CN112485966B - 248nm thick film photoresist resin and its preparation method and use - Google Patents
248nm thick film photoresist resin and its preparation method and use Download PDFInfo
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- CN112485966B CN112485966B CN202011364891.0A CN202011364891A CN112485966B CN 112485966 B CN112485966 B CN 112485966B CN 202011364891 A CN202011364891 A CN 202011364891A CN 112485966 B CN112485966 B CN 112485966B
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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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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Abstract
The invention discloses 248nm thick film photoresist resin and a preparation method and application thereof. The preparation method of the photoresist composition comprises the following steps: uniformly mixing all components in the photoresist composition; the photoresist composition comprises the following components: photoacid generators, resins, and solvents. The glue film formed by the photoresist composition has good performance and good application prospect.
Description
Technical Field
The invention relates to 248nm thick film photoresist resin 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 248nm thick film photoresist resin and a preparation method and application thereof. The photoresist composition prepared by the preparation method provided by the invention has the advantages of difficult cracking of a glue film, uniform thickness, good resolution and sensitivity, good film stripping performance, good shape, good rectangularity, good resolution, good heat resistance, capability of inhibiting fluctuation phenomenon and less metal impurities.
The present invention solves the above technical problems by the following technical solutions.
The invention also provides a preparation method of the photoresist composition, which comprises the following steps: uniformly mixing all components in the photoresist composition;
the photoresist composition comprises the following components: photoacid generators, resins and solvents;
the photoacid generator is PAG1 and/or PAG2, and the structure of the photoacid generator is shown as follows:
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-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
n 1 Is any integer of 1-11;
R 2a and R 2b Independently is C 1-4 Alkyl, hydroxy-substituted C of 1-4 Alkyl, phenyl, R 2a-1 Substituted phenyl, 5-6 membered cycloalkyl or adamantyl;
R 2a-1 is C 1-4 Alkyl or C 1-4 Alkoxy of (2);
or, R 2a And R 2b Together with the nitrogen 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);
in the formula C, the reaction mixture is shown in the formula,
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, n 2 Is 0 or 1;
R 4a and R 4b Independently is H or C 1-4 Alkyl groups of (a); and R is 4a And R 4b Not H at the same time;
in the formula E, R 5 Is H, cyano, C 1-4 Alkyl of R 5a Substituted C 1-4 Alkyl OR- (C = O) OR 5b ；
R 5a Is hydroxy or acetyl;
R 5b is C 1-4 The alkyl group of (1).
In the present invention, the mixing mode may be a mixing mode conventional in the art, and preferably shaking.
In the present invention, the mixing time may be a mixing time conventional in the art, and is preferably 18 to 30 hours, 24 hours.
In the present invention, after the mixing, a filtration step may be further included. The filtration may be performed in a manner conventional in the art, and preferably filtration using a filter is used. 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 by weight of the photoacid generator may be those conventionally used in the art, and preferably 0.6 to 5.5 parts, for example 3 to 5 parts.
In the present invention, the parts by weight of the resin may be those conventional in the art, preferably 10 to 45 parts, such as 20 to 35 parts, and further such as 25 parts, 30 parts.
In the present invention, the weight average molecular weight of the resin is preferably 3000 to 20000, for example 5000 to 18000.
In the present invention, the Polymer Dispersibility Index (PDI) of the resin is preferably 1.2 to 2.5, for example 1.4 to 2.1.
In the present invention, the parts by weight of the monomer represented by formula A may be those conventional in the art, preferably 20 to 55 parts, such as 30 to 40 parts, and further such as 35 parts.
In the present invention, the parts by weight of the monomer represented by formula B may be those conventional in the art, preferably 35 to 65 parts, such as 35 to 50 parts, and further such as 40 parts, 45 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, such as 10 to 20 parts, and further such as 15 parts.
In the invention, the part of the monomer shown in the formula D can be 5-10 parts.
In the invention, the part of the monomer shown in the formula E can be 5-10 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-substituted 5-to 10-membered heterocycloalkyl, said 5-to 10-membered heterocycloalkyl is preferably 5-, 9-or 10-membered heterocycloalkyl.
In the invention, when 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 The substituted 5-to 10-membered 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 said alkyl is substituted, 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, a sec-butyl group, an isobutyl group or a tert-butyl group.
In the present invention, when R is 2a -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 Independently is hydroxy-substituted 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 an ethyl group.
In the present invention, when R is 2a-1 Is C 1-4 When there is an alkoxy group, said C 1-4 The alkoxy group of (A) is preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy, more preferably methoxy or n-butoxy, sec-butoxy, isobutoxy or tert-butoxy.
In the present invention, when R is 2a And R 2b When independently a 5-6 membered cycloalkyl group, said 5-6 membered cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group, more preferably a cyclohexyl group.
In the present invention, when R is 2a And R 2b When the nitrogen atom to which they are bonded forms a 56-membered heterocycloalkyl group, the 5-to 6-membered heterocycloalkyl group is preferably
In the present invention, when R is 2a And R 2b Together with the nitrogen 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 2a And R 2b Together with the nitrogen atom to which they are attached form R 2b-1 In the case of a substituted 5-to 6-membered heterocycloalkyl group, the heteroatom in said 5-to 6-membered heterocycloalkyl group is preferably N.
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, more preferably a methyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group.
In the present invention, when R is 2a And R 2b Together with the nitrogen 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, 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, and 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 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 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 -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.
In the present invention, when R is 3a 、R 3b And R 3c When any two of the groups form a 5-7 membered cycloalkyl group together with the carbon atoms to which they are attached, 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 these groups together with the carbon atoms to which they are attached form a 5-7 membered cycloalkenyl group, the 5-7 membered cycloalkenyl group is preferably cyclopentenyl.
In the present invention, when R is 4a And R 4b Independently is H or 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, an ethyl group or an n-propyl group.
In the present invention, when R is 5 Is R 5a Substituted 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 tert-butyl group.
In the present invention, when R is 5b 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 methyl group or an ethyl group.
In the present invention, when R is 5b 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, 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 present invention, the monomer represented by 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 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) 30 parts of the monomer shown in the formula A, 40 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 1;
(2) 35 parts of the monomer shown in the formula A, 45 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 2;
(3) 40 parts of the monomer shown in the formula A, 48 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, 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 4;
(5) 40 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, 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 5;
(6) 30 parts of the monomer shown in the formula A, 40 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) 35 parts of the monomer shown in the formula A, 45 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) 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, 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
SaidThe monomer shown as the formula E is
Thereby obtaining a resin 9;
(10) 40 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, 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 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 monomers shown in formula A, B, C, D and E can be the conventional mass ratio in the field, such as 6:5.
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 conventional in the art, e.g. 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 solvent may be those conventional in the art, preferably 50 to 85 parts, such as 59 to 70 parts, further such as 60 parts, 69.4 parts, 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 resin and the solvent are the same as those described above.
In a preferred embodiment of the present invention, the photoresist composition comprises 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 1:5 parts PAG1, 25 parts resin 1 and 70 parts cyclohexanone;
and (3) combination 2:0.6 parts of PAG2, 30 parts of resin 2 and 69.40 parts of ethyl acetate;
and (3) combination: 5 parts of PAG2, 10 parts of resin 3 and 85 parts of ethylene glycol monomethyl ether;
and (4) combination: 5 parts PAG1, 35 parts resin 4 and 60 parts cyclohexanone;
and (3) combination 5:5 parts of PAG2, 45 parts of resin 5 and 50 parts of ethylene glycol monomethyl ether;
and (3) combination 6:5 parts of PAG1, 25 parts of resin 6 and 70 parts of ethyl acetate;
combination 7:0.6 parts of PAG2, 30 parts of resin 7 and 69.4 parts of dipropylene glycol monomethyl ether;
and (4) combination 8:3 parts of PAG1, 20 parts of resin 8 and 77 parts of dipropylene glycol monomethyl ether;
combination 9:5 parts of PAG2, 35 parts of resin 9 and 60 parts of ethyl acetate;
combination 10:5 parts of PAG2, 45 parts of resin 10 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 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 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 2.5 to 5 μm (e.g., 2.5 μm, 3.6 μm, 4.5 μm, 5.0 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 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 ring 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
) Or 2-4 ring bridged ring systems (e.g.
)。
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common 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 photoresist composition prepared by the preparation method of the invention has the advantages of difficult cracking of a glue film formed by the composition, uniform thickness, good resolution and sensitivity, good film stripping property, good shape, good rectangularity, good resolution, good heat resistance, and capability of inhibiting fluctuation phenomenon and 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. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with 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:
a monomer B:
a monomer C:
a monomer D:
a monomer E:
step 1: the monomers according to A-E in the table 1 are 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 uniformly stirred, then the mixed solution of ethyl acetate (20 g) and benzoyl peroxide (2 g) is added into the reaction kettle 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 yield 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
| Example numbering | Resin number | Photoacid generators | Solvent(s) | Weight of resin | PAG weight | Weight of solvent |
| 1 | 1 | PAG1 | Cyclohexanone | 25g | 5g | 70g |
| 2 | 2 | PAG2 | Acetic acid ethyl ester | 30g | 0.60g | 69.40g |
| 3 | 3 | PAG2 | Ethylene glycol monomethyl ether | 10g | 5g | 85g |
| 4 | 4 | PAG1 | Cyclohexanone | 35g | 5g | 60g |
| 5 | 5 | PAG2 | Ethylene glycol monomethyl ether | 45g | 5g | 50g |
| 6 | 6 | PAG1 | Ethyl acetate | 25g | 5g | 70g |
| 7 | 7 | PAG2 | Dipropylene glycol monomethyl ether | 30g | 0.60g | 69.40g |
| 8 | 8 | PAG1 | Dipropylene glycol monomethyl ether | 20g | 3g | 77g |
| 9 | 9 | PAG2 | Ethyl acetate | 35g | 5g | 60g |
| 10 | 10 | PAG2 | Ethylene glycol monomethyl ether | 45g | 5g | 50g |
| Comparative example 1 | 11 | PAG1 | Cyclohexanone | 25g | 5g | 70g |
| Comparative example 2 | 12 | PAG1 | Cyclohexanone | 25g | 5g | 70g |
| Comparative example 3 | 13 | PAG1 | Cyclohexanone | 25g | 5g | 70g |
| Comparative example 4 | 14 | PAG1 | Cyclohexanone | 25g | 5g | 70g |
| Comparative example 5 | 15 | PAG1 | Cyclohexanone | 25g | 5g | 70g |
| Comparative example 6 | 1 | PAG3 | Cyclohexanone | 25g | 5g | 70g |
| Comparative example 7 | 1 | PAG4 | Cyclohexanone | 25g | 5g | 70g |
| Comparative example 8 | 2 | PAG3 | Ethyl acetate | 30g | 0.60g | 69.40g |
| Comparative example 9 | 2 | PAG4 | Ethyl acetate | 30g | 0.60g | 69.40g |
| Comparative example 10 | 12 | PAG4 | Cyclohexanone | 25g | 5g | 70g |
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 cold plate chamber, and then exposed in an exposure machineThe wavelength is 248nm, and the exposure intensity is 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 high purity water, and drying to examine the lithography result under 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 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 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 = 4:1) in the resist pattern was evaluated as the resolution limit CD.
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 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 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 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) "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
TABLE 4
Remarking: the "/" in tables 3 and 4 indicates that no testing was performed.
As is clear from Table 3 above, the resist composition of the present invention formed a thick film free from cracking, good in film thickness uniformity (3. Sigma. Is 42 or less), less in defects, 500 to 1000nm in resolution, rectangular in cross-sectional shape, good in resolution (the space width of the resist pattern is 1.1 to 1.8 μm), good in film peeling after treatment (SABC), high in sensitivity (250 to 300 ms), strong in heat resistance (the case where deformation of the resist pattern is hardly observed), capable of suppressing the waving phenomenon, and less in impurities (the minimum can be 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 resist 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: photoacid generators, resins and solvents;
the photoacid generator is PAG1 and/or PAG2, and the structure of the photoacid generator is shown as follows:
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 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
n 1 Is any integer of 1-11;
R 2a and R 2b Independently is C 1-4 Alkyl, hydroxy-substituted C of 1-4 Alkyl, phenyl, R 2a-1 Substituted phenyl, 5-6 membered cycloalkyl or adamantyl;
R 2a-1 is C 1-4 Alkyl or C 1-4 Alkoxy group of (a);
or, R 2a And R 2b Together with the nitrogen 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);
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, n 2 Is 0 or 1;
R 4a and R 4b Independently is H or C 1-4 Alkyl groups of (a); and R is 4a And R 4b Not H at the same time;
in the formula E, R 5 Is H, cyano, C 1-4 Alkyl of R 5a Substituted C 1-4 Alkyl OR- (C = O) OR 5b ；
R 5a Is hydroxy or acetyl;
R 5b is C 1-4 Alkyl groups of (a);
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 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; the aperture of the filter membrane of the filter is 20-50nm.
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 said alkyl is substituted, said C 1-4 Alkyl of (b) is methyl;
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-1 Is C 1-4 When said alkyl is substituted, said C 1-4 Alkyl of (b) is methyl;
and/or when R 2a And R 2b Independently of the other is hydroxySubstituted C 1-4 When there is an alkyl group, said C 1-4 The alkyl group of (a) is ethyl;
and/or when R 2a-1 Is C 1-4 Alkoxy of (2), said C 1-4 Alkoxy of (a) is methoxy or n-butoxy, sec-butoxy, iso-butoxy or tert-butoxy;
and/or when R 2a And R 2b When independently 5-6 membered cycloalkyl, said 5-6 membered cycloalkyl is cyclohexyl;
and/or when R 2a And R 2b Together with the nitrogen atom to which they are attached form R 2b-1 When substituted 5-6 membered heterocycloalkyl, said 5-6 membered heterocycloalkyl is 6 membered heterocycloalkyl;
and/or when R 2a And R 2b Together with the nitrogen atom to which they are attached form R 2b-1 When the heterocyclic alkyl group is substituted by 5-6 membered heterocyclic alkyl, the heteroatom in the heterocyclic alkyl group with 5-6 membered heterocyclic is N;
and/or when R 2b-1 Is C 1-4 When said alkyl is substituted, said C 1-4 Alkyl of (a) is methyl, n-butyl, sec-butyl, isobutyl or tert-butyl;
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 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 said alkyl is substituted, said C 1-5 Alkyl of (A) is ethyl or
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
And/or when R 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, said 5-7 membered cycloalkenyl group is cyclopentenyl;
and/or when R 4a And R 4b Independently is H or C 1-4 When said alkyl is substituted, said C 1-4 Alkyl of (a) is methyl, ethyl or n-propyl;
and/or when R 5 Is R 5a Substituted 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 5b Is C 1-4 When said alkyl is substituted, said C 1-4 The alkyl group of (a) is a methyl group.
5. The method 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
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 when R 2a And R 2b When taken together with the nitrogen atom to which they are attached form a 5-6 membered heterocycloalkyl group, said 5-6 membered heterocycloalkyl group is
And &Or, when R is 2a And R 2b Together with the nitrogen 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
6. The method of claim 5, 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
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 photoacid generator is used in an amount of 0.6 to 5.5 parts;
and/or, the part of the resin is 10-45 parts;
and/or the weight average molecular weight of the resin is 5000-18000;
and/or the polymer dispersity index of the resin is 1.4-2.1;
and/or the part of the monomer shown in the formula A is 20-55 parts;
and/or the part of the monomer shown as the formula B is 35-65 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 in the formula E is 5-10 parts;
and/or, the part of the solvent is 50-85 parts;
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:
and/or the solvent is one or more of ketone solvent, ester solvent and ether solvent.
8. The method according to claim 7, wherein the photoacid generator is used in an amount of 3 to 5 parts;
and/or, the part of the resin is 20-35 parts;
and/or the part of the monomer shown in the formula A is 30-40 parts;
and/or the part of the monomer shown as the formula B is 35-50 parts;
and/or the part of the monomer shown in the formula C is 10-20 parts;
and/or, the part of the solvent is 59-70 parts;
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 E is any one of the following compounds:
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) 30 parts of the monomer shown in the formula A, 40 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 1;
(2) 35 parts of the monomer shown in the formula A, 45 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 2;
(3) 40 parts of the monomer shown in the formula A, 48 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, 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 4;
(5) 40 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, 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 5;
(6) 30 parts of the monomer shown in the formula A, 40 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) 35 parts of the monomer shown in the formula A, 45 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) 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, 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 9;
(10) 40 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, 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 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 1:5 parts PAG1, 25 parts resin 1 and 70 parts cyclohexanone;
and (3) combination 2:0.6 parts of PAG2, 30 parts of resin 2 and 69.40 parts of ethyl acetate;
and (3) combination: 5 parts of PAG2, 10 parts of resin 3 and 85 parts of ethylene glycol monomethyl ether;
and (4) combination: 5 parts PAG1, 35 parts resin 4 and 60 parts cyclohexanone;
and (3) combination 5:5 parts of PAG2, 45 parts of resin 5 and 50 parts of ethylene glycol monomethyl ether;
and (4) combination 6:5 parts of PAG1, 25 parts of resin 6 and 70 parts of ethyl acetate;
combination 7:0.6 parts of PAG2, 30 parts of resin 7 and 69.4 parts of dipropylene glycol monomethyl ether;
and (4) combination 8:3 parts of PAG1, 20 parts of resin 8 and 77 parts of dipropylene glycol monomethyl ether;
combination 9:5 parts of PAG2, 35 parts of resin 9 and 60 parts of ethyl acetate;
combination 10:5 parts of PAG2, 45 parts of resin 10 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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| US6927009B2 (en) * | 2001-05-22 | 2005-08-09 | Fuji Photo Film Co., Ltd. | Positive photosensitive composition |
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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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