Compounds, patterning materials, semiconductor devices, terminals, and patterning methods

Abstract

The present application provides organic mixed metal-oxygen cluster compounds having the general chemical formula: (M1): a (M2) b (M3) c O g (L1) x (L2) y (L3) z where M1 is selected from at least one of Ti, Zr, and Hf; M2 is selected from at least one of Bi, Te, Sn, Pt, Ag, and Au; M3 is selected from at least one of Fe, Ni, Co, and Cu; L1, L2, and L3 are each selected from organic ligands, which can be coordinated to a metal and contain at least one of O, S, Se, N, and P functioning as a coordination atom; a, b, g, x, y, and z are all natural numbers equal to or greater than 1, and c is a natural number equal to or greater than 0. The present application further provides a patterning material containing the organic mixed metal-oxygen cluster compound, a semiconductor device containing the patterning material, a terminal, and a method for patterning a substrate surface. In the method for patterning a substrate surface in the present application, a pattern with small edge roughness can be realized at high resolution using a simple material.

Description

[Technical Field]

[0001] This application claims priority to Chinese Patent Application No. 202111281644.9, titled "Compounds, Patterning Materials, Semiconductor Devices, Terminals, and Patterning Methods," filed with the China National Intellectual Property Administration on 31 October 2021, which is incorporated into this application in its entirety by reference.

[0002] This application relates to an organic mixed metal-oxygen cluster compound, a patterning material containing the organic mixed metal-oxygen cluster compound, a semiconductor device using the patterning material, a terminal, and a substrate surface patterning method. [Background technology]

[0003] With the rapid development of the integrated circuit industry, the development of patterning technology is essential, especially as the computing power of chips per unit area increases, in other words, as the key size corresponding to the chip becomes smaller. A patterning process typically includes the following steps: using a predetermined pattern as a template, irradiating a film layer coated on the surface of a substrate through the template to form an irradiated structure on the film layer having irradiated and unirradiated regions; selectively dissolving and cleaning the irradiated structure or the unirradiated structure, wherein the pattern formed by the residual material is the same as the pattern of the template, and the residual patterning material may have etching resistance in the etching step; and selectively protecting the substrate from being etched or slowly etched, forming a graph for transfer to the substrate, and forming a pattern on the substrate such as a silicon wafer, wherein the pattern is the pattern that was first selectively exposed. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In advanced processes that realize graphics using short-wavelength (less than 15 nm) light rays, the light source transmission efficiency of patterning techniques is low, so patterning materials are required to exhibit high sensitivity, and the exposure energy is typically 30 mJ / cm². 2 The following applies. Currently, there are several patterning material systems, including organic polymer materials and organosilicon materials. Organic polymer materials are the conventional patterning materials. Organic polymer materials were used before short wavelengths of less than 15 nm were applied. However, as the wavelength of the patterning light source decreases to less than 15 nm, it becomes necessary to improve the resolution of the formed pattern. Organosilicon materials have high resolution and small molecular size. However, silicon has low sensitivity to light sources with wavelengths less than 15 nm and requires extremely high exposure energy. [Means for solving the problem]

[0005] In a first embodiment of the present invention, an organic mixed metal-oxygen cluster compound is provided, The general chemical formula is, (M1) a (M2) b (M3) c O g (L1) x (L2) y (L3) z And here M1 is selected from at least one of Ti, Zr, and Hf. M2 is selected from at least one of Bi, Te, Sn, Pt, Ag, and Au. M3 is selected from at least one of Fe, Ni, Co, and Cu. L1, L2, and L3 are each selected from organic ligands, which are capable of coordinating to a metal and contain at least one of O, S, Se, N, and P that functions as a ligating atom. There is provided an organic mixed metal-oxygen cluster compound, wherein a, b, g, x, y, and z are all natural numbers greater than or equal to 1, and c is a natural number greater than or equal to 0.

[0006] In the present application, under exposure to soft X-rays with wavelengths in the range of 1 nm to 15 nm, the organic mixed metal-oxygen cluster compound has high sensitivity and can be finely adjusted. The organic mixed metal-oxygen cluster compound has metals and organic ligands. By adjusting the types and ratios of different metals and / or introducing photosensitive functional groups into the organic ligands, the photosensitivity of the patterning material can be enhanced, the line edge roughness can be improved, and the resolution can be improved from 10 nm to 40 nm.

[0007] In one embodiment of the present application, 2 ≤ a + b + c ≤ 60.

[0008] In one embodiment of the present invention, g + x + y + z ≤ 8(a + b + c).

[0009] g + x + y + z ≤ 8(a + b + c) is determined based on the atomic coordination number.

[0010] In one embodiment of the present invention, 5 ≥ b / (a + c) ≥ 0.1.

[0011] In one implementation form of the present application, the ratio of a:b:c is 5:9:1.

[0012] In one embodiment of the present application, M1 is Ti, M2 is Bi, and M3 is at least one of Co and Ni.

[0013] In one embodiment of the present application, at least one of L1, L2, and L3 contains a functional group, and the functional group is selected from at least one of carboxylic acid, alcohol, phenol, nitrile, alkyne, alcoholamine, pyridine, pyrazole, imidazole, piperazine, and pyrazine.

[0014] Functional groups are introduced into organic ligands L1, L2, and L3 to modulate properties such as the solubility of the organic mixed metal-oxygen cluster compound, thereby affecting the thickness, roughness, resolution, adhesion, and corrosion resistance of the film layer containing the organic mixed metal-oxygen cluster compound.

[0015] In one embodiment of the present application, at least one of L1, L2, and L3 comprises a radiosensitive functional group, the radiosensitive functional group comprising at least one of a double bond, a triple bond, and epoxypropane.

[0016] Radiosensitive functional groups may further improve the photosensitivity of organic mixed metal-oxygen cluster compounds, resulting in improved line edge roughness and resolution.

[0017] In one embodiment of the present invention, one or more L1 and L2 coexist within the same organic ligand.

[0018] In one embodiment of the present application, at least a portion of the metal ions in the organic mixed metal-oxygen cluster compound are replaced by a radiosensitive element, the radiosensitive element being Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y 、 The radiosensitive element for substitution comprises at least one of Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, and Po, wherein the radiosensitive element for substitution is different from the metallic element originally present in the organic mixed metal-oxygen cluster compound.

[0019] Radiosensitive elements can substitute for metal elements in organic mixed metal-oxygen cluster compounds, thereby enhancing the photosensitivity of these compounds.

[0020] In a second aspect of the embodiment of the present application, a patterning material containing an organic mixed metal-oxygen cluster compound is provided. The chemical general formula of the organic mixed metal-oxygen cluster compound is (M1) a (M2) b (M3) c Og(L1) x (L2) y (L3) z where M1 is selected from at least one of Ti, Zr, and Hf, M2 is selected from at least one of Bi, Te, Sn, Pt, Ag, and Au, M3 is selected from at least one of Fe, Ni, Co, and Cu, L1, L2, and L3 are each selected from organic ligands, and the organic ligands contain at least one of O, S, Se, N, and P that directly coordinates to the metal and functions as a coordinating atom, a, b, g, x, y, and z are all natural numbers greater than or equal to 1, and c is a natural number greater than or equal to 0.

[0021] The organic mixed metal-oxygen cluster compound is used as the main material of the patterning material, and the patterning material can satisfy high sensitivity, high etching resistance, high resolution, low outgassing (meaning less gas is released during the exposure process), small molecular size, and material properties that can be finely adjusted by using mixed metals.

[0022] In one embodiment of the present application, 2≦a + b + c≦60, g + x + y + z≦8(a + b + c), and 5≧b / (a + c)≧0.1.

[0023] In one embodiment of the present application, the ratio of a:b:c is 5:9:1, M1 is Ti, M2 is Bi, and M3 is at least one of Co and Ni.

[0024] In one embodiment of the present application, at least one of L1, L2, and L3 comprises a functional group selected from at least one of carboxylic acids, alcohols, phenols, nitriles, alkynes, alcoholamines, pyridines, pyrazoles, imidazoles, piperazines, and pyrazines.

[0025] In one embodiment of the present application, at least one of L1, L2, and L3 comprises a radiosensitive functional group, the radiosensitive functional group comprising at least one of a double bond, a triple bond, and epoxypropane.

[0026] In one embodiment of the present invention, one or more L1 and L2 coexist in the same organic ligand.

[0027] In one embodiment of the present application, at least a portion of the metal ions in the organic mixed metal-oxygen cluster compound are substituted with a radiosensitive element, wherein the radiosensitive element is Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y 、 The radiosensitive element for substitution comprises at least one of Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, and Po, wherein the radiosensitive element for substitution is different from the metallic element originally present in the organic mixed metal-oxygen cluster compound.

[0028] In a third aspect of the embodiments of the present application, the semiconductor device is: circuit board and A functional layer disposed on the surface of the substrate, comprising a patterning material according to a second embodiment of the present invention, A semiconductor device having the following characteristics is provided.

[0029] The functional layer has high pattern resolution and low edge roughness.

[0030] A fourth embodiment of the present invention provides a terminal having a housing and a semiconductor device housed in the housing, wherein the semiconductor device is a semiconductor device according to the third embodiment of the present invention.

[0031] A fifth embodiment of the present invention relates to a method for patterning the surface of a substrate, The steps include providing a substrate and The step of forming a patterning material layer on the surface of the substrate, wherein the patterning material layer comprises an organic mixed metal-oxygen cluster compound, and the general chemical formula of the organic mixed metal-oxygen cluster compound is (M1) a (M2) b (M3) c O g (L1) x (L2) y (L3) z And here M1 is selected from at least one of Ti, Zr, and Hf. M2 is selected from at least one of Bi, Te, Sn, Pt, Ag, and Au. M3 is selected from at least one of Fe, Ni, Co, and Cu. L1, L2, and L3 are each selected from organic ligands, each containing at least one of O, S, Se, N, and P that directly coordinates to the metal and functions as a coordinating atom. a, b, g, x, y, and z are all natural numbers greater than or equal to 1, and c is a natural number greater than or equal to 0. Step... The steps include performing local exposure on the patterning material layer, A step of removing a portion of the patterning material layer using a developing solution, A method for patterning the surface of a substrate is provided, which has the following characteristics.

[0032] The substrate surface patterning method described in this application makes it possible to obtain a patterned patterning material layer having high resolution and low edge roughness, thereby facilitating processing performed using semiconductor devices.

[0033] In one embodiment of the present application, in the general chemical formula of the organic mixed metal-oxygen cluster compound, 2 ≤ a + b + c ≤ 60, g + x + y + z ≤ 8(a + b + c), and 5 ≥ b / (a + c) ≥ 0.1.

[0034] In one embodiment of the present application, in the general chemical formula of the organic mixed metal-oxygen cluster compound, at least one of L1, L2, and L3 comprises a functional group, the functional group being selected from at least one of carboxylic acids, alcohols, phenols, nitriles, alkynes, alcoholamines, pyridines, pyrazoles, imidazoles, piperazines, and pyrazines.

[0035] In one embodiment of the present application, at least one of L1, L2, and L3 comprises a radiosensitive functional group, the radiosensitive functional group comprising at least one of a double bond, a triple bond, and epoxypropane.

[0036] In one embodiment of the present application, at least a portion of the metal ions in the organic mixed metal-oxygen cluster compound are replaced by radiosensitive elements, the radiosensitive elements being Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y 、 The radiosensitive element for substitution comprises at least one of Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, and Po, wherein the radiosensitive element for substitution is different from the metallic element originally present in the organic mixed metal-oxygen cluster compound.

[0037] In one embodiment of the present application, in the general chemical formula of the organic mixed metal-oxygen cluster compound, the ratio of a:b:c is 5:9:1, M1 is Ti, M2 is Bi, and M3 is at least one of Co and Ni.

[0038] In one embodiment of the present invention, the step of performing local exposure on the patterning material layer involves using any single-wavelength or mixed-wavelength soft X-ray in the wavelength range of 1 nm to 15 nm, or using an electron beam, or using extreme ultraviolet radiation.

[0039] In one embodiment of the present invention, a mask is used in the step of performing local exposure of the patterning material layer using soft X-rays, and the soft X-rays that carry pattern information reach the patterning material layer through the mask, and the patterning material layer is locally exposed.

[0040] In one embodiment of the present application, the developer is at least one of isopropanol, N,N-dimethylformamide, 2-acetoxy-1-methoxypropane, ethyl lactate, and water.

[0041] In one embodiment of the present invention, the method for patterning the surface of the substrate further includes the step of etching the substrate using the patterning material film layer remaining on the substrate as a protective layer. [Brief explanation of the drawing]

[0042] [Figure 1] This is a schematic diagram of the patterning process. [Figure 2] This figure schematically shows the cross-sectional structure of a semiconductor device according to one embodiment of the present invention. [Figure 3] This is a schematic diagram of the structure of the organic mixed metal-oxygen cluster compound according to Example 1 of the present invention. [Figure 4] This is the infrared spectrum of an organic mixed metal-oxygen cluster compound according to Example 1 of the present invention. [Figure 5A]Scanning electron microscope images of exposed and developed patterning material coatings. [Figure 5B] Scanning electron microscope images of exposed and developed patterning material coatings. [Figure 6] This is a schematic diagram of the structure of the organic mixed metal-oxygen cluster compound according to Example 2 of the present invention. [Figure 7] This is the infrared spectrum of an organic mixed metal-oxygen cluster compound according to Example 1 of the present invention. [Figure 8A] Scanning electron microscope images of exposed and developed patterning material coatings. [Figure 8B] Scanning electron microscope images of exposed and developed patterning material coatings. [Modes for carrying out the invention]

[0043] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings of embodiments of the present invention.

[0044] In the patterning process, high-precision patterns can be formed by using soft X-rays with wavelengths in the range of 1 nm to 15 nm as the exposure light source, or by using electron beam etching. As shown in Figure 1, the patterning process includes (1) the step of forming a patterning material film layer 20 on a substrate 10, (2) the step of selectively exposing the patterning material film layer 20, (3) the step of developing the exposed patterning material film layer 20 to remove a portion of the patterning material film layer 20, and (4) the step of etching the substrate 10 using the remaining portion of the patterning material film layer 20 as a protective layer.

[0045] Step (1), the step of forming a patterning material film layer on a substrate, comprises: a step of mixing the patterning material with a suitable solvent to form a solution of a specific concentration, the solution concentration of which may be adjusted according to the film thickness requirement, and generally, a higher solution concentration corresponds to a thicker film layer; a step of taking a specific volume of the solution based on the size of the substrate and coating it onto the substrate by a spin coating method, the substrate may be a silicon wafer; and a step of forming a patterning material film layer less than 100 nm thick on a silicon wafer covered with another coating, or on any other coating using a silicon wafer as the final substrate. Before selective exposure, any solvent remaining in the film layer is usually removed by baking.

[0046] In the selective exposure process in step (2), a mask (not shown) may be used. Any single-wavelength or mixed-wavelength light in the soft X-ray range of 1 nm to 15 nm is selectively irradiated onto the patterning material film layer through the mask, and the pattern on the mask is transferred onto the patterning material film layer. After the patterning material is selectively irradiated, the chemical properties and solubility of the irradiated portion of the patterning material are changed.

[0047] In step (3) above, the patterning material to be irradiated is cleaned using a developer (which may be selected from organic solutions, inorganic solutions, pure solvents, mixed solvents, solvents containing additives, etc.). The cleaning is performed for 10 to 300 seconds and may be a single-step or multi-step cleaning. If the patterning material is a positive-type patterning material, the irradiated portion of the cleaned patterning material layer is washed away, and a positive-type pattern is formed. If the patterning material is a negative-type patterning material, the irradiated portion of the cleaned patterning material layer is not washed away, and a negative-type pattern is formed.

[0048] In step (4), the pattern formed by the patterning material selectively protects the substrate during the etching step. After etching is performed under specific conditions, the patterning material and the unprotected portions of the substrate are etched. However, the etching rate of the portions of the substrate protected by the patterning material is slower than that of the unprotected portions, and therefore, a pattern is ultimately formed on the substrate.

[0049] In the aforementioned patterning process, exposure is performed using soft X-rays with wavelengths ranging from 1 nm to 15 nm, or electron beams without a mask. Under these conditions, the resulting pattern is required to have high resolution, low pattern edge roughness, and low exposure energy consumption. However, existing patterning materials have difficulty meeting these requirements.

[0050] Accordingly, this application provides a patterning material that can be used in a process of patterning by exposure using short-wavelength (less than 15 nm) soft X-rays or electron beams. Since the patterning material is highly sensitive to short-wavelength (less than 15 nm) soft X-rays, the resolution of the pattern is increased and the edge roughness of the pattern is improved.

[0051] The patterning material comprises an organic mixed metal-oxygen cluster compound. In addition to the organic mixed metal-oxygen cluster compound, the patterning material may further contain additives, such as stabilizers, dispersants, or solvents.

[0052] The general chemical formula for organic mixed metal-oxygen cluster compounds is (M1) a (M2) b (M3) c O g (L1) x (L2) y (L3) z And here M1 is selected from at least one of the highly reactive / highly decomposable metals Ti, Zr, and Hf; M2 is selected from at least one of the highly sensitive metals Bi, Te, Sn, Pt, Ag, and Au; M3 is selected from at least one of the bridging metals Fe, Ni, Co, and Cu; L1, L2, and L3 are each selected from, but are not limited to, organic ligands that directly coordinate to the metal, and include O, S, Se, N, and P that function as coordinating atoms; a, b, g, x, y, and z are all natural numbers greater than or equal to 1; and c is a natural number greater than or equal to 0.

[0053] In some embodiments, when c=0, this indicates that the organic mixed metal-oxygen cluster compound contains only two metals, M1 and M2.

[0054] In some embodiments, 2 ≤ a + b + c ≤ 60.

[0055] In some embodiments, g+x+y+z≦8(a+b+c). g+x+y+z≦8(a+b+c) is determined based on the atomic coordination number.

[0056] In some embodiments, 5 ≥ b / (a+c) ≥ 0.1.

[0057] In one embodiment, the molar ratio of M1 to M2 to M3 is 5:9:1, that is, the ratio of a to b to c is 5:9:1. Also, M1 is Ti, M2 is Bi, and M3 is at least one of Co and Ni.

[0058] In some embodiments, L1 and L2 may be independent organic ligands. In some other embodiments, one or more L1 and L2 (there may be multiple organic ligands L1 and L2) coexist within the same organic ligand. For example, L1 and L2 coexist within a salicylic acid ligand. In this case, L1 may be an alcohol-based organic ligand and L2 may be a carboxylic acid-based organic ligand.

[0059] In some embodiments, at least some of the metal ions in the organic mixed metal-oxygen cluster compound may be replaced with radiosensitive elements to enhance the photosensitivity of the organic mixed metal-oxygen cluster compound. Radiosensitive elements include Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, and Y. 、 The organic mixed metal-oxygen cluster compounds include at least one of Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, and Po. Since M1, M2, and M3 of the organic mixed metal-oxygen cluster compounds may include at least one of the aforementioned radiosensitive elements Ti, Fe, Co, Ni, Cu, Ag, Sn, Te, Hf, Pt, Au, and Bi, the radiosensitive elements that substitute metal ions in the organic mixed metal-oxygen cluster compounds are different from the metal elements originally contained in the organic mixed metal-oxygen cluster compounds in this application. That is, for example, if the organic mixed metal-oxygen cluster compound contains metal Ti, Ti is not selected as the radiosensitive element for substitution.

[0060] In some embodiments, a radiosensitive functional group may be introduced to at least one of L1, L2, and L3 to further enhance the photosensitivity of the organic mixed metal-oxygen cluster compound, improve line edge roughness, and improve resolution. The radiosensitive functional group includes at least one of a double bond, a triple bond, and epoxypropane.

[0061] In some embodiments, the radiosensitive functional group may be introduced into at least one of the organic ligands L1, L2, and L3. For example, the functional group may be at least one of additionally accessed reactive groups such as carboxylic acids, alcohols, phenols, nitriles, alkynes, alcoholamines, pyridines, pyrazoles, imidazoles, piperazines, and pyrazines, which adjust properties such as the solubility of the organic mixed metal-oxygen cluster compound, thereby affecting film thickness, film roughness, resolution, film adhesion, and corrosion resistance.

[0062] It can be understood that the ratio of coordinating atoms of the organic ligand to the metal ion may be adjusted to improve the sensitivity, line edge roughness, and resolution of the organic mixed metal-oxygen cluster compound.

[0063] In this application, the organic mixed metal-oxygen cluster compound comprises a metal and an organic ligand. By adjusting the types and proportions of different metals and / or introducing photosensitive functional groups into the organic ligand, the photosensitivity of the patterning material may be further enhanced, improving line edge roughness and resolution.

[0064] In this application, under exposure to soft X-rays with wavelengths ranging from 1 nm to 15 nm, the organic mixed metal-oxygen cluster compounds exhibit high sensitivity and may be fine-tuned. The organic mixed metal-oxygen cluster compounds are used as the primary material for patterning materials, thereby solving the problem that patterning materials must satisfy material properties such as high sensitivity, high etching resistance, high resolution, low degassing (meaning less gas is released during the exposure process), small molecular size, and material properties that can be fine-tuned by using mixed metals.

[0065] In this application, the patterning method performed using the aforementioned patterning material comprises the following steps.

[0066] (a) Surface treatment of substrate Hydrophilization treatment: Piranha solution (H2O: 30% hydroxide Ammonium The substrate is purified in a 30% H2O2 (5:1:1) solution for 15 to 20 minutes, then washed with deionized water, and subsequently with isopropanol. Before use, the liquid on the substrate surface is dried using an air gun.

[0067] Hydrophobic treatment: After hydrophilic treatment of the substrate, hexamethyldisilazane (HMDS) is uniformly coated onto the surface of the substrate by vapor-phase plating or spin coating.

[0068] Anti-reflective coating treatment: An anti-reflective layer is added to the bottom layer, or a silicon compound layer or a carbon compound layer is coated to the bottom layer by a spin coating method.

[0069] (b) Solution preparation The prepared organic mixed metal-oxygen cluster compound (white powder) is dissolved in a solvent to form a clarified solution. If obvious insolubility is present, the solvent is re-selected, the organic mixed metal-oxygen cluster compound is dissolved, and a clarified solution is obtained. The solution is then filtered to obtain a patterning material formulation mixture. Suitable solvents include, but are not limited to, N,N-dimethylformamide, ethyl lactate, 2-acetoxy-1-methoxypropane, isopropanol, toluene, and dichloromethane. The concentration of the organic mixed metal-oxygen cluster compound in the solvent is approximately 5 mg / mL to 30 mg / mL.

[0070] (c) Preparation of the film layer Based on the size of the substrate, an appropriate amount of patterning material mixture is used for spin coating. For example, typically, 1 mL to 5 mL of patterning material mixture is spin-coated onto a 4-inch silicon wafer to obtain a patterning material film layer with a uniform thickness of 5 nm to 200 nm and a surface roughness of less than 2 nm. After spin coating, a baking step may be selectively added. The baking temperature to remove residual solvent is in the range of 60°C to 200°C, and the baking time is in the range of 20 seconds to 120 seconds.

[0071] (d) Film layer exposure An electron beam, extreme ultraviolet light, or soft X-rays with a wavelength in the range of 1 nm to 15 nm is selectively irradiated onto the patterning material film layer. A chemical reaction occurs in the irradiated area of ​​the patterning material film layer, changing the solubility of that area. In the step of performing localized exposure of the patterning material layer using soft X-rays, a mask is used. The soft X-rays carrying the pattern information reach the patterning material layer through the mask, and the patterning material layer is locally exposed.

[0072] After exposure, a selective baking step may be added to accelerate any incomplete chemical reactions in the film layer. The baking temperature is in the range of 60°C to 200°C, and the baking time is in the range of 20 seconds to 120 seconds.

[0073] (e) Development process In the developing process, a developer is used to bring the exposed film layer into contact with it, dissolving and removing a portion of the patterning material layer. For example, the film layer may be immersed in the developer. The contact time between the developer and the film layer is usually no more than 10 minutes.

[0074] In some embodiments, the developer includes solvents such as isopropanol, N,N-dimethylformamide, 2-acetoxy-1-methoxypropane, ethyl lactate, and water, or combinations thereof, as well as another solvent that allows the material to exhibit different dissolution rates before and after irradiation.

[0075] In one embodiment, the developer may be a developer comprising the following solvent or a mixture of several of the following solvents: Aqueous solutions of tetramethylammonium hydroxide (TMAH) with concentrations ranging from 0.5% to 5%; Organic solvents such as ketones, for example, cyclohexanone, methyl-2-n-pentyl ketone; Alcohols, for example, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol; Ethers, for example, propylene glycol monomethyl ether, 2-methoxyethanol, propylene glycol monoethyl ether, 2-ethoxyethanol, 1,2-dimethoxypropane, and diethylene glycol dimethyl ether; Esters, for example, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono-tert-butyl ether acetate; Lactones, such as γ-butyrolactone; High-boiling point alcohol solvents, such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, or 1,3-butanediol.

[0076] The development time between the developer and the exposed film layer is in the range of 10 to 120 seconds. After the development process, a water rinse process may be selectively added, and the rinse time may be in the range of 10 to 120 seconds. After the rinse process, a baking process may be selectively added. The baking temperature is in the range of 60°C to 200°C, and the baking time is in the range of 20 to 120 seconds.

[0077] (f) Pattern description The obtained patterns are observed and measured using an electron microscope or an atomic force microscope. The resolution of the obtained patterns ranges from 3 nm to 100 nm, and the edge roughness is 2% to 30% of the pattern resolution.

[0078] (g) Etching process (selective) The substrate may be etched using a patterning material film layer as a protective layer, and the pattern may be transferred to the substrate under etching conditions such as oxygen ions or in an ion implantation process.

[0079] It may be understood that step (a) is performed selectively. In some embodiments, step (a) may be omitted instead, or a hydrophilic or hydrophobic treatment may be performed in step (a).

[0080] It may be understood that step (g) is performed selectively. In some embodiments, step (g) may be omitted instead. This may leave an unetched patterned film layer on the substrate as a functional layer.

[0081] The present invention further provides an electronic device (not shown) having a semiconductor device. In some embodiments, the semiconductor device may be part of an integrated circuit (not shown). As shown in Figure 2, the semiconductor device 100 has a substrate 10 and a patterned functional layer 30 (e.g., a dielectric material layer) formed on the substrate 10. The functional layer 30 contains an organic mixed metal-oxygen cluster compound. The resolution of the pattern of the functional layer 30 is high, reaching from 10 nm to 40 nm. The edge roughness of the pattern is low, within 10% of the resolution.

[0082] The technical solutions in the embodiments of this application will be further described below by using specific embodiments.

[0083] (Example 1) An organomixed metal-oxygen cluster compound is synthesized: Ti5CoBi9O9(C7H4O3)9(C2OO)(C7H4O3)8. In particular, the aforementioned molecular formula is [Ti(C7H4O3)3]3@Ti2Co II It can also be expressed as Bi9O8(μ2-O)(μ2-C2OO)(C7H4O3)8, where @ indicates that [Ti(C7H4O3)3]3 is connected to two central Ti atoms, one O atom is connected to two atoms via a μ2 bridging mechanism, and a (C2OO) group is connected to two atoms via a μ2 bridging mechanism.

[0084] 0.05 mmol of bismuth salicylate, 0.1 mol of cobalt acetate, 0.1 mmol of salicylic acid, and 0.5 ml of tetraisopropoxytitanium are mixed in 8 ml of acetonitrile, heated to 80°C, and cooled to room temperature after 3 days. The precipitated crystals are organic mixed metal-oxygen cluster compounds.

[0085] Figure 3 shows [Ti(C7H4O3)3]3@Ti2Co II A schematic diagram of the structure of Bi9O8(μ2-O)(μ2-C2OO)(C7H4O3)8 is shown. Note that in Figure 3, some atoms such as oxygen, carbon, nitrogen, and hydrogen have been omitted to clarify the structure.

[0086] Figure 4 shows the infrared spectrogram of an organic mixed metal-oxygen cluster compound, from 400 to 892 cm⁻¹. -1 The characteristic peak at this position represents the expansion vibration region of metal-oxygen bonds, suggesting the presence of Bi-O, Ti-O, and Co-O. (1032–1242 cm⁻¹) -1 The characteristic peak located at this position is the expansion oscillation region of CO, from 1349 to 1595 cm⁻¹. -1 The characteristic peak at this position represents the skeletal vibration of the benzene ring, suggesting the presence of a benzene ring. (3000 to 3500 cm) -1 The characteristic peak at this position is the OH / NH expansion vibration region, which is the H2O peak, suggesting that the organic mixed metal-oxygen cluster compound contains trace amounts of water molecules.

[0087] Patterning process Hydrophilization treatment: Piranha solution (H2O: 30% hydroxide Ammonium A cleaning treatment is performed in a 30% H2O2 (5:1:1) solution for 15 to 20 minutes, followed by deionization with water, and then washing with isopropanol. Before use, any liquid on the surface is dried using an air gun. Hydrophobic treatment: After hydrophilization treatment is performed on the silicon wafer, HMDS is uniformly coated onto the surface of the silicon wafer by vapor deposition or spin coating.

[0088] Preparation of the film layer: 5 mg to 20 mg of an organic mixed metal-oxygen cluster compound is dissolved in 1 mL of N,N-dimethylformamide (DMF), the solution is filtered, an appropriate amount of the filtered solution is taken and spin-coated onto the surface of a hydrophilic or hydrophobic silicon wafer to form a metal-organic cluster patterning material coating.

[0089] Radiation exposure: Exposure is performed on the patterning material coating using electron beam etching (EBL) technology.

[0090] Development: The developer combinations used include a mixture of DMF and propylene glycol monomethyl ether acetate (PGMEA) (volume ratio of 10:1 to 1:10), and a mixture of isopropanol (IPA) and PGMEA (volume ratio of 10:1 to 1:10). Development time ranges from 15 to 60 seconds.

[0091] Graphic rendering: A scanning electron microscope (SEM) is used to draw patterns on the exposed and developed patterning material coating.

[0092] As shown in Figures 5A and 5B, the exposed and developed patterned material coating consists of multiple lines extending in the same direction. The line width in Figure 5(a) is 100 nm, and the line width in Figure 5(b) is 50 nm. The resolution of the exposed and developed patterned material coating can reach 100 nm or 50 nm.

[0093] In this embodiment, a new type of metal-oxygen cluster compound mixed with Ti, Co, and Bi can be used as a high-performance patterning material for exposure using light sources and electron beams with wavelengths less than 15 nm. A high-resolution pattern may be formed after exposure. The properties of the patterning material may also be fine-tuned through the proportion of the mixed metals.

[0094] (Example 2) An organic mixed metal-oxygen cluster compound is synthesized: Ti5NiBi9O9(C7H4O3)9(C2OO)(C7H4O3)8. In particular, the aforementioned molecular formula is [Ti(C7H4O3)3]3@Ti2Ni II It can be expressed as Bi9O8(μ2-O)(μ2-C2OO)(C7H4O3)8, where @ indicates that [Ti(C7H4O3)3]3 is bonded to two central Ti atoms, one O atom is bonded to two atoms in a μ2 bridging manner, and a (C2OO) group is bonded to two atoms in a μ2 bridging manner.

[0095] 0.05 mmol of bismuth salicylate, 0.1 mol of nickel acetate, 0.1 mmol of salicylic acid, and 0.5 ml of tetraisopropoxytitanium are mixed in 8 ml of acetonitrile, heated to 80°C, and cooled to room temperature after 3 days. The precipitated crystals are organic mixed metal-oxygen cluster compounds.

[0096] Figure 6 shows [Ti(C7H4O3)3]3@Ti2Ni II A schematic diagram of the structure of Bi9O8(μ2-O)(μ2-C2OO)(C7H4O3)8 is shown in Figure 6. Note that in Figure 6, some atoms such as oxygen, carbon, nitrogen, and hydrogen have been omitted to clarify the structure.

[0097] Figure 7 shows the infrared spectrogram of an organic mixed metal-oxygen cluster compound, from 400 to 892 cm⁻¹. -1 The characteristic peak at this position represents the expansion vibration region of metal-oxygen bonds, suggesting the presence of Bi-O, Ti-O, and Ni-O. (1030–1240 cm⁻¹)-1 The characteristic peak located at this position is the expansion oscillation region of CO, from 1464 to 1608 cm⁻¹. -1 The characteristic peak at this position indicates skeletal vibration of the benzene ring, suggesting the presence of a benzene ring.

[0098] Patterning method Silicon wafer processing: Hydrophilization treatment: A cleaning treatment is performed in a piranha solution (H2O:30% ammonium hydroxide:30% H2O2 = 5:1:1) for 15 to 20 minutes, followed by treatment with deionized water and then washing with isopropanol. Before use, any liquid on the surface of the silicon wafer is dried using an air gun.

[0099] Hydrophobic treatment: After hydrophilic treatment is performed on the silicon wafer, HMDS is uniformly coated onto the surface of the silicon wafer by vapor deposition or spin coating.

[0100] Preparation of the film layer: 5 mg to 30 mg of the solid sample is dissolved in 1 mL of ethyl lactate solvent, the solution is filtered, an appropriate amount of the filtered solution is taken and spin-coated onto the surface of a hydrophilic or hydrophobic silicon substrate to form a mixed metal organic cluster patterning material coating.

[0101] Radiation exposure: In this invention, exposure is performed on the patterning material layer using electron beam etching (EBL) technology.

[0102] Development: The developer combination used in this invention contains isopropanol. The development time is in the range of 15 to 60 seconds.

[0103] Pattern drawing: Pattern drawing is performed on the exposed and developed layer material using a scanning electron microscope (SEM).

[0104] As shown in Figures 8A and 8B, the exposed and developed patterned material coating consists of multiple lines extending in the same direction. The line width in Figure 8(a) is 100 nm, and the line width in Figure 8(b) is 50 nm. The resolution of the exposed and developed patterned material coating may reach 100 nm or 50 nm.

[0105] It should be noted that the foregoing description is merely a specific embodiment of the present application, and the scope of protection of the present application is not limited thereto. It should be noted that any modification or substitution readily apparent to a person skilled in the art within the technical scope described in the present application falls within the scope of protection of the present application. Where there is no inconsistency, the embodiments and features in the embodiments of the present application may be combined with each other. Accordingly, the scope of protection of the present application is subject to the scope of protection of the claims. [Explanation of Symbols]

[0106] 100 Semiconductor Devices 10 circuit boards 20 Patterning material film layers 30 Functional Layers

Claims

1. Organic mixed metal-oxygen cluster compounds, The general chemical formula is, (M1) a (M2) b (M3) c O g (L1) x (L2) y (L3) z And here M1 is Ti, M2 is Bi, M3 is at least one of Co and Ni. L1, L2, and L3 are each selected from organic ligands, which are capable of coordinating to a metal and contain at least one of O, S, Se, N, and P that functions as a ligating atom. An organo-metallic-oxygen cluster compound in which a, b, g, x, y, and z are all natural numbers greater than or equal to 1, and c is a natural number greater than or equal to 0.

2. The organic mixed metal-oxygen cluster compound according to claim 1, wherein 2 ≤ a + b + c ≤ 60.

3. The organic mixed metal-oxygen cluster compound according to claim 1 or 2, wherein g + x + y + z ≤ 8(a + b + c).

4. An organic mixed metal-oxygen cluster compound according to any one of claims 1 to 3, wherein 5 ≥ b / (a ​​+ c) ≥ 0.

1.

5. The organic mixed metal-oxygen cluster compound according to any one of claims 1 to 4, wherein the ratio of a:b:c is 5:9:

1.

6. At least one of L1, L2, and L3 contains a functional group. The organic mixed metal-oxygen cluster compound according to any one of claims 1 to 5, wherein the functional group is selected from at least one of carboxylic acids, alcohols, phenols, nitriles, alkynes, alcoholamines, pyridines, pyrazoles, imidazoles, piperazines, and pyrazines.

7. At least one of L1, L2, and L3 contains a radiosensitive functional group. The organic mixed metal-oxygen cluster compound according to any one of claims 1 to 6, wherein the radiation-sensitive functional group comprises at least one of a double bond, a triple bond, and epoxypropane.

8. The organic mixed metal-oxygen cluster compound according to any one of claims 1 to 7, wherein one or more L1 and L2 coexist in the same organic ligand.

9. The organic mixed metal-oxygen cluster compound further comprises a radiosensitive element, the radiosensitive element is It is replaced by some of the metal ions in M1, or It is replaced by some of the metal ions in M2, or It is substituted for some of the metal ions in M3, The radiation-sensitive element includes at least one of Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, and Po. The organic mixed metal-oxygen cluster compound according to any one of claims 1 to 8, wherein the radiation-sensitive element is a metal element different from the metal element originally contained in the organic mixed metal-oxygen cluster compound.

10. A patterning material containing an organic mixed metal-oxygen cluster compound, The general chemical formula for the aforementioned organic mixed metal-oxygen cluster compound is: (M1) a (M2) b (M3) c Og(L1) x (L2) y (L3) z And here, M1 is Ti, M2 is Bi, M3 is at least one of Co and Ni. L1, L2, and L3 are each selected from organic ligands, each comprising at least one of O, S, Se, N, and P that directly coordinates to the metal and functions as a coordinating atom. A patterning material in which a, b, g, x, y, and z are all natural numbers greater than or equal to 1, and c is a natural number greater than or equal to 0.

11. The patterning material according to claim 10, wherein 2 ≤ a + b + c ≤ 60, g + x + y + z ≤ 8(a + b + c), and 5 ≥ b / (a ​​+ c) ≥ 0.

1.

12. The patterning material according to claim 10 or 11, wherein the ratio of a:b:c is 5:9:

1.

13. The patterning material according to any one of claims 10 to 12, wherein at least one of L1, L2, and L3 comprises a functional group, the functional group being selected from at least one of carboxylic acids, alcohols, phenols, nitriles, alkynes, alcoholamines, pyridines, pyrazoles, imidazoles, piperazines, and pyrazines.

14. The patterning material according to any one of claims 10 to 13, wherein at least one of L1, L2, and L3 comprises a radiosensitive functional group, the radiosensitive functional group comprising at least one of a double bond, a triple bond, and epoxypropane.

15. The patterning material according to any one of claims 10 to 14, wherein one or more L1 and L2 coexist in the same organic ligand.

16. The organic mixed metal-oxygen cluster compound further comprises a radiosensitive element, the radiosensitive element is It is replaced by some of the metal ions in M1, or It is replaced by some of the metal ions in M2, or It is substituted for some of the metal ions in M3, The aforementioned radiation-sensitive element includes at least one of Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, and Po. The patterning material according to any one of claims 10 to 15, wherein the radiation-sensitive element is a metal element different from the metal element originally contained in the organic mixed metal-oxygen cluster compound.

17. A semiconductor device, circuit board and A functional layer disposed on the surface of the substrate, comprising a patterning material according to any one of claims 10 to 16, A semiconductor device having

18. It is a terminal, The casing and A semiconductor device housed in the aforementioned enclosure, It has, The semiconductor device is a terminal having the semiconductor device described in claim 17.

19. A method for patterning the surface of a substrate, The steps include providing a substrate and The step of forming a patterning material layer on the surface of the substrate, wherein the patterning material layer comprises an organic mixed metal-oxygen cluster compound, and the general chemical formula of the organic mixed metal-oxygen cluster compound is (M1) a (M2) b (M3) c O g (L1) x (L2) y (L3) z And here M1 is Ti, M2 is Bi, M3 is at least one of Co and Ni. L1, L2, and L3 are each selected from organic ligands, each containing at least one of O, S, Se, N, and P that directly coordinates to the metal and functions as a coordinating atom. a, b, g, x, y, and z are all natural numbers greater than or equal to 1, and c is a natural number greater than or equal to 0. Step... The steps include performing local exposure on the patterning material layer, A step of removing a portion of the patterning material layer using a developing solution, A method for patterning the surface of a substrate, comprising [the specified element].

20. The method for patterning a substrate surface according to claim 19, wherein in the general chemical formula of the organic mixed metal-oxygen cluster compound, 2 ≤ a + b + c ≤ 60, g + x + y + z ≤ 8(a + b + c), and 5 ≥ b / (a ​​+ c) ≥ 0.

1.

21. In the general chemical formula of the aforementioned organic mixed metal-oxygen cluster compound, at least one of L1, L2, and L3 includes a functional group. The method for patterning a substrate surface according to claim 19 or 20, wherein the functional group is selected from at least one of carboxylic acids, alcohols, phenols, nitriles, alkynes, alcoholamines, pyridines, pyrazoles, imidazoles, piperazines, and pyrazines.

22. A method for patterning a substrate surface according to any one of claims 19 to 21, wherein at least one of L1, L2, and L3 comprises a radiosensitive functional group, the radiosensitive functional group comprising at least one of a double bond, a triple bond, and epoxypropane.

23. The organic mixed metal-oxygen cluster compound further comprises a radiosensitive element, the radiosensitive element is It is replaced by some of the metal ions in M1, or It is replaced by some of the metal ions in M2, or It is substituted for some of the metal ions in M3, The aforementioned radiation-sensitive element includes at least one of Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, and Po. The method for patterning a substrate surface according to any one of claims 19 to 22, wherein the radiation-sensitive element is a metal element different from the metal element originally contained in the organic mixed metal-oxygen cluster compound.

24. A method for patterning a substrate surface according to any one of claims 19 to 23, wherein in the general chemical formula of the organic mixed metal-oxygen cluster compound, the ratio of a:b:c is 5:9:

1.

25. The method for patterning a substrate surface according to any one of claims 19 to 24, wherein in the step of performing local exposure on the patterning material layer, any single-wavelength or mixed-wavelength soft X-ray in the wavelength range of 1 nm to 15 nm is used, or an electron beam is used, or extreme ultraviolet radiation is used.

26. The method for patterning a substrate surface according to claim 25, wherein in the step of performing local exposure of the patterning material layer using the soft X-rays, a mask is used, and the soft X-rays that carry pattern information reach the patterning material layer through the mask, and the patterning material layer is locally exposed.

27. The method for patterning a substrate surface according to any one of claims 19 to 26, wherein the developer is at least one of isopropanol, N,N-dimethylformamide, 2-acetoxy-1-methoxypropane, ethyl lactate, and water.

28. The method for patterning a substrate surface according to any one of claims 19 to 27, further comprising the step of etching the substrate using the patterning material layer remaining on the substrate as a protective layer.

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