Naphthalimide-containing polymer, preparation method thereof, hard mask composition and pattern forming method thereof

Abstract

The present invention belongs to the field of photolithography technology, and specifically relates to a naphthalene-diimide-containing polymer, a preparation method thereof, a hard mask composition, and a method for forming a pattern therein. The naphthalene-diimide-containing polymer has a structure represented by formula (1). The hard mask composition comprises a naphthalene-diimide-containing polymer, a crosslinking agent, a catalyst, a surfactant, and a solvent. The present invention designs and synthesizes a naphthalene-diimide-containing polymer having a specific structure. On the one hand, it can improve the etching resistance of the hard mask composition containing the polymer, and on the other hand, it can also improve the heat resistance of the hard mask composition, providing a solution for ultra-fine photolithography patterns. #imgabs0#

Description

Technical Field

[0001] The present invention belongs to the technical field of photolithography, and in particular relates to a naphthalene diimide-containing polymer and a preparation method thereof, a hard mask composition and a method for forming a pattern thereof. Background Art

[0002] In recent years, with the increasing integration and speed of semiconductor devices, higher requirements have been placed on the precision and size of photolithographic patterns. To achieve ultra-fine patterns with precision sizes ranging from a few nanometers to tens of nanometers, the wavelength of the light source used for photolithography has been shortened, and the thickness of the photoresist film has been gradually reduced to prevent the fine photoresist pattern from collapsing. However, the thinned photoresist film has difficulty providing sufficient etching resistance to achieve pattern transfer. Therefore, in order to form a finer etched pattern, it is necessary to form an intermediate layer of a highly etch-resistant inorganic or organic film between the photoresist and the material layer. This intermediate layer is called a "resist underlayer film" or "hard mask."

[0003] In recent years, spin-on hardmask compositions have gradually replaced chemical vapor deposition hardmasks due to the complex preparation methods, poor film uniformity, and significant startup equipment investment for chemical vapor deposition hardmasks. Currently, spin-on hardmask compositions often utilize high-carbon polymers to enhance etch resistance. However, these high-carbon polymers suffer from poor heat resistance, hindering the formation of refined patterns. Therefore, the research and development of spin-on hardmask compositions that combine excellent heat resistance with etch resistance to enable the formation of finer etch patterns is of great significance. Summary of the Invention

[0004] One of the purposes of the present invention is to address the problem that existing spin-on hard mask compositions have difficulty in simultaneously achieving good heat resistance and etch resistance, and to provide a naphthalene diimide-containing polymer with a specific structure. The naphthalene diimide-containing polymer imparts to the hard mask composition good heat resistance and etch resistance.

[0005] Specifically, the naphthalene diimide-containing polymer has a structure shown in formula (1):

[0006]

[0007] In formula (1), n is an integer of 1 to 300, R1 is hydrogen, C1 to C 10 Alkyl, C6~C 30 Aryl or C6~C 30 substituted aryl, R2 is hydrogen or a C1-C6 alkyl, and R3 is selected from at least one of the following structures:

[0008]

[0009] in, represents the connection bond with other structural units, R4 is hydrogen or a C1-C4 alkyl group, and R5 is hydrogen or a hydroxyl group.

[0010] In a preferred embodiment, the weight average molecular weight of the naphthalene diimide-containing polymer is 2000 to 15000 Da, and the polydispersity PDI is 1.5 to 3.5.

[0011] A second object of the present invention is to provide a method for preparing the above-mentioned naphthalene diimide-containing polymer, which comprises: subjecting a phenol and / or a phenol derivative containing naphthalene diimide-substituted phenol having a structure represented by formula (2) to a condensation reaction with an aldehyde compound and / or a diol compound, to obtain a naphthalene diimide-containing polymer, wherein the phenol derivative containing naphthalene diimide-substituted phenol is a compound in which the hydrogen on the phenolic hydroxyl group of the naphthalene diimide-substituted phenol is substituted with a C1-C6 alkyl group;

[0012]

[0013] In formula (2), R1 is hydrogen, C1~C 10 Alkyl, C6~C 30 Aryl or C6~C 30 The substituted aryl group is R2, and R2 is hydrogen or a C1-C6 alkyl group.

[0014] In a preferred embodiment, the aldehyde compound is an aliphatic aldehyde and / or an aromatic aldehyde.

[0015] In a preferred embodiment, the fatty aldehyde is selected from at least one of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde and butyraldehyde.

[0016] In a preferred embodiment, the aromatic aldehyde is at least one selected from benzaldehyde, naphthalene formaldehyde, anthracene formaldehyde, pyrene formaldehyde and p-hydroxybenzaldehyde.

[0017] In a preferred embodiment, the diol compound is an aromatic diol compound and / or a derivative of an aromatic diol compound.

[0018] In a preferred embodiment, the aromatic diol compound is selected from 1,4-dihydroxymethylbenzene and / or 4,4'-dihydroxymethylbiphenyl.

[0019] In a preferred embodiment, the derivative of the aromatic diol compound is selected from p-bis(methoxymethyl)benzene and / or 4,4'-dimethoxybiphenyl.

[0020] In a preferred embodiment, the molar ratio of the phenol and / or phenol derivative containing naphthalimide substitution to the aldehyde compound is 1:(0.8-2.5).

[0021] In a preferred embodiment, the polycondensation reaction is carried out in the presence of an acid catalyst; the amount of the acid catalyst used is 0.1 to 3.0% of the total mass of the phenol and / or phenol derivative substituted with naphthalimide and the aldehyde compound.

[0022] In a preferred embodiment, the polycondensation reaction conditions include a temperature of 30 to 180° C. and a time of 2 to 50 hours.

[0023] A third object of the present invention is to provide a hard mask composition comprising the above-mentioned naphthalene diimide-containing polymer, a crosslinking agent, a catalyst, a surfactant and a solvent.

[0024] In a preferred embodiment, based on the total mass of the hard mask composition, the content of the naphthalene diimide polymer is 2.0 to 20 wt %, the content of the cross-linking agent is 0.3 to 5 wt %, the content of the catalyst is 0.01 to 0.1 wt %, the content of the surfactant is 0.001 to 0.1 wt %, and the content of the solvent is 76 to 95 wt %.

[0025] A fourth object of the present invention is to provide a pattern forming method, which includes the following steps: providing a material layer on a substrate; applying the above-mentioned hard mask composition on the material layer and heat treating it to form a hard mask; forming a silicon-containing thin layer on the hard mask; forming a photoresist layer on the silicon-containing thin layer; exposing and developing the photoresist layer to form a photoresist pattern; using the photoresist pattern to selectively remove the silicon-containing thin layer and the hard mask to expose a portion of the material layer; and etching the exposed portion of the material layer.

[0026] In a preferred embodiment, the hard mask composition is applied on the material layer by spin coating.

[0027] Compared with the prior art, the beneficial effects of the present invention are as follows: by designing and synthesizing a naphthalene diimide polymer with a specific structure, the present invention can improve the etching resistance of the hard mask composition containing the polymer on the one hand, and on the other hand, it can also improve the heat resistance of the hard mask composition, providing a solution for ultra-fine photolithography patterns. DETAILED DESCRIPTION

[0028] The naphthalene diimide-containing polymer provided by the present invention has a structure shown in formula (1):

[0029]

[0030] In formula (1), n is an integer of 1 to 300, such as 1, 2, 5, 8, 10, 50, 100, 150, 200, 250, 300 or any integer therebetween; R1 is hydrogen, C1 to C 10 Alkyl, C6~C 30 Aryl or C6~C 30 Substituted aryl, C1~C 10 The alkyl group can be: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl -n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl or isoctyl, C6~C 30 The aryl group can be: phenyl, biphenyl, naphthyl, anthracenyl or pyrenyl, C6~C 30The substituted aryl group can be: tolyl, benzyl, naphthylmethyl, anthracenemethyl or pyrenemethyl; R2 is hydrogen or a C1-C6 alkyl group, and the C1-C6 alkyl group can be: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1-ethyl-cyclopropyl, 2 -ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl or 2-isopropyl-cyclopropyl; R3 is selected from at least one of the following structures:

[0031]

[0032] in, Represents the connecting bond with other structural units, R4 is hydrogen or C1~C4 alkyl, C1~C4 alkyl can be: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, R5 is hydrogen or hydroxyl.

[0033] In the present invention, the weight average molecular weight of the naphthalene diimide polymer is preferably 2000-15000 Da, such as 2000 Da, 5000 Da, 8000 Da, 10000 Da, 12000 Da, 15000 Da or any value therebetween; the polydispersity PDI is preferably 1.5-3.5, such as 1.5, 1.8, 2.0, 2.2, 2.5, 2.8, 3.0, 3.5 or any value therebetween.

[0034] The preparation method of the naphthalene imide-containing polymer provided by the present invention comprises: subjecting a phenol and / or phenol derivative containing naphthalene imide-substituted compounds having a structure represented by formula (2) to a condensation reaction with an aldehyde compound and / or a diol compound, and the resulting product is a naphthalene imide-containing polymer, wherein the phenol derivative containing naphthalene imide-substituted compounds are compounds in which the hydrogen atoms on the phenolic hydroxyl groups of the phenol containing naphthalene imide-substituted compounds are substituted by C1-C6 alkyl groups. Specific examples of C1-C6 alkyl groups are as described above. The phenol and / or phenol derivative containing naphthalene imide-substituted compounds can be any compound having a structure represented by formula (2), and their specific type and source are not limited. Preferably, the polymer is prepared by the following method: a halogen-substituted 1,8-naphthalic anhydride is reacted with an organic amine to obtain an intermediate, and the intermediate is reacted with a phenylboronic acid compound to obtain a phenol and / or phenol derivative containing naphthalene imide-substituted compounds having a structure represented by formula (2). The organic amine has a general chemical formula NH2-R1, and is preferably at least one selected from methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, and quinamine.

[0035]

[0036] In formula (2) and formula (3), R1 is hydrogen, C1 to C 10 Alkyl, C6~C 30 Aryl or C6~C 30 substituted aryl, R2 is hydrogen or a C1-C6 alkyl group, and specific examples of R1 and R2 are as described above and are not repeated here.

[0037] In the present invention, the aldehyde compound is a substance capable of undergoing a condensation reaction with a phenol and / or phenol derivative containing a naphthalimide-substituted phenol to provide an R3 group for the naphthalimide-containing polymer, and is preferably an aliphatic aldehyde and / or an aromatic aldehyde. Specific examples of the aliphatic aldehyde include, but are not limited to, at least one of aldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde; specific examples of the aromatic aldehyde include, but are not limited to, at least one of benzaldehyde, naphthaldehyde, anthracenecarboxaldehyde, pyrenecarboxaldehyde, and p-hydroxybenzaldehyde.

[0038] In the present invention, the diol compound is a substance capable of undergoing a condensation reaction with a phenol and / or phenol derivative containing a naphthalimide-substituted compound, thereby providing an R3 group for the naphthalimide-containing polymer. Preferably, the diol compound is an aromatic diol compound and / or an aromatic diol compound derivative. Exemplarily, the aromatic diol compound may be 1,4-dihydroxymethylbenzene and / or 4,4'-dihydroxymethylbiphenyl, or a mixture thereof; and exemplary derivatives of the aromatic diol compound may be p-dimethoxymethylbenzene and / or 4,4'-dimethoxybiphenyl.

[0039] In the present invention, the molar ratio of the phenol and / or phenol derivative containing naphthalene imide substitution to the aldehyde compound is preferably 1:(0.8-2.5), such as 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5 or any value therebetween.

[0040] In the present invention, the polycondensation reaction is preferably carried out in the presence of an acid catalyst, which is more conducive to promoting the polycondensation reaction. The acid catalyst can be an organic acid catalyst and / or an inorganic acid catalyst. Specific examples of organic acid catalysts include, but are not limited to, at least one of p-toluenesulfonic acid, formic acid, oxalic acid, benzoic acid, and salicylic acid; specific examples of inorganic acid catalysts include, but are not limited to, at least one of sulfuric acid, phosphoric acid, perchloric acid, nitric acid, and hydrochloric acid. The amount of the acid catalyst used is preferably 0.1 to 3.0% of the total mass of the phenol and / or phenol derivative substituted with naphthalene diimide and the aldehyde compound, such as 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, or any value therebetween.

[0041] In the present invention, the polycondensation reaction is preferably carried out in the presence of a solvent. The type of solvent is not limited, as long as it is a liquid substance that does not hinder the polycondensation reaction. Specific examples include, but are not limited to, at least one of tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate. Furthermore, if the acid catalyst used is a liquid substance such as formic acid, it can also serve as the solvent.

[0042] In the present invention, the temperature of the polycondensation reaction is preferably 30 to 180° C., such as 30° C., 50° C., 80° C., 100° C., 120° C., 150° C., 180° C., or any value therebetween. The time of the polycondensation reaction can be selected according to the reaction temperature and the molecular weight requirement of the target product, and is preferably 2 to 50 hours, such as 2 hours, 5 hours, 10 hours, 15 hours, 20 hours, 30 hours, 40 hours, 50 hours, or any value therebetween.

[0043] The hard mask composition provided by the present invention contains the above-mentioned naphthalene diimide polymer, a crosslinking agent, a catalyst, a surfactant and a solvent. Based on the total mass of the hard mask composition, the content of the naphthalene diimide polymer is preferably 2.0 to 20 wt%, such as 2 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt% or any value therebetween; the content of the crosslinking agent is preferably 0.3 to 5 wt%, such as 0.3 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% or any value therebetween; the content of the catalyst is preferably 0.01 to 0.1 wt%. t%, such as 0.01wt%, 0.02wt%, 0.05wt%, 0.08wt%, 0.1wt% or any value therebetween; the content of the surfactant is preferably 0.001-0.1wt%, such as 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt% or any value therebetween; the content of the solvent is preferably 76-95wt%, such as 76wt%, 78wt%, 80wt%, 82wt%, 85wt%, 90wt%, 95wt% or any value therebetween.

[0044] In the present invention, the cross-linking agent may be a conventional choice in the prior art, and specific examples thereof include but are not limited to: at least one of glycoluril compounds, epoxy compounds, melamine, melamine derivatives and aromatic compounds.

[0045] In the present invention, the catalyst can be a conventional choice in the prior art and can be an acidic compound, specific examples of which include but are not limited to at least one of p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid and benzene disulfonic acid.

[0046] In the present invention, the surfactant can be a conventional choice in the prior art, and specific examples thereof include but are not limited to at least one of polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0047] In the present invention, the solvent can be a conventional choice in the prior art, as long as it has sufficient solubility or dispersibility for the naphthalene diimide-containing polymer, cross-linking agent, catalyst and surfactant. Specific examples include, but are not limited to, at least one of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), cyclohexanone and ethyl lactate.

[0048] The pattern forming method provided by the present invention comprises the following steps: providing a material layer on a substrate; applying the above-mentioned hard mask composition on the material layer and heat-treating it to form a hard mask; forming a silicon-containing thin layer on the hard mask; forming a photoresist resist layer on the silicon-containing thin layer; exposing and developing the photoresist resist layer to form a photoresist pattern; using the photoresist pattern to selectively remove the silicon-containing thin layer and the hard mask to expose a portion of the material layer; and etching the exposed portion of the material layer.

[0049] In the pattern forming process, the substrate may be selected from at least one of a silicon wafer, a glass substrate, and a polymer substrate. The material layer is the material to be ultimately patterned, and may be a metal layer such as an aluminum layer or a copper layer, a semiconductor layer such as a silicon layer, or an insulating layer such as silicon dioxide or silicon nitride.

[0050] In the above-mentioned pattern formation process, the method for forming the hard mask can be: spin-coating the hard mask composition in the form of a solution on the material layer, and heat-treating the hard mask composition at 200-400°C to form a hard mask. The heat treatment time is about 30s-10min, and the thickness of the hard mask composition is preferably 50-800nm.

[0051] In the pattern forming process, the silicon-containing thin layer can be selected from at least one of silicon nitride, silicon oxide and silicon oxynitride. The photoresist layer exposure can be performed using any one of ArF, KrF or EUV light sources.

[0052] The present invention will be described in detail below through specific examples.

[0053] Synthesis Example 1 Synthesis of Monomer 1

[0054] a. 4-Bromo-1,8-naphthalene dicarboxylic anhydride (5.54 g, 20 mmol) and butylamine (1.76 g, 24 mmol) were dissolved in 50 mL of ethanol solution, reacted at 90°C for 15 h, concentrated under reduced pressure, and diluted with EA (ethyl acetate, 100 mL). The mixture was then washed twice with pure water and saturated brine in sequence. The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel (200-300 mesh) column chromatography to obtain intermediate 1;

[0055] b. Place intermediate 1 (3.32 g, 10 mmol), p-methoxyphenylboronic acid (1.52 g, 10 mmol), tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol), potassium carbonate (2.76 g, 20 mmol), 20 mL of toluene, and 10 mL of water in a three-necked flask, and reflux under nitrogen protection. Monitor by HPLC until the reaction of p-methoxyphenylboronic acid is complete. Terminate the reaction, cool, allow to stand, separate the liquids, wash the organic phase twice with water, dry over anhydrous sodium sulfate, filter, concentrate under reduced pressure, and purify by silica gel (200-300 mesh) column chromatography to obtain monomer 1.

[0056] The synthesis process of monomer 1 is as follows:

[0057]

[0058] The results of nuclear magnetic resonance and mass spectrometry of monomer 1 are shown below, which indicate that monomer 1 indeed has the structure shown in formula (1-1), R1 is n-butyl, and R2 is methyl.

[0059] The results of nuclear magnetic resonance detection of monomer 1: 1 H-NMR(400MHz,CDCl3)δ(ppm)8.72(d,1H,ArH),8.46(d,1H,ArH),8.33(d,1H,ArH),8.04(d,1H,ArH),7.95(t,1H,ArH),7.79(d,2H,P hH),7.21(d,2H,ArH),3.78(s,3H,-OCH3),3.11(t,2H,-NCH2),1.48(m,2H,-NCH2-CH2-),1.25(m,2H,-CH2-CH3),0.88(t,3H,-CH3).

[0060] Mass spectrometry results of monomer 1: HRMS (ESI): m / z calcd.For C 23 H 21 NO3(M+)359.43; found=382.41([M+Na] + ,100).

[0061] Synthesis Example 2 Synthesis of Monomer 2

[0062] a. 4-Bromo-1,8-naphthalene dicarboxylic anhydride (5.54 g, 20 mmol) and octylamine (3.10 g, 24 mmol) were dissolved in 50 mL of ethanol solution, reacted at 90°C for 15 h, concentrated under reduced pressure, and diluted with EA (ethyl acetate, 100 mL). The mixture was then washed twice with pure water and saturated brine in sequence. The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by silica gel (200-300 mesh) column chromatography to obtain intermediate 2;

[0063] b. Place intermediate 2 (3.88 g, 10 mmol), p-methoxyphenylboronic acid (1.52 g, 10 mmol), tetrakistriphenylphosphine palladium (0.35 g, 0.3 mmol), potassium carbonate (2.76 g, 20 mmol), 20 mL of toluene, and 10 mL of water in a three-necked flask, and reflux under nitrogen protection. Monitor by HPLC until the reaction of p-methoxyphenylboronic acid is complete. Terminate the reaction, cool, allow to stand, separate the liquids, wash the organic phase twice with water, dry over anhydrous sodium sulfate, filter, concentrate under reduced pressure, and purify by silica gel (200-300 mesh) column chromatography to obtain monomer 2.

[0064] The synthesis process of monomer 2 is as follows:

[0065]

[0066] The results of nuclear magnetic resonance and mass spectrometry of monomer 2 are shown below, which indicate that monomer 2 indeed has the structure shown in formula (1-2), R1 is an n-octyl group, and R2 is a methyl group.

[0067] The results of nuclear magnetic resonance detection of monomer 2: 1 H-NMR(400MHz,CDCl3)δ(ppm)8.67(d,1H,ArH),8.45(d,1H,ArH),8.29(d,1H,ArH),8.02(d,1H,ArH),7.92(t,1H,ArH),7.68(d,2H,PhH) ,7.16(d,2H,ArH),3.83(s,3H,-OCH3),3.15(t,2H,-NCH2),1.72(m,2H,-NCH2CH2),1.38-1.19(m,10H,-(CH2)5-CH3),0.83(t,3H,-CH3).

[0068] Mass spectrometry results of monomer 2: HRMS (ESI): m / z calcd.For C 27 H 29 NO3(M+)415.53; found=438.47([M+Na] + ,100).

[0069] Synthesis Example 3 Synthesis of Monomer 3

[0070] Monomer 1 (3.59 g, 10 mmol) and 50 mL of dichloromethane were placed in a three-necked flask and stirred evenly. Then, a dichloromethane solution of boron tribromide (configuration ratio: BBr3 (12.53 g, 50 mmol) dissolved in 50 mL of DCM) was slowly added dropwise at 0°C in an ice bath. After the addition was completed, the reaction mixture was reacted for 24 hours. The reaction mixture was then slowly poured into ice water, and the pH value was adjusted to about 7 with NaHCO3. Solids precipitated and were filtered to obtain monomer 3.

[0071] The synthesis process of monomer 3 is as follows:

[0072]

[0073] The results of nuclear magnetic resonance and mass spectrometry of monomer 3 are shown below, which indicate that monomer 3 indeed has the structure shown in formula (1-3), R1 is n-butyl, and R2 is hydrogen.

[0074] The results of nuclear magnetic resonance detection of monomer 3: 1 H-NMR(400MHz,CDCl3)δ(ppm)9.45(s,1H,-OH),8.7(d,1H,ArH),8.48(d,1H,ArH),8.32(d,1H,ArH),8.06(d,1H,ArH),7.93(t,1H, ArH),7.52(d,2H,PhH),6.95(d,2H,ArH),3.10(t,2H,-NCH2),1.46(m,2H,-NCH2-CH2-),1.24(m,2H,-CH2-CH3),0.89(t,3H,-CH3).

[0075] Mass spectrometry results of monomer 3: HRMS (ESI): m / z calcd.For C 22 H 19 NO3(M+)345.39; found=367.98([M+Na] + ,100).

[0076] Synthesis Example 4 Synthesis of Monomer 4

[0077] Monomer 2 (4.16 g, 10 mmol) and 50 mL of dichloromethane were placed in a three-necked flask and stirred evenly. Then, a dichloromethane solution of boron tribromide (configuration ratio: BBr3 (12.53 g, 50 mmol) dissolved in 50 mL of DCM) was slowly added dropwise at 0°C in an ice bath. After the addition was completed, the reaction mixture was reacted for 24 hours. The reaction mixture was then slowly poured into ice water and the pH value was adjusted to about 7 with NaHCO3. Solids precipitated and were filtered to obtain monomer 4.

[0078] The synthesis process of monomer 4 is specifically as follows:

[0079]

[0080] The results of nuclear magnetic resonance and mass spectrometry of monomer 4 are shown below, which indicate that monomer 4 indeed has the structure shown in formula (1-4), R1 is n-octyl, and R2 is hydrogen.

[0081] The results of nuclear magnetic resonance detection of monomer 4: 1 H-NMR(400MHz,CDCl3)δ(ppm)9.56(s,1H,-OH),8.69(d,1H,ArH),8.46(d,1H,ArH),8.31(d,1H,ArH),8.03(d,1H,ArH),7.94(t,1H,ArH),7.71(d, 2H,PhH),7.13(d,2H,ArH),3.81(s,3H,-OCH3),3.16(t,2H,-NCH2),1.74(m,2H,-NCH2CH2),1.37-1.19(m,10H,-(CH2)5-CH3),0.85(t,3H,-CH3).

[0082] Mass spectrometry results of monomer 4: HRMS (ESI): m / z calcd.For C 26 H 27 NO3(M+)401.51; found=424.19([M+Na] + ,100).

[0083] Preparation Example 1 Preparation of Naphthalene Diimide-Containing Polymer 2-1

[0084] At room temperature, 3.59 g (10 mmol) of monomer 1, 0.30 g (10 mmol) of paraformaldehyde, 0.078 g of p-toluenesulfonic acid, and 35.05 g of propylene glycol monomethyl ether acetate (PGMEA) were added to a 100 mL three-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser, and a water separator. Under nitrogen protection, the temperature was raised to 100° C., and after the reactants were completely dissolved, the reaction system began to reflux and reacted for 10 hours. The reaction system was cooled to room temperature, and the reaction solution was slowly added to methanol and stirred for 30 minutes. The precipitate was filtered, and the filter cake was further washed twice with methanol and dried in a vacuum oven at 60° C. for 10 hours to obtain a naphthalene diimide-containing polymer as shown in Chemical Formula 2-1, having a weight-average molecular weight Mw of 6600 Da, a PDI of 2.08, and n of 12.

[0085] Preparation Example 2 Preparation of Naphthalimide-Containing Polymer 2-2

[0086] At room temperature, 4.16 g (10 mmol) of monomer 2, 0.30 g (10 mmol) of paraformaldehyde, 0.089 g of p-toluenesulfonic acid, and 40.10 g of propylene glycol monomethyl ether acetate (PGMEA) were added to a 100 mL three-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser, and a water separator. Under nitrogen protection, the temperature was raised to 100° C., and after the reactants were completely dissolved, the reaction system began to reflux and reacted for 10 hours. The reaction system was cooled to room temperature, and the reaction solution was slowly added to methanol and stirred for 30 minutes. The precipitate was filtered, and the filter cake was further washed twice with methanol and dried in a vacuum oven at 60° C. for 10 hours to obtain a naphthalene diimide-containing polymer as shown in Chemical Formula 2-2, having a weight-average molecular weight Mw of 6200 Da, a PDI of 1.96, and n of 10.

[0087] Preparation Example 3 Preparation of Naphthalimide-Containing Polymer 2-3

[0088] At room temperature, 3.45 g (10 mmol) of monomer 3, 0.30 g (10 mmol) of paraformaldehyde, 0.075 g of p-toluenesulfonic acid, and 33.79 g of propylene glycol monomethyl ether acetate (PGMEA) were added to a 100 mL three-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser, and a water separator. Under nitrogen protection, the temperature was raised to 100° C., and after the reactants were completely dissolved, the reaction system began to reflux and reacted for 10 h. The reaction system was cooled to room temperature, and the reaction solution was slowly added to methanol and stirred for 30 min. The precipitate was filtered, and the filter cake was further washed twice with methanol and dried in a vacuum oven at 60° C. for 10 h to obtain a naphthalene diimide-containing polymer as shown in Chemical Formula 2-3, having a weight-average molecular weight Mw of 7100 Da, a PDI of 2.03, and n of 15.

[0089] Preparation Example 4 Preparation of Naphthalimide-Containing Polymer 2-4

[0090] At room temperature, 4.02 g (10 mmol) of monomer 4, 0.30 g (10 mmol) of paraformaldehyde, 0.086 g of p-toluenesulfonic acid, and 38.84 g of propylene glycol monomethyl ether acetate (PGMEA) were added to a 100 mL three-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser, and a water separator. Under nitrogen protection, the temperature was raised to 100° C., and after the reactants were completely dissolved, the reaction system began to reflux and reacted for 10 h. The reaction system was cooled to room temperature, and the reaction solution was slowly added to methanol and stirred for 30 min. The precipitate was filtered, and the filter cake was further washed twice with methanol and dried in a vacuum oven at 60° C. for 10 h to obtain a naphthalene diimide-containing polymer as shown in Chemical Formula 2-4, having a weight-average molecular weight Mw of 6800 Da, a PDI of 2.00, and n of 13.

[0091] Preparation Example 5 Preparation of Naphthalimide-Containing Polymer 2-5

[0092] At room temperature, 3.45 g (10 mmol) of monomer 3, 1.66 g (10 mmol) of p-bis(methoxymethyl)benzene, 0.10 g of p-toluenesulfonic acid, and 46.05 g of propylene glycol monomethyl ether acetate (PGMEA) were added to a 100 mL three-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser, and a water separator. Under nitrogen protection, the temperature was raised to 100° C., and after the reactants were completely dissolved, the reaction system began to reflux and the reaction timer was set, and the reaction was continued for 10 h. The reaction system was cooled to room temperature, and the reaction solution was slowly added to methanol and stirred for 30 min. The precipitate was filtered, and the filter cake was further washed twice with methanol and dried in a vacuum oven at 60° C. for 10 h to obtain a naphthalene diimide-containing polymer as shown in Chemical Formula 2-5, having a weight-average molecular weight Mw of 7600 Da, a PDI of 2.17, and n of 11.

[0093] Preparation Example 6 Preparation of Naphthalimide-Containing Polymer 2-6

[0094] At room temperature, 4.02 g (10 mmol) of monomer 4, 1.66 g (10 mmol) of p-bis(methoxymethyl)benzene, 0.11 g of p-toluenesulfonic acid, and 51.09 g of propylene glycol monomethyl ether acetate (PGMEA) were added to a 100 mL three-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser, and a water separator. Under nitrogen protection, the temperature was raised to 100° C., and after the reactants were completely dissolved, the reaction system began to reflux and the reaction timer was set, and the reaction was continued for 10 h. The reaction system was cooled to room temperature, and the reaction solution was slowly added to methanol and stirred for 30 min. The precipitate was filtered, and the filter cake was further washed twice with methanol and dried in a vacuum oven at 60° C. for 10 h to obtain a naphthalene diimide-containing polymer as shown in Chemical Formula 2-6, having a weight-average molecular weight Mw of 7400 Da, a PDI of 2.15, and n of 10.

[0095] Preparation Example 7 Preparation of Naphthalimide-Containing Polymer 2-7

[0096] A naphthalene diimide-containing polymer was prepared according to the method of Preparation Example 1, except that the same molar amount of benzaldehyde (1.06 g, 10 mmol) was used instead of paraformaldehyde. The other conditions were the same as those in Preparation Example 1, thereby preparing a naphthalene diimide-containing polymer 2-7 as described in Chemical Formula 2-7, having a weight-average molecular weight Mw of 6900 Da, a PDI of 2.14, and n of 10.

[0097] Preparation Example 8 Preparation of Naphthalimide-Containing Polymer 2-8

[0098] A naphthalene diimide-containing polymer was prepared according to the method of Preparation Example 1, except that the same molar amount of 9-anthracene formaldehyde (2.06 g, 10 mmol) was used instead of paraformaldehyde. The other conditions were the same as those in Preparation Example 1, thereby preparing a naphthalene diimide-containing polymer 2-8 as described in Chemical Formula 2-8, having a weight average molecular weight Mw of 7200 Da, a PDI of 2.21, and n of 9.

[0099]

[0100] Comparative Preparation Example 1 Preparation of Reference Polymer 3-1

[0101] At room temperature, 7.21 g of 1-naphthol, 1.50 g of paraformaldehyde, 0.17 g of p-toluenesulfonic acid and 78.39 g of propylene glycol monomethyl ether acetate (PGMEA) were added to a 100 mL three-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser and a water separator. The temperature was raised to 80° C. under nitrogen protection. After the reactants were completely dissolved, the reaction system began to reflux and reacted for 10 hours; the reaction system was cooled to room temperature, the reaction solution was slowly added to methanol and stirred for 30 minutes, the precipitate was filtered, and the filter cake was further washed twice with methanol and dried in a vacuum oven at 60° C. for 10 hours to obtain a naphthalene diimide-containing polymer as shown in Chemical Formula 3-1, whose weight average molecular weight M w The molecular weight is 6500Da and the PDI is 1.84.

[0102]

[0103] Examples 1 to 8 and Comparative Example 1

[0104] The naphthalene imide-containing polymers of Preparation Examples 1-8 and the polymer of Comparative Preparation Example 1 were added to a clean bottle along with a catalyst, a crosslinker, a solvent, and a surfactant according to the ratios shown in Table 1. The mixture was shaken until all components were completely dissolved. Each sample was then filtered through a 0.2 μm PTFE membrane filter and placed into a new clean bottle to obtain a hard mask composition. The catalyst was p-toluenesulfonic acid, the crosslinker was tetramethoxymethyl glycoluril, the solvent was propylene glycol monomethyl ether acetate (PGMEA), and the surfactant was polyoxyethylene lauryl ether.

[0105] Table 1

[0106]

[0107] Test Case

[0108] The heat resistance and etching resistance of the hard mask compositions prepared in the above examples and comparative examples were tested according to the following methods.

[0109] (1) Heat resistance test: The hard mask composition solutions of Examples 1 to 8 and Comparative Example 1 in Table 1 were respectively coated on silicon wafers using a spin coating machine and heat-treated at 350°C for 150s to form hard masks. The hard masks were scraped from the silicon wafers to obtain powders, and the weight loss rates of the above powders were measured using a thermogravimetric analyzer (TGA) under a nitrogen atmosphere at a temperature of 30°C to 400°C. The results are shown in Table 2.

[0110] The mass loss rate is calculated as follows: mass loss rate = (initial mass - mass at 400° C.) / initial mass × 100%.

[0111] (2) Etching resistance test: The hard mask composition solutions of Examples 1 to 8 and Comparative Example 1 in Table 1 were respectively coated on silicon wafers using a spin coating machine and heat treated at 350°C for 150s to form hard mask films (film thickness 300nm); CF4 gas was used as the etching gas to measure the dry etching rate. The results are shown in Table 2.

[0112] The dry etching rate ratio is calculated as follows: etching rate = (initial hard mask thickness - hard mask thickness after etching) / etching time.

[0113] Table 2

[0114]

[0115] As can be seen from the results in Table 1, compared with Comparative Example 1, when the naphthalene diimide-containing polymer provided in the embodiment of the present invention is used as the hard mask composition, the mass loss rate of the hard mask composition at 400°C is smaller and the dry etching rate is lower, indicating that the hard mask composition has good heat resistance and etching resistance.

[0116] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative 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 purpose of the present invention.

Claims

1. A naphthalimide-containing polymer, characterized in that: The naphthalene diimide-containing polymer has a structure shown in formula (1): In formula (1), n is an integer of 1 to 300, R1 is hydrogen, C1 to C 10 Alkyl, C6~C 30 Aryl or C6~C 30 Substituted aryl, C6~C 30 The substituted aryl group is tolyl, benzyl, naphthylmethyl, anthracenemethyl or pyrenemethyl, R2 is hydrogen or a C1-C6 alkyl group, and R3 is selected from at least one of the following structures: in, Represents the connection bond with other structural units, R4 is hydrogen or C1-C4 alkyl, R5 is hydrogen or hydroxyl; The weight average molecular weight of the naphthalene diimide-containing polymer is 2000-15000 Da, and the polydispersity PDI is 1.5-3.

5.

2. The method for preparing a naphthalene diimide-containing polymer according to claim 1, wherein: The method comprises: subjecting a phenol and / or a phenol derivative substituted with naphthalene imide having a structure represented by formula (2) to a condensation reaction with an aldehyde compound, and the resulting product is a naphthalene imide polymer, wherein the phenol derivative substituted with naphthalene imide is a compound in which the hydrogen on the phenolic hydroxyl group of the phenol substituted with naphthalene imide is substituted with a C1-C6 alkyl group; In formula (2), R1 is hydrogen, C1~C 10 Alkyl, C6~C 30 Aryl or C6~C 30 The substituted aryl group is R2, and R2 is hydrogen or a C1-C6 alkyl group.

3. The method for preparing a naphthalene diimide-containing polymer according to claim 2, wherein: The aldehyde compound is an aliphatic aldehyde and / or an aromatic aldehyde.

4. The method for preparing a naphthalene diimide-containing polymer according to claim 3, wherein: The fatty aldehyde is selected from at least one of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde and butyraldehyde.

5. The method for preparing a naphthalene diimide-containing polymer according to claim 3, wherein: The aromatic aldehyde is selected from at least one of benzaldehyde, naphthalene formaldehyde, anthracene formaldehyde, pyrene formaldehyde and p-hydroxybenzaldehyde.

6. The method for preparing a naphthalene diimide-containing polymer according to claim 2, wherein: The molar ratio of the phenol and / or phenol derivative containing naphthalene diimide substitution to the aldehyde compound is 1:(0.8-2.5).

7. The method for preparing a naphthalene diimide-containing polymer according to claim 2, wherein: The polycondensation reaction is carried out in the presence of an acid catalyst.

8. The method for preparing a naphthalene diimide-containing polymer according to claim 7, wherein: The amount of the acid catalyst used is 0.1-3.0% of the total mass of the phenol and / or phenol derivative substituted with naphthalimide and the aldehyde compound.

9. The method for preparing a naphthalimide-containing polymer according to claim 7, wherein: The conditions of the polycondensation reaction include a temperature of 30 to 180° C. and a time of 2 to 50 hours.

10. A hard mask composition, characterized in that The hard mask composition comprises the naphthalene dicarboximide-containing polymer according to claim 1, a crosslinking agent, a catalyst, a surfactant and a solvent.

11. The hard mask composition according to claim 10, wherein Based on the total mass of the hard mask composition, the content of the naphthalene diimide polymer is 2.0-20 wt %, the content of the crosslinker is 0.3-5 wt %, the content of the catalyst is 0.01-0.1 wt %, the content of the surfactant is 0.001-0.1 wt %, and the content of the solvent is 76-95 wt %.

12. A pattern forming method, characterized in that: The method comprises the following steps: providing a material layer on a substrate; applying the hard mask composition according to claim 10 or 11 on the material layer and heat-treating it to form a hard mask; forming a silicon-containing thin layer on the hard mask; forming a photoresist layer on the silicon-containing thin layer; exposing and developing the photoresist layer to form a photoresist pattern; selectively removing the silicon-containing thin layer and the hard mask using the photoresist pattern to expose a portion of the material layer; and etching the exposed portion of the material layer.

13. The pattern forming method according to claim 12, wherein: The hard mask composition is applied on the material layer by spin coating.

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