Compounds, compositions, methods of making the compounds, and uses of the compounds

Abstract

The present invention relates to organometallic compounds, compositions comprising the organometallic compounds, photolithography processes using the organometallic compounds, optical elements, optically active devices or optical or semiconductor devices obtained by the photolithography processes, hard masks obtained by the photolithography processes, uses of the compounds or compositions, methods of preparation of the compounds.

Description

Technical Field

[0001] This invention relates to organometallic compounds, compositions comprising said compounds, methods for preparing said compounds, and uses of said compounds. Furthermore, this invention relates to photolithography methods using said compounds and hard masks and optical elements, optically active devices, or optical or semiconductor devices obtained by said methods. Specifically, this invention relates to spin-coated compounds for use in metal hard masks. Background Technology

[0002] Amorphous carbon (obtained through chemical vapor deposition (CVD)) and spin-coated carbon-based hard masks are popular in the semiconductor industry. Patterns on semiconductor substrates are formed using photoresist, primarily carbon-based. In advanced semiconductor manufacturing, the photoresist thickness required to form nanoscale patterns is too thin to transfer the patterns onto a carbon-based hard mask. Therefore, the industry uses a pattern transfer layer, often called an interlayer, between the photoresist and the hard mask layer. Traditional interlayer materials are silicon-based, such as SiO2 and SiON. x Si3N4 and similar materials are deposited using CVD or physical vapor deposition (PVD) methods. During deposition, the chamber is typically evacuated, and the temperature of the substrate or wafer is raised if necessary. PVD and CVD methods may be suitable for thin conformal coatings, but they require long processing times when thicker films (>20 nm) are needed. Therefore, the process cycle of these methods consumes valuable time. On the other hand, spin coating processes offer lower ownership costs, good gap-filling performance, and lower defect rates. Efforts have been made to develop spin-coated metal hard masks utilizing metal alkoxy compound-based formulations and metal oxide nanoparticle dispersions.

[0003] One of the main challenges facing traditional hard mask materials (such as silicon-based hard masks) is achieving high etch selectivity. While these materials have reasonable etch resistance, they may not provide the necessary selectivity for advanced patterning processes, especially as feature sizes continue to shrink.

[0004] Furthermore, precise pattern transfer in photolithography requires precise control of reflectivity. Silicon hard masks can control reflectivity to some extent, but optimizing this control to achieve optimal performance can be complex and challenging.

[0005] Rework and cleaning of triple-layer stacks, especially the removal of oxide residues using wet chemicals, presents significant challenges. These challenges impact the overall manufacturability, efficiency, and cost of photolithography processes, making it more difficult to maintain high throughput. For example, materials with excellent etch resistance may be more difficult to remove or may negatively affect other process chemicals.

[0006] Furthermore, with the advancement of photolithography technologies, such as the transition to EUV lithography (EUVL), traditional photoresists and hard mask materials may no longer be fully compatible or effective. This development necessitates the creation of new materials that can better meet the demands of these advanced processes. These new materials may require the use of alternative process chemicals and gases used in semiconductor manufacturing processes, which could be disadvantageous in some ways. For example, dielectric damage can be a problem when applying new etching gas chemicals to transfer patterns from the resist and underlayer to the substrate.

[0007] The application of traditional hard mask materials typically involves expensive methods such as CVD or atomic layer deposition (ALD). These methods require specialized equipment, which limits their practicality and increases the overall cost of the photolithography process. Furthermore, ensuring the long-term stability of the hard mask material and the starting materials used to prepare the hard mask, as well as the stability and shelf life of the solvents and solutions used in the process, is another important issue. Some materials may degrade over time, which can adversely affect their performance in the photolithography process, leading to inconsistencies and defects in the final product.

[0008] Numerous different material methods have been developed for patterning using EUVL. Generally, these methods can be divided into three categories: organic, silicon-based, and metal-containing photoresists.

[0009] To address the challenges of organic photoresists, formulations incorporating radiation-sensitive components into photoresist materials have been developed. Elements with high molar absorptivity of 13.5 nm EUV photons are typically metals. Therefore, there is growing interest in metal-containing photoresists, where metals are added to photoresist materials to enhance sensitivity, or used as molecular photoresists, metal oxide nanoparticles, organometallic precursors, or metal-organic frameworks.

[0010] These photoresists exhibit high sensitivity and resolution, and are therefore considered a leading candidate material for future EUVL photoresists. However, their main drawback is that metals are highly undesirable in integrated circuit manufacturing because they can disrupt transistor function through contamination.

[0011] Despite advancements in existing technologies, there is still a search for photoresists that can provide resolution, line edge roughness, and sensitivity (RLS) characteristics without excessive metal contamination. Summary of the Invention

[0012] The summary portion of this invention is intended to introduce some concepts in a simplified form, which will be further described in the detailed description below. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0013] This invention is defined by the features of the independent claims. Some specific embodiments are defined in the dependent claims.

[0014] The object of the present invention is to provide organometallic compounds or their metal-oxygen clusters, as well as hard masks that eliminate at least some of the problems associated with the art.

[0015] The object of this invention is to provide an organometallic compound of formula (I) or formula (II) or its metal-oxygen cluster:

[0016] in

[0017] Dashed lines indicate optional keys;

[0018] M is a group consisting of metals selected from Ti, Zr, Hf, Sb and W, wherein the metals have an oxidation state selected from +3, +4, +5 or +6;

[0019] X is a group composed of heteroatoms selected from O, N, and S;

[0020] Y is a group composed of heteroatoms selected from O and S;

[0021] Z is a group composed of heteroatoms selected from O and S;

[0022] Each R 1 Independently selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 -A group composed of hydrocarbon groups, this C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms;

[0023] Each R 2 Independently selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 -Hydrocarbon group and C 1-20 The group consisting of -alkoxy groups, the C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms;

[0024] u and v are each independently selected from integers with values ​​in the range of 1 to 20; and

[0025] x is an integer selected from 1 and 2.

[0026] A second object of the present invention is to provide a composition comprising an organometallic compound or a metal-oxygen cluster thereof as defined in this disclosure.

[0027] A third objective of this invention is to provide a photolithography method comprising:

[0028] i) Applying an organometallic compound of formula (I) or (II) or its metal-oxygen cluster, or a composition comprising said organometallic compound or its metal-oxygen cluster, onto a substrate to form a precursor hard mask on said substrate;

[0029] in,

[0030] Dashed lines indicate optional keys;

[0031] M is a group consisting of metals selected from Al, Sn, Zn, Ti, Zr, Hf, Sb, Ta and W, wherein the metals have an oxidation state selected from +3, +4, +5 or +6;

[0032] X, Y, Z, R 1 R 2 u, v, and x are as defined in this disclosure; and

[0033] ii) The formed precursor hard mask is heated at a temperature below 400°C, preferably below 250°C, and most preferably below 200°C, for example at a temperature selected from 60–400°C, 150–400°C, 150–250°C, and 180–200°C, preferably for 1–10 minutes, thereby forming a metal oxide layer on the substrate.

[0034] A fourth object of the present invention is to provide a metal oxide layer that can be obtained by the methods defined in this disclosure.

[0035] A fifth object of the present invention is to provide the use of a compound, its oxygen metal cluster, or a composition as defined in this disclosure in the preparation of hard masks, optical elements, optically active devices, or optical or semiconductor devices.

[0036] A sixth object of the present invention is to provide a method for preparing a compound of formula (I) or formula (II) as defined in this disclosure or an oxygen metal cluster thereof, wherein the method comprises:

[0037] i) Provide a reaction composition containing a compound of formula (V):

[0038] in

[0039] Dashed lines, X, Y, Z, R 1 and R 2 As defined in this disclosure; and

[0040] ii) Provide a salt of X or a hydrate thereof, wherein X is as defined in this disclosure;

[0041] iii) Reacting the compound of formula (V) with a salt of X or its hydrate,

[0042] To obtain a compound of formula (I) or formula (II) or its oxygen metal cluster.

[0043] A seventh object of the present invention is to provide an optical element, an optically active device, or an optical or semiconductor device that can be obtained by the methods defined in this disclosure.

[0044] As another objective, the present invention relates to a patterned substrate comprising: a substrate having a surface and a first coating distributed in selected areas along the surface and not distributed in other areas along the surface, wherein the first coating comprises a metal oxide layer, preferably a hard mask, obtainable by methods defined in this disclosure, and the metal oxide layer, preferably the hard mask, is etched at an etch rate of less than 5 nm / min in an oxygen plasma or ashing process.

[0045] This invention offers significant advantages.

[0046] The metal oxide layers (hard masks) disclosed in this disclosure utilize small-molecule metal oxide precursors, which can be based on ketooxime chemistry and provide spin-coated formulations in solvents such as propylene glycol methyl ether (PGME) and propylene glycol methyl ether acetate (PGMEA) . Surprisingly, the compounds disclosed in this disclosure, or their metal oxide clusters, decompose into metal oxide layers at low temperatures (e.g., between 100–200 °C), which can be used as hard masks in photolithography methods. The metal oxide layers (or hard masks) have refractive indices close to those of their respective amorphous metal oxides. The metal oxide layers (hard masks) also exhibit high etch resistance in oxygen-containing plasmas. Another surprising effect of these compounds or their metal oxide clusters disclosed in this disclosure is the ability to obtain defect-free or at least partially defect-free sub-10 nm metal oxide hard masks (films) after baking them at temperatures of 350 °C or lower, preferably 250 °C or lower, more preferably 200 °C or lower.

[0047] Specifically, the invention described herein addresses the challenge of patterning sub-20 nanometer features. Furthermore, the material exhibits high resistance to oxygen plasma etching, thereby simplifying the photolithography stack. Surprisingly, the organometallic compounds disclosed herein decompose at relatively low decomposition temperatures, such as 350°C or lower or between 100–200°C, making them suitable as precursors for preparing hard masks.

[0048] Therefore, this solution can be used to cast coatings on semiconductor substrates to form patterns through subsequent baking, irradiation, and development steps. Specifically, the present invention allows for industrially feasible control of the microstructure of layers used in the photolithography methods disclosed in this disclosure and at least partially overcomes the shortcomings of the prior art.

[0049] The invention described herein addresses a key etch rate challenge and provides high oxygen plasma etch resistance, thereby enabling a simplified lithography stack.

[0050] The invention offers advantages over commonly used silicon-based hard masks by allowing improved compatibility with alternative etching process gases required for advanced EUV resist materials. In this way, they address the challenge of dielectric damage when using such alternative gases.

[0051] Furthermore, this invention provides a convenient method for determining and evaluating the refractive index after baking and etching, and comparing it with known references. Therefore, industrially feasible high-throughput screening methods (e.g., elliptic polarization) can be used to evaluate the quality of hard masks in the process.

[0052] Further features and advantages of this technology will become apparent from the detailed discussion of the following embodiments. Brief description of the attached figures

[0053] Figure 1 Some embodiments of the photolithography methods disclosed in this disclosure are illustrated schematically, as well as optical elements, optically active devices, or optical or semiconductor devices disclosed in this disclosure;

[0054] Figure 2 The assembly of the four-layer lithography stack is schematically shown in a side view. Specific Implementation

[0055] The following explanations of terms and methods are provided to better describe the composition, porous polysiloxane membrane, semiconductor device, method, and use, and to guide those skilled in the art in practicing the present disclosure. It should also be understood that the terminology used in this disclosure is for describing specific embodiments and examples only and is not intended to be limiting.

[0056] It should be understood that the embodiments of the invention disclosed herein are not limited to the specific structures, processes, or materials disclosed herein, but extend to their equivalents as recognized by those skilled in the art. It should also be understood that the terminology used herein is for describing particular embodiments only and is not intended to be limiting.

[0057] The reference to "an embodiment" or "an embodiment" in this specification means that a particular feature, structure, or characteristic described in relation to that embodiment is included in at least one embodiment of the invention. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing throughout this specification do not necessarily refer to the same embodiment.

[0058] As used herein, for convenience, multiple items, structural elements, compositions, constituent elements, and / or materials may be presented in a common list. However, these lists should be interpreted as if each member of the list were individually identified as a separate and unique member. Therefore, unless otherwise stated, any single member of such a list should not be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group. Furthermore, various embodiments and examples of the invention, as well as alternatives to its various components, may be referenced herein. It should be understood that these embodiments, examples, and alternatives should not be construed as de facto equivalents of each other, but should be considered as separate and independent representations of the invention.

[0059] Furthermore, the described features, structures, or properties can be combined in any suitable manner in one or more embodiments. Numerous specific details, such as examples of weight, quantity, length, width, shape, etc., are provided in the following description to provide a comprehensive understanding of embodiments of the invention. However, those skilled in the art will recognize that the invention can be practiced without one or more specific details, or using other methods, components, polymers (e.g., polysiloxanes), materials, etc. In other instances, well-known structures, materials, or operations have not been shown or described in detail to avoid obscuring aspects of the invention.

[0060] Unless otherwise stated herein or clearly apparent from the context, any percentages mentioned herein are expressed as weight percentages based on the total weight of the respective composition. For example, unless otherwise stated, all mass percentages (e.g., wt%) refer to the mass percentage of the total composition, film, or layer, i.e., the mass of the compound (mi) as a percentage of the total mass of the composition (m). tot mass fraction (w) i ), the denominator is 100 (i.e. (m i / m tot (*100).

[0061] Unless otherwise stated, the terms “molecular weight” or “average molecular weight” refer to weight-average molecular weight (also abbreviated as “MW”).

[0062] As used in this article, molecular weight was measured using polystyrene standards via gel permeation chromatography.

[0063] Unless otherwise stated, the properties measured or determined experimentally herein were measured or determined at room temperature. Unless otherwise stated, room temperature is 25°C.

[0064] "Optional" or "optionally" indicates that the event or situation subsequently described may but not necessarily occur, and the description includes both cases where the event or situation occurs and cases where it does not occur. The same applies to the context of features; features subsequently described may or may not be included.

[0065] The verbs “comprising” and “including” are used in this document as open-ended restrictions, neither excluding nor requiring the presence of any undescribed features. “Comprising” or “including” means that a feature or action described subsequently may, but does not necessarily, include other features or actions. Unless otherwise expressly stated, the features described in the dependent claims may be freely combined with each other. Furthermore, it should be understood that the use of “a” or “an” (i.e., the singular form) in this document does not exclude the plural.

[0066] As used herein, the term "about" means a value ±5% of the stated value. As used herein, the term "about" means an actual given value, as well as an approximation of that given value that can be reasonably inferred by a person skilled in the art, including approximations derived from the experimental and / or measurement conditions of that given value.

[0067] Surprisingly, it was found that the density of the metal oxide layer (hard mask) obtained using the method disclosed in this invention is greater than that of the corresponding formula M(O). x The density of the amorphous metal oxide is 75%, where M and x are as defined in this invention. Furthermore, the Young's modulus of the hard mask is greater than that of the corresponding formula M(O). x It comprises 60% amorphous metal oxides, wherein M and x are as defined in this invention. Furthermore, the coefficient of thermal expansion is greater than that of the corresponding formula M(O). x 70% of the amorphous metal oxides, wherein M and x are as defined in this invention.

[0068] On the one hand, an organometallic compound of formula (I) or formula (II) or its metal-oxygen cluster is provided:

[0069] in

[0070] Dashed lines indicate optional keys;

[0071] M is a group consisting of metals selected from Ti, Zr, Hf, Sb and W, wherein the metals have an oxidation state selected from +3, +4, +5 or +6;

[0072] X is a group composed of heteroatoms selected from O, N, and S;

[0073] Y is a group composed of heteroatoms selected from O and S;

[0074] Z is a group composed of heteroatoms selected from O and S;

[0075] Each R 1 Independently selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 -A group composed of hydrocarbon groups, this C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms;

[0076] Each R 2 Independently selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 -Hydrocarbon group and C 1-20 The group consisting of -alkoxy groups, the C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms;

[0077] u and v are each independently selected from integers with values ​​in the range of 1 to 20; and

[0078] x is an integer selected from 1 and 2.

[0079] As used herein and hereinafter, the term "metal oxy-coated cluster" refers to a nanostructure typically composed of multiple metal centers connected by bridging oxygen atoms. Metal oxy-coated clusters (MOCs) can be considered as metal oxide units with similar structures and electronic properties. In this disclosure, MOCs include organometallic compounds of formula (I) or (II).

[0080] Alternatively, metal-oxygen clusters can be represented by formula (III):

[0081] M a O x (L) y (R) u (III), of which

[0082] M, u, and x are as defined in this disclosure;

[0083] Each L is independently selected from halogens, nitrates, sulfates, hydroxyl groups, and C. 1-12 The group consisting of -alkoxy groups;

[0084] a is an integer selected from 1 to 20, preferably selected from 1 to 12;

[0085] y is an integer selected from 0 to 20, preferably selected from 1 to 12;

[0086] R is a ligand with formula (IIIa):

[0087] in

[0088] Each dashed line, R 1 R 2 X, Y, and Z are as defined in this disclosure.

[0089] It should be understood that the "O" in "Ox" refers to oxygen. Furthermore, R is attached to M via the Z group of R.

[0090] Alternatively, metal-oxygen clusters can be represented by formula (IIIb):

[0091] Mz a O x (L) y (R) u (IIIb), in which

[0092] z is the oxidation state of M, preferably an integer selected from 3–6;

[0093] M and x are as defined in this disclosure; and

[0094] a, L, y, R, and u are as defined in this disclosure;

[0095] The premise is that u≤(z-2x).

[0096] In addition, or alternatively, as defined in this disclosure, organometallic compounds or their metal-oxygen clusters, wherein,

[0097] Each R 1 Selected from H, and saturated or unsaturated, straight-chain, branched or cyclic C. 1-20 -A group composed of hydrocarbon groups, this C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms; and

[0098] Each R 2 Independently selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 -Hydrocarbon group and C 1-20 The group consisting of -alkoxy groups, the C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms.

[0099] In addition, or alternatively, as defined in this disclosure, organometallic compounds or their metal-oxygen clusters, wherein,

[0100] Dashed lines represent keys;

[0101] X is N;

[0102] Y is a group consisting of heteroatoms selected from O and S, preferably O; and

[0103] Z is a group consisting of heteroatoms selected from O and S, preferably O.

[0104] In addition, or alternatively, as defined in this disclosure, organometallic compounds or their metal-oxygen clusters, wherein,

[0105] Each R 1 Selected from saturated linear C 1-10 -hydrocarbon group; and

[0106] Each R 2 Selected from C 1-20 -alkoxy group.

[0107] Alternatively, or as an alternative, an organometallic compound or its metal-oxygen cluster as defined in this disclosure, wherein

[0108] Dashed lines represent keys;

[0109] X is N;

[0110] Y is O;

[0111] Z is O;

[0112] Each R 1 Selected from saturated linear C 1-10 -hydrocarbon group; and

[0113] Each R 2 C 1-20 -alkoxy group.

[0114] Alternatively, organometallic compounds or their metal-oxygen clusters as defined in this disclosure, wherein

[0115] Dashed lines represent keys;

[0116] X is N;

[0117] Y is O;

[0118] Z is O;

[0119] Each R 1 It is methyl or ethyl; and

[0120] Each R 2 Selected from methoxy or ethoxy.

[0121] Alternatively, an organometallic compound or its metal-oxygen cluster as defined in this disclosure may be used, wherein the organometallic compound has formula (II), formula (III), or formula (IIIb), and at least one R is present in the compound. 1 and / or R 2 Other R present in the compound 1 or R 2 different.

[0122] Alternatively, an organometallic compound or its metal-oxygen cluster as defined in this disclosure may be used, wherein the organometallic compound has formula (II), formula (III), or formula (IIIb), and at least one R is present in the compound. 1 Other R present in the compound 1 different.

[0123] Alternatively, an organometallic compound or its metal-oxygen cluster as defined in this disclosure may be used, wherein the organometallic compound has formula (II), formula (III), or formula (IIIb), and at least one R is present in the compound. 2 Other R present in the compound 2 different.

[0124] Alternatively, an organometallic compound or its metal-oxygen cluster as defined in this disclosure may be used, wherein the organometallic compound has formula (II), formula (III), or formula (IIIb), and at least one R is present in the compound. 1 Other R present in the compound 1 Different, and at least one R present in the compound 2 Other R present in the compound 2 different.

[0125] In a second aspect, a composition is provided comprising an organometallic compound or a metal-oxygen cluster thereof as defined in this disclosure.

[0126] In addition, or alternatively, the composition may also contain at least one solvent selected from the group consisting of PGME, PGMEA, 2-heptanone, sec-butyl acetate, tert-butyl acetate, isopropyl acetate, anisole, NBA, or any combination thereof.

[0127] Furthermore, or alternatively, the composition does not contain particles with a diameter greater than 10 nm. For example, an ellipsometry can be used to measure the diameter, but it is not limited thereto. Other techniques for measuring diameter are known to those skilled in the art.

[0128] The third aspect provides a photolithography method, which includes:

[0129] i) Applying an organometallic compound of formula (I) or (II) or its metal-oxygen cluster, or a composition comprising said organometallic compound or its metal-oxygen cluster, onto a substrate to form a precursor hard mask on said substrate;

[0130] in,

[0131] Dashed lines indicate optional keys;

[0132] M is a group consisting of metals selected from Al, Sn, Zn, Ti, Zr, Hf, Sb, Ta and W, wherein the metals have an oxidation state selected from +3, +4, +5 or +6;

[0133] X, Y, Z, R 1 R 2 u, v, and x are as defined in this disclosure; and

[0134] ii) The formed precursor hard mask is heated at a temperature below 400°C, preferably below 250°C, and most preferably below 200°C, for example at a temperature selected from 60–400°C, 150–400°C, 150–250°C, and 180–200°C, preferably for 1–10 minutes, thereby forming a metal oxide layer on the substrate.

[0135] Alternatively, M may be selected from Ti, Zr, Hf, Sb, and W.

[0136] Alternatively, each M may be independently selected from Ti, Zr, Hf, Sb and W, preferably each M is selected from Ti, Zr, Hf, Sb and W.

[0137] Alternatively, metal-oxygen clusters may be represented by formula (III):

[0138] M a O x (L) y (R) u (III), of which

[0139] M is a group consisting of metals selected from Al, Sn, Zn, Ti, Zr, Hf, Sb, Ta and W, preferably selected from the group consisting of Ti, Zr, Hf, Sb and W;

[0140] u and x are as defined in this disclosure;

[0141] Each L is independently selected from halogens, nitrates, sulfates, hydroxyl groups, and C. 1-12 The group consisting of -alkoxy groups;

[0142] a is an integer selected from 1 to 20, preferably selected from 1 to 12;

[0143] y is an integer selected from 0–20, preferably selected from 1–12;

[0144] R is a ligand with formula (IIIa):

[0145] in,

[0146] Each dashed line, R 1 R 2 X, Y, and Z are as defined in this disclosure.

[0147] It should be understood that the "O" in "Ox" refers to oxygen. Furthermore, R is attached to M via the Z group of R.

[0148] Alternatively, metal-oxygen clusters may be represented by formula (IIIb):

[0149] M za O x (L) y (R) u (IIIb), in which

[0150] z is the oxidation state of M, preferably an integer selected from 3–6;

[0151] M and x are as defined in this disclosure; and

[0152] a, L, y, R, and u are as defined in this disclosure;

[0153] The premise is that u≤(z-2x).

[0154] Alternatively, organometallic compounds or their metal-oxygen clusters may be used as defined in this disclosure, wherein,

[0155] Each R 1 Selected from H and saturated or unsaturated, straight-chain, branched or cyclic C 1-20 -A group composed of hydrocarbon groups, this C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms; and

[0156] Each R 2 Independently selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 -Hydrocarbon group and C 1-20 The group consisting of -alkoxy groups, the C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms.

[0157] In addition, or alternatively, the composition may further comprise at least one solvent selected from PGME, PGMEA, 2-heptanone, sec-butyl acetate, tert-butyl acetate, isopropyl acetate, anisole, and NBA, or any combination thereof.

[0158] Furthermore, or alternatively, the composition does not contain particles with a diameter greater than 10 nm. The diameter can be measured, for example, but not limited to, using an ellipsometer. Other techniques for measuring diameter are known to those skilled in the art.

[0159] Alternatively, the metal oxide layer may be a hard mask.

[0160] Alternatively, the metal-oxygen clusters may be as defined in this disclosure.

[0161] Alternatively, in i), applying an organometallic compound, its metal-oxygen cluster, or composition is coating a substrate to form a precursor hard mask on the substrate, preferably a semiconductor substrate, such as a semiconductor wafer or glass.

[0162] Alternatively, the substrate may be made of or substantially of Si, TiO2 or GaAs, or may be a silicon wafer.

[0163] Alternatively, in ii), heating includes first heating the formed precursor hard mask at a temperature selected from 40–100°C, and then heating at a temperature below 350°C, preferably below 250°C, most preferably 200°C or lower, for example, at a temperature selected from 60–350°C, 100–400°C, 150–300°C, 200–250°C, 150–250°C and 180–200°C.

[0164] Alternatively, in ii), heating includes first heating the formed precursor hard mask to a temperature selected from 40–100°C, and then heating it to a temperature below 350°C, preferably below 250°C, most preferably 200°C or lower, for example, heating to a temperature selected from 60–350°C, 100–400°C, 150–300°C, 200–250°C, 150–250°C and 180–200°C.

[0165] Alternatively, in ii), heating includes heating the formed precursor hard mask for 0.5–20 minutes, 0.5–10 minutes, 0.5–5 minutes, 1–10 minutes, 1–5 minutes, 0.5–2 minutes, 0.5–1.5 minutes, or 0.5–1 minutes.

[0166] Alternatively, in ii), heating includes first heating the formed precursor hard mask at a temperature selected from 40–100°C for 0.5–10 minutes, and then heating at a temperature below 350°C, preferably below 250°C, most preferably 200°C or lower, for example, at a temperature selected from 60–350°C, 100–400°C, 150–300°C, 200–250°C, 150–250°C and 180–200°C for 1–10 minutes.

[0167] Alternatively, in ii), the metal oxide layer formed is a hard mask, preferably an etched hard mask.

[0168] Alternatively, the metal oxide layer may be a hard mask, preferably an etched hard mask.

[0169] Alternatively, the metal oxide layer formed may serve as an intermediate layer.

[0170] Alternatively, in ii), the formed metal oxide layer is a hard mask, preferably an etched hard mask, and preferably an intermediate layer, wherein the lower layer is a carbon-based hard mask and the top layer is a photoresist.

[0171] Alternatively, the method may further include, after ii), etching, preferably oxygen plasma etching, to form a metal oxide layer to form an etched metal oxide layer, preferably an etched hard mask. The oxygen plasma etching is preferably performed at an O2 flow rate selected from the range of 25–75 sccm, preferably 40–60 sccm, more preferably 50 sccm; a pressure range of 0.3–0.9 Pa, preferably 0.4–0.8 Pa, more preferably 0.6 Pa; an RF power range of 10–30 W, preferably 15–25 W, more preferably 20 W; an ICP power range of 100–300 W, preferably 150–250 W, more preferably 200 W; and an etching time range of 10–240 s, preferably 10–60 s, more preferably 30 s. Several other conditions may also be applied to those familiar with inductively coupled plasma or reactive ion etching techniques; the above is provided for reference only. Other oxidizing gases or mixtures may be used alone or in combination, and may optionally be diluted with inert gases such as argon and helium.

[0172] Surprisingly, the formed metal oxide layer, preferably the hard mask, is an etch-resistant metal oxide layer, and more preferably an etch-resistant hard mask. The etch-resistant metal oxide layer, preferably the etch-resistant hard mask, exhibits a thickness loss of less than 5 nm / min, preferably less than 2.5 nm / min, during oxygen plasma etching.

[0173] Surprisingly, the formed etched metal oxide layer, preferably an etch hard mask, is an etch-resistant hard mask. The oxygen plasma etching of the formed metal oxide layer forms an etch-resistant hard mask, which exhibits a thickness loss of less than 5 nm / min, preferably less than 2.5 nm / min, during oxygen plasma etching.

[0174] Alternatively, in i), an organometallic compound, its metal-oxygen cluster, or composition is coated onto the surface of an organic lower layer film on a semiconductor substrate to form a precursor hard mask on the surface of the organic lower layer film, preferably a semiconductor substrate, such as a semiconductor wafer, and after ii),

[0175] iii) Applying the composition for forming the underlayer resist film onto the metal oxide layer and heating the applied composition for forming the underlayer resist film to form the underlayer resist film, preferably, the metal oxide layer is a hard mask, preferably, the metal oxide layer is an intermediate layer;

[0176] iv) Apply the composition for the resist to the formed resist underlayer to form a resist film;

[0177] v) Expose the formed resist film to light or electron beam radiation according to a predetermined pattern to form an exposed resist film;

[0178] vi) Develop the exposed resist film to obtain a patterned resist film;

[0179] vii) According to the pattern of the obtained patterned resist film, the resist underlayer film, the metal oxide layer, the organic underlayer film and the substrate are etched to obtain a patterned substrate.

[0180] Alternatively, the heating may be baking.

[0181] The step of exposing the formed photoresist film to light or electron beam radiation according to a predetermined pattern to form an exposed photoresist film may involve irradiating the formed photoresist film along the predetermined pattern with light to form a photoresist film irradiation structure having irradiated areas and unirradiated areas. When the photoresist film irradiation structure with irradiated areas and / or unirradiated areas is developed, a patterned photoresist film is formed.

[0182] In addition, or alternatively, the method may further include, after at least one, preferably after each, etching the photoresist underlayer, metal oxide layer, organic underlayer and substrate according to the pattern of the obtained patterned photoresist film to obtain a patterned substrate.

[0183] Furthermore, or alternatively, the development is or includes development with one or more developing agents or a combination thereof. Furthermore, or alternatively, one or more developing agents are selected from PGME, PGEE, PGPE, and C. 1-10 -A group composed of alcohols.

[0184] Fourthly, a metal oxide layer obtained by the method defined in this disclosure is provided.

[0185] Furthermore, or alternatively, the carbon content of the metal oxide layer is less than 25%, preferably less than 20%, compared to the carbon content of the compound or oxygen metal cluster of formula (I) or (II) in i). This is because the compound or oxygen metal cluster of formula (I) or (II) decomposes upon heating to 250°C in ii), preferably upon heating to 250°C in air at a heating rate of 4°C / min in ii).

[0186] In addition, or alternatively, preferably when heated to a temperature selected from the range of 475-575°C, the carbonization rate of the metal oxide layer is less than 45%, preferably less than 40%, more preferably less than 35%, even more preferably less than 30%, for example 25-30%, 25-35%, 25-40%, or 25-45%.

[0187] Alternatively, the refractive index of the metal oxide layer may be 0.2 or lower than that of the corresponding amorphous metal oxide, preferably 0.1 or lower.

[0188] Alternatively, the refractive index of the metal oxide layer may be higher than that of the corresponding formula M(O). x The refractive index of the amorphous metal oxide is 0.2 or lower, preferably 0.1 or lower, wherein M and x are as defined in this disclosure.

[0189] Alternatively, the metal oxide layer defined in this invention can be obtained by the photolithography method defined in this invention, wherein the photolithography method includes, after ii), etching, preferably oxygen plasma etching, to form an etched metal oxide layer, wherein the refractive index of the metal oxide layer is 0.1 or lower than that of the etched metal oxide layer, preferably 0.07 or lower.

[0190] Alternatively, the refractive index of the metal oxide layer may be 0.1 or lower, preferably 0.07 or lower, than the refractive index of the etched metal oxide layer obtained by the photolithography method defined in this invention, wherein the photolithography method includes, after ii), etching, preferably oxygen plasma etching, to form the etched metal oxide layer.

[0191] Alternatively, the refractive index of the metal oxide layer may be ≤0.1, ≤0.09, ≤0.08, ≤0.06, ≤0.05, ≤0.04, ≤0.03, ≤0.02, or ≤0.01 lower than the refractive index of the etched metal oxide layer, or the refractive index of the metal oxide layer may be the same as that of the etched metal oxide layer, or the refractive index of the metal oxide layer may be ≤0.1, ≤0.05, or ≤0.01 higher than that of the etched metal oxide layer.

[0192] Alternatively, the metal oxide layer may be an etched metal oxide layer.

[0193] Alternatively, the metal oxide layer may be an etched metal oxide layer obtained by the photolithography method defined in this invention, wherein the photolithography method includes, after ii), etching, preferably oxygen plasma etching, the metal oxide layer formed to form an etched metal oxide layer.

[0194] Alternatively, the oxygen plasma etching may be performed with an O2 flow rate selected from the range of 25–75 sccm, preferably 40–60 sccm, more preferably 50 sccm; a pressure range of 0.3–0.9 Pa, preferably 0.4–0.8 Pa, more preferably 0.6 Pa; an RF power range of 10–30 W, preferably 15–25 W, more preferably 20 W; an ICP power range of 100–300 W, preferably 150–250 W, more preferably 200 W; and an etching time range of 10–240 s, preferably 10–60 s, more preferably 30 s. Alternatively, the oxygen plasma etching may have an O2 flow rate of 50 sccm; a gas pressure of 0.6 Pa; an RF power of 20 W; an ICP power of 200 W; and an etching time of 30 s.

[0195] The fifth aspect provides the use of compounds, their oxygen metal clusters, or compositions as defined in this disclosure in the preparation of hard masks, optical elements, optically active devices, or optical or semiconductor devices.

[0196] Sixthly, a method is provided for preparing a compound of formula (I) or formula (II) as defined in this disclosure, or an oxygen metal cluster thereof, wherein the method comprises:

[0197] i) Provide a reaction composition containing a compound of formula (V):

[0198] in

[0199] Dashed lines, X, Y, Z, R 1 and R 2 As defined in this disclosure; and

[0200] ii) Provide a salt of X or a hydrate thereof, wherein X is as defined in this disclosure;

[0201] iii) React the compound of formula (V) with a salt of X or its hydrate.

[0202] To obtain a compound of formula (I) or formula (II) or its oxygen metal cluster.

[0203] Alternatively, the compound of formula (V) may be 2-(methoxyimino)propionic acid.

[0204] Alternatively, the compound of formula (V) may be 2-(methoxyimino)propionic acid, and the salt of X or its hydrate may be selected from titanium tetrachloride, titanium sulfate, tetra(C) chloride, titanium hydrate ... 1-15 - Alcohol) Titanium, Zirconium tetrachloride, Zirconium oxychloride octahydrate, Zirconium propionate oxide, Hafnium butyrate oxide, Hafnium tetrachloride, Hafnium chloride octahydrate, and Tungsten dioxochloride (WO2Cl2).

[0205] In addition, or alternatively, in iii), reacting a compound of formula (V) with a salt or hydrate of X comprises mixing a compound of formula (V) with a salt or hydrate of X to obtain a reaction composition; and optionally heating or cooling the reaction composition at a predetermined temperature.

[0206] Alternatively, the mixing of a compound of formula (V) with a salt of X, or a hydrate thereof, may include mixing a compound of formula (V) with a salt of X, or a hydrate thereof, in at least one solvent to obtain a reaction composition, the reaction composition optionally further comprising an acid or a base.

[0207] Alternatively, the at least one solvent may be selected from the group consisting of methanol, dichloromethane, ethyl acetate, propanol, dichloromethane, ethylene glycol dimethyl ether, water, or mixtures thereof; the optional acid and base may be selected from triethylamine and HCl.

[0208] Alternatively, the method may include heating or cooling the reaction composition at a predetermined temperature selected from -5–120°C.

[0209] In a seventh aspect, an optical element, an optically active device, or an optical or semiconductor device is provided that can be obtained by the methods defined in this disclosure.

[0210] Alternatively, the optical element, optically active device, or optical or semiconductor device may be a patterned substrate comprising a substrate and a first coating, wherein the substrate comprises a surface and the first coating is attached to a selected area of ​​the surface and not to other areas of the surface, wherein the first coating comprises or is a metal oxide layer, preferably a hard mask, obtainable by methods defined in this disclosure, and wherein the thickness loss of the metal oxide layer, preferably a hard mask, during the etching process or ashing process as defined in this disclosure is 5 nm / min or less.

[0211] In some embodiments, the present invention relates to patterning on a semiconductor substrate using an organometallic compound of formula (I) or formula (II) disclosed herein, such as... Figure 1 and Figure 2 As shown.

[0212] Therefore, in a process of this type, an organic underlayer 11 12 is typically coated on the surface of substrate 10, followed by the coating 13 and curing of an inorganic intermediate layer 14, which is typically composed of a high-silicon-content material. On top of this, a photoresist film 15 16 is coated. After exposing the formed photoresist film 16 to light or electron beam radiation (e.g., irradiation 18 using light at a wavelength of 193 nm), a pattern is formed and developed (not shown) to form a patterned photoresist film 16a. In the literature, this combination of layers is often described as a “three-layer” stack (referring to the number of layers).

[0213] Subsequently, a pattern transfer etching process (optional development) can be performed to transfer the pattern formed on the photoresist (patterned photoresist film 16a) to the substrate 10. Figure 1 Therefore, a patterned inorganic intermediate layer 14a, a patterned organic bottom layer 12a, and a patterned substrate 10a, such as a patterned semiconductor substrate 10a, can be obtained. It is worth noting that the stacking of each layer used in the photolithography technique can be higher than three layers.

[0214] Another layer combination is a four-layer stack ( Figure 2 The structure includes a substrate 10, an inorganic intermediate layer 14 or a metal oxide layer (hard mask) 14, an organic bottom antireflective layer 17, and a photoresist (resist film) 16. For a four-layer stack, an organic bottom layer 12 is first coated on the substrate 10, followed by coating to form a precursor hard mask (not shown). The formed precursor hard mask is then cured to form the inorganic intermediate layer 14, which is typically composed of a high-silicon-content material. However, according to the present invention, the inorganic intermediate layer 14 is a metal oxide layer (hard mask) 14 (not shown) obtained from an organometallic compound or composition disclosed in this disclosure. An organic bottom antireflective layer 17 is then applied before the photoresist (resist film) 16 to complete the four-layer stack. Figure 2 ).

[0215] After application by spin coating or other suitable liquid deposition methods, a pre-baking step can be applied to at least partially remove solvents and volatile compounds contained in the coating material. This helps to avoid contamination of the manufacturing equipment. Pre-baking can be performed at different temperatures and times, depending on the boiling point of the solvent and volatile components. Typically, pre-baking can be performed at 60–120°C for 30 seconds to no more than 30 minutes.

[0216] Following the drying or pre-baking step, the coating is exposed to EUV light, an electron beam, or a similar exposure method (18) through an optional mask to create a pattern on the substrate. The required dose for pattern formation is at least 5 mJ / cm². 2 The maximum is 200 mJ / cm 2 .

[0217] Development is performed to remove exposed or unexposed areas, thereby obtaining the designed pattern. In the development step, for example, the exposed or unexposed areas of the photoresist (resist film) 16 are dissolved in the developer to form a patterned resist film 16a.

[0218] The following non-limiting examples illustrate the embodiments.

[0219] Example

[0220] method

[0221] Electron beam lithography was performed on Vistec tools. The solids content of the formulation was 1.3%. The formulation was spin-coated onto the silicon wafer at a spin coater at 1500 rpm for 30 seconds. Then, soft baking was performed on a hot plate at 80°C for 1 minute. Electron beam doses ranged from 100 to 20000 μC / cm² at 100 kV and 1 nA. 2 The process varies. The development step involves immersing the film in various organic developers (e.g., PGME, PGEE, PGPE, alcohol) for 10 seconds. The patterned film is then rinsed with the same solvent for 5 seconds and finally dried with nitrogen.

[0222] EUV lithography: A 1.5–2% solids content formulation is spin-coated onto a silicon wafer at 1500 rpm for 30 seconds. Then, it is soft-baked for 1 minute on a hot plate at 40–80°C (depending on the photoresist). The soft-baked film sample is then irradiated using a XIL-II EUV tool. The dose ranges from 2 to 200 mJ / cm². 2 No. The development step involves immersing the film in various organic developers (such as PGME, PGEE, PGPE, and alcohol) for 10 seconds. Then, the patterned film is rinsed with the same solvent for 5 seconds, and finally dried with nitrogen.

[0223] Compound synthesis (metal hard mask precursor)

[0224] The following is a typical synthesis procedure for preparing metal hard mask precursors.

[0225] Titanium hard mask precursor

[0226] Example 1: Titanium oxide di(methoxyiminopropionate)

[0227]

[0228] To prepare a solution of approximately 12.4 mM, 2.35 g of titanium tetrachloride was added dropwise to 150 mL of acetone. The reaction was exothermic, and the solution slowly turned yellow. 6.7 g of ammonium methoxyiminopropionate was added to the solution. The yellow color of the solution began to fade slowly. The reaction continued for 24 hours. The solution was filtered, and the filtrate was rotary evaporated to remove acetone. The resulting gel was dissolved in 7.5 mL of dichloromethane, and the compound precipitated in hexane. It was dried at 50 °C for 18 hours. The product, titanium dioxide bis(methoxyiminopropionate) (titanium dioxide bis[2-(methoxyimino)propionate]), was obtained in an almost quantitative yield of 96%. The compound was characterized by NMR, FTIR, and TGA.

[0229] The same synthesis can also be performed by bubbling ammonia gas in an organic solvent over a mixture of titanium tetrachloride and 2-(methoxyimino)propionic acid.

[0230] The aforementioned precursor can also be synthesized by reacting titanium sulfate with 2-(methoxyimino)propionic acid in a 1:2 molar ratio under reflux in methanol in the presence of a base.

[0231] Thermogravimetric analysis (TGA) of this compound showed that mass loss began near 100 °C and ended around 225 °C. TGA analysis was performed by heating the compound to 600 °C and measuring its mass loss. Within the range of 100–225 °C, the carbon content of the compound with the largest mass loss appeared to decrease. Subsequently, smaller mass losses led to the formation of amorphous TiO2 (obtained ceramic mass = 27.7%; calculated ceramic mass = 26.9%). These results indicate that the precursor hard mask of this compound decomposes upon heating, and that the carbon content of the resulting hard mask is lower than that of the precursor hard mask due to the heating of the precursor hard mask.

[0232] Comparative Example 2: Oxychloride Titanide Di(Methoxyiminopropionate)

[0233]

[0234] To prepare a solution of approximately 19.6 mM, 3.71 g of titanium tetrachloride was added to 150 mL of dichloromethane. 9.16 g of 2-(methoxyimino)propionic acid was then added to the solution. The solution turned yellow. The reaction continued for 18 hours. The solution was then rotary evaporated to remove the dichloromethane, resulting in a pale yellow solid. The obtained solid was dissolved in 7.5 mL of dichloromethane, and the compound was precipitated in hexane. The solution was dried at 35 °C for 18 hours. The yield of the product, titanium oxide oxy-chlorodi(methoxyimino)propionate (titanium oxide bis[2-(methoxyimino)propionate]chloride), was 7.32 g, 73%. The compound was characterized by NMR, FTIR, and TGA.

[0235] Zirconium hard mask precursor

[0236] Example 3: Zirconium oxyhydroxymethoxyiminopropionate

[0237] To prepare an approximately 8.8 mM solution, 2.06 g of zirconium tetrachloride was added in portions to 150 mL of acetone. The reaction was exothermic, and the solution slowly turned pale yellow. 4.74 g of ammonium methoxyiminopropionate was added to the solution. The yellow color of the solution began to fade slowly. The reaction continued for 24 hours. The solution was filtered, and the filtrate was rotary evaporated to remove acetone. The resulting gel was dissolved in 7.5 mL of dichloromethane, and the compound was precipitated in hexane. It was dried at 38 °C for 18 hours. The yield of the compound zirconium oxyhydroxymethoxyiminopropionate (2-(methoxyimino)propionate oxide) was almost quantitative, at 95%. The compound was characterized by NMR, FTIR, and TGA.

[0238] The same synthesis can also be performed by bubbling ammonia gas in a mixture of zirconium tetrachloride and 2-(methoxyimino)propionic acid in an organic solvent.

[0239] The TGA study of this compound was conducted as described in Example 1, and the results showed that mass loss began near 60 °C and ended around 250 °C. The maximum mass loss appears to occur within this range. At slightly higher temperatures, the formation of amorphous ZrO2 was obtained (ceramic mass obtained = 33.5%; calculated ceramic mass = 35.7%). These results indicate that the precursor hard mask of this compound decomposes upon heating, and the resulting hard mask has a lower carbon content compared to the precursor hard mask due to the heating of the precursor hard mask.

[0240] Example 4: Poly(di(methoxyiminopropionic acid)zirconium)

[0241] To prepare an approximately 30 mM solution, 9.66 g of zirconium oxychloride octahydrate was dissolved in 100 mL of methanol. The solution was cooled to 5 °C in an ice bath. Separately, 7.02 g of 2-(methoxyimino)propionic acid was dissolved in 10 mL of methanol to obtain an approximately 60 mM solution. This made the solution feel cold to the touch. 8.36 mL of triethylamine was added to this solution. The solution was slowly heated. Immediately, this mixture was added dropwise to the cold zirconium oxychloride octahydrate solution. After the addition, the solution was slowly heated to room temperature and stirred for 2 hours, during which time the solution slowly became cloudy.

[0242] After the reaction was complete, methanol was removed from the mixture using a rotary evaporator. 75 mL of THF was added to the resulting dry powder and shaken well. The solution was filtered using a PTFE filter (pore size = 0.45 μm), and then added dropwise to 250 mL of vigorously stirred hexane, forming a grayish-white precipitate. The hexane was poured off, and the collected precipitate was dried under vacuum for 2 hours. Unbound by any theory, the reaction between zirconium oxychloride octahydrate and 2-(methoxyimino)propionic acid (MIPA) with triethylamine in methanol can be described as follows (MIP = methoxyiminopropionic acid ester):

[0243]

[0244] Here, zirconium atoms chelate with MIP ligands.

[0245] Hafnium hard mask precursor

[0246] Example 5: Hafnium oxyhydroxymethoxyiminopropionate

[0247] To prepare an approximately 6 mM solution, 1.92 g of hafnium tetrachloride was added in portions to 150 mL of acetone. The reaction was exothermic, and the solution slowly turned pale yellow. 3.32 g of ammonium methoxyiminopropionate was added to this solution. The reaction continued for 24 hours. The solution was filtered, and the filtrate was rotary evaporated to remove acetone. The resulting gel was dissolved in 5 mL of dichloromethane, and the compound was precipitated in hexane. It was dried at 38 °C for 19 hours. The yield of the product, hafnium oxyhydroxymethoxyiminopropionate, was almost quantitative, at 2.57 g (98%). The compound was characterized by NMR, FTIR, and TGA.

[0248] The same synthesis can also be performed by bubbling ammonia gas in a mixture of hafnium tetrachloride and 2-(methoxyimino)propionic acid in an organic solvent.

[0249] The TGA study of this compound was conducted as described in Example 1, and the results showed that mass loss began near 50 °C and ended around 250 °C. The maximum mass loss appears to occur within this range. At slightly higher temperatures, the formation of amorphous HfO2 was obtained (ceramic mass obtained = 43.3%; calculated ceramic mass = 48.6%). These results indicate that the precursor hard mask of this compound decomposes upon heating, and that the resulting hard mask has a lower carbon content compared to the precursor hard mask due to the heating of the precursor hard mask.

[0250] Example 6: Poly(di(methoxyiminopropionic acid)hafnium)

[0251] To prepare an approximately 15 mM solution, 6.14 g of hafnium chloride oxychloride octahydrate was dissolved in 50 mL of methanol. The solution was cooled to 5 °C in an ice bath. Separately, 3.5 g of 2-(methoxyimino)propionic acid was dissolved in 10 mL of methanol to obtain an approximately 30 mM solution. This made the solution feel cold to the touch. 4.18 mL of triethylamine was added to this solution. The solution was slowly heated. Immediately, this mixture was added dropwise to the cold solution of hafnium chloride oxychloride octahydrate. After the addition, the solution was slowly heated to room temperature and stirred for 2 hours, during which time the solution slowly became turbid.

[0252] After the reaction was complete, methanol was removed from the mixture using a rotary evaporator. 50 mL of THF was added to the resulting dry powder and shaken well. The solution was centrifuged and the clear supernatant was collected. This supernatant was added dropwise to 250 mL of vigorously stirred hexane, forming a grayish-white precipitate. The hexane was poured off and the collected precipitate was dried under vacuum for 2 hours. Unbound by any theory, the reaction between hafnium chloride octahydrate and MIPA with triethylamine in methanol can be as follows (MIP = methoxyiminopropionate):

[0253]

[0254] Here, the hafnium atom is chelated with the 2-(methoxyimino)propionate (MIP) ligand.

[0255] Tungsten hard mask precursor

[0256] Example 7: Dioxodi(methoxyiminopropionic acid)tungsten

[0257]

[0258] This compound (bis[2-(methoxyimino)propionic acid]tungsten dioxide) can be prepared by reacting tungsten dichlorochloride (WO2Cl2) with 2-(methoxyimino)propionic acid in a 1:2 molar ratio in dichloromethane, in the presence of ethylene glycol dimethyl ether and a base.

[0259] Etching performance and film properties of metal hard masks

[0260] The refractive index (RI) and etching performance of the metal hard mask in O2 were tested at different baking temperatures.

[0261] Process conditions

[0262] The compound was coated onto a 6-inch bare Si wafer and soft-baked at 80°C for 2 minutes, followed by curing at 200, 250, or 300°C for 5 minutes. Film thickness and RI (at 633 nm) were measured using a Woollam M2000D. The etch rate of the metal oxide hard mask (also referred to as the “metal oxide layer” and “hard mask”) disclosed in this disclosure in O2 was obtained using a Sentech SI500 with parameters of 50 sccm O2 flow rate, 0.6 Pa pressure, 20 W RF power, 200 W ICP power, and 30 s etch time. Film thickness and RI after etching were measured to calculate the etch rate.

[0263] The results are shown in Tables 1–3 below.

[0264] Table 1. TiO2 obtained using titanium dioxide di(methoxyiminopropionate) from Example 1 as a hard mask precursor x Hard mask etching results.

[0265]

[0266]

[0267] a Thickness refers to the thickness of the hard mask (metal oxide layer, TiO2) formed after curing and before etching. x The thickness of ).

[0268] The residual mass of the hard mask obtained in Example 1 using titanium dimethoxyiminopropionate as a hard mask precursor was determined after baking at different temperatures for 3 minutes: 34.0% after baking at 200℃; 20.0% after baking at 300℃; 19.1% after baking at 350℃; and 18.4% after baking at 400℃.

[0269] Table 2. ZrO obtained using zirconium oxyhydroxymethoxyiminopropionate from Example 3 as a hard mask precursor x Hard mask etching results.

[0270]

[0271] a Thickness refers to the thickness of the hard mask (metal oxide layer, ZrO) formed after curing and before etching. x The thickness of ).

[0272] The residual mass of the hard mask obtained in Example 3 using zirconium oxyhydroxymethoxyiminopropionate as a hard mask precursor was determined after baking at different temperatures for 3 minutes: 41.7% after baking at 205℃; 36.1% after baking at 300℃; and 34.1% after baking at 350℃.

[0273] Table 3. HfO obtained using hafnium oxyhydroxymethoxyiminopropionate as a hard mask precursor in Example 5 x Hard mask etching results.

[0274]

[0275] a Thickness refers to the thickness of the hard mask (metal oxide layer, HfO) formed after curing and before etching. x The thickness of ).

[0276] The residual mass of the hard mask obtained in Example 5 using hafnium oxyhydroxymethoxyiminopropionate as a hard mask precursor was determined after baking at different temperatures for 3 minutes: 47.3% after baking at 209℃; 42.4% after baking at 300℃; and 40.8% after baking at 350℃.

[0277] While exemplary embodiments of this disclosure have been described herein, it should be noted that various changes and modifications may be made to the embodiments of this disclosure without departing from the scope of legal protection defined by the appended claims. In the appended claims, the word "comprising" does not exclude other elements, steps, or operations, and the indefinite articles "a" or "an" do not exclude multiple. The fact that certain measures are described in mutually different dependent claims does not indicate that combinations of these measures cannot be fully utilized.

[0278] Industrial applicability

[0279] Generally, this technology can be used in the semiconductor industry. For example, it can be used to implement complex circuits in microelectronic devices, especially using photolithography processes, such as photolithography.

Claims

1. An organometallic compound of formula (I) or formula (II) or its metal-oxygen cluster: Dashed lines indicate optional keys; M is a group consisting of metals selected from Ti, Zr, Hf, Sb, and W, among which... The metal has an oxidation state selected from +3, +4, +5 or +6; X is a group composed of heteroatoms selected from O, N, and S; Y is a group composed of heteroatoms selected from O and S; Z is a group composed of heteroatoms selected from O and S; Each R 1 Independently selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 -A group composed of hydrocarbon groups, this C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms; Each R 2 Independently selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 - Hydrocarbon group and C 1-20 The group consisting of -alkoxy groups, the C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms; u and v are each independently selected from integers with values ​​in the range of 1 to 20; and x is an integer selected from 1 and 2.

2. The organometallic compound or its metal-oxygen cluster according to claim 1, wherein, The metal-oxygen cluster is represented by formula (III): M a O x (L) y (R) u (III), in which, M, u, and x are as defined in claim 1; Each L is independently selected from halogens, nitrates, sulfates, hydroxyl groups, and C. 1-12 The group consisting of -alkoxy groups; a is an integer selected from 1 to 20; y is an integer selected from 0 to 20; R is a ligand with formula (IIIa): in Each dashed line, R 1 R 2 X, Y, and Z are as defined in claim 1.

3. The organometallic compound or its metal-oxygen cluster as described in claim 1 or 2, wherein, The metal-oxygen cluster is represented by formula (IIIb): M z a O x (L) y (R) u (IIIb), in which, z is the oxidation state of M, and preferably, z is an integer selected from 3–6; M and x are as defined in claim 1; and a, L, y, R, and u are as defined in claim 2; The premise is that u≤(z-2x).

4. The organometallic compound or its metal-oxygen cluster as described in any of the preceding claims, wherein, Each R 1 Selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 -A group composed of hydrocarbon groups, this C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms; and Each R 2 Selected from H, saturated or unsaturated, straight-chain, branched or cyclic C 1-20 - Hydrocarbon group and C 1-20 The group consisting of -alkoxy groups, the C 1-20 -The hydrocarbon group may optionally contain one or more heteroatoms.

5. The organometallic compound or its metal-oxygen cluster as described in any one of the preceding claims, wherein... Dashed lines represent keys; X is N; Y is a heteroatom selected from the group consisting of O and S, preferably O; and Z is a heteroatom selected from the group consisting of O and S, preferably O.

6. An organometallic compound or its metal-oxygen cluster as described in any of the preceding claims, wherein each R 1 Selected from saturated linear C 1-10 -hydrocarbon group; and Each R 2 Selected from C 1-20 -alkoxy group.

7. The organometallic compound or its metal-oxygen cluster as claimed in any of the preceding claims, wherein... Dashed lines represent keys; X is N; Y is O; Z is O; Each R 1 Selected from saturated linear C 1-10 -hydrocarbon group; and Each R 2 C 1-20 -alkoxy group.

8. The organometallic compound or its metal-oxygen cluster as described in any of the preceding claims, wherein... Dashed lines represent keys; X is N; Y is O; Z is O; Each R 1 It is methyl or ethyl; and Each R 2 Selected from methoxy or ethoxy.

9. The organometallic compound or its metal-oxygen cluster as described in any of the preceding claims, wherein, The organometallic compound has formula (II), formula (III), or formula (IIIb), and at least one R is present in the compound. 1 and / or R 2 Other R present in the compound 1 Or R 2 different.

10. A composition comprising an organometallic compound or a metal-oxygen cluster thereof as defined in any of the preceding claims.

11. The composition according to claim 10, wherein, The composition further comprises at least one solvent selected from the group consisting of PGME, PGMEA, 2-heptanone, sec-butyl acetate, tert-butyl acetate, isopropyl acetate, anisole, and NBA.

12. A photolithography method, comprising: i) Applying an organometallic compound of formula (I) or (II) or its metal-oxygen cluster, or a composition comprising said organometallic compound or its metal-oxygen cluster, onto a substrate to form a precursor hard mask on said substrate; The dashed lines represent optional keys; M is a metal selected from the group consisting of Al, Sn, Zn, Ti, Zr, Hf, Sb, Ta and W, wherein the metal has an oxidation state selected from +3, +4, +5 or +6; X, Y, Z, R 1 R 2 u, v, and x are defined as in any one of claims 1–9; and ii) A precursor hard mask formed by heating at a temperature below 400°C is used to form a metal oxide layer on the substrate.

13. The photolithography method as described in claim 12, wherein, The metal-oxygen cluster is as defined in any one of claims 2-9.

14. The photolithography method as described in claim 12 or 13, wherein, In i), the step of applying the organometallic compound, its metal-oxygen cluster, or composition is to coat a substrate to form the precursor hard mask on the substrate, preferably a semiconductor substrate, such as a semiconductor wafer or glass.

15. The photolithography method according to any one of claims 12-14, wherein, The substrate may be made of or primarily of Si, TiO2 or GaAs, or may be a silicon wafer.

16. The photolithography method according to any one of claims 12-15, wherein, In ii), heating includes first heating the formed precursor hard mask at a temperature selected from 40-100°C for 0.5-10 minutes, and then heating it at a temperature below 350°C for 1-10 minutes.

17. The photolithography method according to any one of claims 12-16, wherein, In ii), the metal oxide layer formed is an etched hard mask.

18. The photolithography method according to any one of claims 10-17, wherein, The method further includes: after ii), etching the formed metal oxide layer to form an etched metal oxide layer.

19. The photolithography method according to any one of claims 12-18, wherein, In i), the application of the organometallic compound, its metal-oxygen cluster, or composition is done by coating the surface of an organic lower layer film on a semiconductor substrate, thereby forming the precursor hard mask on the surface of the organic lower layer film. Preferably, the substrate is a semiconductor substrate, such as a semiconductor wafer, and after ii), iii) Apply the composition for forming the underlayer resist film to the metal oxide layer and heat the applied composition for forming the underlayer resist film to form the underlayer resist film; iv) Apply the composition for the resist to the formed resist underlayer to form a resist film; v) Expose the formed resist film to light or electron beam radiation according to a predetermined pattern to form an exposed resist film; vi) Develop the exposed resist film to obtain a patterned resist film; vii) According to the pattern of the obtained patterned resist film, the resist underlayer film, the metal oxide layer, the organic underlayer film and the substrate are etched to obtain a patterned substrate.

20. The metal oxide layer obtained by the method according to any one of claims 10-19.

21. The metal oxide layer according to claim 20, wherein, Compared to the carbon content of the compounds of formulas (I) and (II) or their oxygen metal clusters described in i), the carbon content of the metal oxide layer is less than 25%.

22. The metal oxide layer according to any one of claims 20-21, wherein, The carbon yield of the metal oxide layer is less than 45%.

23. The metal oxide layer according to any one of claims 20-22, wherein, The refractive index of the metal oxide layer is 0.2 or lower than that of the corresponding amorphous metal oxide.

24. The metal oxide layer according to any one of claims 20-23, wherein, The refractive index of the metal oxide layer is 0.1 or lower than that of the etched metal oxide layer obtained by the method according to claim 18.

25. The metal oxide layer according to any one of claims 20-24, wherein, During the etching of the metal oxide layer, the thickness loss of the metal oxide layer is 5 nm / min or less.

26. Use of any compound, its oxygen metal cluster, or composition according to any one of claims 1–11 in the preparation of a hard mask in the manufacture of optical elements, optically active devices, or optical or semiconductor devices.

27. A method for preparing a compound of formula (I) or formula (II) according to any one of claims 1–11, wherein, The method includes: i) Provide a reaction composition containing a compound of formula (V): in Dashed lines, X, Y, Z, R 1 and R 2 As defined in any one of claims 1–11; and ii) Provide a salt of X or a hydrate thereof, wherein X is defined as in any one of claims 1–11; iii) Reacting the compound of formula (V) with the salt of X or its hydrate, To obtain the compound of formula (I) or formula (II) or its oxygen metal cluster.

28. The method according to claim 27, wherein, The compound of formula (V) is 2-(methoxyimino)propionic acid, and the salt or hydrate of X is selected from titanium tetrachloride, titanium sulfate, and tetra(C) chloride. 1-15 - Alcohol) Titanium, Zirconium tetrachloride, Zirconium oxychloride octahydrate, Zirconium propionate oxide, Hafnium butyrate oxide, Hafnium tetrachloride, Hafnium chloride octahydrate, and Tungsten dioxochloride (WO2Cl2).

29. The method according to any one of claims 27-28, wherein, In iii), the step of reacting a compound of formula (V) with a salt or hydrate of X comprises: mixing a compound of formula (V) with a salt or hydrate of X to obtain a reaction composition; and optionally heating or cooling the reaction composition at a predetermined temperature.

30. The method according to claim 29, wherein, The step of mixing a compound of formula (V) with a salt or hydrate of X comprises: mixing a compound of formula (V) with a salt or hydrate of X in at least one solvent to obtain the reaction composition, optionally, the reaction composition further comprising an acid or a base.

31. The method of claim 30, wherein, The at least one solvent is selected from the group consisting of methanol, dichloromethane, ethyl acetate, propanol, dichloromethane, dimethyl ether, water, or mixtures thereof; and the optional acid and base are selected from triethylamine and HCl.

32. The method according to any one of claims 27 to 31, wherein, The method includes heating or cooling the reaction composition to a predetermined temperature selected from -5 to 120°C.

33. An optical element, optically active device or optical semiconductor device obtained by the method of any one of claims 12 to 19.

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