A haloalkyl group of (a);

the R is₂Selected from hydrogen, halogen, C_1～10Alkyl radical, C_1～10Alkoxy or C_1～10A haloalkyl group of (a);

the R is₃Selected from hydrogen, halogen, C_1～10Alkyl radical, C_1～10Cycloalkyl radicals、C_1～10Alkoxy group of (C)_1～10Halogenoalkyl of, C_1～10Rare radicals or C_1～10A ketone group.

3. Use of nitrobenzenesulfonate compounds as accelerators in photoresists according to claim 1, characterized in that R is₁Selected from hydrogen or halogen, said R₂Selected from hydrogen, halogen or C_1～10Alkyl radical, said R₃Is selected from C_1～10Fluoroalkyl or C_1～10A ketone group.

4. Use of a nitrobenzenesulfonate compound as a rate enhancer in a photoresist as claimed in claim 1, wherein the nitrobenzenesulfonate compound is 4-nitrobenzenesulfonate triflate, 4-nitrobenzenesulfonate perfluorobutyl sulfonate, 3-chloro 4-nitrobenzenesulfonate perfluorobutyl sulfonate, or 4-fluoro-3-nitrobenzoic acid camphorsulfonate.

5. The application of the nitrobenzenesulfonate compound as the accelerator in the photoresist according to any one of claims 1 to 4, wherein the addition amount of the nitrobenzenesulfonate compound in the photoresist is 0.1 to 10 wt% of the solid matter of the photoresist;

optionally, the addition amount of the nitrobenzenesulfonate compound in the photoresist is 0.1-5 wt% of the solid matter of the photoresist.

6. A composition for preparing a photoresist, wherein the composition for preparing a photoresist comprises a first solid substance and a solvent, the first solid substance comprises a phenolic resin, a photosensitizer, an acid quencher and a speed increaser;

the structural formula of the accelerator is as follows:

wherein R is₁Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a);

R₂selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a);

R₃selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Cycloalkyl radical, C_1～20Alkoxy group of (C)_1～20Haloalkyl or C_1～20A dilute base.

7. The composition for preparing photoresist according to claim 6, wherein the first solid substance comprises 80 to 94 wt% of the phenolic resin, 5 to 19 wt% of the photosensitizer, 0.1 to 10 wt% of the acid quencher and 0.1 to 10 wt% of the speed accelerator, and the solvent is 1 to 10 times of the mass of the first solid substance;

optionally, the solid matter comprises 80-90 wt% of the phenolic resin, 9-19 wt% of the photosensitizer, 0.1-5 wt% of the acid quenching agent and 0.1-5 wt% of the speed increasing agent, and the solvent is 1-5 times of the mass of the first solid matter.

8. A composition for preparing a photoresist, comprising a second solid substance comprising a matrix resin, an acid generator, an acid quencher, and a speed-increasing agent;

the matrix resin is the matrix resin of the chemically amplified photoresist;

the structural formula of the accelerator is as follows:

wherein R is₁Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a);

R₂selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a);

R₃selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Cycloalkyl radical, C_1～20Alkoxy group of (C)_1～20Haloalkyl or C_1～20A dilute base.

9. The composition for preparing a photoresist according to claim 8, wherein the second solid substance comprises 85 to 95 wt% of the base resin, 2 to 14 wt% of the acid generator, 0.1 to 10 wt% of the acid quencher and 0.1 to 10 wt% of the speed accelerator, and the solvent is 1 to 10 times of the mass of the second solid substance;

optionally, the second solid substance comprises 90-95 wt% of the matrix resin, 4-14 wt% of the acid generator, 0.1-5 wt% of the acid quencher and 0.1-5 wt% of the speed increaser, and the solvent is 2-6 times of the mass of the second solid substance.

10. The composition for preparing photoresist according to claim 8, wherein the base resin comprises poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) t-butyl carbonate, poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) vinyl ether, poly (adamantane methacrylate), poly (2-methoxymethyl-2-adamantane) methacrylate, poly (2-ethoxymethyl-2-adamantane) methacrylate, poly (2-propoxymethyl-2-adamantane) methacrylate, poly (2-isopropoxymethyl-2-adamantane) methacrylate.

Technical Field

The application relates to the technical field of semiconductor materials, in particular to application of a nitrobenzyl alcohol sulfonate compound as a speed increasing agent in photoresist and a composition for preparing the photoresist.

Background

The photoresist is the most critical material in the photoetching process, a designed pattern on the mask is projected on the photoresist through a photoetching machine, the photoresist is subjected to the dual actions of illumination and baking heating to generate chemical reaction, the chemical reaction results in the generation of solubility difference between an exposed area and an unexposed area, after development by a developing solution, the pattern of the mask is completely presented on the photoresist, and the photoresist pattern is used as a barrier layer, so that the next step of selective etching or ion implantation can be realized, and the photoresist with excellent performance is the key point for transferring the pattern of the mask to a substrate wafer.

The excellent properties of the photoresist include fast photospeed, large process window, and excellent etch resistance. Whether the photosensitive speed is fast enough to meet the requirement of yield is an important parameter for whether the photoresist can be used for producing wafers; secondly, on the basis of high enough light sensing speed, the pattern morphology with excellent morphology can be generated, and the premise that the pattern is continuously transferred to the wafer substrate in the next step after photoetching is also provided.

The photoresist is designed for the exposure wavelength, and the exposure wavelengths such as G-line 436nm, H-line 406nm, I-line 365nm, KrF 248nm and ArF 193nm are the mainstream exposure light source wavelengths in the industry at present. When a light source is exposed, the distribution of light intensity in the adhesive film is in a longitudinal gradient distribution, so the photon concentration is also longitudinally uneven, and the induced chemical reaction is also longitudinally uneven, generally, in order to completely and cleanly open the bottom of the pattern, a relatively high exposure is needed, which means that the photosensitive speed of the photoresist is slow, and the greater the exposure is, the greater the difference between the chemical environments at the top and the bottom of the pattern is, the produced pattern is very easy to have defects, such as the situation that the bottom of the trench is not completely developed, like the pattern shape defect of fig. 1 (the situation that 160nm Line/space is not completely opened and is adhered), or the situation that the side wall of the three-dimensional pattern is not vertical enough and the bottom of the three-dimensional pattern is easy to have a trailing phenomenon, like the situation that the pattern shape defect of fig. 2 (the situation that 160. Therefore, it is very important to increase the photosensitive speed properly without affecting or even improving the pattern morphology.

Disclosure of Invention

The application provides an application of a nitrobenzol sulfonate compound as a speed increaser in a photoresist and a composition for preparing the photoresist, which can improve the photosensitive speed of a phenolic resin-diazonaphthoquinone type photoresist and a chemical amplification photoresist.

The embodiment of the application is realized as follows:

in a first aspect, the present application provides the use of a nitrobenzenesulfonate compound as a rate enhancer in a photoresist, the nitrobenzenesulfonate compound having the following structural formula:

wherein R is₁Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a).

R₂Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a).

R₃Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Cycloalkyl radical, C_1～20Alkoxy group of (C)_1～20Halogenoalkyl of, C_1～20Rare radicals or C_1～20A ketone group.

The photoresist comprises phenolic resin-diazonaphthoquinone type photoresist and chemical amplification photoresist.

In the technical scheme, the nitrobenzol sulfonate compound can be decomposed to generate Lewis protonic acid after being heated to a certain temperature, so that the nitrobenzol sulfonate compound can be used as an accelerator to be added into phenolic resin-diazonaphthoquinone type photoresist and chemical amplification photoresist, the photosensitive speed of the photoresist is improved, and the photosensitive capacity of the photoresist is improved by more than 20%.

In a first possible example of the first aspect of the present application, in combination with the first aspect, the above R₁Selected from hydrogen, halogen, C_1～10Alkyl radical, C_1～10Alkoxy or C_1～10A haloalkyl group of (a).

R₂Selected from hydrogen, halogen, C_1～10Alkyl radical, C_1～10Alkoxy or C_1～10A haloalkyl group of (a).

R₃Selected from hydrogen, halogen, C_1～10Alkyl radical, C_1～10Cycloalkyl radical, C_1～10Alkoxy group of (C)_1～10Halogenoalkyl of, C_1～10Rare radicals or C_1～10A ketone group.

In combination with the first aspect, the present applicationIn a second possible example of the first aspect of the present invention, the above R₁Selected from hydrogen or halogen, R₂Selected from hydrogen, halogen or C_1～10Alkyl radical, R₃Is selected from C_1～10Fluoroalkyl or C_1～10A ketone group.

In a third possible example of the first aspect of the present application in combination with the first aspect, the above-mentioned nitrobenzol sulfonate compound is 4-nitrobenzol trifluoromethylsulfonate, 4-nitrobenzol perfluorobutylsulfonate, 3-chloro 4-nitrobenzol perfluorobutylsulfonate or 4-fluoro-3-nitrobenzoic acid camphorsulfonate.

In a fourth possible example of the first aspect of the present application in combination with the first aspect, the nitrobenzenesulfonate compound is added to the photoresist in an amount of 0.1 to 10 wt% based on the solid substance of the photoresist.

Optionally, the addition amount of the nitrobenzyl sulfonate compound in the photoresist is 0.1-5 wt% of the solid matter of the photoresist.

In the above example, the nitrobenzenesulfonate compound is added to the photoresist formulation in a very small amount as a speed accelerator, but the photosensitivity of the photoresist can be improved by more than 20%.

In a second aspect, the present application provides a composition for preparing a photoresist comprising a first solid substance comprising a phenolic resin, a sensitizer, an acid quencher, and an accelerator, and a solvent.

The structural formula of the accelerator is as follows:

wherein R is₁Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a).

R₂Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a).

R₃Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Cycloalkyl radical, C_1～20Alkoxy group of (C)_1～20Haloalkyl or C_1～20A dilute base.

In the technical scheme, the nitrobenzol sulfonate compound can be used as a speed increaser and added into the phenolic resin-diazonaphthoquinone type photoresist. The phenolic resin-diazonaphthoquinone type photoresist is used for exposure under G lines, I lines or H lines, the phenolic resin-diazonaphthoquinone type photoresist is baked after illumination and exposure, a photosensitizer in an exposure area is subjected to intramolecular rearrangement reaction to generate an indene acid structure, and the acid structure can help phenolic resin to be quickly dissolved in alkaline developing solution, so that the exposure area can be opened to obtain a pattern.

On one hand, in the post-exposure baking heating stage, the accelerating agent can generate active Lewis protonic acid after reaching the decomposition temperature, so that the resin can be dissolved in the alkaline developer without completely depending on indene acid generated after photolysis of the photosensitizer. Compared with the phenolic resin-diazonaphthoquinone type photoresist with the traditional formula, the phenolic resin-diazonaphthoquinone type photoresist added with the accelerator can realize the opening of an exposure area and the realization of a pattern only by smaller exposure.

On the other hand, the exposure light source irradiates from the outside of the photoresist to the inside of the photoresist, the illumination intensity is gradually weakened in the glue film along the thickness direction, and the number of photons obtained by the photosensitizer in the photoresist is also reduced along the thickness direction, so that the concentration of the indene acid generated by the reaction of the photosensitizer is also reduced in sequence along the thickness direction of the glue film, a lot of thick film photoresists are difficult to open at the bottom, and the situation that the bottom is not developed completely or trailing often occurs. The heat source is arranged at the bottom of the photoresist, Lewis protonic acid generated by the thermal decomposition of the accelerator is distributed in the adhesive film along the longitudinal gradient of the thickness direction, and the concentration of the Lewis protonic acid at the bottom of the adhesive film is higher than that at the top of the adhesive film. The Lewis protonic acid with higher relative concentration released by the accelerator at the bottom of the adhesive film just makes up the defect of insufficient indene acid generated by the photosensitizer at the bottom of the adhesive film, can help the resin to be quickly dissolved at the bottom of the adhesive film, and improves the pattern quality. In combination with the second aspect, in a first possible example of the second aspect of the present application, the first solid substance includes 80 to 94 wt% of a phenolic resin, 5 to 19 wt% of a photosensitizer, 0.1 to 10 wt% of an acid quencher, and 0.1 to 10 wt% of a speed-increasing agent, and the solvent is 1 to 10 times of the mass of the first solid substance.

Optionally, the solid matter comprises 80-90 wt% of phenolic resin, 9-19 wt% of photosensitizer, 0.1-5 wt% of acid quenching agent and 0.1-5 wt% of speed increasing agent, and the solvent is 1-5 times of the first solid matter in mass.

In a third aspect, the present application provides a composition for preparing a photoresist comprising a second solid substance comprising a matrix resin, an acid generator, an acid quencher, and an accelerator, and a solvent.

The matrix resin is the matrix resin of the chemically amplified photoresist.

The structural formula of the accelerator is as follows:

wherein R is₁Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a).

R₂Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a).

R₃Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Cycloalkyl radical, C_1～20Alkoxy group of (C)_1～20Haloalkyl or C_1～20A dilute base.

In the technical scheme, the nitrobenzyl alcohol sulfonate compound can be used as a speed increasing agent to be added into the chemical amplification photoresist. The chemical amplification photoresist is used for exposure under I line, KrF and ArF, the acid generator in the non-exposure area of the chemical amplification photoresist does not generate chemical reaction, the resin is not dissolved in the developing solution, the acid generator in the exposure area generates photochemical reaction after being irradiated by a light source to generate Lewis protonic acid, when the chemical amplification photoresist is baked after exposure, the resin can be catalyzed to generate deprotection reaction under the dual action of the Lewis protonic acid and heating, a large number of hydrophobic groups are arranged in the resin molecular structure before deprotection, the resin is not dissolved in the developing solution because the developing solution is aqueous solution, a large number of phenolic hydroxyl groups or carboxyl groups are exposed in the resin molecular structure after deprotection, and the acidic groups react with alkali in the developing solution to bring the resin to be rapidly dissolved in the developing solution, so that the solubility difference between the exposure area and the non-exposure area is realized, and a graph is formed. For the chemically amplified photoresist, the accelerator and the acid generator act synergistically to generate a good Lewis protonic acid environment in the exposure area along the longitudinal direction of the thickness of the photoresist film, and the Lewis protonic acid is relatively uniformly distributed along the longitudinal direction of the thickness of the photoresist film, so that the photosensitive speed of the photoresist can be increased, and the shape defects of non-perpendicularity of a pattern and the like can be eliminated.

In combination with the third aspect, in a first possible example of the third aspect of the present application, the second solid substance includes 85 to 95 wt% of the base resin, 2 to 14 wt% of the acid generator, 0.1 to 10 wt% of the acid quencher, and 0.1 to 10 wt% of the speed accelerator, and the solvent is 1 to 10 times of the mass of the second solid substance.

Optionally, the second solid substance comprises 90-95 wt% of matrix resin, 4-14 wt% of acid generator, 0.1-5 wt% of acid quencher and 0.1-5 wt% of accelerator, and the solvent is 2-6 times of the mass of the second solid substance.

In a second possible example of the third aspect of the present application in combination with the third aspect, the above-mentioned base resin includes poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) t-butyl carbonate, poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) vinyl ether, poly (adamantane methacrylate), poly (2-methoxymethyl-2-adamantane) methacrylate, poly (2-ethoxymethyl-2-adamantane) methacrylate, poly (2-propoxymethyl-2-adamantane) methacrylate, and poly (2-isopropoxymethyl-2-adamantane) methacrylate.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.

FIG. 1 is a scanning electron micrograph of a developed photoresist base having a first topographical defect;

FIG. 2 is a scanning electron micrograph of the bottom of the photoresist after development having a second topographical defect;

FIG. 3 is a scanning electron micrograph of the bottom of the photoresist after development according to example 1 of the present application.

Detailed Description

Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The following description is made specifically for the application of the nitrobenzenesulfonate compound as the speed increasing agent in the photoresist:

the application provides an application of a nitrobenzyl alcohol sulfonate compound as a speed increaser in a photoresist.

The inventor finds that a nitrobenzenesulfonate compound can be decomposed to generate Lewis protonic acid after being heated to a certain temperature, so that the nitrobenzenesulfonate compound can be used as a speed increasing agent to be added into phenolic resin-diazonaphthoquinone type photoresist (novolac-DNQ photoresist) and chemical amplification photoresist, the photosensitive speed of the photoresist is increased, and the photosensitive capacity of the photoresist is increased by more than 20%.

The structural formula of the nitrobenzyl sulfonate compound is as follows:

wherein R is₁Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a).

R₂Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Alkoxy or C_1～20A haloalkyl group of (a).

R₃Selected from hydrogen, halogen, cyano, C_1～20Alkyl radical, C_1～20Cycloalkyl radical, C_1～20Alkoxy group of (C)_1～20Halogenoalkyl of, C_1～20Rare radicals or C_1～20A ketone group.

Alternatively, R₁Selected from hydrogen, halogen, C_1～10Alkyl radical, C_1～10Alkoxy or C_1～10A haloalkyl group of (a).

R₂Selected from hydrogen, halogen, C_1～10Alkyl radical, C_1～10Alkoxy or C_1～10A haloalkyl group of (a).

R₃Selected from hydrogen, halogen, C_1～10Alkyl radical, C_1～10Cycloalkyl radical, C_1～10Alkoxy group of (C)_1～10Halogenoalkyl of, C_1～10Rare radicals or C_1～10A ketone group.

Alternatively, R₁Selected from hydrogen or halogen, R₂Selected from hydrogen, halogen or C_1～10Alkyl radical, R₃Is selected from C_1～10Fluoroalkyl or C_1～10A ketone group.

Alternatively, the nitrobenzenesulfonate compound is 4-nitrobenzenesulfonate triflate, 4-nitrobenzenesulfonate perfluorobutyl sulfonate, 3-chloro 4-nitrobenzenesulfonate perfluorobutyl sulfonate, or 4-fluoro-3-nitrobenzoic acid camphorsulfonate.

The structural formula of the 4-nitrobenzyl alcohol trifluoromethanesulfonate is as follows:

the structural formula of the 4-nitrobenzyl alcohol perfluorobutyl sulfonate is as follows:

the structural formula of the 3-chloro-4-nitrobenzol perfluorobutyl sulfonate is as follows:

the structural formula of the 4-fluoro-3-nitrobenzoic acid camphorsulfonate is as follows:

the addition amount of the nitrobenzyl alcohol sulfonate compound in the photoresist is 0.1-10 wt% of the solid matter of the photoresist.

Optionally, the addition amount of the nitrobenzyl sulfonate compound in the photoresist is 0.1-5 wt% of the solid matter of the photoresist.

Optionally, the nitrobenzenesulfonate compound is added to the photoresist in an amount of 0.5 wt% of the solid material of the photoresist.

In one embodiment of the present application, the nitrobenzenesulfonate compound is added to the photoresist in an amount of 0.5 wt% of the solid material of the photoresist. In some other embodiments herein, the nitrobenzenesulfonate compound may also be added to the photoresist in an amount of 0.1 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 5 wt%, or 10 wt% of the solid material of the photoresist.

The present application also provides a composition for preparing a photoresist comprising a first solid substance comprising a phenolic resin, a sensitizer, an acid quencher, and an accelerator, and a solvent.

The accelerator is the nitrobenzyl sulfonate compound.

The nitrobenzenesulfonate compound can be used as a speed increaser and added into the phenolic resin-diazonaphthoquinone type photoresist. The phenolic resin-diazonaphthoquinone type photoresist is used for exposure under the G line 436nm, the I line 365nm or the H line 406nm, the phenolic resin-diazonaphthoquinone type photoresist is baked after illumination and exposure, a photosensitizer in an exposure area is subjected to intramolecular rearrangement reaction to generate an indene acid structure, and the acid structure can help phenolic resin to be quickly dissolved in an alkaline developing solution, so that the exposure area can be opened to obtain a pattern.

On one hand, in the post-exposure baking heating stage, the accelerating agent can generate active Lewis protonic acid after reaching the decomposition temperature, and the resin can be dissolved in the alkaline developing solution without depending on indene acid generated after photolysis of the photosensitizer. Compared with the phenolic resin-diazonaphthoquinone type photoresist with the traditional formula, the phenolic resin-diazonaphthoquinone type photoresist added with the accelerator can realize the opening of an exposure area and the realization of a pattern only by smaller exposure.

On the other hand, the heat source is arranged at the bottom of the photoresist, the Lewis protonic acid generated by the thermal decomposition of the accelerator is distributed in the adhesive film along the longitudinal gradient of the thickness direction, and the concentration of the Lewis protonic acid at the bottom of the adhesive film is higher than that at the top of the adhesive film. The exposure light source irradiates into the photoresist from one side outside the photoresist, generally from top to bottom, namely the photoresist is irradiated from the top to the bottom of the adhesive film, and the photoresist is heated from the bottom to the top of the adhesive film. The intensity of illumination weakens gradually along the thickness direction in the glued membrane, and the photon number that the photosensitizer in the photosensitive resist obtained also reduces along the thickness direction to make the concentration of indene acid that the photosensitizer reaction generated also reduce along the thickness direction of glued membrane in proper order, lead to a lot of thick film photoresist to be difficult to open at the bottom, often appear the bottom and have not developed clean condition or trailing phenomenon. The Lewis protonic acid with higher relative concentration released by the accelerator at the bottom of the adhesive film just makes up the defect of insufficient indene acid generated by the photosensitizer at the bottom of the adhesive film, can help the resin to be quickly dissolved at the bottom of the adhesive film, eliminates the defect of the bottom of the adhesive film that the resin is not developed completely or trailing, and improves the pattern quality.

The first solid matter comprises 80-94 wt% of phenolic resin, 5-19 wt% of photosensitizer, 0.1-10 wt% of acid quenching agent and 0.1-10 wt% of speed increasing agent, and the solvent is 1-10 times of the mass of the first solid matter.

Optionally, the solid matter comprises 80-90 wt% of phenolic resin, 9-19 wt% of photosensitizer, 0.1-5 wt% of acid quenching agent and 0.1-5 wt% of speed increasing agent, and the solvent is 1-5 times of the first solid matter in mass.

Optionally, the solid matter comprises 80-85 wt% of phenolic resin, 12-18 wt% of photosensitizer, 0.5-2 wt% of acid quenching agent and 0.1-1 wt% of speed increasing agent, and the solvent is 2-5 times of the mass of the first solid matter.

Optionally, the solid matter comprises 83.49 wt% of phenolic resin, 15 wt% of photosensitizer, 1 wt% of acid quencher, 0.5 wt% of speed accelerator and 0.01 wt% of leveling agent, and the solvent is 3 times of the mass of the first solid matter.

The present application also provides a composition for preparing a photoresist comprising a second solid substance comprising a matrix resin, an acid generator, an acid quencher, and an accelerator, and a solvent.

The accelerator is the nitrobenzyl sulfonate compound.

The nitrobenzyl sulfonate compound can be used as a speed accelerator to be added into a chemical amplification photoresist. The chemical amplification photoresist is used for exposure under I-line 365nm, KrF 248nm and ArF 193nm, an acid generator in a non-exposure area of the chemical amplification photoresist does not generate chemical reaction, and a large number of hydrophobic groups exist in a resin molecular structure before deprotection because a developing solution is an aqueous solution, and the resin is insoluble in the developing solution. The acid generator in the exposure area generates photochemical reaction after being irradiated by a light source to generate Lewis protonic acid, when the acid generator is baked after exposure, under the dual actions of the Lewis protonic acid and heating, the resin can be catalyzed to generate deprotection reaction, a large amount of phenolic hydroxyl groups or carboxyl groups are exposed in the molecular structure of the resin after deprotection, and the acidic groups react with alkali in the developing solution to bring the resin to be rapidly dissolved in the developing solution, so that the solubility difference between the exposure area and the unexposed area is realized, and a graph is formed. For the chemically amplified photoresist, the accelerator and the acid generator act synergistically to generate a good Lewis protonic acid environment in the exposure area along the longitudinal direction of the thickness of the photoresist film, and the Lewis protonic acid is relatively uniformly distributed along the longitudinal direction of the thickness of the photoresist film, so that the photosensitive speed of the photoresist can be increased, and the shape defects of non-perpendicularity of a pattern and the like can be eliminated.

The matrix resin comprises phenolic resin commonly used for G and I lines and chain polymer resin with a protective group commonly used for chemical amplification glue, the resin is alkali insoluble before acid catalytic deprotection, and after acid catalytic deprotection, the molecular structure forms acidity so as to be converted into alkali soluble.

The second solid substance comprises 85-95 wt% of matrix resin, 2-14 wt% of acid generator, 0.1-10 wt% of acid quenching agent and 0.1-10 wt% of speed increasing agent, and the solvent is 1-10 times of the mass of the second solid substance.

Optionally, the second solid substance comprises 90-95 wt% of matrix resin, 4-14 wt% of acid generator, 0.1-5 wt% of acid quencher and 0.1-5 wt% of accelerator, and the solvent is 2-6 times of the mass of the second solid substance.

Optionally, the second solid substance comprises 90-93 wt% of matrix resin, 6-8 wt% of acid generator, 0.5-2 wt% of acid quenching agent and 0.1-1 wt% of speed increasing agent.

Optionally, the second solid substance comprises 91.49 wt% of matrix resin, 7 wt% of acid generator, 1 wt% of acid quencher, 0.5 wt% of speed increaser, and 0.01 wt% of leveling agent.

Alternatively, the matrix resin includes poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) t-butyl carbonate, poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) vinyl ether, poly (adamantane methacrylate), poly (2-methoxymethyl-2-adamantane) methacrylate, poly (2-ethoxymethyl-2-adamantane) methacrylate, poly (2-propoxymethyl-2-adamantane) methacrylate, poly (2-isopropoxymethyl-2-adamantane) methacrylate.

The application of the nitrobenzenesulfonate compounds of the present application as accelerators in photoresists, compositions for preparing photoresists, are described in further detail below with reference to the examples.

Example 1

The embodiment of the application provides a composition for preparing a photoresist, which comprises a solid substance and a solvent, wherein the solid substance comprises 83.49 wt% of phenolic resin, 15 wt% of 2,3,4,4' -tetrahydroxybenzophenone-2, 1, 4-diazonaphthoquinone sulfonate, 1 wt% of 1-methylpiperazine, 0.5 wt% of 4-nitrobenzyl alcohol trifluoromethyl sulfonate and 0.01 wt% of a flatting agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 3 times that of the solid substance.

Example 2

The embodiment of the present application provides a composition for preparing a photoresist, which includes a solid substance and a solvent, wherein the solid substance includes 91.49 wt% of poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) tert-butyl carbonate, 7 wt% of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1 wt% of 1-methylpiperazine, 0.5 wt% of 4-nitrobenzol trifluoromethanesulfonate and 0.01 wt% of a leveling agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 5 times that of the solid substance.

Example 3

The embodiment of the application provides a composition for preparing a photoresist, which comprises solid substances and a solvent, wherein the solid substances comprise 83.49 wt% of poly adamantane methacrylate, 15 wt% of trifluoromethanesulfonic acid sulfosalt, 1 wt% of 1-methylpiperazine, 0.5 wt% of 4-nitrobenzol trifluoromethanesulfonate and 0.01 wt% of a flatting agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 5 times that of the solid substances.

Example 4

The embodiment of the present application provides a composition for preparing a photoresist, which includes a solid substance and a solvent, wherein the solid substance includes 91.49 wt% of poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) tert-butyl carbonate, 7 wt% of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1 wt% of 1-methylpiperazine, 0.5 wt% of 4-fluoro-3-nitrobenzoic acid camphorsulfonate and 0.01 wt% of a leveling agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 5 times that of the solid substance.

Example 5

The embodiment of the present application provides a composition for preparing a photoresist, which includes a solid substance and a solvent, wherein the solid substance includes 91.49 wt% of poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) tert-butyl carbonate, 7 wt% of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1 wt% of 1-methylpiperazine, 0.5 wt% of 4-nitrobenzol perfluorobutyl sulfonate and 0.01 wt% of a leveling agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 5 times that of the solid substance.

Example 6

The embodiment of the application provides a composition for preparing a photoresist, which comprises a solid substance and a solvent, wherein the solid substance comprises 73.99 wt% of phenolic resin, 15 wt% of 2,3,4,4' -tetrahydroxybenzophenone-2, 1, 4-diazonaphthoquinone sulfonate, 1 wt% of 1-methylpiperazine, 10 wt% of 4-nitrobenzyl alcohol trifluoromethyl sulfonate and 0.01 wt% of a flatting agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 3 times that of the solid substance.

Example 7

The embodiment of the application provides a composition for preparing a photoresist, which comprises a solid substance and a solvent, wherein the solid substance comprises 83.89 wt% of phenolic resin, 15 wt% of 2,3,4,4' -tetrahydroxybenzophenone-2, 1, 4-diazonaphthoquinone sulfonate, 1 wt% of 1-methylpiperazine, 0.1 wt% of 4-nitrobenzyl alcohol trifluoromethyl sulfonate and 0.01 wt% of a flatting agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 3 times that of the solid substance.

Example 8

The embodiment of the present application provides a composition for preparing a photoresist, which includes a solid substance and a solvent, wherein the solid substance includes 81.99 wt% of poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) tert-butyl carbonate, 7 wt% of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1 wt% of 1-methylpiperazine, 10 wt% of 4-nitrobenzol trifluoromethanesulfonate and 0.01 wt% of a leveling agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 5 times that of the solid substance.

Example 9

The embodiment of the present application provides a composition for preparing a photoresist, which includes a solid substance and a solvent, wherein the solid substance includes 91.89 wt% of poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) tert-butyl carbonate, 7 wt% of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1 wt% of 1-methylpiperazine, 0.1 wt% of 4-nitrobenzol trifluoromethanesulfonate and 0.01 wt% of a leveling agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 5 times that of the solid substance.

Comparative example 1

The comparative example of the present application provides a composition for preparing a photoresist, which includes a solid substance and a solvent, the solid substance includes 83.99 wt% of a phenolic resin, 15 wt% of 2,3,4,4' -tetrahydroxybenzophenone-2, 1, 4-diazonaphthoquinone sulfonate, 1 wt% of 1-methylpiperazine and 0.01 wt% of a leveling agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 3 times that of the solid substance.

Comparative example 2

The comparative example of the present application provides a composition for preparing a photoresist, which includes a solid substance and a solvent, the solid substance includes 91.99 wt% of poly (p-hydroxystyrene) -co-poly (p-hydroxystyrene) t-butyl carbonate, 7 wt% of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1 wt% of 1-methylpiperazine and 0.01 wt% of a leveling agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 5 times that of the solid substance.

Comparative example 3

The comparative example of the present application provides a composition for preparing a photoresist, which includes a solid substance and a solvent, the solid substance includes 83.99 wt% of poly adamantane methacrylate, 15 wt% of trifluoromethanesulfonic acid sulfonium salt, 1 wt% of 1-methylpiperazine and 0.01 wt% of a leveling agent BYK307, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA), and the mass of the solvent is 5 times that of the solid substance.

Test example 1

The compositions for preparing the photoresist of examples 1 to 5 and comparative examples 1 to 3 were mixed and filtered with a PTFE filter with a pore size of 0.1 μm to prepare a photoresist solution, the photoresist solution was coated on a polished silicon wafer by spin coating, and the solvent was dried with a hot plate to obtain a coating film, wherein the coating film thickness of the phenolic resin was 3 μm, the coating film thickness of the poly-p-hydroxystyrene-co-poly-p-hydroxystyrene t-butyl carbonate was 0.6 μm, and the coating film thickness of the poly-adamantane methacrylate was 0.3 μm.

The polished silicon wafers with the adhesive films of examples 1 and comparative examples 1 were exposed using a NIKON I9I line exposure machine, the polished silicon wafers with the adhesive films of examples 2, 4, 5 and comparative examples 2 were exposed using a PAS 5500/850D KrF exposure machine, and the polished silicon wafers with the adhesive films of examples 3 and comparative examples 3 were exposed using an NXT1965Ci ArF exposure machine. After exposure, the hot plate bakes the glue film for deprotection reaction, and the glue film enters 2.38% TMAH for development to obtain a required pattern, as shown in FIG. 3 (160nm Line/space), the side wall of the pattern of the embodiment 1 of the present application is vertical.

The optimum exposure for examples 1-5 and comparative examples 1-3 was measured using critical dimension measurement-scanning electron microscopy measurements, as shown in tables 1 and 2.

TABLE 1 optimum exposure for photoresists of examples 1-5

Examples	1	2	3	4	5
						Optimum exposure (mj/cm)2)	160	20	12	22	23

TABLE 2 optimum exposure for photoresists of comparative examples 1-3

Comparative example	1	2	3
				Optimum exposure (mj/cm)2)	200	30	15

In summary, according to the application of the nitrobenzenesulfonate compound as the accelerator in the photoresist and the composition for preparing the photoresist provided by the embodiment of the application, the nitrobenzenesulfonate compound can be decomposed to generate lewis protonic acid after being heated to a certain temperature, so that the nitrobenzenesulfonate compound can be used as the accelerator to be added into phenolic resin-diazonaphthoquinone type photoresist and chemical amplification photoresist, the photosensitive speed of the photoresist is increased, and the photosensitive capacity of the photoresist is increased by more than 20%.

The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.