CN112485961B - Thick film type DUV photoresist composition and preparation method and application thereof - Google Patents

Thick film type DUV photoresist composition and preparation method and application thereof Download PDF

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CN112485961B
CN112485961B CN202011360558.2A CN202011360558A CN112485961B CN 112485961 B CN112485961 B CN 112485961B CN 202011360558 A CN202011360558 A CN 202011360558A CN 112485961 B CN112485961 B CN 112485961B
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CN112485961A (en
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王溯
崔中越
耿志月
唐晨
薛新斌
王世建
王志勇
黄桂华
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Shanghai Xinyang Semiconductor Material Co Ltd
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/32Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals

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Abstract

The invention discloses a thick film type DUV photoresist composition and a preparation method and application thereof. The photoresist composition of the invention comprises the following components: a photoacid generator, a resin, and a solvent. The glue film formed by the photoresist composition has good performance and good application prospect.

Description

Thick film type DUV photoresist composition and preparation method and application thereof
Technical Field
The invention relates to a thick film type DUV photoresist composition and a preparation method and application thereof.
Background
Currently, in the field of semiconductor manufacturing, during the chip manufacturing process of LCD (liquid crystal display)/BUMP/MEMS micro-electro-mechanical system/3D-NAND memory, krF light source thick film photoresist is used, which is different from the conventional KrF thin layer photoresist and the ArF light source photoresist, but has unique performance.
At present, although the manufacturing technology of integrated circuit semiconductor chips is rapidly developed, the technology of the thick film photoresist matched with the KrF light source is not completely mature, and the KrF photoresist is a hot spot field for researching the KrF photoresist at present.
The KrF light source thick film photoresist has many problems, such as film cracking, poor film thickness uniformity, many defects, poor resolution and sensitivity, poor film peeling, poor shape, poor rectangularity, poor resolution, insufficient heat resistance, and the like.
Therefore, there is a need in the art to develop a thick film photoresist that addresses the above problems in combination.
Disclosure of Invention
The invention aims to solve the technical problems of cracking, poor film thickness uniformity, more defects, poor resolution and sensitivity, poor film stripping performance, poor shape, poor rectangularity, poor resolution, poor heat resistance, incapability of inhibiting fluctuation phenomenon or serious impurities and the like of a KrF light source thick film photoresist film in the prior art, and provides a thick film type DUV photoresist composition, a preparation method and application thereof, and a preparation method and application thereof. The glue film formed by the photoresist composition at least has the following advantages: the film has the advantages of difficult cracking, uniform thickness, good resolution and sensitivity, good film stripping performance, good shape, good rectangularity, good resolution, good heat resistance, and can inhibit fluctuation phenomenon and has less metal impurities.
The present invention solves the above technical problems by the following technical solutions.
The invention provides a photoresist composition, which comprises the following components: a resin, a photoacid generator, and a solvent;
the resin is prepared by the following preparation method, and the preparation method of the resin comprises the following steps:
in the presence of benzoyl peroxide, carrying out polymerization reaction on a monomer shown as a formula A, a monomer shown as a formula B, a monomer shown as a formula C, a monomer shown as a formula D and a monomer shown as a formula E in ethyl acetate to obtain the resin; wherein the monomer shown as the formula D accounts for 1-10 parts by weight, and the monomer shown as the formula E accounts for 1-10 parts by weight;
the temperature of the polymerization reaction is 75-80 ℃;
Figure GDA0003828532940000011
in the formula A, R 1 Is R 1a Substituted 5-10 membered heterocycloalkyl or-CH 2 (C=O)OR 1b
R 1b Is R 1b-1 Substituted 5-10 membered heterocycloalkyl;
R 1a and R 1b-1 Independently oxo, cyano or C 1-4 Alkyl groups of (a);
said R 1a Substituted 5-10 membered heterocycloalkyl and said R 1b-1 The heteroatom in the substituted 5-10 membered heterocycloalkyl is O, and the number of the heteroatoms is 1 or 2;
in the formula B, R 2 Is composed of
Figure GDA0003828532940000021
M is ethylene or cyclohexylene; n is 2, 3, 4,5, 6 or 7; y is
Figure GDA0003828532940000022
R 2a And R 2b Independently is C 1-4 Alkyl of R 2a-1 Substituted C 1-4 Alkyl, phenyl, naphthyl, R 2a-2 Substituted phenyl or 5-6 membered cycloalkyl;
R 2a-1 is hydroxy or adamantyl;
R 2a-2 is C 1-4 Alkyl or C 1-4 Alkoxy group of (a);
or, R 2a And R 2b Together with the carbon atom to which they are attachedTo form a 5-6 membered heterocycloalkyl or R 2b-1 Substituted 5-6 membered heterocycloalkyl, said 5-6 membered heterocycloalkyl and R 2b-1 The heteroatoms in the substituted 5-6 membered heterocycloalkyl are independently selected from O and N, and the number is 1 or 2;
R 2b-1 is C 1-4 An alkyl or amino protecting group of (a);
and Y is not
Figure GDA0003828532940000023
In the formula C, the reaction mixture is shown in the formula,
Figure GDA0003828532940000024
is a single bond or a double bond;
R 3a 、R 3b and R 3c Independently H, hydroxy, cyano, - (C = O) OR 3a-1 、-O(C=O)R 3a-2 、C 1-4 Alkyl or hydroxy-substituted C 1-4 Alkyl groups of (a); and R is 3a 、R 3b And R 3c Not H at the same time;
R 3a-1 is H, C 1-5 Alkyl group of (A) or (B),
Figure GDA0003828532940000025
R 3a-2 Is C 1-4 Alkyl or phenyl of (a);
or, R 3a 、R 3b And R 3c Any two of which taken together with the carbon atom to which they are attached form a phenyl group, a 5-7 membered cycloalkyl group, a 5-7 membered cycloalkenyl group,
Figure GDA0003828532940000026
In the formula D, Q is N or O;
R 4 is composed of
Figure GDA0003828532940000031
In the formula E, R 5 Is C 1-6 Alkyl of R 5-1 Substituted C 1-6 Alkyl of 5 to 6 memberedCycloalkyl of, R 5-2 Substituted 5-6 membered cycloalkyl, R 5-3 Substituted phenyl or
Figure GDA0003828532940000032
R 5-1 、R 5-2 And R 5-3 Independently is hydroxy or
Figure GDA0003828532940000033
The photoacid generator is PAG1 and/or PAG2, and the structure of the photoacid generator is shown as follows:
Figure GDA0003828532940000034
in the present invention, the parts by weight of the resin may be those conventional in the art, preferably 10 to 45 parts, and may preferably be 20 to 45 parts, such as 25 parts, 30 parts, and 35 parts.
In the present invention, the weight average molecular weight of the resin is preferably 3000 to 20000, and may be preferably 5000 to 20000.
In the present invention, the Polymer Dispersibility Index (PDI) of the resin is preferably 1.2 to 2.5, for example 1.3 to 2.5.
In the present invention, the parts by weight of the monomer represented by formula a may be those conventional in the art, preferably 35 to 65 parts, and further preferably 35 to 48 parts, for example 40 parts or 45 parts.
In the present invention, the parts of the monomer represented by formula B may be the parts conventional in the art, preferably 20 to 55 parts, and further preferably 30 to 40 parts, for example 35 parts.
In the present invention, the parts by weight of the monomer represented by formula C may be those conventional in the art, preferably 10 to 25 parts, and further preferably 10 to 20 parts, for example 15 parts.
In the invention, the part of the monomer shown in formula D can be 5-10 parts, such as 6 parts and 7 parts.
In the present invention, the amount of the monomer represented by formula E may be 5 to 10 parts, for example, 6 parts, 7 parts, 8 parts, 9 parts.
In the present invention, when R is 1 Is R 1a When substituted with a 5-to 10-membered heterocycloalkyl group, the 5-to 10-membered heterocycloalkyl group is preferably a 5-, 6-, 9-or 10-membered heterocycloalkyl group.
In the present invention, when R is 1b Is R 1b-1 When a substituted 5-to 10-membered heterocycloalkyl group is used, the 5-to 10-membered heterocycloalkyl group is preferably a 5-, 9-or 10-membered heterocycloalkyl group.
In the present invention, when said R is 1a And R 1b-1 Independently is C 1-4 When said alkyl is substituted, said C 1-4 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group, and more preferably a methyl group.
In the present invention, when R is 1 Is R 1a When substituted with 5-to 10-membered heterocycloalkyl, said R 1a The substituted 5-to 10-membered heterocycloalkyl group is preferably
Figure GDA0003828532940000041
Figure GDA0003828532940000042
More preferably
Figure GDA0003828532940000043
Figure GDA0003828532940000044
In the present invention, when said R is 1b Is R 1b-1 When substituted with 5-to 10-membered heterocycloalkyl, said R 1b-1 The substituted 5-to 10-membered heterocycloalkyl group is preferably
Figure GDA0003828532940000045
Figure GDA0003828532940000046
More preferably
Figure GDA0003828532940000047
In the present invention, when M is cyclohexylene, the cyclohexylene group is preferably
Figure GDA0003828532940000048
In the present invention, when R is 2a And R 2b Independently is C 1-4 When there is an alkyl group, said C 1-4 The alkyl group of (a) is preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl group.
In the present invention, when R is 2a And R 2b Independently is R 2a-1 Substituted C 1-4 When said alkyl is substituted, said C 1-4 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group, more preferably a methyl group or an ethyl group.
In the present invention, when R is 2a-2 Is C 1-4 When there is an alkyl group, said C 1-4 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group, and more preferably a methyl group.
In the present invention, when R is 2a-2 Is C 1-4 Alkoxy of (2), said C 1-4 The alkoxy group of (b) is preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group or a tert-butoxy group, and more preferably a methoxy group.
In the present invention, when R is 2a And R 2b When they form a 5-to 6-membered heterocycloalkyl group together with the N atom to which they are attached, the 5-to 6-membered heterocycloalkyl group is preferably
Figure GDA0003828532940000051
In the present invention, when R is 2a And R 2b Together with the N atom to which they are attached form R 2b-1 When substituted with a 5-6 membered heterocycloalkyl group, the 5-6 membered heterocycloalkyl group is preferably a 6-heterocycloalkyl group.
In the present invention, when R is 2b-1 Is C 1-4 When it is an alkyl group, theC of (A) 1-4 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group, and more preferably a methyl group.
In the present invention, when R is 2a And R 2b Together with the N atom to which they are attached form R 2b-1 When substituted with 5-to 6-membered heterocycloalkyl, said R 2b-1 The substituted 5-to 6-membered heterocycloalkyl group is preferably
Figure GDA0003828532940000052
In the present invention, Y is preferably
Figure GDA0003828532940000053
Figure GDA0003828532940000054
In the present invention, when R is 3a 、R 3b And R 3c Independently is C 1-4 When there is an alkyl group, said C 1-4 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group, more preferably a tert-butyl group.
In the present invention, when R is 3a 、R 3b And R 3c Independently is hydroxy-substituted C 1-4 When said alkyl is substituted, said C 1-4 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group, and more preferably a methyl group.
In the present invention, when R is 3a-1 Is C 1-5 When there is an alkyl group, said C 1-5 Alkyl of (A) is preferably ethyl or
Figure GDA0003828532940000055
In the present invention, when R is 3a-1 Is C 6-10 Aryl of (2), said C 6-10 Aryl of (c) is preferably phenyl.
In the present invention, when R is 3a-2 Is C 1-4 When there is an alkyl group, said C 1-4 Alkyl of (2) is preferably methyl。
In the present invention, when R is 3a-2 Is C 6-10 Aryl of (2), said C 6-10 Aryl of (c) is preferably phenyl.
In the present invention, when R is 3a 、R 3b And R 3c When any two groups form a 5-7 membered cycloalkyl group together with the carbon atom to which they are attached, said 5-7 membered cycloalkyl group is preferably cyclopentyl, cyclohexyl or
Figure GDA0003828532940000061
In the present invention, when R is 3a 、R 3b And R 3c When any two of the groups form a 5-7 membered cycloalkenyl group together with the carbon atom to which they are attached, the 5-7 membered cycloalkenyl group is preferably cyclopentenyl.
In the present invention, when R is 5 Is R 5-1 Substituted C 1-6 When there is an alkyl group, said C 1-6 Alkyl of (2) is preferably
Figure GDA0003828532940000062
Figure GDA0003828532940000063
In the present invention, when R is 5 Is R 5-1 Substituted C 1-6 When said alkyl is (a), said R 5-1 Substituted C 1-6 Alkyl of (2) is preferably
Figure GDA0003828532940000064
In the present invention, when R is 5 Is R 5-2 When substituted with 5-to 6-membered cycloalkyl, said R 5-2 The substituted 5-to 6-membered cycloalkyl is preferably
Figure GDA0003828532940000065
In the present invention, when R is 5 Is R 5-3 When substituted phenyl, said R 5-3 The substituted phenyl radical is preferably
Figure GDA0003828532940000066
Figure GDA0003828532940000067
In the present invention, the monomer represented by formula a is preferably any one of the following compounds:
Figure GDA0003828532940000071
more preferably any of the following compounds:
Figure GDA0003828532940000072
in the present invention, the monomer represented by formula B is preferably any of the following compounds:
Figure GDA0003828532940000081
Figure GDA0003828532940000091
Figure GDA0003828532940000101
more preferably any of the following compounds:
Figure GDA0003828532940000102
in the invention, the monomer shown in the formula C is preferably any one of the following compounds:
Figure GDA0003828532940000111
more preferably any of the following compounds:
Figure GDA0003828532940000112
in the present invention, the monomer represented by formula D is preferably any one of the following compounds:
Figure GDA0003828532940000113
in the present invention, the monomer represented by formula E is preferably any one of the following compounds:
Figure GDA0003828532940000121
more preferably any of the following compounds:
Figure GDA0003828532940000122
in the present invention, the resin is produced by a production method in which each monomer and the amount thereof are as shown in any one of the following groups (1) to (10), and accordingly, resins 1to 10 are obtained in order:
(1) 40 parts of the monomer shown in the formula A, 30 parts of the monomer shown in the formula B, 20 parts of the monomer shown in the formula C, 4 parts of the monomer shown in the formula D and 6 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000123
The monomer shown as the formula B is
Figure GDA0003828532940000124
The monomer shown as the formula C is
Figure GDA0003828532940000125
The monomer shown as the formula D is
Figure GDA0003828532940000131
The monomer shown as the formula E is
Figure GDA0003828532940000132
Thereby obtaining a resin 1;
(2) 45 parts of the monomer shown in the formula A, 35 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 3 parts of the monomer shown in the formula D and 7 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000133
The monomer shown as the formula B is
Figure GDA0003828532940000134
The monomer shown as the formula C is
Figure GDA0003828532940000135
The monomer shown as the formula D is
Figure GDA0003828532940000136
The monomer shown as the formula E is
Figure GDA0003828532940000137
Thereby obtaining a resin 2;
(3) 48 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 1 part of the monomer shown in the formula D and 1 part of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000138
The monomer shown as the formula B is
Figure GDA0003828532940000139
The monomer shown as the formula C is
Figure GDA00038285329400001310
The monomer shown as the formula D is
Figure GDA0003828532940000141
The monomer shown as the formula E is
Figure GDA0003828532940000142
Thereby obtaining a resin 3;
(4) 30 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 15 parts of the monomer shown in the formula C, 6 parts of the monomer shown in the formula D and 9 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000143
The monomer shown as the formula B is
Figure GDA0003828532940000144
The monomer shown as the formula C is
Figure GDA0003828532940000145
The monomer shown as the formula D is
Figure GDA0003828532940000146
The monomer shown as the formula E is
Figure GDA0003828532940000147
Thereby obtaining a resin 4;
(5) 35 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 7 parts of the monomer shown in the formula D and 8 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000148
The monomer shown as the formula B is
Figure GDA0003828532940000149
The monomer shown as the formula C is
Figure GDA00038285329400001410
The monomer shown as the formula D is
Figure GDA0003828532940000151
The monomer shown as the formula E is
Figure GDA0003828532940000152
Thereby obtaining a resin 5;
(6) 40 parts of the monomer shown in the formula A, 30 parts of the monomer shown in the formula B, 20 parts of the monomer shown in the formula C, 5 parts of the monomer shown in the formula D and 5 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000153
The monomer shown as the formula B is
Figure GDA0003828532940000154
The monomer shown as the formula C is
Figure GDA0003828532940000155
The monomer shown as the formula D is
Figure GDA0003828532940000156
The monomer shown as the formula E is
Figure GDA0003828532940000157
Thereby obtaining a resin 6;
(7) 45 parts of the monomer shown in the formula A, 35 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 5 parts of the monomer shown in the formula D and 5 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000158
The monomer shown as the formula B is
Figure GDA0003828532940000159
The monomer shown as the formula C is
Figure GDA0003828532940000161
The monomer shown as the formula D is
Figure GDA0003828532940000162
The monomer shown as the formula E is
Figure GDA0003828532940000163
Thereby obtaining a resin 7;
(8) 40 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 5 parts of the monomer shown in the formula D and 5 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000164
The monomer shown as the formula B is
Figure GDA0003828532940000165
The monomer shown as the formula C is
Figure GDA0003828532940000166
The monomer shown as the formula D is
Figure GDA0003828532940000167
The monomer shown as the formula E is
Figure GDA0003828532940000168
Thereby obtaining a resin 8;
(9) 40 parts of the monomer shown in the formula A, 30 parts of the monomer shown in the formula B, 15 parts of the monomer shown in the formula C, 10 parts of the monomer shown in the formula D and 5 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000169
The monomer shown as the formula B is
Figure GDA00038285329400001610
The monomer shown as the formula C is
Figure GDA0003828532940000171
The monomer shown as the formula D is
Figure GDA0003828532940000172
The monomer shown as the formula E is
Figure GDA0003828532940000173
Thereby obtaining a resin 9;
(10) 35 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 5 parts of the monomer shown in the formula D and 10 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure GDA0003828532940000174
The monomer shown as the formula B is
Figure GDA0003828532940000175
The monomer shown as the formula C is
Figure GDA0003828532940000176
The monomer shown as the formula D is
Figure GDA0003828532940000177
The monomer shown as the formula E is
Figure GDA0003828532940000178
Thereby obtaining a resin 10.
In the polymerization reaction, the mass ratio of the benzoyl peroxide to the monomers shown in formula a, the monomers shown in formula B, the monomers shown in formula C, the monomers shown in formula D and the monomers shown in formula E can be a mass ratio which is conventional in the art, for example, 1.
In the polymerization reaction, the mass ratio of the ethyl acetate to the "monomer shown in formula a, the monomer shown in formula B, the monomer shown in formula C, the monomer shown in formula D, and the monomer shown in formula E" may be a mass ratio that is conventional in the art, for example, 6.
In the polymerization, the polymerization temperature is preferably 77 ℃.
In the polymerization, the polymerization time may be a time conventional in the art, for example, 7 hours.
The post-treatment after the completion of the polymerization reaction is preferably carried out by the following steps: cooling, precipitating and drying.
Wherein the number of precipitations may be a number of precipitations as conventional in the art, for example 3.
Wherein, the solvent used in the precipitation can be an alcohol solvent, and further can be methanol.
Wherein, the drying is preferably carried out in a vacuum drying oven.
In a preferred embodiment of the present invention, the resin is prepared by the method of the embodiment (i.e., steps 1-3 of the resin preparation).
In the present invention, the parts by weight of the photoacid generator may be those conventionally used in the art, preferably 0.5 to 5 parts, and further preferably 3 to 5 parts.
In the present invention, the parts by weight of the solvent may be those conventional in the art, preferably 50 to 85 parts, and may also preferably be 59 to 85 parts, and further, for example, 69.5 parts, 70 parts, and 77 parts.
In the present invention, the solvent may be one conventional in the art, and preferably one or more of a ketone solvent, an ester solvent and an ether solvent. When the solvent is a ketone solvent, the ketone solvent may be cyclohexanone. The ester solvent may be ethyl acetate. The ether solvent can be ethylene glycol monomethyl ether and/or dipropylene glycol monomethyl ether.
In a preferred embodiment of the present invention, the photoresist composition further comprises an additive selected from at least one of a leveling agent, a plasticizer, an organic base, a dissolution rate enhancer, and a photosensitizer. The parts of the additive by weight are preferably 5-10 parts.
In a preferred embodiment of the present invention, the method for preparing the resin comprises the steps of:
under the protection of nitrogen, adding the mixed solution of ethyl acetate and benzoyl peroxide into the mixed solution of the monomer shown in the formula A, the monomer shown in the formula B, the monomer shown in the formula C, the monomer shown in the formula D, the monomer shown in the formula E and ethyl acetate;
wherein, the adding time is preferably 10min.
In a preferred embodiment of the present invention, the photoresist composition is composed of the following components: said photoacid generator, said resin, and said solvent; the parts of the photoacid generator, the types and parts of the resin, and the types and parts of the solvent are as described above.
In a preferred embodiment of the present invention, the photoresist composition is composed of the following components: said photoacid generator, said resin, said solvent, and said additive; the parts of the photoacid generator, the kind and parts of the resin, the kind and parts of the solvent, and the "kind and parts of the additive" are the same as described above.
In a preferred embodiment of the present invention, the photoresist composition is any one of the following combinations:
combination 1:25 parts of resin 1,5 parts of PAG1 and 70 parts of cyclohexanone;
and (3) combination 2:30 parts of resin 2,0.5 part of PAG2 and 69.50 parts of ethyl acetate;
and (3) combination: 10 parts of resin 3,5 parts of PAG2 and 85 parts of ethylene glycol monomethyl ether;
and (4) combination: 35 parts of resin 4,5.5 parts of PAG1 and 59 parts of cyclohexanone;
and (4) combination 5:45 parts of resin 5,5 parts of PAG2 and 50 parts of ethylene glycol monomethyl ether;
and (4) combination 6:25 parts of resin 6,5 parts of PAG1 and 70 parts of ethyl acetate;
and (3) combination 7:30 parts of resin 7,0.5 part of PAG2 and 69.5 parts of dipropylene glycol monomethyl ether;
and (4) combination 8:20 parts of resin 8,3 parts of PAG1 and 77 parts of dipropylene glycol monomethyl ether;
combination 9:35 parts of resin 9,5.5 parts of PAG2 and 59 parts of ethyl acetate;
combination 10:45 parts of resin 10,5 parts of PAG2 and 50 parts of ethylene glycol monomethyl ether;
wherein said resin 1, said resin 2, said resin 3, said resin 4, said resin 5, said resin 6, said resin 7, said resin 8, said resin 9 and said resin 10 are as described above.
The invention also provides a preparation method of the photoresist composition, which comprises the following steps: mixing the above components uniformly.
In the preparation method, the mixing mode can be a mixing mode conventional in the field, and shaking is preferred.
In the preparation method, the mixing time can be the mixing time conventional in the field, and is preferably 18 to 30 hours and 24 hours.
After the mixing, the method can further comprise a filtering step. The filtration may be performed in a manner conventional in the art, and is preferably performed using a filter. The number of said filtrations is preferably 2-3, for example 2. The filter membrane pore size of the filter is preferably 20-50nm or 2-20nm. When the filtration frequency is 2 times, the filter membrane pore size of the first filter is larger than that of the second filter. The filter membrane pore size of the first filter is preferably 20-50nm. The filter membrane pore size of the first filter is preferably 2-20nm.
The invention also provides a method for forming a photolithographic pattern, comprising the steps of:
step 1: coating the photoresist composition on the surface of a substrate to form a photoresist composition layer;
step 2: baking the photoresist composition layer;
and step 3: cooling the baked photoresist composition layer;
and 4, step 4: copying the pattern on the mask plate to the baked photoresist composition layer through exposure;
and 5: baking the exposed photoresist composition layer;
step 6: and applying a developer to the baked photoresist composition layer for development to obtain a photoetching pattern.
In step 1, the substrate is preferably pretreated with HMDS.
In step 1, the substrate is preferably 12 silicon wafers.
In step 1, the coating mode is preferably spin coating.
In step 1, the thickness of the photoresist composition layer is preferably 10 to 15 μm (e.g., 10 μm, 12 μm, 12.5 μm, 13 μm, 15 μm).
In step 2, the baking temperature is preferably 120-150 ℃.
The baking time in step 2 is preferably 80 to 150 seconds.
In step 3, the cooling temperature is preferably to room temperature.
In step 4, the wavelength of the exposure is preferably 248nm.
In step 4, the intensity of the exposure is preferably 10-50mJ/cm 2
In step 5, the baking temperature is preferably 90-120 ℃.
In step 5, the baking time is preferably 90 to 130 seconds.
In step 6, the developer is preferably an aqueous tetramethylammonium hydroxide (TMAH) solution, e.g., 2.38% TMAH.
In step 6, the development time is preferably 50 to 70 seconds, for example, 60 seconds. After the development in step 6 is finished, a rinsing step may be further included. The solvent used for the washing is water, such as pure water.
In the present invention, "alkyl" means a straight-chain or branched alkyl group having the specified number of carbon atoms.
As used herein, "cycloalkyl" refers to a saturated monocyclic ring system (e.g., cyclopentyl, cyclohexyl) or a saturated 2-4 membered bridged ring system (e.g., cyclopentyl, cyclohexyl) having a stable ring system
Figure GDA0003828532940000201
)。
As used herein, "heterocycloalkyl" refers to a monocyclic ring containing 1 or more heteroatoms of N, O or S (e.g., a heterocycle)
Figure GDA0003828532940000202
Figure GDA0003828532940000203
) Or 2-4 membered bridged ring systems (e.g.
Figure GDA0003828532940000204
)。
The above preferred conditions may be combined arbitrarily to obtain preferred embodiments of the present invention without departing from the general knowledge in the art.
The resin is self-made, and other used reagents and raw materials are commercially available.
The positive progress effects of the invention are as follows: the glue film formed by the photoresist composition of the invention at least has any one of the following advantages: the film has the advantages of difficult cracking, uniform thickness, good resolution and sensitivity, good film stripping performance, good shape, good rectangularity, good resolution, good heat resistance, and can inhibit fluctuation phenomenon and has less metal impurities.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples and comparative examples, the operation temperature is not specifically limited, and the operation is carried out at room temperature.
Preparation of the resin
The resins 1to 15 used in the examples or comparative examples were prepared in the following manner. The individual monomers used are as follows:
monomer A:
Figure GDA0003828532940000211
a monomer B:
Figure GDA0003828532940000212
a monomer C:
Figure GDA0003828532940000213
a monomer D:
Figure GDA0003828532940000221
a monomer E:
Figure GDA0003828532940000222
step 1: the amount of the monomers A-E in the table 1 is added into a reaction kettle filled with nitrogen, then 100g of ethyl acetate is added into the reaction kettle, the reaction kettle is heated to 77 ℃ after being stirred uniformly, then the mixed solution of ethyl acetate (20 g) and benzoyl peroxide (2 g) is added into the reaction kettle dropwise again, and the dropwise addition is finished within 10min. Reacting at 77 ℃ for 7 hours, stopping the reaction, and cooling the temperature of the reaction liquid to room temperature;
step 2: after the reaction solution was cooled to room temperature, methanol (1000 g) was added to the reaction vessel to produce a precipitate. After 1h, discharging liquid in the reaction kettle, and adding ethyl acetate into the reaction kettle until precipitate is dissolved (120 g);
and step 3: methanol (1000 g) was added to the reaction vessel in step 2, and the operation of step 2 was repeated 3 times to obtain a solid precipitate. The solid precipitate was dried in a vacuum oven to give 78g of modified film-forming resin.
The weight average molecular weight and Polymer Dispersibility Index (PDI) of the modified film-forming resin were measured using a Gel Permeation Chromatography (GPC) apparatus.
TABLE 1
Figure GDA0003828532940000223
Figure GDA0003828532940000231
In the following examples or comparative examples, photoresist compositions were prepared as follows:
examples 1to 10 and comparative examples 1to 10
Photoacid generators:
Figure GDA0003828532940000232
Figure GDA0003828532940000241
the starting materials as in Table 2 were added to a new clean 100mL glass bottle. The mixture was shaken in a bottle for 24 hours at room temperature to be sufficiently dissolved, and then the photoresist solution was filtered with a 0.22 micron and a 0.02 micron filter in sequence to obtain a photoresist composition.
TABLE 2
Figure GDA0003828532940000242
Figure GDA0003828532940000251
Effects of the embodiment
And depositing gaseous HMDS on the surface of the wafer substrate in an HMDS cavity of the spin coater. The photoresists of examples 1-10 and comparative examples 1-10 were spin coated on 12' silicon wafers pretreated with HMDS, and spin-coated at 1000-3000 rpm to form a film, baked on a hot plate at 120 ℃ for 90 seconds, cooled to room temperature in a cold plate cavity, and exposed on an exposure machine with a wavelength of 248nm and an exposure intensity of 10-50mJ/cm 2 . Baking at 110 deg.C for 90 s after exposure, developing in 2.38% TMAH developer for 60 s, rinsing with pure water, and drying to check the lithography result with an electron microscope.
The lithography machine model is 248nm KrFstepper.
1. Crack resistance
The resist film surface crack resistance was observed using an SEM apparatus (equipment name "S8840"; manufactured by Hitachi Corporation).
2. Viscosity test
The viscosity (25 ℃) of the thick film resist was measured by an automatic viscosity measuring apparatus VMC-252 (manufactured by CLUTCH CORPORATION).
3. Film thickness measurement
The resist film thickness (nm) at the measurement point on the wafer 49 was measured by a nano-meter (manufactured by Nanometrics) measuring apparatus.
4. Evaluation of in-plane uniformity of film thickness
3 σ is a value (3 σ) which is 3 times the standard error (σ) calculated from the measurement results at 49 positions. When the value of 3 σ is smaller, the in-plane unevenness of the film thickness becomes smaller, and a resist having high in-plane uniformity can be obtained.
5. Defect evaluation
The number of defects on the substrate was evaluated by measuring the defects with a surface defect measuring apparatus KLA2132 (trade name) manufactured by KLA-TENCORPORATION.
6. Resolution limit CD (Critical Dimension) (nm)
Observation was performed with an electron microscope, and the spatial width of the substrate interface in the cross section of the non-resist portion (line/space = 4.
7. Evaluation of shape
From the results of SEM of the cross section of the developed wafer, the substrate was recognized, and the one with good pattern linearity (rectangular shape) was evaluated as a, and the one with poor pattern linearity (bottom-protruded one) which was not recognized to the substrate was evaluated as B.
8. Evaluation of rectangularity of cross-sectional shape of pattern
When the cross-sectional shape of the pattern was observed by SEM, a cut out of the side surface almost vertically was defined as a, a cut out of the side surface into a substantially conical shape was defined as B, a cut out of the side surface into a wavy shape was defined as C, and a cut out of the side surface into a wavy shape was defined as D.
9. Evaluation of resolution
The exposure amount was changed by using the mask, and the spatial width of the photoresist pattern was observed. The finest space width (unit: micrometer) among the space widths was used as an index for evaluation of the resolution.
10. Evaluation of film peeling after vacuum treatment
The evaluation pattern wafer was placed in a pressure-resistant vessel and subjected to vacuum treatment (left at 0.01Torr for 15 minutes). The vacuum-treated wafer was observed by an optical microscope (manufactured by Olympus Corporation) using a scanning type confocal laser microscope (model: LEXT OLS 3100) in an optical microscope mode, and film peeling on the surface of the wafer was observed. The number of cases where the film peeling exceeded 100 was counted as D, the number of cases where the film peeling was 6 to 100 was counted as C, the number of cases where the film peeling was 2 to 5 was counted as B, the number of cases where the film peeling was 1 was counted as A, and the number of cases where the film peeling was 0 was counted as S.
11. Evaluation of sensitivity
The exposure time required to form a pattern composed of line-and-space width (L & S) (1: 1) components each having a width of 1.5 μm according to the aforementioned photolithography method is expressed in units of milliseconds (ms) (Eop exposure).
12. Evaluation of waving phenomena
The profile of the obtained resist pattern was observed from the right side through an L & S resist pattern having a width of 1.5 μm using a critical dimension measuring SEM. The case where the hunting phenomenon cannot be recognized is designated as "a", and the case where the hunting phenomenon can be recognized is designated as "B".
13. Measurement of depth of field (DOF)
The Eop exposure amount required for the prescribed dimensions of the mask pattern (line width: 1.5 μm, L & S resist pattern: 1) was used as a standard exposure amount, and then, a cross-sectional SEM photograph of the L & S (line width: 1.5 μm, L & S resist pattern: 1) profile was taken using an SEM in an irradiation dose under a condition of moving the focus up and down, followed by exposure and observation of further development. The maximum value of the focus deviation (μm) required to obtain a rectangular resist pattern having a width of 1.5 μm within a prescribed size of ± 10% in the SEM micrograph is considered to be the depth of field.
14. Heat resistance test
In the same manner as described above, an L & S resist pattern having a width of 1.5 μm was formed in the exposure amount (Eop) obtained by the above sensitivity test, and heat treatment at 140 ℃ was performed for 300 seconds. Then, the cross-sectional profile was observed by SEM. The case where the deformation of the resist pattern was hardly observed was designated as "a", and the case where the shrinkage of the resist pattern was observed was designated as "B".
15. Metallic impurities
The amounts of metal impurity components of 25 kinds (Na, K, ca, fe, cu, mg, mn, al, li, cr, ni, sn, zn, ag, as, au, ba, cd, co, pb, ti, V, W, mo, zr) contained in each composition were measured with an ICP-MS apparatus (inductively coupled plasma Mass spectrometer) "Agilent7500cs" manufactured by Agilent Technologies, inc., and the content of the metal impurity having the highest content was regarded As B in a ppb-greater amount; less than 10ppb was taken as A.
TABLE 3
Figure GDA0003828532940000271
TABLE 4
Figure GDA0003828532940000272
Figure GDA0003828532940000281
Remarking: the "/" in tables 3 and 4 indicates that no test was performed.
As is clear from Table 3 above, the resist composition of the present invention formed a thick film (10 to 15 μm) having no cracking, good film thickness uniformity (3. Sigma. Is 42 or less), few defects, a resolution limit of 527 to 736nm, a rectangular cross-sectional shape, good resolution (a space width of the resist pattern is 1.2 to 1.8 μm), little film peeling after treatment (SABC), high sensitivity (260 to 394 ms), strong heat resistance (deformation of the resist pattern hardly observed), suppressed waving, and few impurities (preferably less than 10 ppb).
Taking the evaluation of film peeling after vacuum treatment as an example, the evaluation indexes of film peeling after vacuum treatment of "example 1 and comparative examples 1to 5" (changing the kind of resin), "example 1 and comparative examples 6 to 7" and "example 2 and comparative examples 8 to 9" (changing the kind of photoacid generator), "example 1 and comparative example 10" (changing the kind of resin and photoacid generator simultaneously) in tables 3 and 4 are compared to each other: the photoresist composition of the present invention forms a resist film having less film peeling than a resist film formed from a photoresist composition of "resin and photoacid generator" or "resin and photoacid generator" that is not within the scope of the present invention. The photoresist composition within the scope of the present invention forms less peeling of the glue film. It can be seen that photoresist compositions within the scope of the invention have superior performance.

Claims (11)

1. A photoresist composition comprising the following components: a resin, a photoacid generator, and a solvent;
the resin is prepared by the following preparation method, and the preparation method of the resin comprises the following steps:
in the presence of benzoyl peroxide, carrying out polymerization reaction on a monomer shown as a formula A, a monomer shown as a formula B, a monomer shown as a formula C, a monomer shown as a formula D and a monomer shown as a formula E in ethyl acetate to obtain the resin; wherein the monomer shown as the formula D accounts for 1-10 parts by weight, and the monomer shown as the formula E accounts for 1-10 parts by weight;
the temperature of the polymerization reaction is 75-80 ℃;
Figure FDA0003828532930000011
in the formula A, R 1 Is R 1a Substituted 5-10 membered heterocycloalkyl or-CH 2 (C=O)OR 1b
R 1b Is R 1b-1 Substituted 5-10 membered heterocycloalkyl;
R 1a and R 1b-1 Independently is oxo, cyano or C 1-4 Alkyl groups of (a);
said R 1a Substituted 5-10 membered heterocycloalkyl and said R 1b -1 or 2 heteroatoms in the 1-substituted 5-to 10-membered heterocycloalkyl group are O;
in the formula B, R 2 Is composed of
Figure FDA0003828532930000012
M is ethylene or cyclohexylene; n is 2, 3, 4,5, 6 or 7; y is
Figure FDA0003828532930000013
R 2a And R 2b Independently is C 1-4 Alkyl of R 2a-1 Substituted C 1-4 Alkyl, phenyl, naphthyl, R 2a-2 Substituted phenyl or 5-6 membered cycloalkyl;
R 2a-1 is hydroxy or adamantyl;
R 2a-2 is C 1-4 Alkyl or C 1-4 Alkoxy of (2);
or, R 2a And R 2b Together with the N atom to which they are attached form a 5-6 membered heterocycloalkyl or R 2b-1 Substituted 5-6 membered heterocycloalkyl, said 5-6 membered heterocycloalkyl and R 2b-1 The heteroatoms in the substituted 5-6 membered heterocycloalkyl are independently selected from O and N, and the number is 1 or 2;
R 2b-1 is C 1-4 An alkyl or amino protecting group of (a);
and Y is other than
Figure FDA0003828532930000014
In the formula C, the reaction mixture is shown in the formula,
Figure FDA0003828532930000015
is a single bond or a double bond;
R 3a 、R 3b and R 3c Independently H, hydroxy, cyano, - (C = O) OR 3a-1 、-O(C=O)R 3a-2 、C 1-4 Alkyl or hydroxy-substituted C 1-4 Alkyl groups of (a); and R is 3a 、R 3b And R 3c Not H at the same time;
R 3a-1 is H, C 1-5 Alkyl group of (A) or (B),
Figure FDA0003828532930000021
R 3a-2 Is C 1-4 Alkyl or phenyl of (a);
or, R 3a 、R 3b And R 3c Any two of which taken together with the carbon atoms to which they are attached form a phenyl, 5-7 membered cycloalkyl, 5-7 membered cycloalkenyl,
Figure FDA0003828532930000022
In the formula D, Q is N or O;
R 4 is composed of
Figure FDA0003828532930000023
In the formula E, R 5 Is C 1-6 Alkyl of R 5-1 Substituted C 1-6 Alkyl of (2), cycloalkyl of 5 to 6 membered, R 5-2 Substituted 5-6 membered cycloalkyl, R 5-3 Substituted phenyl or
Figure FDA0003828532930000024
R 5-1 、R 5-2 And R 5-3 Independently is hydroxy or
Figure FDA0003828532930000025
The photoacid generator is PAG1 and/or PAG2, and the structure of the photoacid generator is shown as follows:
Figure FDA0003828532930000026
the weight average molecular weight of the resin is 3000-20000;
the polymer dispersity index of the resin is 1.2-2.5.
2. The photoresist composition of claim 1, wherein when R is 1 Is R 1a (ii) when substituted 5-10 membered heterocycloalkyl, said 5-10 membered heterocycloalkyl is 5, 6, 9 or 10 membered heterocycloalkyl;
and/or when R 1b Is R 1b-1 Substituted 5-to 10-membered heterocycloalkyl, as describedThe 5-to 10-membered heterocycloalkyl of (a) is a 5-, 9-or 10-membered heterocycloalkyl;
and/or, when said R is 1a And R 1b-1 Independently is C 1-4 When said alkyl is substituted, said C 1-4 Alkyl of (a) is methyl;
and/or, when M is cyclohexylene, said cyclohexylene is
Figure FDA0003828532930000031
And/or when R 2a And R 2b Independently is C 1-4 When said alkyl is substituted, said C 1-4 Alkyl of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;
and/or when R 2a And R 2b Independently is R 2a-1 Substituted C 1-4 When said alkyl is substituted, said C 1-4 Alkyl of (b) is methyl or ethyl;
and/or when R 2a-2 Is C 1-4 When said alkyl is substituted, said C 1-4 Alkyl of (a) is methyl;
and/or when R 2a-2 Is C 1-4 Alkoxy of (2), said C 1-4 Alkoxy of (b) is methoxy;
and/or when R 2a And R 2b When taken together with the N atom to which they are attached to form a 5-6 membered heterocycloalkyl group, said 5-6 membered heterocycloalkyl group is
Figure FDA0003828532930000032
And/or when R 2a And R 2b Together with the N atom to which they are attached form R 2b-1 When substituted with 5-to 6-membered heterocycloalkyl, said R 2b-1 Substituted 5-6 membered heterocycloalkyl
Figure FDA0003828532930000033
And/or when R 2b-1 Is C 1-4 When there is an alkyl group, said C 1-4 Alkyl of (b) is methyl;
and/or when R 3a 、R 3b And R 3c Independently is C 1-4 When said alkyl is substituted, said C 1-4 The alkyl group of (a) is a tert-butyl group;
and/or when R 3a 、R 3b And R 3c Independently is hydroxy-substituted C 1-4 When there is an alkyl group, said C 1-4 Alkyl of (b) is methyl;
and/or when R 3a-1 Is C 1-5 When said alkyl is substituted, said C 1-5 Alkyl of (A) is ethyl or
Figure FDA0003828532930000034
And/or when R 3a 、R 3b And R 3c When any two groups form a 5-7 membered cycloalkyl group together with the carbon atom to which they are attached, said 5-7 membered cycloalkyl group is cyclopentyl, cyclohexyl or
Figure FDA0003828532930000035
And/or when R 3a 、R 3b And R 3c When any two of them form a 5-7 membered cycloalkenyl group together with the carbon atom to which they are attached, said 5-7 membered cycloalkenyl group is cyclopentenyl;
and/or when R 5 Is R 5-1 Substituted C 1-6 When said alkyl is substituted, said C 1-6 Alkyl of (A) is
Figure FDA0003828532930000041
Figure FDA0003828532930000042
3. The photoresist composition of claim 2, wherein when R is 1 Is R 1a When substituted with 5-to 10-membered heterocycloalkyl, said R 1a Substituted 5-to 10-membered heterocycloalkyl group
Figure FDA0003828532930000043
Figure FDA0003828532930000044
And/or, when said R is 1b Is R 1b-1 When substituted with 5-to 10-membered heterocycloalkyl, said R 1b-1 Substituted 5-to 10-membered heterocycloalkyl group
Figure FDA0003828532930000045
Figure FDA0003828532930000046
And/or Y is
Figure FDA0003828532930000047
Figure FDA0003828532930000048
When R is 5 Is R 5-1 Substituted C 1-6 When said alkyl is (a), said R 5-1 Substituted C 1-6 Alkyl of (A) is
Figure FDA0003828532930000049
Figure FDA0003828532930000051
And/or when R 5 Is R 5-2 When substituted with 5-to 6-membered cycloalkyl, said R 5-2 Substituted 5-to 6-membered cycloalkyl is
Figure FDA0003828532930000052
And/or when R 5 Is R 5-3 When the phenyl group is substituted, said R 5-3 Substituted phenyl is
Figure FDA0003828532930000053
Figure FDA0003828532930000054
4. The photoresist composition of claim 3,
when R is 1 Is R 1a When substituted with 5-to 10-membered heterocycloalkyl, said R 1a Substituted 5-to 10-membered heterocycloalkyl group
Figure FDA0003828532930000055
And/or, when said R is 1b Is R 1b-1 When substituted with 5-to 10-membered heterocycloalkyl, said R 1b-1 Substituted 5-to 10-membered heterocycloalkyl group
Figure FDA0003828532930000056
5. The photoresist composition according to claim 1, wherein the resin is present in an amount of 10 to 45 parts;
and/or the part of the monomer shown in the formula A is 35-65 parts;
and/or the part of the monomer shown as the formula B is 20-55 parts;
and/or the part of the monomer shown in the formula C is 10-25 parts;
and/or the part of the monomer shown in the formula D is 5-10 parts;
and/or the part of the monomer shown as the formula E is 5-10 parts;
and/or, the part of the photoacid generator is 0.5-5.5 parts;
and/or, the part of the solvent is 50-85 parts;
and/or the solvent is one or more of ketone solvent, ester solvent and ether solvent;
and/or the monomer shown in the formula A is any one of the following compounds:
Figure FDA0003828532930000061
and/or the monomer shown in the formula B is any one of the following compounds:
Figure FDA0003828532930000062
and/or the monomer shown in the formula C is any one of the following compounds:
Figure FDA0003828532930000071
and/or the monomer shown in the formula D is any one of the following compounds:
Figure FDA0003828532930000072
and/or the monomer shown in the formula E is any one of the following compounds:
Figure FDA0003828532930000073
6. the photoresist composition according to claim 5, wherein the resin is present in an amount of 20 to 45 parts;
and/or the weight average molecular weight of the resin is 5000-20000;
and/or the part of the monomer shown in the formula A is 35-48 parts;
and/or the part of the monomer shown as the formula B is 30-40 parts;
and/or the part of the monomer shown in the formula C is 10-20 parts;
and/or the parts of the photoacid generator are 3-5 parts;
and/or, the part of the solvent is 59-85 parts;
and/or the solvent is one or more of cyclohexanone, ethyl acetate, ethylene glycol monomethyl ether and dipropylene glycol monomethyl ether.
7. The photoresist composition according to claim 1, wherein the resin is prepared by a method in which each monomer and the amount thereof are represented by any one of the following groups (1) to (10), and resins 1to 10 are obtained in order, respectively:
(1) 40 parts of the monomer shown in the formula A, 30 parts of the monomer shown in the formula B, 20 parts of the monomer shown in the formula C, 4 parts of the monomer shown in the formula D and 6 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000081
The monomer shown as the formula B is
Figure FDA0003828532930000082
The monomer shown as the formula C is
Figure FDA0003828532930000083
The monomer shown as the formula D is
Figure FDA0003828532930000084
The monomer shown as the formula E is
Figure FDA0003828532930000085
Thereby obtaining a resin 1;
(2) 45 parts of the monomer shown in the formula A, 35 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 3 parts of the monomer shown in the formula D and 7 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000086
The monomer shown as the formula B is
Figure FDA0003828532930000087
The monomer shown as the formula C is
Figure FDA0003828532930000088
The monomer shown as the formula D is
Figure FDA0003828532930000089
The monomer shown as the formula E is
Figure FDA0003828532930000091
Thereby obtaining a resin 2;
(3) 48 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 1 part of the monomer shown in the formula D and 1 part of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000092
The monomer shown as the formula B is
Figure FDA0003828532930000093
The monomer shown as the formula C is
Figure FDA0003828532930000094
The monomer shown as the formula D is
Figure FDA0003828532930000095
The formula is shown as the formula EIs a monomer of
Figure FDA0003828532930000096
Thereby obtaining a resin 3;
(4) 30 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 15 parts of the monomer shown in the formula C, 6 parts of the monomer shown in the formula D and 9 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000097
The monomer shown as the formula B is
Figure FDA0003828532930000098
The monomer shown as the formula C is
Figure FDA0003828532930000099
The monomer shown as the formula D is
Figure FDA0003828532930000101
The monomer shown as the formula E is
Figure FDA0003828532930000102
Thereby obtaining a resin 4;
(5) 35 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 7 parts of the monomer shown in the formula D and 8 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000103
The monomer shown as the formula B is
Figure FDA0003828532930000104
The monomer shown as the formula C is
Figure FDA0003828532930000105
The monomer shown as the formula D is
Figure FDA0003828532930000106
The monomer shown as the formula E is
Figure FDA0003828532930000107
Thereby obtaining a resin 5;
(6) 40 parts of the monomer shown in the formula A, 30 parts of the monomer shown in the formula B, 20 parts of the monomer shown in the formula C, 5 parts of the monomer shown in the formula D and 5 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000108
The monomer shown as the formula B is
Figure FDA0003828532930000109
The monomer shown as the formula C is
Figure FDA00038285329300001010
The monomer shown as the formula D is
Figure FDA0003828532930000111
The monomer shown as the formula E is
Figure FDA0003828532930000112
Thereby obtaining a resin 6;
(7) 45 parts of the monomer shown in the formula A, 35 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 5 parts of the monomer shown in the formula D and 5 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000113
The monomer shown as the formula B is
Figure FDA0003828532930000114
The monomer shown as the formula C is
Figure FDA0003828532930000115
The monomer shown as the formula D is
Figure FDA0003828532930000116
The monomer shown as the formula E is
Figure FDA0003828532930000117
Thereby obtaining a resin 7;
(8) 40 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 5 parts of the monomer shown in the formula D and 5 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000118
The monomer shown as the formula B is
Figure FDA0003828532930000119
The monomer shown as the formula C is
Figure FDA00038285329300001110
The monomer shown as the formula D is
Figure FDA0003828532930000121
The monomer shown as the formula E is
Figure FDA0003828532930000122
Thereby obtaining a resin 8;
(9) 40 parts of the monomer shown in the formula A, 30 parts of the monomer shown in the formula B, 15 parts of the monomer shown in the formula C, 10 parts of the monomer shown in the formula D and 5 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000123
The monomer shown as the formula B is
Figure FDA0003828532930000124
The monomer shown as the formula C is
Figure FDA0003828532930000125
The monomer shown as the formula D is
Figure FDA0003828532930000126
The monomer shown as the formula E is
Figure FDA0003828532930000127
Thereby obtaining a resin 9;
(10) 35 parts of the monomer shown in the formula A, 40 parts of the monomer shown in the formula B, 10 parts of the monomer shown in the formula C, 5 parts of the monomer shown in the formula D and 10 parts of the monomer shown in the formula E;
the monomer shown as the formula A is
Figure FDA0003828532930000128
The monomer shown as the formula B is
Figure FDA0003828532930000129
The monomer shown as the formula C is
Figure FDA00038285329300001210
The monomer shown as the formula D is
Figure FDA00038285329300001211
The monomer shown as the formula E is
Figure FDA0003828532930000131
Thereby obtaining a resin 10.
8. The photoresist composition of claim 1, wherein the resin is prepared by a process comprising the steps of:
under the protection of nitrogen, adding the mixed solution of ethyl acetate and benzoyl peroxide into the mixed solution of the monomer shown in the formula A, the monomer shown in the formula B, the monomer shown in the formula C, the monomer shown in the formula D and the monomer shown in the formula E and ethyl acetate;
wherein the adding time is 10min.
9. The photoresist composition of claim 1, further comprising an additive selected from at least one of a leveling agent, a plasticizer, an organic base, a dissolution rate enhancer, and a photosensitizer; the additive is 5-10 parts by weight.
10. The photoresist composition of any one of claims 1to 7, wherein the photoresist composition consists of: the photoacid generator, the resin, and the solvent.
11. The photoresist composition of claim 1, wherein the photoresist composition is any combination of: combination 1:25 parts of resin 1,5 parts of PAG1 and 70 parts of cyclohexanone;
and (3) combination 2:30 parts of resin 2,0.5 part of PAG2 and 69.50 parts of ethyl acetate;
combination 3:10 parts of resin 3,5 parts of PAG2 and 85 parts of ethylene glycol monomethyl ether;
and (4) combination: 35 parts of resin 4,5.5 parts of PAG1 and 59 parts of cyclohexanone;
and (4) combination 5:45 parts of resin 5,5 parts of PAG2 and 50 parts of ethylene glycol monomethyl ether;
and (4) combination 6:25 parts of resin 6,5 parts of PAG1 and 70 parts of ethyl acetate;
combination 7:30 parts of resin 7,0.5 part of PAG2 and 69.5 parts of dipropylene glycol monomethyl ether;
and (4) combination 8:20 parts of resin 8,3 parts of PAG1 and 77 parts of dipropylene glycol monomethyl ether;
combination 9:35 parts of resin 9,5.5 parts of PAG2 and 59 parts of ethyl acetate;
combination 10:45 parts of resin 10,5 parts of PAG2 and 50 parts of ethylene glycol monomethyl ether;
wherein said resin 1, said resin 2, said resin 3, said resin 4, said resin 5, said resin 6, said resin 7, said resin 8, said resin 9 and said resin 10 are as defined in claim 7.
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CN101872117A (en) * 2009-04-23 2010-10-27 住友化学株式会社 Produce the photoresist method of patterning
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CN111205385A (en) * 2020-02-28 2020-05-29 宁波南大光电材料有限公司 Modified film-forming resin containing acid inhibitor, preparation method thereof and photoresist composition

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US6927009B2 (en) * 2001-05-22 2005-08-09 Fuji Photo Film Co., Ltd. Positive photosensitive composition
JP4568668B2 (en) * 2005-09-22 2010-10-27 富士フイルム株式会社 Positive resist composition for immersion exposure and pattern forming method using the same
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CN101021683A (en) * 2006-02-15 2007-08-22 住友化学株式会社 Chemical-amplification positive photoresist composition
CN101872117A (en) * 2009-04-23 2010-10-27 住友化学株式会社 Produce the photoresist method of patterning
WO2013024756A1 (en) * 2011-08-16 2013-02-21 Jsr株式会社 Photoresist composition
CN111205385A (en) * 2020-02-28 2020-05-29 宁波南大光电材料有限公司 Modified film-forming resin containing acid inhibitor, preparation method thereof and photoresist composition

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