WO2023231819A1 - Metal compound, and preparation method therefor and use thereof - Google Patents

Metal compound, and preparation method therefor and use thereof Download PDF

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Publication number
WO2023231819A1
WO2023231819A1 PCT/CN2023/095568 CN2023095568W WO2023231819A1 WO 2023231819 A1 WO2023231819 A1 WO 2023231819A1 CN 2023095568 W CN2023095568 W CN 2023095568W WO 2023231819 A1 WO2023231819 A1 WO 2023231819A1
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transition metal
metal compound
ligand
atom
deposition
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PCT/CN2023/095568
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French (fr)
Chinese (zh)
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刘宇
景可欣
丁玉强
赵文勇
周慧慧
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华为技术有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/16—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metal carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36—Carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • H01L21/2003—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate
    • H01L21/2015—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate the substrate being of crystalline semiconductor material, e.g. lattice adaptation, heteroepitaxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation

Definitions

  • the present application relates to the field of chemical deposition technology, specifically to a metal compound and its preparation method and application.
  • SiO 2 as a gate dielectric material can no longer meet the high integration requirements of field effect transistor devices, and materials with high dielectric constant (High-K) are needed to replace traditional SiO 2 .
  • High-K high dielectric constant
  • lanthanum-containing oxides are considered to be ideal High-K materials that can be used in semiconductor devices due to their characteristics such as high dielectric constant, high thermal stability, wide bandgap, high breakdown field strength, and low leakage current.
  • Chemical Vapor Deposition (CVD) technology and Atomic Layer Deposition (ALD) technology have become commonly used thin film deposition technologies in the preparation process of semiconductor devices because they can precisely control the deposition thickness and morphology of thin films. If these two technologies are used to grow lanthanum-containing oxide films, the corresponding lanthanum precursor must have a lower melting point, good volatility, high reactivity, and certain thermal stability. However, existing lanthanum precursors cannot satisfy the above characteristics at the same time.
  • embodiments of the present application provide a metal compound to simultaneously meet various performance requirements of CVD/ALD technology for precursor materials containing metal elements.
  • the first aspect of the embodiment of the present application provides a metal compound.
  • the metal compound includes a transition metal atom and at least one ⁇ -diketone ligand coordinated with the transition metal atom. It also includes a transition metal atom coordinated with the transition metal atom.
  • the two nitrogen atoms in the ligand are coordinated or coordinated with the nitrogen atoms in the monoamine ligand.
  • the metal compound provided in the embodiments of the present application has a low melting point, good volatility, good structural stability, high chemical reactivity, and is non-corrosive to the substrate, and is suitable for use as a precursor material for CVD or ALD deposition reactions. , thus enabling the growth of films containing transition metal elements with controllable film thickness and morphology.
  • the transition metal atoms include lanthanide elements, yttrium, scandium, hafnium, titanium, vanadium, zirconium, chromium, tungsten, manganese, iron, cobalt, nickel, ruthenium, zinc, copper, palladium, and platinum , iridium, rhenium, osmium, tantalum, rhodium or niobium.
  • the metal compound includes three ⁇ -diketone ligands.
  • the coordination number of the central transition atom is 8, the melting point is lower, the volatility is better, and the structural stability is higher.
  • the diamine ligand includes dibasic alkylamine.
  • the resistance of the binary alkyl amine to coordinate with the transition metal atoms is small, and it is not easy to be separated from the above-mentioned metal compound, thus ensuring the good thermal stability of the metal compound.
  • the general structural formula of the dibasic alkyl amine is expressed as N(R 3 )(R 4 )-C(R 7 )-C(R 8 )-N(R 5 )(R 6 ) , wherein R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups.
  • the number of carbon atoms of the alkyl group is 1-6.
  • Diary alkylamines containing alkyl groups with fewer carbon atoms have less resistance to coordination with transition metal atoms.
  • the monoamine ligand includes a monoalkylamine containing one nitrogen atom or a nitrogen heterocyclic ligand.
  • the general structural formula of the monoalkyl amine is expressed as N(R 3 ') (R 4 ') (R 5 '), where R 3 ', R 4 ', and R 5 ' are independent are selected from hydrogen atoms and alkyl groups, and at least one of R 3 ' to R 5 ' is an alkyl group;
  • the nitrogen heterocyclic ligand includes pyridine, piperidine, pyrrole or derivatives thereof.
  • monoalkyl amines have less steric hindrance in binding to transition metal atoms than nitrogen heterocyclic ligands, and the resulting complexes have higher thermal stability.
  • the metal compound has a general structural formula represented by formula (I) or formula (II):
  • M represents a transition metal atom.
  • R 1 and R 2 are independently selected from alkyl groups, and R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups; in formula (II), R 1 ' , R 2 ' is independently selected from an alkyl group, R' is independently selected from a monoamine ligand having one nitrogen atom, and the nitrogen atom in R' is coordinated with the M atom.
  • the embodiments of the present application also provide a method for preparing a metal compound, which includes the following steps:
  • a coordination compound composed of a transition metal atom and at least one ⁇ -diketone ligand Take a coordination compound composed of a transition metal atom and at least one ⁇ -diketone ligand, perform a coordination reaction with a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent to obtain a reaction liquid, Remove the organic solvent in the reaction solution to obtain a metal compound;
  • the transition metal atom in the metal compound is coordinated with at least one oxygen atom in the ⁇ -diketone ligand, and coordinated with two nitrogen atoms in one of the diamine ligands or with Two nitrogen atoms in the two monoamine ligands are coordinated.
  • the preparation method of the above-mentioned metal compound has simple process, easy operation, low cost, and the obtained metal compound has high structural stability.
  • “carrying out a coordination reaction between a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent” specifically includes:
  • the second solution is added dropwise to the first solution, and the coordination reaction is performed under stirring conditions.
  • the above-mentioned feeding method is more conducive to the diamine ligand or monoamine ligand being able to fully coordinate with the transition metal atoms in the six-coordination compound.
  • the second aspect of the embodiments of this application provides the application of the metal compound described in the first aspect of the embodiments of this application in preparing a thin film containing a transition metal element.
  • the above-mentioned metal compounds can serve as sources of transition metal elements. They have low melting points, good volatility, and good thermal stability. Films containing transition metal elements can be deposited by CVD or ALD. .
  • the third aspect of the embodiments of this application provides the application of the metal compound described in the first aspect of the embodiments of this application in preparing electronic devices. Specifically, the above-mentioned metal compounds are used to prepare films containing transition metal elements in electronic devices.
  • the fourth aspect of the embodiments of the present application provides a thin film containing a transition metal element, which is prepared by using the metal compound described in the first aspect of the embodiments of the present application.
  • the thin film containing transition metal elements can be prepared by using the above-mentioned metal compound as a transition metal source through a vapor deposition method such as CVD or ALD.
  • the prepared thin film containing transition metal elements has good morphology and controllable thickness.
  • the fifth aspect of the embodiments of the present application provides an electronic device, which has a transition metal element-containing film as described in the fourth aspect of the embodiments of the present application.
  • Films containing transition metal elements have good morphology, controllable thickness, and good quality, which are beneficial to ensuring the stable and long-lasting operation of electronic devices.
  • the sixth aspect of the embodiment of the present application provides a device for preparing a thin film containing a transition metal element.
  • the device includes a connected container chamber and a deposition chamber.
  • the container chamber is used to store as described in the first aspect of the embodiment of the present application.
  • the metal compound has a substrate placed in the deposition chamber, the metal compound can be transported into the deposition chamber, and deposited on the surface of the substrate to form a thin film containing transition metal elements. Wherein, the metal compound can be transported into the deposition chamber in gaseous form.
  • This device can be used to produce the aforementioned films containing transition metal elements with good quality.
  • the seventh aspect of the embodiment of the present application provides a method for depositing a thin film containing a transition metal element, including the following steps:
  • the vaporized metal compound described in the first aspect of the embodiment of the present application is introduced into a deposition chamber in which a substrate is placed in a deposition device, so as to deposit and form a thin film containing a transition metal element on the surface of the substrate.
  • the deposition method further includes: introducing reactant species into the deposition chamber.
  • the reactant species can be selected according to the material of the film containing transition metal elements to be prepared. It can be a source of a certain constituent element of the film, or other gases required for the deposition reaction.
  • the reactant species can be a gaseous reagent itself, or a vapor of a liquid reagent.
  • the film containing transition metal elements also contains oxygen elements; the reactant species includes an oxygen source, and the oxygen source includes one of oxygen, ozone, H 2 O, and H 2 O 2 or more.
  • the film containing transition metal elements formed can be a metal oxide film, which usually has a high dielectric constant and has good application scenarios in electronic devices.
  • the reaction activity between the aforementioned oxygen source and the aforementioned metal compound is high, and the introduction of impurities can be minimized.
  • the deposition method further includes: introducing other metal sources into the deposition chamber, wherein the other metal sources include metal elements different from the transition metal elements of the metal compound.
  • the metal elements here may include transition metal elements, main group metal elements, etc.
  • the deposition is specifically a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. These two vapor deposition technologies can better control the deposition thickness and morphology of films containing transition metal elements.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • Figure 1 is a schematic diagram of a common structure of CVD or ALD deposition equipment.
  • Figure 2 is the nuclear magnetic resonance spectrum of the lanthanum-containing compound La(thd) 3 (DMEDA) in Example 1 of the present application.
  • FIG 3 shows the thermogravimetric analysis (TG) curve and differential scanning calorimetry (DSC) curve of the lanthanum-containing compound La(thd) 3 (DMEDA) in Example 1 of the present application.
  • Figure 4 is a graph of the saturated vapor pressure versus temperature of the lanthanum-containing compound La(thd) 3 (DMEDA) in Example 1 of the present application.
  • Figure 5 is a characteristic data diagram of a La 2 O 3 film deposited by ALD using La(thd) 3 (DMEDA) as raw material.
  • Figure 6 is a scanning electron microscope photograph of a section of a La 2 O 3 film produced by the ALD method using La(thd) 3 (DMEDA).
  • Figure 7 is the XRD pattern of a La 2 O 3 film prepared by the ALD method using La(thd) 3 (DMEDA).
  • Figure 8 is the nuclear magnetic resonance spectrum of the lanthanum-containing compound La(ibpm) 3 (DMEDA) in Example 2 of the present application.
  • Figure 9 is a TG-DSC curve chart of the lanthanum-containing compound La(ibpm) 3 (DMEDA) in Example 2 of the present application.
  • Figure 10 is a graph of the saturated vapor pressure versus temperature of the lanthanum-containing compound La(ibpm) 3 (DMEDA) in Example 2 of the present application.
  • Figure 11 is the NMR spectrum of the lanthanum-containing compound La(tmod) 3 (DMEDA) in Example 3 of the present application.
  • Figure 12 is a TG-DSC curve chart of the lanthanum-containing compound La(tmod) 3 (DMEDA) in Example 3 of the present application.
  • Figure 13 is a graph of the saturated vapor pressure versus temperature of the lanthanum-containing compound La(tmod) 3 (DMEDA) in Example 3 of the present application.
  • Figure 14 is the nuclear magnetic resonance spectrum of the lanthanum-containing compound La(thd) 3 (Py) 2 in Example 4 of the present application.
  • Figure 15 is a TG-DSC curve chart of the lanthanum-containing compound La(thd) 3 (Py) 2 in Example 4 of the present application.
  • Figure 16 is the nuclear magnetic resonance spectrum of the lanthanum-containing compound La(thd) 3 (DPA) 2 in Example 5 of the present application.
  • Figure 17 is a TG-DSC curve chart of the lanthanum-containing compound La(thd) 3 (DPA) 2 in Example 5 of the present application.
  • FIG. 1 is a schematic diagram of a common structure of CVD or ALD deposition equipment.
  • the deposition equipment 100 includes a container chamber 10 for storing precursor materials for thin film deposition and a deposition chamber 20 for realizing a thin film deposition reaction.
  • the container chamber 10 and the deposition chamber 20 are connected through pipelines.
  • the container room 10 mainly houses storage containers 11 (usually stainless steel cylinders) that store each precursor material.
  • the precursor materials stored in each storage container 11 can be gasified and passed through the transportation pipeline (the pipeline can be equipped with a valve) Transported to deposition chamber 20.
  • the substrate 21 is placed in the deposition chamber 20, and a heating component 22 can be provided outside the deposition chamber 20 to control the temperature of the deposition chamber 20 to reach the reaction temperature of the precursor.
  • the precursor material should have a low melting point and good volatility so that it can be smoothly vaporized and transported from the container chamber 10 to the deposition chamber 20 (the vaporization can be achieved by controlling the heating temperature of the storage container 11 and the transportation pipeline), to avoid Due to changes in pipeline temperature, the precursor condenses and causes pipeline pollution; the precursor material should also have a certain thermal stability to ensure its stability during transportation from the container chamber 10 to the deposition chamber 20 and to minimize its The phenomenon of uneven film deposition on the surface of the substrate caused by thermal decomposition.
  • the precursor material should not corrode the base material 21 , for example, it is best not to contain halogen elements that corrode metals.
  • the CVD deposition process usually includes the following steps: after the vaporized precursor material is transported to the deposition chamber 20, it diffuses to the surface of the substrate 21 and is adsorbed on the surface of the substrate, and the precursor undergoes a chemical reaction on the surface of the substrate (usually (Assisted by heat, plasma or electric field) deposition to form a thin film, the reaction byproducts are desorbed from the surface of the substrate 21 and are eliminated from the deposition chamber 20 .
  • ALD alternately introduces a variety of precursor materials (usually two types, as shown in Figure 1) through cycles, and uses inert gases (such as argon, nitrogen, etc.) in the gap between different types of precursors entering the deposition chamber 20.
  • the purge takes away excess precursor, thereby achieving atomic layer deposition with self-limiting characteristics (that is, the thickness of the film deposited in each cycle is atomic level). Continuous deposition of multiple atomic layer thicknesses can be achieved through multiple cycles.
  • the ALD deposition process does not allow thermal decomposition reactions of precursor materials to avoid uncontrollable changes in deposition speed and film thickness, and only allows self-limiting chemical reactions to occur on the surface of the substrate. Due to the difference in working mechanism between the CVD technology and the ALD technology, the precursor material is allowed to undergo a certain decomposition reaction in the deposition chamber 20 without affecting the film deposition quality.
  • the metal compound provided by the embodiments of the present application includes a transition metal atom and at least one ⁇ -diketone ligand coordinated with the transition metal atom, and also includes a diamine ligand coordinated with the transition metal atom. Or two monoamine ligands, wherein the transition metal atom is coordinated with two oxygen atoms in the ⁇ -diketone ligand and coordinated with two nitrogen atoms in the diamine ligand. or coordinate with the nitrogen atom in the monoamine ligand.
  • the ⁇ -diketone ligand achieves strong binding with the transition metal atom through the O atom derived from the ketone group, and at the same time, the monofunctional amine (i.e., monoamine) or the difunctional amine ( That is, diamine) interacts with transition gold by virtue of the slightly weaker binding force between N atoms and transition metal atoms (the binding force is weaker than the binding force between O atoms and transition metal atoms).
  • the metal atoms are combined, and the binding steric hindrance between each ligand and the transition metal atom will not be too large to easily detach.
  • the overall compound not only have a certain structural stability, but also has a lower melting point and good volatility, making it suitable for use as a precursor material for CVD or ALD deposition reactions.
  • the metal compound provided by this application does not contain halogen atoms, its volatilization or thermal decomposition products are non-corrosive, and the preparation cost is low.
  • transition metal atoms may include atoms of all transition metal elements in the periodic table of elements.
  • the transition metal atoms may include but are not limited to lanthanide elements, yttrium (Y), scandium (Sc) ), hafnium (Hf), titanium (Ti), vanadium (V), zirconium (Zr), chromium (Cr), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni ), ruthenium (Ru), zinc (Zn), copper (Cu), palladium (Pd), platinum (Pt), iridium (Ir), rhenium (Re), osmium (Os), tantalum (Ta), rhodium (Rh) ) or niobium (Nb), etc.
  • lanthanide elements can include 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).
  • the transition metal atoms are lanthanide elements (such as La, Ce, Pr, etc.), Y, Sc, Ta, Zr, Hf, etc.
  • the metal compound includes three ⁇ -diketone ligands.
  • the coordination number of the central transition atom is 8, which is close to but not in an electron saturated state.
  • the metal compound has a lower melting point, better volatility, and higher structural stability.
  • the transition metal elements are lanthanide elements (such as La, Ce, Pr, etc.), Y, Sc, Ta, Zr, Hf, etc.
  • the alkyl group here may be a substituted or unsubstituted alkyl group, wherein the substituted alkyl group may be an alkoxy-substituted alkyl group, etc.
  • the alkyl group may be a straight chain or branched chain alkyl group, and the number of carbon atoms of the alkyl group may be 1-10, further may be 1-6, and is preferably 1-4.
  • the alkyl group may be methyl, ethyl, propyl, isobutyl, tert-butyl, etc.
  • diamine ligands include dibasic alkyl amines, dibasic aryl amines, dibasic cycloalkyl amines, etc.
  • the diamine ligand includes dibasic alkylamine. Compared with dibasic arylamines and cycloalkylamines, dibasic alkylamines have less resistance when coordinating with transition metal atoms, and they are not easily separated from the above-mentioned metal compounds, thus ensuring good thermal stability of the metal compounds. .
  • the general formula of the dibasic alkylamine is N(R 3 )(R 4 )-C(R 7 )-C(R 8 )-N(R 5 )(R 6 ) , wherein R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups, and at least one of R 3 , R 4 , R 5 , and R 6 is an alkyl group (that is, R 3 , R 4 , R 5 , R 6 are not hydrogen atoms at the same time).
  • the alkyl group here can be a straight chain or branched chain alkyl group, and the number of carbon atoms of the alkyl group can be 1-10, further can be 1-6, preferably 1-4.
  • the alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc.
  • H atoms may include 1 H atoms (also known as “protium atoms”), 2 H atoms (also known as “deuterium atoms”), and 3 H atoms (also known as "tritium atoms").
  • the monoamine ligand includes a monoalkylamine containing one nitrogen atom or a nitrogen heterocyclic ligand.
  • monoalkyl amines have less steric hindrance in binding to transition metal atoms than nitrogen heterocyclic ligands.
  • the general structural formula of the monoalkyl amine can be expressed as N(R 3 ') (R 4 ') (R 5 '), where, R 3 ', R 4 ', R 5 ' are independently selected from hydrogen atoms and alkyl groups, and at least one of R 3 ', R 4 ', and R 5 ' is an alkyl group.
  • Chain-like monoalkyl amines have less resistance when coordinating with transition metal atoms, and are less likely to lose their coordination relationship with transition metal atoms in metal compounds, thus ensuring good thermal stability of metal compounds.
  • the alkyl group here may be a straight chain or branched chain alkyl group, and the number of carbon atoms of the alkyl group may be 1-10, further may be 1-6, preferably 1-4.
  • the alkyl group may be methyl, ethyl, propyl, isobutyl, tert-butyl, etc.
  • nitrogen heterocyclic ligand refers to a substance whose ring heteroatom is an N atom.
  • the nitrogen heterocyclic ligand may include pyridine, piperidine, pyrrole or derivatives thereof. Compared with other nitrogen heterocyclic compounds, these types of substances have low molecular weight and relatively small steric hindrance, and are easier to coordinate with transition metal atoms to form complexes.
  • pyridine, piperidine, Derivatives of pyrrole may include pyridine, piperidine, substituted by an alkyl group with 1 to 6 carbon atoms (such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl). Pyrrole etc.
  • the metal compound has a general structural formula represented by formula (I) or formula (II):
  • M represents a transition metal atom.
  • R 1 and R 2 are independently selected from alkyl groups, and R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups; in formula (II), R 1 ' , R 2 ' is independently selected from an alkyl group, R' is independently selected from a monoamine ligand having one nitrogen atom, and the nitrogen atom in R' is coordinated with the transition metal atom M.
  • R 1 to R 8 For the selection range of R 1 to R 8 , please refer to the previous description of this application.
  • the selection range of R 1 ' and R 2 ' can also refer to the previous description of R 1 and R 2 .
  • R' may be the same or different monoamine ligands.
  • R' is independently selected from monoalkyl amine or nitrogen heterocyclic ligand. The selection range of the monoalkyl amine or nitrogen heterocyclic ligand can be found in the previous description of this application and will not be described again here.
  • the metal compound is a lanthanum complex, which may specifically include any one of the following substances:
  • the embodiments of the present application also provide a method for preparing a metal compound, which includes the following steps:
  • a coordination compound composed of a transition metal atom and at least one ⁇ -diketone ligand perform a coordination reaction with a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent to obtain a reaction liquid, Remove the organic solvent in the reaction solution to obtain a metal compound; wherein the transition metal atom in the metal compound is coordinated with an oxygen atom in at least one ⁇ -diketone ligand, and is coordinated with a diamine ligand Coordinated with two nitrogen atoms in or coordinated with two nitrogen atoms in two monoamine ligands.
  • “carrying out a coordination reaction between a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent” specifically includes:
  • the above-mentioned feeding method is more conducive to the diamine ligand or monoamine ligand being able to fully coordinate with the transition metal atoms in the above-mentioned coordination compound.
  • "dropping the second solution into the first solution” can be performed at room temperature.
  • the stirring rate of the stirring condition may be 200-1000 rpm.
  • the coordination reaction can be carried out for 1-4 hours, for example, 2-4 hours.
  • the organic solvent can dissolve monoamine or diamine ligands, and the organic solvent includes but is not limited to one or more of toluene, tetrahydrofuran, chloroform, n-hexane, etc.
  • the organic solvent is toluene.
  • the solubility of the coordination compound composed of the transition metal atom and the ⁇ -diketone ligand, the diamine or the monoamine ligand is relatively high in toluene.
  • the diamine ligand or monoamine ligand and the coordination compound can also be directly dispersed in an organic solvent to perform the coordination reaction.
  • the preparation method of the above-mentioned metal compound has simple process, easy operation, low cost, and the obtained metal compound has high structural stability.
  • the embodiments of the present application also provide the application of the above-mentioned metal compounds in preparing films containing transition metal elements.
  • the material of the thin film containing transition metal elements may be a compound containing transition metal elements (such as metal oxide, nitride, carbide, carbonitride, etc.) or a simple substance.
  • the metal oxide can be a monovalent oxide containing a transition metal element, or a multi-element metal oxide.
  • the metal oxide may contain one or more metal elements, such as one or more transition metal elements.
  • the compound containing a transition metal element when it is a La-containing oxide, it may specifically be lanthanum oxide (La 2 O 3 ), a lanthanum-containing binary or multi-element metal oxide (such as lanthanum-hafnium oxide, Lanthanum zirconium oxide, lanthanum aluminum oxide, lanthanum cerium oxide, lanthanum yttrium oxide, lanthanum tantalum oxide, lanthanum lutetium oxide, lanthanum strontium oxide, etc.).
  • lanthanum oxide La 2 O 3
  • a lanthanum-containing binary or multi-element metal oxide such as lanthanum-hafnium oxide, Lanthanum zirconium oxide, lanthanum aluminum oxide, lanthanum cerium oxide, lanthanum yttrium oxide, lanthanum tantalum oxide, lanthanum lutetium oxide, lanthanum strontium oxide, etc.
  • the raw materials required to prepare a La 2 O 3 thin film by vapor deposition include the aforementioned metal compound whose central atom is a La atom, and an oxygen source; when preparing a binary or lanthanum-containing
  • the required raw materials also include precursors corresponding to other metal elements. Specifically, they can be the aforementioned metal compounds whose central atom is not La, or any metal precursor known or later developed.
  • the oxygen source may include one or more of oxygen (O 2 ), ozone (O 3 ), water vapor (H 2 O), and hydrogen peroxide (H 2 O 2 ). These oxygen sources have high reactivity with the above-mentioned metal compounds and can minimize the introduction of impurities.
  • the oxygen source is ozone.
  • the above metal compound is prepared by a vapor deposition method to obtain a thin film containing transition metal elements.
  • the vapor deposition method may specifically be chemical vapor deposition (CVD) or atomic layer deposition (ALD).
  • the CVD can be conventional CVD or a modified vapor deposition process, such as plasma enhanced CVD (PEVCD), low pressure CVD (LPVCD), atmospheric pressure CVD (APVCD), pulse CVD (P-CVD), hot wire CVD (HWVCD) , the energy source in the hot wire charging deposition process).
  • ALD can be conventional ALD or its modified vapor deposition process, such as plasma enhanced ALD (PEALD), spatial ALD, thermal ALD (Thermal ALD), etc.
  • the above-mentioned metal compounds can be used as raw materials to provide transition metal elements.
  • the above-mentioned metal compounds have a low melting point, are easier to volatilize and vaporize, and can smoothly reach the substrate to be deposited. Surface, and little thermal decomposition occurs before it reaches the substrate, especially when deposited using the ALD method. This ensures that the thickness of the film containing transition metal elements is accurately controllable, the film quality is high, and the conformality is good.
  • the embodiments of the present application also provide applications of the above metal compounds in preparing electronic devices.
  • the above-mentioned metal compounds can be used to prepare films containing transition metal elements in electronic devices.
  • the electronic device may in particular be a semiconductor device.
  • the produced electronic device usually includes a substrate and a thin film containing a transition metal element located on the substrate.
  • the film containing transition metal elements can be produced by the CVD method or the ALD method using the above metal compounds.
  • the film containing transition metal elements can be an oxide, nitride, carbide or carbonitride containing transition metal elements, etc. .
  • the substrate can It is not just a simple substrate, such as silicon, quartz, SiC, SiGe, GaAs, GaN, sapphire, etc., but also a substrate with films of other materials on the surface.
  • the above-mentioned metal compound is used as a transition metal source to prepare a film containing a transition metal element in an electronic device.
  • the metal compound has a low melting point, is easier to vaporize, can smoothly reach the surface of the substrate to be deposited, and has high reactivity in the vapor deposition reaction. High, the morphology and deposition thickness of the produced film can be precisely controlled, and the quality is good, which is conducive to ensuring the stable and long-lasting operation of electronic devices.
  • the ALD method when used to prepare a film containing transition metal elements, it rarely thermally decomposes before reaching the substrate.
  • the thickness of the film is accurately controllable and has high conformality and uniformity.
  • the embodiments of the present application also provide a thin film containing transition metal elements, which is prepared by using the metal compound mentioned above in the embodiments of the present application.
  • a thin film containing transition metal elements which is prepared by using the metal compound mentioned above in the embodiments of the present application.
  • specific preparation methods please refer to the description below in this application.
  • the device used to prepare the thin film containing transition metal elements is first introduced.
  • the device for preparing a thin film containing a transition metal element may include a connected container chamber and a deposition chamber.
  • the container chamber is used to store the metal compound described in the embodiment of the present application.
  • a substrate is placed in the deposition chamber.
  • the metal compound can be transported into the deposition chamber and deposited on the surface of the substrate to form a thin film containing transition metal elements.
  • the above-mentioned device may specifically be a CVD deposition device or an ALD deposition device.
  • a CVD deposition device or an ALD deposition device.
  • ALD deposition device Regarding the specific structure of the device, reference may be made to the introduction of Figure 1 throughout this application.
  • the container chamber 10 of the device can be placed with at least one storage container 11, and the metal compound mentioned in the embodiment of the present application can be placed in the corresponding storage container 11.
  • a heating device (not shown in FIG. 1 ) may be provided on the outside of each storage container 11 for heating the storage container so that the metal compound is transported into the deposition chamber 20 in a gaseous form.
  • Each transport pipeline connecting each storage container 11 and the deposition chamber 20 may be provided with a valve.
  • a heating component 22 is provided outside the deposition chamber 20 for making the temperature in the deposition chamber 20 reach the deposition reaction temperature.
  • the above device can be used to prepare the aforementioned thin film containing transition metal elements with good quality.
  • the deposition method of a thin film containing transition metal elements includes the following steps:
  • the gasified metal compound is introduced into a deposition chamber in which the substrate is placed in the deposition equipment to deposit a thin film containing a transition metal element on the surface of the substrate.
  • the substrate on which the transition metal element-containing film is to be deposited can be determined according to the intended end use.
  • the substrate may include, but is not limited to, silicon (Si), quartz (SiO 2 ), SiC, SiGe, GaAs, GaN, sapphire, glass, plastic, metal or the aforementioned substrate with a thin film of other materials on the surface. Materials etc.
  • other material films on the substrate can be metal layers (such as Pd, Pt, Au, Al, W, Ti, etc.), nitrides (such as TaN, TiN, TiSN, Si 3 N 4 , etc.), Oxides (such as SiO 2 , SiON, HfO 2 , ZrO 2 , Al 2 O 3 , etc.) or combinations thereof, etc.
  • metal layers such as Pd, Pt, Au, Al, W, Ti, etc.
  • nitrides such as TaN, TiN, TiSN, Si 3 N 4 , etc.
  • Oxides such as SiO 2 , SiON, HfO 2 , ZrO 2 , Al 2 O 3 , etc.
  • the substrate 21 in the deposition chamber 20 can be heated to a sufficient temperature so that the vaporized metal compound can react on its surface to obtain the desired transition metal element-containing film.
  • the temperature in the deposition chamber 20 should be greater than the vaporization temperature of the aforementioned metal compound.
  • the stability of the metal compound material during transportation from the container chamber 10 to the deposition chamber 20 should be ensured to avoid the occurrence of accidents during transportation. condensation.
  • the temperature in the deposition chamber should be lower than the decomposition temperature of the metal compound. In this way, the problem of uneven film deposition caused by thermal decomposition of the metal compound can be avoided on the premise of reaching the reaction temperature of the above-mentioned metal compound.
  • the above-mentioned metal compound may be introduced above the substrate 21 in the form of vapor, and the vapor may be formed by solid or liquid metal compound, for example, by sublimation or evaporation thereof.
  • a solid metal compound can be heated to reach a liquidus temperature and have a sufficient vapor pressure temperature to vaporize.
  • a carrier gas such as argon, helium, nitrogen, etc.
  • a metal compound and an organic solvent can be mixed to form a solution, and then the solution can be heated and vaporized to allow the metal compound to enter the deposition chamber 20 , and a carrier gas can also be blown into the solution.
  • the above-mentioned deposition method further includes: introducing reactant species into the deposition chamber.
  • the reactant species may be a source of a certain element of the thin film to be prepared (such as oxygen), or other gases required for the deposition reaction.
  • the reactant species may be a gaseous reagent or a vapor of a liquid reagent.
  • the above-mentioned reactant species may be a reducing gas, such as hydrogen (H 2 ).
  • the above-mentioned deposition chamber 20 may be equipped with a hydrogen generator to generate hydrogen gas.
  • the film containing a transition metal element when the film containing a transition metal element also contains an oxygen (O) element, the film containing a transition metal element may be specifically a metal oxide (such as La 2 O 3 ).
  • the above reactant species may include an oxygen source, which may be one or more of O 2 , O 3 , H 2 O, H 2 O 2, etc.
  • the oxygen source is ozone ( O3 ).
  • the above-described deposition chamber 20 may be equipped with an isozone generator for generating ozone.
  • the above-mentioned reactant species may include a nitrogen source
  • the nitrogen source may include, but is not limited to, one or more of nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), and the like.
  • the above-mentioned reactant species may include a carbon source.
  • the carbon source may include, but is not limited to, one or more of methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), propylene (C 3 H 6 ), and the like.
  • the deposition method for forming a thin film containing transition metal elements may be a CVD method.
  • the reactant species may be introduced into the deposition chamber 20 where the substrate 21 is placed together with the aforementioned metal compound.
  • the deposition method for forming a thin film containing transition metal elements may be the ALD method.
  • the reactant species and the aforementioned metal compound are alternately introduced into the deposition chamber 20 where the substrate 21 is placed, so that the reactant species and the metal compound alternate. Exposed to substrate 21.
  • the aforementioned metal compound whose central atom is a lanthanum atom (referred to as La complex) and an oxygen source can be first placed in different storage containers 11 of the container chamber 10 of the deposition equipment 100 in Figure 1 , heating the storage container 11 can achieve their respective gasification.
  • the vaporized La complex and the oxygen source can be transported to the deposition chamber 20 of the deposition equipment 100 together.
  • the vaporized La complex and the gaseous oxygen source or oxygen source vapor are alternately transported to the deposition chamber 20 of the deposition equipment 100 .
  • the vaporized La complex can be first introduced into the deposition chamber 20, and then the excess complex that is not adsorbed on the surface of the substrate 21 can be taken away by purging with inert gas, and then the gaseous oxygen source can be introduced into the deposition chamber.
  • the La complex adsorbed on the substrate reacts with the oxygen source diffused to the surface of the substrate (the ALD process relies on a self-limiting saturated surface reaction), and then the surface of the substrate 21 is taken away by purging with inert gas.
  • the redundant oxygen source is thus a cycle; the above cycle is repeated multiple times to achieve self-limiting atomic layer deposition on the surface of the substrate 21 .
  • the surface-controlled nature of the ALD process enables the growth of La2O3 films with high conformality and uniformity through precise thickness control.
  • the above-mentioned deposition method further includes: introducing other metal sources into the deposition chamber 20 in which the substrate 21 is placed.
  • the thin film containing transition metal elements to be prepared may contain two metal elements (for ease of understanding, transition metal elements can also be regarded as within the broad range of metal elements).
  • other metal sources may contain metal elements different from the transition metal atoms in the above-mentioned metal compounds, such as other transition metal atoms, main group metal atoms, etc.; the other metal sources may be one or more.
  • the required metal source includes, in addition to the aforementioned metal compound whose central atom is a lanthanum atom, also includes corresponding precursors of other metal elements.
  • Other metal sources may still be metal compounds defined previously in this application, or existing metal complexes well known in the art.
  • Other metal sources can be introduced into the deposition chamber together with the aforementioned metal compounds, e.g.
  • metal sources can be mixed with the aforementioned metal compounds to be vaporized before being introduced into the deposition chamber.
  • other metal sources can also be introduced into the deposition chamber alternately with the aforementioned metal compounds.
  • the metal compound of lanthanum mentioned above in this application be recorded as raw material A
  • the precursor of hafnium as raw material B and ozone as raw material C.
  • A can be used first and then B.
  • the latter C method makes them alternately exposed to the surface of the substrate 21, and are purged by inert gas in the gap between different raw materials entering the deposition chamber.
  • the embodiments of the present application also provide a thin film containing transition metal elements, which is prepared by using the metal compound mentioned above in the embodiments of the present application.
  • the reaction raw materials used in addition to the above-mentioned metal compounds, may also include the above-mentioned reactant species, other metal sources, etc.
  • the prepared thin film containing transition metal elements is as described previously in this application and will not be described again here.
  • An embodiment of the present application also provides an electronic device, which has the transition metal element-containing film described in the embodiment of the present application.
  • the electronic device includes a substrate and a film containing transition metal elements located on the substrate.
  • the substrate and the film containing transition metal elements please refer to the previous description of this application.
  • a lanthanum-containing compound La(thd) 3 (DMEDA), where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and DMEDA represents N,N'dimethylethylenedione amine.
  • the synthesis route of the lanthanum-containing compound is as follows:
  • the preparation method of the above-mentioned lanthanum-containing compound includes: weighing 41.3g of the six-coordinate compound La(thd) 3 of lanthanum (Chinese name: tris(2,2,6,6-tetramethyl-3,5-heptanedi) Ketone) Lanthanum (III)) was placed in a 1L flask, 500 mL of toluene was added and stirred to obtain a white turbid La(thd) 3 dispersion. Weigh 5.3g of N,N' dimethylethylenediamine (DMEDA) into another 100mL beaker, add 50mL of toluene, stir and dissolve, and obtain a DMEDA solution.
  • DMEDA N,N' dimethylethylenediamine
  • the nuclear magnetic resonance spectrum of the above-mentioned lanthanum-containing compound La(thd) 3 is shown in Figure 2.
  • These nuclear magnetic resonance results show that the present application successfully prepared the lanthanum-containing compound with the general structural formula shown above.
  • thermogravimetric analysis (TG or TGA) curve and differential scanning calorimetry (DSC) curve were as follows: As shown in Figure 3, the saturated vapor pressure versus temperature curve of the lanthanum-containing compound is shown in Figure 4. It can be known from Figures 3 and 4 that the lanthanum-containing compound has a low melting point (about 135°C) and high thermal stability (decomposition temperature >300°C). In phase The lower the volatilization temperature of the material under the same vapor pressure, the better the volatility of the material.
  • the volatilization temperature of the lanthanum-containing compound in Example 1 at a saturated vapor pressure of 0.1 Torr is 130°C, which is lower than that of La(thd) 3 at 0.1
  • the volatilization temperature under torr indicates that the lanthanum-containing compound has good volatility.
  • the lanthanum-containing compound La(thd) 3 (DMEDA) is used to deposit La 2 O 3 thin films: La(thd) 3 (DMEDA) is used as the lanthanum precursor material, ozone O 3 is used as the oxidant, and quartz (SiO 2 ) is used The sheet is used as the substrate, and a La 2 O 3 film is deposited on the substrate by the ALD method, wherein the evaporation temperature of the lanthanum-containing compound is controlled to 150°C (that is, a container containing the lanthanum-containing compound is placed in the container chamber 10 of Figure 1 The storage container 11 is heated to 150°C to vaporize it), and the temperature of the connecting pipeline between the container chamber 10 and the deposition chamber 20 is controlled to 170°C to ensure that the lanthanum-containing compound is transported to the deposition chamber 20 Will not condense.
  • the lanthanum-containing compound and O 3 are circulated and alternately introduced into the deposition chamber 20 , and excess precursor raw materials are
  • the relevant data of the deposited La 2 O 3 film is shown in Figure 5. It can be known from the four small figures (a)-(d) in Figure 5 that the La 2 O 3 film obtained by ALD deposition using La(thd) 3 (DMEDA) as raw material conforms to the ALD deposition characteristics, where La(thd ) 3 (DMEDA) saturation pulse time is 7s, O 3 saturation pulse time is 90s, ALD temperature window is 210-250°C, the thickness of La 2 O 3 film increases linearly with the number of cycles, calculated La 2 O 3 The film formation rate is
  • the slice scanning electron microscope (SEM) photos and XRD patterns of the La 2 O 3 thin film produced by the ALD method using La(thd) 3 (DMEDA) are shown in Figure 6 and Figure 7 respectively. It can be seen from Figure 6 that a continuous and uniform La 2 O 3 film can be deposited using La(thd) 3 (DMEDA). According to the aforementioned film formation rate of the La 2 O 3 film is It can be calculated that a La 2 O 3 film with a thickness of 23.8 nm corresponds to approximately 529 deposition cycles. It can be seen from Figure 7 that the deposited La 2 O 3 film is specifically h-La 2 O 3 in the hexagonal phase. The sharp diffraction peak of the (101) crystal plane of h-La 2 O 3 can be seen in the figure.
  • a lanthanum-containing compound La(ibpm) 3 (DMEDA), where ibpm represents 2,2,6-trimethyl-3,5-heptanedione and DMEDA represents N,N'dimethylethylenediamine.
  • the synthesis route of the lanthanum-containing compound is as follows:
  • the preparation method of the above-mentioned lanthanum-containing compound includes: weighing 48.5g of the six-coordinated lanthanum complex La(ibpm) 3 (Chinese name: tris(2,2,6-trimethyl-3,5-heptanedione) ) Lanthanum (III)) was placed in a 1L flask, 500 mL of toluene was added and stirred to obtain a white turbid La(ibpm) 3 dispersion. Weigh 8.5g of N,N'dimethylethylenediamine (DMEDA) into another 100mL beaker, add 50mL of toluene, stir and dissolve, and obtain a DMEDA solution.
  • DMEDA N,N'dimethylethylenediamine
  • the thermal properties of the above lanthanum-containing compound La(ibpm) 3 (DMEDA) were analyzed, and the obtained TG-DSC curve is shown in Figure 9.
  • the saturated vapor pressure versus temperature curve of the lanthanum-containing compound is shown in Figure 10. It can be seen from Figures 9 and 10 that the lanthanum-containing compound La(ibpm) 3 (DMEDA) has a low melting point (about 57°C), high thermal stability (decomposition temperature >300°C), and good volatility. It is at 0.1Torr The volatilization temperature under saturated vapor pressure is 116°C. Therefore, the lanthanum-containing compound La(ibpm) 3 (DMEDA) is suitable for depositing a thin film containing lanthanum element by ALD method or CVD method.
  • a lanthanum-containing compound La(tmod) 3 (DMEDA), where tmod represents 2,2,6,6-tetramethyl-3,5-octanedione and DMEDA represents N,N'dimethylethylenedione amine.
  • the preparation method of the above-mentioned lanthanum-containing compound includes: weighing 50g of the six-coordinated lanthanum complex La(tmod) 3 (Chinese name: tris(2,2,6,6-tetramethyl-3,5-octanedi) Ketone) Lanthanum (III)) was placed in a 1L flask, 500 mL of toluene was added and stirred to obtain a white turbid La(tmod) 3 dispersion. Weigh 8.8g of N,N'dimethylethylenediamine (DMEDA) into another 100mL beaker, add 50mL of toluene, stir and dissolve, and obtain a DMEDA solution.
  • DMEDA N,N'dimethylethylenediamine
  • the synthesis route of the lanthanum-containing compound is as follows:
  • the nuclear magnetic resonance spectrum of the above-mentioned lanthanum-containing compound La(tmod) 3 is shown in Figure 11.
  • These NMR results show that the present application successfully prepared the lanthanum-containing compound La(tmod) 3 (DMEDA) with the general structural formula shown above.
  • the thermal properties of the above-mentioned lanthanum-containing compound La(tmod) 3 (DMEDA) were analyzed, and the obtained TG-DSC curve is shown in Figure 12.
  • the saturated vapor pressure versus temperature curve of the lanthanum-containing compound is shown in Figure 13. It can be seen from the TG curve in Figure 12 that the T50 of the lanthanum-containing compound La(tmod) 3 (DMEDA) is 266°C, the volatilization end temperature is 286.6°C, and the residual amount is 1.35%, indicating that the compound has good volatility and high thermal stability. , and its thermal decomposition temperature is >300°C.
  • the DSC curve in Figure 12 shows that the peak at 74°C represents the crystal form transformation of the compound La(tmod) 3 (DMEDA), and the endothermic peak at 166°C represents the melting of the compound.
  • the volatilization temperature of La(tmod) 3 (DMEDA) at a saturated vapor pressure of 0.1 Torr is 154°C, indicating good volatility. Therefore, the lanthanum-containing compound La(tmod) 3 (DMEDA) is suitable for depositing lanthanum-containing thin films by ALD or CVD.
  • a lanthanum-containing compound La(thd) 3 (Py) 2 , where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and Py represents pyridine.
  • the synthesis route of the lanthanum-containing compound is as follows:
  • the preparation method of the above-mentioned lanthanum-containing compound includes: weighing 13.8g of La(thd) 3 and placing it in a 1L flask, adding 100mL of toluene, and adding dropwise a mixed solution of 1.8g of pyridine and 5mL of toluene. Heat and reflux at 120°C for 3 hours to carry out coordination reaction. After that, after the temperature of the flask returned to room temperature, the volatile matter in the reaction solution was removed under reduced pressure to obtain light yellow powder La(thd) 3 (Py) 2 .
  • the thermal properties of the above lanthanum-containing compound La(thd) 3 (Py) 2 were analyzed, and the obtained TG-DSC curve is shown in Figure 15. It can be seen from Figure 12 that the TG curve of La(thd) 3 (Py) 2 has two steps before 300°C. Among them, the weight loss of about 16% before 100°C corresponds to the shedding of the neutral ligand pyridine, indicating that pyridine and The binding force of lanthanum atoms is slightly weaker, and the thermal stability of the lanthanum-containing compound is slightly lower than that of the lanthanum-containing compound of Examples 1-3. Therefore, the lanthanum-containing compound La(thd) 3 (Py) 2 is suitable for depositing a lanthanum-containing compound film or a lanthanum elemental film through CVD method (less suitable for ALD method).
  • a lanthanum-containing compound La(thd) 3 (DPA) 2 , where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and DPA represents dipropylamine.
  • DPA La(thd) 3
  • the preparation method of the above-mentioned lanthanum-containing compound includes: weighing 45g of La(thd) 3 into a 1L flask, adding 100 mL of n-hexane and stirring to obtain a white turbid La(thd) 3 dispersion. Weigh 10.1g of dipropylamine (DPA) into another 100mL beaker, add 50mL of n-hexane, stir and dissolve, and obtain a DPA solution. At room temperature, the DPA solution was dropwise added to the La(thd) 3 dispersion, and stirred for 2 hours to perform the coordination reaction. Then, n-hexane in the obtained reaction liquid was removed by distillation under reduced pressure, and 51.7 g of La(thd) 3 (DPA) 2 was obtained.
  • DPA dipropylamine
  • the nuclear magnetic resonance spectrum of the above-mentioned lanthanum-containing compound La(thd) 3 (DPA) 2 is shown in Figure 16.
  • the thermal properties of the above lanthanum-containing compound La(thd) 3 (DPA) 2 were analyzed, and the results are shown in Figure 17. It can be known from the TG curve that the complex has two weight loss steps before 300°C. The weight loss of the first step is about 21.82%, which corresponds to the weight loss of two molecules. The propylamine is detached; the weight loss of the second step is about 77.89%, which is the weight loss step of La(thd) 3 ; the residual mass is about -0.06%, which shows that the volatility of the compound La(thd) 3 (DPA) 2 is good.
  • the lanthanum-containing compound La(thd) 3 (DPA) 2 has a melting point much lower than La(thd) 3 (the melting point is about 38°C), and it can be transported in a liquid state, which is beneficial to reducing the transportation energy and
  • the lanthanum-containing compound La(thd) 3 (DPA) 2 has good volatility after being transported to a higher temperature deposition chamber, and at the same time the monoamine ligand is preferentially detached after the temperature is raised.
  • the lanthanum-containing compound La(thd) 3 (DPA) 2 is particularly suitable for CVD method (less Suitable for depositing thin films containing lanthanum using ALD method.
  • a cerium-containing compound Ce(thd) 3 (DMEDA), where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and DMEDA represents N,N'dimethylethylenedione amine.
  • the preparation method of the above-mentioned cerium-containing compound includes: weighing 40g of Ce(thd) 3 into a 1L flask, adding 100 mL of toluene and stirring to obtain a white turbid Ce(thd) 3 dispersion. Weigh 5.4g of N,N'dimethylethylenediamine (DMEDA) into another 100mL beaker, add 50mL of toluene, stir and dissolve, and obtain a DMEDA solution. At room temperature, the DMEDA solution was added dropwise to the Ce(thd) 3 dispersion, and stirred for 2 hours to proceed with the coordination reaction. Thereafter, toluene in the obtained reaction liquid was removed by distillation under reduced pressure, and 45.2 g of Ce(thd) 3 (DMEDA) was obtained.
  • DMEDA N,N'dimethylethylenediamine
  • the thermal properties of the cerium-containing compound Ce(thd) 3 (DMEDA) 2 provided in Example 6 were analyzed.
  • the compound has a low melting point ( ⁇ 135°C), high thermal stability (decomposition temperature >300°C), and good volatility.
  • its volatilization temperature at a saturated vapor pressure of 0.1Torr is about 140°C, which is lower than the volatilization temperature of La(thd) 3 at 0.1torr.

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Abstract

Provided in the embodiments of the present application are a metal compound, and a preparation method therefor and the use thereof. The metal compound comprises a transition metal atom, at least one β-diketone ligand coordinated with the transition metal atom, and one diamine ligand or two monoamine ligands coordinated with the transition metal atom, wherein the transition metal atom is coordinated with two oxygen atoms in the β-diketone ligand and is coordinated with two nitrogen atoms in the diamine ligand or coordinated with the nitrogen atom in the monoamine ligand. The metal compound has the characteristics of a low melting point, good volatility, a certain thermal stability, etc. at the same time, and is suitable for preparing a thin film containing a transition metal element by means of a chemical vapor deposition method or an atomic layer deposition method.

Description

金属化合物及其制备方法和应用Metal compounds and their preparation methods and applications
本申请要求于2022年5月31日提交至中国专利局、申请号为202210612617.3、申请名称为“金属化合物及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims priority to the Chinese patent application submitted to the China Patent Office on May 31, 2022, with application number 202210612617.3 and the application title "Metal Compounds and Preparation Methods and Applications thereof", the entire content of which is incorporated herein by reference. Applying.
技术领域Technical field
本申请涉及化学沉积技术领域，具体涉及一种金属化合物及其制备方法和应用。The present application relates to the field of chemical deposition technology, specifically to a metal compound and its preparation method and application.
背景技术Background technique
随着半导体器件的尺寸微缩，SiO2作为栅介质材料已不能满足场效应晶体管器件高集成度的需求，需要具有高介质常数(High-K)的材料来替代传统SiO2。其中，含镧氧化物因具有高介电常数、高热稳定性、宽禁带、高击穿场强、低漏电流等特点而被认为是可用于半导体器件中的理想High-K材料。As the size of semiconductor devices shrinks, SiO 2 as a gate dielectric material can no longer meet the high integration requirements of field effect transistor devices, and materials with high dielectric constant (High-K) are needed to replace traditional SiO 2 . Among them, lanthanum-containing oxides are considered to be ideal High-K materials that can be used in semiconductor devices due to their characteristics such as high dielectric constant, high thermal stability, wide bandgap, high breakdown field strength, and low leakage current.
化学气相沉积(Chemical Vapor Deposition，简称CVD)技术和原子层沉积(Atomic Layer Deposition，简称ALD)技术因能精密控制薄膜的沉积厚度、形貌而成为半导体器件制备过程中常用的薄膜沉积技术。若采用这两种技术生长含镧氧化物薄膜，则需要相应的镧前驱体能具有较低的熔点、良好的挥发性、较高的反应活性、一定的热稳定性等特性。然而，现有的镧前驱体并不能同时满足上述特性。Chemical Vapor Deposition (CVD) technology and Atomic Layer Deposition (ALD) technology have become commonly used thin film deposition technologies in the preparation process of semiconductor devices because they can precisely control the deposition thickness and morphology of thin films. If these two technologies are used to grow lanthanum-containing oxide films, the corresponding lanthanum precursor must have a lower melting point, good volatility, high reactivity, and certain thermal stability. However, existing lanthanum precursors cannot satisfy the above characteristics at the same time.
发明内容Contents of the invention
鉴于此，本申请实施例提供了一种金属化合物，以同时满足CVD/ALD技术对含金属元素的前驱体材料的各项性能要求。In view of this, embodiments of the present application provide a metal compound to simultaneously meet various performance requirements of CVD/ALD technology for precursor materials containing metal elements.
本申请实施例第一方面提供了一种金属化合物，所述金属化合物包括过渡金属原子及与过渡金属原子配位的至少一个β-二酮类配体，还包括与所述过渡金属原子配位的一个二元胺配体或者两个一元胺配体，其中，所述过渡金属原子与所述β-二酮类配体中的两个氧原子配位，并与所述二元胺配体中的两个氮原子配位或者与所述一元胺配体中的氮原子配位。The first aspect of the embodiment of the present application provides a metal compound. The metal compound includes a transition metal atom and at least one β-diketone ligand coordinated with the transition metal atom. It also includes a transition metal atom coordinated with the transition metal atom. One diamine ligand or two monoamine ligands, wherein the transition metal atom coordinates with the two oxygen atoms in the β-diketone ligand and coordinates with the diamine ligand The two nitrogen atoms in the ligand are coordinated or coordinated with the nitrogen atoms in the monoamine ligand.
本申请实施例提供的金属化合物，其熔点较低、挥发性良好，同时结构稳定性良好，且化学反应活性高、对基材无腐蚀性，适合用作进行CVD或ALD沉积反应的前驱体材料，从而可以生长得到成膜厚度及形貌可控的含过渡金属元素的薄膜。The metal compound provided in the embodiments of the present application has a low melting point, good volatility, good structural stability, high chemical reactivity, and is non-corrosive to the substrate, and is suitable for use as a precursor material for CVD or ALD deposition reactions. , thus enabling the growth of films containing transition metal elements with controllable film thickness and morphology.
本申请一些实施方式中，所述过渡金属原子包括镧系元素、钇、钪、铪、钛、钒、锆、铬、钨、锰、铁、钴、镍、钌、锌、铜、钯、铂、铱、铼、锇、钽、铑或铌。In some embodiments of the present application, the transition metal atoms include lanthanide elements, yttrium, scandium, hafnium, titanium, vanadium, zirconium, chromium, tungsten, manganese, iron, cobalt, nickel, ruthenium, zinc, copper, palladium, and platinum , iridium, rhenium, osmium, tantalum, rhodium or niobium.
本申请一些实施方式中，所述金属化合物包括三个β-二酮类配体。此时，上述金属化合物中，中心过渡原子的配位数为8，熔点更低、挥发性更好，结构稳定性较高。In some embodiments of the present application, the metal compound includes three β-diketone ligands. At this time, in the above-mentioned metal compound, the coordination number of the central transition atom is 8, the melting point is lower, the volatility is better, and the structural stability is higher.
本申请实施方式中，所述β-二酮类配体的结构通式表示为R1-C(＝O)-CH2-C(＝O)-R2，R1、R2独立地选自烷基。In the embodiment of the present application, the general structural formula of the β-diketone ligand is expressed as R 1 -C(=O)-CH 2 -C(=O)-R 2 , R 1 and R 2 are independently selected From alkyl.
本申请一些实施方式中，所述二元胺配体包括二元烷基胺。二元烷基胺与过渡金属原子配位的阻力较小，其不易从上述金属化合物中脱离，从而可保证金属化合物的良好热稳定性。 In some embodiments of the present application, the diamine ligand includes dibasic alkylamine. The resistance of the binary alkyl amine to coordinate with the transition metal atoms is small, and it is not easy to be separated from the above-mentioned metal compound, thus ensuring the good thermal stability of the metal compound.
本申请实施方式中，所述二元烷基胺的结构通式表示为N(R3)(R4)-C(R7)-C(R8)-N(R5)(R6)，其中，R3至R8独立地选自氢原子、烷基。本申请一些实施方式中，所述烷基的碳原子数为1-6。含较少碳原子数烷基的二元烷基胺与过渡金属原子配位时的阻力更小。In the embodiment of the present application, the general structural formula of the dibasic alkyl amine is expressed as N(R 3 )(R 4 )-C(R 7 )-C(R 8 )-N(R 5 )(R 6 ) , wherein R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups. In some embodiments of the present application, the number of carbon atoms of the alkyl group is 1-6. Diary alkylamines containing alkyl groups with fewer carbon atoms have less resistance to coordination with transition metal atoms.
本申请实施方式中，所述一元胺配体包括含一个氮原子的一元烷基胺或氮杂环配体。In the embodiment of the present application, the monoamine ligand includes a monoalkylamine containing one nitrogen atom or a nitrogen heterocyclic ligand.
本申请一些实施方式中，所述一元烷基胺的结构通式表示为N(R3’)(R4’)(R5’)，其中，R3’、R4’、R5’独立地选自氢原子、烷基，且R3’至R5’中的至少一个为烷基；所述氮杂环配体包括吡啶、哌啶、吡咯或其衍生物。一般地，一元烷基胺比氮杂环配体与过渡金属原子的结合位阻小，所形成的配合物的热稳定性更高。In some embodiments of the present application, the general structural formula of the monoalkyl amine is expressed as N(R 3 ') (R 4 ') (R 5 '), where R 3 ', R 4 ', and R 5 ' are independent are selected from hydrogen atoms and alkyl groups, and at least one of R 3 ' to R 5 ' is an alkyl group; the nitrogen heterocyclic ligand includes pyridine, piperidine, pyrrole or derivatives thereof. Generally, monoalkyl amines have less steric hindrance in binding to transition metal atoms than nitrogen heterocyclic ligands, and the resulting complexes have higher thermal stability.
本申请一些实施方式中，所述金属化合物具有式(Ⅰ)或式(Ⅱ)所示的结构通式：
In some embodiments of the present application, the metal compound has a general structural formula represented by formula (I) or formula (II):
其中，M代表过渡金属原子，式(Ⅰ)中，R1、R2独立地选自烷基，R3至R8独立地选自氢原子、烷基；式(Ⅱ)中，R1’、R2’独立地选自烷基，R’独立地选自具有一个氮原子的一元胺配体，所述R’中的氮原子与M原子配位。Among them, M represents a transition metal atom. In formula (I), R 1 and R 2 are independently selected from alkyl groups, and R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups; in formula (II), R 1 ' , R 2 ' is independently selected from an alkyl group, R' is independently selected from a monoamine ligand having one nitrogen atom, and the nitrogen atom in R' is coordinated with the M atom.
本申请实施例还提供了一种金属化合物的制备方法，包括以下步骤：The embodiments of the present application also provide a method for preparing a metal compound, which includes the following steps:
取过渡金属原子与至少一个β-二酮类配体构成的配位化合物，将二元胺配体或一元胺配体与所述配位化合物在有机溶剂中进行配位反应，得到反应液，去除所述反应液中的有机溶剂，得到金属化合物；Take a coordination compound composed of a transition metal atom and at least one β-diketone ligand, perform a coordination reaction with a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent to obtain a reaction liquid, Remove the organic solvent in the reaction solution to obtain a metal compound;
其中，所述金属化合物中的过渡金属原子与至少一个所述β-二酮类配体中的氧原子配位，并与一个所述二元胺配体中的两个氮原子配位或与两个所述一元胺配体中的两个氮原子配位。Wherein, the transition metal atom in the metal compound is coordinated with at least one oxygen atom in the β-diketone ligand, and coordinated with two nitrogen atoms in one of the diamine ligands or with Two nitrogen atoms in the two monoamine ligands are coordinated.
上述金属化合物的制备方法，工艺简单，易于操作，成本低廉，所得金属化合物的结构稳定性高。The preparation method of the above-mentioned metal compound has simple process, easy operation, low cost, and the obtained metal compound has high structural stability.
本申请实施方式中，“将二元胺配体或一元胺配体与所述配位化合物在有机溶剂中进行配位反应”具体包括：In the embodiment of the present application, "carrying out a coordination reaction between a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent" specifically includes:
将所述配位化合物分散在有机溶剂中，得到第一溶液；将二元胺配体或一元胺配体溶于有机溶剂，得到第二溶液；Disperse the coordination compound in an organic solvent to obtain a first solution; dissolve a diamine ligand or a monoamine ligand in an organic solvent to obtain a second solution;
将所述第二溶液滴加到所述第一溶液中，于搅拌条件下进行所述配位反应。The second solution is added dropwise to the first solution, and the coordination reaction is performed under stirring conditions.
上述加料方式更利于二元胺配体或一元胺配体能充分与六配位化合物中的过渡金属原子配位。The above-mentioned feeding method is more conducive to the diamine ligand or monoamine ligand being able to fully coordinate with the transition metal atoms in the six-coordination compound.
本申请实施例第二方面提供了本申请实施例第一方面所述的金属化合物在制备含过渡金属元素的薄膜中的应用。The second aspect of the embodiments of this application provides the application of the metal compound described in the first aspect of the embodiments of this application in preparing a thin film containing a transition metal element.
在制备含过渡金属元素的薄膜时，上述金属化合物可充当过渡金属元素源，其熔点低、挥发性好，并具有良好的热稳定性，可通过CVD法或ALD法沉积含过渡金属元素的薄膜。When preparing films containing transition metal elements, the above-mentioned metal compounds can serve as sources of transition metal elements. They have low melting points, good volatility, and good thermal stability. Films containing transition metal elements can be deposited by CVD or ALD. .
本申请实施例第三方面提供了本申请实施例第一方面所述的金属化合物在制备电子器件中的应用。具体地，上述金属化合物用于制备电子器件中的含过渡金属元素的薄膜。The third aspect of the embodiments of this application provides the application of the metal compound described in the first aspect of the embodiments of this application in preparing electronic devices. Specifically, the above-mentioned metal compounds are used to prepare films containing transition metal elements in electronic devices.
本申请实施例第四方面提供了一种含过渡金属元素的薄膜，其采用本申请实施例第一方面所述的金属化合物制备得到。 The fourth aspect of the embodiments of the present application provides a thin film containing a transition metal element, which is prepared by using the metal compound described in the first aspect of the embodiments of the present application.
含过渡金属元素的薄膜可以具体以上述金属化合物作为过渡金属源，通过CVD法或ALD法等气相沉积法制备得到，制得的含过渡金属元素的薄膜的形貌良好、厚度可控。The thin film containing transition metal elements can be prepared by using the above-mentioned metal compound as a transition metal source through a vapor deposition method such as CVD or ALD. The prepared thin film containing transition metal elements has good morphology and controllable thickness.
本申请实施例第五方面提供了一种电子器件，其具有如本申请实施例第四方面所述的含过渡金属元素的薄膜。含过渡金属元素的薄膜的形貌良好、厚度可控，质量较好，利于保证电子器件的稳定持久运行。The fifth aspect of the embodiments of the present application provides an electronic device, which has a transition metal element-containing film as described in the fourth aspect of the embodiments of the present application. Films containing transition metal elements have good morphology, controllable thickness, and good quality, which are beneficial to ensuring the stable and long-lasting operation of electronic devices.
本申请实施例第六方面提供了一种制备含过渡金属元素的薄膜的装置，所述装置包括连通的容器室和沉积室，所述容器室用于储存如本申请实施例第一方面所述的金属化合物，所述沉积室中放置有基材，所述金属化合物能被输送至所述沉积室中，并在所述基材的表面沉积形成含过渡金属元素的薄膜。其中，该金属化合物能以气态形式输送至所述沉积室中。The sixth aspect of the embodiment of the present application provides a device for preparing a thin film containing a transition metal element. The device includes a connected container chamber and a deposition chamber. The container chamber is used to store as described in the first aspect of the embodiment of the present application. The metal compound has a substrate placed in the deposition chamber, the metal compound can be transported into the deposition chamber, and deposited on the surface of the substrate to form a thin film containing transition metal elements. Wherein, the metal compound can be transported into the deposition chamber in gaseous form.
采用该装置能制得前述质量良好的含过渡金属元素的薄膜。This device can be used to produce the aforementioned films containing transition metal elements with good quality.
本申请实施例第七方面提供了一种含过渡金属元素的薄膜的沉积方法，包括以下步骤：The seventh aspect of the embodiment of the present application provides a method for depositing a thin film containing a transition metal element, including the following steps:
将气化的本申请实施例第一方面所述的金属化合物引入到沉积设备的放置有基材的沉积室中，以在所述基材表面沉积形成含过渡金属元素的薄膜。The vaporized metal compound described in the first aspect of the embodiment of the present application is introduced into a deposition chamber in which a substrate is placed in a deposition device, so as to deposit and form a thin film containing a transition metal element on the surface of the substrate.
本申请实施方式中，所述沉积方法还包括：将反应物物种引入到所述沉积室内。反应物物种可根据待制备的含过渡金属元素的薄膜的材质进行选择，其可以是薄膜的某一构成元素源，或者进行沉积反应所需的其他气体。该反应物物种可以本身就是气态试剂，或者是液态试剂的蒸气。In an embodiment of the present application, the deposition method further includes: introducing reactant species into the deposition chamber. The reactant species can be selected according to the material of the film containing transition metal elements to be prepared. It can be a source of a certain constituent element of the film, or other gases required for the deposition reaction. The reactant species can be a gaseous reagent itself, or a vapor of a liquid reagent.
本申请一些实施方式中，所述含过渡金属元素的薄膜还含有氧元素；所述反应物物种包括氧源，所述氧源包括氧气、臭氧、H2O、H2O2中的一种或多种。此时，形成的含过渡金属元素的薄膜可以是金属氧化物薄膜，其介电常数通常较高，在电子器件中有良好应用场景。此外，前述氧源与上述金属化合物的反应活性高，且可尽量减少杂质的引入。In some embodiments of the present application, the film containing transition metal elements also contains oxygen elements; the reactant species includes an oxygen source, and the oxygen source includes one of oxygen, ozone, H 2 O, and H 2 O 2 or more. At this time, the film containing transition metal elements formed can be a metal oxide film, which usually has a high dielectric constant and has good application scenarios in electronic devices. In addition, the reaction activity between the aforementioned oxygen source and the aforementioned metal compound is high, and the introduction of impurities can be minimized.
本申请一些实施方式中，所述沉积方法还包括：将其他金属源引入到所述沉积室内，其中，所述其他金属源包括与所述金属化合物的过渡金属元素不同的金属元素。这里的金属元素可包括过渡金属元素、主族金属元素等。In some embodiments of the present application, the deposition method further includes: introducing other metal sources into the deposition chamber, wherein the other metal sources include metal elements different from the transition metal elements of the metal compound. The metal elements here may include transition metal elements, main group metal elements, etc.
本申请实施方式中，所述沉积具体是化学气相沉积(CVD)过程，或者原子层沉积(ALD)过程。这两种气相沉积技术能较好地调控含过渡金属元素的薄膜的沉积厚度、形貌。In the embodiment of the present application, the deposition is specifically a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. These two vapor deposition technologies can better control the deposition thickness and morphology of films containing transition metal elements.
附图说明Description of the drawings
图1为CVD或ALD沉积设备的常见结构示意图。Figure 1 is a schematic diagram of a common structure of CVD or ALD deposition equipment.
图2为本申请实施例1中含镧化合物La(thd)3(DMEDA)的核磁共振谱图。Figure 2 is the nuclear magnetic resonance spectrum of the lanthanum-containing compound La(thd) 3 (DMEDA) in Example 1 of the present application.
图3示出了本申请实施例1中含镧化合物La(thd)3(DMEDA)的热重分析(TG)曲线和差示扫描量热(DSC)曲线。Figure 3 shows the thermogravimetric analysis (TG) curve and differential scanning calorimetry (DSC) curve of the lanthanum-containing compound La(thd) 3 (DMEDA) in Example 1 of the present application.
图4为本申请实施例1中含镧化合物La(thd)3(DMEDA)的饱和蒸气压对温度的曲线图。Figure 4 is a graph of the saturated vapor pressure versus temperature of the lanthanum-containing compound La(thd) 3 (DMEDA) in Example 1 of the present application.
图5为采用La(thd)3(DMEDA)作原料通过ALD沉积得到的La2O3薄膜的特性数据图。Figure 5 is a characteristic data diagram of a La 2 O 3 film deposited by ALD using La(thd) 3 (DMEDA) as raw material.
图6为采用La(thd)3(DMEDA)通过ALD法制得的La2O3薄膜的切片扫描电子显微镜照片。Figure 6 is a scanning electron microscope photograph of a section of a La 2 O 3 film produced by the ALD method using La(thd) 3 (DMEDA).
图7为采用La(thd)3(DMEDA)通过ALD法制得的La2O3薄膜的XRD图谱。Figure 7 is the XRD pattern of a La 2 O 3 film prepared by the ALD method using La(thd) 3 (DMEDA).
图8为本申请实施例2中含镧化合物La(ibpm)3(DMEDA)的核磁共振谱图。Figure 8 is the nuclear magnetic resonance spectrum of the lanthanum-containing compound La(ibpm) 3 (DMEDA) in Example 2 of the present application.
图9为本申请实施例2中含镧化合物La(ibpm)3(DMEDA)的TG-DSC曲线图。Figure 9 is a TG-DSC curve chart of the lanthanum-containing compound La(ibpm) 3 (DMEDA) in Example 2 of the present application.
图10为本申请实施例2中含镧化合物La(ibpm)3(DMEDA)的饱和蒸气压对温度的曲线图。Figure 10 is a graph of the saturated vapor pressure versus temperature of the lanthanum-containing compound La(ibpm) 3 (DMEDA) in Example 2 of the present application.
图11为本申请实施例3中含镧化合物La(tmod)3(DMEDA)的核磁共振谱图。Figure 11 is the NMR spectrum of the lanthanum-containing compound La(tmod) 3 (DMEDA) in Example 3 of the present application.
图12为本申请实施例3中含镧化合物La(tmod)3(DMEDA)的TG-DSC曲线图。 Figure 12 is a TG-DSC curve chart of the lanthanum-containing compound La(tmod) 3 (DMEDA) in Example 3 of the present application.
图13为本申请实施例3中含镧化合物La(tmod)3(DMEDA)的饱和蒸气压对温度的曲线图。Figure 13 is a graph of the saturated vapor pressure versus temperature of the lanthanum-containing compound La(tmod) 3 (DMEDA) in Example 3 of the present application.
图14为本申请实施例4中含镧化合物La(thd)3(Py)2的核磁共振谱图。Figure 14 is the nuclear magnetic resonance spectrum of the lanthanum-containing compound La(thd) 3 (Py) 2 in Example 4 of the present application.
图15为本申请实施例4中含镧化合物La(thd)3(Py)2的TG-DSC曲线图。Figure 15 is a TG-DSC curve chart of the lanthanum-containing compound La(thd) 3 (Py) 2 in Example 4 of the present application.
图16为本申请实施例5中含镧化合物La(thd)3(DPA)2的核磁共振谱图。Figure 16 is the nuclear magnetic resonance spectrum of the lanthanum-containing compound La(thd) 3 (DPA) 2 in Example 5 of the present application.
图17为本申请实施例5中含镧化合物La(thd)3(DPA)2的TG-DSC曲线图。Figure 17 is a TG-DSC curve chart of the lanthanum-containing compound La(thd) 3 (DPA) 2 in Example 5 of the present application.
具体实施方式Detailed ways
下面将结合本申请实施例中的附图，对本申请技术方案进行说明。The technical solution of the present application will be described below with reference to the drawings in the embodiments of the present application.
图1为CVD或ALD沉积设备的常见结构示意图。其中，沉积设备100包括用于储存沉积薄膜用前驱体材料的容器室10和实现薄膜沉积反应的沉积室20，容器室10与沉积室20通过管路连通。容器室10主要放置储存各前驱体材料的储料容器11(通常为不锈钢钢瓶)，各储料容器11中储存的前驱体材料可以经气化后通过输送管路(管路上可设置有阀门)输送至沉积室20。沉积室20内放置有基材21，沉积室20的外侧可设置加热组件22，以控制沉积室20的温度达到前驱体的反应温度。其中，前驱体材料应具有低熔点和良好的挥发性，以便可顺利气化从容器室10输送至沉积室20(气化可以通过控制储料容器11及输送管路的加热温度实现)，避免因管路温度变化而使前驱体冷凝进而造成管路污染；前驱体材料还应具有一定的热稳定性，保证其从容器室10至沉积室20的输送过程中的稳定性，以及尽量减少其热分解所造成的基材表面薄膜沉积不均匀的现象。此外，前驱体材料还应不腐蚀基材21，如最好不含有腐蚀金属的卤素元素。Figure 1 is a schematic diagram of a common structure of CVD or ALD deposition equipment. The deposition equipment 100 includes a container chamber 10 for storing precursor materials for thin film deposition and a deposition chamber 20 for realizing a thin film deposition reaction. The container chamber 10 and the deposition chamber 20 are connected through pipelines. The container room 10 mainly houses storage containers 11 (usually stainless steel cylinders) that store each precursor material. The precursor materials stored in each storage container 11 can be gasified and passed through the transportation pipeline (the pipeline can be equipped with a valve) Transported to deposition chamber 20. The substrate 21 is placed in the deposition chamber 20, and a heating component 22 can be provided outside the deposition chamber 20 to control the temperature of the deposition chamber 20 to reach the reaction temperature of the precursor. Among them, the precursor material should have a low melting point and good volatility so that it can be smoothly vaporized and transported from the container chamber 10 to the deposition chamber 20 (the vaporization can be achieved by controlling the heating temperature of the storage container 11 and the transportation pipeline), to avoid Due to changes in pipeline temperature, the precursor condenses and causes pipeline pollution; the precursor material should also have a certain thermal stability to ensure its stability during transportation from the container chamber 10 to the deposition chamber 20 and to minimize its The phenomenon of uneven film deposition on the surface of the substrate caused by thermal decomposition. In addition, the precursor material should not corrode the base material 21 , for example, it is best not to contain halogen elements that corrode metals.
其中，CVD沉积过程通常包括以下步骤：气化的前驱体材料在输送至沉积室20后，其扩散至基材21的表面并在基材表面吸附，前驱体在基材表面发生化学反应(通常在受热、等离子体或电场辅助下)沉积形成薄膜，反应副产物从基材21表面脱附，并被排除出沉积室20。而ALD则是通过循环交替通入多种前驱体材料(通常为两种，如图1所示)并在不同种前驱体通入沉积室20的间隙借助惰性气体(如氩气、氮气等)的吹扫带走多余的前驱体，从而实现具有自限制特性的原子层沉积(即，每一个循环沉积的薄膜厚度都是原子级)。通过多次循环可实现多个原子层厚度的连续沉积。为实现单原子层厚度的薄膜精密沉积，ALD沉积过程不允许前驱体材料发生热分解反应，以免沉积速度和薄膜厚度发生不可控变化，只允许在基材表面发生自限制的化学反应。而CVD技术因与ALD技术的工作机理的不同，允许前驱体材料在不影响薄膜沉积质量的条件下在沉积室20发生一定的分解反应。Among them, the CVD deposition process usually includes the following steps: after the vaporized precursor material is transported to the deposition chamber 20, it diffuses to the surface of the substrate 21 and is adsorbed on the surface of the substrate, and the precursor undergoes a chemical reaction on the surface of the substrate (usually (Assisted by heat, plasma or electric field) deposition to form a thin film, the reaction byproducts are desorbed from the surface of the substrate 21 and are eliminated from the deposition chamber 20 . ALD, on the other hand, alternately introduces a variety of precursor materials (usually two types, as shown in Figure 1) through cycles, and uses inert gases (such as argon, nitrogen, etc.) in the gap between different types of precursors entering the deposition chamber 20. The purge takes away excess precursor, thereby achieving atomic layer deposition with self-limiting characteristics (that is, the thickness of the film deposited in each cycle is atomic level). Continuous deposition of multiple atomic layer thicknesses can be achieved through multiple cycles. In order to achieve precise deposition of thin films with a single atomic layer thickness, the ALD deposition process does not allow thermal decomposition reactions of precursor materials to avoid uncontrollable changes in deposition speed and film thickness, and only allows self-limiting chemical reactions to occur on the surface of the substrate. Due to the difference in working mechanism between the CVD technology and the ALD technology, the precursor material is allowed to undergo a certain decomposition reaction in the deposition chamber 20 without affecting the film deposition quality.
虽然CVD、ALD技术对前驱体材料的热稳定性要求的严苛程度不同，但总体说来，这两种技术都要求前驱体材料具有良好的挥发性、较高的反应活性等特性。而对于沉积含过渡金属元素的薄膜(如含镧氧化物)来说，现有的过渡金属元素的前驱体并不能兼顾低熔点、良好挥发性、较高的反应活性、一定的热稳定性、无腐蚀性等特性。因此，本申请实施例提供了可兼顾上述特性的金属化合物。Although CVD and ALD technologies have different requirements on the thermal stability of precursor materials, generally speaking, both technologies require precursor materials to have good volatility, high reactivity and other characteristics. For the deposition of films containing transition metal elements (such as lanthanum-containing oxides), existing transition metal element precursors cannot combine low melting point, good volatility, high reactivity, certain thermal stability, Non-corrosive and other properties. Therefore, the embodiments of the present application provide metal compounds that can take into account the above characteristics.
具体地，本申请实施例提供的金属化合物，包括过渡金属原子及与过渡金属原子配位的至少一个β-二酮类配体，还包括与该过渡金属原子配位的一个二元胺配体或者两个一元胺配体，其中，所述过渡金属原子与所述β-二酮类配体中的两个氧原子配位，并与所述二元胺配体中的两个氮原子配位或者与所述一元胺配体中的氮原子配位。Specifically, the metal compound provided by the embodiments of the present application includes a transition metal atom and at least one β-diketone ligand coordinated with the transition metal atom, and also includes a diamine ligand coordinated with the transition metal atom. Or two monoamine ligands, wherein the transition metal atom is coordinated with two oxygen atoms in the β-diketone ligand and coordinated with two nitrogen atoms in the diamine ligand. or coordinate with the nitrogen atom in the monoamine ligand.
本申请提供的上述金属化合物中，β-二酮类配体借助源自酮基的O原子与过渡金属原子实现较强结合，同时单官能度胺(即，一元胺)或二官能度胺(即，二元胺)借助N原子与过渡金属原子的稍弱结合力(该结合力弱于O原子与过渡金属原子之间的结合力)与过渡金 属原子实现结合，各配体与过渡金属原子的结合位阻不会过大而易脱离，这使得整体化合物在具有一定结构稳定性的同时，还具有较低的熔点和良好挥发性，适合用作进行CVD或ALD沉积反应的前驱体材料。此外，本申请提供的金属化合物不含卤素原子，其挥发或热分解产物无腐蚀性，制备成本低。Among the above-mentioned metal compounds provided by this application, the β-diketone ligand achieves strong binding with the transition metal atom through the O atom derived from the ketone group, and at the same time, the monofunctional amine (i.e., monoamine) or the difunctional amine ( That is, diamine) interacts with transition gold by virtue of the slightly weaker binding force between N atoms and transition metal atoms (the binding force is weaker than the binding force between O atoms and transition metal atoms). The metal atoms are combined, and the binding steric hindrance between each ligand and the transition metal atom will not be too large to easily detach. This makes the overall compound not only have a certain structural stability, but also has a lower melting point and good volatility, making it suitable for use As a precursor material for CVD or ALD deposition reactions. In addition, the metal compound provided by this application does not contain halogen atoms, its volatilization or thermal decomposition products are non-corrosive, and the preparation cost is low.
本申请中，过渡金属原子可包含指元素周期表中的所有过渡金属元素的原子，本申请实施方式中，所述过渡金属原子可以包括但不限于镧系元素、钇(Y)、钪(Sc)、铪(Hf)、钛(Ti)、钒(V)、锆(Zr)、铬(Cr)、钨(W)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、钌(Ru)、锌(Zn)、铜(Cu)、钯(Pd)、铂(Pt)、铱(Ir)、铼(Re)、锇(Os)、钽(Ta)、铑(Rh)或铌(Nb)等。其中，镧系元素可以包括镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)。本申请一些实施方式中，所述过渡金属原子为镧系元素(如La、Ce、Pr等)、Y、Sc、Ta、Zr、Hf等。In this application, transition metal atoms may include atoms of all transition metal elements in the periodic table of elements. In embodiments of this application, the transition metal atoms may include but are not limited to lanthanide elements, yttrium (Y), scandium (Sc) ), hafnium (Hf), titanium (Ti), vanadium (V), zirconium (Zr), chromium (Cr), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni ), ruthenium (Ru), zinc (Zn), copper (Cu), palladium (Pd), platinum (Pt), iridium (Ir), rhenium (Re), osmium (Os), tantalum (Ta), rhodium (Rh) ) or niobium (Nb), etc. Among them, lanthanide elements can include 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). In some embodiments of the present application, the transition metal atoms are lanthanide elements (such as La, Ce, Pr, etc.), Y, Sc, Ta, Zr, Hf, etc.
本申请一些实施方式中，所述金属化合物包括三个β-二酮类配体。此时，上述金属化合物中，中心过渡原子的配位数为8，其接近但并非电子饱和状态，该金属化合物的熔点更低、挥发性更好，结构稳定性较高。进一步地，此时，所述过渡金属元素为镧系元素(如La、Ce、Pr等)、Y、Sc、Ta、Zr、Hf等。In some embodiments of the present application, the metal compound includes three β-diketone ligands. At this time, in the above-mentioned metal compound, the coordination number of the central transition atom is 8, which is close to but not in an electron saturated state. The metal compound has a lower melting point, better volatility, and higher structural stability. Further, at this time, the transition metal elements are lanthanide elements (such as La, Ce, Pr, etc.), Y, Sc, Ta, Zr, Hf, etc.
本申请实施方式中，所述β-二酮类配体的结构通式可以表示为R1-C(＝O)-CH2-C(＝O)-R2，其中，R1、R2独立地选自烷基。这里烷基可以是取代或未取代的烷基，其中，取代的烷基可以是烷氧基取代的烷基等。烷基可以是直链或支链烷基，烷基的碳原子数可以是1-10，进一步可以是1-6，优选为1-4。示例性的，烷基可以是甲基、乙基、丙基、异丁基、叔丁基等。In the embodiment of the present application, the general structural formula of the β-diketone ligand can be expressed as R 1 -C(=O)-CH 2 -C(=O)-R 2 , where R 1 , R 2 Independently selected from alkyl. The alkyl group here may be a substituted or unsubstituted alkyl group, wherein the substituted alkyl group may be an alkoxy-substituted alkyl group, etc. The alkyl group may be a straight chain or branched chain alkyl group, and the number of carbon atoms of the alkyl group may be 1-10, further may be 1-6, and is preferably 1-4. Illustratively, the alkyl group may be methyl, ethyl, propyl, isobutyl, tert-butyl, etc.
本申请，二元胺配体包括二元烷基胺、二元芳基胺、二元环烷基胺等。本申请一些实施方式中，所述二元胺配体包括二元烷基胺。相较于二元芳基胺、环烷基胺，二元烷基胺与过渡金属原子配位时的阻力较小，其不易从上述金属化合物中脱离，从而可保证金属化合物的良好热稳定性。In this application, diamine ligands include dibasic alkyl amines, dibasic aryl amines, dibasic cycloalkyl amines, etc. In some embodiments of the present application, the diamine ligand includes dibasic alkylamine. Compared with dibasic arylamines and cycloalkylamines, dibasic alkylamines have less resistance when coordinating with transition metal atoms, and they are not easily separated from the above-mentioned metal compounds, thus ensuring good thermal stability of the metal compounds. .
本申请一些实施方式中，所述二元烷基胺的通式表示为N(R3)(R4)-C(R7)-C(R8)-N(R5)(R6)，其中，R3至R8独立地选自氢原子、烷基，且R3、R4、R5、R6中至少一个为烷基(也即，R3、R4、R5、R6不同时为氢原子)。类似地，这里的烷基可以是直链或支链烷基，烷基的碳原子数可以是1-10，进一步可以是1-6，优选为1-4。示例性的，烷基可以是甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基等。其中，H原子可以包括1H原子(又称“氕原子”)、2H原子(又称“氘原子”)、3H原子(又称“氚原子”)。In some embodiments of the present application, the general formula of the dibasic alkylamine is N(R 3 )(R 4 )-C(R 7 )-C(R 8 )-N(R 5 )(R 6 ) , wherein R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups, and at least one of R 3 , R 4 , R 5 , and R 6 is an alkyl group (that is, R 3 , R 4 , R 5 , R 6 are not hydrogen atoms at the same time). Similarly, the alkyl group here can be a straight chain or branched chain alkyl group, and the number of carbon atoms of the alkyl group can be 1-10, further can be 1-6, preferably 1-4. Illustratively, the alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. Among them, H atoms may include 1 H atoms (also known as "protium atoms"), 2 H atoms (also known as "deuterium atoms"), and 3 H atoms (also known as "tritium atoms").
本申请实施方式中，所述一元胺配体包括含一个氮原子的一元烷基胺或氮杂环配体。一般地，一元烷基胺比氮杂环配体与过渡金属原子的结合位阻小。In the embodiment of the present application, the monoamine ligand includes a monoalkylamine containing one nitrogen atom or a nitrogen heterocyclic ligand. Generally, monoalkyl amines have less steric hindrance in binding to transition metal atoms than nitrogen heterocyclic ligands.
本申请一些实施方式中，所述一元烷基胺的结构通式可以表示为N(R3’)(R4’)(R5’)，其中，R3’、R4’、R5’独立地选自氢原子、烷基，且R3’、R4’、R5’中至少一个为烷基。链状的一元烷基胺与过渡金属原子配位时的阻力较小，其不易与金属化合物中的过渡金属原子失去配位关系，可保证金属化合物的良好热稳定性。类似地，类似地，这里的烷基可以是直链或支链烷基，烷基的碳原子数可以是1-10，进一步可以是1-6，优选为1-4。示例性的，烷基可以是甲基、乙基、丙基、异丁基、叔丁基等。In some embodiments of the present application, the general structural formula of the monoalkyl amine can be expressed as N(R 3 ') (R 4 ') (R 5 '), where, R 3 ', R 4 ', R 5 ' are independently selected from hydrogen atoms and alkyl groups, and at least one of R 3 ', R 4 ', and R 5 ' is an alkyl group. Chain-like monoalkyl amines have less resistance when coordinating with transition metal atoms, and are less likely to lose their coordination relationship with transition metal atoms in metal compounds, thus ensuring good thermal stability of metal compounds. Similarly, the alkyl group here may be a straight chain or branched chain alkyl group, and the number of carbon atoms of the alkyl group may be 1-10, further may be 1-6, preferably 1-4. Illustratively, the alkyl group may be methyl, ethyl, propyl, isobutyl, tert-butyl, etc.
本申请中，氮杂环配体是指环杂原子为N原子的物质。本申请一些实施方式中，所述氮杂环配体可以包括吡啶、哌啶、吡咯或其衍生物。相对于其他氮杂环化合物，这几类物质的分子量低、位阻相对较小，与过渡金属原子较易配位形成配合物。示例性地，吡啶、哌啶、 吡咯的衍生物可包括被碳子数为1-6的烷基(如甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基)取代的吡啶、哌啶、吡咯等。In this application, nitrogen heterocyclic ligand refers to a substance whose ring heteroatom is an N atom. In some embodiments of the present application, the nitrogen heterocyclic ligand may include pyridine, piperidine, pyrrole or derivatives thereof. Compared with other nitrogen heterocyclic compounds, these types of substances have low molecular weight and relatively small steric hindrance, and are easier to coordinate with transition metal atoms to form complexes. Exemplarily, pyridine, piperidine, Derivatives of pyrrole may include pyridine, piperidine, substituted by an alkyl group with 1 to 6 carbon atoms (such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl). Pyrrole etc.
本申请一些实施方式中，所述金属化合物具有式(Ⅰ)或式(Ⅱ)所示的结构通式：
In some embodiments of the present application, the metal compound has a general structural formula represented by formula (I) or formula (II):
其中，M代表过渡金属原子，式(Ⅰ)中，R1、R2独立地选自烷基，R3至R8独立地选自氢原子、烷基；式(Ⅱ)中，R1’、R2’独立地选自烷基，R’独立地选自具有一个氮原子的一元胺配体，所述R’中的氮原子与过渡金属原子M配位。Among them, M represents a transition metal atom. In formula (I), R 1 and R 2 are independently selected from alkyl groups, and R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups; in formula (II), R 1 ' , R 2 ' is independently selected from an alkyl group, R' is independently selected from a monoamine ligand having one nitrogen atom, and the nitrogen atom in R' is coordinated with the transition metal atom M.
其中，关于R1至R8的选择范围可参见本申请前文的描述。R1’、R2’的选择范围也可参见前文关于R1、R2的描述。For the selection range of R 1 to R 8 , please refer to the previous description of this application. The selection range of R 1 ' and R 2 ' can also refer to the previous description of R 1 and R 2 .
需要说明的是，式(Ⅱ)中的两个R’可以是相同或者不同的一元胺配体。本申请一些实施方式中，R’独立地选自一元烷基胺或氮杂环配体。一元烷基胺或氮杂环配体的选择范围可参见本申请前文的描述，这里不再赘述。It should be noted that the two R's in formula (II) may be the same or different monoamine ligands. In some embodiments of the present application, R' is independently selected from monoalkyl amine or nitrogen heterocyclic ligand. The selection range of the monoalkyl amine or nitrogen heterocyclic ligand can be found in the previous description of this application and will not be described again here.
本申请一些实施方式中，所述金属化合物是镧配合物，具体可以包括以下物质中的任意一种：
In some embodiments of the present application, the metal compound is a lanthanum complex, which may specifically include any one of the following substances:
本申请实施例还提供了一种金属化合物的制备方法，包括以下步骤：The embodiments of the present application also provide a method for preparing a metal compound, which includes the following steps:
取过渡金属原子与至少一个β-二酮类配体构成的配位化合物，将二元胺配体或一元胺配体与所述配位化合物在有机溶剂中进行配位反应，得到反应液，去除所述反应液中的有机溶剂，得到金属化合物；其中，所述金属化合物中的过渡金属原子与至少一个β-二酮类配体中的氧原子配位，并与一个二元胺配体中的两个氮原子配位或与两个一元胺配体中的两个氮原子配位。Take a coordination compound composed of a transition metal atom and at least one β-diketone ligand, perform a coordination reaction with a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent to obtain a reaction liquid, Remove the organic solvent in the reaction solution to obtain a metal compound; wherein the transition metal atom in the metal compound is coordinated with an oxygen atom in at least one β-diketone ligand, and is coordinated with a diamine ligand Coordinated with two nitrogen atoms in or coordinated with two nitrogen atoms in two monoamine ligands.
本申请一些实施方式中，“将二元胺配体或一元胺配体与所述配位化合物在有机溶剂中进行配位反应”具体包括：In some embodiments of the present application, "carrying out a coordination reaction between a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent" specifically includes:
1)将所述配位化合物分散在有机溶剂中，得到第一溶液；将二元胺配体或一元胺配体溶于有机溶剂，得到第二溶液； 1) Disperse the coordination compound in an organic solvent to obtain a first solution; dissolve a diamine ligand or a monoamine ligand in an organic solvent to obtain a second solution;
2)将所述第二溶液滴加到所述第一溶液中，于搅拌条件下进行所述配位反应。2) Add the second solution dropwise to the first solution, and perform the coordination reaction under stirring conditions.
上述加料方式更利于二元胺配体或一元胺配体能充分与上述配位化合物中的过渡金属原子配位。其中，将“第二溶液滴加在第一溶液中”，可以在室温下进行。可选地，所述搅拌条件的搅拌速率可以是200-1000转/分。所述配位反应进行的时间可以是1-4小时，例如是2-4小时。其中，所述有机溶剂能够溶解一元胺或二元胺配体，所述有机溶剂包括但不限于甲苯、四氢呋喃、氯仿、正己烷等中的一种或多种。在一些实施方式中，该有机溶剂为甲苯，此时过渡金属原子与β-二酮类配体构成的配位化合物、二元胺或一元胺配体在甲苯中的溶解度较高。The above-mentioned feeding method is more conducive to the diamine ligand or monoamine ligand being able to fully coordinate with the transition metal atoms in the above-mentioned coordination compound. Wherein, "dropping the second solution into the first solution" can be performed at room temperature. Optionally, the stirring rate of the stirring condition may be 200-1000 rpm. The coordination reaction can be carried out for 1-4 hours, for example, 2-4 hours. Wherein, the organic solvent can dissolve monoamine or diamine ligands, and the organic solvent includes but is not limited to one or more of toluene, tetrahydrofuran, chloroform, n-hexane, etc. In some embodiments, the organic solvent is toluene. In this case, the solubility of the coordination compound composed of the transition metal atom and the β-diketone ligand, the diamine or the monoamine ligand is relatively high in toluene.
可以理解的是，本申请其他实施方式中，还可以将二元胺配体或一元胺配体与配位化合物直接一起分散在有机溶剂中，进行所述配位反应。It can be understood that in other embodiments of the present application, the diamine ligand or monoamine ligand and the coordination compound can also be directly dispersed in an organic solvent to perform the coordination reaction.
上述金属化合物的制备方法，工艺简单，易于操作，成本低廉，所得金属化合物的结构稳定性高。The preparation method of the above-mentioned metal compound has simple process, easy operation, low cost, and the obtained metal compound has high structural stability.
本申请实施例还提供了上述金属化合物在制备含过渡金属元素的薄膜中的应用。The embodiments of the present application also provide the application of the above-mentioned metal compounds in preparing films containing transition metal elements.
其中，上述含过渡金属元素的薄膜的材质可以是含过渡金属元素的化合物(如金属氧化物、氮化物、碳化物、碳氮化物等)或单质。金属氧化物可以是含一种过渡金属元素的一元氧化物，或多元金属氧化物。换言之，金属氧化物中可以含有一种或者多种金属元素，例如含有一种或多种过渡金属元素。Wherein, the material of the thin film containing transition metal elements may be a compound containing transition metal elements (such as metal oxide, nitride, carbide, carbonitride, etc.) or a simple substance. The metal oxide can be a monovalent oxide containing a transition metal element, or a multi-element metal oxide. In other words, the metal oxide may contain one or more metal elements, such as one or more transition metal elements.
本申请一些实施方式中，当含过渡金属元素的化合物是含La氧化物时，其具体可以是氧化镧(La2O3)、含镧的二元或多元金属氧化物(例如氧化镧铪、氧化镧锆、氧化镧铝、氧化镧铈、氧化镧钇、氧化镧钽、氧化镧镥、氧化镧锶等)等。可以理解的，当制备La2O3时，通过气相沉积法制备La2O3薄膜所需的原料，包括前述中心原子是La原子的金属化合物，以及氧源；当制备含镧的二元或多元金属氧化物时，所需要的原料还包括其他金属元素对应的前驱体，具体可以是中心原子不为La的前述金属化合物，或已知或以后开发的任何金属前驱体。其中，氧源可以包括氧气(O2)、臭氧(O3)、水蒸气(H2O)、过氧化氢(H2O2)中的一种或多种。这些氧源与上述金属化合物的反应活性高，且可尽量减少杂质的引入。在一些实施方式中，所述氧源为臭氧。In some embodiments of the present application, when the compound containing a transition metal element is a La-containing oxide, it may specifically be lanthanum oxide (La 2 O 3 ), a lanthanum-containing binary or multi-element metal oxide (such as lanthanum-hafnium oxide, Lanthanum zirconium oxide, lanthanum aluminum oxide, lanthanum cerium oxide, lanthanum yttrium oxide, lanthanum tantalum oxide, lanthanum lutetium oxide, lanthanum strontium oxide, etc.). It can be understood that when preparing La 2 O 3 , the raw materials required to prepare a La 2 O 3 thin film by vapor deposition include the aforementioned metal compound whose central atom is a La atom, and an oxygen source; when preparing a binary or lanthanum-containing In the case of multi-element metal oxides, the required raw materials also include precursors corresponding to other metal elements. Specifically, they can be the aforementioned metal compounds whose central atom is not La, or any metal precursor known or later developed. The oxygen source may include one or more of oxygen (O 2 ), ozone (O 3 ), water vapor (H 2 O), and hydrogen peroxide (H 2 O 2 ). These oxygen sources have high reactivity with the above-mentioned metal compounds and can minimize the introduction of impurities. In some embodiments, the oxygen source is ozone.
其中，上述金属化合物通过气相沉积法制备得到含过渡金属元素的薄膜。其中，气相沉积法具体可以是化学气相沉积法(CVD)或原子层沉积法(ALD)。该CVD可以是常规的CVD或其变形的气相沉积工艺，例如等离子体增强CVD(PEVCD)、低压CVD(LPVCD)、常压CVD(APVCD)、脉冲CVD(P-CVD)、热丝CVD(HWVCD，热丝充电沉积过程中的能量源)。ALD可以是常规的ALD或其变形的气相沉积工艺，例如等离子体增强ALD(PEALD)、空间ALD、热ALD(Thermal ALD)等。Wherein, the above metal compound is prepared by a vapor deposition method to obtain a thin film containing transition metal elements. The vapor deposition method may specifically be chemical vapor deposition (CVD) or atomic layer deposition (ALD). The CVD can be conventional CVD or a modified vapor deposition process, such as plasma enhanced CVD (PEVCD), low pressure CVD (LPVCD), atmospheric pressure CVD (APVCD), pulse CVD (P-CVD), hot wire CVD (HWVCD) , the energy source in the hot wire charging deposition process). ALD can be conventional ALD or its modified vapor deposition process, such as plasma enhanced ALD (PEALD), spatial ALD, thermal ALD (Thermal ALD), etc.
在采用CVD法或ALD法沉积含过渡金属元素的薄膜时，上述金属化合物可用作提供过渡金属元素的原材料，上述金属化合物的熔点低、较易挥发气化，能顺利到达待沉积的基材表面，且在其到达基材之前很少发生热分解，特别是采用ALD法沉积时，这样可保证含过渡金属元素的薄膜的厚度精确可控，薄膜质量较高，共形性好。When using the CVD method or ALD method to deposit films containing transition metal elements, the above-mentioned metal compounds can be used as raw materials to provide transition metal elements. The above-mentioned metal compounds have a low melting point, are easier to volatilize and vaporize, and can smoothly reach the substrate to be deposited. Surface, and little thermal decomposition occurs before it reaches the substrate, especially when deposited using the ALD method. This ensures that the thickness of the film containing transition metal elements is accurately controllable, the film quality is high, and the conformality is good.
本申请实施例还提供了上述金属化合物在制备电子器件中的应用。具体地，上述金属化合物可以用于制备电子器件中的含过渡金属元素的薄膜。该电子器件可以具体是半导体器件。The embodiments of the present application also provide applications of the above metal compounds in preparing electronic devices. Specifically, the above-mentioned metal compounds can be used to prepare films containing transition metal elements in electronic devices. The electronic device may in particular be a semiconductor device.
制得的电子器件通常包括基材，以及位于基材上的含过渡金属元素的薄膜。如上所述，含过渡金属元素的薄膜可以采用上述金属化合物通过CVD法或ALD法制得，该含过渡金属元素的薄膜可以是含过渡金属元素的氧化物、氮化物、碳化物或碳氮化物等。此外，基材可 以不仅仅是单纯的衬底，诸如硅、石英、SiC、SiGe、GaAs、GaN、蓝宝石等，还可以是表面带有其他材料薄膜的衬底。The produced electronic device usually includes a substrate and a thin film containing a transition metal element located on the substrate. As mentioned above, the film containing transition metal elements can be produced by the CVD method or the ALD method using the above metal compounds. The film containing transition metal elements can be an oxide, nitride, carbide or carbonitride containing transition metal elements, etc. . In addition, the substrate can It is not just a simple substrate, such as silicon, quartz, SiC, SiGe, GaAs, GaN, sapphire, etc., but also a substrate with films of other materials on the surface.
采用上述金属化合物作为过渡金属源制备电子器件中的含过渡金属元素的薄膜，该金属化合物的熔点低、较易气化，能顺利到达待沉积的基材表面，且进行气相沉积反应的反应活性高，所制得的薄膜的形貌、沉积厚度可以进行精密调控，质量较好，利于保证电子器件的稳定持久运行。其中，在采用ALD法制备含过渡金属元素的薄膜时，其在到达基材之前很少发生热分解，薄膜的厚度精确可控，共形性、均匀性高。The above-mentioned metal compound is used as a transition metal source to prepare a film containing a transition metal element in an electronic device. The metal compound has a low melting point, is easier to vaporize, can smoothly reach the surface of the substrate to be deposited, and has high reactivity in the vapor deposition reaction. High, the morphology and deposition thickness of the produced film can be precisely controlled, and the quality is good, which is conducive to ensuring the stable and long-lasting operation of electronic devices. Among them, when the ALD method is used to prepare a film containing transition metal elements, it rarely thermally decomposes before reaching the substrate. The thickness of the film is accurately controllable and has high conformality and uniformity.
本申请实施例还提供了一种含过渡金属元素的薄膜，其采用本申请实施例上述的金属化合物制备得到。具体的制备方法可参见本申请下文的描述。The embodiments of the present application also provide a thin film containing transition metal elements, which is prepared by using the metal compound mentioned above in the embodiments of the present application. For specific preparation methods, please refer to the description below in this application.
在介绍该含过渡金属元素的薄膜的制备方法之前，先介绍制备含过渡金属元素的薄膜所用的装置。Before introducing the preparation method of the thin film containing transition metal elements, the device used to prepare the thin film containing transition metal elements is first introduced.
本申请实施例提供的制备含过渡金属元素的薄膜的装置，可以包括连通的容器室和沉积室，所述容器室用于储存本申请实施例上述的金属化合物，所述沉积室中放置有基材，所述金属化合物能被输送至所述沉积室中，并在所述基材的表面沉积形成含过渡金属元素的薄膜。The device for preparing a thin film containing a transition metal element provided by the embodiment of the present application may include a connected container chamber and a deposition chamber. The container chamber is used to store the metal compound described in the embodiment of the present application. A substrate is placed in the deposition chamber. The metal compound can be transported into the deposition chamber and deposited on the surface of the substrate to form a thin film containing transition metal elements.
上述装置可以具体是CVD沉积设备或ALD沉积设备，关于该装置的具体构造，可参考本申请全文对图1的介绍。The above-mentioned device may specifically be a CVD deposition device or an ALD deposition device. Regarding the specific structure of the device, reference may be made to the introduction of Figure 1 throughout this application.
具体地，该装置的容器室10可以放置有至少一个储料容器11，本申请实施例上述的金属化合物可放置在对应的储料容器11中。各储料容器11的外部可设有加热设备(图1中未示出)，用于对所述储料容器进行加热，以便上述金属化合物以气态形式被输送至沉积室20内。各储料容器11与沉积室20连通的各输送管路可设置有阀门。其中，沉积室20的外部设置有加热组件22，用于使沉积室20内的温度达到沉积反应温度。Specifically, the container chamber 10 of the device can be placed with at least one storage container 11, and the metal compound mentioned in the embodiment of the present application can be placed in the corresponding storage container 11. A heating device (not shown in FIG. 1 ) may be provided on the outside of each storage container 11 for heating the storage container so that the metal compound is transported into the deposition chamber 20 in a gaseous form. Each transport pipeline connecting each storage container 11 and the deposition chamber 20 may be provided with a valve. A heating component 22 is provided outside the deposition chamber 20 for making the temperature in the deposition chamber 20 reach the deposition reaction temperature.
采用上述装置能制备得到前述质量良好的含过渡金属元素的薄膜。The above device can be used to prepare the aforementioned thin film containing transition metal elements with good quality.
下面介绍含过渡金属元素的薄膜的沉积方法。本申请实施例提供的含过渡金属元素的薄膜的沉积方法，包括以下步骤：The following describes the deposition method of thin films containing transition metal elements. The deposition method of a thin film containing transition metal elements provided by the embodiment of the present application includes the following steps:
将气化的前述金属化合物引入到沉积设备中放置有基材的沉积室内，以在基材表面沉积形成含过渡金属元素的薄膜。The gasified metal compound is introduced into a deposition chamber in which the substrate is placed in the deposition equipment to deposit a thin film containing a transition metal element on the surface of the substrate.
其中，待沉积含过渡金属元素的薄膜的所述基材可以根据预期的最终用途来定。本申请一些实施方式中，该基材可以包括但不限于硅(Si)、石英(SiO2)、SiC、SiGe、GaAs、GaN、蓝宝石、玻璃、塑料、金属或者表面具有其他材料薄膜的前述基材等。对于半导体器件来说，基材上的其他材料薄膜可以是金属层(如Pd、Pt、Au、Al、W、Ti等)、氮化物(如TaN、TiN、TiSN、Si3N4等)、氧化物(如SiO2、SiON、HfO2、ZrO2、Al2O3等)或其组合等。The substrate on which the transition metal element-containing film is to be deposited can be determined according to the intended end use. In some embodiments of the present application, the substrate may include, but is not limited to, silicon (Si), quartz (SiO 2 ), SiC, SiGe, GaAs, GaN, sapphire, glass, plastic, metal or the aforementioned substrate with a thin film of other materials on the surface. Materials etc. For semiconductor devices, other material films on the substrate can be metal layers (such as Pd, Pt, Au, Al, W, Ti, etc.), nitrides (such as TaN, TiN, TiSN, Si 3 N 4 , etc.), Oxides (such as SiO 2 , SiON, HfO 2 , ZrO 2 , Al 2 O 3 , etc.) or combinations thereof, etc.
可以将沉积室20内的基材21加热至足够温度，以使气化的前述金属化合物能在其表面反应获得所需的含过渡金属元素的薄膜。在沉积过程中，沉积室20内的温度应大于前述金属化合物的气化温度，同时还应保证该金属化合物材料从容器室10至沉积室20输送过程中的稳定性，以免在输送过程中发生冷凝。此外，当进行的是ALD沉积时，沉积室内的温度还应小于金属化合物的分解温度。这样可在达到上述金属化合物反应温度的前提下，避免因金属化合物的热分解而造成薄膜沉积不均匀问题。The substrate 21 in the deposition chamber 20 can be heated to a sufficient temperature so that the vaporized metal compound can react on its surface to obtain the desired transition metal element-containing film. During the deposition process, the temperature in the deposition chamber 20 should be greater than the vaporization temperature of the aforementioned metal compound. At the same time, the stability of the metal compound material during transportation from the container chamber 10 to the deposition chamber 20 should be ensured to avoid the occurrence of accidents during transportation. condensation. In addition, when ALD deposition is performed, the temperature in the deposition chamber should be lower than the decomposition temperature of the metal compound. In this way, the problem of uneven film deposition caused by thermal decomposition of the metal compound can be avoided on the premise of reaching the reaction temperature of the above-mentioned metal compound.
其中，上述金属化合物可以以蒸气的形式引入到基材21的上方，该蒸气可以通过固态或液态的金属化合物形成，例如借助其升华或蒸发实现。在一些实施方式中，可以将固态的金属化合物加热，以达到液相温度，并具有足够的蒸气压温度，以便气化。在另一些实施方式中，可以将载气(如氩气、氦气、氮气等)传送至装有金属化合物的容器中，以助于金属化 合物的气化。在又一些实施方式中，可以将金属化合物与有机溶剂混合配置成溶液，再将该溶液加热气化，可使金属化合物进入沉积室20内，还可以向该溶液中鼓入载气。The above-mentioned metal compound may be introduced above the substrate 21 in the form of vapor, and the vapor may be formed by solid or liquid metal compound, for example, by sublimation or evaporation thereof. In some embodiments, a solid metal compound can be heated to reach a liquidus temperature and have a sufficient vapor pressure temperature to vaporize. In other embodiments, a carrier gas (such as argon, helium, nitrogen, etc.) can be delivered to the container containing the metal compound to facilitate metallization gasification of the compound. In some embodiments, a metal compound and an organic solvent can be mixed to form a solution, and then the solution can be heated and vaporized to allow the metal compound to enter the deposition chamber 20 , and a carrier gas can also be blown into the solution.
本申请一些实施方式中，上述沉积方法还包括：将反应物物种引入到所述沉积室内。该反应物物种可以是待制备薄膜的某一构成元素源(例如是氧元素)，或者进行沉积反应所需的其他气体。该反应物物种可以是气态试剂或者是液态试剂的蒸气。In some embodiments of the present application, the above-mentioned deposition method further includes: introducing reactant species into the deposition chamber. The reactant species may be a source of a certain element of the thin film to be prepared (such as oxygen), or other gases required for the deposition reaction. The reactant species may be a gaseous reagent or a vapor of a liquid reagent.
在一些实施例中，当含过渡金属元素的薄膜具体是过渡金属单质时(如Cu)，上述反应物物种可以是还原性气体，例如氢气(H2)。此时，上述沉积室20可配备氢气发生器以产生氢气。In some embodiments, when the film containing a transition metal element is specifically a transition metal element (such as Cu), the above-mentioned reactant species may be a reducing gas, such as hydrogen (H 2 ). At this time, the above-mentioned deposition chamber 20 may be equipped with a hydrogen generator to generate hydrogen gas.
在另一些实施例中，当含过渡金属元素的薄膜还含有氧(O)元素时，此时含过渡金属元素的薄膜可具体为金属氧化物(如La2O3)。上述反应物物种可以包括氧源，该氧源可以是O2、O3、H2O、H2O2等中的一种或多种。在一些实施方式中，氧源为臭氧(O3)。上述沉积室20可配有用于产生臭氧的等臭氧发生器。In other embodiments, when the film containing a transition metal element also contains an oxygen (O) element, the film containing a transition metal element may be specifically a metal oxide (such as La 2 O 3 ). The above reactant species may include an oxygen source, which may be one or more of O 2 , O 3 , H 2 O, H 2 O 2, etc. In some embodiments, the oxygen source is ozone ( O3 ). The above-described deposition chamber 20 may be equipped with an isozone generator for generating ozone.
在又一些实施例中，当含过渡金属元素的薄膜还含有氮(N)元素时，例如含过渡金属元素的薄膜是氮化镧、碳氮化镧时，上述反应物物种可以包括氮源，该氮源可以包括但不限于氮气(N2)、氨(NH3)、肼(N2H4)等中的一种或多种。In some embodiments, when the film containing a transition metal element also contains a nitrogen (N) element, for example, when the film containing a transition metal element is lanthanum nitride or lanthanum carbonitride, the above-mentioned reactant species may include a nitrogen source, The nitrogen source may include, but is not limited to, one or more of nitrogen (N 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), and the like.
在又一些实施例中，当含过渡金属元素的薄膜还含有碳(C)元素时，例如含过渡金属元素的薄膜是碳化镧、碳氮化镧时，上述反应物物种可以包括碳源，该碳源可以包括但不限于甲烷(CH4)、乙烷(C2H6)、乙烯(C2H4)、丙烯(C3H6)等中的一种或多种。In some embodiments, when the film containing a transition metal element also contains a carbon (C) element, for example, when the film containing a transition metal element is lanthanum carbide or lanthanum carbonitride, the above-mentioned reactant species may include a carbon source. The carbon source may include, but is not limited to, one or more of methane (CH 4 ), ethane (C 2 H 6 ), ethylene (C 2 H 4 ), propylene (C 3 H 6 ), and the like.
其中，形成含过渡金属元素的薄膜的沉积方法可以是CVD法，此种情况下，反应物物种可以与前述金属化合物一起引入到放置有基材21的沉积室20内。形成含过渡金属元素的薄膜的沉积方法可以是ALD法，此种情况下，反应物物种与前述金属化合物交替引入到放置有基材21的沉积室20内，以使反应物物种、金属化合物交替暴露于基材21。The deposition method for forming a thin film containing transition metal elements may be a CVD method. In this case, the reactant species may be introduced into the deposition chamber 20 where the substrate 21 is placed together with the aforementioned metal compound. The deposition method for forming a thin film containing transition metal elements may be the ALD method. In this case, the reactant species and the aforementioned metal compound are alternately introduced into the deposition chamber 20 where the substrate 21 is placed, so that the reactant species and the metal compound alternate. Exposed to substrate 21.
以沉积制备La2O3薄膜为例，将中心原子为镧原子的前述金属化合物(简称La配合物)与氧源可以先置于图1中沉积设备100的容器室10的不同储料容器11中，对储料容器11进行加热可以实现它们的各自气化。当采用CVD法沉积制备La2O3薄膜时，可以将气化的La配合物及氧源一起输送到沉积设备100的沉积室20中。当采用ALD法沉积制备La2O3薄膜时，气化的La配合物及气态的氧源或氧源蒸气是交替输送到沉积设备100的沉积室20中。具体地，可以先将气化的La配合物通入沉积室20中，之后借助惰性气体的吹扫带走基材21表面未被吸附的多余配合物，接着将气态的氧源通入沉积室20中，基材上吸附的La配合物与扩散到基材表面的氧源发生反应(ALD工艺依赖于具有自限性的饱和表面反应)，再借助惰性气体的吹扫带走基材21表面多余的氧源，至此为一个循环；重复上述多次循环，在基材21表面实现具有自限制特性的原子层沉积。ALD工艺的表面控制性质使得其能够通过精确的厚度控制来生长具有高共形性和均匀性的La2O3薄膜。Taking the deposition preparation of La 2 O 3 thin films as an example, the aforementioned metal compound (referred to as La complex) whose central atom is a lanthanum atom (referred to as La complex) and an oxygen source can be first placed in different storage containers 11 of the container chamber 10 of the deposition equipment 100 in Figure 1 , heating the storage container 11 can achieve their respective gasification. When a La 2 O 3 film is deposited and prepared by the CVD method, the vaporized La complex and the oxygen source can be transported to the deposition chamber 20 of the deposition equipment 100 together. When the ALD method is used to deposit and prepare a La 2 O 3 film, the vaporized La complex and the gaseous oxygen source or oxygen source vapor are alternately transported to the deposition chamber 20 of the deposition equipment 100 . Specifically, the vaporized La complex can be first introduced into the deposition chamber 20, and then the excess complex that is not adsorbed on the surface of the substrate 21 can be taken away by purging with inert gas, and then the gaseous oxygen source can be introduced into the deposition chamber. In 20, the La complex adsorbed on the substrate reacts with the oxygen source diffused to the surface of the substrate (the ALD process relies on a self-limiting saturated surface reaction), and then the surface of the substrate 21 is taken away by purging with inert gas. The redundant oxygen source is thus a cycle; the above cycle is repeated multiple times to achieve self-limiting atomic layer deposition on the surface of the substrate 21 . The surface-controlled nature of the ALD process enables the growth of La2O3 films with high conformality and uniformity through precise thickness control.
本申请一些实施方式中，上述沉积方法还包括：将其他金属源引入放置有基材21的沉积室20内。此时，待制备的含过渡金属元素的薄膜可以含有两种金属元素(为理解方便，可将过渡金属元素也视为在广义的金属元素范围内)。In some embodiments of the present application, the above-mentioned deposition method further includes: introducing other metal sources into the deposition chamber 20 in which the substrate 21 is placed. At this time, the thin film containing transition metal elements to be prepared may contain two metal elements (for ease of understanding, transition metal elements can also be regarded as within the broad range of metal elements).
其中，其他金属源可以含有与上述金属化合物中的过渡金属原子不同的金属元素，如其他过渡金属原子、主族金属原子等；其他金属源可以是一种或多种。举例来说，当制备含镧的二元或多元金属氧化物时，所需要的金属源除了包括中心原子为镧原子的前述金属化合物外，还包括其他金属元素对应的前驱体。其他金属源可以仍是本申请前文定义的金属化合物，或本领域周知的已有金属配合物。其他金属源可以与前述金属化合物一起引入到沉积室，例 如其他金属源可以与前述金属化合物先混合，以在引入到沉积室内之前被气化。当然，其他金属源也可以与前述金属化合物交替引入到沉积室内。例如，将如本申请前文的镧的金属化合物记作原料A，将铪的前驱体记作原料B，将臭氧记作原料C，在通过ALD工艺制备氧化镧铪时，可以按先A再B后C的方式使它们交替暴露于基材21表面，并在不同原料通入沉积室的间隙通过惰性气体进行吹扫。Among them, other metal sources may contain metal elements different from the transition metal atoms in the above-mentioned metal compounds, such as other transition metal atoms, main group metal atoms, etc.; the other metal sources may be one or more. For example, when preparing a binary or multi-element metal oxide containing lanthanum, the required metal source includes, in addition to the aforementioned metal compound whose central atom is a lanthanum atom, also includes corresponding precursors of other metal elements. Other metal sources may still be metal compounds defined previously in this application, or existing metal complexes well known in the art. Other metal sources can be introduced into the deposition chamber together with the aforementioned metal compounds, e.g. For example, other metal sources can be mixed with the aforementioned metal compounds to be vaporized before being introduced into the deposition chamber. Of course, other metal sources can also be introduced into the deposition chamber alternately with the aforementioned metal compounds. For example, let the metal compound of lanthanum mentioned above in this application be recorded as raw material A, the precursor of hafnium as raw material B, and ozone as raw material C. When preparing lanthanum-hafnium oxide through the ALD process, A can be used first and then B. The latter C method makes them alternately exposed to the surface of the substrate 21, and are purged by inert gas in the gap between different raw materials entering the deposition chamber.
本申请实施例还提供了一种含过渡金属元素的薄膜，其采用本申请实施例上述的金属化合物制备得到。The embodiments of the present application also provide a thin film containing transition metal elements, which is prepared by using the metal compound mentioned above in the embodiments of the present application.
可以理解地，在该含过渡金属元素的薄膜的制备过程中，所采用的反应原料除了上述金属化合物外，还可以包括上述反应物物种、其他金属源等。所制得的含过渡金属元素的薄膜如本申请前文所述，这里不再赘述。It can be understood that in the preparation process of the film containing transition metal elements, the reaction raw materials used, in addition to the above-mentioned metal compounds, may also include the above-mentioned reactant species, other metal sources, etc. The prepared thin film containing transition metal elements is as described previously in this application and will not be described again here.
本申请实施例还提供了一种电子器件，该电子器件具有本申请实施例上述的含过渡金属元素的薄膜。An embodiment of the present application also provides an electronic device, which has the transition metal element-containing film described in the embodiment of the present application.
其中，该电子器件包括基材，以及位于该基材上的含过渡金属元素的薄膜。对于基材、含过渡金属元素的薄膜，可参见本申请前文的描述。Wherein, the electronic device includes a substrate and a film containing transition metal elements located on the substrate. For the substrate and the film containing transition metal elements, please refer to the previous description of this application.
下面再通过具体的实施例对本申请实施例的技术方案进行进一步的说明。The technical solutions of the embodiments of the present application will be further described below through specific examples.
实施例1Example 1
一种含镧化合物：La(thd)3(DMEDA)，其中，thd代表2,2,6,6-四甲基-3,5-庚二酮，DMEDA代表N,N’二甲基乙二胺。A lanthanum-containing compound: La(thd) 3 (DMEDA), where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and DMEDA represents N,N'dimethylethylenedione amine.
该含镧化合物的合成路线如下：
The synthesis route of the lanthanum-containing compound is as follows:
上述含镧化合物的制备方法，包括：称取41.3g的镧的六配位化合物La(thd)3(中文名：三(2,2,6,6-四甲基-3,5-庚二酮)镧(III))置于1L的烧瓶中，加入500mL的甲苯并搅拌，得到白色浑浊状的La(thd)3分散液。称取5.3g的N,N’二甲基乙二胺(DMEDA)置于另外一个100mL的烧杯中，并加入50mL的甲苯搅拌溶解，得到DMEDA溶液。室温下，将DMEDA溶液滴加至La(thd)3分散液中，搅拌4小时以进行配位反应。之后，通过减压蒸馏除去所得反应液中的甲苯，得到46.5g的La(thd)3(DMEDA)。The preparation method of the above-mentioned lanthanum-containing compound includes: weighing 41.3g of the six-coordinate compound La(thd) 3 of lanthanum (Chinese name: tris(2,2,6,6-tetramethyl-3,5-heptanedi) Ketone) Lanthanum (III)) was placed in a 1L flask, 500 mL of toluene was added and stirred to obtain a white turbid La(thd) 3 dispersion. Weigh 5.3g of N,N' dimethylethylenediamine (DMEDA) into another 100mL beaker, add 50mL of toluene, stir and dissolve, and obtain a DMEDA solution. At room temperature, the DMEDA solution was added dropwise to the La(thd) 3 dispersion, and stirred for 4 hours to proceed with the coordination reaction. Thereafter, toluene in the obtained reaction liquid was removed by distillation under reduced pressure, and 46.5 g of La(thd) 3 (DMEDA) was obtained.
其中，上述含镧化合物La(thd)3(DMEDA)的核磁共振谱图如图2所示。具体可获知的核磁共振数据为：1H-NMR(400MHz,C6D6)：δ5.86(s,3H,O＝C-CH-C＝O),2.41(s,6H,N-CH 3),2.24(s,4H,-CH 2-N),1.28(s,54H,-CH 3).这些核磁共振结果表明，本申请成功制得结构通式如上所示的含镧化合物。Among them, the nuclear magnetic resonance spectrum of the above-mentioned lanthanum-containing compound La(thd) 3 (DMEDA) is shown in Figure 2. The specific available nuclear magnetic resonance data are: 1 H-NMR (400MHz, C 6 D 6 ): δ5.86 (s, 3H, O＝CC H -C＝O), 2.41 (s, 6H, NC H 3 ) ,2.24(s,4H,-C H 2 -N), 1.28(s,54H,-C H 3 ). These nuclear magnetic resonance results show that the present application successfully prepared the lanthanum-containing compound with the general structural formula shown above.
对上述含镧化合物La(thd)3(DMEDA)进行热性能分析，所得热重分析(Thermogravimetric Analysis，简写为TG或TGA)曲线、差示扫描量热(differential scanning calorimetry，简写为DSC)曲线如图3所示，该含镧化合物的饱和蒸气压对温度的曲线如图4所示。从图3-图4可以获知，该含镧化合物的熔点低(约为135℃)，热稳定性高(分解温度>300℃)。在相 同蒸气压下材料的挥发温度越低，代表材料的挥发性越好，其中实施例1的含镧化合物在0.1Torr的饱和蒸气压的挥发温度为130℃，低于La(thd)3在0.1torr下的挥发温度(约在200℃以上)，表明该含镧化合物的挥发性良好。The thermal properties of the above lanthanum-containing compound La(thd) 3 (DMEDA) were analyzed, and the obtained thermogravimetric analysis (TG or TGA) curve and differential scanning calorimetry (DSC) curve were as follows: As shown in Figure 3, the saturated vapor pressure versus temperature curve of the lanthanum-containing compound is shown in Figure 4. It can be known from Figures 3 and 4 that the lanthanum-containing compound has a low melting point (about 135°C) and high thermal stability (decomposition temperature >300°C). In phase The lower the volatilization temperature of the material under the same vapor pressure, the better the volatility of the material. The volatilization temperature of the lanthanum-containing compound in Example 1 at a saturated vapor pressure of 0.1 Torr is 130°C, which is lower than that of La(thd) 3 at 0.1 The volatilization temperature under torr (approximately above 200°C) indicates that the lanthanum-containing compound has good volatility.
将含镧化合物La(thd)3(DMEDA)用于沉积制备La2O3薄膜：以La(thd)3(DMEDA)作镧前驱体材料，以臭氧O3为氧化剂，以石英(SiO2)片作基材，通过ALD法在基材上沉积La2O3薄膜，其中，控制该含镧化合物的蒸发温度为150℃(即，将图1容器室10中装有该含镧化合物的一储料容器11加热至150℃，使其气化)，控制容器室10与沉积室20之间的连接管路的温度为170℃，以保证该含镧化合物在输送至沉积室20的过程中不会冷凝。将该含镧化合物与O3循环交替通入沉积室20，并在这两种气化物通入沉积室的间隙通过氩气来吹扫多余的前驱原料。The lanthanum-containing compound La(thd) 3 (DMEDA) is used to deposit La 2 O 3 thin films: La(thd) 3 (DMEDA) is used as the lanthanum precursor material, ozone O 3 is used as the oxidant, and quartz (SiO 2 ) is used The sheet is used as the substrate, and a La 2 O 3 film is deposited on the substrate by the ALD method, wherein the evaporation temperature of the lanthanum-containing compound is controlled to 150°C (that is, a container containing the lanthanum-containing compound is placed in the container chamber 10 of Figure 1 The storage container 11 is heated to 150°C to vaporize it), and the temperature of the connecting pipeline between the container chamber 10 and the deposition chamber 20 is controlled to 170°C to ensure that the lanthanum-containing compound is transported to the deposition chamber 20 Will not condense. The lanthanum-containing compound and O 3 are circulated and alternately introduced into the deposition chamber 20 , and excess precursor raw materials are purged by argon gas in the gap between the two vapors entering the deposition chamber.
沉积得到的La2O3薄膜的相关数据如图5所示。从图5中(a)-(d)四个小图可以获知，以该La(thd)3(DMEDA)作原料通过ALD沉积得到的La2O3薄膜符合ALD沉积特性，其中，La(thd)3(DMEDA)的饱和脉冲时间为7s，O3的饱和脉冲时间为90s，ALD温度窗口在210-250℃，La2O3薄膜的厚度随循环次数的进行线性增加，算得La2O3薄膜的成膜速率是 The relevant data of the deposited La 2 O 3 film is shown in Figure 5. It can be known from the four small figures (a)-(d) in Figure 5 that the La 2 O 3 film obtained by ALD deposition using La(thd) 3 (DMEDA) as raw material conforms to the ALD deposition characteristics, where La(thd ) 3 (DMEDA) saturation pulse time is 7s, O 3 saturation pulse time is 90s, ALD temperature window is 210-250℃, the thickness of La 2 O 3 film increases linearly with the number of cycles, calculated La 2 O 3 The film formation rate is
采用La(thd)3(DMEDA)通过ALD法制得的La2O3薄膜的切片扫描电子显微镜(Scanning Electron Microscope，SEM)照片和XRD图谱分别如图6、图7所示。从图6可以获知，采用La(thd)3(DMEDA)可以沉积连续且均匀的La2O3薄膜，根据前述La2O3薄膜的成膜速率是可算得厚度为23.8nm的La2O3薄膜约对应529个沉积循环。从图7可以获知，沉积所得La2O3薄膜具体为六方相的h-La2O3，图中可见h-La2O3的(101)晶面的尖锐衍射峰。The slice scanning electron microscope (SEM) photos and XRD patterns of the La 2 O 3 thin film produced by the ALD method using La(thd) 3 (DMEDA) are shown in Figure 6 and Figure 7 respectively. It can be seen from Figure 6 that a continuous and uniform La 2 O 3 film can be deposited using La(thd) 3 (DMEDA). According to the aforementioned film formation rate of the La 2 O 3 film is It can be calculated that a La 2 O 3 film with a thickness of 23.8 nm corresponds to approximately 529 deposition cycles. It can be seen from Figure 7 that the deposited La 2 O 3 film is specifically h-La 2 O 3 in the hexagonal phase. The sharp diffraction peak of the (101) crystal plane of h-La 2 O 3 can be seen in the figure.
实施例2Example 2
一种含镧化合物：La(ibpm)3(DMEDA)，其中，ibpm代表2,2,6-三甲基-3,5-庚二酮，DMEDA代表N,N’二甲基乙二胺。A lanthanum-containing compound: La(ibpm) 3 (DMEDA), where ibpm represents 2,2,6-trimethyl-3,5-heptanedione and DMEDA represents N,N'dimethylethylenediamine.
该含镧化合物的合成路线如下：
The synthesis route of the lanthanum-containing compound is as follows:
上述含镧化合物的制备方法，包括：称取48.5g的六配位的镧配合物La(ibpm)3(中文名：三(2,2,6-三甲基-3,5-庚二酮)镧(III))置于1L的烧瓶中，加入500mL的甲苯并搅拌，得到白色浑浊状的La(ibpm)3分散液。称取8.5g的N,N’二甲基乙二胺(DMEDA)置于另外一个100mL的烧杯中，并加入50mL的甲苯搅拌溶解，得到DMEDA溶液。室温下，将DMEDA溶液滴加至La(ibpm)3分散液中，搅拌3小时以进行配位反应。之后，通过减压蒸馏除去所得反应液中的甲苯，得到55.4g的La(ibpm)3(DMEDA)。The preparation method of the above-mentioned lanthanum-containing compound includes: weighing 48.5g of the six-coordinated lanthanum complex La(ibpm) 3 (Chinese name: tris(2,2,6-trimethyl-3,5-heptanedione) ) Lanthanum (III)) was placed in a 1L flask, 500 mL of toluene was added and stirred to obtain a white turbid La(ibpm) 3 dispersion. Weigh 8.5g of N,N'dimethylethylenediamine (DMEDA) into another 100mL beaker, add 50mL of toluene, stir and dissolve, and obtain a DMEDA solution. At room temperature, the DMEDA solution was added dropwise to the La(ibpm) 3 dispersion, and stirred for 3 hours to perform the coordination reaction. Thereafter, toluene in the obtained reaction liquid was removed by distillation under reduced pressure, and 55.4 g of La(ibpm) 3 (DMEDA) was obtained.
其中，上述含镧化合物La(ibpm)3(DMEDA)的核磁共振谱图如图8所示。具体可获知的核磁共振数据有：1H NMR(400MHz,CDCl3)δ5.37(s,3H,O＝CCHC＝O),2.72(s,4H,CH 2N),2.48(s,6H,NCH 3),2.29(3H,m,CH(CH3)2),1.06(s,27H,C(CH 3)3).1.01(d,18H,CH(CH 3)2).这些核磁共振结果表明，本申请成功制得结构通式如上所示的含镧化合物La(ibpm)3(DMEDA)。Among them, the nuclear magnetic resonance spectrum of the above-mentioned lanthanum-containing compound La(ibpm) 3 (DMEDA) is shown in Figure 8. The specific available nuclear magnetic resonance data are: 1 H NMR (400MHz, CDCl 3 ) δ5.37 (s, 3H, O = C H C = O), 2.72 (s, 4H, C H 2 N), 2.48 (s ,6H,NC H 3 ),2.29(3H,m,C H (CH 3 ) 2 ),1.06(s,27H,C(C H 3 ) 3 ).1.01(d,18H,CH(C H 3 ) 2 ). These NMR results show that the present application successfully prepared the lanthanum-containing compound La(ibpm) 3 (DMEDA) with the general structural formula shown above.
对上述含镧化合物La(ibpm)3(DMEDA)进行热性能分析，所得TG-DSC曲线如图9所示， 该含镧化合物的饱和蒸气压对温度的曲线如图10所示。从图9-图10可以获知，含镧化合物La(ibpm)3(DMEDA)的熔点低(约为57℃)，热稳定性高(分解温度>300℃)，挥发性良好，其在0.1Torr的饱和蒸气压下的挥发温度为116℃。因此，该含镧化合物La(ibpm)3(DMEDA)适合通过ALD法或CVD法沉积制备含镧元素的薄膜。The thermal properties of the above lanthanum-containing compound La(ibpm) 3 (DMEDA) were analyzed, and the obtained TG-DSC curve is shown in Figure 9. The saturated vapor pressure versus temperature curve of the lanthanum-containing compound is shown in Figure 10. It can be seen from Figures 9 and 10 that the lanthanum-containing compound La(ibpm) 3 (DMEDA) has a low melting point (about 57°C), high thermal stability (decomposition temperature >300°C), and good volatility. It is at 0.1Torr The volatilization temperature under saturated vapor pressure is 116°C. Therefore, the lanthanum-containing compound La(ibpm) 3 (DMEDA) is suitable for depositing a thin film containing lanthanum element by ALD method or CVD method.
实施例3Example 3
一种含镧化合物：La(tmod)3(DMEDA)，其中，tmod代表2,2,6,6-四甲基-3,5-辛二酮，DMEDA代表N,N’二甲基乙二胺。A lanthanum-containing compound: La(tmod) 3 (DMEDA), where tmod represents 2,2,6,6-tetramethyl-3,5-octanedione and DMEDA represents N,N'dimethylethylenedione amine.
上述含镧化合物的制备方法，包括：称取50g的六配位的镧配合物La(tmod)3(中文名：三(2,2,6,6-四甲基-3,5-辛二酮)镧(III))置于1L的烧瓶中，加入500mL的甲苯并搅拌，得到白色浑浊状的La(tmod)3分散液。称取8.8g的N,N’二甲基乙二胺(DMEDA)置于另外一个100mL的烧杯中，并加入50mL的甲苯搅拌溶解，得到DMEDA溶液。室温下，将DMEDA溶液滴加至La(tmod)3分散液中，搅拌2小时以进行配位反应。之后，通过减压蒸馏除去所得反应液中的甲苯，得到56.3g的La(tmod)3*DMEDA。The preparation method of the above-mentioned lanthanum-containing compound includes: weighing 50g of the six-coordinated lanthanum complex La(tmod) 3 (Chinese name: tris(2,2,6,6-tetramethyl-3,5-octanedi) Ketone) Lanthanum (III)) was placed in a 1L flask, 500 mL of toluene was added and stirred to obtain a white turbid La(tmod) 3 dispersion. Weigh 8.8g of N,N'dimethylethylenediamine (DMEDA) into another 100mL beaker, add 50mL of toluene, stir and dissolve, and obtain a DMEDA solution. At room temperature, the DMEDA solution was added dropwise to the La(tmod) 3 dispersion, and stirred for 2 hours to proceed with the coordination reaction. Thereafter, toluene in the obtained reaction liquid was removed by distillation under reduced pressure, and 56.3 g of La(tmod) 3 *DMEDA was obtained.
该含镧化合物的合成路线如下：
The synthesis route of the lanthanum-containing compound is as follows:
其中，上述含镧化合物La(tmod)3(DMEDA)的核磁共振谱图如图11所示。具体可获知的核磁共振数据有：1H NMR(400MHz,CDCl3)δ,5.52(m,3H,O＝CCHC＝O),2.71(s,4H,-NCH 2),2.48(s,6H,-NCH 3),1.44(q,6H,CH 2CH3),1.078(s,27H,C(CH 3)3),1.02(s.18H,C(CH 3)2),0.74(t,9H,CH2CH 3).这些核磁共振结果表明，本申请成功制得结构通式如上所示的含镧化合物La(tmod)3(DMEDA)。Among them, the nuclear magnetic resonance spectrum of the above-mentioned lanthanum-containing compound La(tmod) 3 (DMEDA) is shown in Figure 11. The specific available nuclear magnetic resonance data are: 1 H NMR (400MHz, CDCl 3 ) δ, 5.52 (m, 3H, O = CC H C = O), 2.71 (s, 4H, -NC H 2 ), 2.48 (s ,6H,-NC H 3 ),1.44(q,6H,C H 2 CH 3 ),1.078(s,27H,C(C H 3 ) 3 ),1.02(s.18H,C(C H 3 ) 2 ), 0.74(t,9H,CH 2 CH 3 ). These NMR results show that the present application successfully prepared the lanthanum-containing compound La(tmod) 3 (DMEDA) with the general structural formula shown above.
对上述含镧化合物La(tmod)3(DMEDA)进行热性能分析，所得TG-DSC曲线如图12所示，该含镧化合物的饱和蒸气压对温度的曲线如图13所示。从图12的TG曲线可以获知，含镧化合物La(tmod)3(DMEDA)的T50为266℃，挥发结束温度为286.6℃，残留量为1.35％，说明化合物的挥发性良好，热稳定性高，且其热分解温度>300℃。图12的DSC曲线表明，74℃处的峰值代表化合物La(tmod)3(DMEDA)的晶型转化，166℃的吸热峰代表化合物熔化。从图13可以获知，La(tmod)3(DMEDA)在0.1Torr的饱和蒸气压下的挥发温度为154℃，挥发性良好。因此，该含镧化合物La(tmod)3(DMEDA)适合通过ALD法或CVD法沉积制备含镧元素的薄膜。The thermal properties of the above-mentioned lanthanum-containing compound La(tmod) 3 (DMEDA) were analyzed, and the obtained TG-DSC curve is shown in Figure 12. The saturated vapor pressure versus temperature curve of the lanthanum-containing compound is shown in Figure 13. It can be seen from the TG curve in Figure 12 that the T50 of the lanthanum-containing compound La(tmod) 3 (DMEDA) is 266°C, the volatilization end temperature is 286.6°C, and the residual amount is 1.35%, indicating that the compound has good volatility and high thermal stability. , and its thermal decomposition temperature is >300℃. The DSC curve in Figure 12 shows that the peak at 74°C represents the crystal form transformation of the compound La(tmod) 3 (DMEDA), and the endothermic peak at 166°C represents the melting of the compound. As can be seen from Figure 13, the volatilization temperature of La(tmod) 3 (DMEDA) at a saturated vapor pressure of 0.1 Torr is 154°C, indicating good volatility. Therefore, the lanthanum-containing compound La(tmod) 3 (DMEDA) is suitable for depositing lanthanum-containing thin films by ALD or CVD.
实施例4Example 4
一种含镧化合物：La(thd)3(Py)2，其中，thd代表2,2,6,6-四甲基-3,5-庚二酮，Py代表吡啶。A lanthanum-containing compound: La(thd) 3 (Py) 2 , where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and Py represents pyridine.
该含镧化合物的合成路线如下：
The synthesis route of the lanthanum-containing compound is as follows:
上述含镧化合物的制备方法，包括：称取13.8g的La(thd)3置于1L的烧瓶中，加入100mL的甲苯，逐滴滴加1.8g的吡啶与5mL的甲苯构成的混合溶液，在120℃下加热回流3小时，以进行配位反应。之后，待烧瓶温度恢复至室温，通过减压除去所得反应液中的易挥发物，得到淡黄色粉末La(thd)3(Py)2。The preparation method of the above-mentioned lanthanum-containing compound includes: weighing 13.8g of La(thd) 3 and placing it in a 1L flask, adding 100mL of toluene, and adding dropwise a mixed solution of 1.8g of pyridine and 5mL of toluene. Heat and reflux at 120°C for 3 hours to carry out coordination reaction. After that, after the temperature of the flask returned to room temperature, the volatile matter in the reaction solution was removed under reduced pressure to obtain light yellow powder La(thd) 3 (Py) 2 .
其中，上述含镧化合物La(thd)3(Py)2的核磁共振谱图如图14所示。具体可获知的核磁共振数据有：1HNMR：δ8.66(d,6H,py),7.68(t,3H,py),7.27(m,6H,py),5.68(s,3H，O＝C-CH-C＝O),1.09(s,54H,-CH 3).这些核磁共振结果表明，本申请成功制得结构通式如上所示的镧配合物La(thd)3(Py)2。Among them, the nuclear magnetic resonance spectrum of the above-mentioned lanthanum-containing compound La(thd) 3 (Py) 2 is shown in Figure 14. The specific available NMR data are: 1 HNMR: δ8.66(d,6H,py),7.68(t,3H,py),7.27(m,6H,py),5.68(s,3H,O=CC H -C=O), 1.09 (s, 54H, -C H 3 ). These NMR results show that the present application successfully prepared the lanthanum complex La(thd) 3 (Py) 2 with the general structural formula shown above.
对上述含镧化合物La(thd)3(Py)2进行热性能分析，所得TG-DSC曲线如图15所示。从图12可以获知，该La(thd)3(Py)2的TG曲线在300℃之前具有两个台阶，其中，100℃之前的失重约16％对应中性配体吡啶的脱落，说明吡啶与镧原子的结合力略弱，该含镧化合物的热稳定性略低于实施例1-3的含镧化合物。因此，该含镧化合物La(thd)3(Py)2适合通过CVD法(不太适合采用ALD法)沉积制备含镧元素的化合物薄膜或镧单质薄膜。The thermal properties of the above lanthanum-containing compound La(thd) 3 (Py) 2 were analyzed, and the obtained TG-DSC curve is shown in Figure 15. It can be seen from Figure 12 that the TG curve of La(thd) 3 (Py) 2 has two steps before 300°C. Among them, the weight loss of about 16% before 100°C corresponds to the shedding of the neutral ligand pyridine, indicating that pyridine and The binding force of lanthanum atoms is slightly weaker, and the thermal stability of the lanthanum-containing compound is slightly lower than that of the lanthanum-containing compound of Examples 1-3. Therefore, the lanthanum-containing compound La(thd) 3 (Py) 2 is suitable for depositing a lanthanum-containing compound film or a lanthanum elemental film through CVD method (less suitable for ALD method).
实施例5Example 5
一种含镧化合物：La(thd)3(DPA)2，其中，thd代表2,2,6,6-四甲基-3,5-庚二酮，DPA代表二丙胺。该含镧化合物的合成路线如下：
A lanthanum-containing compound: La(thd) 3 (DPA) 2 , where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and DPA represents dipropylamine. The synthesis route of the lanthanum-containing compound is as follows:
上述含镧化合物的制备方法，包括：称取45g的La(thd)3置于1L的烧瓶中，加入100mL的正己烷并搅拌，得到白色浑浊状的La(thd)3分散液。称取10.1g的二丙胺(DPA)置于另外一个100mL的烧杯中，并加入50mL的正己烷搅拌溶解，得到DPA溶液。室温下，将DPA溶液滴加至La(thd)3分散液中，搅拌2小时以进行配位反应。之后，通过减压蒸馏除去所得反应液中的正己烷，得到51.7g的La(thd)3(DPA)2。The preparation method of the above-mentioned lanthanum-containing compound includes: weighing 45g of La(thd) 3 into a 1L flask, adding 100 mL of n-hexane and stirring to obtain a white turbid La(thd) 3 dispersion. Weigh 10.1g of dipropylamine (DPA) into another 100mL beaker, add 50mL of n-hexane, stir and dissolve, and obtain a DPA solution. At room temperature, the DPA solution was dropwise added to the La(thd) 3 dispersion, and stirred for 2 hours to perform the coordination reaction. Then, n-hexane in the obtained reaction liquid was removed by distillation under reduced pressure, and 51.7 g of La(thd) 3 (DPA) 2 was obtained.
其中，上述含镧化合物La(thd)3(DPA)2的核磁共振谱图如图16所示。具体可获知的核磁共振数据有：1HNMR：δ5.64(s,3H，O＝C-CH-C＝O),2.57(t,8H，N-CH 2-CH 2-CH3),1.63–1.40(m,6H,N-CH2-CH2-CH 3),1.09(s,54H,-C(CH3)3).这些核磁共振结果表明，本申请成功制得结构通式如上所示的含镧化合物La(thd)3(DPA)2。Among them, the nuclear magnetic resonance spectrum of the above-mentioned lanthanum-containing compound La(thd) 3 (DPA) 2 is shown in Figure 16. The specific available nuclear magnetic resonance data are: 1 HNMR: δ5.64(s,3H,O＝CC H -C＝O),2.57(t,8H,NC H 2 -C H 2 -CH 3 ),1.63– 1.40(m,6H,N-CH 2 -CH 2 -C H 3 ), 1.09(s,54H,-C(CH 3 ) 3 ). These nuclear magnetic resonance results show that this application successfully prepared the structural formula as above The lanthanum-containing compound La(thd) 3 (DPA) 2 is shown.
对上述含镧化合物La(thd)3(DPA)2进行热性能分析，结果如图17所示。从TG曲线可以获知，该配合物在300℃之前有两个失重台阶，第一个台阶失重约21.82％，对应两分子的二 丙胺脱离；第二个台阶失重约77.89％，为La(thd)3的失重台阶；残余质量约为-0.06％，这说明该化合物La(thd)3(DPA)2的挥发性良好。从DSC曲线上的吸热峰可知，38℃对应的是La(thd)3(DPA)2的熔点峰，77℃、105℃依次对应脱去两分子的二丙胺的失重峰，176℃为La(thd)3的晶型的转化峰，263℃为La(thd)3的熔点峰。The thermal properties of the above lanthanum-containing compound La(thd) 3 (DPA) 2 were analyzed, and the results are shown in Figure 17. It can be known from the TG curve that the complex has two weight loss steps before 300°C. The weight loss of the first step is about 21.82%, which corresponds to the weight loss of two molecules. The propylamine is detached; the weight loss of the second step is about 77.89%, which is the weight loss step of La(thd) 3 ; the residual mass is about -0.06%, which shows that the volatility of the compound La(thd) 3 (DPA) 2 is good. It can be seen from the endothermic peaks on the DSC curve that 38°C corresponds to the melting point peak of La(thd) 3 (DPA) 2 , 77°C and 105°C correspond to the weight loss peaks of two molecules of dipropylamine, respectively, and 176°C is La. The transformation peak of the crystal form of (thd) 3 , and 263°C is the melting point peak of La(thd) 3 .
这些热性能数据表明，上述含镧化合物La(thd)3(DPA)2具有远低于La(thd)3的熔点(熔点约为38℃)，其可以以液态输送，利于降低输送能量，并在输送至较高温度的沉积室后具有良好的挥发性，同时在升高温度后一元胺配体优先脱离，该含镧化合物La(thd)3(DPA)2特别适合通过CVD法(不太适合采用ALD法)沉积制备含镧元素的薄膜。These thermal property data show that the above-mentioned lanthanum-containing compound La(thd) 3 (DPA) 2 has a melting point much lower than La(thd) 3 (the melting point is about 38°C), and it can be transported in a liquid state, which is beneficial to reducing the transportation energy and The lanthanum-containing compound La(thd) 3 (DPA) 2 has good volatility after being transported to a higher temperature deposition chamber, and at the same time the monoamine ligand is preferentially detached after the temperature is raised. The lanthanum-containing compound La(thd) 3 (DPA) 2 is particularly suitable for CVD method (less Suitable for depositing thin films containing lanthanum using ALD method.
实施例6Example 6
一种含铈化合物：Ce(thd)3(DMEDA)，其中，thd代表2,2,6,6-四甲基-3,5-庚二酮，DMEDA代表N,N’二甲基乙二胺。A cerium-containing compound: Ce(thd) 3 (DMEDA), where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and DMEDA represents N,N'dimethylethylenedione amine.
上述含铈化合物的制备方法，包括：称取40g的Ce(thd)3置于1L的烧瓶中，加入100mL的甲苯并搅拌，得到白色浑浊状的Ce(thd)3分散液。称取5.4g的N,N’二甲基乙二胺(DMEDA)置于另外一个100mL的烧杯中，并加入50mL的甲苯搅拌溶解，得到DMEDA溶液。室温下，将DMEDA溶液滴加至Ce(thd)3分散液中，搅拌2小时以进行配位反应。之后，通过减压蒸馏除去所得反应液中的甲苯，得到45.2g的Ce(thd)3(DMEDA)。The preparation method of the above-mentioned cerium-containing compound includes: weighing 40g of Ce(thd) 3 into a 1L flask, adding 100 mL of toluene and stirring to obtain a white turbid Ce(thd) 3 dispersion. Weigh 5.4g of N,N'dimethylethylenediamine (DMEDA) into another 100mL beaker, add 50mL of toluene, stir and dissolve, and obtain a DMEDA solution. At room temperature, the DMEDA solution was added dropwise to the Ce(thd) 3 dispersion, and stirred for 2 hours to proceed with the coordination reaction. Thereafter, toluene in the obtained reaction liquid was removed by distillation under reduced pressure, and 45.2 g of Ce(thd) 3 (DMEDA) was obtained.
对实施例6提供的含铈化合物Ce(thd)3(DMEDA)2进行热性能分析，该化合物的熔点低(<135℃)，热稳定性高(分解温度>300℃)，其挥发性良好，其在0.1Torr的饱和蒸气压的挥发温度约为140℃，低于La(thd)3在0.1torr下的挥发温度。The thermal properties of the cerium-containing compound Ce(thd) 3 (DMEDA) 2 provided in Example 6 were analyzed. The compound has a low melting point (<135°C), high thermal stability (decomposition temperature >300°C), and good volatility. , its volatilization temperature at a saturated vapor pressure of 0.1Torr is about 140°C, which is lower than the volatilization temperature of La(thd) 3 at 0.1torr.
以上所述仅表达了本申请的几种示例性实施方式，其描述较为具体和详细，但并不能因此而理解为对本申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。 The above description only expresses several exemplary embodiments of the present application. The descriptions are relatively specific and detailed, but should not be construed as limiting the patent scope of the present application. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all fall within the protection scope of the present application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims (22)

  1. 一种金属化合物，其特征在于，所述金属化合物包括过渡金属原子及与所述过渡金属原子配位的至少一个β-二酮类配体，还包括与所述过渡金属原子配位的一个二元胺配体或者两个一元胺配体，其中，所述过渡金属原子与所述β-二酮类配体中的两个氧原子配位，并与所述二元胺配体中的两个氮原子配位或者与所述一元胺配体中的氮原子配位。A metal compound, characterized in that the metal compound includes a transition metal atom and at least one β-diketone ligand coordinated with the transition metal atom, and further includes a diketone ligand coordinated with the transition metal atom. A monoamine ligand or two monoamine ligands, wherein the transition metal atom coordinates with two oxygen atoms in the β-diketone ligand and coordinates with two oxygen atoms in the diamine ligand. coordinated with a nitrogen atom or coordinated with a nitrogen atom in the monoamine ligand.
  2. 如权利要求1所述的金属化合物，其特征在于，所述过渡金属原子包括镧系元素、钇、钪、铪、钛、钒、锆、铬、钨、锰、铁、钴、镍、钌、锌、铜、钯、铂、铱、铼、锇、钽、铑或铌。The metal compound of claim 1, wherein the transition metal atoms include lanthanide elements, yttrium, scandium, hafnium, titanium, vanadium, zirconium, chromium, tungsten, manganese, iron, cobalt, nickel, ruthenium, Zinc, copper, palladium, platinum, iridium, rhenium, osmium, tantalum, rhodium or niobium.
  3. 如权利要求1或2所述的金属化合物，其特征在于，所述金属化合物包括三个所述β-二酮类配体。The metal compound according to claim 1 or 2, characterized in that the metal compound includes three of the β-diketone ligands.
  4. 如权利要求1-3任一项所述的金属化合物，其特征在于，所述β-二酮类配体的结构通式表示为R1-C(＝O)-CH2-C(＝O)-R2，R1、R2独立地选自烷基。The metal compound according to any one of claims 1 to 3, wherein the general structural formula of the β-diketone ligand is R 1 -C(=O)-CH 2 -C(=O )-R 2 , R 1 and R 2 are independently selected from alkyl.
  5. 如权利要求1-4任一项所述的金属化合物，其特征在于，所述二元胺配体包括二元烷基胺。The metal compound according to any one of claims 1 to 4, wherein the diamine ligand includes a dibasic alkylamine.
  6. 如权利要求5所述的金属化合物，其特征在于，所述二元烷基胺的结构通式表示为N(R3)(R4)-C(R7)-C(R8)-N(R5)(R6)，其中，R3至R8独立地选自氢原子、烷基。The metal compound according to claim 5, wherein the general structural formula of the dibasic alkyl amine is N(R 3 )(R 4 )-C(R 7 )-C(R 8 )-N (R 5 )(R 6 ), wherein R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups.
  7. 如权利要求6所述的金属化合物，其特征在于，所述烷基的碳原子数为1-6。The metal compound of claim 6, wherein the alkyl group has 1-6 carbon atoms.
  8. 如权利要求1-4任一项所述的金属化合物，其特征在于，所述一元胺配体包括含一个氮原子的一元烷基胺或氮杂环配体。The metal compound according to any one of claims 1 to 4, wherein the monoamine ligand includes a monoalkylamine containing one nitrogen atom or a nitrogen heterocyclic ligand.
  9. 如权利要求8所述的金属化合物，其特征在于，所述一元烷基胺的结构通式表示为N(R3’)(R4’)(R5’)，其中，R3’、R4’、R5’独立地选自氢原子、烷基，且R3’至R5’中的至少一个为烷基；所述氮杂环配体包括吡啶、哌啶、吡咯或其衍生物。The metal compound according to claim 8, wherein the general structural formula of the monoalkylamine is N(R 3 ') (R 4 ') (R 5 '), where R 3 ', R 4 ', R 5 ' are independently selected from hydrogen atoms and alkyl groups, and at least one of R 3 ' to R 5 ' is an alkyl group; the nitrogen heterocyclic ligand includes pyridine, piperidine, pyrrole or derivatives thereof .
  10. 如权利要求1-9任一项所述的金属化合物，其特征在于，所述金属化合物具有式(Ⅰ)或式(Ⅱ)所示的结构通式：
    The metal compound according to any one of claims 1 to 9, characterized in that the metal compound has a general structural formula represented by formula (I) or formula (II):
    其中，M代表过渡金属原子，式(Ⅰ)中，R1、R2独立地选自烷基，R3至R8独立地选自氢原子、烷基；式(Ⅱ)中，R1’、R2’独立地选自烷基，R’独立地选自具有一个氮原子的一元胺配体，所述R’中的氮原子与M原子配位。Among them, M represents a transition metal atom. In formula (I), R 1 and R 2 are independently selected from alkyl groups, and R 3 to R 8 are independently selected from hydrogen atoms and alkyl groups; in formula (II), R 1 ' , R 2 ' is independently selected from an alkyl group, R' is independently selected from a monoamine ligand having one nitrogen atom, and the nitrogen atom in R' is coordinated with the M atom.
  11. 一种金属化合物的制备方法，其特征在于，包括以下步骤：A method for preparing a metal compound, which is characterized by comprising the following steps:
    取过渡金属原子与至少一个β-二酮类配体构成的配位化合物，将二元胺配体或一元胺配体与所述配位化合物在有机溶剂中进行配位反应，得到反应液，去除所述反应液中的有机溶剂，得到金属化合物；Take a coordination compound composed of a transition metal atom and at least one β-diketone ligand, perform a coordination reaction with a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent to obtain a reaction liquid, Remove the organic solvent in the reaction solution to obtain a metal compound;
    其中，所述金属化合物中的过渡金属原子与至少一个所述β-二酮类配体中的氧原子配位，并与一个所述二元胺配体中的两个氮原子配位或与两个所述一元胺配体中的两个氮原子配位。Wherein, the transition metal atom in the metal compound is coordinated with at least one oxygen atom in the β-diketone ligand, and coordinated with two nitrogen atoms in one of the diamine ligands or with Two nitrogen atoms in the two monoamine ligands are coordinated.
  12. 如权利要求1-10任一项所述的金属化合物在制备含过渡金属元素的薄膜中的应用。The application of the metal compound according to any one of claims 1 to 10 in the preparation of films containing transition metal elements.
  13. 如权利要求1-10任一项所述的金属化合物在制备电子器件中的应用。 Application of the metal compound according to any one of claims 1 to 10 in the preparation of electronic devices.
  14. 一种含过渡金属元素的薄膜，其特征在于，采用如权利要求1-10任一项所述的金属化合物制备得到。A thin film containing transition metal elements, characterized in that it is prepared by using the metal compound according to any one of claims 1-10.
  15. 如权利要求14所述的含过渡金属元素的薄膜，其特征在于，所述含过渡金属元素的薄膜通过化学气相沉积法或者原子层沉积法制备得到。The film containing transition metal elements according to claim 14, characterized in that the film containing transition metal elements is prepared by a chemical vapor deposition method or an atomic layer deposition method.
  16. 如权利要求14或15所述的含过渡金属元素的薄膜，其特征在于，所述含过渡金属元素的薄膜包括含过渡金属元素的氧化物、氮化物、碳化物或碳氮化物。The transition metal element-containing film according to claim 14 or 15, characterized in that the transition metal element-containing film includes an oxide, nitride, carbide or carbonitride containing a transition metal element.
  17. 一种电子器件，其特征在于，所述电子器件具有如权利要求14-16任一项所述的含过渡金属元素的薄膜。An electronic device, characterized in that the electronic device has the transition metal element-containing film according to any one of claims 14 to 16.
  18. 一种制备含过渡金属元素的薄膜的装置，其特征在于，所述装置包括连通的容器室和沉积室，所述容器室用于储存如权利要求1-10任一项所述的金属化合物，所述沉积室中放置有基材，所述金属化合物能被输送至所述沉积室中，并在所述基材的表面沉积形成含过渡金属元素的薄膜。A device for preparing a thin film containing transition metal elements, characterized in that the device includes a connected container chamber and a deposition chamber, and the container chamber is used to store the metal compound according to any one of claims 1-10, A substrate is placed in the deposition chamber, and the metal compound can be transported into the deposition chamber and deposited on the surface of the substrate to form a thin film containing transition metal elements.
  19. 一种含过渡金属元素的薄膜的沉积方法，其特征在于，包括以下步骤：A method for depositing a thin film containing transition metal elements, characterized by comprising the following steps:
    将气化的如权利要求1-10任一项所述的金属化合物引入到沉积设备的放置有基材的沉积室中，以在所述基材表面沉积形成含过渡金属元素的薄膜。The vaporized metal compound according to any one of claims 1 to 10 is introduced into a deposition chamber of a deposition device in which a substrate is placed, so as to deposit and form a thin film containing a transition metal element on the surface of the substrate.
  20. 如权利要求19所述的沉积方法，其特征在于，所述沉积方法还包括：将反应物物种引入到所述沉积室内。The deposition method of claim 19, further comprising: introducing reactant species into the deposition chamber.
  21. 如权利要求20所述的沉积方法，其特征在于，所述含过渡金属元素的薄膜还含有氧元素；所述反应物物种包括氧源，所述氧源包括氧气、臭氧、H2O、H2O2中的一种或多种。The deposition method of claim 20, wherein the transition metal element-containing film further contains oxygen element; the reactant species includes an oxygen source, and the oxygen source includes oxygen, ozone, H 2 O, H One or more of 2 O 2 .
  22. 如权利要求19-21任一项所述的沉积方法，其特征在于，所述沉积具体是化学气相沉积过程，或者原子层沉积过程。 The deposition method according to any one of claims 19 to 21, wherein the deposition is specifically a chemical vapor deposition process or an atomic layer deposition process.
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