Organic silicon polymer and silicon-containing bottom anti-reflection coating composition as well as preparation method and application of organic silicon polymer and silicon-containing bottom anti-reflection coating composition

Abstract

The invention belongs to the technical field of photoetching materials, and particularly relates to an organosilicon polymer and silicon-containing bottom anti-reflection coating composition as well as a preparation method and application thereof. The organosilicon polymer comprises a first structural unit derived from a monomer A1 as shown in a formula (1), a second structural unit derived from a monomer A2 as shown in a formula (2), and an optional third structural unit derived from a siloxane monomer A3 as shown in a formula (3). The key of the invention lies in that the cyano-containing organosilicon polymer with a specific structure is designed and synthesized, the cyano-containing organosilicon polymer is used as a raw material of the bottom anti-reflection coating composition to form the anti-reflection film, and due to the introduction of cyano, the hydrophilicity of the anti-reflection film is reduced, the adhesion of the anti-reflection film to the surface of photoresist is improved, and the anti-reflection effect is improved. Meanwhile, the anti-reflection film is stable in film thickness, good in anti-reflection performance and high in etching rate, developed photoresist patterns are not prone to collapse, the forming effect is good, and the application prospect in semiconductor device machining is good. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of photolithography materials, and in particular relates to an organic silicon polymer and a silicon-containing bottom anti-reflective coating composition, and a preparation method and application thereof. Background Art

[0002] In the process of manufacturing semiconductor devices, photolithography technology using photoresist is used to micro-process semiconductor components. At present, chemically amplified photoresists are usually used in photolithography technology to obtain photoresist patterns with different precisions. The exposure light source has gradually changed from KRF excimer laser (248nm) to ARF excimer laser (193nm), F2 excimer (157nm), extreme ultraviolet laser (EUV), electron light, X-ray and other short-wavelength light sources. The use of short-wavelength exposure light sources can increase the fineness of the photoresist pattern.

[0003] During exposure, since light will shine on the semiconductor substrate through the photoresist, some reflected light will be generated at the interface between the photoresist and the substrate. These reflected lights will interfere with the incident light to form a standing wave effect on the photoresist pattern, affecting the formation effect of the photoresist pattern. The prior art often solves the problem of the standing wave effect by using an anti-reflective coating at the bottom of the photoresist. The anti-reflective coating generally has the following characteristics: a certain absorbance to the exposure light source, no mutual dissolution with the photoresist, stable performance, and an etching speed greater than the etching speed of the photoresist. Among them, the organosilicon anti-reflective coating has a higher etching rate, which can eliminate the standing wave phenomenon in the photolithography process. It is generally used in combination with spin-on carbon (SOC) to obtain ultra-fine size photoresist patterns, but this type of silicon-containing polymer has poor storage stability, unstable film thickness during actual use, and poor adhesion to the photoresist. The photoresist pattern formed above this type of anti-reflective coating will not be vertical, tailing, etc. Summary of the invention

[0004] The purpose of the present invention is to provide an organosilicon polymer and a silicon-containing bottom anti-reflective coating composition and a preparation method and application thereof to address the problems of poor film thickness stability and poor adhesion of the anti-reflective coating formed with the photoresist in the prior art, which affects the photoresist pattern formation effect.

[0005] In a first aspect, the present invention provides an organosilicon polymer, the organosilicon polymer comprising a structural unit 1 derived from a monomer A1 represented by formula (1), a structural unit 2 derived from a monomer A2 represented by formula (2), and optionally a structural unit 3 derived from a siloxane monomer A3 represented by formula (3);

[0006]

[0007] In formula (1), R1 is C1~C 12Alkylene, C3~C 12 Cycloalkylene or C6~C 20 The arylene group, R 21 , R 31 , R 41 At least two of them are C1-C5 alkoxy or hydroxyl groups and the rest are independently H, C1-C5 alkyl or C6-C 18 The aromatic group, R6 is none, -CO-R 61 -or-SO2-R 62 -, R 61 and R 62 Each is independently a C1-C5 alkylene group, R7 is a C1-C 12 Alkylene, C3~C 12 Cycloalkylene, C6~C 20 Arylene or C6~C 20 Heteroarylene;

[0008] In formula (2), R 22 , R 32 , R 42 At least two of them are C1-C5 alkoxy or hydroxyl groups and the rest are independently H, C1-C5 alkyl or C6-C 18 R5 is a group having a hydroxyl group and / or a carboxyl group or a group having a hydroxyl group and / or a carboxyl group that can be generated by the action of an acid and / or heat;

[0009] In formula (3), R 23 , R 33 , R 43 At least one of them is a C1-C5 alkoxy group or a hydroxyl group and the others are independently H, a C1-C5 alkyl group or a C6-C 18 The aryl group, R6 is C6~C 18 The aromatic group.

[0010] In a preferred embodiment, the weight average molecular weight of the organosilicon polymer is 2000-50000 g / mol, and the PDI is 1-5.

[0011] In a preferred embodiment, the molar ratio of the structural unit 1, the structural unit 2 and the structural unit 3 is 1:(0.5-100):(0.5-100).

[0012] In a preferred embodiment, the organosilicon polymer is prepared by the following method: a monomer A1 having a structure represented by formula (1), a monomer A2 having a structure represented by formula (2), and an optional siloxane monomer A3 having a structure represented by formula (3) are polymerized in the presence of a catalyst to obtain an organosilicon polymer.

[0013] In a preferred embodiment, the monomer A1 is prepared by the following method: a silicone compound S1 having a structure represented by formula (4) is subjected to a substitution reaction with a cyanide-containing compound S2 having a structure represented by formula (5), thereby obtaining a monomer A1 having a structure represented by formula (1);

[0014]

[0015] In formula (4), R1 is C1~C 12 Alkylene, C3~C 12 Cycloalkylene or C6~C 20 The arylene group, R 21 , R 31 , R 41 At least one of them is a C1-C5 alkoxy group or a hydroxyl group and the others are independently H, a C1-C5 alkyl group or a C6-C 18 The aromatic group;

[0016] In formula (5), R6 is none, -CO-R 61 -or-SO2-R 62 -, R 61 and R 62 Each is independently a C0-C5 alkylene group, and R7 is a C1-C 12 Alkylene, C3~C 12 Cycloalkylene, C6~C 20 Arylene or C6~C 20 wherein X is fluorine, chlorine or bromine.

[0017] In a preferred embodiment, the molar ratio of the organosilicon compound S1 to the cyano compound S2 is 1:(1-3).

[0018] In a preferred embodiment, the temperature of the substitution reaction is 25-100°C.

[0019] In a preferred embodiment, the molar ratio of the monomer A1, the monomer A2 and the monomer A3 is 1:(0.5-100):(0.5-100).

[0020] In a preferred embodiment, the polymerization reaction conditions include: temperature of 45 to 205° C. and time of 1 to 24 hours.

[0021] In a preferred embodiment, the catalyst is an acidic catalyst and / or a basic catalyst.

[0022] In a second aspect, the present invention provides a silicon-containing bottom anti-reflective coating composition, wherein the silicon-containing bottom anti-reflective coating composition comprises the above-mentioned organosilicon polymer, a photoacid generator, an organic solvent I and optional additives.

[0023] In a preferred embodiment, based on the total mass of the silicon-containing bottom anti-reflective coating composition, the content of the silicone polymer is 0.1 to 99 wt %, the content of the photoacid generator is 0.01 to 0.5 wt %, the content of the organic solvent I is 0.1 to 99 wt %, and the content of the additive is 0 to 0.5 wt %.

[0024] In a third aspect, the present invention provides a method for preparing the above silicon-containing bottom anti-reflective coating composition, which comprises: mixing an organic silicon polymer with an optional acid generator, an organic solvent and an additive to obtain the silicon-containing bottom anti-reflective coating composition.

[0025] In a fourth aspect, the present invention provides a method for forming a photoresist pattern, the method comprising: applying the above-mentioned silicon-containing bottom anti-reflective coating composition on a substrate to form an anti-reflective coating, applying the photoresist composition on the anti-reflective coating to form a photoresist coating, and obtaining a photoresist pattern after exposure and development.

[0026] In a fifth aspect, the present invention also provides the use of the above-mentioned organosilicon polymer and / or silicon-containing bottom anti-reflective coating composition in semiconductor devices.

[0027] The key to the present invention is to design and synthesize a cyano-containing organic silicon polymer with a specific structure, and use the organic silicon polymer as a raw material of a bottom anti-reflective coating composition to form an anti-reflective film. The introduction of cyano groups reduces the hydrophilicity of the anti-reflective film and improves its adhesion to the surface of the photoresist. The developed photoresist pattern is not easy to collapse and has a good molding effect. It is beneficial to improve the resolution of the photoresist pattern in the processing of semiconductor devices. At the same time, the anti-reflective film has a stable film thickness, good anti-reflective performance and a high etching rate, and has a good application prospect. DETAILED DESCRIPTION

[0028] The organosilicon polymer provided by the present invention comprises a structural unit 1 derived from a monomer A1 shown in formula (1), a structural unit 2 derived from a monomer A2 shown in formula (2), and optionally a structural unit 3 derived from a siloxane monomer A3 shown in formula (3);

[0029]

[0030] In formula (1), R1 is C1~C 12 Alkylene, C3~C 12 Cycloalkylene or C6~C 20 The arylene group, R 21 , R 31 , R 41At least two of them are C1-C5 alkoxy or hydroxyl groups and the rest are independently H, C1-C5 alkyl or C6-C 18 The aromatic group, R6 is none, -CO-R 61 -or-SO2-R 62 -, R 61 and R 62 Each is independently a C0-C5 alkylene group, and R7 is a C1-C 12 Alkylene, C3~C 12 Cycloalkylene, C6~C 20 Arylene or C6~C 20 wherein the C1~C 12 Specific examples of the alkylene group include, but are not limited to, one of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, undecylene, and dodecylene. 12 Specific examples of the cycloalkylene group include, but are not limited to, one of cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylenemethyl, cyclohexylenemethyl, cyclooctylene or adamantylene. 20 Specific examples of the arylene group include, but are not limited to, one of phenylene, tolylene, ethylenephenylene, biphenylene, tolylene, triphenylene, naphthylene, and anthracene. Specific examples of the C1-C5 alkoxy group include, but are not limited to, one of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isopentyloxy, tert-pentyloxy, and neopentyloxy. Specific examples of the C1-C5 alkyl group include, but are not limited to, one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, and neopentyl. 18 Specific examples of the aryl group include, but are not limited to, one of phenyl, tolyl, ethylphenyl, biphenyl, ditolyl, naphthyl, and anthracenyl. 20 Specific examples of the heteroarylene group include, but are not limited to, one of benzofuranylene, benzothiophenylene, quinolylene, isoquinolylene, benzo(1,4)dioxinylene, and 2,3-dihydrobenzo(1,4)dioxinylene.

[0031] In formula (2), R 22 , R 32 , R 42 At least two of them are C1-C5 alkoxy or hydroxyl groups and the rest are independently H, C1-C5 alkyl or C6-C 18R5 is a group with a hydroxyl group and / or a carboxyl group or a group with a hydroxyl group and / or a carboxyl group that can be generated by the action of acid and / or heat. 18 Specific examples of the aromatic group are as described above and will not be repeated here one by one. Specific examples of the group with hydroxyl and / or carboxyl groups include, but are not limited to: -OH, -CH2OH, -CH2CH2OH, -CH(CH3)OH, -(CH2)5OH, -C(CH3)2CH(OH)CH2, -C(CH3)2CH2CH(OH)(CH2)3CH3, -COOH, -CH2COOH, -(CH2)5COOH, -CH(COOH)CH2CH3, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, 1-hydroxy-2,4-methyl-6-neobutylbenzene-3-methyl. Specific examples of the group that can generate hydroxyl groups due to acid / heat include, but are not limited to: C2~C 12 Epoxyalkyl, C2~C 12 Ester group, C2~C 12 Ester groups with hydroxyl groups and C2~C 12 One of the ester groups with a thiol group. 12 Specific examples of the alkylene oxide include, but are not limited to, -CH2-[CH(O)CH2], -CH2CH2-[CH(O)CH2], -CH2CH2CH2-[CH(O)CH2], and -CH(CH3)CH2-[CH(O)CH2]. 12 Specific examples of the ester group include, but are not limited to, -COOCH3, -COOCH2CH3, -COO(CH2)2CH3, -COOCH(CH3)2, -COO(CH2)3CH3, -COOC(CH3)3, -COO(CH2)5CH3, and -COO(CH2)8CH3. 12 Specific examples of ester groups with hydroxyl groups include, but are not limited to, -COOCH2CH2OH, -COO(CH2)3OH, -COOC(CH3)2CH2OH, and -COO(CH2)6OH. 12 Specific examples of ester groups with thiol groups include, but are not limited to, -COOCH2CH2SH, -COO(CH2)3SH, -COOC(CH3)2CH2SH, and -COO(CH2)6SH. In formula (3), R 23 , R 33 , R 43 At least one of them is a C1-C5 alkoxy group or a hydroxyl group and the others are independently H, a C1-C5 alkyl group or a C6-C18 The aryl group, R6 is C6~C 18 The C1-C5 alkoxy, C1-C5 alkyl, C6-C 18 Specific examples of the aryl group are as described above and will not be repeated here one by one.

[0032] In the present invention, the structural unit 1 is derived from the structure shown in formula (1), wherein R 21 , R 31 , R 41 There may be two C1-C5 alkoxy or hydroxy groups and the remaining one may be H, C1-C5 alkyl or C6-C 18 In this case, the structural unit 1 can be used as the terminal structural unit and / or the intermediate structural unit in the organosilicon polymer structure; or, R 21 , R 31 , R 41 There may be three alkoxy groups or hydroxyl groups, all of which are C1 to C5. In this case, the structural unit 1 can be used as an end structural unit and / or an intermediate structural unit in the organic silicon polymer structure. The specific structure of the structural unit 1 includes but is not limited to at least one of the structures shown in formula (1-1), formula (1-2), and formula (1-3).

[0033]

[0034] In the present invention, the structural unit 2 is derived from the structure shown in formula (2), wherein R 22 , R 32 , R 42 There may be two C1-C5 alkoxy or hydroxy groups and the remaining one may be H, C1-C5 alkyl or C6-C 18 In this case, the structural unit 2 can be used as the terminal structural unit and / or the intermediate structural unit in the organosilicon polymer structure; or, R 22 , R 32 , R 42 There may be three alkoxy groups or hydroxyl groups, all of which are C1 to C5. In this case, the structural unit 2 can be used as an end structural unit and / or an intermediate structural unit in the organic silicon polymer structure. The specific structure of the structural unit 2 includes but is not limited to at least one of the structures shown in formula (2-1), formula (2-2), and formula (2-3).

[0035]

[0036] In the present invention, the structural unit three is derived from the structure shown in formula (3), wherein R 23 , R 33 , R 43There may be one C1-C5 alkoxy or hydroxyl group and the other two independently hydrogen, C1-C5 alkyl or C6-C 18 In this case, the structural unit 3 can be used as the terminal structural unit in the organosilicon polymer structure; or, R 23 , R 33 , R 43 There may be two C1-C5 alkoxy or hydroxy groups and the remaining one may be H, C1-C5 alkyl or C6-C 18 In this case, the structural unit 3 can be used as the terminal structural unit and / or the intermediate structural unit in the organosilicon polymer structure; or, R 23 , R 33 , R 43 There may be three alkoxy groups or hydroxyl groups, all of which are C1 to C5. In this case, the structural unit three can be used as an end structural unit and / or an intermediate structural unit in the organic silicon polymer structure. The specific structure of the structural unit three includes, but is not limited to, at least one of the structures shown in formula (3-1), formula (3-2), formula (3-3), formula (3-4), and formula (3-5).

[0037]

[0038] In the present invention, the weight average molecular weight of the organosilicon polymer is preferably 2000-50000 g / mol, such as 2000 g / mol, 3500 g / mol, 5000 g / mol, 8000 g / mol, 10000 g / mol, 20000 g / mol, 50000 g / mol or any value therebetween; PDI is preferably 1-5, such as 1, 2, 3, 4, 5 or any value therebetween. The molar ratio of the structural unit 1, the structural unit 2 and the structural unit 3 is preferably 1:(0.5-100):(0.5-100). Taking the molar amount of the structural unit 1 as 1 mol, the molar amount of the structural unit 2 is preferably 0.5-100 mol, such as 0.5 mol, 0.8 mol, 1 mol, 5 mol, 8 mol, 10 mol, 20 mol, 50 mol, 80 mol, 100 mol or any value therebetween; the molar amount of the structural unit 3 is preferably 0.5-100 mol, such as 0.5 mol, 0.8 mol, 1 mol, 5 mol, 8 mol, 10 mol, 20 mol, 50 mol, 80 mol, 100 mol or any value therebetween. The molar ratio of the structural unit 1, the structural unit 2 and the structural unit 3 is controlled within the above preferred range, so that the obtained organosilicon polymer has good molecular chain rigidity, which is more conducive to increasing the film thickness stability of the anti-reflection film and the contact angle between the anti-reflection film and the photoresist surface. The larger the contact angle, the better the adhesion between the anti-reflection film and the photoresist surface, thereby achieving improved adhesion.

[0039] In the present invention, the organosilicon polymer is preferably prepared by the following method: a monomer A1 having a structure shown in formula (1), a monomer A2 having a structure shown in formula (2), and an optional siloxane monomer A3 having a structure shown in formula (3) are subjected to polymerization reaction in the presence of a catalyst to obtain an organosilicon polymer. The molar ratio of the monomer A1, the monomer A2, and the monomer A3 is preferably 1:(0.5-100):(0.5-100). Taking the molar amount of the monomer A1 as 1 mol, the molar amount of the monomer A2 is preferably 0.5-100 mol, such as 0.5 mol, 0.8 mol, 1 mol, 1.2 mol, 1.5 mol, 1.8 mol, 2 mol, 20 mol, 50 mol, 80 mol, 100 mol, or any value therebetween. The molar amount of the monomer A3 is preferably 0.5 to 100 mol, such as 0.5 mol, 0.8 mol, 1 mol, 1.2 mol, 1.5 mol, 1.8 mol, 2 mol, 20 mol, 50 mol, 80 mol, 100 mol or any value therebetween. The conditions of the polymerization reaction include: the temperature is preferably 45 to 205°C, more preferably 45 to 120°C, such as 45°C, 60, 80°C, 100°C, 120°C or any value therebetween; the time is preferably 1 to 24h, more preferably 4 to 10h, such as 4h, 5h, 6h, 7h, 8h, 9h, 10h or any value therebetween. The temperature and time of the polymerization reaction are controlled within the above-mentioned preferred range, which is more conducive to the occurrence of the polymerization reaction between the monomer A1, the monomer A2 and the monomer A3, and the organosilicon polymer with uniform particle size distribution is obtained. The polymerization reaction can also be carried out in the presence of an organic solvent II, which is more conducive to the polymerization reaction between the reaction monomers in the organic solvent II. Specific examples of the organic solvent II include, but are not limited to, at least one of acetonitrile, tetrahydrofuran, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and propylene glycol monopropyl ether.

[0040] In the present invention, the catalyst is preferably an acidic catalyst and / or a basic catalyst. The acidic catalyst can be an inorganic acid, an organic acid catalyst and / or an inorganic acid catalyst. Specific examples of the organic acid catalyst include, but are not limited to, at least one of p-toluenesulfonic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid and salicylic acid. Specific examples of the inorganic acid catalyst include, but are not limited to, at least one of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid and phosphoric acid. Specific examples of the basic catalyst include, but are not limited to, at least one of methylamine, ethylamine, propylamine, butylamine, ethylenediamine, hexamethylenediamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, triethanolamine, hexamethylenetetramine, aniline, N,N-dimethylaniline, pyridine, pyrrole, picoline, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide and barium hydroxide.

[0041] In the present invention, the monomer A1 is preferably prepared by the following method: a silicone compound S1 having a structure represented by formula (4) is subjected to a substitution reaction with a cyanide-containing compound S2 having a structure represented by formula (5) to obtain a monomer A1 having a structure represented by formula (1).

[0042]

[0043] In formula (4), R1 is C1~C 12 Alkylene, C3~C 12 Cycloalkylene or C6~C 20 The arylene group, R 21 , R 31 , R 41 At least one of them is a C1-C5 alkoxy group or a hydroxyl group and the others are independently H, a C1-C5 alkyl group or a C6-C 18 In formula (5), R6 is null, -CO-R 61 -or-SO2-R 62 -, R 61 and R 62 Each is independently a C1-C5 alkylene group, R7 is a C1-C 12 Alkylene, C3~C 12 Cycloalkylene, C6~C 20 Arylene or C6~C 20 wherein X is fluorine, chlorine or bromine. 12 Alkylene, C3~C 12 Cycloalkylene, C6~C 20 arylene, C1-C5 alkoxy, C1-C5 alkyl, C6-C 18 Aryl, C6~C 20Specific examples of the heteroarylene group are the same as those described above and will not be repeated here one by one.

[0044] In the preparation method of the above-mentioned monomer A1, the molar ratio of the organosilicon compound S1 to the cyano compound S2 is preferably 1:(1-3), such as 1:1, 1.5, 1:2, 1:2.5, 1:3 or any value therebetween. The temperature of the substitution reaction is preferably 25-100°C, more preferably 40-80°C, such as 40°C, 50°C, 60°C, 70°C, 80°C or any value therebetween, which is more conducive to the polymerization reaction of the organosilicon compound S1 and the cyano compound S2, reducing the occurrence of side reactions. The time of the substitution reaction can be selected according to the actual situation of the reaction, preferably 6-10h, such as 6h, 7h, 8h, 9h, 10h or any value therebetween.

[0045] In the preparation method of the above-mentioned monomer A1, the substitution reaction is preferably carried out under an inert gas atmosphere, and specific examples of the inert gas include but are not limited to: at least one of nitrogen, helium, neon and argon. The substitution reaction can also be carried out in the presence of an organic solvent III, which is more conducive to the contact reaction between the reaction raw materials, thereby obtaining a monomer A1 having a structure shown in formula (1). Specific examples of the organic solvent III include but are not limited to: at least one of benzene, toluene, xylene, propylene glycol diacetate, methyl methoxyacetate, ethyl acetate, butyl acetate, ethyl lactate, dibutyl ether, tetrahydrofuran, and γ-butyrolactone.

[0046] In the present invention, the silicon-containing bottom anti-reflective coating composition contains an organic silicon polymer, a photoacid generator, an organic solvent I and optional additives. Based on the total mass of the silicon-containing bottom anti-reflective coating composition, the content of the organic silicon polymer is preferably 0.1 to 99 wt%, such as 1 wt%, 5 wt%, 10 wt%, 20 wt%, 50 wt%, 70 wt%, 90 wt%, 99 wt% or any value therebetween; the content of the photoacid generator is preferably 0.01 to 0.5 wt%, such as 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt% or any value therebetween; the content of the organic solvent I is preferably 0.1-99wt%, such as 1wt%, 5wt%, 10wt%, 20wt%, 50wt%, 70wt%, 90wt%, 99wt% or any value therebetween; the content of the additive is preferably 0-0.5wt%, such as 0wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt% or any value therebetween.

[0047] In the present invention, the photoacid generator is preferably selected from at least one of an onium salt compound, a diazomethane derivative, an oxime derivative, a bissulfone derivative, a nitrobenzyl sulfonate derivative and a sulfonic acid derivative. Specific examples of the onium salt compound include, but are not limited to, at least one of diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium p-toluenesulfonate, triphenyl sulfonium trifluoromethanesulfonate, diphenyl sulfonium trifluoromethanesulfonate, triphenyl sulfonium p-toluenesulfonate, diphenyl sulfonium p-toluenesulfonate, triphenyl sulfonium nonafluorobutanesulfonate, triphenyl sulfonium butanesulfonate, trimethyl sulfonium trifluoromethanesulfonate and trimethyl sulfonium p-toluenesulfonate. Specific examples of the diazomethane derivatives include, but are not limited to, at least one of bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, and 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane. Specific examples of the glyoxime derivatives include, but are not limited to, at least one of bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(methanesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime. Specific examples of the bissulfone derivatives include, but are not limited to, at least one of bis-naphthylsulfonylmethane, bis-trifluoromethylsulfonylmethane, bis-methylsulfonylmethane, bis-ethylsulfonylmethane, bis-propylsulfonylmethane, bis-isopropylsulfonylmethane, and bis-p-toluenesulfonylmethane. Specific examples of the nitrobenzyl sulfonate derivatives include, but are not limited to, 2,6-dinitrobenzyl p-toluenesulfonate and / or 2,4-dinitrobenzyl p-toluenesulfonate. Specific examples of the sulfonic acid derivatives include, but are not limited to, at least one of N-hydroxysuccinimide methane sulfonate, N-hydroxysuccinimide trifluoromethane sulfonate, N-hydroxysuccinimide ethane sulfonate, N-hydroxysuccinimide 1-propane sulfonate, N-hydroxysuccinimide-2-propane sulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxysuccinimide methoxytoluenesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide methane sulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimide trifluoromethane sulfonate, and N-hydroxy-5-norbornene-2,3-dicarboxyimide p-toluenesulfonate.

[0048] In the present invention, the organic solvent is preferably selected from at least one of benzene, toluene, xylene, acetone, butanone, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, methyl methoxyacetate, ethyl acetate, butyl acetate, ethyl lactate, dibutyl ether, tetrahydrofuran and γ-butyrolactone.

[0049] In the present invention, the additive can be a conventional choice in the prior art, preferably a stabilizer, which is beneficial to improve the storage and film-forming stability of the silicon-containing bottom anti-reflective coating composition. The stabilizer is preferably C1-C 30 Specific examples of the organic acid include, but are not limited to, at least one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, benzoic acid, phthalic acid, isophthalic acid, phthalic acid, terephthalic acid, salicylic acid, trifluoroacetic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, propylmalonic acid, butylmalonic acid, itaconic acid, maleic acid, fumaric acid and citric acid.

[0050] In the present invention, the method for forming the photoresist pattern preferably includes: applying a spin-on carbon (SOC) composition on a substrate, thermally curing to obtain a spin-on carbon organic film, spin-coating a silicon-containing organic anti-reflective composition on the spin-on carbon organic film, thermally curing to obtain a bottom anti-reflective coating, spin-coating a photoresist on the bottom anti-reflective coating, baking to form a photoresist coating, and then obtaining a photoresist pattern through exposure and development processes. The conditions for thermal curing include: the temperature is preferably 100-250°C, such as 100°C, 120°C, 150°C, 180°C, 200°C, 250°C or any value therebetween; the time is preferably 0.5-5min, such as 0.5min, 1min, 2min, 3min, 4min, 5min or any value therebetween. The spin-on carbon (SOC) composition and the photoresist can be a type of substance commonly used in the art.

[0051] The present invention will be described in detail below through specific embodiments.

[0052] Synthesis Examples 1 to 9 Synthesis of Monomer A1

[0053] 0.05 mol of organosilicon compound S1 and a certain mass of cyano compound S2 were placed in a three-necked flask, 200 mL of tetrahydrofuran was added, and the mixture was heated to reflux at 60°C under nitrogen environment protection. After 8 hours, the heating was stopped, and the reaction solution was cooled to room temperature to obtain a light yellow liquid. The excess solvent was removed by a rotary evaporator, and the remaining yellow liquid was sunk in water to obtain a light yellow solid, which was monomer A1. Among them, the organosilicon compound S1, cyano compound S2 and their amounts used in Synthesis Examples 1 to 9, and the yields of the prepared monomer A1 are shown in Table 1, and the prepared monomers A1 are respectively recorded as H1 to H9.

[0054] Table 1

[0055]

[0056]

[0057] H1 13 C NMR (DMSO) detection results are: 130.8 (1C), 112.5 (1C), 133.1 (1C), 134.2 (1C), 136.5 (1C), 129.3 (1C), 16.4 (1C), 165.9 (1C), 56.6 (1C), 50.2 (3C), 118.6 (1C).

[0058] H2 13 C NMR (DMSO) detection results are: 165.8 (1C), 102 (2C), 137.1 (2C), 121.7 (1C), 17.1 (1C), 55.8 (1C), 50.2 (3C), 115.8 (2C).

[0059] H3 13 C NMR (DMSO) detection results are: 138.1 (1C), 99.0 (1C), 46.2 (1C), 45.3 (1C), 113.2 (1C), 129.8 (1C), 141.5 (1C), 123.9 (1C), 17.9 (1C), 58.4 (1C), 50.2 (3C), 117.3 (1C).

[0060] H4 13 C NMR (DMSO) detection results are: 141.2 (1C), 113.3 (1C), 129.7 (1C), 132.1 (1C), 132.9 (1C), 126.4 (1C), 55.7 (1C), 16.1 (1C), 46.3 (1C), 50.2 (3C), 115.8 (1C).

[0061] H5 13C NMR (DMSO) detection results are: 172.0 (1C), 172.4 (1C), 157.8 (1C), 161.9 (1C), 108.2 (1C), 77.4 (1C), 122.0 (1C), 133.2 (1C), 134.0 (1C), 125.3 (1C), 17.1 (1C), 56.8 (1C), 50.2 (3C), 115.8 (1C).

[0062] H6 13 C NMR (DMSO) detection results are: 167.8 (1C), 118.6 (1C), 81.9 (1C), 126.6 (1C), 14.7 (1C), 55 (1C), 50.2 (3C), 110.6 (1C).

[0063] H7 13 C NMR (DMSO) detection results are: 134.2 (1C), 135.1 (1C), 128.9 (1C), 153.9 (1C), 114.4 (1C), 106.8 (1C), 95.5 (1C), 17.1 (1C), 56.3 (1C), 50.2 (3C), 115.8 (1C).

[0064] H8 13 C NMR (DMSO) detection results are: 36.8 (1C), 70.6 (1C), 112.5 (1C), 130.8 (1C), 133.1 (1C), 134.2 (1C), 136.5 (1C), 129.3 (1C), 12.6 (2C), 34.2 (2C), 165.9 (1C), 56.5 (3C), 118.6 (1C).

[0065] H9 13 C NMR (DMSO) detection results are: 139.1 (1C), 150.7 (1C), 130.9 (1C), 112.5 (1C), 132.9 (1C), 121.2 (1C), 133.5 (1C), 134.6 (1C), 132.9 (1C), 121.2 (1C), 137.4 (1C), 129.3 (1C), 165.2 (1C), 55.8 (3C), 118.6 (1C).

[0066] Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 2 Preparation of Organosilicon Polymers

[0067] Take a certain mass of monomer A1 obtained in the synthesis example, 11.817g (0.05mol) of 3-glycidoxytrimethoxysilane and 9.9145g (0.05mol) of phenyltrimethoxysilane in 100mL of tetrahydrofuran, add 0.1g of tetramethylammonium hydroxide, heat and reflux at 50°C under nitrogen environment protection, stop heating after 8h of reaction, cool to room temperature, add 100mL of PGEE (propylene glycol methyl ether), and distill under reduced pressure to obtain an organosilicon polymer with a solid content of 30%. Among them, the monomer A1 used in Preparation Examples 1 to 10 and its dosage, as well as the weight average molecular weight Mw and PDI values ​​of the prepared organosilicon polymers P1 to P10 are shown in Table 2, and the raw materials used in Comparative Preparation Examples 1 to 2 and their dosage, as well as the weight average molecular weight Mw and PDI values ​​of the prepared reference organosilicon polymers DP1 to DP2 are shown in Table 2.

[0068] Table 2

[0069]

[0070]

[0071] Examples 1 to 10, Comparative Examples 1 to 2

[0072] 1 part by weight of the organosilicon polymers P1-P10 of Preparation Examples 1-10 and the organosilicon polymers DP1-DP2 of Comparative Preparation Examples 1-2 were respectively mixed with 0.06 part by weight of maleic acid, 0.06 part by weight of triphenylsulfonium perfluorobutanesulfonate, and 98 parts by weight of propylene glycol monoethyl ether (PGEE), and the resulting mixed solution was filtered with a 0.2 μm PTFE filter to obtain the silicon-containing bottom anti-reflective coating compositions of Examples 1-10 and Comparative Preparation Examples 1-2, respectively.

[0073] Test Case

[0074] 1. The silicon-containing bottom anti-reflective coating composition obtained in the above Examples 1 to 10 and Comparative Examples 1 to 2 was applied on a silicon wafer, baked at 200° C. for 120 seconds, and cured to form an anti-reflective film. The relevant performance tests were performed according to the following method. The results are shown in Table 3:

[0075] (1) An ellipsometer (JA Woolam, VUV-303) was used to measure the refractive index n, extinction coefficient k and film thickness of the antireflection film at 193 nm.

[0076] (2) Use a contact angle meter (KRUSS, DSA100L) to test the contact angle of the anti-reflection film.

[0077] (3) A dry etching device TE-8500P manufactured by Tokyo Electron was used to etch the anti-reflective film with CHF3 / CF4 gas, and the etching rate was tested. The etching conditions specifically include: a processing chamber pressure of 40 Pa, a PF power of 1300 W, a gap of 9 mm, a CHF3 gas flow rate of 30 mL / min, a CF4 gas flow rate of 30 mL / min, an Ar gas flow rate of 100 mL / min, and an etching time of 10 s.

[0078] (4) The anti-reflection film is immersed in a mixed solvent of 7 parts by weight of propylene glycol methyl ether acetate (PGMEA) and 3 parts by weight of propylene glycol methyl ether (PGME) for 7 days, and the film thickness of the anti-reflection film after immersion is measured. Film thickness change rate = (film thickness after 7 days - initial film thickness) / initial film thickness * 100.

[0079] Table 3

[0080]

[0081] 2. Performance evaluation of photoresist pattern: First, SOC was spin-coated on a silicon wafer and heated at 220°C for 60s to form a spin-coated carbon organic film. Then, the organic silicon polymers obtained in Examples 1 to 7 and Comparative Examples 1 to 2 were spin-coated on the spin-coated carbon organic film and heated at 200°C for 60s to form silicon-containing antireflection films (Film1 to Film9). Then, a positive photoresist (PR-1) was spin-coated on the silicon-containing antireflection film and heated at 100°C for 90s to form a photoresist film. ArF exposure equipment (manufactured by NIKON) was used. The photoresist pattern was exposed by a 2.38% tetramethylammonium hydroxide aqueous solution (S305B), heated at 110°C for 90s (PEB), and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution to form a positive photoresist pattern with a line width of 0.13μm. The size of the obtained photoresist pattern was measured by an electron microscope (CG6300) manufactured by Hitachi High-Technologies Corporation, the pattern collapse and cross-sectional shape were measured by an electron microscope (S4700) manufactured by Hitachi, and the line width roughness (LWR) was measured by an electron microscope (CG4000) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 4.

[0082] The composition of the PR-1 polymer is: 1 part by weight of polymer W1, 0.05 parts by weight of photoacid generator PAG1, 0.01 parts by weight of quencher Q1, and 2.5 parts by weight of solvent PGMEA.

[0083] The polymer W1 has a structure shown in formula (I), m:n=0.4:0.6, molecular weight Mw=8800 g / mol, PDI=1.81. The photoacid generator PAG1 has a structure shown in formula (II). The quencher Q1 has a structure shown in formula (III).

[0084]

[0085] Table 4

[0086]

[0087]

[0088] It can be seen from the results of Table 3 and Table 4 that, compared with Comparative Examples 1 and 2, the anti-reflection film containing the organosilicon polymer provided by the present invention has a larger front contact angle, indicating that it has good hydrophobicity and good adhesion to the photoresist surface. It also has a higher refractive index and extinction coefficient, good anti-reflection performance, and stable film thickness. The line width roughness (LWR) of the photoresist pattern after development is small, the shape is good, and there is no collapse.

[0089] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. An organosilicon polymer, characterized in that: The organosilicon polymer comprises a structural unit 1 derived from a monomer A1 of formula (1), a structural unit 2 derived from a monomer A2 of formula (2), and optionally a structural unit 3 derived from a siloxane monomer A3 of formula (3); In formula (1), R1 is C1~C 12 Alkylene, C3~C 12 Cycloalkylene or C6~C 20 The arylene group, R 21 , R 31 , R 41 At least two of them are C1-C5 alkoxy or hydroxyl groups and the rest are independently H, C1-C5 alkyl or C6-C 18 The aromatic group, R6 is none, -CO-R 61 -or-SO2-R 62 -, R 61 and R 62 Each is independently a C0-C5 alkylene group, and R7 is a C1-C 12 Alkylene, C3~C 12 Cycloalkylene, C6~C 20 Arylene or C6~C 20 Heteroarylene; In formula (2), R 22 , R 32 , R 42 At least two of them are C1-C5 alkoxy or hydroxyl groups and the rest are independently H, C1-C5 alkyl or C6-C 18 R5 is a group having a hydroxyl group and / or a carboxyl group or a group having a hydroxyl group and / or a carboxyl group that can be generated by the action of an acid and / or heat; In formula (3), R 23 , R 33 , R 43 At least one of them is a C1-C5 alkoxy group or a hydroxyl group and the others are independently H, a C1-C5 alkyl group or a C6-C 18 The aryl group, R6 is C6~C 18 The aromatic group.

2. The organosilicon polymer according to claim 1, characterized in that The weight average molecular weight of the organosilicon polymer is 2000-50000 g / mol, and the PDI is 1-5; preferably, the molar ratio of the structural unit 1, the structural unit 2 and the structural unit 3 is 1:(0.5-100):(0.5-100).

3. The organosilicon polymer according to claim 1, characterized in that The organosilicon polymer is prepared by the following method: a monomer A1 having a structure shown in formula (1), a monomer A2 having a structure shown in formula (2), and an optional siloxane monomer A3 having a structure shown in formula (3) are subjected to a polymerization reaction in the presence of a catalyst to obtain an organosilicon polymer.

4. The organosilicon polymer according to claim 3, characterized in that The monomer A1 is prepared by the following method: a silicone compound S1 having a structure represented by formula (4) is subjected to a substitution reaction with a cyano compound S2 having a structure represented by formula (5), thereby obtaining a monomer A1 having a structure represented by formula (1); In formula (4), R1 is C1~C 12 Alkylene, C3~C 12 Cycloalkylene or C6~C 20 The arylene group, R 21 , R 31 , R 41 At least one of them is a C1-C5 alkoxy group or a hydroxyl group and the others are independently H, a C1-C5 alkyl group or a C6-C 18 The aromatic group; In formula (5), R6 is none, -CO-R 61 -or-SO2-R 62 -, R 61 and R 62 Each is independently a C1-C5 alkylene group, R7 is a C1-C 12 Alkylene, C3~C 12 Cycloalkylene, C6~C 20 Arylene or C6~C 20 wherein X is fluorine, chlorine or bromine.

5. The organosilicon polymer according to claim 4, characterized in that The molar ratio of the organosilicon compound S1 to the cyano compound S2 is 1:(1-3); Preferably, the temperature of the substitution reaction is 25-100°C.

6. The organosilicon polymer according to claim 3, characterized in that The molar ratio of the monomer A1, the monomer A2 and the monomer A3 is 1:(0.5-100):(0.5-100); Preferably, the polymerization reaction conditions include: temperature of 45 to 205°C and time of 1 to 24 hours; Preferably, the catalyst is an acidic catalyst and / or a basic catalyst.

7. A silicon-containing bottom anti-reflective coating composition, characterized in that: The silicon-containing bottom anti-reflective coating composition comprises the organosilicon polymer according to any one of claims 1 to 6, a photoacid generator, an organic solvent I, and optional additives; Preferably, based on the total mass of the silicon-containing bottom anti-reflective coating composition, the content of the silicone polymer is 0.1-99wt%, the content of the photoacid generator is 0.01-0.5wt%, the content of the organic solvent is 0.1-99wt%, and the content of the additive is 0-0.5wt%.

8. The method for preparing the silicon-containing bottom anti-reflective coating composition according to claim 7, characterized in that: The method comprises: mixing an organic silicon polymer with an optional acid generator, an organic solvent and an additive to obtain a silicon-containing bottom anti-reflective coating composition.

9. A method for forming a photoresist pattern, characterized in that: The method comprises: coating the silicon-containing bottom anti-reflective coating composition of claim 7 on a substrate to form an anti-reflective coating, coating a photoresist composition on the anti-reflective coating to form a photoresist coating, and obtaining a photoresist pattern after exposure and development.

10. Use of the organosilicon polymer according to any one of claims 1 to 6 and / or the silicon-containing bottom anti-reflective coating composition according to claim 7 in a semiconductor device.

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