Metal compound, anti-reflective metal hard mask composition, preparation method and application thereof

Abstract

The present invention provides a metal compound, an anti-reflective metal hard mask composition, a preparation method and an application thereof, wherein the metal compound is a C2-C containing a C=C double bond. 12 The alkylene group or branched alkylene group is a chromophore. The antireflective metal hardmask composition comprises the following components in a weight ratio: 5-40 parts of the metal compound; 0.1-1 parts of the siloxane compound; and 60-95 parts of an organic solvent. The metal compound of the present invention contains abundant chromophores. The antireflective metal hardmask composition containing the metal compound exhibits excellent optical properties and high etching selectivity, and has promising application prospects and large-scale promotion potential in the field of patterning in semiconductor chip manufacturing.

Description

Technical Field

[0001] The present invention relates to metal hard mask technology, and in particular to a metal compound, an anti-reflective metal hard mask composition, and a preparation method and application thereof. Background Art

[0002] In integrated circuit manufacturing, as chip feature sizes enter the nanoscale, etching processes place increasingly stringent demands on the etch resistance of mask materials. Currently, mainstream metal-containing hard masks rely primarily on chemical vapor deposition (CVD) or atomic layer deposition (ALD) processes for fabrication. While these technologies can achieve high-quality thin film deposition, they suffer from inherent drawbacks such as high equipment costs and complex processes. In contrast, spin coating, with its advantages of process simplicity and strong equipment compatibility, has become a key research direction for the development of new hard masks / anti-reflective coatings.

[0003] Organic polymer hardmasks based on spin-coating processes require good solubility in the solvent system to achieve uniform film formation, while also exhibiting excellent resistance to plasma etching. However, there is an inherent conflict between these two core performance indicators—solubility and etch resistance: increasing crosslink density enhances etch resistance but reduces the material's solubility in organic solvents; conversely, optimizing solubility often results in a decrease in material density. This interdependent relationship makes the development of spin-coating hardmask systems with excellent overall performance a significant challenge. Summary of the Invention

[0004] The present invention aims to address the problem that existing spin-on hard mask materials cannot achieve both solubility and etching resistance. It proposes a metal compound containing a rich chromophore group (straight-chain or branched alkyl group containing a carbon-carbon double bond). The anti-reflective metal hard mask composition containing the metal compound has excellent optical properties and high etching selectivity, and has good application prospects and large-scale promotion potential in the field of patterning in semiconductor chip manufacturing.

[0005] It should be noted that, in the present invention, unless otherwise specified, the specific meaning of "including" in relation to composition limitations and descriptions includes both open-ended "including", "comprising", etc. and similar meanings, as well as closed-ended "composed of", "composed of", etc. and similar meanings.

[0006] To achieve the above-mentioned purpose, the technical solution adopted by the present invention is: a metal compound, the structural formula of which is shown in formula (1):

[0007]

[0008] In formula (1), M is a metal, and n is a natural number from 1 to 20;

[0009] L 1 and L2 is an organic ligand, L 1 and L 2 Can be the same or different;

[0010] The organic ligand contains the structure in the dotted line of formula (2):

[0011]

[0012] In formula (2), R 1 and R 2 are independently selected from halogen, C1-C 20 Alkyl or C1~C 20 The alkoxy group, R 3 C2~C containing C=C double bond 12 an alkylene group or a branched alkylene group.

[0013] Furthermore, the metal is one or more of Group 4, 5, 6 and 13 metals.

[0014] Furthermore, the metal is preferably one or more of titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum.

[0015] Furthermore, the halogen is one or more of fluorine, chlorine, bromine and iodine.

[0016] Furthermore, the halogen is preferably fluorine and / or chlorine.

[0017] Furthermore, the C1 to C 20 The alkyl group is preferably a C1 to C4 alkyl group.

[0018] Furthermore, the C1 to C 20 The alkyl group is more preferably a methyl group, an ethyl group or a tert-butyl group.

[0019] Furthermore, the C1 to C 20 The alkyl group is most preferably methyl.

[0020] Furthermore, the C1 to C 20 The alkoxy group is preferably a C1-C3 alkoxy group.

[0021] Furthermore, the C1 to C 20 The alkoxy group is more preferably a methoxy group, an ethoxy group or an isopropoxy group.

[0022] Furthermore, the C1 to C 20 The alkoxy group is most preferably isopropoxy.

[0023] Furthermore, the R 3 Preferably, C2 to C 10 Alkylene or C3~C12 Branched chain alkylene.

[0024] Furthermore, the R 3 More preferred is a vinyl group or an allyl group.

[0025] Furthermore, the R 3 Most preferred is vinyl.

[0026] Another object of the present invention is to disclose a method for preparing a metal compound, comprising the following steps:

[0027] Step 1: Synthesis of an organic ligand: The organic ligand is a product of a condensation reaction between an acetylacetone derivative and a cyclohexane derivative;

[0028] The specific synthesis method of the organic ligand is as follows: dissolving an acetylacetone derivative and a cyclohexane derivative in a solvent, heating to 50-100° C., and performing a Knoevenagel condensation reaction under the catalysis of a catalyst for 1-10 hours to obtain a condensation product, which is the organic ligand;

[0029] Step 2: Synthesis of metal compounds:

[0030] Step 2.1: dissolving a metal alkoxide in an organic solvent to obtain a metal alkoxide solution; dissolving an organic ligand in an organic solvent to obtain an organic ligand solution;

[0031] The metal alkoxide solution is added to a reaction vessel under a N2 atmosphere, heated to 30-50°C while stirring, and then the organic ligand solution is added dropwise to the metal alkoxide solution, and the mixture is heated to 60-80°C, reacted for 1-5 hours, and then cooled to room temperature to obtain a mixed solution;

[0032] Step 2.2: Deionized water is slowly added dropwise to the mixed solution, reacted at 30-80° C. for 1-5 hours, then cooled to room temperature, concentrated under reduced pressure, filtered to remove impurities, and the filter cake is retained to obtain a metal compound.

[0033] Furthermore, in step 2.1, there is no specific requirement for the amount of organic solvent added, as long as it can dissolve the metal alkoxide and the organic ligand.

[0034] Furthermore, the structure of the acetylacetone derivative is shown in formula (3):

[0035]

[0036] In formula (3), R 1 and R 2 are independently selected from halogen, C1-C 20 Alkyl or C1~C 20 of alkoxy.

[0037] Furthermore, the acetylacetone derivative is one or more of acetylacetone, 3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, dimethyl malonate, diethyl malonate, diisopropyl malonate and malonyl chloride.

[0038] Furthermore, the structure of the cyclohexane derivative is shown in formula (4):

[0039]

[0040] In formula (4), R 4 C0~C9 alkylene or C2~C 11 Branched chain alkylene.

[0041] Furthermore, the cyclohexane derivative is one or more of cyclohexylcarboxaldehyde, cyclohexylacetaldehyde and cyclohexylpropionaldehyde.

[0042] Furthermore, the molar ratio of the acetylacetone derivative to the cyclohexane derivative is 1:1-1:1.2.

[0043] Furthermore, the preferred molar ratio of the acetylacetone derivative to the cyclohexane derivative is 1:1.

[0044] The reaction formula for the Knoevenagel condensation reaction of acetylacetone derivatives and cyclohexane derivatives under the catalysis of piperidine is as follows:

[0045]

[0046] Among them, R 1 and R 2 are independently selected from halogen, C1-C 20 Alkyl or C1~C 20 The alkoxy group, R 3 For vinyl, R 4 C0~C9 alkylene or C2~C 11 Branched chain alkylene.

[0047] Furthermore, in step 1, the solvent is toluene and / or DMF. There is no specific requirement for the amount of solvent added, as long as it can dissolve the acetylacetone derivative and the cyclohexane derivative.

[0048] Furthermore, in step 1, the solvent is preferably toluene.

[0049] Furthermore, in step 1, the catalyst is piperidine and / or ammonium acetate.

[0050] Furthermore, in step 1, the catalyst is preferably piperidine.

[0051] Furthermore, the amount of the catalyst used is 5%-20% of the total molar amount of the reactants (acetylacetone derivatives and cyclohexane derivatives).

[0052] Furthermore, the preferred amount of the catalyst is 10% of the total molar amount of the reactants.

[0053] Furthermore, in step 1, the mixture is heated to 60° C. and reacted for 2 hours.

[0054] Furthermore, thin layer chromatography was used in step 1 to track the reaction progress in order to reduce the generation of by-products.

[0055] Furthermore, the metal alkoxide is one or more of titanium ethoxide, titanium isopropoxide, titanium n-butoxide, zirconium isopropoxide, zirconium n-butoxide and hafnium n-butoxide.

[0056] Furthermore, the metal alkoxide is preferably one or more of titanium isopropoxide, zirconium n-butoxide and hafnium n-butoxide.

[0057] Furthermore, the amount of the metal alkoxide used is 23%-44% of the total molar amount of the reactants (acetylacetone derivative and cyclohexane derivative).

[0058] Furthermore, the amount of the metal alkoxide used is 43% of the total molar amount of the reactants (acetylacetone derivative and cyclohexane derivative).

[0059] Furthermore, in step 2.1, the organic solvent is one or more of alcohol, glycol ether, ester, amide, aromatic and diketone.

[0060] Furthermore, the alcohol is a C1-C6 lower alcohol and / or diol.

[0061] Furthermore, the C1-C6 lower alcohol is one or more of isopropanol, n-butanol, tert-butanol, n-pentanol and 4-methyl-2-pentanol.

[0062] Furthermore, the diol is ethylene glycol and / or propylene glycol.

[0063] Furthermore, the glycol ether is one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether and diethylene glycol dimethyl ether.

[0064] Furthermore, the ester is glycol ether ester and / or carboxylic acid ester.

[0065] Furthermore, the glycol ether ester is one or more of ethylene glycol ethyl ether acetate, methyl glycol ethyl ether acetate and propylene glycol methyl ether acetate.

[0066] Furthermore, the carboxylic acid ester is one or more of ethyl acetate, n-butyl acetate and amyl acetate.

[0067] Furthermore, the amide is dimethylacetamide and / or dimethylformamide.

[0068] Furthermore, the aromatic group is anisole and / or benzoic acid.

[0069] Furthermore, the diketone is acetylacetone and / or 2,5-hexanedione.

[0070] Furthermore, in step 2.1, the metal alkoxide solution is added to the reaction vessel under N2 atmosphere and heated to 40°C while stirring.

[0071] Furthermore, in step 2.1, the organic ligand solution is added dropwise to the metal alkoxide solution, and the mixture is heated to 60° C. and reacted for 3 hours.

[0072] Furthermore, in step 2.1, the reaction process is monitored using gas chromatography (GC), and the reaction is stopped when the content of the organic ligand remains unchanged.

[0073] Furthermore, in step 2.2, deionized water is added dropwise to the mixed solution within 30 minutes, and then the mixture is reacted at 70° C. for 3 hours. Slowly adding deionized water can control the reaction rate and prevent precipitation.

[0074] Furthermore, in step 2.2, the amount of deionized water used is 0.2-3 times the molar amount of the metal alkoxide.

[0075] Furthermore, in step 2.2, the mixture is concentrated under reduced pressure using a rotary evaporator.

[0076] Furthermore, in step 2.2, the filtration uses a 0.2-0.5 μm PTFE filter membrane.

[0077] Another object of the present invention is to disclose an application of a metal compound in the field of anti-reflective metal hard mask.

[0078] Another object of the present invention is to disclose an anti-reflective metal hard mask composition, comprising the following components in the following weight proportions:

[0079] 5-40 parts of the metal compound;

[0080] 0.1-1 part of silicone compound;

[0081] 60-95 parts of organic solvent.

[0082] Furthermore, the metal compound is preferably 20-40 parts.

[0083] Furthermore, the siloxane compound is one or more of trimethoxysilane, triethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 3-(methacryloyloxy)propyltrimethoxysilane.

[0084] Furthermore, the siloxane compound is preferably 3-(methacryloyloxy)propyltrimethoxysilane.

[0085] The siloxane compound aids in crosslinking during the thermal curing of the metal hardmask composition, further improving coating performance. The siloxane compound undergoes hydrolysis during film formation. The siloxy groups in the siloxane compound undergo hydrolysis in the presence of water, generating silanol groups. The hydrolyzed silanol groups are highly reactive and can undergo polycondensation with metal compounds. Through dehydration and condensation, metal-oxygen-silicon (MO-Si) bonds are formed, linking the metal compound molecules to form a larger molecular structure, ultimately forming a three-dimensional network-like polymer film.

[0086] In addition, due to its special molecular structure, when the siloxane compound is coated on the substrate, it will quickly spread on the surface of the substrate, thereby forming hydrogen bonds with the substrate to enhance the coating performance.

[0087] Furthermore, the siloxane compound is preferably 0.1-0.5 parts.

[0088] Furthermore, the organic solvent is one or more of alcohol, glycol ether, ester, amide, aromatic and diketone.

[0089] Furthermore, the alcohol is a C1-C6 lower alcohol and / or diol.

[0090] Furthermore, the C1-C6 lower alcohol is one or more of isopropanol, n-butanol, tert-butanol, n-pentanol and 4-methyl-2-pentanol.

[0091] Furthermore, the diol is ethylene glycol and / or propylene glycol.

[0092] Furthermore, the glycol ether is one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether and diethylene glycol dimethyl ether.

[0093] Furthermore, the ester is glycol ether ester and / or carboxylic acid ester.

[0094] Furthermore, the glycol ether ester is one or more of ethylene glycol ethyl ether acetate, methyl glycol ethyl ether acetate and propylene glycol methyl ether acetate.

[0095] Furthermore, the carboxylic acid ester is one or more of ethyl acetate, n-butyl acetate and amyl acetate.

[0096] Furthermore, the amide is dimethylacetamide and / or dimethylformamide.

[0097] Furthermore, the aromatic group is anisole and / or benzoic acid.

[0098] Furthermore, the diketone is acetylacetone and / or 2,5-hexanedione.

[0099] Furthermore, the organic solvent is more preferably a mixture of glycol ether ester and glycol ether.

[0100] Furthermore, the mass ratio of the glycol ether ester to the glycol ether is 1:9-9:1.

[0101] Furthermore, the mass ratio of the glycol ether ester to the glycol ether is preferably 7:3.

[0102] Furthermore, the organic solvent is preferably 70-95 parts.

[0103] Another object of the present invention is to disclose a method for preparing an anti-reflective metal hard mask composition, comprising the following steps: weighing each component in its respective amount; adding all components into a sealed container, mixing and stirring to obtain the anti-reflective metal hard mask composition.

[0104] Furthermore, the mixing and stirring temperature is 20-30°C.

[0105] Furthermore, the mixing time is 5-10 min.

[0106] Another object of the present invention is to disclose an application of an anti-reflective metal hard mask composition in the field of patterning in semiconductor chip manufacturing.

[0107] The anti-reflective metal hard mask composition has excellent optical properties. When it is spin-coated on a substrate to form a coating, the reflectivity between the photoresist and the substrate can be minimized. At the same time, the anti-reflective metal hard mask composition also has high etching selectivity. In deep ultraviolet lithography (DUV) or extreme ultraviolet lithography (EUV) processes, it can replace chemical vapor deposition (CVD) or atomic layer deposition (ALD) metals, metal oxides, metal nitrides and spin-on silicon coatings as hard masks.

[0108] Furthermore, the antireflective metal hard mask composition is suitable for positive pattern transfer (hard mask lithography, the photoresist retained area determines the metal mask pattern) or tone reversal pattern transfer (hard mask reversal, the metal mask fills the photoresist gap to form a reversal pattern).

[0109] Furthermore, the metal hard mask composition contains 10-60 wt % of metal oxide after baking.

[0110] The metal compound, anti-reflective metal hard mask composition, and preparation method and application thereof of the present invention have the following advantages compared with the prior art:

[0111] 1) The metal hard mask prepared by the present invention has a uniform microstructure, few crystal defects and impurities, and has excellent filling performance. The obtained metal hard mask is more transparent than existing hard mask materials and can show higher selectivity in the etching process.

[0112] 2) The metal compound of the present invention is a C2-C 12 Alkylene or branched alkylene (R 3 ) is a chromophore, so that the metal hard mask composition containing the metal compound has a refractive index n=1.63 to 2.64 and an extinction coefficient k of 0.1 to 0.5 at an exposure wavelength of 193 nm. This optical property enables it to be used as an anti-reflection layer in ArF (193 nm) lithography process.

[0113] 3) The present invention directly adds a siloxane compound to the metal hard mask composition. Compared with the traditional method of directly introducing a siloxane group into a metal compound, the metal hard mask composition of the present invention can spread rapidly on the surface, thereby forming hydrogen bonds with the substrate to enhance the coating performance.

[0114] 4) The metal compound and siloxane of the present invention significantly improve the film-forming performance of the metal hardmask composition through a synergistic effect. The specific mechanism is as follows: Siloxane undergoes hydrolysis during the film-forming process. The siloxy groups (e.g., -Si-OR, where R is an organic group such as an alkyl group) in the siloxane molecule undergo hydrolysis in the presence of water, forming silanol groups (-Si-OH). The resulting silanol groups are highly reactive and can undergo a polycondensation reaction with the metal compound. Through dehydration and condensation, metal-oxygen-silicon (MO-Si) bonds are formed, linking the metal compound molecules to form a larger molecular structure, ultimately forming a three-dimensional network-like polymer film.

[0115] In summary, the present invention utilizes multi-ligand metal compound synthesis technology to embed metal elements into organic polymers. This allows the metal elements to form organic compounds and, through the construction of a superior organic solvent system, enhance the solubility of the metal elements in the hard mask, increasing the metal and oxygen content in the metal hard mask and ensuring its etch resistance. The anti-reflective metal hard mask composition of the present invention combines optical compatibility, structural stability, and process-friendliness, possessing promising application prospects and potential for large-scale adoption in the field of patterning in semiconductor chip manufacturing. BRIEF DESCRIPTION OF THE DRAWINGS

[0116] Figure 1 This is the H NMR spectrum of the metal compound ligand 3-(cyclohexylmethylene)-2,4-pentanedione in Example 1;

[0117] Figure 2 This is the H NMR spectrum of the metal compound in Example 1. DETAILED DESCRIPTION

[0118] The present invention will be further described below with reference to the following examples. The following description of the technical features is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

[0119] Unless otherwise stated, the units used in this specification are international standard units, and the numerical values ​​and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0120] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints A and B.

[0121] In this specification, the numerical range expressed using "above" or "below" means a numerical range including the number.

[0122] In this specification, the use of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0123] In this specification, the use of "optional" or "optional" indicates that certain substances, components, execution steps, application conditions and other factors are used or not used.

[0124] In this specification, when "normal temperature" or "room temperature" is used, the temperature may be 15-25°C.

[0125] In this manual, the reagents or instruments used without indicating the manufacturer are all conventional products that can be obtained through commercial purchase.

[0126] Examples 1-7

[0127] Examples 1-7 disclose a variety of metal compounds, the raw materials and proportions of which are shown in Table 1, and the preparation methods thereof are as follows:

[0128] Step 1: Synthesis of organic ligand: Dissolve the acetylacetone derivative and the cyclohexane derivative in 100 g of toluene and heat to 60°C. Knoevenagel condensation reaction occurs in the presence of a catalyst. The reaction progress is tracked by thin-layer chromatography. The reaction is allowed to proceed for 2 hours. The resulting condensation product is the organic ligand.

[0129] Step 2: Synthesis of metal compounds:

[0130] Step 2.1: Dissolve the metal alkoxide in 100 g of an organic solvent (a 70 / 30 mass ratio mixture of propylene glycol methyl ether acetate (PGMEA) and propylene glycol methyl ether (PGME)) to obtain a metal alkoxide solution. Dissolve the organic ligand in 100 g of an organic solvent (a 70 / 30 mass ratio mixture of propylene glycol methyl ether acetate (PGMEA) and propylene glycol methyl ether (PGME)) to obtain an organic ligand solution.

[0131] The metal alkoxide solution was added to a reaction vessel under a nitrogen atmosphere. The temperature was raised to 40°C while stirring. The organic ligand solution was then added dropwise to the reaction vessel. The temperature was further raised to 60°C and the reaction was continued for 3 hours. The reaction process was monitored using GC. The reaction was terminated when the organic ligand content remained constant and the mixture was cooled to room temperature to obtain a mixed solution.

[0132] Step 2.2: Slowly add deionized water dropwise to the mixed solution (addition should be completed within 30 minutes). Continue the reaction at 70°C for 3 hours, then cool to room temperature and concentrate under reduced pressure using a rotary evaporator. Filter the resulting metal compound solution through a 0.45 μm PTFE filter membrane, retaining the filter cake. The resulting filter cake is the metal compound. The raw materials and proportions of the metal compounds of Examples 1-7 are shown in Table 1.

[0133] Table 1 Raw materials and proportions of metal compounds in Examples 1-7

[0134]

[0135] Figure 1 This is the nuclear magnetic hydrogen spectrum of the metal compound ligand 3-(cyclohexylmethylene)-2,4-pentanedione in Example 1. The hydrogen on the carbon connected to the methylene on the cyclohexyl group has a chemical shift of 2.09 ppm due to the influence of the cyclohexyl structure and the connection to the methylene. The other hydrogen atoms on the cyclohexyl group are in a relatively isolated saturated environment, with a chemical shift of 1.52 ppm. The electron cloud density of the methylene part connected to the carbonyl conjugated system of the cyclohexyl and pentanedione is affected, and the chemical shift of its hydrogen atoms is 5.44 ppm. The hydrogen on the methyl group adjacent to the carbonyl group in the pentanedione part has a chemical shift of about 2.24 ppm due to the electron-withdrawing effect of the carbonyl group. The determination of the chemical shift and the number of hydrogen integrals proves that the present invention has synthesized 3-(cyclohexylmethylene)-2,4-pentanedione.

[0136] Figure 2 is the H NMR spectrum of the metal compound of Example 1, wherein L 1 and L 2All are 3-(cyclohexylmethylene)-2,4-pentanedione. Similar to the ligand 3-(cyclohexylmethylene)-2,4-pentanedione, the chemical shift of the hydrogen on the carbon attached to the methylene group on the cyclohexyl group is approximately 2.0 ppm and exhibits multiple peaks. The chemical shift of the other hydrogen atoms on the cyclohexyl group remains at 1.52 ppm. After coordination with zirconium, the chemical shift of the methylene hydrogen atoms changes to approximately 5.75 ppm. The hydrogen on the methyl group adjacent to the carbonyl group in the pentanedione portion is affected by the carbonyl group and coordination with zirconium, with a chemical shift of approximately 2.0 ppm. The change in chemical shift and the number of hydrogen integrals demonstrate that the present invention has synthesized a metal compound with 3-(cyclohexylmethylene)-2,4-pentanedione as a ligand.

[0137] Comparative Examples 1-4

[0138] Comparative Examples 1-4 disclose a variety of metal compounds, whose raw materials and proportions are shown in Table 2, and their preparation methods are the same as those of Example 1.

[0139] Table 2 Raw materials and ratios of metal compounds in Comparative Examples 1-4

[0140]

[0141] Examples 8-14

[0142] Examples 8-14 disclose various antireflective metal hardmask compositions. The components and total weight ratios are shown in Table 3. The compositions are prepared as follows: Each component is weighed in its intended amount. All components are added to a sealed container at 25°C and stirred for 10 minutes until all materials are thoroughly mixed and homogeneous and transparent. The antireflective metal hardmask compositions are thus prepared.

[0143] Table 3 Composition and ratio of the metal hard mask compositions of Examples 8-14

[0144]

[0145] Comparative Examples 5-8

[0146] Comparative Examples 5-8 disclose a variety of metal hard mask compositions, the components and weight ratios of which are shown in Table 4. The preparation methods thereof are the same as those of Example 8.

[0147] Table 4 Composition and ratio of metal hard mask compositions of Comparative Examples 5-8

[0148]

[0149] The anti-reflective metal hard mask compositions of Examples 8-14 and the metal hard mask compositions of Comparative Examples 5-8 were tested, and the test results are shown in Table 5.

[0150] Table 5 Test results

[0151]

[0152] Based on the data in Table 5, the metal hard masks of Examples 8-14, containing the metal compounds of Examples 1-7, exhibit excellent etch resistance in oxygen, while maintaining high etch rates in fluorine-based plasmas. Their etch selectivity (CF₄ / O₂) is excellent, making them suitable for use as hard masks in pattern transfer from photoresist to substrate. Ellipsometer measurements of the metal hard masks revealed a refractive index n ranging from 1.63 to 2.64, and an absorptivity k ranging from 0.1 to 0.5, demonstrating that these metal hard masks can function as antireflective coatings at an exposure wavelength of 193 nm.

[0153] The metal compound used in Comparative Example 5 does not contain a C=C double bond, resulting in a decrease in the refractive index n value; while the metal compound in Comparative Example 6 contains a C=C double bond but does not contain a cyclic alkyl group, which also results in a decrease in the refractive index n value.

[0154] In Comparative Example 7, since deionized water was not added during the preparation of the metal compound, polymerization could not be performed, resulting in a decrease in the refractive index n value and a decrease in the etching selectivity;

[0155] In Comparative Example 8, a siloxane group is directly introduced into the metal compound, resulting in an increase in the amount of organic components in the hard mask and a decrease in the metal content (wt %), which in turn leads to a decrease in the etching selectivity.

[0156] in:

[0157] The test method for performance 1 refractive index n is:

[0158] Step 1: Prepare a solution containing 10 wt% of a metal compound.

[0159] Step 2: Spin-coat an appropriate amount of the solution on the corresponding substrate, and then bake on a hot plate at 125° C. for 60 seconds to form a metal hard mask coating.

[0160] Step 3: Measure the refractive index n value of the metal hard mask coating on an ellipsometer.

[0161] Performance 2 The test method for CF4 dry etching rate is:

[0162] The cured film was chemically etched using a CF4 etch tool. The CF4 etch was run at a power of 100 W and an etch time of 45 seconds. The etch rate was determined using the film thickness loss at the corresponding etch time.

[0163] Performance 3 The test method for O2 dry etching rate is:

[0164] The cured film was chemically etched using an O2 etch tool. The O2 etch process was run at a power of 90 W and an etch time of 60 seconds. The etch rate was determined using the film thickness loss at the corresponding etch time.

[0165] 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 it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A metal compound, characterized in that The structural formula is shown in formula (1): ； In formula (1), M is a metal, and n is a natural number from 1 to 20; L 1 and L 2 is an organic ligand; The organic ligand contains the structure in the dotted line of formula (2): ； In formula (2), R 1 and R 2 are independently selected from halogen, C1-C 20 Alkyl or C1~C 20 The alkoxy group, R 3 C2~C containing C=C double bond 12 Alkylene or branched alkylene; The preparation method of the metal compound comprises the following steps: Step 1: Synthesis of organic ligand: dissolve an acetylacetone derivative and a cyclohexane derivative in a solvent, heat to 50-100°C, and carry out a condensation reaction under the catalysis of a catalyst for 1-10 hours. The obtained condensation product is the organic ligand; Step 2: Synthesis of metal compounds: Step 2.1: dissolving a metal alkoxide in an organic solvent to obtain a metal alkoxide solution; dissolving an organic ligand in an organic solvent to obtain an organic ligand solution; adding the metal alkoxide solution to a reaction vessel under a nitrogen atmosphere, heating to 30-50° C. while stirring, then adding the organic ligand solution dropwise to the metal alkoxide solution, continuing to heat to 60-80° C., reacting for 1-5 hours, and then cooling to room temperature to obtain a mixed solution; Step 2.2: Deionized water is added dropwise to the mixed solution, reacted at 30-80°C for 1-5 hours, then cooled to room temperature, concentrated under reduced pressure, and filtered to obtain a metal compound; The structure of the acetylacetone derivative is shown in formula (3): ； In formula (3), R 1 and R 2 are independently selected from halogen, C1-C 20 Alkyl or C1~C 20 Alkoxy; And / or, the structure of the cyclohexane derivative is shown in formula (4): ； In formula (4), R 4 C0~C9 alkylene or C2~C 11 branched chain alkylene; and / or, the catalyst is piperidine and / or ammonium acetate; And / or, the metal alkoxide is one or more of titanium ethoxide, titanium isopropoxide, titanium n-butoxide, zirconium isopropoxide, zirconium n-butoxide and hafnium n-butoxide.

2. A method for preparing the metal compound according to claim 1, characterized in that: The following steps are involved: Step 1: Synthesis of organic ligand: dissolve an acetylacetone derivative and a cyclohexane derivative in a solvent, heat to 50-100°C, and carry out a condensation reaction under the catalysis of a catalyst for 1-10 hours. The obtained condensation product is the organic ligand; Step 2: Synthesis of metal compounds: Step 2.1: dissolving a metal alkoxide in an organic solvent to obtain a metal alkoxide solution; dissolving an organic ligand in an organic solvent to obtain an organic ligand solution; adding the metal alkoxide solution to a reaction vessel under a nitrogen atmosphere, heating to 30-50° C. while stirring, then adding the organic ligand solution dropwise to the metal alkoxide solution, continuing to heat to 60-80° C., reacting for 1-5 hours, and then cooling to room temperature to obtain a mixed solution; Step 2.2: Deionized water is added dropwise to the mixed solution, reacted at 30-80°C for 1-5 hours, then cooled to room temperature, concentrated under reduced pressure, and filtered to obtain a metal compound; The structure of the acetylacetone derivative is shown in formula (3): ； In formula (3), R 1 and R 2 are independently selected from halogen, C1-C 20 Alkyl or C1~C 20 Alkoxy; And / or, the structure of the cyclohexane derivative is shown in formula (4): ； In formula (4), R 4 C0~C9 alkylene or C2~C 11 branched chain alkylene; and / or, the catalyst is piperidine and / or ammonium acetate; And / or, the metal alkoxide is one or more of titanium ethoxide, titanium isopropoxide, titanium n-butoxide, zirconium isopropoxide, zirconium n-butoxide and hafnium n-butoxide.

3. The method for preparing the metal compound according to claim 2, wherein: The molar ratio of the acetylacetone derivative to the cyclohexane derivative is 1:1-1:1.2; and / or, the amount of the catalyst is 5%-20% of the total molar amount of the reactants; and / or, the amount of the metal alkoxide is 23%-44% of the total molar amount of the reactants; And / or, the amount of deionized water is 0.2-3 times the molar amount of the metal alkoxide.

4. An anti-reflective metal hard mask composition, characterized in that The composition comprises the following components in the following weight ratios: 5-40 parts of the metal compound according to claim 1; 0.1-1 part of silicone compound; 60-95 parts of organic solvent.

5. The antireflective metal hard mask composition according to claim 4, wherein: The siloxane compound is one or more of trimethoxysilane, triethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 3-(methacryloyloxy)propyltrimethoxysilane.

6. The antireflective metal hard mask composition according to claim 4, wherein: The organic solvent is one or more of alcohol, glycol ether, ester, amide, aromatic and diketone.

7. A method for preparing the antireflective metal hard mask composition according to any one of claims 4 to 6, characterized in that: The method comprises the following steps: respectively weighing each component in its respective amount; mixing and stirring all the components under a closed condition to obtain the anti-reflective metal hard mask composition.

8. Use of the antireflective metal hard mask composition according to any one of claims 4 to 6 in the field of patterning in semiconductor chip manufacturing.

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