Organic material and method for etching si-containing member

Abstract

The purpose is to provide an organic material capable of further enhancing reactivity of hydrogen fluoride gas with an Si-containing member. The organic material not showing crosslinkability shows the action of enhancing reactivity of hydrogen fluoride gas with a Si-containing member. The Si-containing member contains silicon (Si) and oxygen (O) and / or nitrogen (N). The organic material has an organic molecule having a molecular weight of more than 500. The organic molecule has a value of dHF which is a distance between the hydrogen atom and the fluorine atom in the hydrogen fluoride molecule assuming the absorption structure of 0.965 (Å) or more as calculated with the 6-31+G(d) basis function and the B3LYP correlation-exchange functional.

Description

Method for etching organic materials and Si-containing components

[0001] The present invention relates to a method for etching organic-based materials and Si-containing components.

[0002] Various methods have been proposed and put into practical use as processing techniques capable of forming a recess structure on the surface of a Si-containing member such as quartz glass.

[0003] For example, Patent Document 1 describes that a quartz glass substrate can be locally etched by placing a specific organic compound on a portion of the surface of the quartz glass substrate and exposing the quartz glass substrate to hydrogen fluoride gas.

[0004] WO 2023 / 119899

[0005] The method of Patent Document 1 makes it possible to form minute features on the surface of a quartz glass substrate.

[0006] However, the etching rate of the method of Patent Document 1 for a quartz glass substrate is not sufficiently high, and therefore, a method capable of etching a quartz glass substrate more quickly is desired.

[0007] The present invention has been made in view of the above background, and an object of the present invention is to provide an organic material that can further enhance the reactivity of hydrogen fluoride gas with Si-containing members.

[0008] The present invention provides a non-crosslinkable organic material that exhibits the action of increasing the reactivity of hydrogen fluoride gas with a Si-containing member, wherein the Si-containing member contains silicon (Si) and oxygen (O) and / or nitrogen (N), and the organic material has organic molecules with a molecular weight of more than 500, in which the value of the distance dHF between the hydrogen atom and the fluorine atom in the hydrogen fluoride molecule when assuming an adsorption structure, calculated using 6-31+G(d) basis functions and a B3LYP correlation-exchange functional, is 0.965 (Å) or greater.

[0009] The present invention can provide an organic material that can further enhance the reactivity of hydrogen fluoride gas with a Si-containing member.

[0010] 1 is a diagram schematically showing an optimized three-dimensional structure of molecule X obtained by the ETKDG method and atoms with negative Gasteiger charges. 2 is a diagram schematically showing a three-dimensional structure of a structure obtained by the ETKDG method in which a hydrogen atom is added to molecule X. 3 is a diagram schematically showing a state in which a fluorine atom is added to molecule Y to form a complex compound. 4 is a diagram schematically showing a structure of molecule Z optimized by DFT calculation. 5 is a graph showing the relationship between the dHF of an organic molecule contained in an organic-based material according to one embodiment of the present invention and the hydrogen fluoride gas etching rate of a quartz glass substrate on which such an organic-based material is placed. 6 is a diagram schematically showing an example of a flow when etching a Si-containing member using an organic-based material according to one embodiment of the present invention. 7 is a graph showing the relationship between the dHF of an organic molecule obtained from the evaluation results of various samples and the etching rate of a quartz glass substrate.

[0011] An embodiment of the present invention will be described below.

[0012] As described above, the etching rate for a quartz glass substrate using the method described in Patent Document 1 is not sufficiently high. Therefore, the inventors of the present application have been conducting extensive research and development into a method for etching Si-containing members more quickly.

[0013] The present inventors have found that some non-crosslinkable organic materials have the function of significantly increasing the reactivity of hydrogen fluoride gas with Si-containing components. In particular, they have found that when etching a Si-containing component provided with an organic material containing organic molecules having a "dHF" value of 0.965 (Å) or more, a significantly higher etching rate can be obtained with hydrogen fluoride gas.

[0014] Therefore, one embodiment of the present invention provides a non-crosslinkable organic material that exhibits the action of increasing the reactivity of hydrogen fluoride gas with a Si-containing member, wherein the Si-containing member contains silicon (Si) and oxygen (O) and / or nitrogen (N), and the organic material has organic molecules with a molecular weight of more than 500, in which the value of the distance dHF between the hydrogen atom and the fluorine atom in the hydrogen fluoride molecule when assuming an adsorption structure, calculated using 6-31+G(d) basis sets and a B3LYP correlation-exchange functional, is 0.965 (Å) or greater.

[0015] As will be described later, when an etching process of a Si-containing member using hydrogen fluoride gas is performed using an organic material according to one embodiment of the present invention, the Si-containing member can be etched at a significantly higher etching rate.

[0016] Here, the dHF of an organic molecule is calculated by the following procedure.

[0017] First, structural information of a target organic molecule (hereinafter referred to as "molecule X") is obtained from SMILES using the RDKit library, and a three-dimensional structure is generated by the ETKDG method.

[0018] Next, the Gasteiger charge is calculated to determine atoms with negative Gasteiger charge (hereinafter referred to as site atoms P).

[0019] As an example, Figure 1 shows a schematic diagram of the optimized structure of molecule X obtained by the above method and the site atom P determined for molecule X. In this example, molecule X is an organic molecule whose general formula is represented by formula (1) described below, and there is only one site atom P. In Figure 1, the large gray spheres represent carbon atoms, the black spheres represent nitrogen atoms, and the smallest white spheres represent hydrogen atoms.

[0020] Next, a conjugate acid compound (hereinafter referred to as "compound Y") is formed by adding an H atom to molecule X according to the following procedure, and the three-dimensional coordinates of compound Y are generated.

[0021] First, using the RDKit library, add 1 to the formal charge of the site atom P of molecule X.

[0022] Next, a hydrogen atom H is bonded to the site atom P of the molecule X, and a three-dimensional structure is generated by the ETKDG method.

[0023] 2 shows a schematic representation of the three-dimensional structure of compound Y, the site atom P, and the added hydrogen atom H. The three-dimensional structure of compound Y thus generated is converted into an sdf file to obtain three-dimensional coordinates.

[0024] Next, a fluorine atom is added to compound Y to form a composite compound (hereinafter referred to as "compound Z"), and the three-dimensional coordinates of compound Z are generated in the following manner.

[0025] First, a new fluorine atom F is placed at a position 1.0 Å away from the added hydrogen atom H, and a three-dimensional structure is generated by the ETKDG method.

[0026] In this case, the site atom P, the hydrogen atom H, and the fluorine atom F must be arranged on a straight line.

[0027] 3 shows a schematic representation of the three-dimensional structure of compound Z, site atoms P, hydrogen atoms H, and fluorine atoms F. The dashed arrows indicate the lines they share.

[0028] The three-dimensional structure of compound Z thus generated is used as the initial structure, and structural optimization is performed by DFT calculation. Figure 4 shows the structure of compound Z structurally optimized by DFT calculation.

[0029] From the obtained optimized structure, the distance between the added hydrogen atom H and the fluorine atom F is calculated and determined as dHF.

[0030] When the target compound has a plurality of site atoms, the above procedure is repeated with each atom as a site atom, and the bond length of the largest hydrogen fluoride molecule is determined to be dHF.

[0031] All DFT calculations were performed using the gaussian16 package, and geometry optimization was performed using the DFT method, 6-31+G(d) basis set, B3LYP correlation-exchange functional, default spin, charge ±0, and singlet state. For atomic species with atomic numbers greater than Kr, LanL2DZ basis set was used.

[0032] When the target organic compound has a plurality of site atoms, this procedure is repeated for each site atom, and the largest distance between the hydrogen atom and the fluorine atom is taken as dHF.

[0033] When this molecular calculation is applied to polymer molecules having a repeating structure or molecules with a large molecular weight, it is possible to perform calculations by decomposing the molecules.

[0034] The site of decomposition must be a carbon atom 12 atoms or more away from the atom on which HF is adsorbed, must not be an atom forming a ring with the atom on which HF is adsorbed, and must be a position 12 atoms or more away from the aromatic ring containing the atom on which HF is adsorbed. The cleaved carbon atom is terminated with hydrogen.

[0035] In addition to decomposing the polymer molecules and calculating, it is also possible to estimate the dHF by extracting the repeating structure, and the dHF values ​​of the repeating structure alone and its multimer are in good agreement.

[0036] When performing decomposition and calculation, it is desirable to perform the calculation with a number of atoms other than hydrogen in the range of 15 to 100. If the number of atoms is too small, the necessary intramolecular interactions cannot be reflected, while if the number of atoms is too large, the calculation does not converge. When evaluating whether the intramolecular interactions are sufficiently reflected, this can be confirmed by the change in the value of dHF when the decomposition point is changed, and if ΔdHF = ±0.002 or less, it can be said that a structure sufficient for evaluating dHF has been extracted.

[0037] Although the location of decomposition is not specified, it is desirable to cleave at the methylene chain or the bond between aromatic rings.

[0038] The organic molecules contained in the organic material according to one embodiment of the present invention are characterized in that the dHF obtained by such calculation is 0.965 Å or more.

[0039] Here, the reason why the reactivity between the Si-containing member and hydrogen fluoride gas increases when an organic material containing organic molecules with dHF of 0.965 (Å) or more is used is considered to be as follows.

[0040] That is, while ordinary organic materials have a weak interaction with HF, when an organic material with a large dHF is used, electrons are donated from the organic material to the antibonding orbital of HF, increasing the H-F bond length. This increases the basicity of F, which in turn increases its nucleophilicity toward nearby Si atoms, which is expected to increase reactivity.

[0041] Figure 5 shows the hydrogen fluoride gas etching rate of quartz glass with various organic materials attached, where the horizontal axis represents dHF, an organic molecule contained in the organic material, and the vertical axis represents the etching rate (expressed as a natural logarithm) of the quartz glass substrate.

[0042] FIG. 5 shows the results obtained from an experiment in which an organic material containing various organic molecules with different dHF values ​​was applied to the surface of a quartz glass substrate, and then the substrate was heated to 250° C. and exposed to hydrogen fluoride gas.

[0043] 5, it can be seen that the higher the dHF of the organic molecules contained in the organic material, the higher the etching rate of the silica glass tends to be. In particular, when the dHF of the organic molecules is 0.965 or more, the etching rate of the silica glass is significantly higher.

[0044] In this way, when the organic material according to one embodiment of the present invention is placed on a Si-containing member and the Si-containing member is etched with hydrogen fluoride gas, the Si-containing member can be etched more quickly.

[0045] Whether or not a target organic material has the "effect of increasing the reactivity of hydrogen fluoride gas with respect to a Si-containing member" can be confirmed by comparing the etching rate of the Si-containing member with hydrogen fluoride gas at 250°C when the target organic material is placed on the surface of the Si-containing member and when it is not placed on the surface.

[0046] In other words, if the etching rate is higher when an organic material is provided than when it is not provided, it can be said that such an organic material has the function of "enhancing reactivity" with respect to the Si-containing component.

[0047] The Si-containing member to which the organic material according to the embodiment of the present invention is applied during etching contains silicon (Si), oxygen (O) and / or nitrogen (N). For example, the Si-containing member may be SiO ｘ or SiN ｙ It may contain SiO ｘ The x in the formula is a number that satisfies 0<x, and preferably 1.2≦x≦2. ｙ The y in the formula is a number satisfying 0<y, and preferably 0.8≦y≦4 / 3.

[0048] In particular, SiO ２ The Si-containing member may be silica glass, phosphorus-doped silica glass, or boron-doped silica glass.

[0049] (Organic Material According to One Embodiment of the Present Invention) Next, an organic material according to one embodiment of the present invention will be described in more detail with reference to the drawings.

[0050] The organic material according to one embodiment of the present invention is characterized by not exhibiting crosslinkability.

[0051] As described above, the organic material according to one embodiment of the present invention includes at least one organic molecule having a dHF of 0.965 (Å) or more. Two or more types of such organic molecules may be included.

[0052] Examples of organic molecules contained in the organic material according to one embodiment of the present invention will be described below.

[0053] (Organic Molecule) The organic molecule is selected from those having a dHF of 0.965 (Å) or more.

[0054] The dHF of the organic molecule is preferably 0.97 (Å) or more, and more preferably 0.975 (Å) or more.

[0055] For example, the organic molecule may have at least one of: (i) a ring structure portion containing at least one of nitrogen and oxygen; (ii) a secondary amine structure portion; and (iii) a tertiary amine structure portion.

[0056] Representative examples of organic molecules of type (i) include pyridine, imidazole, pyrrole, and oxazoline. Here, the ring structure portion containing nitrogen and / or oxygen, i.e., the heterocyclic structure, includes a pyridine ring, a lactone ring, an imidazole ring, a benzimidazole ring, a benzoxazole ring, a porphyrin ring, and graphitic carbon nitride. Representative examples of organic molecules of type (ii) include morpholine. Representative examples of organic molecules of type (iii) include trimethylamine and triethanolamine.

[0057] Alternatively, the organic molecule is (iv) a primary amine, and the primary amine has an adsorption energy E ａｄｓ may be 0.35 eV or more.

[0058] Here, the adsorption energy E of the primary amine with the HF molecule is ａｄｓ Is E ａｄｓ (eV) = E １ (eV) + E ＨＦ (eV)-E ２ (eV) Calculated from equation (A1).

[0059] Here, E １ is the energy obtained when the three-dimensional structure of the target organic molecule X (see Figure 1) used in the calculation of dHF described above is optimized by DFT calculation, and E ＨＦ is the energy (constant value) of the optimal structure of the HF molecule, and E ２ is the energy of the target organic molecule (see "Compound Y") in which HF molecules are arranged and the structure is optimized, which was used in the calculation of the maximum dHF described above.

[0060] Among the above-mentioned (i) to (iv), examples of the organic molecule (i) include compounds of the following chemical formulas (1) and (2):

[0061]

[0062] The dHF of the organic molecule of chemical formula (1) is 0.982 Å, and the dHF of the organic molecule of chemical formula (2) is 0.979 Å.

[0063] Furthermore, examples of the organic molecules of (ii) include compounds of the following chemical formula (3):

[0064] The dHF of the organic molecule of formula (3) is 0.999 Å.

[0065] The compound of chemical formula (3) also falls under the above-mentioned (i).

[0066] Furthermore, examples of the organic molecules of (iii) include compounds of the following chemical formula (4):

[0067] The dHF of the organic molecule of formula (4) is 0.969 Å.

[0068] Furthermore, examples of the organic molecules of (iii) include compounds of the following chemical formulas (4-1) to (4-3):

[0069]

[0070]

[0071] The dHF of the organic molecules of chemical formulas (4-1) and (4-2) are 0.9994 (Å), 1.0040, and 1.0041 (Å), respectively. These materials are independently crosslinkable. The material of chemical formula (4-1) is morpholine.

[0072] Compounds having a benzimidazole ring include compounds of the following chemical formulas (4-5) and (4-6):

[0073] The dHF of this compound of chemical formula (4-5) is 0.9851 (Å).

[0074] The dHF of this compound of chemical formula (4-6) is 0.9844 (Å).

[0075] Examples of compounds having a benzoxazole ring include compounds of the following chemical formula (4-7).

[0076] The dHF of this compound of chemical formula (4-7) is 0.9738 (Å).

[0077] Examples of compounds having a porphyrin ring include tetraphenylporphyrin (dHF: 0.9745 Å) represented by the chemical formula (4-8) and tetrapyridylporphyrin (dHF: 0.9809 Å) represented by the chemical formula (4-9).

[0078]

[0079]

[0080] The compound having graphite carbon nitride in its partial structure is g-C represented by the following structural formula (4-10): ３ N ４ (Graphitic carbon nitride) (dHF: 0.9734 Å).

[0081]

[0082] Furthermore, examples of the organic molecule (iv) include compounds of the following chemical formula (5):

[0083] The dHF of the organic molecule of chemical formula (5) is 0.975 Å. The adsorption energy E ａｄｓ (see formula A1 above) is 0.55 eV.

[0084] Furthermore, examples of the organic molecule (iv) include compounds of the following chemical formulas (5-1) to (5-4):

[0085]

[0086]

[0087]

[0088] The dHF of the organic molecules of chemical formulas (5-1) to (5-4) are 0.975 (Å), 0.995 (Å), 1.007 (Å), and 0.9746 (Å), respectively. Of these materials, the organic molecules of chemical formulas (5-1) to (5-2) are independently crosslinkable. On the other hand, the organic molecules of chemical formulas (5-3) and (5-4) are not independently crosslinkable.

[0089] The organic molecules of the chemical formulas (5-1) to (5-4) each have an adsorption energy E calculated by the above-mentioned formula (A1) ａｄｓ are 0.51 eV, 0.71 eV, 0.73 eV and 0.55 eV.

[0090] The organic molecules contained in the organic material according to one embodiment of the present invention do not necessarily have to be of one type, and the organic molecules contained in the organic material according to one embodiment of the present invention may include a second organic molecule having a dHF of 0.965 (Å) or more, and further may include a third organic molecule having a dHF of 0.965 (Å) or more.

[0091] The organic molecules described above may be monomers or polymers as long as they have a dHF value of 0.965 (Å) or more. Polymers can be obtained by polymerizing organic molecules having a dHF value of 0.965 (Å) or more with organic molecules having reactive functional groups such as (meth)acryloyl groups, vinyl groups, epoxy groups, oxetane groups, thiol groups, carbonyl groups, and amino groups through radical, cationic, or condensation polymerization. Polymers can also be obtained by copolymerizing a monomer having an organic molecule having a dHF value of 0.965 (Å) or more with a monomer not having such an organic molecule.

[0092] (Etching Method Using Organic Material According to One Embodiment of the Present Invention) The organic material according to one embodiment of the present invention having the above-described characteristics can be applied to hydrogen fluoride gas etching of Si-containing members.

[0093] An example of an etching method using an organic material according to one embodiment of the present invention will be described below with reference to FIG.

[0094] FIG. 6 is a schematic diagram showing the flow of a method for etching a Si-containing member using an organic material according to one embodiment of the present invention (hereinafter referred to as "first method").

[0095] As shown in FIG. 6 , the first method includes: (1) a step of providing an organic material on at least a part of the surface of a Si-containing member (step S110); and (2) a step of exposing the Si-containing member on which the organic material is provided to hydrogen fluoride gas (step S120).

[0096] Each step will be described below.

[0097] (Step S110) First, a Si-containing member to be etched is provided.

[0098] The Si-containing component includes silicon (Si) and oxygen (O) and / or nitrogen (N). For example, the Si-containing component may be SiO ２ Alternatively, it may contain SiN.

[0099] In particular, SiO ２ The Si-containing member may be quartz glass, boron-containing quartz glass, or phosphorus-containing quartz glass.

[0100] The form of the Si-containing member is not particularly limited, and various shapes such as a plate, a thin film, or a block may be used.

[0101] Next, an organic material is applied to part or all of the processed surface of the Si-containing member.

[0102] The organic material is selected from the organic materials according to one embodiment of the present invention having the characteristics described above.

[0103] The organic material may be applied to the surface to be processed by, for example, a coating method, a printing method, a spin coating method, a spray method, etc. Therefore, the organic material may contain a solvent and / or a binder, etc.

[0104] (Step S120) Next, the Si-containing member is exposed to hydrogen fluoride gas, which selectively etches the portion of the surface of the Si-containing member where the organic material is provided (hereinafter referred to as the "covered region").

[0105] The concentration of the hydrogen fluoride gas may be in the range of, for example, 0.1 vol % to 100 vol %, and the temperature of the etching process may be in the range of, for example, 80°C to 500°C.

[0106] By performing the etching process on the Si-containing member under these conditions, the coated region can be selectively etched, forming a recessed structure in the coated region. Furthermore, if the coated region covers the entire surface of the Si-containing member, the Si-containing member can be thinned (slimmed).

[0107] Examples will be described below. In the following description, Examples 1 to 5 and 21 are Examples, and Examples 11 to 12 and 31 are Comparative Examples.

[0108] Example 1 An evaluation sample was prepared by the following method.

[0109] (Preparation of Organic Material) First, an organic material was prepared by the following method.

[0110] 1.0 g of the organic molecule was dissolved in 9.0 g of methyl ethyl ketone as a solvent to prepare a 10 wt % solution.

[0111] The organic molecule used was an organic substance represented by the above-mentioned chemical formula (5). The dHF of this organic molecule was 0.975 Å.

[0112] (Preparation of Evaluation Sample) Next, a coating film was formed on a substrate to prepare an evaluation sample. A quartz glass substrate was used as the substrate. The dimensions of the substrate were 50 mm long x 50 mm wide x 0.5 mm thick.

[0113] First, the solution prepared by the above method was spin-coated onto a first surface of a substrate (one surface measuring 50 mm long x 50 mm wide) at 1250 rpm for 30 seconds, and then the substrate was baked at 80°C for 120 seconds.

[0114] The obtained substrate was cut into a size of 50 mm length x 10 mm width to obtain an evaluation sample (hereinafter referred to as "Sample 1").

[0115] Example 2 An evaluation sample (hereinafter referred to as "Sample 2") was prepared in the same manner as in Example 1.

[0116] However, in Example 2, the material shown in the above-mentioned chemical formula (1) was used as the organic molecule. The dHF of this material was 0.982. Furthermore, 1-methoxy-2-propanol was used as the solvent.

[0117] Example 3 An evaluation sample (hereinafter referred to as "Sample 3") was prepared in the same manner as in Example 1.

[0118] However, in Example 3, the material shown in the above-mentioned chemical formula (2) was used as the organic molecule. The dHF of this material was 0.979. Furthermore, N,N-dimethylformamide was used as the solvent.

[0119] Example 4 An evaluation sample (hereinafter referred to as "Sample 4") was prepared in the same manner as in Example 1.

[0120] However, in Example 4, the material shown in the above-mentioned chemical formula (4) was used as the organic molecule. The dHF of this material was 0.969. Furthermore, water was used as the solvent.

[0121] Example 5 An evaluation sample (hereinafter referred to as "Sample 5") was prepared in the same manner as in Example 1.

[0122] However, in Example 5, the material shown in the above-mentioned chemical formula (3) was used as the organic molecule. The dHF of this material was 0.999. Furthermore, water was used as the solvent.

[0123] Example 11 An evaluation sample (hereinafter referred to as "Sample 11") was prepared in the same manner as in Example 1.

[0124] However, in Example 11, the material represented by the following chemical formula (6) was used as the organic molecule.

[0125] The dHF of this material is 0.956. Methyl ethyl ketone was used as the solvent.

[0126] Example 12 An evaluation sample (hereinafter referred to as "Sample 12") was prepared in the same manner as in Example 1.

[0127] However, in Example 12, the material shown in the following chemical formula (7) was used as the organic molecule.

[0128] The dHF of this material is 0.954. Methyl ethyl ketone was used as the solvent.

[0129] Table 1 below summarizes the organic molecules used in each example and the dHF of the organic molecules.

[0130]

[0131] (Evaluation) Etching treatment was carried out using each sample.

[0132] Specifically, each sample was placed in a reactor maintained at 250°C, and a mixture of hydrogen fluoride and nitrogen (HF:N ２ The substrate was etched by supplying a mixture of HCl and HCl (20:80 vol%) into the furnace for 300 seconds.

[0133] After the etching process, the sample was removed from the reactor and the etching rate of the substrate was evaluated.

[0134] The etching rate was calculated from the weight loss per unit area of ​​the substrate. Specifically, the etching rate v (μm / min) of the substrate was calculated using the following formula: v (μm / min) = (ΔW) / {(ρ×S) / t)}×10 ４ where ΔW is the weight loss (g) of the substrate before and after treatment, and ρ is the density of the substrate (g / cm ３ ), and S is the area of ​​the substrate coverage (cm ２ ) and t is the etching time (minutes).

[0135] The weight of the coating film placed on the substrate was extremely small compared to the total weight, and therefore the weight of the coating film was not taken into consideration in the calculation of ΔW.

[0136] Furthermore, when a similar etching treatment was carried out without providing a coating film on the surface of the quartz glass substrate, almost no weight loss was observed, and therefore it was found that the etching rate was zero.

[0137] The "etching rate" column in Table 1 above shows the evaluation results of the etching rate obtained in each example.

[0138] 7 shows the relationship between the dHF of the organic molecules and the etching rate obtained from the evaluation results of each sample. In Fig. 7, the horizontal axis represents the dHF of the organic molecules contained in the organic material, and the vertical axis represents the etching rate of the substrate (expressed as a natural logarithm).

[0139] In addition, in FIG. 7, the black circle symbols represent plots of Samples 1 to 5, and the white triangle symbols represent plots of Samples 11 and 12.

[0140] The results show that Samples 1 to 5 have significantly improved etching rates for the quartz glass substrate compared to Samples 11 and 12.

[0141] (Samples 21 and 31) (Example 21) An evaluation sample (hereinafter referred to as "Sample 21") was prepared in the same manner as in Example 2 above.

[0142] However, in Example 21, a substrate in which a SiN film was formed to a thickness of 3 μm on a Si substrate was used as the substrate, and 1-methoxy-2-propanol was used as the solvent.

[0143] Example 31 An evaluation sample (hereinafter referred to as "Sample 31") was prepared in the same manner as in Example 21.

[0144] However, in Example 31, the organic molecule used was the material represented by the above-mentioned chemical formula (6), and methyl ethyl ketone was used as the solvent.

[0145] Table 2 below summarizes the organic molecules and the dHFs of the organic molecules used in each example.

[0146]

[0147] The above-described evaluation was carried out using Sample 21 and Sample 31.

[0148] As a result, as shown in Table 2, it was found that the etching rate of the SiN film in Sample 21 was significantly improved compared to Sample 31.

[0149] (Samples 41-48) (Example 41) A recessed structure was formed on the first surface of a substrate using the same method as in Example 1. However, in Example 41, a polymer compound synthesized by the following method was used as the catalyst material, dimethylacetamide was used as the solvent, and no crosslinker was used. <Polymer Compound> First, isophthalic acid chloride, metaphenylenediamine, and 5-amino-2-(4-aminophenyl)benzimidazole were mixed with dimethylacetamide in a molar ratio of 2:1:1 and stirred at room temperature for 30 minutes. After dispersing the mixture in methanol, the precipitate was filtered and dried in a vacuum at 150°C for one day. This resulted in a polymer compound represented by chemical formula (18) having a monomer of an organic substance (dHF0.9851 (Å)) represented by chemical formula (4-5) as a partial structure.

[0150]

[0151] The processed body obtained after the etching process is referred to as "Sample 41."

[0152] The etching rate of sample 41 was 2.5 μm min －１ It was.

[0153] Example 42: A recessed structure was formed on the first surface of a substrate using a method similar to that of Example 1. However, in Example 42, a polymer compound synthesized by the following method was used as the catalyst material, dimethylacetamide was used as the solvent, and no crosslinker was used. <Polymer Compound> First, isophthalic acid chloride, metaphenylenediamine, and 5,3'-diamino-2-phenylbenzimidazole were mixed with dimethylacetamide in a molar ratio of 2:1:1 and stirred at room temperature for 30 minutes. The solution was dispersed in methanol, and the precipitate was collected by filtration and dried in vacuum at 150°C for one day. This resulted in a polymer compound represented by chemical formula (19), which has a monomer of the organic substance (dHF0.9844 (Å)) represented by chemical formula (4-6) in its partial structure.

[0154]

[0155] The processed body obtained after the etching process is referred to as "sample 42."

[0156] The etching rate of sample 42 was 2.4 μm min －１ It was.

[0157] Example 43: A recessed structure was formed on the first surface of a substrate using a method similar to that of Example 1. However, in Example 43, a polymer compound synthesized by the following method was used as the catalyst material, dimethylacetamide was used as the solvent, and no crosslinker was used. <Polymer Compound> First, isophthalic acid chloride, metaphenylenediamine, and 5-amino-2-(4-aminophenyl)benzoxazole were mixed with dimethylacetamide in a molar ratio of 2:1:1 and stirred at room temperature for 30 minutes. The solution was dispersed in methanol, and the precipitate was collected by filtration and dried in vacuum at 150°C for one day. This resulted in a polymer compound represented by chemical formula (20), which has a monomer of the organic substance (dHF0.9738 (Å)) represented by chemical formula (4-7) in its partial structure.

[0158]

[0159] The processed body obtained after the etching process is referred to as "Sample 43."

[0160] The etching rate of sample 43 was 1.4 μm min －１ It was.

[0161] Example 44 Etching was carried out in the same manner as in Example 43, except that the treatment temperature was 300°C.

[0162] The processed body obtained after the etching process is referred to as "Sample 44."

[0163] The etching rate of sample 44 was 2.4 μm min －１ It was.

[0164] Example 45 Etching was carried out in the same manner as in Example 43, except that the treatment temperature was 300°C.

[0165] The processed body obtained after the etching process is referred to as "Sample 45."

[0166] The etching rate of sample 45 was 3.4 μm min －１ It was.

[0167] Example 46 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 46, the catalyst material was an organic substance (dHF0.9745 (Å)) represented by the above-mentioned chemical formula (4-8). In addition, chloroform was used as the solvent, and no crosslinking agent was used.

[0168] The processed body obtained after the etching process is referred to as "Sample 46."

[0169] The etching rate of sample 46 was 2.1 μm min －１ It was.

[0170] Example 47 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 47, the catalyst material was an organic substance (dHF0.9809 (Å)) represented by the above-mentioned chemical formula (4-9). In addition, chloroform was used as the solvent, and no crosslinking agent was used.

[0171] The processed body obtained after the etching process is referred to as "Sample 47."

[0172] The etching rate of sample 47 was 2.3 μm min －１ It was.

[0173] Example 48 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 48, the catalyst material was an organic substance (dHF0.9734 (Å)) represented by the above-mentioned chemical formula (4-10). Furthermore, methanol was used as the solvent, and no crosslinking agent was used.

[0174] The processed body obtained after the etching process is referred to as "Sample 48."

[0175] The etching rate of sample 48 was 1.8 μm min －１ Table 3 below summarizes the organic molecules used in each example, the processing temperature, the dHF of the organic molecules, and the etching rate.

[0176]

[0177] The results show that Samples 41 to 48 also have significantly improved etching rates for the quartz glass substrate compared to Samples 11 and 12.

[0178] (Aspects of the Invention) One aspect of the invention will be described below.

[0179] (Aspect 1) A non-crosslinkable organic material exhibits the effect of increasing the reactivity of hydrogen fluoride gas with a Si-containing member, wherein the Si-containing member contains silicon (Si) and oxygen (O) and / or nitrogen (N), and the organic material has organic molecules with a molecular weight of more than 500, wherein the organic molecules have a distance dHF between a hydrogen atom and a fluorine atom in the hydrogen fluoride molecule, calculated using 6-31+G(d) basis functions and a B3LYP correlation-exchange functional, of 0.965 (Å) or greater when assuming an adsorption structure.

[0180] (Aspect 2) The organic material according to aspect 1, wherein the organic molecule has at least one of: (i) a ring structure portion containing nitrogen and / or oxygen; (ii) a secondary amine structure portion; and (iii) a tertiary amine structure portion.

[0181] (Aspect 3) The organic molecule is a primary amine, and the primary amine has an adsorption energy E ａｄｓ 2. The organic material according to embodiment 1, wherein the .lambda.

[0182] (Aspect 4) The Si-containing member is SiO ｘ or SiN ｙ 4. The organic material according to any one of aspects 1 to 3, comprising:

[0183] (Aspect 5) The organic material according to aspect 4, wherein the Si-containing member is silica glass.

[0184] (Aspect 6) A method for etching a Si-containing member, the method comprising: (1) a step of disposing an organic material on at least a part of a surface of the Si-containing member, the Si-containing member containing silicon (Si) and oxygen (O) and / or nitrogen (N); and (2) a step of contacting the Si-containing member on which the organic material is disposed with hydrogen fluoride gas, wherein the organic material is the organic material according to any one of Aspects 1 to 5; and after the step (2), the surface of the Si-containing member on which the organic material is disposed is selectively etched.

[0185] (Aspect 7) The method according to aspect 6, wherein the step (2) is carried out at a temperature of 80°C to 500°C.

[0186] (Embodiment 8) The Si-containing member is SiO ｘ or SiN ｙ 8. The method of claim 6 or 7, comprising:

[0187] This application claims priority based on Japanese Patent Application No. 2024-105342, filed on June 28, 2024, the disclosure of which is incorporated herein in its entirety by reference.

Claims

1. A non-crosslinkable organic material that exhibits the effect of increasing the reactivity of hydrogen fluoride gas with a Si-containing member, wherein the Si-containing member contains silicon (Si) and oxygen (O) and / or nitrogen (N), and the organic material has organic molecules with a molecular weight of more than 500, in which the distance dHF between the hydrogen atom and the fluorine atom in the hydrogen fluoride molecule when assuming an adsorption structure, calculated using the 6-31+G(d) basis set and the B3LYP correlation-exchange functional, is 0.965 (Å) or greater.

2. The organic material according to claim 1, wherein the organic molecule has at least one of: (i) a ring structure portion containing nitrogen and / or oxygen; (ii) a secondary amine structure portion; and (iii) a tertiary amine structure portion.

3. The organic molecule is a primary amine, and the primary amine has an adsorption energy E ａｄｓ The organic material according to claim 1 , wherein the .lambda.

4. The Si-containing member is SiO ｘ or SiN ｙ The organic-based material of claim 1 , comprising:

5. The organic material according to claim 1, wherein the Si-containing member is silica glass.

6. A method for etching a Si-containing component, comprising: (1) a step of disposing an organic material on at least a portion of a surface of the Si-containing component, the Si-containing component containing silicon (Si) and oxygen (O) and / or nitrogen (N); and (2) a step of contacting the Si-containing component on which the organic material has been disposed with hydrogen fluoride gas, wherein the organic material is the organic material defined in claim 1; and after the step (2), the surface of the Si-containing component on which the organic material has been disposed is selectively etched.

7. The method of claim 6, wherein step (2) is carried out at a temperature of 80°C to 500°C.

8. The Si-containing member is SiO ｘ or SiN ｙ The method of claim 6, comprising:

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