CN112485960B - Thick film type photoresist composition and preparation method and application thereof - Google Patents
Thick film type photoresist composition and preparation method and application thereof Download PDFInfo
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- CN112485960B CN112485960B CN202011360556.3A CN202011360556A CN112485960B CN 112485960 B CN112485960 B CN 112485960B CN 202011360556 A CN202011360556 A CN 202011360556A CN 112485960 B CN112485960 B CN 112485960B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers 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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses a thick film type photoresist composition and a preparation method and application thereof. The preparation method of the thick film type photoresist composition comprises the following steps: uniformly mixing all components in the photoresist composition; the photoresist composition 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
Technical Field
The invention relates to a thick film type 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 method is a hot 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 photoresist composition, a preparation method and application thereof. The glue film formed by the photoresist composition obtained by the preparation method of the invention at least has the following advantages: the film has the advantages of difficult cracking, uniform thickness, poor 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 preparation method of a photoresist composition, which comprises the following steps: uniformly mixing all components in the photoresist composition;
the photoresist composition 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 ℃;
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 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
M is ethylene or cyclohexylene; n is 2, 3, 4,5, 6 or 7; y is
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 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 not
In the formula C, the reaction solution is shown in the specification,
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),
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,
In the formula D, Q is N or O;
R 4 is composed of
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
R 5-1 、R 5-2 And R 5-3 Independently is hydroxy or
The photoacid generator is PAG1 and/or PAG2, and the structure of the photoacid generator is shown as follows:
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.
In the present invention, the parts of the resin by weight may be the parts conventional in the art, preferably 10 to 45 parts, and may preferably be 20 to 45 parts, such as 25 parts, 30 parts, 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 the parts conventional in the art, preferably 35 to 65 parts, and may also be preferably 35 to 48 parts, for example 40 parts, 45 parts.
In the present invention, the parts by weight of the monomer represented by formula B may be those 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 the parts conventionally used in the art, preferably 10 to 25 parts, and may also be preferably 10 to 20 parts, for example 15 parts.
In the invention, the part of the monomer shown in the 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 substituted with a 5-to 10-membered heterocycloalkyl group, 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 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 1 Is R 1a When substituted with 5-to 10-membered heterocycloalkyl, said R 1a Substituted 5-to 10-memberedThe heterocycloalkyl group is preferably
More preferably
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
More preferably
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 group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or a 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 When there is an alkoxy group, said C 1-4 The alkoxy group of (A) 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
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 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 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
In the present invention, Y is preferably
In the present invention, when R is 3a 、R 3b And R 3c 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, more preferably a tert-butyl group.
In the present invention, when R is 3a 、R 3b And R 3c Independently 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
In the present invention, when R is 3a-1 Is C 6-10 Aryl of (b), said C 6-10 Aryl of (b) 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 The alkyl group of (2) is preferably a methyl group.
In the present invention, when R is 3a-2 Is C 6-10 Aryl of (b), said C 6-10 Aryl of (b) is preferably phenyl.
In the present invention, when R is 3a 、R 3b And R 3c When any two of the groups together with the carbon atom to which they are attached form a 5-7 membered cycloalkyl group, said 5-7 membered cycloalkyl group is preferably cyclopentyl, cyclohexyl or
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
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 Is preferably alkyl
In the present invention, when R is 5 Is R 5-2 When the cycloalkyl group is substituted by 5 to 6 members, the R group 5-2 The substituted 5-to 6-membered cycloalkyl is preferably
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
In the present invention, the monomer represented by formula a is preferably any one of the following compounds:
more preferably any of the following compounds:
in the present invention, the monomer represented by formula B is preferably any one of the following compounds:
more preferably any of the following compounds:
in the invention, the monomer shown in the formula C is preferably any one of the following compounds:
more preferably any of the following compounds:
in the present invention, the monomer represented by formula D is preferably any one of the following compounds:
in the present invention, the monomer represented by formula E is preferably any one of the following compounds:
more preferably any of the following compounds:
in the present invention, the resin is prepared by a 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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
Of the formulaThe monomer shown as B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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 represented by formula a, the monomer represented by formula B, the monomer represented by formula C, the monomer represented by formula D, and the monomer represented by 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 5.5 parts, and may also preferably be 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 and 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 (3) 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 previously described.
The present invention also provides a method of forming a lithographic pattern, the method 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 3, 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 cooled 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 solution of tetramethylammonium hydroxide (TMAH), for example 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 rinsing 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
)。
As used herein, "heterocycloalkyl" refers to a monocyclic ring containing 1 or more heteroatoms of N, O or S (e.g., a heterocycle)
) Or 2-4 membered bridged ring systems (e.g.
)。
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 as follows. The individual monomers used are as follows:
monomer A:
a monomer B:
a monomer C:
a monomer D:
a monomer E:
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 3, 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
In the following examples or comparative examples, photoresist compositions were prepared as follows:
examples 1to 10 and comparative examples 1to 10
Photoacid generators:
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
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, spin-coated at 1000-3000 rpm, baked on a hot plate at 120 ℃ for 90 seconds, cooled to room temperature in the cavity of the cold plate, and then 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, nikon S204B,0.55NA,0.33Sigma (NA: numerical aperture; sigma: iris).
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 using an automatic viscosity measuring apparatus VMC-252 (manufactured by Clutch Co.).
3. Film thickness measurement
The resist film thickness (nm) at the measurement point of the wafer 49 was measured by a nano-meter (manufactured by Nanometrics) using a resist film thickness 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. 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 the SEM cross section of the developed wafer, the substrate was recognized, and the one with good linearity of the pattern (rectangular one) was evaluated as a, and the one with poor linearity of the pattern (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 case where the side surface was cut almost vertically was denoted as a, a case where the side surface was formed into a substantially conical shape was denoted as B, a case where the side surface was formed into a wavy shape was denoted as C, and a case where the side surface was formed into a wavy shape was denoted as D.
9. Evaluation of resolution
The exposure amount was varied 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 size 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 SEM in an irradiation dose with the focus moved 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 is hardly observed is designated as "a", and the case where the shrinkage of the resist pattern is observed is 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) "Agilent 7500cs" 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
TABLE 4
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 outside 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 (13)
1. A method for preparing a photoresist composition, comprising the steps of: uniformly mixing all components in the photoresist composition;
the photoresist composition 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 weight-average molecular weight of the resin is 3000-20000;
the polymer dispersibility index of the resin is 1.2-2.5;
the temperature of the polymerization reaction is 75-80 ℃;
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-to 10-membered heterocycloalkyl is O, and the number of the heteroatom is 1 or 2;
in the formula B, R 2 Is composed of
M is ethylene or cyclohexylene; n is 2, 3, 4,5, 6 or 7; y is
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 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 not
In the formula C, the reaction solution is shown in the specification,
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),
R 3a-2 Is C 1-4 Alkyl or phenyl of (a);
or, R 3a 、R 3b And R 3c With any two groups in phase therewithThe carbon atoms to which they are attached together form a phenyl group, a 5-7 membered cycloalkyl group, a 5-7 membered cycloalkenyl group,
In the formula D, Q is N or O;
R 4 is composed of
In the formula E, R 5 Is C 1-6 Alkyl of R 5-1 Substituted C 1-6 Alkyl of (3), cycloalkyl of 5 to 6 membered, R 5-2 Substituted 5-6 membered cycloalkyl, R 5-3 Substituted phenyl or
R 5-1 、R 5-2 And R 5-3 Independently of one another is hydroxy or
The photoacid generator is PAG1 and/or PAG2, and the structure of the photoacid generator is shown as follows:
2. the method of claim 1, wherein the mixing is performed by shaking; and/or, the mixing time is 18-30 hours;
and/or, after the mixing, the method can further comprise a filtering step, wherein the filtering mode adopts a filter for filtering.
3. The method of claim 2, wherein the number of filtrations is 2 to 3;
and/or the pore diameter of the filter membrane of the filter is 2-50nm.
4. The method 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 (ii) when substituted 5-10 membered heterocycloalkyl, said 5-10 membered heterocycloalkyl is 5, 9 or 10 membered heterocycloalkyl;
and/or, when said R is 1a And R 1b-1 Independently is C 1-4 When there is an alkyl group, said C 1-4 Alkyl of (a) is methyl;
and/or, when M is cyclohexylene, said cyclohexylene is
And/or when R 2a And R 2b Independently is C 1-4 When there is an alkyl group, 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 there is an alkyl group, 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;
when R is 2a And R 2b When taken together with the N atom to which they are attached form a 5-6 membered heterocycloalkyl group, said 5-6 membered heterocycloalkyl group is
And/or when R 2a And R 2b To which is attached the N atom oneForm R 2b-1 When substituted with 5-to 6-membered heterocycloalkyl, said R 2b-1 Substituted 5-6 membered heterocycloalkyl
And/or when R 2b-1 Is C 1-4 When said alkyl is substituted, said C 1-4 Alkyl of (a) is methyl;
and/or when R 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 (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 (a) is methyl;
and/or when R 3a-1 Is C 1-5 When there is an alkyl group, said C 1-5 Alkyl of (A) is ethyl or
And/or when R 3a 、R 3b And R 3c When any two of the groups together with the carbon atoms to which they are attached form a 5-7 membered cycloalkyl group, said 5-7 membered cycloalkyl group is cyclopentyl, cyclohexyl or
And/or when R 3a 、R 3b And R 3c When any two of the groups together with the carbon atoms to which they are attached form a 5-7 membered cycloalkenyl group, said 5-7 membered cycloalkenyl group is cyclopentenyl;
and/or when R 5 Is R 5-1 Substituted C 1-6 When there is an alkyl group, said C 1-6 Alkyl of (A) is
5. The method of claim 4, 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
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
And/or Y is
When R is 5 Is R 5-1 Substituted C 1-6 When said alkyl is substituted, said R 5-1 Substituted C 1-6 Alkyl of (A) is
And/or when R 5 Is R 5-2 When the cycloalkyl group is substituted by 5 to 6 members, the R group 5-2 Substituted 5-6 membered cycloalkyl is
And/or when R 5 Is R 5-3 When the phenyl group is substituted, said R 5-3 Substituted phenyl is
6. The method of claim 4, 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
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
7. The method of claim 1, wherein the resin is present in an amount of from 10 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 35-65 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 as 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:
and/or the monomer shown in the formula B is any one of the following compounds:
and/or the monomer shown in the formula C is any one of the following compounds:
and/or the monomer shown in the formula D is any one of the following compounds:
and/or the monomer shown in the formula E is any one of the following compounds:
8. the process according to claim 1, wherein the resin is used in an amount of 20 to 45 parts;
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.
9. The process according to claim 1, wherein the resin is produced by a process in which the monomers and the amount used are as shown in any one of the following groups (1) to (10), and the resins 1to 10 are obtained in this 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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
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
The monomer shown as the formula B is
The monomer shown as the formula C is
The monomer shown as the formula D is
The monomer shown as the formula E is
Thereby obtaining a resin 10.
10. The method of claim 1, wherein the resin is prepared by a method 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.
11. The method according to claim 1, wherein 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 additive is 5-10 parts by weight.
12. The process of any one of claims 1-10, wherein the photoresist composition is comprised of: the photoacid generator, the resin, and the solvent.
13. The method of claim 1, wherein 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;
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;
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 defined in claim 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| 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 |
| CN110494806B (en) * | 2017-05-19 | 2024-03-15 | 富士胶片株式会社 | Actinic-ray-or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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