Resist composition, method for preparing photoacid generator, and method for forming pattern

Abstract

Disclosed are a resist composition comprising a first photoacid generator represented by formula (1), a base resin, a fluorine-containing resin, a quencher, and 0-1.0 part by mass of a second photoacid generator represented by formula (2), and a pattern forming method which ultimately obtains a resist pattern with improved sensitivity and LWR.

Description

Technical Field

[0001] This invention relates to the field of chemically amplified photoresists, and more specifically, to a photoresist composition, a method for preparing a photoacid generator, and a patterning method. Background Technology

[0002] In the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), photolithography is used for microfabrication by employing photoresist compositions. Photoresist materials used in the photolithography process typically consist of photosensitive resin, photoacid generator, quencher, and solvent. The photoacid generator is one of the main components of chemically amplified photoresists; it is a substance that decomposes under light to produce acid (H₂O). + The photosensitive compound is exposed to light through methods such as excimer laser, electron beam, or extreme ultraviolet light. The acid-generating agent in the exposed area decomposes to produce a strong acid. Through post-exposure baking (PEB), this acid acts as a catalyst, causing the unstable acid groups in the photosensitive resin to detach, thus altering the resin's polarity. The resin in the exposed area becomes readily soluble in an alkaline developer, and the resulting pattern is obtained through development.

[0003] Besides developing new photolithography processes and chemically amplifying photoresists, researching and improving photoacid generators is also crucial to meeting the rapid advancements in current microfabrication technologies. Commonly used photoacid generators include triphenylthionium cations, diphenyliodonium cations, and perfluoroalkyl sulfonic acid anions. These onionium salts have a wide diffusion range in photoresists, causing LWR and photosensitivity to fail to meet performance requirements.

[0004] Therefore, it is necessary to develop a novel photoacid-generating agent and its preparation method to solve the problems of LWR and photosensitivity in traditional photoresist compositions. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides a photoresist composition comprising 1 to 10 parts by weight of a first photoacid generator as shown in formula (1), 80 to 100 parts by weight of a base resin, 1.0 to 10 parts by weight of a fluorinated resin, 1 to 5 parts by weight of a quencher, and 0 to 1.0 parts by weight of a second photoacid generator as shown in formula (2).

[0006]

[0007] Among them, R1, R2, and R3 are each independently selected from C1-C atoms substituted with heteroatoms or heteroatom-containing groups. 30a C1-C8 linear, branched or cyclic hydrocarbon group containing a heteroatom group, and R 51 , R 52 , R 53 , R 54 are each independently a hydrogen atom, a fluorine atom or a fluoroalkyl group, and R 51 , R 52 , R 53 , R 54 are each independently a hydrogen atom, a fluorine atom or a fluoroalkyl group, and R 30 at least two of R 30 are fluorine-containing groups;

[0008] Formula (2)

[0009] wherein R6, R7, R8, R9are each independently selected from a hydrogen atom, or a C1-C 101 monovalent hydrocarbon group, or a C1-C 102 monovalent hydrocarbon group substituted with a heteroatom or a heteroatom-containing group, and R 103 , R 104 , R 105 , R 106 are each independently a hydrogen atom, a fluorine atom or a fluoroalkyl group;

[0010] Further, said R1, R2, R3are each independently a C4-C 30 monovalent cyclic group containing an oxygen atom;

[0011] Preferably, said R1, R2, R3are each independently a C 10 -C 30 monovalent cyclic group containing an oxygen atom;

[0012] Further, said second photoacid generator is:

[0013] ;

[0014] Further, said R1, R2, R3are each independently selected from the following structural formulae:

[0015] ;

[0016] Preferably, said R1, R2, R3are each independently selected from the following structural formulae:

[0017] ;

[0018] More preferably, said R1, R2, R3are each independently selected from the following structural formulae:

[0019] ;

[0020] Further, each of the R4 is independently one or both of an amino group, a methylene group, in combination;

[0021] Preferably, the R4 is a methylene group;

[0022] Further, the base resin comprises a repeating unit having formula (a) and a repeating unit having formula (b):

[0023]

[0024] wherein G1 and G4 are each independently hydrogen, fluorine, methyl or trifluoromethyl, G2 and G5 can be a single bond, a phenylene group, a naphthylene group, G3 is an acid labile group, and G6 is hydrogen or a polar group comprising at least one structure selected from the group consisting of a hydroxyl group, a cyano group, a carbonyl group, a carboxyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate ester bond, a lactone ring, a sultone ring and a carboxylic anhydride;

[0025] The fluorine-containing resin comprises the following general structure:

[0026]

[0027] wherein R1, R2 are fluoroalkyl groups, R3 is a C1-C20 monovalent hydrocarbon group which can contain a heteroatom-containing group; 30

[0028] Further, the base resin comprises a monomer synthesized from:

[0029] A1, A2, A3, A4, A5

[0030] The fluorine-containing resin is:

[0031] ;

[0032] Further, the resist composition comprises 1 ~ 10 parts by mass of a first photoacid generator represented by formula (1), 80 ~ 100 parts by mass of a base resin, 1.0 ~ 10 parts by mass of a fluorine-containing resin, 1 ~ 5 parts by mass of a quencher and 0.01 ~ 1 parts by mass of a second photoacid generator represented by formula (2).

[0033] The second aspect of the present application provides a pattern forming method, the method comprising the steps of:

[0034] S1, applying the resist composition of the first aspect of the present application to a substrate, baking to form a resist film;​

[0035] S2, exposing selected regions of the resist film to a KrF excimer laser, an ArF excimer laser, EB, or EUV;

[0036] S3, developing the exposed resist film with a developer.

[0037] Advantages:

[0038] (1) The present application proposes a resist composition comprising a first photoacid generator represented by formula (1), the molecular type photoacid generator is grafted with side groups, the flexible side groups have good compatibility with the resin, which can better reduce the acid diffusion length, and thus form a resist pattern with improved photosensitivity and LWR. Further, the long chain side group with a cyclic group can reduce the entanglement of the photoacid generator with the resin chain, the side group with oxygen atom has good compatibility, and the photoacid generator is not easy to aggregate in the resist composition, which can further improve the photosensitivity and LWR performance of the resist pattern;

[0039] (2) The photosensitive group and the acid precursor group of the molecular type photoacid generator are connected by one or more combinations of C1-C8 linear, branched or cyclic hydrocarbon groups containing heteroatom groups, which improves the photosensitivity and LWR performance of the resist pattern; further preferred connecting groups are one or a combination of amino or methylene, which can further improve the photosensitivity and LWR performance of the resist pattern;

[0040] (3) The resist composition can further comprise a second photoacid generator, which can better balance the acid diffusion. DETAILED DESCRIPTION

[0041] The technical solutions in the embodiments of the present application will be described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0042] <Resist composition>

[0043] The resist composition in the present application comprises 80 ~ 100 mass parts of base resin, 1 ~ 10 mass parts of fluorine-containing resin, 1 ~ 10 mass parts of first photoacid generator, 0 ~ 1.0 mass parts of second photoacid generator, 1 ~ 5 mass parts of quenching agent and 2000 ~ 3000 mass parts of organic solvent.

[0044] Base resin

[0045] The base resin contains a polymer comprising repeating units having formula (a) and repeating units having formula (b):

[0046]

[0047] G1and G4are each independently hydrogen, fluorine, methyl or trifluoromethyl, G2and G5may be a single bond, phenylene, naphthylene, G3is an acid-labile group, and G6is hydrogen or a polar group comprising at least one structure selected from the group consisting of a hydroxyl group, a cyano group, a carbonyl group, a carboxyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate ester bond, a lactone ring, a sultone ring, and a carboxylic anhydride.

[0048] The repeating unit of formula (a) accounts for 40 to 60% of the total polymer, and the repeating unit of formula (b) accounts for 40 to 60% of the total polymer.

[0049] The base resin is synthesized from monomers including:

[0050] A1, A2, A3, A4, A5.

[0051] Fluorine-containing resin

[0052] The resist composition of the present application further comprises a fluorine-containing resin represented by the following formula:

[0053]

[0054] wherein R1, R2are fluoroalkyl groups, and R3is a C1-C 30 monovalent hydrocarbon group which can contain a heteroatom-containing group.

[0055] An exemplary fluorine-containing resin is:

[0056] .

[0057] Photoacid generator

[0058] The resist composition comprises a first photoacid generator represented by the following formula (1):

[0059]

[0060] wherein R1, R2, R3are each independently selected from the group consisting of a C1-C 30a monovalent hydrocarbon group, and R1, R2, R3 do not contain carbon-carbon double bond, R4, R5 are each independently one or more combinations of a heteroatom-containing C1-C8 linear, branched or cyclic hydrocarbon group, R 51 , R 52 , R 53 , R 54 are each independently a hydrogen atom, a fluorine atom or a fluoroalkyl group, and R 51 , R 52 , R 53 , R 54 at least two of which are fluorine-containing groups.

[0061] The molecular photoacid generator is grafted with side groups, the flexible side groups have good compatibility with the resin, and the acid diffusion length can be reduced, so that the resist pattern with improved photosensitivity and LWR is formed.

[0062] Preferably, R1, R2, R3 are each independently a C4-C 30 monovalent cyclic group containing an oxygen atom, and further preferably, R1, R2, R3 are each independently a C 10 -C 30 monovalent cyclic group containing an oxygen atom. The C4-C 30 monovalent cyclic group containing an oxygen atom includes a C4-C 30 monovalent cyclic group containing an ether bond or an ester group. The C 10 -C 30 monovalent cyclic group containing an oxygen atom includes a C 10 -C 30 monovalent cyclic group containing an oxygen atom. The side group with a long chain of cyclic group can reduce the entanglement of photoacid generator and resin chain, the group with hydroxyl or ether bond has good compatibility, and the photoacid generator is not easy to aggregate in the resist composition, which can further improve the photosensitivity and LWR performance of the resist pattern.

[0063] Illustratively, R1, R2, R3 are each independently selected from the following structural formulae:

[0064] .

[0065] Preferably, R1, R2, R3 are each independently selected from the following structural formulae:

[0066] .

[0067] Further preferably, R1, R2, R3 are each independently selected from the following structural formulae:

[0068] .

[0069] R4, R5 are each independently one or more combinations of heteroatom-containing C1-C8 linear, branched or cyclic hydrocarbon groups, preferably R4 is one or both combinations of amino, methylene, further preferably R4 is methylene. The connection between the photosensitive group and the acid precursor group of the molecular photoacid generator through one or more combinations of heteroatom-containing C1-C8 linear, branched or cyclic hydrocarbon groups improves the photosensitivity and LWR performance of the resist pattern; preferably the connecting group is one or both combinations of amino or methylene, further preferably the connecting group is methylene, which can further improve the photosensitivity and LWR performance of the resist pattern.

[0070] Illustratively, the first photoacid generator of formula (1) includes the following structures:

[0071] PAG-1 PAG-2

[0072] PAG-3 PAG-4

[0073] PAG-5 PAG-6

[0074] PAG-7 PAG-8

[0075] PAG-9 PAG-10

[0076] The resist composition further includes 0 ~ 1.0 parts by mass of a second photoacid generator of formula (2) below, further preferably 0.01 ~ 1.0 parts by mass of a second photoacid generator of formula (2) below, which can better balance acid diffusion:

[0077] Formula (2)

[0078] wherein R6, R7, R8, R9 are each independently selected from a hydrogen atom, or a C1-C 30 monovalent hydrocarbon group, or a C1-C 30 monovalent hydrocarbon group substituted with a heteroatom or a heteroatom-containing group, R 101 , R 102 , R 103 , R 104 , R 105 , R 106 are each independently a hydrogen atom, a fluorine atom or a fluoroalkyl group.

[0079] The preferred second photoacid generator is:

[0080] .

[0081] Quencher

[0082] The resist composition can further comprise a quencher, which has the main function of neutralizing and controlling the diffusion of photo-generated acid. It can effectively capture and neutralize the excess acid molecules diffused to the unexposed area or the boundary area which should not react, thereby inhibiting unnecessary acid diffusion reaction, ensuring the accuracy and clarity of the pattern profile, and ultimately achieving the purpose of improving the photosensitivity and reducing the line edge roughness. The selection of the quencher includes but is not limited to small molecule bases such as aliphatic amines, aromatic amines, nitrogen-containing heterocyclic compounds, ammonium hydroxide salts, photodegradable bases such as carboxylic acid ammonium salts, carbamate compounds, polymers, etc. Quenchers that can be listed are .

[0083] Organic solvent

[0084] The solvent in the resist composition can be selected from propylene glycol ether acetate such as propylene glycol methyl ether acetate (PGMEA), lactate such as ethyl lactate, ketone such as cyclohexanone, ether such as propylene glycol methyl ether (PGME). In the resist composition of the present application, PGME is often used in combination with PGMEA, which plays a role in adjusting the evaporation rate and improving the leveling property.

[0085] Other components

[0086] The resist composition can further comprise a surfactant that is insoluble or substantially insoluble in water and soluble in an alkaline developer, and / or a surfactant that is insoluble or substantially insoluble in water and an alkaline developer, and other substances.

[0087] <Method for preparing the first photoacid generator>

[0088] The method for preparing the first photoacid generator represented by formula (1) comprises the following steps:

[0089]

[0090] wherein R1, R2, R3, R4, R5, R 51 , R 52 , R 53 , R 54 have the same definition as in formula (1), X is a halogen element, and M + is a metal ion;

[0091] S1, under the protection of an inert gas, a compound q dissolved in an organic solvent is added to a bottle, and an appropriate amount of an organic base is added under stirring to obtain a mixed solution K-1;

[0092] S2, dissolving compound p in an organic solvent under the protection of inert gas to obtain a mixed solution K-2;

[0093] S3, adding the mixed solution K-2 to the mixed solution K-1 at a temperature of -10 ~ 10℃ to obtain a reaction solution including the first photoacid generator shown in formula (1) through esterification reaction.

[0094] The organic base in step S1 includes one or more combinations of pyridine, triethylamine, diisopropylethylamine, and 1,8-diazabicycloundec-7-ene.

[0095] Preferably, the operation steps of the synthesis route further include at least one of the following process technical features:

[0096] 1) the molar ratio of compound p to compound q is 1:0.6 to 1:5;

[0097] 2) in step S1, the molar ratio of compound q to organic base is 1:1 to 1:10;

[0098] 3) the inert gas in steps S1 and S2 is at least one selected from argon, nitrogen, and helium;

[0099] 4) the organic solvent in steps S1 and S2 is one selected from dichloromethane, acetonitrile, tetrahydrofuran, 1,4-dioxane, N.N-dimethylformamide, and pyridine;

[0100] 5) the specific step in step S3 is: controlling the temperature at -5 ~ 5℃, adding the mixed solution K-2 dropwise into the mixed solution K-1 to obtain a mixed solution, and after the dropwise addition is completed, stirring at 20 ~ 35℃ for 1 ~ 12 hours until the reaction is completed.

[0101] The purification step after the operation steps of the esterification reaction synthesis route is:

[0102] a1) after the reaction is completed, quenching in the reaction solution by adding saturated sodium bicarbonate;

[0103] a2) reducing pressure to concentrate the solution obtained in step a1), and then dissolving the obtained solid in ethyl acetate;

[0104] a3) washing the solution obtained in step a2) with deionized water, reducing pressure to obtain a solid, and then beating or recrystallizing to obtain the compound shown in formula (1).

[0105] <Pattern forming method>

[0106] The method for forming a pattern using the above-mentioned resist composition includes the following steps:

[0107] S1, the above-mentioned resist composition is applied to a substrate, and baked to form a resist film;

[0108] S2, a selected area of the resist film is exposed to a KrF excimer laser, an ArF excimer laser, an EB, or an EUV;

[0109] S3, the exposed resist film is developed with a developer.

[0110] The above and other advantages of the present application will become more apparent by describing the following embodiments of the present application, which are not intended to limit the scope of the present application.

[0111] EMBODIMENT

[0112] The following examples are given to illustrate the present application, but the present application is not limited by the following examples.

[0113] Synthesis Example 1, synthesis of PAG-1

[0114] S1, synthesis of intermediate II-1

[0115]

[0116] At 0°C, 1.0 eq of compound I (Shanghai Haohong Biomedical Science and Technology Co., Ltd.) was dissolved in 2V of tetrahydrofuran, and was added dropwise to a 5V tetrahydrofuran solution containing a catalytic amount of iodine and 1.5 eq of magnesium turnings. The reaction was allowed to react at room temperature overnight, and then the reaction solution was added to a 0°C saturated ammonium chloride solution. 3V of ethyl acetate was added, the organic layer was separated and concentrated under reduced pressure to obtain an oily product II-1.

[0117] S2, synthesis of intermediate III

[0118]

[0119] Under nitrogen protection, 1.0 eq of compound II-2 (Suzhou Yuanqi Material Technology Co., Ltd.) was dissolved in 5V of tetrahydrofuran, and 1.5 eq of intermediate II-1 was added dropwise to the solution under ice bath. The reaction was allowed to react at room temperature overnight, and then the reaction solution was added to a 0°C saturated ammonium chloride solution. 3V of ethyl acetate was added, the organic layer was separated and concentrated under reduced pressure to obtain a white solid. Diisopropyl ether was added to the product, the precipitated solid was filtered and dried in vacuum to obtain a white crystalline sulfonium compound III.

[0120] S3, synthesis of intermediate IV

[0121]

[0122] To a solution of 1.0 eq of intermediate III in 5 V of tetrahydrofuran at 0 °C was added dropwise a solution of 1.1 eq of sodium hydride in 2 V of tetrahydrofuran. The reaction was allowed to proceed overnight at room temperature, then the reaction was added to a solution of 1.0 eq of 2-adamantanol and 1.2 eq of pyridine in 5 V of tetrahydrofuran at 0 °C. The reaction was allowed to proceed overnight at room temperature, then the reaction was added to a solution of saturated ammonium chloride at 0 °C. 3 V of ethyl acetate was added, the organic layer was separated and concentrated under reduced pressure to give the product as an oil. Diisopropyl ether was added to the product, the precipitated solid was filtered and dried under vacuum to give the sulfonium compound IV as a white crystalline solid.

[0123] S4, synthesis of intermediate V:

[0124]

[0125] To a solution of 1.0 eq of intermediate IV in 8 V of deionized water and 2 V of methanol at room temperature was added 1.2 eq of sodium hydroxide. The reaction was allowed to proceed overnight at room temperature, then the reaction was concentrated under reduced pressure to give a solution of V in water. The reaction was then adjusted to pH 2 with a 3 M solution of hydrochloric acid, the precipitated white solid was filtered and dried under vacuum to give the sulfonium compound V as a white solid.

[0126] S5, synthesis of intermediate VI:

[0127]

[0128] To a solution of 1.0 eq of intermediate V in 5 V of dichloromethane at less than 5 °C was added dropwise a solution of 3.0 eq of oxalyl chloride in 2 V of dichloromethane. The reaction was allowed to proceed overnight at room temperature, then the reaction was concentrated under reduced pressure to give the product VI as an oil.

[0129] S6, synthesis of PAG-1:

[0130]

[0131] To a solution of 1.0 eq of intermediate IV in 5 V of tetrahydrofuran at less than 5 °C was added dropwise a solution of 1.1 eq of sodium 1,1,2,2-tetrafluoro-4- hydroxybutane-1-sulfonate (Suzhou Yuanqi Material Technology Co., Ltd.) and 2.0 eq of pyridine in 5 V of tetrahydrofuran. The reaction was allowed to proceed overnight at room temperature, then the reaction was diluted with deionized water, the organic phase was separated and concentrated under reduced pressure to give a white solid. Diisopropyl ether was added to the product, the precipitated solid was filtered and dried under vacuum to give the sulfonium compound PAG-1 as a white crystalline solid.

[0132] Synthesis example 2, synthesis of PAG-2

[0133] The compound II-2 in the synthesis example 1 S2 was changed to 4-sulfinylfluorobenzene (Shanghai Bide Pharmaceutical Technology Co., Ltd.), the 2-adamantanol in the synthesis example 1 S3 was changed to dehydrocholic acid (Sigma-Aldrich Shanghai Trading Co., Ltd.), and other steps were the same as the raw material and synthesis example 1, to obtain PAG-2 of the following formula.

[0134] PAG-2

[0135] Synthesis example 3, synthesis of PAG-3

[0136] The 2-adamantanol in the synthesis example 1 S3 was changed to acetic acid (Sigma-Aldrich Shanghai Trading Co., Ltd.), and other steps were the same as the raw material and synthesis example 1, to obtain PAG-3 of the following formula.

[0137] PAG-3

[0138] Synthesis example 4, synthesis of PAG-4

[0139] The compound II-2 in the synthesis example 1 S2 was changed to 4,4'-sulfinylbis(fluorobenzene), the 2-adamantanol in the synthesis example 1 S3 was changed to methoxyacetic acid, and the 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate in the synthesis example 1 S6 was changed to 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sodium sulfonate (Shao Yuan Technology (Shanghai) Co., Ltd.), and other steps were the same as the raw material and synthesis example 1, to obtain PAG-4 of the following formula.

[0140] PAG-4

[0141] Synthesis example 5, synthesis of PAG-5

[0142] The compound II-2 in the synthesis example 1 S2 was changed to 4,4'-sulfinylbis(fluorobenzene), the 2-adamantanol in the synthesis example 1 S3 was changed to 1-adamantane carboxylic acid (Shanghai Haohong Biological Medicine Technology Co., Ltd.), and the 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sodium sulfonate in the synthesis example 1 S6 was changed to 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sodium sulfonate, and other steps were the same as the raw material and synthesis example 1, to obtain PAG-5 of the following formula.

[0143] PAG-5

[0144] Synthesis example 6, synthesis of PAG-6

[0145] The compound II-2 in Synthesis Example 1 S2 was changed to 4,4'-sulfinylbis(fluorobenzene), 2-adamantanole in Synthesis Example 1 S3 was changed to 1,1,1,3,3,3-hexafluoropropan-2-ol (Shanghai Hao Hong Biological Medicine Science and Technology Co., Ltd.), 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid sodium in Synthesis Example 1 S6 was changed to 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonic acid sodium, and other steps were the same as those in Synthesis Example 1 to obtain PAG-6 of the following formula.

[0146] PAG-6

[0147] Synthesis Example 7, synthesis of PAG-7

[0148] 2-adamantanole in Synthesis Example 1 S3 was changed to 2-hydroxyethylcyclohexanecarboxylate (Shaanxi DeDu New Material Co., Ltd.), 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid sodium in Synthesis Example 1 S6 was changed to 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonic acid sodium, and other steps were the same as those in Synthesis Example 1 to obtain PAG-7 of the following formula.

[0149] PAG-7

[0150] Synthesis Example 8, synthesis of PAG-8

[0151] The compound II-2 in Synthesis Example 1 S2 was changed to 4,4'-sulfinylbis(fluorobenzene), 2-adamantanole in Synthesis Example 1 S3 was changed to 4-hydroxydihydrofuran-2(3H)-one (Shanghai Bide Pharmaceutical Technology Co., Ltd.), 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid sodium in Synthesis Example 1 S6 was changed to 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonic acid sodium, and other steps were the same as those in Synthesis Example 1 to obtain PAG-8 of the following formula.

[0152] PAG-8

[0153] Synthesis Example 9, synthesis of PAG-9

[0154] The compound I in Synthesis Example 1 S1 was changed to 3-bromophenyl carbamate (Shanghai Bide Pharmaceutical Technology Co., Ltd.), and other steps were the same as those in Synthesis Example 1 to obtain PAG-9 of the following formula.

[0155] PAG-9

[0156] Synthesis Example 10, synthesis of PAG-10

[0157] The compound I in Synthesis Example 1 S1 was changed to 3-bromophenyl ethyl methyl carbonate (Shanghai Bide Pharmaceutical Technology Co., Ltd.), and the other steps were the same as the raw material and synthesis example 1, to obtain PAG-10 of the following formula.

[0158] PAG-10

[0159] Synthesis Example 11, synthesis of base resin

[0160] A1, A2, A3, A4, A5

[0161] Copolymer P-1 was prepared from monomers A1 (Shanghai Daran Chemical Co., Ltd.), A2 (Shanghai Bide Pharmaceutical Technology Co., Ltd.), A3 (Shanghai Haohong Biological Pharmaceutical Technology Co., Ltd.), A4 (Shanghai Huawnix New Material Technology Co., Ltd.), A5 (Xi'an Ruilian New Material Co., Ltd.) in a molar feed ratio of 10 / 10 / 40 / 30 / 10. A feed solution was prepared by dissolving A1 (10 g, 42.3 mmol), A2 (7.2 g, 42.3 mmol), A3 (37.6 g, 169.3 mmol), A4 (24.9 g, 127.0 mmol), A5 (12.2 g, 42.3 mmol), and 7.5 g of azo initiator dimethyl 2,2'-azobis(2-methylpropanoate) (obtained as V-601 from Wako Chemicals USA) in 307 g of butanone, and a three-necked round-bottom flask equipped with a water condenser and a thermometer was charged with 153 g of butanone and the temperature was raised to 65 °C. The feed solution was supplied to the reactor using a syringe pump over a period of 4 hours, followed by a further 2 hours at 65 °C. The contents were cooled to room temperature, diluted to 25 wt% with tetrahydrofuran, and precipitated into a 10-fold (by weight) mixture of heptane and methanol in a 7:3 (w / w) ratio. The resulting copolymer P1 was isolated by filtration and dried under vacuum at 50 °C for 24 hours.

[0162] Fluorine-containing resin P-2 was used in combination with copolymer P-1, and fluorine-containing resin P-2 is as follows:

[0163] P-2

[0164] In addition to the first photoacid generators PAG-1~10 obtained by the above synthesis examples, other photoacid generators used in the examples and comparative examples are as follows:

[0165] PAG-11

[0166] PAG-A

[0167] PAG-B

[0168] PAG-C

[0169] PAG-D

[0170] PAG-E

[0171] PAG-F

[0172] PAG-G

[0173] Quenchers are as follows:

[0174] Q-1

[0175] Example 1

[0176] The resist composition in each example contains 80.0 parts by mass of copolymer P-1, 2.0 parts by mass of fluorine-containing resin P-2, 1.0 part by mass of quencher Q-1, 1600 parts by mass of PGMEA, and 400 parts by mass of PGME.

[0177] The specific components and ratios of the various resist compositions are shown in the following table.

[0178] Table 1

[0179]

[0180] The above-described resist compositions were subjected to ArF lithography testing: On a silicon substrate, an antireflection coating solution (ARC29A, Nissan Chemical Corp.) was applied and baked at 200°C for 60 seconds to form a 100-nm-thick ARC. Each resist composition was spin-coated on the ARC and prebaked on a hot plate at 100°C for 60 seconds to form a 95-nm-thick photoresist film on the ARC. The resist film was exposed by ArF excimer laser immersion lithography using an ArF immersion lithography scanner (NSR-610C, Nikon Corp., NA 1.30, dipole illumination, Cr mask). Water was used as the immersion liquid. The resist film was baked (PEB) at 90°C for 60 seconds and developed in a 2.38% by weight aqueous TMAH solution for 60 seconds.

[0181] Sensitometric evaluation

[0182] A 40 nm 1 : 1 line-space pattern was observed under SEM. The best dose (Eop) was the dose (mJ / cm2) that provided a line width of 40 nm. The pattern printed at the best dose was observed to determine if the profile was acceptable. 2 ) The pattern printed at the best dose was observed to determine if the profile was acceptable.

[0183] Line width roughness (LWR) evaluation

[0184] The width of the lines of a 40 nm 1 : 1 line-space pattern was measured under SEM to determine the line width variation (30 points were measured and the 3 sigma value was calculated), denoted as LWR. The smaller the LWR value, the less fluctuation in the line pattern and the better the profile.

[0185] The results of the above performance tests in the examples and comparative examples are shown in Table 2 below:

[0186] Table 2

[0187]

[0188] It should be noted that the above-mentioned embodiments can be changed and modified by those skilled in the art according to the explanations and elaborations in the above description. Therefore, the present application is not limited to the specific embodiments disclosed and described above, and some equivalent modifications and changes of the present application should be within the scope of protection of the claims of the present application. In addition, although some specific terms are used in the present description, these terms are only for convenience of explanation and do not constitute any limitation on the application.

Claims

1. A corrosion resist composition, characterized in that, The photoresist composition comprises 1 to 10 parts by weight of a first photoacid generator as shown in formula (1), 80 to 100 parts by weight of a base resin, 1 to 10 parts by weight of a fluorinated resin, 1 to 5 parts by weight of a quencher, and 0 to 1.0 parts by weight of a second photoacid generator as shown in formula (2). Among them, R1, R2, and R3 are each independently selected from C1-C atoms substituted with heteroatoms or heteroatom-containing groups. 30 The monovalent hydrocarbon group, wherein R1, R2, and R3 do not contain carbon-carbon double bonds, and R4 and R5 are each independently one or more combinations of straight-chain, branched, or cyclic hydrocarbon groups of C1-C8 containing heteroatoms. 51 R 52 R 53 R 54 Each is independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and R 51 R 52 R 53 R 54 At least two of them are fluorine-containing groups; Equation (2) Among them, R6, R7, R8, and R9 are each independently selected from hydrogen atoms, or C1-C atoms. 30 Monovalent hydrocarbon group, or C1-C substituted by heteroatoms or heteroatom-containing groups. 30 monovalent hydrocarbon group, R 101 R 102 R 103 R 104 R 105 R 106 Each atom is a hydrogen atom, a fluorine atom, or a fluorinated alkyl group.

2. The resist composition according to claim 1, characterized in that, R1, R2, and R3 are each independently a C4-C structure containing oxygen atoms. 30 The monovalent cyclic group, preferably R1, R2, and R3, is each independently a carbon atom containing an oxygen atom. 10 -C 30 Monovalent cyclic groups.

3. The resist composition according to claim 2, characterized in that, The second photoacid-generating agent is: 。 4. The resist composition according to claim 1, characterized in that, R1, R2, and R3 are each independently selected from the following structural formulas: Preferably, R1, R2, and R3 are each independently selected from the following structural formulas: Further preferably, R1, R2, and R3 are each independently selected from the following structural formulas: 。 5. The resist composition according to claim 1, characterized in that, R4 is one or a combination of amino and methylene, preferably methylene.

6. The resist composition according to claim 1, characterized in that, The base resin comprises repeating units having formula (a) and repeating units having formula (b): Wherein, G1 and G4 are each independently hydrogen, fluorine, methyl or trifluoromethyl, G2 and G5 can be single bonds, phenylene, naphthylene, G3 is an acid-unstable group, and G6 is hydrogen or a polar group containing at least one structure selected from the group consisting of hydroxyl, cyano, carbonyl, carboxyl, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulopentalide ring and carboxylic anhydride. The fluorinated resin includes the following general structural formula: Wherein, R1 and R2 are fluoroalkyl groups, and R3 is a C1-C group that may contain heteroatomic groups. 30 Monovalent hydrocarbon group.

7. The resist composition according to claim 6, characterized in that, The monomers used to synthesize the base resin include: A1, A2, A3, A4 A5.

8. The resist composition according to claim 6, characterized in that, The fluorinated resin is: 。 9. The resist composition according to claim 1, characterized in that, The photoresist composition comprises 1 to 10 parts by weight of a first photoacid generator of formula (1), 80 to 100 parts by weight of a base resin, 1.0 to 10 parts by weight of a fluorinated resin, 1 to 5 parts by weight of a quencher, and 0.01 to 1 part by weight of a second photoacid generator of formula (2).

10. A method for forming a pattern, characterized in that, The method includes the following steps: S1, applying the resist composition according to any one of claims 1 to 9 onto a substrate and baking to form a resist film; S2, expose a selected area of ​​the resist film to a KrF excimer laser, an ArF excimer laser, an EB laser, or an EUV laser; S3, develop the exposed resist film with a developer.

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