Patterned material, patterned composition, and pattern forming method

Abstract

The present application relates to a kind of patterning material, patterning composition and pattern forming method.The patterning material of the present application has metal oxygen cluster skeleton, radiation-sensitive organic ligand and second ligand, the radiation-sensitive organic ligand is coordinated with metal M via coordination atom, the coordination atom is at least one selected from oxygen atom, sulfur atom, selenium atom, nitrogen atom, phosphorus atom, and the radiation-sensitive organic ligand is monodentate ligand or is two or more ligands;The second ligand is inorganic ion or coordination group.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of patterning material, radiation-sensitive patterning composition, pattern forming method, patterned substrate, patterning method of substrate, and integrated circuit device, and in particular to a patterning material, a radiation-sensitive patterning composition comprising the patterning material, a pattern forming method using the patterning material, a patterned substrate formed using the patterning material, a patterning method of substrate using the patterned substrate, and an integrated circuit device comprising a surface structure formed using the patterning method of substrate. BACKGROUND

[0002] With the miniaturization and high performance of consumer electronic products, especially various terminals such as tablets, laptops, digital cameras, mobile phones, wearable electronic devices, virtual reality devices, etc., the demand for high integration of integrated circuit (IC) devices is also increasing, and the chip computing power per unit area needs to be gradually improved, and the performance of electronic products needs to be higher and higher. To support the rapid development of the integrated circuit industry, especially for the improvement of chip computing power per unit area, that is, the critical dimension is getting smaller and smaller, the rapid development of patterning technology is indispensable. For the patterning process of integrated circuits, the current development has reached the level of supporting mass production of N5nm process nodes. In particular, the patterning process generally includes the following steps: using a predetermined pattern as a template, irradiating a coated substrate film through the template to form an irradiated structure having an irradiated coating region and an unirradiated coating region; and selectively dissolving and cleaning the irradiated structure or the unirradiated structure, the remaining material forms a pattern identical to the pattern on the template; the remaining patterning material usually has etch resistance in the etching step, and optionally a protective bottom layer material can be provided, so that the substrate is not etched or is slowly etched, thereby forming a pattern transferred to the bottom substrate, forming a pattern on the substrate such as a silicon wafer, which pattern comes from the initially selected exposure pattern. The specific process is shown in Figure 1

[0003] In the most advanced application of short-wavelength 15nm or less rays to realize the process of patterning, the light source transmission efficiency of the patterning technology is low, and the sensitivity of the patterning material is required to be high, and the exposure energy usually needs to be 30mJ / cm 2 ​In order to meet the requirement of the highest resolution of 20 nm or less and the requirement of the LER / LWR edge roughness of 8% or less of the resolution, the current patterned material cannot meet the highest resolution of 10 nm or less that can be theoretically achieved by the most advanced patterning. The current material systems include organic polymer type, organic small molecule type, metal organic type, and organosilicon type. The organic polymer type material system is the traditional patterning material, and is used before the application of 15 nm or less short wavelength. However, when the wavelength of the patterning light source is reduced to 15 nm or less, the resolution requirement of the formed pattern is increased. However, the resolution limit of the pattern formed by the current organic polymer material system is about 13 nm, and therefore various material systems are explored in the industry. The resolution of the organosilicon material system is high, and the molecular size is small. However, the sensitivity of silicon to the light source of 15 nm or less is low, and the required exposure energy is extremely high.

[0004] The metal organic cluster type patterning material of the metal organic type material system is highly regarded. The cluster material has been studied for many years in various fields, and has a mature material library. The sensitivity of the cluster material to the light source of 15 nm or less is high, and the composition elements and the mode are diversified. The size range of the molecular cluster that can be selected is large, and the adjustable range of the properties is large. In particular, the use of the cluster type molecule with a size of less than 2 nm has potential advantages of improving the final pattern resolution, reducing the edge roughness, and improving the sensitivity. The current material library is large. However, the performance of the metal organic cluster type patterning material is not perfect, and the multi-path exploration is still in progress.

[0005] However, the metal organic cluster type patterning material developed in the prior art usually causes the generation of CO2 and other gases after exposure, which pollutes the inside of the exposure machine, thereby making it difficult to be used in industrial mass production, and adversely affecting the resolution and edge roughness of the formed pattern. In addition, the structure stability and radiation sensitivity of the metal organic cluster type patterning material in the prior art also have room for improvement. SUMMARY

[0006] Therefore, a patterning material is provided. The structure of the patterning material is stable and uniform, and is flexible and adjustable. The molecular size is small, and the sensitivity to radiation (such as ultraviolet light, X-ray, or electron beam, especially ultraviolet light, X-ray, and electron beam with a wavelength of 15 nm or less) is high (for ultraviolet light and X-ray, the exposure energy is 200 mJ / cm 2 For electron beam, the exposure energy is 100 μC / cm 2The patterning material can be used as a positive or negative patterning material and is suitable for different scenarios, can obtain a pattern with high resolution (the resolution can be less than 100 nm, and further can be less than 10 nm), high pattern edge definition (the edge roughness can be less than 30% of the pattern resolution) and strong etching resistance after exposure, and almost no gas pollution to the exposure equipment cavity during the exposure process; in addition, the synthesis method and process of the patterning material are simple, and mass production is facilitated.

[0007] A radiation-sensitive patterning composition is also provided, which can be used as a positive or negative patterning composition and is suitable for different scenarios, can obtain a pattern with high resolution, high pattern edge definition and strong etching resistance after exposure, and almost no gas pollution to the exposure equipment cavity during the exposure process.

[0008] A pattern forming method is also provided, which can form a pattern with high resolution, high pattern edge definition and strong etching resistance with high efficiency, and almost no gas pollution to the exposure equipment cavity during the exposure process.

[0009] A patterned substrate is also provided, which contains a patterned film capable of having a pattern with high resolution, high pattern edge definition and strong etching resistance, and is suitable for forming a surface structure with high resolution and high pattern edge definition on various substrates in various application scenarios.

[0010] A patterning method of a substrate is also provided, which can obtain a surface structure with high resolution and high pattern edge definition on various substrates by using the above-mentioned patterned substrate, and is particularly suitable for preparing an integrated circuit with excellent high integration and high resolution and high pattern edge definition.

[0011] An integrated circuit device is also provided, which can have excellent high integration by using the above-mentioned patterning method of a substrate to form a surface structure.

[0012] In a first aspect, embodiments of the present application provide a patterning material having a metal oxygen cluster skeleton composed of metal M-oxygen bridge bonds, a radiation-sensitive organic ligand and a second ligand,

[0013] The radiation-sensitive organic ligand is coordinated to the metal M via a coordination atom selected from at least one of an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom and a phosphorus atom, and the radiation-sensitive organic ligand is a monodentate ligand or a ligand with two or more dentate; the second ligand is an inorganic ion or a coordination group.

[0014] In this case, the patterning material of the present application is a metal oxo cluster type material, which has a stable and uniform structure, is flexible and adjustable, has a small molecular size, and has high sensitivity to radiation (e.g., to ultraviolet light, X-rays, or electron beams, especially to ultraviolet light, X-rays, and electron beams with a wavelength of 15 nm or less) (for ultraviolet light and X-rays, the exposure energy is 200 mJ / cm 2 For electron beams, the exposure energy is 100 μC / cm 2 In the exposure process, almost no harmful gas is generated (i.e., the low outgassing property is excellent), so that the patterning material can be used as a positive or negative patterning material and is suitable for different scenarios, and after exposure, a pattern with high resolution (the resolution can be 100 nm or less, and further can be 10 nm or less), high pattern edge definition (the edge roughness can be 30% or less of the pattern resolution), and strong etching resistance can be obtained, and in the exposure process, almost no gas pollution to the exposure equipment cavity is generated; in addition, the synthesis method and process of the patterning material are simple, and mass production is facilitated.

[0015] According to the first aspect, in a first possible implementation manner of the patterning material, the patterning material is represented by the following general formula (1):

[0016] M x O y (OH) n (L1) a (L2) b (L3) c (L4) d X m General formula (1)

[0017] In general formula (1), 3≤x≤72, 0≤y≤72, 0≤a≤72, 0≤b≤72, 0≤c≤72, 0≤d≤72, 0≤n≤72, 0≤m≤72, y+n+a+b+c+d+m≤8x, x, y, a, b, c, d, m, n are all integers and a, b, c, d are not all 0 at the same time; L1, L2, L3, L4 are each independently or in the form of two or more coexisting in the same ligand as the radiation-sensitive organic ligand; X is the second ligand.

[0018] In this case, the patterning material of the present application can have a more suitable molecular structure, more excellent radiation sensitivity, and / or more excellent low outgassing property.

[0019] According to the first aspect, in the first or second possible implementation manner of the patterning material, the metal M comprises at least one selected from indium, tin, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, palladium, platinum, silver, cadmium, antimony, tellurium, hafnium, tungsten, gold, lead, bismuth.

[0020] In this case, the patterning material of the present application can have a more stable structure and more excellent radiation sensitivity.

[0021] According to the first aspect, in the third possible implementation manner of the patterning material, the metal M further comprises at least one selected from sodium, magnesium, aluminum, potassium, calcium, scandium, gallium, germanium, arsenic, rubidium, strontium, yttrium, technetium, ruthenium, rhodium, cesium, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, tantalum, rhenium, osmium, iridium, mercury, polonium.

[0022] In this case, the structure of the patterning material of the present application is more flexible and adjustable without losing stability, and has more excellent radiation sensitivity.

[0023] According to the first aspect, in any one of the first to fourth possible implementation manners of the patterning material, the coordination atom is an oxygen atom, and the oxygen atom in the radiation-sensitive organic ligand does not form a carboxyl group and a peroxide bond.

[0024] In this case, the patterning material of the present application can have a more stable structure and more excellent low outgassing property.

[0025] According to the first aspect, in any one of the first to fifth possible implementation manners of the patterning material, the radiation-sensitive organic ligand is formed by at least one of an alcohol amine, an alcohol, a phenol, a nitrogen-containing heterocyclic compound, a nitrile, a phosphine, a phosphonic acid, a thiol, and an organic selenium compound.

[0026] In this case, the patterning material of the present application can have more excellent radiation sensitivity and more excellent low outgassing property.

[0027] According to the first aspect, in any one of the first to sixth possible implementation manners of the patterning material, the coordination group is at least one selected from a halogen group, a carboxylic acid group, a sulfonic acid group, a nitro group, an aliphatic alcohol group, an aromatic alcohol group, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group; and the inorganic ion is at least one selected from a halogen ion, SO4 2- , NO3 - .

[0028] In this case, the patterning material of the present application can have a more stable structure, more excellent radiation sensitivity, and / or more excellent low outgassing property.

[0029] According to the first aspect, in a second possible implementation mode of the patterning material, the L1, L2, L3, L4 are derived from at least one of alcohol amines, alcohols, phenols, nitrogen-containing heterocyclic compounds, nitriles, phosphines, phosphonic acids, thiols, and organoselenium compounds, respectively.

[0030] In this case, the patterning material of the present application can have a more stable structure, more excellent radiation sensitivity, and more excellent low outgassing, and is more easily obtained.

[0031] According to the first aspect, in any one of the first to eighth possible implementation modes of the patterning material, the patterning material is an indium-oxygen cluster type material represented by the following general formula (1-1):

[0032] [M4(μ4-O)] x1 M x2 O y (OH) n X m (L1) a (L2) b (L3) c (L4) d General formula (1-1)

[0033] In general formula (1-1), M contains at least indium; 1≤x1≤12, 0≤x2≤24, 0≤y≤24, 0≤a≤36, 0≤b≤36, 0≤c≤36, 0≤d≤36, 0≤n≤24, 0≤m≤24, y+n+m+a+b+c+d≤31(x1)+8(x2), x1, x2, y, a, b, c, d, m, n are all integers and a, b, c, d are not simultaneously 0; the L1, L2, L3, L4 are each independently or in a manner of coexisting in the same ligand in two or more as the radiation-sensitive organic ligand; and X is the second ligand.

[0034] The structure of such indium-oxygen cluster type material of the present application is stable, uniform, and flexible, has more excellent radiation sensitivity, and more excellent low outgassing.

[0035] According to the first aspect, in a ninth possible implementation mode of the patterning material, the radiation-sensitive organic ligand in the indium-oxygen cluster type material is coordinated with the metal M via a nitrogen atom or an oxygen atom as a coordination atom, and the L1, L2, L3, L4 are derived from at least one of alcohol amines, alcohols, phenols, and nitrogen-containing heterocyclic compounds, respectively.

[0036] In this case, the indium-oxygen cluster type material of the present application can be more easily obtained, and has further excellent radiation sensitivity.

[0037] According to the first aspect, in any one of the ninth to eleventh possible implementations of the patterned material, the patterned material is an indium oxo-cluster type material represented by the following general formula (1-11):

[0038] In this case, the indium oxo-cluster type material of the present application has particularly excellent radiation sensitivity.

[0039] According to the first aspect, in any one of the ninth to eleventh possible implementations of the patterned material, the patterned material is an indium oxo-cluster type material represented by the following general formula (1-11):

[0040] [In4(μ4-O)] x1 In x2 O y (OH) n (L1) a (L2) b X m General formula (1-11)

[0041] In general formula (1-11), x1, x2, y, a, b, m, n are each an integer and a and b are not simultaneously 0, 1≤x1≤4, 2≤x2≤8, 1≤y≤4, 0≤a≤8, 0≤b≤12, 0≤n≤10, 0≤m≤8, L1 is OR 1 , L2 is NR 2 (CR 3 R 4 CR 5 R 6 O)2, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 each independently is H, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 14 ring-forming atoms, the heteroatoms in the heterocyclic group including oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms; X each independently is -F, -Cl, -Br.

[0042] In the case of using the indium oxo-cluster type material represented by general formula (1-11), the above technical effects of the present application can be particularly advantageously obtained.

[0043] According to the first aspect, in any one of the ninth to eleventh possible implementations of the patterned material, the patterned material is an indium oxo-cluster type material represented by the following general formula (1-11):

[0044] M x O y (L1) a(L2) b X m General formula (1-2)

[0045] In general formula (1-2), M contains at least tin; 3≤x≤34, 0≤y≤51, 0≤a≤51, 0≤b≤51, 0≤m≤51, y+a+b+m≤8x, x, y, a, b, m are all integers and a, b are not simultaneously 0; the L1, L2 are each independently or coexist in two or more in the same ligand as the radiation-sensitive organic ligand; X is the second ligand.

[0046] The structure of such tin-oxygen cluster type material of the present application is stable, uniform, flexible and adjustable, has more excellent radiation sensitivity and more excellent low outgassing property.

[0047] According to the first aspect, in a thirteenth possible implementation of the patterned material, the radiation-sensitive organic ligand in the tin-oxygen cluster type material is coordinated with the metal M via a nitrogen atom as a coordination atom, and the L1, L2 are respectively derived from at least one of alcohol amine, nitrogen-containing heterocyclic compound, nitrile.

[0048] In this case, the tin-oxygen cluster type material of the present application can be more easily obtained, and has further excellent radiation sensitivity.

[0049] According to the first aspect, in the thirteenth or fourteenth possible implementation of the patterned material, at least one of the X is a halogen ion or a halogen group.

[0050] In this case, the tin-oxygen cluster type material of the present application has particularly excellent radiation sensitivity.

[0051] According to the first aspect, in any one of the thirteenth to fifteenth possible implementations of the patterned material, the patterned material is a tin-oxygen cluster type material represented by the following general formula (1-21):

[0052] Sn x O y (L1) a X m General formula (1-21)

[0053] In general formula (1-21), x, y, a, m are all integers, 4≤x≤15, 6

[0054] The technical effects of the present application can be particularly advantageously obtained in the case of using a tin-oxygen cluster type material represented by the general formula (1-21).

[0055] In a second aspect, embodiments of the present application provide a radiation-sensitive patterning composition comprising the patterning material according to any one of the first to sixteenth possible implementation manners of the first aspect and a solvent.

[0056] In this case, the radiation-sensitive patterning composition of the present application can be used as a positive type patterning composition or a negative type patterning composition and is suitable for different scenarios, and can obtain a pattern with high resolution, high pattern edge definition and strong etching resistance after exposure, and almost no gas pollution to the exposure equipment cavity during the exposure process.

[0057] According to the second aspect, in the first possible implementation manner of the radiation-sensitive patterning composition, the solvent is at least one selected from carboxylic acid esters, alcohols with 1-8 carbon atoms, aromatic hydrocarbons, halogenated hydrocarbons, and amides.

[0058] In this case, the radiation-sensitive patterning composition of the present application has better coatability.

[0059] In a third aspect, embodiments of the present application provide a pattern forming method, comprising the steps of:

[0060] forming a coated substrate comprising a radiation-sensitive coating, wherein the radiation-sensitive coating comprises the patterning material according to any one of the first to sixteenth possible implementation manners of the first aspect;

[0061] exposing the coated substrate to radiation in a desired pattern to form an exposed structure comprising a region with an exposed coating and a region with an unexposed coating; and

[0062] selectively developing the exposed structure to form a patterned substrate with a patterned film.

[0063] In this case, the pattern forming method of the present application can form a pattern with high resolution, high pattern edge definition and strong etching resistance with high efficiency, and almost no gas pollution to the exposure equipment cavity during the exposure process.

[0064] According to the third aspect, in the first possible implementation manner of the pattern forming method, the radiation-sensitive coating is formed directly on a silicon wafer, or on a silicon wafer covered by an intermediate material layer.

[0065] In this case, the integrated circuit device can be obtained with high efficiency using the image forming method of the present application.

[0066] According to the third aspect, in the first or second possible implementation manner of the pattern forming method, the radiation-sensitive coating is formed on the substrate covered by the intermediate material layer by a coating method.

[0067] In this case, the patterned substrate with a patterned film with more uniform thickness can be obtained, and the use of the obtained patterned substrate is more extensive.

[0068] According to the third aspect, in any one of the first to third possible implementation manners of the pattern forming method, the radiation includes X-rays, electron beams, and ultraviolet light.

[0069] In this case, the effect of exposure can be better achieved, so that it is easier to form a pattern with high resolution, high pattern edge clarity, and strong etching resistance.

[0070] According to the third aspect, in any one of the first to fourth possible implementation manners of the pattern forming method, the developing solution for the developing is an aqueous solution-based developing solution or an organic solvent-based developing solution.

[0071] In this case, the effect of developing can be better achieved, so that it is easier to form a pattern with high resolution, high pattern edge clarity, and strong etching resistance.

[0072] According to the fourth aspect, the embodiments of the present application provide a patterned substrate, comprising a patterned film and a substrate, the patterned film being present in selected regions on the substrate and being absent in other regions on the substrate, and the patterned film being formed by the patterned material according to any one of the first to sixteenth possible implementation manners of the first aspect.

[0073] In this case, the patterned substrate of the present application comprises a patterned film with a pattern with high resolution, high pattern edge clarity, and strong etching resistance, and is suitable for forming a surface structure with high resolution and high pattern edge clarity on various substrates in various application scenarios.

[0074] According to the fourth aspect, in the first possible implementation manner of the patterned substrate, the pattern resolution of the pattern of the patterned film is between 3-100 nm, and the edge roughness is 2-30% of the pattern resolution.

[0075] In this case, the patterned film contained in the patterned substrate of the present application can have a pattern with higher resolution and higher pattern edge clarity.

[0076] According to the fifth aspect, the embodiments of the present application provide a patterned method of a substrate, characterized in that it comprises: etching or electron injection on the patterned substrate according to the first or second possible implementation manner of the fourth aspect to form a patterned structure on the surface of the substrate.

[0077] In this case, the patterning method of the substrate of the present application, since it is performed using the above-described patterned substrate, can obtain a surface structure having high resolution and high pattern edge definition on various substrates, and is particularly suitable for producing an integrated circuit having high integration, which is desired to have high resolution and high pattern edge definition.

[0078] In a sixth aspect, an embodiment of the present application provides an integrated circuit device, including: a surface structure formed on a silicon wafer as a substrate by the patterning method of the substrate according to the implementation of the fifth aspect.

[0079] In this case, the integrated circuit device of the present application, since the surface structure is formed using the above-described patterning method of the substrate, can have excellent high integration.

[0080] These and other aspects of the present application will become more fully understood from the following (a plurality of) embodiment descriptions. BRIEF DESCRIPTION OF DRAWINGS

[0081] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments, features, and aspects of the present application and serve to explain the principles of the present application.

[0082] Figure 1 An exemplary flowchart of a patterning process is shown.

[0083] Figure 2 An exemplary structural formula of an indium-oxygen cluster type material of the present application represented by general formula (1-11) is shown.

[0084] Figure 3 An exemplary structural formula of a tin-oxygen cluster type material of the present application represented by general formula (1-21) is shown.

[0085] Figure 4 An exemplary manufacturing flowchart of a patterning method of the present application is shown.

[0086] Figure 5 An exemplary manufacturing flowchart of a patterning method of the present application is shown.

[0087] Figure 6 A specific manufacturing flowchart of an integrated circuit device of the present application is shown.

[0088] Figure 7 Infrared spectra of indium-oxygen cluster type compounds 1 to 8 of the present application are shown.

[0089] Figure 8 An EDX spectrum of an indium-oxygen cluster type compound 9 of the present application is shown.

[0090] Figure 9 A line pattern formed using indium oxo-cluster compound 3 in this application is shown.

[0091] Figure 10 A line pattern formed using indium oxo-cluster compound 3 in this application is shown.

[0092] Figure 11 A line pattern formed using indium oxo-cluster compound 2 in this application is shown.

[0093] Figure 12 A line pattern formed using indium oxo-cluster compound 2 in this application is shown.

[0094] Figure 13 A line pattern formed using indium oxo-cluster compound 9 in this application is shown.

[0095] Figure 14 A line pattern formed using indium oxo-cluster compound 9 in this application is shown.

[0096] Figure 15 An infrared spectrum of tin oxo-cluster compound 1 of this application is shown.

[0097] Figure 16 An infrared spectrum of tin oxo-cluster compound 2 of this application is shown.

[0098] Figure 17 A line pattern formed using tin oxo-cluster compound 1 in this application is shown.

[0099] Figure 18 A line pattern formed using tin oxo-cluster compound 2 in this application is shown. DETAILED DESCRIPTION

[0100] Various exemplary embodiments, features, and aspects of the present application will be described herein below with reference to the accompanying drawings. Like reference numerals in the drawings denote like or similar elements. Although various aspects of the embodiments are illustrated in the drawings, the drawings are not necessarily drawn to scale unless specifically noted.

[0101] The term "exemplary" is used herein to mean "serving as an example, instance, or illustration." Any implementation described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other implementations.

[0102] In addition, for the purpose of convenience and brevity, detailed descriptions of well-known functions and structures incorporated in the application will be omitted. It will be appreciated that those skilled in the art will be able to devise various modes of implementing the application without the benefits of these particulars. In some instances, well-known methods, structures and techniques have not been described in detail in order to avoid obscuring the application.

[0103] <First aspect>

[0104] To solve the above-described technical problem, the present application provides a patterning material having a metal oxygen cluster skeleton composed of metal M-oxygen bridge bonds, a radiation-sensitive organic ligand, and a second ligand,

[0105] The radiation-sensitive organic ligand is coordinated to the metal M via a coordination atom selected from at least one of an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, and a phosphorus atom, and the radiation-sensitive organic ligand is a monodentate ligand or a ligand of two or more dentates; and the second ligand is an inorganic ion or a coordination group.

[0106] In the present application, in some preferred embodiments, when the above-described coordination atom is an oxygen atom, the oxygen atom in the radiation-sensitive organic ligand does not form a carboxyl group and a peroxide bond. Here, "the oxygen atom in the radiation-sensitive organic ligand does not form a carboxyl group and a peroxide bond" means that, when the organic ligand is coordinated to the metal M via the oxygen atom as the coordination atom, an acyloxy metal structure and a peroxide metal structure are not formed.

[0107] The patterning material of the present application can be sensitive to various types of radiation such as ultraviolet light, X-rays, or electron beams (even to a specific wavelength or wavelength range within the various types of radiation), depending on the specific structure, which means that the radiation changes the properties of the material, thereby changing the solubility of the material. Specifically, after being subjected to radiation (exposure), the exposed material and the unexposed material differ greatly in solubility in a developing solution, and thus can be used to form a specific pattern.

[0108] The patterning material of the present application is a radiation-sensitive metal oxygen cluster type material, and is small in molecular size and uniform in structural stability due to having a metal oxygen cluster skeleton (particularly, can be represented by the following general formula (1)), and is flexible in structure and adjustable in structure due to having the above-described specific radiation-sensitive organic ligand and second ligand, and is sensitive to radiation (for ultraviolet light and X-rays, the exposure energy is 200 mJ / cm 2 The following can achieve a significant change in the properties of the material, and for electron beams, the exposure energy is 100 μC / cm 2The following can achieve a significant change in material properties), and hardly generates harmful gas during exposure (i.e., low outgassing is excellent). Thus, the patterning material of the present application can be used as a positive or negative patterning material and is suitable for different scenarios, and can achieve a pattern with high resolution (resolution of 100 nm or less, further resolution of 10 nm or less), high pattern edge definition (edge roughness of 30% or less of the pattern resolution), and strong etching resistance after exposure, and hardly causes gas contamination in the exposure equipment cavity during exposure. In addition, the synthesis method and process of the patterning material of the present application are simple, and are suitable for mass production.

[0109] In some preferred embodiments, the patterning material of the present application is represented by the following general formula (1):

[0110] M x O y (OH) n (L1) a (L2) b (L3) c (L4) d X m General formula (1)

[0111] In general formula (1), 3≤x≤72, 0≤y≤72, 0≤a≤72, 0≤b≤72, 0≤c≤72, 0≤d≤72, 0≤n≤72, 0≤m≤72, y+n+a+b+c+d+m≤8x, x, y, a, b, c, d, m, n are all integers and a, b, c, d are not all 0 at the same time; L1, L2, L3, L4 are each independently or coexist in the same ligand in two or more ways as the radiation-sensitive organic ligand; X is the second ligand.

[0112] In this case, the patterning material of the present application can have a more suitable molecular structure, more excellent radiation sensitivity and / or more excellent low outgassing.

[0113] The metal-oxygen cluster framework and the ligand will be described in detail below.

[0114] (Metal-oxygen cluster framework)

[0115] As described above, the metal-oxygen cluster framework of the present application is a cluster structure composed of metal M-oxygen bridge bonds, and as long as this is the case, the specific structure of the metal-oxygen cluster framework is not particularly limited, and can be a single metal-oxygen cluster framework, or a heterometallic oxygen cluster framework having two or more metals, and can be appropriately changed as needed. In some specific embodiments, a single metal-oxygen cluster is represented by "M x O y " in the above general formula (1).

[0116] In the present application, the term "metal M" is a concept that encompasses both metal elements and metalloid elements. In some preferred embodiments, the metal M comprises at least one selected from the group consisting of indium (In), tin (Sn), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), platinum (Pt), silver (Ag), cadmium (Cd), antimony (Sb), tellurium (Te), hafnium (Hf), tungsten (W), gold (Au), lead (Pb), bismuth (Bi). In some more preferred embodiments, the metal M comprises at least indium or tin.

[0117] Furthermore, in some specific embodiments, the metal M constituting the framework of the metal oxo cluster optionally further comprises at least one selected from the group consisting of sodium (Na), magnesium (Mg), aluminum (Al), potassium (K), calcium (Ca), scandium (Sc), gallium (Ga), germanium (Ge), arsenic (As), rubidium (Rb), strontium (Sr), yttrium (Y), technetium (Tc), ruthenium (Ru), rhodium (Rh), cesium (Cs), barium (Ba), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), tantalum (Ta), rhenium (Re), osmium (Os), iridium (Ir), mercury (Hg), polonium (Po).

[0118] (ligand)

[0119] In the present application, both the radiation-sensitive organic ligand (sometimes also referred to as the first ligand) and the second ligand are coordinated to the metal M as ligands.

[0120] In the present application, the first ligand is an organic ligand having radiation sensitivity (e.g., sensitivity to ultraviolet light, X-rays, or electron beams, particularly ultraviolet light, X-rays, or electron beams having a wavelength of 15 nm or less), and the second ligand optionally has such radiation sensitivity. Thus, the performance of the patterning material of the present application is mainly influenced by the structure of the first ligand (particularly the coordination atom). In particular, the radiation-sensitive organic ligand of the present application, as compared with the ligands containing a carbon-metal bond, ligands containing a peroxide bond, and ligands containing a carboxylic acid-metal bond, which are used as radiation-sensitive ligands in the prior art, can achieve excellent low outgassing while ensuring high radiation sensitivity. For the first ligand, as long as the above requirements for the radiation-sensitive organic ligand are satisfied (the radiation-sensitive organic ligand is coordinated to the metal M via at least one coordination atom selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, and a phosphorus atom, and is a monodentate ligand or a ligand having two or more dentate), the patterning material can have the desired performance of the present application.

[0121] In some preferred embodiments, the radiation-sensitive organic ligand is formed using at least one of an alcohol amine, an alcohol, a phenol, a nitrogen-containing heterocyclic compound, a nitrile, a phosphine, a phosphonic acid, a mercaptan, and an organoselenium compound.

[0122] Generally, in the present application, the number ratio of the coordination atom of the radiation-sensitive organic ligand to the metal atom is not particularly limited. In order to further improve the radiation sensitivity of the material of the present application, and further improve the pattern edge definition and resolution of the resulting pattern, in some preferred embodiments, the number ratio of the coordination atom of the radiation-sensitive organic ligand to the metal atom is preferably 1:2 to 4:1.

[0123] In some preferred embodiments, in the case where the patterning material of the present application is represented by the above general formula (1), the above L1, L2, L3, and L4 constituting the radiation-sensitive organic ligand are preferably derived from at least one of an alcohol amine, an alcohol, a phenol, a nitrogen-containing heterocyclic compound, a nitrile, a phosphine, a phosphonic acid, a mercaptan, and an organoselenium compound, respectively.

[0124] The alcohol amine is a compound that can be represented by NQ3(wherein at least one of Q is a hydrocarbon group having a hydroxyl group (preferably, an alkyl group having a hydroxyl group), and the other Qs are each independently H or a hydrocarbon group having a carbon number of 1 to 18), and examples thereof include, but are not limited to, primary alcohol amines (such as methanol amine, ethanol amine, dimethyl ethanol amine, methyl ethyl ethanol amine, diethyl vinyl propyl amine, and the like), secondary alcohol amines (such as diethanol amine, methyl diethanol amine, methyl methyl ethanol amine, and ethyl diethanol amine, and the like), tertiary alcohol amines (such as triethanol amine, tripropyl amine, tributyl amine, and the like), and the like.

[0125] Examples of the alcohols include, but are not limited to, monohydric alcohols such as methanol, ethanol, propanol, butanol, n-hexanol, cyclohexanol, and the like; polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, glycerol, butane triol, pentaerythritol, dipentaerythritol, and the like.

[0126] Examples of the phenols include, but are not limited to, phenol, alkylphenols (e.g., cresol, ethylphenol, phenylphenol), alkenylphenols (e.g., vinylphenol, allylphenol, and the like), alkynylphenols (e.g., ethynylphenol, propynylphenol), and the like.

[0127] Examples of the nitrogen-containing heterocyclic compounds include, but are not limited to, pyridines (substituted or unsubstituted pyridines), pyrazoles (substituted or unsubstituted pyrazoles), imidazoles (substituted or unsubstituted imidazoles), piperazines (substituted or unsubstituted piperazines), pyrazines (substituted or unsubstituted pyrazines). Here, the substituents in "substituted or unsubstituted" include, but are not limited to, deuterium atoms, cyano groups, nitro groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and the like; straight-chain or branched alkyl groups such as methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, t-butyl groups, n-pentyl groups, isopentyl groups, neopentyl groups, n-hexyl groups, and the like; straight-chain or branched alkoxy groups such as methyloxy groups, ethyloxy groups, propyloxy groups, and the like; alkenyl groups such as vinyl groups, allyl groups, and the like; aryloxy groups such as phenyloxy groups, tolyloxy groups, and the like; aralkyloxy groups such as benzyloxy groups, phenethyloxy groups, and the like; aromatic hydrocarbon groups or fused polycyclic aromatic groups such as phenyl groups, biphenyl groups, terphenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, fluorenyl groups, indenyl groups, pyrenyl groups, perylenyl groups, fluoranthenyl groups, benzophenanthryl groups, and the like; aromatic heterocyclic groups such as pyridyl groups, pyrazolyl groups, pyrazinyl groups, piperazinyl groups, imidazolyl groups, pyrimidinyl groups, triazinyl groups, thienyl groups, furanyl groups, pyrrolyl groups, quinolyl groups, isoquinolyl groups, benzofuranyl groups, benzothienyl groups, indolyl groups, carbazolyl groups, benzoxazolyl groups, benzothiazolyl groups, quinoxalyl groups, benzimidazolyl groups, dibenzofuranyl groups, dibenzothienyl groups, carbolinyl groups, and the like; arylethenyl groups such as styryl groups, naphthylethenyl groups, and the like; acyl groups such as acetyl groups, benzoyl groups, and the like, which are optionally further substituted with the aforementioned exemplified substituents. Furthermore, these substituents are optionally bonded to each other via single bonds, substituted or unsubstituted methylene groups, oxygen atoms, nitrogen atoms, selenium atoms, phosphorus atoms, or sulfur atoms to form a ring.

[0128] Examples of the nitriles include, but are not limited to, alkyl nitriles such as acetonitrile, propionitrile, and the like; alkenyl nitriles such as vinyl nitrile, allyl nitrile, styryl nitrile, and the like; alkynyl nitriles such as ethynyl nitrile, phenylethynyl nitrile, and the like.

[0129] Phosphines are compounds represented by PQ3(wherein each Q is independently H, a hydrocarbon group having a carbon number of 1 to 18, or a hydrocarbonoxy group having a carbon number of 1 to 18), examples of which include, but are not limited to, monohydrocarbyl phosphines such as dihydrogen methyl phosphine, dihydrogen ethyl phosphine, dihydrogen propyl phosphine, dihydrogen phenyl phosphine, dihydrogen naphthyl phosphine, dihydrogen vinyl phosphine, dihydrogen acetylenyl phosphine, and the like, dihydrocarbyl phosphines such as hydrogen dimethyl phosphine, hydrogen diethyl phosphine, hydrogen dipropyl phosphine, hydrogen dibutyl phosphine, hydrogen methylethyl phosphine, hydrogen methylpentyl phosphine, hydrogen methylphenyl phosphine, hydrogen diphenyl phosphine, hydrogen divinyl phosphine, hydrogen methylethyl phosphine, hydrogen diacetylenyl phosphine, and the like, trihydrocarbyl phosphines such as trimethyl phosphine, triethyl phosphine, tripropyl phosphine, triphenyl phosphine, dimethylphenyl phosphine, diethylphenyl phosphine, dipropylphenyl phosphine, dibutylphenoxy phosphine, and the like, monohydrocarbyloxy phosphines such as dihydrogen methoxy phosphine, dihydrogen ethyloxy phosphine, dihydrogen propyloxy phosphine, dihydrogen phenyloxy phosphine, dihydrogen naphthyloxy phosphine, dihydrogen vinyloxy phosphine, dihydrogen acetylenoxy phosphine, and the like, dihydrocarbyloxy phosphines such as hydrogen dimethoxy phosphine, hydrogen diethoxy phosphine, hydrogen dipropyloxy phosphine, hydrogen dibutoxy phosphine, hydrogen methoxyethoxy phosphine, hydrogen methoxy-pentyloxy phosphine, hydrogen methoxyphenyloxy phosphine, hydrogen diphenyloxy phosphine, hydrogen divinyloxy phosphine, hydrogen methylethyloxy phosphine, hydrogen diacetylenoxy phosphine, and the like, trihydrocarbyloxy phosphines such as trimethoxy phosphine, triethoxy phosphine, tripropyloxy phosphine, triphenoxy phosphine, dimethylphenoxy phosphine, diethylphenoxy phosphine, dipropylphenoxy phosphine, dibutoxyphenoxy phosphine, and the like.

[0130] Examples of phosphonic acids include, but are not limited to, butyl phosphonic acid, pentyl phosphonic acid, hexyl phosphonic acid, heptyl phosphonic acid, octyl phosphonic acid, (1-methylheptyl) phosphonic acid, (2-ethylhexyl) phosphonic acid, decyl phosphonic acid, dodecyl phosphonic acid, octadecyl phosphonic acid, oleyl phosphonic acid, phenyl phosphonic acid, (p-nonylphenyl) phosphonic acid, butylbutyl phosphonic acid, pentylpentyl phosphonic acid, hexylhexyl phosphonic acid, heptylheptyl phosphonic acid, octyloctyl phosphonic acid, (1-methylheptyl)(1-methylheptyl) phosphonic acid, (2-ethylhexyl)(2-ethylhexyl) phosphonic acid, decyldecyl phosphonic acid, dodecyldodecyl phosphonic acid, octadecyloctadecyl phosphonic acid, oleyloleyl phosphonic acid, phenylphenyl phosphonic acid, (p-nonylphenyl)(p-nonylphenyl) phosphonic acid, butyl(2-ethylhexyl) phosphonic acid, (2-ethylhexyl)butyl phosphonic acid, (1-methylheptyl)(2-ethylhexyl) phosphonic acid, (2-ethylhexyl)(1-methylheptyl) phosphonic acid, (2-ethylhexyl)(p-nonylphenyl) phosphonic acid, and (p-nonylphenyl)(2-ethylhexyl) phosphonic acid, and the like.

[0131] Thiols include, but are not limited to, monothiols such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, n-hexyl mercaptan, cyclohexyl mercaptan, and the like, polythiols such as ethanedithiol, propanedithiol, butanedithiol, propanetriol, butanetriol, butanetetraol, and the like, and the like.

[0132] The organic selenium compound includes, but is not limited to, an organic selenoic acid, a selenol, a selenoether, a selenol, a hydrocarbylselenium, a hydrocarbyloxy selenium, and the like.

[0133] For the second ligand, the second ligand can be any inorganic ion that binds to the metal M via an ionic bond or any coordination group that binds to the metal M via a covalent bond (including so-called general covalent bond and coordination covalent bond).

[0134] In some preferred embodiments, in the case where the patterning material of the present application is represented by the above general formula (1), the second ligand preferably satisfies X in general formula (1) in the patterning material.

[0135] In some preferred embodiments in the present application, in the case where the second ligand is a coordination group (binding to the metal M via a covalent bond), the second ligand is preferably at least one selected from a flexible-coordinating halogen group (such as -F, -Cl, -Br, -I, and the like), a carboxylic acid group, a sulfonic acid group, a nitro group, an aliphatic alcohol group, an aromatic alcohol group, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group. Here, the term "flexible-coordinating" means that the ligand can be monodentate or polydentate, and the same ligand can coordinate to the same or different metal center.

[0136] In some other preferred embodiments in the present application, in the case where the second ligand is an inorganic ion (binding to the metal M via an ionic bond), the second ligand is preferably at least one selected from a halogen ion (such as F - , Cl - , Br - , I - , SO4 2- , NO3 - , and the like.

[0137] Further, from the viewpoint of further enhancing the radiation sensitivity, further improving the line edge roughness, and further improving the resolution, in some specific embodiments, the radiation-sensitive organic ligand and / or the second ligand as a coordination group can be optionally substituted with any radiation-sensitive functional group. Examples of such radiation-sensitive functional groups include, but are not limited to, a double bond, a triple bond, an epoxy propane group, or a combination thereof.

[0138] Further, from the viewpoint of adjusting the solubility and the like of the patterning material of the present application, thereby further improving the thickness uniformity, roughness, adhesion, and etch resistance of the patterning film formed using the patterning material of the present application, and the pattern resolution of the resulting pattern, in some specific embodiments, the radiation-sensitive organic ligand and / or the second ligand as a coordination group can be optionally substituted with any functional group. Such functional groups include, but are not limited to, electrophilic or electron-donating groups, for example, halogen groups such as -F, -Cl, -Br, and -I, a nitro group, a sulfonic acid group, a carboxylic acid group, an ester group, and the like.

[0139] The following will more specifically describe two preferred embodiments of the patterning material of the present application.

[0140] (First Embodiment)

[0141] The patterning material of the present application can more preferably be an indium-oxygen cluster type material represented by the following general formula (1-1):

[0142] [M4(μ4-O)] x1 M x2 O y (OH) n X m (L1) a (L2) b (L3) c (L4) d General formula (1-1)

[0143] In general formula (1-1), M contains at least indium; 1≤x1≤12, 0≤x2≤24, 0≤y≤24, 0≤a≤36, 0≤b≤36, 0≤c≤36, 0≤d≤36, 0≤n≤24, 0≤m≤24, y+n+m+a+b+c+d≤31(x1)+8(x2), x1, x2, y, a, b, c, d, m, n are all integers and a, b, c, d are not simultaneously 0.

[0144] Here, the term "M4(μ4-O)" means that one oxygen (O) atom bridges 4 metals M.

[0145] In general formula (1-1), L1, L2, L3, L4 are as described with respect to general formula (1). Specifically, L1, L2, L3, L4 each individually serve as the aforementioned radiation-sensitive organic ligand of the present application or in a manner that two or more coexist in the same ligand. In some preferred embodiments, L1, L2, L3, L4 each independently originate from at least one of alcohol amines, alcohols, phenols, nitrogen-containing heterocyclic compounds, nitriles, phosphines, phosphonic acids, mercaptans, organoselenium compounds. Here, examples of each of alcohol amines, alcohols, phenols, nitrogen-containing heterocyclic compounds, nitriles, phosphines, phosphonic acids, mercaptans, organoselenium compounds are also as described above. In addition, L1, L2, L3, L4 each independently are optionally substituted with the aforementioned radiation-sensitive functional groups and / or functional groups.

[0146] Further preferably, the aforementioned radiation-sensitive organic ligand in the indium-oxygen cluster type material of the present application coordinates with the metal M via a nitrogen atom or an oxygen atom as a coordination atom, and L1, L2, L3, L4 each independently originate from at least one of alcohol amines, alcohols, phenols, nitrogen-containing heterocyclic compounds, nitriles.

[0147] In General Formula (1-1), X is the above-mentioned second ligand of the present application, i.e., the above-mentioned inorganic ion or the above-mentioned coordination group. Further preferably, at least one of X is a halogen ion or a halogen group, thereby making the patterning material have particularly excellent radiation sensitivity.

[0148] In some preferred embodiments, the ratio of the number of coordination atoms (the total number of nitrogen atoms and oxygen atoms) to the number of metal atoms M is preferably 3:2 to 3:1.

[0149] In some particularly specific embodiments, the patterning material of the present application can be particularly preferably an indium-oxygen cluster type material represented by the following General Formula (1-11):

[0150] [In4(μ4-O)] x1 In x2 O y (OH) n (L1) a (L2) b X m General Formula (1-11)

[0151] In General Formula (1-11), x1, x2, y, a, b, m, n are each an integer and a and b are not simultaneously 0, 1≤x1≤4, preferably x1 is 2; 2≤x2≤8, preferably x2 is 4; 1≤y≤4, preferably y is 2; 0≤a≤8, 0≤b≤12, preferably a is 4 and b is 8; 0≤n≤10, preferably n is 2; 0≤m≤8, preferably m is 6.

[0152] In General Formula (1-11), L1 is OR 1 , L2 is NR 2 (CR 3 R 4 CR 5 R 6 O)2, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently H, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 14 ring-forming atoms (wherein the heteroatoms include, without limitation, oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, and the like), and here, examples of the substituents in "substituted or unsubstituted" are preferably -F, -Cl, -Br, -NO2, -SO3; X are each independently -F, -Cl, -Br.

[0153] The technical effects of the present application can be particularly advantageously obtained in the case of using an indium-oxygen cluster type material represented by General Formula (1-11).

[0154] The technical effects of the present application Figure 2 An exemplary structural formula of an indium-oxygen cluster type material represented by General Formula (1-11) is shown.

[0155] (Second Embodiment)

[0156] The patterning material of the present application can more preferably be a tin-oxygen cluster type material represented by the following General Formula (1-2):

[0157] M x O y (L1) a (L2) b X m General Formula (1-2)

[0158] In General Formula (1-2), M contains at least tin; 3≤x≤34, 0≤y≤51, 0≤a≤51, 0≤b≤51, 0≤m≤51, y+a+b+m≤8x, x, y, a, b, m are all integers and a, b are not simultaneously 0.

[0159] In General Formula (1-2), L1, L2 are as described with respect to General Formula (1). Specifically, L1, L2 each individually serve as the aforementioned radiation-sensitive organic ligand of the present application or in a manner that two or more coexist in the same ligand serve as the aforementioned radiation-sensitive organic ligand of the present application. In some preferred embodiments, L1, L2 each independently originate from at least one of an alcohol amine, an alcohol, a phenol, a nitrogen-containing heterocyclic compound, a nitrile, a phosphine, a phosphonic acid, a mercaptan, an organoselenium compound. Here, examples of each of the alcohol amine, the alcohol, the phenol, the nitrogen-containing heterocyclic compound, the nitrile, the phosphine, the phosphonic acid, the mercaptan, the organoselenium compound are also as described above. In addition, L1, L2 each independently are optionally substituted with the aforementioned radiation-sensitive functional group and / or functional group.

[0160] Further preferably, the radiation-sensitive organic ligand in the aforementioned tin-oxygen cluster type material of the present application coordinates with the metal M via a nitrogen atom as a coordination atom, and L1, L2 each independently originate from at least one of an alcohol amine, a nitrogen-containing heterocyclic compound, a nitrile.

[0161] In General Formula (1-2), X is the aforementioned second ligand of the present application, i.e., the aforementioned inorganic ion or the aforementioned coordination group. Further preferably, at least one of X is a halogen ion or a halogen group, thereby making the patterning material have particularly excellent radiation sensitivity.

[0162] In some preferred embodiments, the ratio of the number of coordination atoms (total number of nitrogen atoms) to the number of metal atoms M is preferably 2:3 to 3:2.

[0163] In some particularly specific embodiments, the patterning material of the present application can be particularly preferably a tin-oxygen cluster type material represented by the following general formula (1-21):

[0164] Sn x O y (L1) a X m General formula (1-21)

[0165] In general formula (1-21), x, y, a, m are each an integer, 4≤x≤15, preferably x is 10; 6

[0166] In general formula (1-21), L1is each independently a substituted or unsubstituted pyrazole, a substituted or unsubstituted pyridine, a substituted or unsubstituted imidazole, a substituted or unsubstituted piperazine, a substituted or unsubstituted pyrazine, and the substituent in "substituted or unsubstituted" is preferably a linear or branched alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and such an alkyl group as a substituent can further have a substituent, examples of the substituent of such an alkyl group include, but are not limited to, -F, -Cl, -Br, -NO2, -SO3; X is each independently -F, -Cl, -Br.

[0167] In the case of using a tin-oxygen cluster type material represented by general formula (1-21), the technical effects of the present application can be particularly advantageously obtained.

[0168] The patterning material of the present application Figure 3 Exemplary structural formulas (a: L = 3-methylpyrazole, b: L = 4-methylpyrazole) of the tin-oxygen cluster type material represented by general formula (1-21) are shown.

[0169] (Method for producing the patterning material)

[0170] The patterning material of the present application can be obtained according to a production method known in the art without particular limitation, according to the desired structure.

[0171] For example, the patterning material of the present application can be obtained by mixing M x X m , a precursor of a radiation-sensitive organic ligand (for example, at least one of a compound from which L1derives, a compound from which L2derives, a compound from which L3derives, a compound from which L4derives), and an optional solvent, heating to 80 to 120°C for 1 to 4 days, and then cooling to room temperature, and the product is the crystal that precipitates. In the above method, the precursor of the radiation-sensitive organic ligand can itself serve as the solvent, or as the solute.

[0172] In some specific embodiments, a metal halide including indium, at least one of an alcohol amine, an alcohol, a phenol, and an optionally added solvent are mixed in a reaction vessel, heated to 80 to 120°C for 1 to 4 days, and then cooled to room temperature, and a colorless crystal precipitated is the product.

[0173] In some specific embodiments, a metal halide including tin is dissolved in at least one of a pyrazole, an alcohol amine, a pyridine, a pyrazole, a piperazine, a pyrazine, heated to 80 to 120°C for 1 to 4 days, and then cooled to room temperature, and a colorless crystal precipitated is the product.

[0174] <Second Aspect>

[0175] The present application also provides a radiation-sensitive patterning composition including the above-described patterning material of the present application and a solvent.

[0176] The radiation-sensitive patterning composition of the present application, due to the inclusion of the above-described patterning material of the present application, can be applied to different application scenarios, and after exposure, can obtain a pattern with high resolution, high pattern edge clarity, and strong etching resistance, and during the exposure process, will hardly cause gas pollution to the exposure device cavity.

[0177] The patterning material of the present application has been described as above in the <First Aspect>, and will not be described here again.

[0178] Therefore, the following will describe in detail the components of the radiation-sensitive patterning composition of the present application, except for the patterning material of the present application.

[0179] (Solvent)

[0180] In the present application, as long as each component of the radiation-sensitive patterning composition can be dissolved, there is no particular limitation on the specific type of the solvent, and it can be appropriately selected according to the coating film thickness, viscosity, etc.

[0181] In the present application, in some preferred embodiments, the solvent is at least one selected from carboxylic acid esters, alcohols having 1 to 8 carbon atoms, aromatic hydrocarbons, halogenated hydrocarbons, amides.

[0182] Examples of carboxylic acid esters include, but are not limited to, carboxylic acid ether esters such as ethylene glycol methyl ether formate, propylene glycol methyl ether formate, ethylene glycol ethyl ether formate, propylene glycol ethyl ether formate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, ethylene glycol methyl ether propionate, etc.; carboxylic acid alkyl esters such as methyl formate, methyl acetate, ethyl acetate, n-butyl acetate, n-pentyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, etc.

[0183] Examples of the alcohol having 1 to 8 carbon atoms include, but are not limited to, methanol, ethanol, isopropanol, n-butanol, cyclohexanol, and the like.

[0184] Examples of the aromatic hydrocarbon include, but are not limited to, benzene, toluene, xylene, and the like.

[0185] Examples of the halogenated hydrocarbon include, but are not limited to, dichloromethane, trichloromethane, and the like.

[0186] Examples of the amide include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, and the like.

[0187] In the present application, in some preferred embodiments, the solvent is at least one of ethyl lactate, propylene glycol methyl ether acetate, isopropanol, toluene, dichloromethane, N,N-dimethylformamide, and ethyl acetate.

[0188] In the present application, the concentration of the above-described patterning material of the present application in the radiation-sensitive patterning composition is not particularly limited. The solution concentration can be adjusted according to the film thickness requirement, and generally the higher the solution concentration, the thicker the film layer. In some preferred embodiments, the concentration of the above-described patterning material of the present application in the radiation-sensitive patterning composition is preferably 3 to 30 mg / mL of the solvent. When the concentration of the patterning material is within the above-described range, the thickness of the radiation-sensitive coating layer obtained using the radiation-sensitive patterning composition can be more uniform and more easily adjusted.

[0189] Generally, the preferred range of the above-described concentration can be appropriately adjusted according to the specific type of the patterning material. In some specific embodiments, when the above-described indium oxygen cluster type material of the present application is used, the above-described concentration is more preferably about 5 to 30 mg / mL of the solvent. In other specific embodiments, when the above-described indium oxygen cluster type material of the present application is used, the above-described concentration is more preferably about 8 to 30 mg / mL of the solvent.

[0190] (Other components)

[0191] In addition to the above-described patterning material of the present application and the solvent, the radiation-sensitive patterning composition of the present application can also contain other components as needed within the range that does not impair the technical effects of the present application, for example, stabilizers, dispersants, photosensitizers, pigments, dyes, adhesion aids, thickening agents, thixotropic agents, anti-settling agents, antioxidants, pH adjustors, leveling agents, plasticizers, and the like. These other components can be used alone or in combination of two or more.

[0192] The amount of these other components can be appropriately selected according to the actual needs.

[0193] (Use of the radiation-sensitive resin composition)

[0194] The type of the radiation-sensitive patterning composition of the present application can be either a positive type patterning composition or a negative type patterning composition, which is typically appropriately selected depending on the specific structure of the patterning material.

[0195] In the present application, the positive type patterning composition and the negative type patterning composition each have the meaning known in the art. In other words, the radiation-sensitive coating obtained using the positive type patterning composition is capable of washing away the exposed patterning material after development by a developer, thereby forming a positive type pattern; the radiation-sensitive coating obtained using the negative type patterning composition is capable of washing away the unexposed patterning material after development by a developer, thereby forming a negative type pattern.

[0196] In the present application, preferably, the type of the radiation-sensitive patterning composition of the present application is a negative type patterning composition.

[0197] In the present application, the use of the radiation-sensitive patterning composition is not particularly limited, and for example, can be used for forming a passivation film, an interlayer insulating film, a surface protection film, an insulating film for rewiring, and the like of a semiconductor element, a display device, a light emitting device, and the like.

[0198] In particular, since the above-mentioned patterning material of the present application has very excellent performance, in some preferred embodiments, it is particularly suitable for obtaining a fine pattern having a pattern resolution of 3 to 100 nm and a edge roughness of 2 to 30% of the pattern resolution.

[0199] <Third Aspect>

[0200] The present application also provides a pattern forming method, which comprises the steps of: forming a coated substrate comprising a radiation-sensitive coating, wherein the radiation-sensitive coating comprises the above-mentioned patterning material of the present application; exposing the coated substrate with radiation in a desired pattern to form an exposed structure comprising a region having an exposed coating and a region having an unexposed coating; and selectively developing the exposed structure to form a patterned substrate having a patterned film.

[0201] By the pattern forming method of the present application, a pattern having high resolution, high pattern edge clarity, and strong etching resistance can be formed with high efficiency, and gas contamination of the exposure device cavity is hardly caused during the exposure process.

[0202] In addition, the application scenario of the pattern forming method is not particularly limited, and can be used as needed in the process of manufacturing a semiconductor element, a display device, a light emitting device, and the like.

[0203] Figure 4 An exemplary manufacturing flow chart of the pattern forming method of the present application is shown (the intermediate material layers are not shown). Each step will be described in detail below.

[0204] (Formation of coated substrate)

[0205] In this step, a coated substrate comprising a radiation-sensitive coating layer is formed, wherein the radiation-sensitive coating layer comprises the above-mentioned patterning material of the present application.

[0206] Details of the patterning material of the present application are as described above in the <First aspect>, which will not be repeated here.

[0207] In this step, the kind of the substrate is not particularly limited, and a wide variety of synthetic resins such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polycarbonate, cellulose triacetate, cellophane, polyimide, polyamide, polyphenylene sulfide, polyetherimide, polyether sulfone, aromatic polyamide, or polysulfone, semiconductor substrates such as silicon wafers, wiring substrates, glass, metals such as copper, titanium, or aluminum, ceramics, and the like can be used. In addition, the form of the substrate is not particularly limited, and can be any object on which a patterned film is desired to be formed and can have any shape.

[0208] In this step, in some preferred embodiments, the substrate is a silicon wafer.

[0209] In this step, the surface of the substrate can or can not be pretreated as desired. Examples of the pretreatment method that can be performed on the surface of the substrate include, but are not limited to, neutral liquid (e.g., water, or an organic solvent such as ethanol or toluene) washing, acidic liquid washing, alkaline liquid washing, corona treatment, electrolytic plating liquid treatment, non-electrolytic plating liquid treatment, primer treatment, vapor deposition treatment, and the like. These methods can be used alone or in combination of two or more.

[0210] In this step, in some preferred embodiments, the substrate is preferably pretreated to be hydrophilic or hydrophobic before the formation of the radiation-sensitive coating layer.

[0211] In some specific embodiments, the substrate is preferably a silicon wafer, and the surface of the silicon wafer is preferably treated to be hydrophilic. For example, examples of the hydrophilic treatment include, but are not limited to, cleaning the silicon wafer in a Piranha solution (H2O: 30% ammonia water: 30% H2O2=5:1:1) for 15 to 20 minutes, followed by deionized water washing, and then alcohol washing with alcohols such as methanol, ethanol, and isopropanol, and further blowing dry the surface liquid.

[0212] In other specific embodiments, the substrate is preferably a silicon wafer, and the surface of the silicon wafer is preferably treated to be hydrophobic. For example, examples of the hydrophobic treatment include, but are not limited to, uniformly covering the surface of the hydrophilic-treated silicon wafer with a silicon azane compound such as hexamethyldisilazane (HMDS) or the like by means of vapor deposition or coating (preferably, spin coating).

[0213] In this step, for the coated substrate, the radiation-sensitive coating of the present application can be formed directly on the substrate, or on the substrate on which an intermediate material layer is formed in advance. Here, examples of the intermediate material layer include, but are not limited to, an anti-reflective layer, an anti-etching layer, an absorbing layer. Each of these intermediate material layers is those known in the art. For example, examples of the anti-reflective layer include, but are not limited to, a bottom anti-reflective coating (BARC), or a spin on glass (SOC), a spin on carbon (SOG), and the like. In addition, these intermediate material layers can be used as a single layer or as two or more layers.

[0214] In some specific embodiments, the substrate is preferably a silicon wafer, and the radiation-sensitive coating is formed directly on the silicon wafer. In other specific embodiments, the substrate is preferably a silicon wafer, and an intermediate material layer, such as an anti-reflective layer or an anti-etching layer or an absorbing layer, can be formed on the surface of the silicon wafer before forming the radiation-sensitive coating.

[0215] In this step, the method for forming the radiation-sensitive coating is not particularly limited, and various methods known in the art can be used. In some preferred embodiments, the radiation-sensitive coating is formed by a coating method. In some more preferred embodiments, the radiation-sensitive coating is formed by a coating method on a substrate covered with an intermediate material layer, and more specifically, the radiation-sensitive coating is formed by a coating method on a silicon wafer covered with an intermediate material layer.

[0216] In some more preferred embodiments, the radiation-sensitive coating is formed by coating the above-described radiation-sensitive patterning composition of the present application. Details of the radiation-sensitive patterning composition of the present application are described above in the <Second aspect>, and are not repeated here.

[0217] In this step, the coating method can be a coating method known in the art. Examples of such coating methods include, but are not limited to, dip coating, spin coating, bar coating, blade coating, curtain coating, screen printing, spray coating, slit coating, and the like. These methods can be used alone or in combination of two or more. In some preferred embodiments, the coating method is preferably performed using spin coating, spray coating, dip coating, or blade coating, and more preferably using spin coating.

[0218] In this step, after coating, a drying process can also be optionally performed. The drying method is not particularly limited, and a drying method known in the art can be used.

[0219] In this step, after drying, a baking treatment can optionally be performed to remove residual solvent. In general, the baking conditions vary depending on the specific kind of metal-oxo cluster type material and solvent employed. In some preferred embodiments, the baking temperature is preferably 60 to 2000C, and the baking time is preferably 20 to 120 seconds.

[0220] In some specific embodiments, the thickness of the radiation-sensitive coating formed is preferably 2 to 200 nm, more preferably 5 to 180 nm. In other specific embodiments, the surface roughness of the radiation-sensitive coating formed is less than 2 nm.

[0221] In some particularly specific embodiments, this step is performed by spin coating 1 to 5 mL, typically, on a 4-inch silicon wafer to obtain a radiation-sensitive coating of any thickness between 2 to 200 nm uniformly, and the surface roughness of the radiation-sensitive coating is less than 2 nm.

[0222] (Exposure of the coated substrate)

[0223] In this step, the coated substrate is exposed to radiation in a desired pattern to form an exposed structure including a region having an exposed coating and a region having an unexposed coating.

[0224] In this step, the exposure method is not particularly limited, and various forms known in the art can be employed. In some specific embodiments, for example, the coated substrate is directly exposed to radiation. In other specific embodiments, the coated substrate is exposed to radiation via a mask.

[0225] Here, the term "via a mask" means that the radiation used for exposure is modified by a mask, but the modification method is not limited, for example, the radiation can pass through the mask, or the radiation can be reflected on the mask.

[0226] Here, the structure of the mask itself is not particularly limited, and can have a patterned cutout or can not have a cutout; and can have a reflective portion or can not have a reflective portion.

[0227] In this step, the kind of the exposure radiation is not particularly limited, as long as it can cause the solubility of the patterning material of the present application to change. The patterning material of the present application can be sensitive to a specific wavelength or wavelength range within various types of radiation depending on its specific structure, and exhibit different solubility changes. In some specific embodiments, among the exposed structures, the exposed coating layer (containing the exposed patterning material of the present application) can be removed in the subsequent development process, i.e., positive development; in other specific embodiments, the unexposed coating layer (containing the unexposed patterning material of the present application) can be removed in the subsequent development process, i.e., negative development.

[0228] In some preferred embodiments, the exposure radiation is preferably ultraviolet light, X-rays, or electron beams. In some specific embodiments, ultraviolet light or X-rays are used to expose the coated substrate via a mask. In other specific embodiments, electron beams are used to directly expose the coated substrate.

[0229] In some more preferred embodiments, the exposure radiation is more specifically ultraviolet light having a wavelength of 15 nm or less, X-rays, or electron beams, further more specifically ultraviolet light having a wavelength of 15 nm or less within the ultraviolet light range, soft X-rays within the X-ray range, or electron beams.

[0230] In some specific embodiments, the exposure device can use various devices known in the art, such as a contact aligner, mirror projection, a step-and-exposure machine, a laser direct exposure device, an X-ray exposure machine, an electron accelerator, and the like.

[0231] In this step, the exposure energy is not particularly limited. The patterning material of the present application has excellent radiation sensitivity, and as described above, the exposure energy is 200 mJ / cm 2 The following can achieve the exposure effect, and for electron beams, the exposure energy is 100 μC / cm 2 The following can achieve the exposure effect. In some specific embodiments, for ultraviolet light and X-rays, the exposure energy is preferably 100 mJ / cm 2 The following, more preferably 30 mJ / cm 2 The following. In other specific embodiments, for electron beams, the exposure energy is 80 μC / cm 2 The following.

[0232] In this step, after exposure, baking can be optionally performed to promote the progress of the chemical reaction in the coating layer. Generally, the baking conditions vary depending on the specific kind of the metal-oxygen cluster type material used. In some preferred embodiments, the baking temperature is preferably 60 to 200°C, and the baking time is preferably 20 to 120 seconds.

[0233] (developing)

[0234] In this step, the exposed structure is selectively developed to form a patterned substrate having a patterned film.

[0235] In this step, in some specific embodiments, where the patterning material of the present application is a positive type patterning material, the selective development can remove the exposed coating in the exposed structure. In other specific embodiments, where the patterning material of the present application is a negative type patterning material, the selective development can remove the unexposed coating in the exposed structure.

[0236] In this step, the developing method is not particularly limited, and a developing method known in the art can be employed. In some preferred embodiments, the development is performed by contacting a developing solution with the exposed structure.

[0237] In this step, the contacting method of the developing solution is not particularly limited, and a method of applying a developing solution known in the art can be employed. Examples of such methods include, without limitation: dip coating (optionally, which can be performed under irradiation of ultrasonic waves), spin coating, spray coating, and the like. These methods can be used alone or in combination of two or more.

[0238] In the case where a developing solution is employed, the number of times of contacting the developing solution with the exposed structure is not particularly limited, and can be only once, or two or more times. In each time of contacting, the same developing solution can be employed, or different developing solutions can be employed.

[0239] In the case where a developing solution is employed, the specific kind of the developing solution is not particularly limited, and can be appropriately selected depending on the specific kind of the patterning material. In some preferred embodiments, the developing solution is preferably an aqueous solution-based developing solution or an organic solvent-based developing solution.

[0240] In some specific embodiments, the aqueous solution-based developing solution is preferably an alkaline aqueous solution. Examples of the alkaline substance contained in the alkaline aqueous solution include, without limitation: inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, and the like; organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, and the like; quaternary ammonium salts such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and the like; and the like. More preferably, the aqueous solution-based developing solution is a tetramethylammonium hydroxide aqueous solution having a concentration of 0.5 to 5 mass %.

[0241] In other embodiments, the organic solvent contained in the organic solvent-based developer is at least one selected from the group consisting of ketone solvents, alcohol solvents, ether solvents, ester solvents, and amide solvents. In addition, the organic solvent-based developer can be free of water, or can contain water. In the case of containing a plurality of organic solvents (and water), the ratio between each of the organic solvents (and water) is not particularly limited, and can be appropriately adjusted as necessary.

[0242] Specific examples of the ketone solvents include, but are not limited to, for example, cyclopentanone, cyclohexanone, and methyl-2-n-pentyl ketone.

[0243] Specific examples of the alcohol solvents include, but are not limited to, for example, monohydric alcohols such as methanol, ethanol, isopropyl alcohol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; and polyhydric alcohols such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, or 1,3-butanediol.

[0244] Specific examples of the ether solvents include, but are not limited to, for example, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether.

[0245] Specific examples of the ester solvents include, but are not limited to, for example, chain esters such as propylene glycol methyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, ethyl pyruvate, butyl acetate, 3-methoxypropyl acetate, 3-ethoxypropyl acetate, t-butyl acetate, t-butyl propionate, and propylene glycol mono-t-butyl ether acetate; and lactones such as γ-butyrolactone.

[0246] Examples of the amide solvents include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, and the like.

[0247] In some preferred embodiments, in the case of using the indium oxo-cluster type material of the present application, the developer contains an alcohol solvent, an ester solvent, an amide solvent, or a combination thereof, more specifically, isopropyl alcohol, N,N-dimethylformamide, propylene glycol methyl ether acetate, or a combination thereof. More preferably, the developer is a mixture of N,N-dimethylformamide and propylene glycol methyl ether acetate (PGMEA) (volume ratio range 10:1 to 1:10) or a mixture of isopropyl alcohol and PGMEA (volume ratio range 10:1 to 1:10).

[0248] In other preferred embodiments, in the case of using the tin oxo-cluster type material of the present application, the developer contains an alcohol solvent, an ester solvent, an amide solvent, water, or a combination thereof, more specifically, isopropyl alcohol, N,N-dimethylformamide, propylene glycol methyl ether acetate, ethyl lactate, water, or a combination thereof. More preferably, the developer is a mixture of isopropyl alcohol and water (volume ratio range 10:1 to 1:10) or a mixture of isopropyl alcohol and PGMEA (volume ratio range 10:1 to 1:10).

[0249] In addition, in some specific embodiments, the developer can further contain a surfactant and a viscosity reducer, etc. as needed, in any amount.

[0250] In the case of using the developer, the contact time of the developer with the exposed structure (development time) is not particularly limited and can be appropriately selected depending on the specific structure of the metal oxo-cluster type material. Generally, the contact time is preferably 10 seconds to 10 minutes, and more preferably 10 seconds to 300 seconds.

[0251] In some more specific embodiments, in the case of using the indium oxo-cluster type material of the present application, the contact time is preferably 10 seconds to 120 seconds, and more preferably 15 seconds to 60 seconds.

[0252] In other more specific embodiments, in the case of using the tin oxo-cluster type material of the present application, the contact time is preferably 10 seconds to 10 minutes, and more preferably 15 seconds to 60 seconds.

[0253] In this step, in some specific embodiments, after development, a water rinse treatment can be optionally added, and generally, the rinse conditions vary depending on the specific kind of the metal oxo-cluster type material used and the development method (e.g., the kind and application method of the developer, etc.). In some preferred embodiments, the rinse time is preferably 10 to 120 seconds. In other preferred embodiments, the rinse temperature is preferably ambient temperature.

[0254] In this step, in some specific embodiments, after development, baking can be optionally performed, and generally, the baking conditions vary depending on the specific kind of the metal oxo-cluster type material used and the development method (e.g., the kind and application method of the developer, etc.). In some preferred embodiments, the baking temperature is preferably 60 to 200°C, and the baking time is preferably 20 to 120 seconds.

[0255] In particular, since the above-described patterning material of the present application has very excellent performance, the pattern forming method of the present application is particularly suitable for obtaining a fine pattern having a pattern resolution of 100 nm or less (preferably, between 3 and 100 nm) and an edge roughness of 30% or less (preferably, 2 to 30%) of the pattern resolution.

[0256] (Other steps)

[0257] In the present application, the pattern forming method of the present application can further include other steps as needed. Examples of the other steps include, but are not limited to, a rinsing step, a drying step, and the like.

[0258] In some specific embodiments, rinsing and / or drying and the like of the substrate are performed before the formation of the radiation-sensitive coating (in the presence of the pretreatment, before the pretreatment).

[0259] In some specific embodiments, rinsing and / or drying and the like of the formed patterned film are performed after the development step.

[0260] <Fourth aspect>

[0261] The present application also provides a patterned substrate comprising a patterned film present in selected areas on a substrate and absent in other areas on the substrate thereby forming a pattern on the substrate, and formed using the above-described patterned material of the present application.

[0262] Here, "formed using the above-described patterned material of the present application" means that the patterned film is formed using at least the above-described patterned material of the present application as a raw material. In some specific embodiments, the patterned film comprises at least the exposed patterned material. In other specific embodiments, the patterned film comprises at least the unexposed patterned material.

[0263] The patterned substrate of the present application can comprise a patterned film having a pattern with high resolution, high pattern edge clarity, and strong etching resistance.

[0264] In addition, the patterned substrate of the present application can optionally have an intermediate material layer between the patterned film and the substrate. In some preferred embodiments, the patterned substrate of the present application has an intermediate material layer between the patterned film and the substrate.

[0265] In the present application, the method for forming the patterned substrate is not particularly limited, and various methods known in the art can be used. In some specific embodiments, the patterned substrate is formed by the above-described pattern forming method of the present application.

[0266] Details of the patterned material of the present application, the intermediate material layer, the substrate, and the pattern forming method of the present application are each as described above in the <First aspect> and the <Third aspect>, and will not be described here again.

[0267] In the present application, the resolution and edge roughness of the pattern of the patterned film on the patterned substrate are not particularly limited. In the present application, as described above, the resolution of the patterned film can be high, and the resolution can be achieved to be 100 nm or less; the pattern edge clarity can be high, and the edge roughness can be achieved to be 30% or less of the resolution of the pattern. In the present application, the resolution and edge roughness of the pattern of the patterned film can be measured by a scanning electron microscope.

[0268] In some preferred embodiments, the resolution of the pattern formed by the patterned film in the patterned substrate is preferably 3-100 nm, more preferably 3-50 nm, further preferably 3-20 nm, and particularly preferably 3-10 nm.

[0269] In some preferred embodiments, the edge roughness of the pattern formed by the patterned film in the patterned substrate is preferably 2-30% of the resolution of the pattern, and more preferably 2-8% of the resolution of the pattern.

[0270] In the present application, the pattern formed by the patterned film is not particularly limited and can be arbitrarily designed as needed.

[0271] <5th Aspect>

[0272] The present application also provides a method for patterning a substrate, comprising: etching or ion implanting the above-mentioned patterned substrate of the present application to form a patterned structure on the surface of the substrate. Figure 5 An exemplary manufacturing flow chart of the method for patterning a substrate of the present application is shown in FIG. 1 (without showing the intermediate material layer).

[0273] In the present application, the etching method and ion implantation method are not particularly limited and various methods known in the art can be used.

[0274] In some specific embodiments, an etching method is preferably used. In the present application, the etching conditions are not particularly limited and can be changed according to the process requirements, etching selectivity and etching rate. In some preferred embodiments, examples of etching gas include, but are not limited to, Cl2+O2, HBr+Cl2, SF6, CF4+O2, CHF3+O2, BCl3. In addition, in some preferred embodiments, the etching selectivity of the relative supporting layer material such as Barc, the substrate material such as SiO2 is between 10:1 and 1:10.

[0275] In the present application, the patterned structure formed on the substrate is not particularly limited and can be arbitrarily designed as needed and is generally dependent on the specific pattern of the patterned film of the patterned substrate used.

[0276] <6th Aspect>

[0277] The present application also provides an integrated circuit device including a surface structure formed on a silicon wafer as a substrate by the above-described patterning method of a substrate of the present application.

[0278] In the present application, the specific type of integrated circuit device is not particularly limited. In some preferred embodiments, the integrated circuit device of the present application can be applied to various terminals such as tablet computers, notebook computers, digital cameras, mobile phones, wearable electronic devices, virtual reality devices, and the like.

[0279] In the present application, the surface structure is not particularly limited and can be arbitrarily designed as needed and is generally dependent on the specific pattern of the patterning film of the patterning substrate employed in the above-described patterning method of a substrate of the present application.

[0280] (Specific Examples)

[0281] In the present application, in some particularly specific embodiments, the manufacturing method of the integrated circuit device (or a preform thereof) of the present application is as follows:

[0282] First, a metal oxide cluster type material is dissolved in a suitable solvent to form a solution, and an arbitrary volume of the solution is coated on a silicon wafer or a silicon wafer covered with an intermediate material layer by a spin coating process according to the size of the substrate to form a patterned material film layer of less than 100 nm in thickness, as shown in Figure 6 (1, 2). The solvent remaining in the film layer is generally removed by a baking process before exposure, as shown in Figure 6 (3);

[0283] The patterned material film layer is then selectively irradiated with a single wavelength or a mixed wavelength in the range of 1 to 15 nm of Soft X-ray (Soft X-ray) reflected by a mask plate to transfer the pattern on the mask plate to the patterned material film layer, as shown in Figure 6 (4);

[0284] The irradiated patterned material film layer is cleaned with a developing solution for a developing time of 10 to 300 seconds.

[0285] In the patterned material film layer after development, the irradiated portion is not washed away, forming a negative pattern, and the patterned material is referred to as a negative patterned material, as shown in Figure 6 (5a); the irradiated portion is washed away, forming a positive pattern, and the patterned material is referred to as a positive patterned material, as shown in Figure 6 (5b);

[0286] The pattern formed by the patterned material provides a selective protection to the substrate (a silicon wafer or a silicon wafer covered by an intermediate material layer) during the etching step. After etching, the patterned material and the unprotected substrate are etched away, but the etching rate is slower at the places protected by the patterned material than at the unprotected places, and finally a pattern is formed on the substrate, as shown in Figure 6 (6a) The resulting pattern is a negative pattern. Figure 6 (6b) The resulting pattern is a positive pattern.

[0287] <Embodiment>

[0288] The following detailed description of the embodiments of the present application, but the present application is not limited to the following examples.

[0289] Example 1: Radiation-sensitive indium oxo-cluster-based material

[0290] Example 1-1: Synthesis of radiation-sensitive indium oxo-cluster-based material

[0291] The following radiation-sensitive indium-oxygen cluster type materials were prepared:

[0292] Indium-oxygen cluster type compound 1: [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 , R 1 = C6H5; L2 = NH(CH2CH2O)2; X = Cl).

[0293] Synthesis method: InX3 (1 mmol, X = Cl) was dissolved in a mixture of 2-3 mL phenol and 1 mL diethanolamine, heated to 100°C for two days, and then cooled to room temperature. Colorless crystals were precipitated.

[0294] Indium-oxygen cluster type compounds 2 and 3: [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 , R 1 = CH3; L2 = NH(CH2CH2O)2; X = Cl (compound 3), Br (compound 2)).

[0295] Synthesis method: InX3 (1 mmol, X = Cl or Br) was dissolved in a mixture of 3-4 mL CH3OH and 1 mL diethanolamine, heated to 100°C for two days, and then cooled to room temperature. Colorless crystals were precipitated, which were the products.

[0296] Indium-oxygen cluster type compounds 4-9: [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 , R 1= C6H4F; L2= NH(CH2CH2O)2; X = Br), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR 1 = C6H4F; L2= NH(CH2CH2O)2; X = Cl), [{In4(μ4-O)}2In4O2(OH)2(L1)4(L2)8X6] (L1 = OR

[0297] Synthesis: InX3 (1 mmol, X = Cl, Br) and R 1 OH (5 mmol, R 1 = C6H4F, C6H4Cl or C6H4NO2; ) were dissolved in a mixture of 3 mL tetrahydrofuran and 1 mL diethanolamine. After heating to 100 °C for two days and cooling to room temperature, crystals were precipitated.

[0298] The above indium oxo-cluster compounds 1-8 were characterized by infrared solid analysis, the infrared spectra were obtained by Brucker VERTEX 70 and shown in Figure 7 ; and the EDX spectra of indium oxo-cluster compound 9 were obtained by JEOL JSM6700F + Oxford INCA and shown in Figure 8 :

[0299] Example 1-2: Pattern formation method using radiation-sensitive indium oxo-cluster-based material

[0300] (1) Pretreatment of silicon wafer

[0301] Hydrophilic treatment: The silicon wafer was cleaned in Piranha solution (H2O: 30% ammonia water: 30% H2O2=5:1:1) for 15-20 mins, then deionized water, and isopropanol, and the surface liquid was blown dry with an air gun before use;

[0302] Hydrophobic treatment: The silicon wafer treated by the above hydrophilic treatment was uniformly covered with HMDS on the surface of the silicon wafer by evaporation or spin coating.

[0303] (2) Coating step

[0304] 5-20 mg of indium oxo-cluster compounds 1-8 were dissolved in 1 mL of N,N-dimethylformamide (DMF), the solution was filtered, and an appropriate amount of the filtered solution (negative patterned composition) was transferred to the surface of the above hydrophilic or hydrophobic silicon substrate to form an indium oxo-cluster patterned material coating by spin coating.

[0305] (3) Exposure step

[0306] Radiation exposure: Electron beam lithography (EBL) was used to expose the indium oxo-cluster patterned material coating.

[0307] (4) Development step

[0308] The developer included a mixture of DMF and propylene glycol methyl ether acetate (PGMEA) (volume ratio range 10:1-1:10) and a mixture of isopropyl alcohol (IPA) and PGMEA (volume ratio range 10:1-1:10). The development time was 15-60 s.

[0309] (5) Pattern characterization

[0310] The patterned substrates after development were characterized using a scanning electron microscope (SEM). The resolution could reach 100 nm, and even 50 nm. The details are as follows:

[0311] After the patterned substrate was formed using indium oxo-cluster compound 3, the SEM characterization of the exposed line width was 100 nm, as shown in FIG. 3. Figure 9

[0312] After the patterned substrate was formed using indium oxo-cluster compound 3, the SEM characterization of the exposed line width was 50 nm, as shown in FIG. 4. Figure 10

[0313] After the patterned substrate was formed using indium oxo-cluster compound 2, the SEM characterization of the exposed line width was 100 nm, as shown in FIG. 5. Figure 11

[0314] After the patterned substrate was formed using indium oxo-cluster compound 2, the SEM characterization of the exposed line width was 50 nm, as shown in FIG. 6.​​​Figure 12 as shown in FIG. 1.

[0315] After the patterned substrate was formed using indium oxo-cluster compound 9, the width of the exposed lines was characterized by SEM to be 100 nm, as shown in FIG. 2. Figure 13

[0316] After the patterned substrate was formed using indium oxo-cluster compound 9, the width of the exposed lines was characterized by SEM to be 50 nm, as shown in FIG. 3. Figure 14

[0317] Example 2: Radiation-sensitive tin oxo-cluster-based material

[0318] Example 2-1: Synthesis of radiation-sensitive tin oxo-cluster-based material

[0319] The following radiation-sensitive tin oxo-cluster type materials were prepared:

[0320] Tin oxo-cluster compound 1 : [Sn 10 O 12 (L1) 12 X8] (L1 = 3-methylpyrazole; X = Cl),

[0321] Synthesis: SnX n (1 mmol, X = Cl, n = 4) was dissolved in 3 ml of 3-methylpyrazole. After heating at 100 °C for three days, the solution was cooled to room temperature and colorless crystals precipitated.

[0322] Tin oxo-cluster compound 2: [Sn 10 O 12 (L1) 12 X8] (L1 = 4-methylpyrazole; X = Cl),

[0323] Synthesis: SnX n (1 mmol, X = Cl, n = 4) was dissolved in 2 ml of 4-methylpyrazole. After heating at 100 °C for three days, the solution was cooled to room temperature and colorless crystals precipitated.

[0324] The above tin oxo-cluster compounds 1 and 2 were characterized using infrared solid state analysis, and the infrared spectra were obtained using a Brucker VERTEX 70 and are shown in FIGS. 4 and 5, respectively. Figure 15 16

[0325] Example 2-2: Pattern formation method using radiation-sensitive tin oxo-cluster-based material

[0326] (1) Pretreatment of the silicon wafer

[0327] ​​​​Hydrophilic treatment: Clean the silicon wafer in Piranha solution (H2O:30% ammonia:30% H2O2=5:1:1) for 15-20 minutes, then rinse with deionized water and then with isopropyl alcohol. Dry the surface liquid with an air gun before use.

[0328] Hydrophobic treatment: Using the hydrophilic treated silicon wafer, HMDS is evenly covered on the surface of the silicon wafer by evaporation or spin coating.

[0329] (2) Coating step

[0330] 8-20 mg of tin oxide cluster compounds 1 and 2 were dissolved in ethyl acetate respectively, and the solution was filtered. An appropriate amount of the filtered solution (negative patterning composition) was transferred and spin-coated on the surface of the hydrophilic or hydrophobic silicon substrate to form a tin oxide cluster radiation-sensitive coating.

[0331] (3) Exposure step

[0332] Radiation exposure: Electron beam lithography (EBL) is used to expose the indium oxide cluster type patterned material layer.

[0333] (4) Development step

[0334] The developer solution includes a mixture of isopropyl alcohol and water (volume ratio range of 10:1 to 1:10) and a mixture of isopropyl alcohol (IPA) and PGMEA (volume ratio range of 10:1 to 1:10). The development time is 15 to 60 seconds.

[0335] (5) Pattern representation

[0336] Scanning electron microscopy (SEM) was used to characterize the patterns of each of the patterned substrates after development. The resolution can reach 100nm or even 50nm. The details are as follows:

[0337] After forming a patterned substrate using tin oxide cluster compound 2, the width of the exposed line was 100 nm as shown by SEM. Figure 17 As shown in .

[0338] After forming a patterned substrate using tin oxide cluster compound 2, the width of the exposed line shown by SEM is 50 nm. Figure 18 As shown in .

[0339] The computer program product of the second aspect can include a computer readable storage medium. The computer readable storage medium can include instructions. The instructions can include one or both of: instructions for causing a computer to implement a method as described above; and instructions for causing a computer to operate based on a product of design as described above.

[0340] It is also noted that each of the blocks of the flowchart, and / or combinations of the blocks, along with combinations of the flowchart and / or the block diagram, can be implemented by hardware, software, and / or firmware. Such hardware, software, and / or firmware can be implemented within one or both of the processor and / or the processing platform that form a part of the processing system. The

[0341] Although the present application has been described in connection with various embodiments, it will be understood that the application is capable of further modifications. This application is intended to cover any variations, uses or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. It is intended to cover and embrace all adaptations or modifications of the application. The above description and drawings are illustrative and not restrictive. This description best known to one skilled in the art to which the application pertains has been made to enable any person skilled in the art to practice the application as claimed below.

[0342] Embodiments of the application have been described above. The description is illustrative of the embodiments of the application and is not restrictive. Many modifications and variations of the disclosed embodiments are possible in light of this disclosure. It is, therefore, to be understood that changes can be made in the particular embodiments of the application recited and / or shown in the drawings without departing from the scope and spirit of the application. The scope of the application is to be determined by the following claims.

Claims

1. A patterned material, characterized in that: It has: a metal oxygen cluster skeleton composed of a metal M-oxygen bridge bond, a radiation-sensitive organic ligand and a second ligand, The radiation-sensitive organic ligand is coordinated with the metal M via a coordinating atom, wherein the coordinating atom is at least one selected from an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, and a phosphorus atom, and the radiation-sensitive organic ligand is a monodentate ligand or a ligand with two or more dentates; the second ligand is an inorganic ion or a coordinating group, When the coordinating atom is an oxygen atom, the oxygen atom in the radiation-sensitive organic ligand does not form a carboxyl group or a peroxide bond.

2. The patterned material according to claim 1, wherein The patterned material is represented by the following general formula (1): M x O y (OH) n (L1) a (L2) b (L3) c (L4) d X m General formula (1) In the general formula (1), 3≤x≤72, 0≤y≤72, 0≤a≤72, 0≤b≤72, 0≤c≤72, 0≤d≤72, 0≤n≤72, 0≤m≤72, y+n+a+b+c+d+m≤8x, x, y, a, b, c, d, m, n are all integers and a, b, c, d are not 0 at the same time; L1, L2, L3, L4 each serve as the radiation-sensitive organic ligand individually or in a manner where two or more coexist in the same ligand; X is the second ligand.

3. The patterned material according to claim 1 or 2, characterized in that The metal M includes at least one selected from indium, tin, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, palladium, platinum, silver, cadmium, antimony, tellurium, hafnium, tungsten, gold, lead, and bismuth.

4. The patterned material according to claim 3, wherein The metal M further comprises at least one selected from sodium, magnesium, aluminum, potassium, calcium, scandium, gallium, germanium, arsenic, rubidium, strontium, yttrium, technetium, ruthenium, rhodium, cesium, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, tantalum, rhenium, osmium, iridium, mercury, and polonium.

5. The patterned material according to any one of claims 1, 2, and 4, characterized in that: The coordination group is at least one selected from halogen groups, carboxylic acid groups, sulfonic acid groups, nitro groups, aliphatic alcohol groups, aromatic alcohol groups, aliphatic hydrocarbon groups, and aromatic hydrocarbon groups; the inorganic ions are at least one selected from halogen ions, SO4 2- 、NO3 - At least one of .

6. The patterned material according to claim 2, wherein The L1, L2, L3, and L4 are respectively derived from at least one of alcoholamines, alcohols, phenols, nitrogen-containing heterocyclic compounds, nitriles, phosphines, phosphonic acids, thiols, and organic selenium compounds.

7. The patterned material according to any one of claims 1, 2, 4, and 6, wherein: The patterned material is an indium oxide cluster material represented by the following general formula (1-1): [M4(μ4-O)] x1 M x2 O y (OH) n X m (L1) a (L2) b (L3) c (L4) d General formula (1-1) In the general formula (1-1), M contains at least indium; 1≤x1≤12, 0≤x2≤24, 0≤y≤24, 0≤a≤36, 0≤b≤36, 0≤c≤36, 0≤d≤36, 0≤n≤24, 0≤m≤24, y+n+m+a+b+c+d≤31(x1)+8(x2), x1, x2, y, a, b, c, d, m, n are all integers and a, b, c, d are not 0 at the same time; L1, L2, L3, L4 each serve as the radiation-sensitive organic ligand individually or in a manner where two or more coexist in the same ligand; X is the second ligand.

8. The patterned material according to claim 7, wherein The radiation-sensitive organic ligand in the indium oxo cluster material coordinates with the metal M via a nitrogen atom or an oxygen atom as a coordination atom, and L1, L2, L3, and L4 are respectively derived from at least one of alcoholamines, alcohols, phenols, nitrogen-containing heterocyclic compounds, and nitriles.

9. The patterned material according to claim 7, wherein: At least one of the Xs is a halogen ion or a halogen group.

10. The patterned material according to any one of claims 1, 2, 4, and 6, wherein: The patterned material is a tin oxide cluster material represented by the following general formula (1-2): M x O y (L1) a (L2) b X m General formula (1-2) In the general formula (1-2), M contains at least tin; 3≤x≤34, 0≤y≤51, 0≤a≤51, 0≤b≤51, 0≤m≤51, y+a+b+m≤8x, x, y, a, b, m are all integers and a and b are not 0 at the same time; L1 and L2 each serve as the radiation-sensitive organic ligand individually or in a manner where two or more coexist in the same ligand; and X is the second ligand.

11. The patterned material according to claim 10, wherein The radiation-sensitive organic ligand in the tin oxo cluster material coordinates with the metal M via a nitrogen atom as a coordination atom, and L1 and L2 are each derived from at least one of alcoholamines, nitrogen-containing heterocyclic compounds, and nitriles.

12. The patterned material according to claim 10, wherein At least one of the Xs is a halogen ion or a halogen group.

13. A radiation-sensitive patterning composition, characterized in that The method comprises the patterning material according to any one of claims 1 to 12 and a solvent.

14. The radiation-sensitive patterning composition according to claim 13, wherein The solvent is at least one selected from carboxylates, alcohols with 1 to 8 carbon atoms, aromatic hydrocarbons, halogenated hydrocarbons, and amides.

15. A pattern forming method, characterized in that: The following steps are involved: forming a coated substrate comprising a radiation-sensitive coating, wherein the radiation-sensitive coating comprises the patterned material according to any one of claims 1 to 12; exposing the coated substrate with radiation in a desired pattern to form an exposed structure comprising areas having exposed coating and areas having unexposed coating; and The exposed structure is selectively developed to form a patterned substrate having a patterned film.

16. The pattern forming method according to claim 15, wherein: The radiation-sensitive coating is formed directly on a silicon wafer or on a silicon wafer covered by an intermediate material layer.

17. The pattern forming method according to claim 15 or 16, characterized in that: The radiation-sensitive coating is formed on the substrate covered by the intermediate material layer by a coating method.

18. The pattern forming method according to claim 15 or 16, characterized in that: Such radiation includes X-rays, electron beams, and ultraviolet light.

19. The pattern forming method according to claim 15 or 16, wherein: The developer used for the development is an aqueous developer or an organic solvent developer.

20. A patterned substrate, characterized in that The invention comprises a patterned film and a substrate, wherein the patterned film exists in a selected area on the substrate and does not exist in other areas on the substrate, and the patterned film is formed by using the patterned material according to any one of claims 1 to 12.

21. The patterned substrate according to claim 20, wherein The pattern resolution of the patterned film is between 3 and 100 nm, and the edge roughness is 2 to 30% of the pattern resolution.

22. A method for patterning a substrate, characterized in that: include: The patterned substrate according to claim 20 or 21 is subjected to etching or electron injection to form a patterned structure on the surface of the substrate.

23. An integrated circuit device, characterized in that: include: A surface structure formed on a silicon wafer serving as the substrate by the substrate patterning method according to claim 22.

Images