Bottom anti-reflection coating composition as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of photoetching, and particularly relates to a bottom anti-reflection coating composition as well as a preparation method and application thereof. The bottom anti-reflection coating composition at least contains a polymer A and a polymer B; the polymer A contains a structural unit I derived from a first monomer as shown in a formula (1), a structural unit III derived from a third monomer as shown in a formula (3), a structural unit IV derived from a fourth monomer as shown in a formula (4) and an optional structural unit II derived from a second monomer as shown in a formula (2); the polymer B contains a fifth structural unit derived from a fifth monomer as shown in a formula (5), a sixth structural unit derived from a sixth monomer as shown in a formula (6) and a seventh structural unit derived from a seventh monomer as shown in a formula (7). The key of the invention lies in that the polymer A and the polymer B with specific structures are introduced into the bottom anti-reflection coating composition, so that the bottom anti-reflection coating has excellent anti-reflection performance and developing performance, the problem of photoresist residue is effectively solved, and the resolution of the developed photoresist pattern is improved.

Description

Technical Field

[0001] This invention belongs to the field of photolithography technology, specifically relating to a bottom anti-reflective coating composition, its preparation method, and its application. Background Technology

[0002] With the increasing integration of semiconductor devices, photolithography is playing an increasingly important role in microelectronics manufacturing. However, during photolithography, the reflection of light by the substrate causes a standing wave effect within the photoresist, resulting in uneven exposure and wavy, jagged defects on the sidewalls of the pattern, thus affecting the accuracy and resolution of the pattern. To solve this problem, a bottom anti-reflective coating is typically used between the substrate and the photoresist layer to improve the exposure effect of the photoresist and the formation of high-resolution patterns.

[0003] Currently, commonly used bottom antireflective coatings (BARCs) are mainly divided into two categories: inorganic and organic. Inorganic antireflective coating materials such as SiON and TiN typically require complex preparation processes and expensive equipment to form the antireflective coating. Early-generation organic BARCs were based on organic polymers such as polyimide and phenolic resin, achieving antireflective functionality by adding anthraquinone derivatives as light absorbers. Organic antireflective coatings are widely used due to their simple preparation process and high light absorption rate. However, existing organic antireflective coatings still have some problems, such as poor adhesion to photoresist, uneven film thickness, and high edge roughness. Especially after exposure and development, photoresist residue is a prominent issue, severely affecting the formation of photoresist patterns.

[0004] Therefore, developing an antireflective coating composition with excellent developability can effectively solve the problem of photoresist residue and improve the accuracy of photoresist patterns, which has become an important research direction in the current photolithography field. Summary of the Invention

[0005] The purpose of this invention is to address the problem of photoresist residue leading to decreased resolution of photolithographic patterns in practical applications of existing organic antireflective coatings. This invention provides an antireflective coating composition with excellent developability, which ensures both good antireflective performance and developability, thereby solving the problem of photoresist residue and improving the accuracy of photoresist patterns.

[0006] In a first aspect, the present invention provides a bottom anti-reflective coating composition. The bottom anti-reflective coating composition contains at least polymer A and polymer B; polymer A contains structural unit one derived from a first monomer of formula (1), structural unit three derived from a third monomer of formula (3), and structural unit four derived from a fourth monomer of formula (4), and optionally structural unit two derived from a second monomer of formula (2); polymer B contains structural unit five derived from a fifth monomer of formula (5), structural unit six derived from a sixth monomer of formula (6), and structural unit seven derived from a seventh monomer of formula (7);

[0007]

[0008] In formula (1), R1 is a C1-C5 alkylene or fluorinated alkylene, R2 is a single bond, a C1-C5 alkylene or a C1-C5 ketene carbonyl, R3 and R4 are each independently a C1-C5 fluorinated alkylene or a C1-C5 fluorinated ether alkylene, or R3 or R4 is connected to R1 to form a cyclic group structure;

[0009] In formulas (2) to (4), R5', R6' and R7' are each independently a hydrogen atom or a C1 to C5 alkyl group, R5 is a crosslinkable group, R6 is an acid-unstable group, R7 is any one of hydrogen atom, C1 to C5 alkyl group, C3 to C6 epoxy group, C5 to C8 cycloalkyl group, C6 to C12 aryl or alkylaryl group, C6 to C20 aryl or heteroaryl group, and R8 and R9 are each independently a hydrogen atom, a C1 to C5 alkyl group or a C3 to C20 cycloalkyl group;

[0010] In equations (5) to (7), R 14 ˋ、R 15 ˋ and R 16 Each ˋ is independently a hydrogen atom or a C1-C5 alkyl group, R 10 ~R 14 Each is independently a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, R 15 R is a crosslinkable group. 16 It is an acid-labile group.

[0011] Secondly, the present invention provides a method for preparing the above-mentioned bottom anti-reflective coating composition. The method comprises mixing polymer A, polymer B, and optionally a crosslinking agent, a photoacid-producing agent, solvent I, a neutralizing agent, and a surfactant, the resulting mixture being the bottom anti-reflective coating composition.

[0012] Thirdly, the present invention provides the application of the above-mentioned bottom anti-reflective coating composition in photolithography.

[0013] Beneficial effects: The key to this invention lies in using polymers A and B, which have specific structures, as the main film-forming components of the bottom anti-reflective coating composition. Polymer A includes a fluorine-containing structural unit 1, a structural unit 3 containing an acid-instable group, and a structural unit 4 containing a light-absorbing group. Polymer B includes a phenyl-containing structural unit 5, a structural unit 6 containing a crosslinkable group, and a structural unit 7 containing an acid-instable group. Through the synergistic effect of polymers A and B, the bottom anti-reflective coating not only has excellent anti-reflective properties but also good photosensitivity. It develops completely after exposure, effectively solving the problem of photoresist residue and thus improving the resolution of the photoresist pattern obtained after development, showing good application prospects. Detailed Implementation

[0014] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. Furthermore, unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present invention.

[0015] The bottom anti-reflective coating composition provided by the present invention contains at least polymer A and polymer B. Polymer A contains structural unit one derived from the first monomer shown in formula (1), structural unit three derived from the third monomer shown in formula (3), structural unit four derived from the fourth monomer shown in formula (4), and optionally structural unit two derived from the second monomer shown in formula (2); polymer B contains structural unit five derived from the fifth monomer shown in formula (5), structural unit six derived from the sixth monomer shown in formula (6), and structural unit seven derived from the seventh monomer shown in formula (7).

[0016]

[0017] In formula (1), R1 is a C1-C5 alkylene or fluorinated alkylene, R2 is a single bond, a C1-C5 alkylene or a C1-C5 ketene carbonyl, R3 and R4 are each independently a C1-C5 fluorinated alkylene or a C1-C5 fluorinated ether alkylene, or R3 or R4 is connected to R1 to form a cyclic group structure. Specific examples of C1 to C5 alkylene groups include, but are not limited to: -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -C(CH3)2-, -(CH2)4-, -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, -C(CH3)2CH2-, -(CH2)5-, -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, -C(CH3)2CH2CH2-, -CH2C(CH3)2CH2-, -CH(CH3)CH(CH3)CH2-, or -C(CH2CH3)CH2CH2-. A C1-C5 fluorinated alkylene group refers to an alkylene group in which at least one hydrogen atom is replaced by a fluorine atom. Specific examples include, but are not limited to: -CF2-, -CF2CF2-, -CF(CF3)-, -CF2CF2CF2-, -C(CF3)2-, -(CF2)4-, -C(CF3)2CF2-, -(CF2)5-, or -C(CF3)2CH2CH2-. Specific examples of C1-C5 ketone carbonyl groups include, but are not limited to: -CO-, -CH2CO-, -CH2COCH2-, -CH2CH2COCH2-, or -CH(CH3)CH2COCH2-. Fluorinated alkyl groups of C1 to C5 refer to alkyl groups in which at least one hydrogen atom is replaced by a fluorine atom. Specific examples include, but are not limited to: -CF3, -CF2CF3, -CH2CF3, -CF2CF2CF3, -CF(CF3)2, -(CF2)3CF3, -C(CF3)2CF3, -(CF2)4CF3, or -C(CF3)2CH2CH3. Fluorinated ether alkyl groups of C1 to C5 refer to ether alkyl groups in C1 to C5 in which at least one hydrogen atom is replaced by a fluorine atom. Specific examples include, but are not limited to: -OCF3, -OCF2CF3, -OCH2CF3, -O(CF2)3CF3, -O(CH2)3CF3, -OC(CF3)3, -O(CF2)4CF3, -O(CH2)4CF3, -OCH2C(CF3)3, or -OCF2C(CF3)3.

[0018] In formulas (2) to (4), R5ˋ, R6ˋ and R7ˋ are each independently a hydrogen atom or a C1 to C5 alkyl group, R5 is a crosslinkable group, R6 is an acid-unstable group, R7 is any one of hydrogen atom, C1 to C5 alkyl group, C3 to C6 epoxy group, C5 to C8 cycloalkyl group, C6 to C12 aralkyl or alkylaryl group, C6 to C20 aryl or heteroaryl group, and R8 and R9 are each independently a hydrogen atom, a C1 to C5 alkyl group or a C3 to C20 cycloalkyl group. Specific examples of C1 to C5 alkyl groups include, but are not limited to: -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -(CH2)3CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -C(CH3)2CH3, -(CH2)4CH3, -CH(CH3)CH2CH2CH3, -CH2CH(CH3)CH2CH3, -C(CH3)2CH2CH3, -CH2C(CH3)2CH3, -CH(CH3)CH(CH3)CH3 or -C(CH2CH3)CH2CH3. Specific examples of C3-C6 epoxy groups include, but are not limited to: CH2-[CH(O)CH2], -CH2CH2-[CH(O)CH2], -CH2CH2CH2-[CH(O)CH2], -CH2CH2-[CH(O)CH]-CH3, or -(CH2)4-[CH(O)CH2]. Specific examples of C5-C8 cycloalkyl groups include, but are not limited to: cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl. Specific examples of C6-C12 aralkyl groups include, but are not limited to (Ph represents a benzene ring): -CH2Ph, -CH2CH2Ph, -CH2CH2CH2Ph, or -CH2CH(CH3)CH2Ph. Specific examples of C6-C12 alkylaryl groups include, but are not limited to (Ph represents a benzene ring): -Ph, -Ph-CH3, -PhCH2CH3, -PhCH2CH2CH3, -PhCH(CH3)CH3, or -PhC(CH3)3. Specific examples of aryl groups from C6 to C20 include, but are not limited to: phenyl, biphenyl, triphenyl, naphthyl, anthracene, phenanthryl, pyrene, or benzo[a]pyrene. Specific examples of heteroaryl groups from C6 to C20 include, but are not limited to: benzofuranyl, benzothiophene, quinolinyl, isoquinolinyl, benzo-1,4-dioxinyl, or 2,3-dihydro-benzo-1,4-dioxinyl. Specific examples of cycloalkyl groups from C3 to C20 include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotetradecyl, cyclohexadecyl, cyclooctadecyl, or cycloeicosyl.

[0019] In equations (5) to (7), R 14 ˋ、R 15ˋ and R 16 Each ˋ is independently a hydrogen atom or a C1-C5 alkyl group, R 10 ~R 14 Each is independently a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, R 15 R is a crosslinkable group. 16 It is an acid-labile group. Specific examples of C1 to C5 alkyl groups include, but are not limited to: -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -(CH2)3CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -C(CH3)2CH3, -(CH2)4CH3, -CH(CH3)CH2CH2CH3, -CH2CH(CH3)CH2CH3, -C(CH3)2CH2CH3, -CH2C(CH3)2CH3, -CH(CH3)CH(CH3)CH3 or -C(CH2CH3)CH2CH3. Specific examples of C1 to C5 alkoxy groups include, but are not limited to: -O-CH3, -O-CH2CH3, -O-CH2CH2CH3, -O-CH(CH3)2, -O-(CH2)3CH3, -O-CH(CH3)CH2CH3, -O-CH2CH(CH3)CH3, -OC(CH3)2CH3, -O-(CH2)4CH3, -O-CH(CH3)CH2CH2CH3, -O-CH2CH(CH3)CH2CH3, -OC(CH3)2CH2CH3, -O-CH2C(CH3)2CH3, -O-CH(CH3)CH(CH3)CH3 or -OC(CH2CH3)CH2CH3.

[0020] In equations (2) and (6), R5 and R 15 Each hydroxyl group is preferably substituted with a hydrogen atom or a hydroxyl group substituted with a C1-C5 alkyl group, a C3-C20 cycloalkyl group, a C6-C10 alkylaryl group, or a C5-C10 heteroaryl group. Specific examples of hydroxyl groups substituted with C1-C5 alkyl groups include, but are not limited to: -CH2-OH, -CH2CH2-OH, -CH(OH)CH3, -CH2CH2CH2-OH, -(CH2)4-OH, or -(CH2)5-OH. Specific examples of hydroxyl groups substituted with C3-C20 cycloalkyl groups include, but are not limited to: -C5H8-OH, -C6 ... 10 -OH, -CH2-C6H9(CH3)-OH, -C7H 12 -OH, -C8H 14 -OH or -C 10 H 18-OH. Specific examples of hydroxyl groups substituted with alkylaryl groups from C6 to C10 include, but are not limited to: -Ph-OH, -Ph-CH2-OH, -Ph-CH2-CH2-OH, -Ph-CH2-CH2-CH2-OH, -Ph-CH2-CH2-CH2-CH2-OH. Specific examples of hydroxyl groups substituted with heteroaryl groups from C5 to C10 include, but are not limited to: 2-hydroxypyridine, 2-hydroxybenzothiazole, 3-hydroxy-2-indolone, 5,6-dihydroxyindole, or 3-hydroxy-2-methyl-γ-pyranone, as shown in the following structures, where * indicates the location where the R5 group is bonded to an oxygen bond.

[0021]

[0022] In equations (3) and (7), R6 and R 16 Each is preferably an alkyl group of C1 to C5, an epoxy group of C3 to C6, or a cycloalkyl group of C3 to C10. Specific examples of C1 to C5 alkyl groups include, but are not limited to: -CH3, -CH2CH3, -(CH2)2CH3, -(CH2)3CH3, -C(CH3)3, -(CH2)4CH3, or -CH2C(CH3)3. Specific examples of C3 to C6 epoxy groups include, but are not limited to: -CH2-[CH(O)CH2], -CH2CH2-[CH(O)CH2], -CH2CH2CH2-[CH(O)CH2], -CH2CH2-[CH(O)CH]-CH3, or -(CH2)4-[CH(O)CH2]. Specific examples of C3 to C10 cycloalkyl groups include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, cyclooctyl, cyclononyl, cyclodecyl, or adamantyl.

[0023] In this invention, the preferred mass ratio of polymer A to polymer B is 1:(0.25-20), such as 1:0.25, 1:0.5, 1:0.8, 1:1, 1:2, 1:5, 1:8, 1:10, 1:15, 1:20, or any value between them. Controlling the mass ratio of polymer A to polymer B within the above-mentioned preferred range is more conducive to improving the development speed of the exposed portion of the anti-reflective coating in the developer solution, optimizing the development effect, and solving the problem of photoresist residue, while ensuring good anti-reflective performance.

[0024] In this invention, based on the total molar amount of structural unit one, structural unit two, structural unit three, and structural unit four, the molar content of structural unit one in polymer A is preferably 0.01% to 50%, such as 0.01%, 0.05%, 0.1%, 0.5%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, or any value between them, more preferably 1% to 20%; the molar content of structural unit two in polymer A is preferably 0% to 80%, such as 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%. The molar content of structural unit three in polymer A is preferably 10-80%, such as 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or any value between them, more preferably 20-60%; the molar content of structural unit four in polymer A is preferably 0.02-80%, such as 0.02%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or any value between them, more preferably 10-40%. When the molar content of structural unit one, structural unit two, structural unit three, and structural unit four in polymer A is within the above-mentioned preferred or more preferred ranges, it is more conducive to adjusting the solubility of polymer A, so that it can better exert the effect of improving the anti-reflective performance and developability of the anti-reflective coating composition, which is beneficial to the formation of good photolithographic patterns in the anti-reflective coating film manufacturing process.

[0025] This invention does not impose any particular limitation on the distribution of structural units one, two, three, and four in the polymer A structure. That is, structural units one, two, three, and four in the polymer A structure provided in this invention can be distributed in any manner, such as random copolymerization, alternating copolymerization, block copolymerization, or graft copolymerization, preferably random copolymerization. The terms "one," "two," "three," and "four" in structural units one, two, three, and four are merely for distinguishing purposes and have no other special meaning.

[0026] In this invention, based on the total molar amount of structural unit five, structural unit six, and structural unit seven, the molar content of structural unit five in polymer B is preferably 0.1% to 60%, such as 0.1%, 1%, 5%, 10%, 15%, 20%, 30%, 40%, 45%, 50%, 60%, or any value between them, more preferably 15% to 45%; the molar content of structural unit six in polymer B is preferably 1% to 70%, such as 1%, 5%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, or any value between them, more preferably 15% to 50%; the molar content of structural unit seven in polymer B is preferably 1% to 70%, such as 1%, 5%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, or any value between them, more preferably 15% to 50%. When the molar percentages of structural units five, six and seven in polymer B are within the preferred or more preferred ranges described above, it is more advantageous to further improve the anti-reflective effect of the anti-reflective coating under 193nm exposure while ensuring that the anti-reflective coating has excellent development effect.

[0027] This invention does not impose any particular limitation on the distribution of structural units five, six, and seven in the polymer B structure. That is, structural units five, six, and seven in the polymer B structure provided in this invention can be distributed in any manner, such as random copolymerization, alternating copolymerization, block copolymerization, or graft copolymerization, preferably random copolymerization. The terms "five," "six," and "seven" in structural units five, six, and seven are merely for distinguishing purposes and have no other special meaning.

[0028] In this invention, the weight-average molecular weight (Mw) of polymer A is preferably 1000–20000 Daltons, such as 1000, 2000, 5000, 8000, 10000, 12000, 15000, 18000, 20000 Daltons or any value between them, and the PDI is preferably 0.8–3.0, such as 0.8, 1.0, 1.5, 2.0, 2.5, 3.0 or any value between them. The weight-average molecular weight (Mw) of polymer B is 2000–15000 Daltons, such as 2000, 5000, 8000, 10000, 12000, 15000 Daltons or any value between them, and the PDI is 0.5–2.0, such as 0.5, 0.8, 1.0, 1.2, 1.5, 1.8, 2.0 or any value between them.

[0029] In this invention, polymer A can be prepared by the following method: a first polymerization reaction is carried out in the presence of a first monomer shown in formula (1), a third monomer shown in formula (3), a fourth monomer shown in formula (4), and an optional second monomer shown in formula (2), and the resulting reaction product is polymer A. Polymer B can be prepared by the following method: a second polymerization reaction is carried out in the presence of a second initiator of a fifth monomer shown in formula (5), a sixth monomer shown in formula (6), and a seventh monomer shown in formula (7), and the resulting reaction product is polymer B.

[0030] In this invention, the molar ratio of the first monomer, second monomer, third monomer, and fourth monomer is preferably (0.01–50%):(0–80%):(10–80%):(0.02–80%), more preferably (1–20%):(20–60%):(20–60%):(10–40%). Based on the total molar amount of the first monomer, second monomer, third monomer, and fourth monomer, the molar percentage of the first monomer is preferably 0.01–50%, such as 0.01%, 0.05%, 0.1%, 0.5%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, or any value between them, more preferably 1–20%; the molar percentage of the second monomer is preferably 0–80%, such as 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%. The molar percentage of the third monomer is preferably 10% to 80%, such as 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or any value between them, more preferably 20% to 60%; the molar percentage of the fourth monomer is preferably 0.02% to 80%, such as 0.02%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or any value between them, more preferably 10% to 40%.

[0031] In this invention, the molar ratio of the fifth monomer, the sixth monomer and the seventh monomer is preferably (0.1-60%):(1-70%):(1-70%), more preferably (15-45%):(15-50%):(15-50%). Based on the total molar amount of the fifth, sixth, and seventh monomers, the molar amount of the fifth monomer is preferably 1-60%, such as 0.1%, 1%, 5%, 10%, 15%, 20%, 30%, 40%, 45%, 50%, 60%, or any value between them, more preferably 15-45%; the molar amount of the sixth monomer is preferably 1-70%, such as 1%, 5%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, or any value between them, more preferably 15-50%; the molar amount of the sixth monomer is preferably 1-70%, such as 1%, 5%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, or any value between them, more preferably 15-50%.

[0032] In this invention, the conditions for the first polymerization reaction and the second polymerization reaction are preferably independently included as follows: the reaction is carried out in an inert gas atmosphere, such as nitrogen, argon, neon, xenon, radon, etc.; the temperature is 30 to 120°C, such as 30°C, 50°C, 80°C, 100°C or any value between them; and the time is 1 to 10 hours, such as 1 hour, 2 hours, 5 hours, 8 hours, 10 hours or any value between them.

[0033] In this invention, the first initiator and the second initiator are each independently preferred from at least one of peroxide initiators, azo initiators, and redox initiators, with azo initiators being more preferred. Specific examples of the azo initiators include, but are not limited to, at least one of: dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azodicarbonamide, azobisisopropylimidazoline hydrochloride, azoisobutylcyanoformamide, azodicyclohexylformonitrile, azodicyanovalerate, azobisisopropylimidazoline, azobisisobutyronitrile, azobisisovalerate, and azobisisoheptanenitrile.

[0034] In this invention, the first polymerization reaction and the second polymerization reaction are preferably carried out independently in the presence of solvent II, which is more conducive to the reaction of each monomer raw material in a random copolymerization manner to generate polymer. Specific examples of solvent II include, but are not limited to: at least one of benzene, toluene, xylene, acetone, methanol, ethanol, ethylene 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, more preferably at least one of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and ethyl lactate.

[0035] In this invention, the bottom anti-reflective coating composition preferably contains polymer A, polymer B, a crosslinking agent, a photoacid-generating agent, solvent I, and optionally a neutralizing agent and a surfactant.

[0036] In this invention, based on the total mass of the bottom antireflective coating composition, the sum of the contents of polymer A and polymer B is preferably 0.1–10 wt%, such as 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, or any value between them; the content of the crosslinking agent is preferably 0.001–10 wt%, such as 0.001 wt%, 0.01 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, or any value between them; the content of the photoacid-generating agent is preferably 0.001–10 wt%, such as 0.001 wt%, 0.01 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, or any value between them; The solvent I is preferably 70-99 wt%, such as 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 99 wt%, or any value between them; the neutralizing agent is preferably 0-10 wt%, such as 0 wt%, 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, or any value between them; the surfactant is preferably 0-20 wt%, such as 0 wt%, 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, or any value between them.

[0037] In this invention, the crosslinking agent may be selected from at least one of urea, glycourea, polymeric glycourea, melamine, benzo[a]melamine, hydroxyalkylamide, epoxy resin, isocyanate, and vinyl ether-terminated compounds, preferably vinyl ether-terminated compounds. Specific examples of the vinyl ether-terminated compounds include, but are not limited to, at least one of: bis(4-(ethoxy)butyl)adipate, bis(4-(ethoxy)butyl)succinate, bis(4-(ethoxy)butyl)terephthalate, bis[(4-ethoxymethyl)cyclohexylmethyl]glutarate, tris(4-ethoxybutyl)trimethoxymethyl, di[[4-(ethoxy)methyl]cyclohexylmethyl]isophthalate, di[4-(ethoxy)butyl](4-methyl-1,3-phenylene)dicarbamate, triethylene glycol divinyl ether, and 1,4-cyclohexanediethanol divinyl ether.

[0038] In this invention, the photoacid generator (PAG) can be selected from at least one of sulfonium salt-based compounds, iodine salt-based compounds, phosphonium salt-based compounds, and organic sulfonic acid compounds. Specific examples of the acid generator include, but are not limited to: dodecylbenzenesulfonic acid, p-toluenesulfonic acid, phthalimide trifluoromethanesulfonate, phthalimide trifluoromethanesulfonate, dinitrobenzyltoluenesulfonate, dinitrobenzyltoluenesulfonate, n-decyl disulfone, naphthylimide trifluoromethanesulfonate, naphthylimide trifluoromethanesulfonate, diphenyliodotrifluoromethanesulfonate, diphenyliodoperfluorobutyl sulfonate, diphenyliodohexafluorophosphate, diphenyliodohexafluoroarsenate, diphenyliodohexafluoroantimonate, diphenyl-p-methoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-p-toluenesulfonate, diphenyl The following is a list of at least one of the following: diphenyl-p-tert-butylphenylsulfonium trifluoromethanesulfonate, diphenyl-p-isobutylphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, tri(p-tert-butylphenyl)sulfonium trifluoromethanesulfonate, diphenyl-p-methoxyphenylsulfonium perfluorobutyl sulfonate, diphenyl-p-tolylsulfonium perfluorobutyl sulfonate, diphenyl-p-tert-butylphenylsulfonium perfluorobutyl sulfonate, diphenyl-p-isobutylphenylsulfonium perfluorobutyl sulfonate, triphenylsulfonium perfluorobutyl sulfonate, triphenyl-p-tert-butylphenylsulfonium perfluorobutyl sulfonate, hexafluoroarsenate, hexafluoroarsenate, triphenylsulfonium hexafluoroantimonate, and dibutylnaphthylsulfonium trifluoromethanesulfonate.

[0039] In this invention, specific examples of solvent I include, but are not limited to, at least one of: benzene, toluene, xylene, acetone, methanol, ethanol, 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.

[0040] In this invention, the neutralizing agent is a compound that can inhibit the diffusion of acid generated by PAG in the photoresist film or antireflective film. The compound is generally an alkaline compound or a substance that can generate an alkaline compound after exposure. The alkaline compound can be selected from aliphatic primary amines, secondary amines, tertiary amines, mixed amines, aromatic amines or heterocyclic amines. Specific examples of the neutralizing agents include, but are not limited to: methylamine, ethylamine, n-propylamine, isopropylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, methyldiamine, ethylenediamine, tetraethylenepentamine, triethylamine, trimethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triethanolamine, triethanolamine, triisopropanolamine, aniline, benzylamine, phenethylamine, N,N-dimethylbenzylamine, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline The following are all of the following: ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, naphthylamine, diaminonaphthalene, pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, pyrrolidone, N-methylpyrrolidone, pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4-pyrrolidinylpyridine, aminopyridine, dimethylaminopyridine, quinoline, and 3-quinoline nitrile.

[0041] In this invention, specific examples of the surfactants include, but are not limited to: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene glycerol ether; polyoxyethylene alkyl aryl ether surfactants such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; and sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol monooleate, and sorbitol trioleate. Surfactants such as sorbitol tristearate and other sorbitol fatty acid esters, polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tristearate and other polyoxyethylene sorbitol fatty acid esters, and at least one of the following fluorochemical surfactants from 3M: FC-4430, FC-433, FC-431, etc.

[0042] The preparation method of the bottom anti-reflective coating composition provided by the present invention includes: mixing polymer A, polymer B, and optionally a crosslinking agent, a photoacid-producing agent, solvent I, a neutralizing agent and a surfactant, and the resulting mixture is the bottom anti-reflective coating composition.

[0043] This invention also provides the application of the above-mentioned bottom anti-reflective coating composition in photolithography. In practical applications, the bottom anti-reflective coating composition can be used together with a positive photoresist composition, and the method of use is as follows: the bottom anti-reflective coating composition is coated on a substrate, and a bottom anti-reflective coating is formed by thermal curing; then, a photoresist composition is coated on the bottom anti-reflective coating to form a photoresist coating; and then, after exposure and development, a photoresist pattern is obtained.

[0044] In the above practical applications, the coating method can be spin coating, spray coating, etc. Specific examples of the substrate include, but are not limited to, at least one of silicon, silicon oxide, gallium arsenide, silicon carbide, copper, quartz, and ceramic substrates.

[0045] In the above practical application, the conditions for the thermosetting treatment are such that the formed bottom anti-reflective coating is substantially insoluble in the photoresist composition solution and the developer solution. Specifically, the conditions for the thermosetting treatment may include: a temperature of 150–250°C, such as 150°C, 180°C, 200°C, 220°C, 250°C, or any value between them; and a time of 0.5–5 min, such as 0.5 min, 1 min, 2 min, 3 min, 4 min, 5 min, or any value between them. The thickness of the bottom anti-reflective coating is preferably 0.02–0.5 μm, such as 0.02 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, or any value between them, more preferably 0.02–0.2 μm.

[0046] In the above practical applications, the photoresist composition, the method for forming the photoresist coating, and the methods for exposure and development can all be obtained from existing technologies.

[0047] Furthermore, the terms "first," "second," "third," "fourth," "fifth," "sixth," "seventh," "I," and "II" are used for descriptive purposes and should not be construed as a specific limitation on the type or number of technical features.

[0048] The present invention will be described in detail below through specific embodiments. These embodiments are intended to explain the invention and should not be construed as limiting it. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0049] The monomer structures used in the following synthesis examples are shown below:

[0050]

[0051]

[0052] Synthesis Example 1: Synthesis of Polymer A1

[0053] 1.88 g (5 mmol) of monomer A1, 13.04 g (100 mmol) of monomer B1, 14.22 g (100 mmol) of monomer C1, 7.61 g (50 mmol) of monomer D1, and 85.74 g of propylene glycol methyl ether acetate (PGMEA) were placed in a 250 mL three-necked flask equipped with a condenser and a thermometer. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C for 10 min. The temperature was then raised to 60 °C, and 0.37 g of the solution was collected. Azobisisobutyronitrile was dissolved in 10g of propylene glycol ethyl ether, and the resulting solution was added dropwise to a three-necked flask containing the reaction solution over 30 minutes. The reaction was then carried out for 3 hours, followed by heating to 100℃ and holding for another 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The resulting transparent viscous liquid was diluted with tetrahydrofuran to a solid content of 20%, and then precipitated in n-heptane. After drying at 80℃, polymer A1 was obtained, with the following structural formula: Mw = 9800 Daltons, PDI = 1.16.

[0054]

[0055] Synthesis Example 2: Synthesis of Polymer A2

[0056] 1.88 g (5 mmol) of monomer A1, 18.42 g (100 mmol) of monomer B2, 10.01 g (100 mmol) of monomer C2, 12.14 g (50 mmol) of monomer D2, and 99.05 g of propylene glycol methyl ether acetate (PGMEA) were placed in a 250 mL three-necked flask equipped with a condenser and a thermometer. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C for 10 min. The temperature was then raised to 60 °C, and 0.42 g of the solution was taken. Azobisisobutyronitrile was dissolved in 10g of propylene glycol ethyl ether, and the resulting solution was added dropwise to a three-necked flask containing the reaction solution over 30 minutes. The reaction was then carried out for 3 hours, followed by heating to 100℃ and holding for another 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The resulting transparent viscous liquid was diluted with tetrahydrofuran to a solid content of 20%, and then precipitated in n-heptane. After drying at 80℃, polymer A2 was obtained, with the following structural formula: Mw = 9650 Daltons, PDI = 1.09.

[0057]

[0058] Synthesis Example 3: Synthesis of Polymer A3

[0059] 1.71 g (5 mmol) of monomer A2, 13.04 g (100 mmol) of monomer B1, 10.01 g (100 mmol) of monomer C2, 7.61 g (50 mmol) of monomer D1, and 75.52 g of propylene glycol methyl ether acetate (PGMEA) were placed in a 250 mL three-necked flask equipped with a condenser and a thermometer. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C for 10 min. The temperature was then raised to 60 °C, and 0.32 g of the solution was taken. Azobisisobutyronitrile was dissolved in 10g of propylene glycol ethyl ether, and the resulting solution was added dropwise to a three-necked flask containing the reaction solution over 30 minutes. The reaction was then carried out for 3 hours, followed by heating to 100℃ and holding for another 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The resulting transparent viscous liquid was diluted with tetrahydrofuran to a solid content of 20%, and then precipitated in n-heptane. After drying at 80℃, polymer A3 was obtained, with the following structural formula: Mw = 9700 Daltons, PDI = 1.14.

[0060]

[0061] Synthesis Example 4: Synthesis of Polymer A4

[0062] 2.42 g (5 mmol) of monomer A3, 13.04 g (100 mmol) of monomer B1, 14.22 g (100 mmol) of monomer C1, 12.14 g (50 mmol) of monomer D2, and 95.92 g of propylene glycol methyl ether acetate (PGMEA) were placed in a 250 mL three-necked flask equipped with a condenser and a thermometer. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C for 10 min. The temperature was then raised to 60 °C, and 0.41 g of the solution was taken. Azobisisobutyronitrile was dissolved in 10g of propylene glycol ethyl ether, and the resulting solution was added dropwise to a three-necked flask containing the reaction solution over 30 minutes. The reaction was then carried out for 3 hours, followed by heating to 100℃ and holding for another 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The resulting transparent viscous liquid was diluted with tetrahydrofuran to a solid content of 20%, and then precipitated in n-heptane. After drying at 80℃, polymer A4 was obtained, with the following structural formula: Mw = 9846 Daltons, PDI = 1.12.

[0063]

[0064] Synthesis Example 5: Synthesis of Polymer A5

[0065] 1.88 g (5 mmol) of monomer A1, 18.42 g (100 mmol) of monomer B2, 10.01 g (100 mmol) of monomer C2, 7.61 g (50 mmol) of monomer D1, and 88.47 g of propylene glycol methyl ether acetate (PGMEA) were placed in a 250 mL three-necked flask equipped with a condenser and a thermometer. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C for 10 min. The temperature was then raised to 60 °C, and 0.38 g of the solution was taken. Azobisisobutyronitrile was dissolved in 10g of propylene glycol ethyl ether, and the resulting solution was added dropwise to a three-necked flask containing the reaction solution over 30 minutes. The reaction was then carried out for 3 hours, followed by heating to 100℃ and holding for another 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The resulting transparent viscous liquid was diluted with tetrahydrofuran to a solid content of 20%, and then precipitated in n-heptane. After drying at 80℃, polymer A5 was obtained, with the following structural formula: Mw = 9500 Daltons, PDI = 1.08.

[0066]

[0067] Synthesis Example 6: Synthesis of Polymer A6

[0068] 1.71 g (5 mmol) of monomer A2, 13.04 g (100 mmol) of monomer B1, 14.21 g (100 mmol) of monomer C4, 12.14 g (50 mmol) of monomer D2, and 86.1 g of propylene glycol methyl ether acetate (PGMEA) were placed in a 250 mL three-necked flask equipped with a condenser and a thermometer. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C for 10 min. The temperature was then raised to 60 °C, and 0.37 g of the solution was collected. Azobisisobutyronitrile was dissolved in 10g of propylene glycol ethyl ether, and the resulting solution was added dropwise to a three-necked flask containing the reaction solution over 30 minutes. The reaction was then carried out for 3 hours, followed by heating to 100℃ and holding for another 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The resulting transparent viscous liquid was diluted with tetrahydrofuran to a solid content of 20%, and then precipitated in n-heptane. After drying at 80℃, polymer A6 was obtained, with the following structural formula: Mw = 9956 Daltons, PDI = 1.22.

[0069]

[0070] Synthesis Example 7: Synthesis of Polymer A7

[0071] Polymer A was prepared according to the method of Synthesis Example 1, except that 175 mmol of monomer A1, 37.5 mmol of monomer B1, 25 mmol of monomer C1, and 12.5 mmol of monomer D1 were used, and all other conditions were the same as in Synthesis Example 1. Polymer A7 was thus prepared with Mw = 10085 Daltons and PDI = 1.30.

[0072] Synthesis Example 8: Synthesis of Polymer A8

[0073] Polymer A was prepared according to the method of Synthesis Example 1, except that 25 mmol of monomer A1, 50 mmol of monomer B1, 50 mmol of monomer C1, and 125 mmol of monomer D1 were used, and all other conditions were the same as in Synthesis Example 1. Polymer A8 was thus prepared with Mw = 9748 Daltons and PDI = 1.25.

[0074] Synthesis Example 9: Synthesis of Polymer B1

[0075] 10.42 g (100 mmol) of monomer E1, 18.42 g (100 mmol) of monomer B2, 14.22 g (100 mmol) of monomer C1, and 100.5 g of propylene glycol methyl ether acetate (PGMEA) were placed in a 500 mL three-necked flask equipped with a condenser and a thermometer. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C for 10 min. The temperature was then raised to 60 °C, and 0.37 g of azobisisobutyronitrile was dissolved in... The solution was added dropwise to a three-necked flask containing the reaction solution over 30 minutes in 10 g of propylene glycol ethyl ether and reacted for 3 hours. The temperature was then raised to 100°C and maintained for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The resulting transparent viscous liquid was diluted with tetrahydrofuran to a solid content of 20%, and then precipitated in n-heptane. After drying at 80°C, polymer B1 was obtained, with the following structural formula: Mw = 8910 Daltons, PDI: 1.04.

[0076]

[0077] Synthesis Example 10: Synthesis of Polymer B2

[0078] 11.82 g (100 mmol) of monomer E2, 13.01 g (100 mmol) of monomer B4, 14.22 g (100 mmol) of monomer C1, and 91.1 g of propylene glycol methyl ether acetate (PGMEA) were placed in a 500 mL three-necked flask equipped with a condenser and a thermometer. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C for 10 min. The temperature was then raised to 60 °C, and 0.39 g of azobisisobutyronitrile was dissolved in... The solution was added dropwise to a three-necked flask containing the reaction solution over 30 minutes in 10 g of propylene glycol ethyl ether and reacted for 3 hours. The temperature was then raised to 100°C and maintained for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The resulting transparent viscous liquid was diluted with tetrahydrofuran to a solid content of 20%, and then precipitated in n-heptane. After drying at 80°C, polymer B2 was obtained, with the following structural formula: Mw = 7900 Daltons, PDI = 1.02.

[0079]

[0080] Synthesis Example 11: Synthesis of Polymer B3

[0081] 11.82 g (100 mmol) of monomer E3, 21.23 g (100 mmol) of monomer B3, 18.63 g (100 mmol) of monomer C3, and 120.59 g of propylene glycol methyl ether acetate (PGMEA) were placed in a 500 mL three-necked flask equipped with a condenser and a thermometer. Nitrogen gas was introduced for protection, and the mixture was stirred at 30 °C for 10 min. The temperature was then raised to 60 °C, and 0.51 g of azobisisobutyronitrile solution was taken. The solution was added dropwise to a three-necked flask containing the reaction solution over 30 minutes in 10 g of propylene glycol ethyl ether and reacted for 3 hours. The temperature was then raised to 100°C and maintained for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature. The resulting transparent viscous liquid was diluted with tetrahydrofuran to a solid content of 20%, and then precipitated in n-heptane. After drying at 80°C, polymer B3 was obtained, with the following structural formula: Mw = 7860 Daltons, PDI = 1.05.

[0082]

[0083] Synthesis Example 12: Synthesis of Polymer B4

[0084] Polymer B was prepared according to the method of Synthesis Example 8, except that 240 mmol of monomer E1, 30 mmol of monomer B2, and 30 mmol of monomer C1 were used, while the other conditions were the same as in Synthesis Example 8. Polymer B4 was thus prepared with Mw = 8690 Daltons and PDI = 1.22.

[0085] Comparative Synthesis Example 1: Synthesis of Reference Polymer DA1

[0086] The reference polymer was prepared according to the method of Synthesis Example 1, except that the amount of monomer A1 was 0, and all other conditions were the same as in Synthesis Example 1. The reference polymer DA1 prepared in this way has the following structural formula: Mw = 6500 Daltons, PDI = 1.02.

[0087]

[0088] Synthesis of Reference Polymer DA2 in Comparative Synthesis Example 2

[0089] The reference polymer was prepared according to the method of Synthesis Example 7, except that the amount of monomer D1 was 0, and the other conditions were the same as those of Synthesis Example 1. The reference polymer DA2 prepared therefrom has the following structural formula: Mw = 6920 Daltons, PDI = 1.21.

[0090]

[0091] Examples 1-13 and Comparative Examples 1-3

[0092] Polymer A and Polymer B obtained from the above synthesis examples and comparative synthesis examples were formulated with a crosslinking agent, a photoacid-generating agent, a neutralizing agent, a surfactant, and a solvent to prepare bottom antireflective coating compositions. After filtration through a 0.1 nm PTFE membrane, the bottom antireflective coating compositions were obtained. The amounts of each component are shown in Table 1. The crosslinking agent was bis(4-(ethoxy)butyl)succinate, the photoacid-generating agent was triphenylsulfonate trifluoromethanesulfonate (CAS: 66003-78-9), the neutralizing agent was triethanolamine, the surfactant was FC4430 purchased from 3M, and the solvent was propylene glycol monomethyl ether acetate (PGMEA).

[0093] Table 1 (Unit: Parts by Mass)

[0094]

[0095]

[0096] Test case

[0097] (1) The bottom anti-reflective coating composition obtained in the above examples and comparative examples is applied to a silicon wafer and baked at 180°C for 120s to obtain a bottom anti-reflective coating film. The refractive index (n) and extinction coefficient (k) of the bottom antireflective coating film at 193 nm were measured using an ellipticity meter (manufacturer: JAWoolam, equipment name: VUV-303). The initial film thickness was determined using a thin film thickness gauge manufactured by KMAC. The bottom antireflective coating film was immersed in OK73 solvent (purchased from Aladdin, item number D301826) for 120 s, and the film thickness was measured again. The film thickness change rate was calculated as (initial film thickness - film thickness after immersion) / initial film thickness * 100. Powder of the bottom antireflective coating film was scraped from a silicon wafer and its thermal stability was tested using a thermogravimetric analyzer (TGA) under a nitrogen atmosphere, heated from 40 °C to 500 °C. The decomposition temperature was defined as the temperature at which the weight loss was 5%. The contact angle of the bottom antireflective coating film before and after exposure was measured using a contact angle meter (KRUSS, DSA100L), and exposure was performed using an ArF exposure device (NIKON S305B). The test results are shown in Table 2.

[0098] (2) Development effect and linewidth roughness test: Positive photoresist (purchased from Fujifilm, brand PTD FAIR) was spin-coated onto a silicon wafer containing an anti-reflective coating film. The film was baked at 100°C for 90 seconds to form a photoresist film. Exposure was performed using an ArF exposure apparatus (NIKON S305B), followed by heating at 110°C for 90 seconds. Development was then performed with a 2.38% tetramethylammonium hydroxide aqueous solution to form a positive photoresist pattern with a linewidth of 0.13 μm. The residual photoresist after development was observed using a Hitachi electron microscope (S4700), and the linewidth roughness (LWR) was measured using a Hitachi electron microscope (CG4000). The test results are shown in Table 2.

[0099] Table 2

[0100]

[0101]

[0102] As shown in Table 1, compared with Comparative Examples 1-3, the bottom anti-reflective coating compositions provided in Examples 1-13 of the present invention not only have higher refractive index and extinction coefficient and better anti-reflective performance, but also have a smaller film thickness change rate before and after immersion in OK73 solvent and a higher contact angle before exposure. This indicates that the anti-reflective coating has a lower probability of mutual solubility with photoresist, and better adhesion and bonding effect at the contact interface with photoresist, with no residue after development. As a result, the photolithographic pattern obtained has a lower line width roughness.

[0103] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

Claims

1. A bottom anti-reflective coating composition, characterized in that, The bottom antireflective coating composition contains at least polymer A and polymer B; polymer A contains structural unit one derived from the first monomer shown in formula (1), structural unit three derived from the third monomer shown in formula (3), and structural unit four derived from the fourth monomer shown in formula (4), as well as optional structural unit two derived from the second monomer shown in formula (2); polymer B contains structural unit five derived from the fifth monomer shown in formula (5), structural unit six derived from the sixth monomer shown in formula (6), and structural unit seven derived from the seventh monomer shown in formula (7); In formula (1), R1 is a C1-C5 alkylene or fluorinated alkylene, R2 is a single bond, a C1-C5 alkylene or a C1-C5 ketene carbonyl, R3 and R4 are each independently a C1-C5 fluorinated alkylene or a C1-C5 fluorinated ether alkylene, or R3 or R4 is connected to R1 to form a cyclic group structure; In formulas (2) to (4), R5', R6' and R7' are each independently a hydrogen atom or a C1 to C5 alkyl group, R5 is a crosslinkable group, R6 is an acid-unstable group, R7 is any one of hydrogen atom, C1 to C5 alkyl group, C3 to C6 epoxy group, C5 to C8 cycloalkyl group, C6 to C12 aryl or alkylaryl group, C6 to C20 aryl or heteroaryl group, and R8 and R9 are each independently a hydrogen atom, a C1 to C5 alkyl group or a C3 to C20 cycloalkyl group; In equations (5) to (7), R 14 ˋ、R 15 ˋ and R 16 Each ˋ is independently a hydrogen atom or a C1-C5 alkyl group, R 10 ~R 14 Each is independently a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, R 15 R is a crosslinkable group. 16 It is an acid-labile group.

2. The bottom anti-reflective coating composition according to claim 1, characterized in that, The mass ratio of polymer A to polymer B is 1:(0.25~20); Preferably, based on the total molar amount of structural unit one, structural unit two, structural unit three, and structural unit four, the molar content of structural unit one in polymer A is 0.01-50%, the molar content of structural unit two in polymer A is 0-80%, the molar content of structural unit three in polymer A is 10-80%, and the molar content of structural unit four in polymer A is 0.02-80%. Preferably, based on the total molar amount of structural unit five, structural unit six and structural unit seven, the molar content of structural unit five in polymer B is 0.1% to 60%, the molar content of structural unit six in polymer B is 1% to 70%, and the molar content of structural unit seven in polymer B is 1% to 70%. Preferably, the polymer A has a weight-average molecular weight of 1,000 to 20,000 Daltons and a PDI of 0.8 to 3.0; Preferably, the polymer B has a weight-average molecular weight of 2000-15000 Daltons and a PDI of 0.5-2.

0.

3. The bottom anti-reflective coating composition according to claim 1, characterized in that, R5 and R 15 Each is independently a hydrogen atom or a hydroxyl group substituted with a C1–C5 alkyl group, a C3–C20 cycloalkyl group, a C6–C10 alkylaryl group, or a C5–C10 heteroaryl group; R6 and R 16 Each is independently an alkyl group of C1 to C5, an epoxy group of C3 to C6, or a cycloalkyl group of C3 to C10.

4. The bottom anti-reflective coating composition according to claim 1, characterized in that, The polymer A is prepared by the following method: the first monomer shown in formula (1), the third monomer shown in formula (3), the fourth monomer shown in formula (4), and the optional second monomer shown in formula (2) are subjected to a first polymerization reaction in the presence of a first initiator, and the resulting reaction product is polymer A. The polymer B is prepared by the following method: the fifth monomer shown in formula (5), the sixth monomer shown in formula (6) and the seventh monomer shown in formula (7) are subjected to a second polymerization reaction in the presence of a second initiator, and the resulting reaction product is polymer B.

5. The bottom anti-reflective coating composition according to claim 4, characterized in that, The molar ratio of the first monomer, the second monomer, the third monomer, and the fourth monomer is (0.01–50%):(0–80%):(10–80%):(0.02–80%). Preferably, the molar ratio of the fifth monomer, the sixth monomer, and the seventh monomer is (0.1–60%):(1–70%):(1–70%). Preferably, the conditions for the first polymerization reaction and the second polymerization reaction each independently include: being carried out in an inert gas atmosphere, at a temperature of 30–120°C, and for a time of 1–10 hours.

6. The bottom anti-reflective coating composition according to claim 1, characterized in that, The first initiator and the second initiator are each independently selected from at least one of peroxide initiators, azo initiators, and redox initiators.

7. The bottom anti-reflective coating composition according to claim 1, characterized in that, The bottom antireflective coating composition contains polymer A, polymer B, a crosslinking agent, a photoacid-producing agent, solvent I, and optionally a neutralizing agent and a surfactant.

8. The bottom anti-reflective coating composition according to claim 7, characterized in that, Based on the total mass of the bottom antireflective coating composition, the sum of the contents of polymer A and polymer B is 0.1–10 wt%, the content of the crosslinking agent is 0.001–10 wt%, the content of the photoacid-producing agent is 0.001–10 wt%, the content of solvent I is 70–99 wt%, the content of the neutralizing agent is 0–10 wt%, and the content of the surfactant is 0–20 wt%.

9. A method for preparing the bottom anti-reflective coating composition according to any one of claims 1 to 8, characterized in that, The preparation method includes mixing polymer A, polymer B, and optionally a crosslinking agent, a photoacid-producing agent, solvent I, a neutralizing agent, and a surfactant, and the resulting mixture is the bottom anti-reflective coating composition.

10. The application of the bottom anti-reflective coating composition according to any one of claims 1 to 8 in photolithography.

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