Antireflective compositions and antireflective films and uses thereof

Abstract

The present application belongs to the field of semiconductor processing, and provides an antireflection composition, an antireflection film and application thereof. The antireflection composition comprises a polymer, an acid generator, a crosslinking agent, a solvent and an optional surfactant, wherein the polymer is formed by a condensation reaction of compound A and compound B, and L is an alkylene group with 1-8 carbon atoms. The antireflection film prepared from the antireflection composition has solvent resistance, can prevent intermixing with a photoresist layer, and has high refractive index, low extinction coefficient and excellent etching rate.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of semiconductor processing, and particularly provides an antireflection composition, a preparation method and application thereof. BACKGROUND

[0002] In the manufacture of semiconductor devices, photolithography using a photoresist composition is a necessary means for realizing the key steps of accurate etching of circuit patterns, thin film deposition, etc. The microfabrication of semiconductor devices generally refers to a processing method in which a photoresist film is formed on a substrate such as a silicon wafer, active light such as ultraviolet light is irradiated through a mask pattern in which a semiconductor device pattern is drawn on the film, and the obtained resist pattern is used as a protective film to etch the silicon wafer. In recent years, with the continuous development of high integration of semiconductor devices, the active light used also has a tendency of shortening the wavelength from i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm) to ArF excimer laser (wavelength 193 nm). At the same time, the influence of the diffuse reflection of active light from the substrate and the standing wave becomes a big problem. In order to improve the accuracy of photolithography and the resolution of the pattern, methods of providing an antireflection film between the photoresist film and the substrate are increasingly widely studied.

[0003] The antireflection film refers to adding an antireflection material between the photoresist and the substrate, which can effectively eliminate the interference standing wave caused by light reflection. The antireflection film can increase the exposure energy range and focal length, reduce the influence of the geometric structure difference of the substrate on the critical dimension uniformity, and at the same time reduce the circular notch caused by the scattering of reflected light, and alleviate the swing curve effect and the concave defect effect caused by the different thicknesses of the photoresist due to the configuration of the substrate. Nowadays, the field of semiconductor and integrated circuit manufacturing is still striving to improve the resolution of the photoresist pattern, and therefore higher requirements are put forward for the performance of the antireflection coating composition.

[0004] At present, isocyanurate compounds are often used in antireflection coating compositions. Although the existing isocyanurate compounds have high antireflection effect, they have poor optical properties, i.e. low refractive index and high extinction absorption, which limits their application in the field of photolithography. SUMMARY

[0005] In view of the above problems existing in the prior art, the purpose of the present application is to provide an antireflection composition and an antireflection film and application thereof. The antireflection film prepared from the antireflection composition has solvent resistance, can prevent intermixing with the photoresist layer, and has high refractive index, low extinction coefficient and excellent etching rate.

[0006] In a first aspect, the present invention provides an antireflective composition comprising a polymer, an acid generator, a crosslinking agent, a solvent, and an optional surfactant, wherein the polymer is a product formed by a condensation reaction of compound A and compound B, the compound A is a triazine compound having a structure as shown in Formula 1, and the compound B is a compound having two epoxy groups.

[0007]

[0008] In Formula 1, L is selected from an alkylene group having 1 to 8 carbon atoms or an arylene group having 6 to 12 carbon atoms. The anti-reflective composition of the present invention comprises a condensation product of a triamine-carboxyl-substituted triazine and a diepoxy compound. The condensation product comprises a main chain structure composed of nitrogen-containing heterocycles (triazine), amino groups, and ester groups (-COO-, formed by the condensation of epoxy groups and carboxyl groups), and nitrogen-containing side chain structures formed by amino groups (-NH-). The polymer meeting these structural characteristics can significantly improve the etching rate, and the polymer also has a high refractive index n and a low absorbance k. Thus, the polymer is applied to anti-reflective adhesives and interacts with components such as crosslinking agents, surfactants, and acid generators to improve the optical properties of the resulting anti-reflective film, increasing solvent resistance and etching rate.

[0009] In a second aspect, the present invention provides an anti-reflection film, which is formed by coating the anti-reflection composition described in the first aspect of the present invention on a substrate and curing the coating.

[0010] In particular, the antireflection film can efficiently absorb reflected light from a substrate when ArF excimer laser (wavelength 193 nm) is used in microfabrication in a photolithography process, and has a high refractive index, a low extinction coefficient, and a higher dry etching rate.

[0011] In a third aspect, the present invention provides use of the anti-reflective composition described in the first aspect or the anti-reflective film described in the second aspect in preparing photolithographic patterns.

[0012] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. DETAILED DESCRIPTION

[0013] 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 understood as limiting the present invention.

[0014] The "ranges" disclosed herein are defined in terms of lower and / or upper limits, with a given range being defined by selecting a lower limit and / or an upper limit. Ranges defined in this manner may be inclusive or exclusive of the end values ​​and may be combined arbitrarily, i.e., any lower limit may be combined with any upper limit to form an unspecified range, and any lower limit may be combined with any other lower limit to form an unspecified range, and similarly, any upper limit may be combined with any other upper limit to form an unspecified range. In addition, each separately disclosed point or single value may itself be combined as a lower limit or upper limit with any other point or single value, or with other lower limits or upper limits to form an unspecified range.

[0015] 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.

[0016] In the present invention, alkyl groups may include straight-chain alkyl groups and branched-chain alkyl groups. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, heptyl, n-octyl, 2-ethylhexyl, and the like. An alkylene group refers to a divalent group formed by further losing a hydrogen atom from an alkyl group. The number of carbon atoms in the alkylene group may be 1 to 8, specifically 1, 2, 3, 4, 5, 6, 7, or 8.

[0017] In the present invention, an arylene group refers to a divalent group formed by losing a hydrogen atom from an aryl group, wherein specific examples of the aryl group include phenyl, naphthyl, and biphenyl.

[0018] In the present invention, Indicates a connecting bond. Further, the non-positioned connecting bond involved in the ring refers to the one extending from the ring system. It means that one end of the connecting bond can be connected to any position in the ring system that the bond passes through, and the other end is connected to the rest of the compound structure. For example, the group shown in formula a below includes any possible connection method shown in formulas a-1 to a-3:

[0019]

[0020] A first aspect of the present invention provides an antireflective composition comprising a polymer, an acid generator, a crosslinking agent, a solvent, and an optional surfactant, wherein the polymer is a condensation polymer formed by a condensation reaction of compound A and compound B.

[0021] In the present invention, the compound A is a triazine compound having a structure as shown in Formula 1,

[0022]

[0023] In Formula 1, L is selected from an alkylene group having 1 to 8 carbon atoms or an arylene group having 6 to 12 carbon atoms.

[0024] Compound B is a compound having two epoxy groups (a diepoxy compound). The epoxy group in compound B undergoes a ring-opening reaction with the carboxyl group in compound A during the polycondensation reaction to form an ester group, thereby obtaining a polycondensate having a molecular structure of triazine, amine (-NH-), and ester (-COO-).

[0025] In some embodiments, in Formula 1, L is selected from an alkylene group or a phenylene group having 1 to 5 carbon atoms.

[0026] Specifically, in Formula 1, Any one of the following groups:

[0027]

[0028] Wherein, n is 1, 2, 3, 4 or 5; R is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isopropyl, tert-butyl, etc.

[0029] In some embodiments, the compound A is selected from at least one of the following compounds A-1 to A-6:

[0030]

[0031] In the present invention, the compound A can be obtained commercially or synthesized by methods well known in the art, for example, in the presence of a base and a solvent (such as water), cyanuric chloride (TCT) and compound C (structure ) was prepared by high temperature reflux or microwave irradiation according to the following synthetic route. The specific synthetic method can be found in the literature: Karuehanon et al. Microwave-assisted S N Ar reaction of 2,4,6-trichloro-1,3,5-triazine for therapid synthesis of C3-symmetrical polycarboxylate ligands[J], Tetrahedron Letters 53(2012)3486–3489.

[0032]

[0033] In some embodiments, the compound B may be selected from diepoxy compounds containing a sulfur atom (S).

[0034] Furthermore, the compound B is selected from at least one of 4,4'-sulfonyldiphenol diglycidyl ether (as shown in formula b-1), 4,4'-bis(glycidoxy)diphenyl disulfide (as shown in formula b-2) and 1,1'-dioxirane ethyl sulfide (as shown in formula b-3):

[0035]

[0036] In some embodiments, the molar ratio of compound A to compound B is (0.8-2.0):1, for example, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.5:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, etc.

[0037] In some embodiments, the conditions of the polycondensation reaction include: a temperature of 80 to 100°C, for example, 80°C, 85°C, 90°C, 92°C, 95°C, 98°C, 100°C, etc.; and a time of 5 to 10h, for example, 5h, 6h, 7.5h, 8h, 8.5h, 9h, 10h, etc.

[0038] In the present invention, the polycondensation method may include solution polycondensation.

[0039] As some specific embodiments, the polymer can be prepared by a method comprising the following steps:

[0040] (1) Under the protection of an inert gas, in the presence of a catalyst and an organic solvent, compound A and compound B are subjected to a reflux reaction under stirring conditions to form a resin (i.e., a polymer), thereby obtaining a reaction solution containing the polymer;

[0041] (2) diluting the reaction solution with an organic solvent to obtain a reaction dilution solution;

[0042] (3) Under stirring conditions, the reaction dilution solution is dropped into water to disperse and precipitate the polymer, which is then recovered (e.g., by centrifugal separation), washed, and dried to obtain the polymer.

[0043] In step (1), the inert gas is, for example, nitrogen.

[0044] In step (1), the catalyst can be selected from alkaline catalysts commonly used in polycondensation reactions.

[0045] Furthermore, the catalyst is at least one of benzyltriethylammonium chloride, tetrabutylammonium chloride and tetraethylammonium bromide.

[0046] Furthermore, based on the total mass of the compound A and the compound B, the mass dosage of the catalyst is 0.5% to 2%, for example, 0.55%, 0.6%, 0.65%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.5%, 1.7%, 1.8%, etc.

[0047] In step (1) and step (2), the organic solvent used can be selected from various inert solvents. Further, the organic solvent is selected from at least one of propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, butyl lactate, propylene glycol monomethyl ether and N-methyl pyrrolidone.

[0048] In step (1), the mass ratio of the total mass of the compound A and the compound B to the organic solvent can be 1:(1.5-3), for example, 1:1.5, 1:1.6, 1:1.8, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.7, etc.

[0049] The mass ratio of the organic solvent in step (2) to the organic solvent in step (1) can be (0.8-1.5):1, for example, 0.8:1, 0.9:1, 1:1, 1.2:1, etc.

[0050] In step (3), the solvent used for washing may be water.

[0051] In step (3), the drying may be vacuum drying.

[0052] In some embodiments, the structure of the polymer includes at least one of the repeating units shown in Formula I to Formula III:

[0053]

[0054] In the repeating unit, the carboxyl group retained in the side chain can improve the solubility of the polymer in the composition. As some examples, the repeating unit can specifically be the following structure:

[0055]

[0056]

[0057] In some embodiments, the weight average molecular weight (M w ) is 1500 to 5000, preferably 2000 to 4500, and the molecular weight distribution index PDI (M w / M n , M n is the number average molecular weight) can be 1.2 to 2.0.

[0058] In the present invention, the molecular weight of the polymer can be measured by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0059] In some embodiments, based on the total mass of the anti-reflective composition, the mass content of the polymer can be 5% to 15%, for example, 5%, 6%, 7%, 7.5%, 8%, 9%, 9.5%, 9.8%, 9.9%, 10%, 10.2%, 10.5%, 11%, 12%, 13%, 15%, etc.

[0060] In the present invention, the acid generator can be used as a catalyst for the curing reaction, and can be specifically selected from a thermal acid generator and / or a photoacid generator, preferably a thermal acid generator.

[0061] In the present invention, the thermal acid generator can be selected from various sulfonic acid compounds and carboxylic acid compounds. As some examples, the thermal acid generator can be selected from at least one of p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, pyridinium phenolsulfonic acid, pyridinium p-hydroxybenzenesulfonate, pyridinium trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0062] In the present invention, the photoacid generator can be selected from various onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0063] As some examples, the onium salt compound can be one or more of diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate.

[0064] As some examples, the sulfonimide compound may be one or more of N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0065] As some examples, the disulfonyldiazomethane compound may be one or more of bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0066] In some embodiments, based on the total weight of the anti-reflective composition, the mass content of the acid generator is 0.1% to 5%, for example, 0.1%, 0.2%, 0.5%, 0.6%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 2%, 3%, 3.5%, 4%, 5%, etc.

[0067] In the present invention, the addition of the crosslinking agent can prevent the antireflective film from mixing with the photoresist. Generally, the crosslinking agent can be selected from various substituted urea compounds. According to some embodiments, the crosslinking agent is selected from at least one of 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0068] In some embodiments, based on the total weight of the anti-reflective composition, the mass content of the crosslinking agent is 1% to 10%, for example, 1%, 2%, 2.5%, 3%, 3.2%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 9%, 10%, etc.

[0069] In the present invention, the antireflective composition may or may not contain a surfactant. According to some embodiments, the surfactant may be a fluorinated surfactant and / or a non-fluorinated surfactant, preferably a non-ionic fluorinated surfactant.

[0070] As some examples, the non-ionic fluorinated surfactant can be a perfluorinated C4 surfactant (e.g., FC-4430, FC-4432 surfactants from 3M) or a fluorodiol (e.g., POLYFOX PF-636, PF-6320, PF-656, PF-6520 fluorosurfactants from Omnova).

[0071] In some embodiments, based on the total weight of the anti-reflective composition, the mass content of the surfactant is 0-5%, for example, 0.01%, 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.7%, 2%, 2.1%, 2.8%, 3%, 3.5%, 4%, 4.5%, etc.

[0072] The present invention does not particularly limit the solvent used in the composition, as long as it can dissolve other components in the composition and make the composition satisfy the solution state. Specific examples of the solvent include, but are not limited to, one or more of the following solvents: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, Ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide.

[0073] In some embodiments, based on the total weight of the anti-reflective composition, the mass content of the solvent is 80% to 90%, for example, 80%, 82%, 82.6%, 83%, 84%, 85%, 86%, 87%, 88%, 90%, etc.

[0074] In the present invention, the polymer, acid generator, cross-linking agent and optional surfactant may be uniformly mixed with the solvent, and optionally filtered to prepare the anti-reflective composition.

[0075] A second aspect of the present invention provides an anti-reflection film, which is formed by coating the anti-reflection composition on a substrate and curing the coating.

[0076] In the present invention, the substrate can be selected from semiconductor substrates used in various photolithography processes, such as silicon wafers, germanium wafers, or compound substrates such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0077] In the present invention, the curing method may include heat treatment, the temperature of the heat treatment may be 100-200° C., and the time may be 0.5-20 min, preferably 0.5-10 min.

[0078] The antireflection film of the present invention has strong absorption at short wavelengths. In particular, it can efficiently absorb light reflected from semiconductor substrates when using ArF excimer lasers (wavelength 193 nm) in microfabrication processes such as photolithography. Furthermore, the antireflection film has a high refractive index, a low extinction coefficient, and a high dry etching rate.

[0079] To this end, the third aspect of the present invention provides use of the anti-reflective composition or the anti-reflective film in preparing a photolithographic pattern.

[0080] According to the present invention, the application method may include: first coating the anti-reflective composition on a substrate and curing to form the anti-reflective layer; then coating a photoresist composition on the anti-reflective layer to form a photoresist layer, followed by exposure and development.

[0081] In some embodiments, the application further comprises: before performing the development, baking the exposed photoresist layer to enhance the solubility difference between the exposed and non-exposed areas in the photoresist layer.

[0082] According to the present invention, the developer used in the development may generally be a water-based developer, preferably an alkaline water-based developer.

[0083] Furthermore, the application further comprises: after development, baking the photoresist layer at 100-150° C. for several minutes to harden the developed exposed areas.

[0084] Furthermore, the application also includes: etching the area without the photoresist layer on the developed substrate, for example, using a hydrofluoric acid etching solution or chemical gas (such as O2, CF4, CHF3, Ar) plasma to perform etching.

[0085] The following embodiments of the present invention are described. The following embodiments are exemplary and are only used to explain the present invention, and should not be understood as limiting the present invention.

[0086] The following synthesis examples are used to illustrate the preparation methods of compound A and polymers used in the examples.

[0087] Synthesis Example 1: Synthesis of Compound A-1

[0088]

[0089] Dissolve m-aminobenzoic acid (0.26 g, 1.94 mmol) and NaOH (0.22 g, 5.40 mmol) in 1 mL of water, and add the above solution dropwise to a 20 mL test tube containing 1 mL of cyanuric chloride (0.1 g, 0.54 mmol) aqueous solution (0 ° C). The resulting mixture was heated to room temperature, zeolite was added, and the test tube was placed on the turntable of a microwave oven (Samsung GB872, 850W, 2.54 GHz) and irradiated at 180 W for 2 minutes. The test tube was irradiated 5 times under this condition, and the product was cooled in a water bath during each irradiation. After the microwave was turned off, the product was cooled and acidified with concentrated hydrochloric acid, the precipitate was collected by filtration, washed with water and ethanol in turn, and then dried at 80 ° C to obtain a solid product (Compound A-1) as a white powder. 1H NMR, 13 The results of the C NMR characterization of the product are as follows: 1 H NMR (D2O, 400 MHz): δ 7.24 (t, J = 7.9 Hz, 3H), 7.43 (d, J = 7.7 Hz, 3H), 7.51 (d, J = 7.9 Hz, 3H), 7.74 (s, 3H) ppm; 13 C NMR (DMSO-d6, 100 MHz) δ 171.6, 165.9, 138.5, 136.8, 128.6, 124.5, 123.8, 122.0.

[0090] Synthesis Example 2: Synthesis of Compound A-2

[0091]

[0092] Valine (0.23 g, 1.94 mmol) and NaOH (0.22 g, 5.40 mmol) were dissolved in 1 mL of water, and the solution was dropped into a 20 mL test tube containing 1 mL of an aqueous solution of cyanuric chloride (0.1 g, 0.54 mmol) (0°C). The resulting mixture was heated to room temperature, zeolite was added, and the test tube was placed on the turntable of a microwave oven (Samsung GB872, 850 W, 2.54 GHz), irradiated at 180 W for 2 min, and irradiated under the same conditions 5 times, with the product being cooled in a water bath during each irradiation. After the microwave was turned off, the product was cooled and acidified with concentrated hydrochloric acid, the precipitate was collected by filtration, washed with water and ethanol, and then dried at 80°C to obtain a solid product (Compound A-2) as a white powder. The product was characterized by 1 H NMR, 13 The results of the C NMR characterization of the product are as follows: 1 H NMR (D2O, 400 MHz): δ 0.67 (dd, J = 28.6, 6.8, 18H), 1.65-1.70 (m, 3H) 2.82 (dd, J = 5.2 Hz, 3H) ppm; 13 C NMR (D2O, 100 MHz): δ 17.0, 31.8, 61.7, 168.5, 183.1.

[0093] Synthesis Examples 3 to 5

[0094] Compounds A-3 to A-5 were prepared according to the method of Synthesis Example 1, except that m-aminobenzoic acid was replaced with the reactants shown in Table 1, respectively.

[0095] Table 1

[0096]

[0097] Synthesis Example 6: Synthesis of Polymer S-1

[0098] At room temperature, 53.50g of compound A-1, 36.24g of 4,4'-sulfonyldiphenol diglycidyl ether, 0.89g of tetrabutylammonium chloride and 210g of propylene glycol monomethyl ether acetate (PGMEA) were added to a 2L 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 90°C. After the reactants were completely dissolved, the timing was started and the reflux reaction was carried out for 8 hours to form a resin (ie, a polymer). After the reaction was completed, the system was cooled to room temperature and 210g of PGMEA was added thereto and stirred evenly to obtain a reaction dilution. The above reaction dilution was added dropwise to 5L of water under high-speed stirring to disperse and precipitate the resin. The resin was recovered, washed with water, and vacuum dried to obtain a resin product (ie, polymer S-1). Polymer S-1 includes repeating units shown in formula I-1. GPC test (using polystyrene as the standard sample, the same below) M w =3000, PDI=1.6.

[0099]

[0100] Synthesis Example 7: Synthesis of Polymer S-2

[0101] At room temperature, 58.36g of compound A-1, 36.25g of 4,4'-bis(epoxypropoxy)diphenyl disulfide, 0.95g of tetrabutylammonium chloride and 220g of PGMEA were added to a 2L 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 90°C. After the reactants were completely dissolved, the timing was started and the reflux reaction was carried out for 8 hours to form a resin. After the reaction was completed, the system was cooled to room temperature, and 220g of PGMEA was added thereto and stirred evenly to obtain a reaction dilution. The above reaction dilution was added dropwise to 5L of water under high-speed stirring to disperse and precipitate the resin, recover the resin, wash with water, and vacuum dry to obtain a resin product (i.e., polymer S-2). Polymer S-2 includes the repeating unit shown in formula II-2. After GPC testing, M w =3500, PDI=2.0.

[0102]

[0103] Synthesis Example 8: Synthesis of Polymer S-3

[0104] At room temperature, 51.14g of compound A-2, 36.24g of 4,4'-sulfonyldiphenol diglycidyl ether, 0.87g of tetrabutylammonium chloride and 203g of PGMEA were added to a 2L 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 90°C. After the reactants were completely dissolved, the timing was started and the reflux reaction was carried out for 8.5h to form a resin. After the reaction was completed, the system was cooled to room temperature, and 203g of PGMEA was added thereto and stirred evenly to obtain a reaction dilution. The above reaction dilution was added dropwise to 5L of water under high-speed stirring to disperse and precipitate the resin, recover the resin, wash it with water, and vacuum dry it to obtain a resin product (i.e., polymer S-3). Polymer S-3 includes the repeating unit shown in formula I-2. After GPC testing, M w =4135, PDI=1.4.

[0105]

[0106] Synthesis Example 9: Synthesis of Polymer S-4

[0107] At room temperature, 51.14g of compound A-2, 14.62g of 1,1'-dioxirane ethyl sulfide, 0.69g of tetrabutylammonium chloride and 160g of PGMEA were added to a 2L 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 90°C. After the reactants were completely dissolved, the reflux reaction was started for 8 hours to form a resin. After the reaction was completed, the system was cooled to room temperature, and 160g of PGMEA was added thereto and stirred evenly to obtain a reaction dilution. The above reaction dilution was added dropwise to 5L of water under high-speed stirring to disperse and precipitate the resin. The resin was recovered, washed with water, and vacuum dried to obtain a resin product (i.e., polymer S-4). Polymer S-4 includes the repeating unit shown in formula III-4. GPC test showed that M w =2890, PDI=1.6.

[0108]

[0109] Synthesis example 10

[0110] Polymer S-5 was synthesized according to the method of Synthesis Example 6, except that Compound A-1 was replaced with an equal molar amount of Compound A-3. Polymer S-5 includes the repeating unit shown in Formula I-3. GPC test showed that M w =3642, PDI=1.2.

[0111]

[0112] Synthesis example 11

[0113] Polymer S-6 was synthesized according to the method of Synthesis Example 7, except that Compound A-1 was replaced with an equal molar amount of Compound A-4. Polymer S-6 includes the repeating unit shown in Formula II-2. GPC test showed that M w =2030, PDI=1.3.

[0114]

[0115] Synthesis example 12

[0116] Polymer S-7 was synthesized according to the method of Synthesis Example 9, except that Compound A-2 was replaced by an equal molar amount of Compound A-5. Polymer S-7 includes the repeating unit shown in Formula III-2. GPC test showed that M w =4326, PDI=1.8.

[0117]

[0118] Comparative Synthesis Example 1

[0119] At room temperature, 37.97g of tris (2-carboxyethyl) isocyanurate (0.11mol), 36.24g of 4,4'-sulfonyl diphenol diglycidyl ether, 0.74g of tetrabutylammonium chloride and 173g of PGMEA were added to a 2L 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 90°C. After the reactants were completely dissolved, the timing was started and the reflux reaction was carried out for 8 hours to form a resin. The reaction solution was then cooled to room temperature, and PGMEA173g was added thereto and stirred evenly to obtain a reaction dilution. The above reaction dilution was added dropwise to 5L of water under high-speed stirring to disperse and precipitate the resin. The resin was recovered, washed with water, and vacuum dried to obtain a resin product, which was recorded as polymer S-D1. Polymer S-D1 includes the structural unit shown in formula V. GPC test showed that M w =3940, PDI=2.2.

[0120]

[0121] Examples 1 to 7 and Comparative Example 1

[0122] After the polymer, solvent, acid generator, crosslinking agent and surfactant were prepared according to the mass percentages in Table 2, they were added to a clean bottle and shaken until the components were completely dissolved. Then, each sample was filtered through a 0.2 μm polyethylene microporous filter to obtain an anti-reflective composition.

[0123] The solvent is propylene glycol monomethyl ether, the acid generator is p-toluenesulfonic acid, the cross-linking agent is 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, and the surfactant is FC-4430 from 3M Company.

[0124] Table 2

[0125]

[0126] Test Example

[0127] Test Example

[0128] 1. Preparation of Anti-Reflective Film

[0129] The anti-reflective compositions of Examples 1-7 and Comparative Example 1 were spin-coated on silicon wafers, baked at 200°C for 60s, to form anti-reflective films with thickness of 1000A (measured by KLA film thickness meter).

[0130] 2. Performance Test

[0131] 1) Optical Properties: The refractive index (n value) and extinction coefficient (k value) of the anti-reflective films at 193 nm were measured by a spectroscopic ellipsometer (purchased from Woollman).

[0132] 2) Etching Rate: The etching rate of the films was measured by a TEL-8500P etching device (purchased from TEL), under the following etching conditions: CHF3 / CF4 / Ar gas was used to etch the anti-reflective films, the processing chamber pressure was 40 Pa, the PF power was 1300 W, the gap was 9 mm, the CHF3gas flow rate was 30 mL / min, the CF4gas flow rate was 30 mL / min, the Ar gas flow rate was 100 mL / min, and the etching time was 10 s.

[0133] 3) Solvent Resistance: The silicon wafer with anti-reflective film was soaked in propylene glycol methyl ether acetate (PGMEA) for 5 min, and then baked at 200°C for 60 s. The refractive index (n value), extinction coefficient (k value), and film thickness of the anti-reflective film after PGMEA soaking were measured. The test results are shown in Table 4.

[0134] The test results of the unsoaked anti-reflective films are shown in Table 3, and the test results of the soaked anti-reflective films are shown in Table 4.

[0135] Table 3

[0136]

[0137] As shown in Table 3, compared with Comparative Example 1, the anti-reflective films formed by the anti-reflective compositions of Examples 1-7 have higher refractive index, lower extinction coefficient, and higher etching rate.

[0138] Table 4

[0139] As shown in Table 3, compared with Comparative Example 1, the anti-reflective films formed by the anti-reflective compositions of Examples 1-7 have higher refractive index, lower extinction coefficient, and higher etching rate.

[0140] Comparing the data in Table 3 and Table 4, the refractive index and extinction coefficient of the anti-reflection film prepared by using the anti-reflection composition provided in Comparative Example 1 were reduced after being immersed in PGMEA, and the film thickness was reduced from Down to After immersion in PGMEA for 5 minutes, the refractive index and extinction coefficient of the antireflective films prepared using the antireflective compositions of Examples 1-7 remained virtually unchanged, and the film thickness remained unchanged. This indicates that the antireflective films prepared using the antireflective film compositions of Examples 1-7 exhibit excellent solvent resistance.

[0141] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and description of the present invention. In particular, as long as there is no structural conflict, the various technical features mentioned in the various embodiments can be combined in any way. The present invention is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

Claims

1. An antireflective composition, characterized in that Comprising a polymer, an acid generator, a cross-linking agent, a solvent and an optional surfactant, wherein the polymer is a condensation polymer formed by a polycondensation reaction of compound A and compound B, and the compound A is a triazine compound having a structure as shown in Formula 1; Formula 1 In Formula 1, L is selected from an alkylene group having 1 to 8 carbon atoms or an arylene group having 6 to 12 carbon atoms; The compound B is selected from at least one of 4,4'-sulfonyldiphenol diglycidyl ether, 4,4'-bis(glycidoxy)diphenyl disulfide and 1,1'-dioxirane ethyl sulfide.

2. The antireflective composition according to claim 1, wherein In formula 1, Any one of the following groups: ； Here, n is any integer from 1 to 5, and R is an alkyl group having 1 to 4 carbon atoms.

3. The antireflective composition according to claim 1, wherein The compound A is selected from at least one of the following compounds A-1 to A-6:

4. The antireflective composition according to any one of claims 1 to 3, characterized in that The molar ratio of the compound A to the compound B is (0.8-2.0):

1.

5. The antireflective composition according to any one of claims 1 to 3, characterized in that The conditions of the polycondensation reaction include: temperature of 80-100° C. and time of 5-10 hours.

6. The antireflective composition according to any one of claims 1 to 3, characterized in that The weight average molecular weight of the polymer is 1500-5000, and the molecular weight distribution index is 1.2-2.

0.

7. The anti-reflective composition according to any one of claims 1 to 3, wherein The structure of the polymer includes at least one of the repeating units shown in Formula I to Formula III: Formula I Formula II Formula III.

8. The antireflective composition according to any one of claims 1 to 3, characterized in that The acid generator is a thermal acid generator and / or a photoacid generator.

9. The antireflective composition according to any one of claims 1 to 3, characterized in that The acid generator is a thermal acid generator.

10. The antireflective composition according to claim 9, characterized in that The thermal acid generator is at least one selected from p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, pyridinium phenolsulfonic acid, pyridinium p-hydroxybenzenesulfonate, pyridinium trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid and hydroxybenzoic acid.

11. The antireflective composition according to any one of claims 1 to 3, characterized in that The crosslinking agent is at least one selected from 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-di(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea.

12. The antireflective composition according to any one of claims 1 to 3, characterized in that The surfactant is a fluorinated surfactant and / or a non-fluorinated surfactant.

13. The antireflective composition according to any one of claims 1 to 3, characterized in that The surfactant is a nonionic fluorinated surfactant.

14. The antireflective composition according to any one of claims 1 to 3, characterized in that Based on the total weight of the anti-reflective composition, the mass content of the polymer is 5% to 15%, the mass content of the acid generator is 0.1% to 5%, the mass content of the cross-linking agent is 1% to 10%, the mass content of the surfactant is 0 to 5%, and the mass content of the solvent is 80% to 90%.

15. An anti-reflection film, characterized in that: The anti-reflection film is formed by coating the anti-reflection composition according to any one of claims 1 to 14 on a substrate and curing the coating.

16. The antireflection film according to claim 15, wherein The curing method includes heat treatment, the heat treatment temperature is 100-200° C., and the time is 0.5-20 minutes.

17. Use of the antireflection composition according to any one of claims 1 to 14 or the antireflection film according to any one of claims 15 to 16 in preparing photolithographic patterns.

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