阅读说明：本技术 一种光刻胶组合物 (Photoresist composition ) 是由 马洁 李冰 孙嘉 郑金红 陈昕 王文芳 董栋 张宁 于 2021-06-29 设计创作，主要内容包括：本申请提供一种光刻胶组合物,属于光刻技术领域。光刻胶组合物包括：100重量份化学放大正性光刻胶基体树脂、0.2～30重量份光致产酸剂和0.01～5重量份碱性添加剂。光致产酸剂包括三嗪类化合物,碱性添加剂包括含有氧原子的胺类化合物。本申请将三嗪类光致产酸剂与含有氧原子的胺类化合物配合,能够使得化学放大正性光刻胶的加工窗口DOF显著提升。同时,三嗪类光致产酸剂与含有氧原子的胺类化合物配合还能够改善光刻胶的顶部形貌,降低顶部损失,降低粗糙度。(The application provides a photoresist composition, belonging to the technical field of photoetching. The photoresist composition comprises: 100 parts by weight of chemically amplified positive resist base resin, 0.2 to 30 parts by weight of a photoacid generator and 0.01 to 5 parts by weight of an alkaline additive. The photoacid generator includes triazine compounds, and the basic additive includes amine compounds containing oxygen atoms. According to the application, the triazine photo-acid generator is matched with the amine compound containing oxygen atoms, so that the DOF (degree of freedom) of a processing window of the chemically amplified positive photoresist can be obviously improved. Meanwhile, the triazine photoacid generator and the amine compound containing oxygen atoms can be matched to improve the top appearance of the photoresist, reduce the top loss and reduce the roughness.)

1. A photoresist composition, wherein the photoresist composition comprises: 100 parts by weight of chemically amplified positive resist matrix resin, 0.2 to 30 parts by weight of a photoacid generator and 0.01 to 5 parts by weight of an alkaline additive;

wherein the photoacid generator comprises a triazine-based compound, and the basic additive comprises an amine-based compound containing an oxygen atom.

2. The photoresist composition of claim 1, wherein the triazine compound has the following structural formula:

wherein R is selected from C_1～20Alkyl, phenyl, styryl, naphthyl, substituted C_1～20Phenyl, substituted styryl or substituted naphthyl.

3. The photoresist composition of claim 2, wherein the triazine compound comprises any one of the following structures:

4. the photoresist composition according to any one of claims 1 to 3, wherein the amine compound comprises any one or more of 2-methoxyethoxyethyl-2-triamine, isopropanolamine, ethyl N, N-dimethylaminoacetate, N-dimethylglycine, N-dimethylethanolamine, 4' -diaminodiphenyl ether, N-t-butoxycarbonyldi-N-octylamine, N-dimethylformamide, acetamide, N-methylacetamide and benzamide.

5. The photoresist composition according to any one of claims 1 to 3, wherein the matrix resin comprises poly-p-hydroxystyrene with a protecting group.

6. The photoresist composition of claim 1, wherein the structural formula of the matrix resin is as follows:

wherein R is a protective group, and R comprises any one or more of tert-butoxycarbonyl, 1-methoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-tert-butoxyethyl, 1-isobutoxyethyl and cyclopentene oxide;

x + y is 100, and x is an integer between 60 and 80.

7. The photoresist composition of claim 6, wherein the molecular weight of the matrix resin is 3000 to 30000.

8. The photoresist composition according to any one of claims 1 to 3, further comprising an auxiliary agent, wherein the auxiliary agent comprises any one or more of a surfactant, a dissolution inhibitor, a stabilizer, a colorant, a plasticizer and an antihalation agent.

9. The photoresist composition according to any one of claims 1 to 3, further comprising a solvent, wherein the mass of the solvent is 10 to 90 wt% of the mass of the photoresist composition.

10. The photoresist composition of claim 9, wherein the solvent comprises any one or more of propylene glycol methyl ether acetate, ethyl lactate, and ethyl acetate.

Technical Field

The application relates to the technical field of photoetching, in particular to a photoresist composition.

Background

From a chemical composition perspective, the photoresist is a mixture, exemplified by a KrF chemically amplified positive resist, whose components include a resin, an acid generator, a base, other auxiliaries, and a solvent. The acid generator in the photoresist generates H after KrF exposure⁺，H⁺The poly (p-hydroxystyrene) resin with a protective group is catalyzed to carry out deprotection reaction, so that the dissolution rate of the resin in a developing solution is greatly improved, the solubility of the photoresist in an exposed area and the solubility of the photoresist in an unexposed area in the developing solution are greatly different, and a pattern is formed by utilizing the characteristic.

In order to produce photoresist with excellent comprehensive performance, a large number of photoacid generators and alkaline compounds with different structures are developed, and the performances of the photoresist are optimized by different acid generators and alkaline compounds at different angles and different degrees respectively. For example, patent No. ZL201080035613.9 discloses a photoacid generator of an aromatic sulfonium salt compound having a specific structure, and a photoresist using the same can be sufficiently developed in a fine pattern. Patent No. ZL200910140187.4 discloses a carboxyl group-containing basic compound, and a photoresist using the basic compound is significantly optimized in resolution and morphology after photolithography. However, these photoacid generators have limited ability to optimize the process window, particularly the depth of focus (DOF), when used with basic compounds in the base formulation of a photoresist composition.

Therefore, depending on the existing photoresist component materials, there is a need to develop a photoresist composition formulation, which can significantly improve the process window of the final photoresist product, especially the depth of focus.

Disclosure of Invention

The present application provides a photoresist composition with a better process window DOF.

The embodiment of the application is realized as follows:

in a first aspect, the present application provides a photoresist composition comprising: 100 parts by weight of chemically amplified positive resist base resin, 0.2 to 30 parts by weight of a photoacid generator and 0.01 to 5 parts by weight of an alkaline additive.

Wherein the photoacid generator comprises a triazine compound, and the alkaline additive comprises an amine compound containing an oxygen atom.

In the technical scheme, the triazine photo-acid generator is matched with the amine compound containing oxygen atoms, so that the DOF (degree of freedom) of the processing window of the chemically amplified positive photoresist can be obviously improved. Meanwhile, the triazine photoacid generator and the amine compound containing oxygen atoms can be matched to improve the top appearance of the photoresist, reduce the top loss and reduce the roughness.

In a first possible example of the first aspect of the present application in combination with the first aspect, the structural formula of the triazine compound is as follows:

wherein R is selected from C_1～20Alkyl, phenyl, styryl, naphthyl, substituted C_1～20Phenyl, substituted styryl or substituted naphthyl.

In a second possible example of the first aspect of the present application in combination with the first aspect, the triazine compound includes any one of the following structures:

in a third possible example of the first aspect of the present application in combination with the first aspect, the amine compound includes any one or more of 2-methoxyethoxyethyl-2-triamine, isopropanolamine, ethyl N, N-dimethylaminoethoacetate, N-dimethylglycine, N-dimethylethanolamine, 4' -diaminodiphenyl ether, N-t-butoxycarbonyl di-N-octylamine, N-dimethylformamide, acetamide, N-methylacetamide and benzamide.

In a fourth possible example of the first aspect of the present application in combination with the first aspect, the base resin includes poly-p-hydroxystyrene with a protective group.

In the above examples, the protecting group can be detached by the action of an acid, so that the base resin is changed from alkali-insoluble to alkali-soluble.

With reference to the first aspect, in a fifth possible example of the first aspect of the present application, the structural formula of the matrix resin is as follows:

wherein R is a protective group, and R comprises any one or more of tert-butoxycarbonyl, 1-methoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-tert-butoxyethyl, 1-isobutoxyethyl and cyclopentene oxide.

x + y is 100, and x is an integer between 60 and 80.

In the above examples, when R is taken from one kind of protecting group, the matrix resin herein may be a diblock polymer, and when R is taken from a plurality of kinds of protecting groups, the matrix resin herein may be a multiblock polymer.

In a sixth possible example of the first aspect of the present application in combination with the first aspect, the matrix resin has a molecular weight of 3000 to 30000.

In a seventh possible example of the first aspect of the present application in combination with the first aspect, the above-mentioned photoresist composition further includes an auxiliary agent including any one or more of a surfactant, a dissolution inhibitor, a stabilizer, a colorant, a plasticizer, and an antihalation agent.

In an eighth possible example of the first aspect of the present application in combination with the first aspect, the photoresist composition further includes a solvent, and the mass of the solvent is 10 to 90 wt% of the mass of the photoresist composition.

In a ninth possible example of the first aspect of the present application in combination with the first aspect, the solvent includes any one or more of propylene glycol methyl ether acetate, ethyl lactate, and ethyl acetate.

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 microscope image of a pattern formed after developing the photoresist of example 1 of the present application at a focal length of-0.5 to 0;

FIG. 2 is a scanning electron microscope image of a pattern formed after the photoresist of example 1 of the present application is developed at a focal length of 0.1 to 0.6;

FIG. 3 is a scanning electron microscope image of a pattern formed after developing the photoresist of comparative example 1 of the present application at a focal length of-0.5 to 0;

FIG. 4 is a scanning electron microscope image of a pattern formed after developing the photoresist of comparative example 1 of the present application at a focal length of 0.1 to 0.6;

FIG. 5 is a scanning electron microscope image of a pattern formed after developing the photoresist of comparative example 2 of the present application at a focal length of-0.5 to 0;

FIG. 6 is a scanning electron microscope image of a pattern formed after developing the photoresist of comparative example 2 of the present application at a focal length of 0.1 to 0.6;

FIG. 7 is a scanning electron microscope image of a pattern formed after developing the photoresist of comparative example 3 of the present application at a focal length of-0.5 to 0;

FIG. 8 is a scanning electron microscope image of a pattern formed after developing the photoresist of comparative example 3 of the present application at a focal length of 0.1 to 0.6;

FIG. 9 is a scanning electron microscope image of the pattern formed after developing the photoresist of comparative example 4 of the present application at a focal length of-0.5 to 0;

FIG. 10 is a scanning electron microscope image of the pattern formed after developing the photoresist of comparative example 4 of the present application at focal lengths of 0.1 to 0.6.

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 is a detailed description of a photoresist composition of the embodiments of the present application:

the present application provides a photoresist composition comprising: 100 parts by weight of chemically amplified positive resist base resin, 0.2 to 30 parts by weight of a photoacid generator and 0.01 to 5 parts by weight of an alkaline additive.

Wherein the chemically amplified positive resist base resin comprises poly-p-hydroxystyrene having a protecting group. The protecting group can be detached under the action of acid, so that the matrix resin is changed from alkali-insoluble to alkali-soluble.

Alternatively, the chemically amplified positive resist base resin is poly-p-hydroxystyrene with a protecting group.

The structural formula of the poly-p-hydroxystyrene with the protective group is as follows:

wherein R is a protective group, and R comprises any one or more of tert-butoxycarbonyl, 1-methoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-tert-butoxyethyl, 1-isobutoxyethyl and cyclopentene oxide.

x + y is 100, and x is an integer between 60 and 80.

Alternatively, x is 70 and y is 30.

The molecular weight of the matrix resin is 3000-30000.

When R is any one of tert-butoxycarbonyl, 1-methoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-tert-butoxyethyl, 1-isobutoxyethyl and cyclopentene oxide, the poly (p-hydroxystyrene) is a diblock polymer; when R is any of tert-butoxycarbonyl, 1-methoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxypropyl, 1-tert-butoxyethyl, 1-isobutoxyethyl and cyclopentene oxide, the poly-p-hydroxystyrene is a multi-block polymer.

The photoacid generator includes triazines.

Triazine generally refers to six-membered heterocyclic compounds containing 3 nitrogen atoms, and there are mainly three isomers, namely 1,2, 3-triazine, 1,3, 5-s-triazine, 1,3, 4-triazine.

The structural formula of the triazine compound is as follows:

wherein R is selected from C_1～20Alkyl, phenyl, styryl, naphthyl, substituted C_1～20Phenyl, substituted styryl or substituted naphthyl.

The triazine compound comprises any one of the following structures:

the basic additive includes an amine compound containing an oxygen atom.

The amine compound includes any one or more of 2-methoxyethoxyethyl-2-triamine, isopropanolamine, ethyl N, N-dimethylaminoethylacetate, N-dimethylglycine, N-dimethylethanolamine, 4' -diaminodiphenyl ether, N-tert-butoxycarbonyldi-N-octylamine, N-dimethylformamide, acetamide, N-methylacetamide and benzamide.

Optionally, the photoresist composition comprises: 100 parts by weight of a chemically amplified positive resist base resin, 0.33 to 30 parts by weight of a photoacid generator and 0.01 to 5 parts by weight of an alkaline additive.

It should be noted that the photoresist composition of the present application may further include additives having a mixing property according to the requirement, for example, any one or more of a surfactant, a dissolution inhibitor, a stabilizer, a colorant, a plasticizer, and an antihalation agent, which improve coating performance, may be added, and other additives may be added.

Optionally, the photoresist composition comprises: 100 parts by weight of chemically amplified positive resist base resin, 1 to 10 parts by weight of a photoacid generator, 0.1 to 5 parts by weight of an alkaline additive, and 0.0001 to 0.5 part by weight of an auxiliary.

Optionally, the photoresist composition comprises: 100 parts by weight of chemically amplified positive resist matrix resin, 2-8 parts by weight of photoacid generator, 1-5 parts by weight of alkaline additive and 0.001-0.01 part by weight of auxiliary agent.

The photoresist composition also includes a solvent. The solvent needs to have good solubility for chemically amplified positive photoresist matrix resin, photoacid generator, alkaline additive and auxiliary agent, and the boiling point is more than or equal to 100 ℃.

Alternatively, the solvent comprises any one or more of propylene glycol methyl ether acetate, ethyl lactate and ethyl acetate.

Optionally, the mass of the solvent is 10-90 wt% of the mass of the photoresist composition.

The amount of the solvent is determined according to the desired thickness of the photoresist.

One of the photoresist compositions of the present application is described in further detail below with reference to examples.

Example 1

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of a triazine compound, 0.18g of 2-methoxyethoxyethyl-2-triamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

the structural formula of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) is as follows:

example 2

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.015g of a triazine compound, 0.00045g of 2-methoxyethoxyethyl ester-2-triamine, 0.025g of a 1% by weight solution of a surfactant in propylene glycol methyl ether acetate, and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

example 3

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 1.35g of a triazine compound, 0.225g of 2-methoxyethoxyethyl-2-triamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

example 4

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of a triazine compound, 0.18g of 2-methoxyethoxyethyl-2-triamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

example 5

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of a triazine compound, 0.18g of 2-methoxyethoxyethyl-2-triamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

example 6

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of a triazine compound, 0.18g of 2-methoxyethoxyethyl-2-triamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

example 7

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of a triazine compound, 0.18g of isopropanolamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

example 8

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of a triazine compound, 0.18g of N, N-dimethylethanolamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

example 9

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of a triazine compound, 0.18g of acetamide, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

example 10

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30 wt% propylene glycol methyl ether acetate solution of poly (4-hydroxystyrene-co-t-butyloxystyrene), 1.35g of a triazine compound, 0.225g of 2-methoxyethoxyethyl ester-2-triamine, 0.025g of a 1 wt% propylene glycol methyl ether acetate solution of a surfactant and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

the structural formula of poly (4-hydroxystyrene-co-t-butyloxystyrene) is as follows:

example 11

An embodiment of the present application provides a photoresist composition, which includes: 15g of a 30 wt% propylene glycol methyl ether acetate solution of 4-hydroxystyrene-co-epoxypentyloxystyrene, 1.35g of a triazine compound, 0.225g of 2-methoxyethoxyethyl ester-2-triamine, 0.025g of a 1 wt% propylene glycol methyl ether acetate solution of a surfactant and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

the structural formula of the 4-hydroxystyrene-co-epoxypentenyloxystyrene is as follows:

comparative example 1

The comparative example of the present application provides a photoresist composition comprising: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of trifluoromethanesulfonate sulfonium salt, 0.18g of 2-methoxyethoxyethyl ester-2-triamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the trifluoromethanesulfonate sulfonium salt of the embodiment of the application is as follows:

comparative example 2

The comparative example of the present application provides a photoresist composition comprising: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of perfluorobutylsulfonatosulfonium salt, 0.18g of 2-methoxyethoxyethyl-2-triamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate and 31g of propylene glycol methyl ether acetate.

The structural formula of the perfluorobutyl sulfonate sulfonium salt of the embodiment of the application is as follows:

comparative example 3

The comparative example of the present application provides a photoresist composition comprising: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol monomethyl ether acetate, 0.22g of a triazine compound, 0.18g of trioctylamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol monomethyl ether acetate and 31g of propylene glycol monomethyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

comparative example 4

The comparative example of the present application provides a photoresist composition comprising: 15g of a 30% by weight solution of poly (4-hydroxystyrene-co-t-butoxycarbonyloxystyrene) in propylene glycol methyl ether acetate, 0.22g of a triazine compound, 0.18g of triethylamine, 0.025g of a 1% by weight solution of surfactant in propylene glycol methyl ether acetate, and 31g of propylene glycol methyl ether acetate.

The structural formula of the triazine compound of the embodiment of the application is as follows:

test example 1

The photoresists of examples 1 to 12 and comparative examples 1 to 4 were taken and filtered through a 0.2 μm Teflon filter to obtain a photoresist solution. Coating the substrate treated by hexamethyldisilane with the photoresist solution, prebaking the substrate coated with the photoresist at 100 ℃/60s by using a hot plate after coating is finished, adjusting the rotating speed to ensure that the dried film thickness is 0.8 mu m, then exposing the substrate by using a DUV exposure machine, gradually changing the exposure amount, postbaking the exposed substrate by using the hot plate at 115 ℃/60s, and finally spraying and developing the substrate by using 2.38 percent tetramethylammonium hydroxide for 60 s. After the operation, the pattern formed after the development was observed with a scanning electron microscope, as shown in FIGS. 1 to 10.

As can be seen from comparison of example 1 with comparative examples 1 to 2, the opening degree of the photoresist using the sulfonium salt type photoacid generator at the positive and negative Focus is significantly inferior to that of the photoresist using the triazine type photoacid generator.

As is clear from comparison between example 1 and comparative examples 3 to 4, the resist using the amine compound not containing an oxygen atom has significantly inferior openness at the positive and negative Focus than the resist using the amine compound containing an oxygen atom.

And as can be seen from comparison of example 1 and comparative example, the triazine photoacid generator and the amine compound containing an oxygen atom cooperate with each other to not only increase the process window DOF of the photoresist, but also reduce the top loss and roughness.

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.