Metal compound, and method for preparing the same and use thereof

Abstract

Embodiments of the present application provide a metal compound, as well as a method for preparing the same and uses thereof. The metal compound includes a transition metal atom and at least one β-diketone ligand that coordinates with the transition metal atom, and further includes one diamine ligand that coordinates with the transition metal atom or two monoamine ligands that coordinate with the transition metal atom. The transition metal atom coordinates with two oxygen atoms in the β-diketone ligand and coordinates with two nitrogen atoms in the diamine ligand or coordinates with the nitrogen atom in the monoamine ligand. The metal compound can have characteristics such as a low melting point, high volatility, and thermal stability, and is suitable for preparing a film containing a transition metal element by using a chemical vapor deposition method or an atomic layer deposition method.

Description

Technical Field

[0001] This application claims the priority of Chinese Patent Application No. 202210612617.3, entitled "METALLIC COMPOUND, AND PREPARATION METHOD AND APPLICATION THEREOF", filed with the China National Intellectual Property Administration on May 31, 2022, the entire content of which is incorporated herein by reference.

[0002] This application relates to the field of chemical deposition technology, and particularly to metallic compounds, as well as their preparation methods and uses.

Background Art

[0003] With the miniaturization of semiconductor devices, SiO2 as a gate dielectric material cannot meet the requirements of high integration of field effect transistor devices. There is a need for high dielectric constant (High-K) materials to replace conventional SiO2. Lanthanum-containing oxides are considered desirable High-K materials for semiconductor devices due to characteristics such as high dielectric constant, high thermal stability, wide bandgap, high breakdown electric field strength, and low leakage current.

[0004] Chemical Vapor Deposition (CVD) technology and Atomic Layer Deposition (ALD) technology have become common film deposition technologies in the preparation process of semiconductor devices due to their precise control over film deposition thickness and morphology. When these two technologies are used to deposit lanthanum-containing oxide films, the corresponding lanthanum precursors need to have characteristics such as low melting point, high volatility, high reactivity, and specific thermal stability. However, existing lanthanum precursors cannot meet all of these characteristics.

Summary of the Invention

[0005] In view of this, one embodiment of the present application provides a metal compound that meets all the performance requirements of the CVD / ALD technology for metal-containing precursor materials. **Means for Solving the Problems**

[0006] According to a first aspect, one embodiment of the present application provides a metal compound. The metal compound includes a transition metal atom and at least one β-diketone ligand that coordinates with the transition metal atom, and further includes one diamine ligand that coordinates with the transition metal atom or two monoamine ligands that coordinate with the transition metal atom. The transition metal atom coordinates with two oxygen atoms in the β-diketone ligand and coordinates with two nitrogen atoms in the diamine ligand or coordinates with the nitrogen atom in the monoamine ligand.

[0007] The metal compound provided in this embodiment of the present application has a low melting point, high volatility, high structural stability, and high reactivity, is not corrosive to the substrate, is suitable as a precursor material for CVD reactions or ALD reactions, contains transition metal elements, and deposits a film with controllable thickness and morphology.

[0008] In some implementation forms of the present application, the transition metal atom includes a lanthanide element, yttrium, scandium, hafnium, titanium, vanadium, zirconium, chromium, tungsten, manganese, iron, cobalt, nickel, ruthenium, zinc, copper, palladium, platinum, iridium, rhenium, osmium, tantalum, rhodium, or niobium.

[0009] In some implementation forms of the present application, the metal compound includes three β-diketone ligands. In this case, for the metal compound, the coordination number of the central transition atom is 8, the melting point is low, the volatility is high, and the structural stability is high.

[0010] In one implementation form of the present application, the general structural formula of the β-diketone ligand is represented as R1-C(=O)-CH2-C(=O)-R2, and R1 and R2 are independently selected from alkyl groups.

[0011] In some embodiments of the present application, the diamine ligand contains a dialkylamine. The dialkylamine has lower steric hindrance when coordinating with a transition metal atom and is less likely to separate from the metal compound. This ensures high thermal stability of the metal compound.

[0012] In an embodiment of the present application, the general structural formula of the dialkylamine is represented as N(R3)(R4)-C(R7)-C(R8)-N(R5)(R6), and R3 to R8 are independently selected from a hydrogen atom or an alkyl. In some embodiments of the present application, the number of carbon atoms of the alkyl ranges from 1 to 6. The dialkylamine containing an alkyl with fewer carbon atoms has lower steric hindrance when coordinating with a transition metal atom.

[0013] In one embodiment of the present application, the monoamine ligand includes a monoalkylamine containing one nitrogen atom or a nitrogen heterocyclic ligand.

[0014] In some embodiments of the present application, the general structural formula of the monoalkylamine is represented as N(R3’)(R4’) and (R5’), and R3’, R4’ and R5’ are independently selected from a hydrogen atom or an alkyl, at least one of R3’ to R5’ is an alkyl, and the nitrogen heterocyclic ligand includes pyridine, piperidine, pyrrole or derivatives thereof. Generally, the monoalkylamine has lower steric hindrance than the nitrogen heterocyclic ligand when binding to a transition metal atom, and the coordination complex formed by the monoalkylamine has higher thermal stability.

[0015] In some embodiments of the present application, the metal compound has the general structural formula shown in formula (I) or formula (II):

Chemical formula

Chemical formula

[0016] M represents a transition metal atom. In formula (I), R1 and R2 are independently selected from alkyl, R3 to R8 are independently selected from a hydrogen atom or alkyl. In formula (II), R1’ and R2’ are independently selected from alkyl, R’ is independently selected from a monoamine ligand having one nitrogen atom, and the nitrogen atom in R’ coordinates with atom M.

[0017] One embodiment of the present application includes the following steps. A step of obtaining a coordination compound containing a transition metal atom and at least one β-diketone ligand, a step of performing a coordination reaction on a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent to obtain a reaction solution, and a step of removing the organic solvent from the reaction solution to obtain a metal compound are further provided, which is a method for preparing a metal compound.

[0018] The transition metal atom in the metal compound coordinates with the oxygen atom in the β-diketone ligand and coordinates with two nitrogen atoms in one diamine ligand, or coordinates with two nitrogen atoms in two monoamine ligands.

[0019] The above method for preparing a metal compound has a simple process, is easy to operate, has a low cost, and the obtained metal compound has high structural stability.

[0020] In one implementation form of the present application, the step of "performing a coordination reaction on a diamine ligand or a monoamine ligand and a coordination compound in an organic solvent" specifically includes a step of dispersing the coordination compound in an organic solvent to obtain a first solution, a step of dissolving a diamine ligand or a monoamine ligand in an organic solvent to obtain a second solution, and a step of dropping the second solution into the first solution and performing a coordination reaction under stirring conditions.

[0021] The above addition mode helps the diamine ligand or the monoamine ligand to completely coordinate with the transition metal atom in the hexa-coordination compound.

[0022] According to a second aspect, an embodiment of the present application provides an application of a metal compound according to the first aspect of the embodiments of the present application when preparing a film containing a transition metal element.

[0023] When preparing a film containing a transition metal element, the metal compound may be used as a transition metal element source. The metal compound has a low melting point, high volatility, high thermal stability, and can deposit a film containing a transition metal element based on the CVD method or the ALD method.

[0024] According to a third aspect, an embodiment of the present application provides an application of a metal compound according to the first aspect of the embodiments of the present application when preparing an electronic device. Specifically, the metal compound is used to prepare a film containing a transition metal element in the electronic device.

[0025] According to a fourth aspect, an embodiment of the present application provides a film containing a transition metal element. The film is prepared by using the metal compound according to the first aspect of the embodiments of the present application.

[0026] Specifically, the film containing a transition metal element may be prepared by using the metal compound as a transition metal precursor based on a deposition method such as the CVD method or the ALD method. The prepared film containing a transition metal element has a good morphology and a controllable thickness.

[0027] According to a fifth aspect, an embodiment of the present application provides an electronic device. The electronic device has a film containing a transition metal element according to the fourth aspect of the embodiments of the present application. The film containing a transition metal element has a good morphology, a controllable thickness, and good quality, and helps to ensure the stable and continuous operation of the electronic device.

[0028] According to a sixth aspect, an embodiment of the present application provides a preparation apparatus for a film containing a transition metal element. The apparatus includes a container chamber and a deposition chamber that communicate with each other. The container chamber is configured to store a metal compound according to the first aspect of the embodiment of the present application. A substrate is disposed in the deposition chamber. The metal compound can be transported to the deposition chamber and deposited on the surface of the substrate to form a film containing a transition metal element. The metal compound can be transported to the deposition chamber in a gaseous form.

[0029] By using this apparatus, a high-quality film containing a transition metal element can be prepared.

[0030] According to a seventh aspect, an embodiment of the present application includes the following steps. A deposition method for a film containing a transition metal element is provided, which includes introducing a vaporized metal compound according to the first aspect of the embodiment of the present application into a deposition chamber of a deposition device in which a substrate is disposed to form a film containing a transition metal element, and depositing the metal compound on the surface of the substrate.

[0031] In one implementation form of the present application, the deposition method further includes a step of introducing a reaction species into the deposition chamber. The reaction species may be selected based on the material of the film to be prepared containing a transition metal element, may be a source of the constituent elements of the film, or may be other gases required for the deposition reaction. The reaction species can be a vapor of a gaseous reagent or a liquid reagent.

[0032] In some implementation forms of the present application, the film containing a transition metal element further contains an oxygen element, the reaction species includes an oxygen source, and the oxygen source includes one or more of oxygen, ozone, H2O, and H2O2. In this case, the formed film containing a transition metal element may be a metal oxide film. Usually, the dielectric constant of the film is relatively high and can be well applied to electronic devices. In addition, the oxygen source has high reactivity with the metal compound and can minimize the intrusion of impurities.

[0033] In some implementations of the present application, the deposition method further includes a step of introducing another metal source into the deposition chamber, where the other metal source contains a metal element other than the transition metal element of the metal compound. Here, the metal elements may include transition metal elements, main group metal elements, etc.

[0034] In an implementation form 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 techniques can better control the deposition thickness and morphology of the film containing transition metal elements.

Brief Description of the Drawings

[0035]

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Mode for Carrying Out the Invention

[0036] Hereinafter, with reference to the accompanying drawings in the embodiments of the present application, the technical solutions in the present application will be described.

[0037] FIG. 1 is a common diagram of the configuration of a CVD deposition device or an ALD deposition device. The deposition device 100 includes a container chamber 10 for storing a precursor material used for film formation, and a deposition chamber 20 for performing a film formation reaction of the film. The container chamber 10 and the deposition chamber 20 communicate with each other by using a pipeline. The container chamber 10 is mainly used to accommodate a material storage container 11 (usually a stainless steel cylinder) for storing the precursor material. The precursor material stored in each material storage container 11 may be vaporized and then conveyed to the deposition chamber 20 through a conveying pipeline (a valve may be provided in the pipeline). A substrate 21 is disposed in the deposition chamber 20, and a heating component 22 may be disposed outside the deposition chamber 20 to control the temperature of the deposition chamber 20 to reach the reaction temperature of the precursor. In order to avoid pipeline contamination caused by precursor condensation due to changes in the pipeline temperature, the precursor material needs to have a low melting point and high volatility so that the precursor material can be smoothly vaporized (vaporized by controlling the heating temperature of the material storage container 11 and the conveying pipeline) and conveyed from the container chamber 10 to the deposition chamber 20. Further, the precursor material needs to have specific thermal stability to ensure the stability of the precursor material in the process of being conveyed from the container chamber 10 to the deposition chamber 20 and to minimize non-uniform film formation on the substrate surface caused by thermal decomposition of the precursor material. Also, the precursor material preferably does not corrode the substrate 21, for example, does not contain a halogen element that corrodes metal.

[0038] The CVD process generally includes the following steps: after being transported to the deposition chamber 20, the vaporized precursor material diffuses on the surface of the substrate 21 and is adsorbed on the surface of the substrate; the precursor is deposited on the surface of the substrate by a chemical reaction (usually assisted by heating, plasma, or an electric field) to form a film; and the reaction by-products are desorbed from the surface of the substrate 21 and removed from the deposition chamber 20. In ALD, multiple types of precursor materials (usually two types as shown in FIG. 1) are periodically transported alternately, and excess precursors are removed through a purge using an inert gas (such as argon and nitrogen) at intervals of transporting different precursor materials to the deposition chamber 20, thereby implementing atomic layer deposition with a self-limiting function (i.e., the thickness of the film deposited in each cycle is at the atomic level). Continuous deposition with a thickness of multiple atomic layers can be implemented through multiple cycles. In order to implement the accurate deposition of a film with a thickness of a single atomic layer and avoid uncontrollable changes in the deposition rate and film thickness, in the ALD process, thermal decomposition reactions of precursor materials are not allowed, and only self-limiting chemical reactions are allowed on the surface of the substrate. However, since the CVD technology has a different mechanism of action from the ALD technology, it is allowed for the precursor material to undergo a specific decomposition reaction in the deposition chamber 20 without affecting the film formation quality.

[0039] The CVD technology and the ALD technology have different requirements regarding the thermal stability of precursor materials. However, generally, for these two technologies, the precursor material needs to have characteristics such as high volatility and high reactivity. However, existing precursors of transition metal elements cannot have characteristics such as low melting point, high volatility, high reactivity, specific thermal stability, and non-corrosiveness for the deposition of films containing transition metal elements (such as lanthanum-containing oxides). Therefore, one embodiment of the present application provides a metal compound that can have these characteristics.

[0040] Specifically, the metal compound provided in this embodiment of the present application includes a transition metal atom and at least one β-diketone ligand that coordinates with the transition metal atom, and further includes one diamine ligand that coordinates with the transition metal atom or two monoamine ligands that coordinate with the transition metal atom. The transition metal atom coordinates with two oxygen atoms in the β-diketone ligand and coordinates with two nitrogen atoms in the diamine ligand or coordinates with the nitrogen atom in the monoamine ligand.

[0041] In the metal compound provided in the present application, the β-diketone ligand uses the O atom derived from the ketone group to achieve a relatively strong bond with the transition metal atom, and the monofunctional amine (i.e., monoamine) or bifunctional amine (i.e., diamine) realizes the bond with the transition metal atom by using a bond strength that is slightly weaker than the bond strength between the N atom and the transition metal atom (compared to the bond strength between the O atom and the transition metal atom). Each ligand has no excessive steric hindrance when bonding to the transition metal atom and is difficult to desorb from the metal compound. Thus, the entire compound has specific structural stability, a low melting point, and high volatility, and is suitable as a precursor material for CVD reactions and ALD reactions. Furthermore, the metal compound provided in the present application does not contain halogen atoms, the volatile or thermally decomposed products of the metal compound are non-corrosive, and the preparation cost is low.

[0042] In this application, the transition metal atom may contain atoms of all transition metal elements in the periodic table of elements. In one implementation form of this application, the transition metal atom may include, but is 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), niobium (Nb), etc. The lanthanide elements may 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 implementation forms of this application, the transition metal atom is a lanthanide element (e.g., La, Ce, and Pr), Y, Sc, Ta, Zr, Hf, etc.

[0043] In some implementation forms of this application, the metal compound contains three β-diketone ligands. In this case, for the metal compound, the coordination number of the central transition atom is 8, and the central transition atom is close to but not at electron saturation. The metal compound has a low melting point, high volatility, and high structural stability. Further, in this case, the transition metal element is a lanthanide element (e.g., La, Ce, and Pr), Y, Sc, Ta, Zr, Hf, etc.

[0044] In one implementation of the present application, the general structural formula of the β-diketone ligand is represented as R1-C(=O)-CH2-C(=O)-R2, and R1 and R2 are independently selected from alkyls. Here, the alkyl may be a substituted or unsubstituted alkyl, and the substituted alkyl may be an alkoxy-substituted alkyl or the like. The alkyl may be linear or branched, and the number of carbon atoms of the alkyl may be from 1 to 10, and further may be from 1 to 6, preferably from 1 to 4. For example, the alkyl may be methyl, ethyl, propyl, isobutyl, tert-butyl, or the like.

[0045] In the present application, the diamine ligand includes dialkylamine, diarylamine, dicycloalkylamine, and the like. In some implementations of the present application, the diamine ligand includes dialkylamine. Compared with diarylamine and bidentate cycloalkylamine, dialkylamine has less steric hindrance when coordinating with transition metal atoms and is difficult to separate from the metal compound. Thereby, high thermal stability of the metal compound is guaranteed.

[0046] In some implementations of the present application, the general structural formula of the dialkylamine is represented as N(R3)(R4)-C(R7)-C(R8)-N(R5)(R6), and R3 to R8 are independently selected from a hydrogen atom or an alkyl, and at least one of R3, R4, R5, and R6 is an alkyl (that is, R3, R4, R5, and R6 are not all hydrogen atoms). Similarly, the alkyl herein may be linear or branched, and the number of carbon atoms of the alkyl may be from 1 to 10, and further may be from 1 to 6, preferably from 1 to 4. For example, the alkyl may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, or the like. The H atom 1 H atom (also known as the "protium" atom), 2 H atom (also known as the "deuterium" atom), and 3 H atom (also known as the "tritium" atom) may be included.

[0047] In one implementation of the present application, the monoamine ligand includes a monoalkylamine containing one nitrogen atom or a nitrogen heterocyclic ligand. Generally, when a monoalkylamine binds to a transition metal atom, it has less steric hindrance than a nitrogen heterocyclic ligand.

[0048] In some implementations of the present application, the general structural formula of the monoalkylamine is represented as N(R3’)(R4’) and (R5’), where R3’, R4’ and R5’ are independently selected from a hydrogen atom or an alkyl, and at least one of R3’, R4’ and R5’ is an alkyl. The chain monoalkylamine has less steric hindrance when coordinating with a transition metal atom and is less likely to lose the coordination relationship with the transition metal atom in the metal compound. This ensures high thermal stability of the metal compound. Similarly, the alkyl herein may be linear or branched, and the number of carbon atoms of the alkyl may be from 1 to 10, and may further be from 1 to 6, preferably from 1 to 4. For example, the alkyl can be methyl, ethyl, propyl, isobutyl, tert-butyl, etc.

[0049] In the present application, the nitrogen heterocyclic ligand is a substance in which the heteroatom is an N atom. In some implementations of the present application, the nitrogen heterocyclic ligand includes pyridine, piperidine, pyrrole, or derivatives thereof. These substances have a small molecular weight, less steric hindrance compared to other nitrogen heterocyclic compounds, and are likely to coordinate with a transition metal atom to form a coordination complex. For example, derivatives of pyridine, piperidine and pyrrole may include pyridine, piperidine and pyrrole substituted with an alkyl having several carbon atoms in the range of 1 to 6 (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl).

[0050] In some implementations of the present application, the metal compound has the formula (I) or formula (II):

Chemical formula

Chemical formula

[0051] M represents a transition metal atom. In formula (I), R1 and R2 are independently selected from alkyl, R3 to R8 are independently selected from a hydrogen atom or alkyl. In formula (II), R1’ and R2’ are independently selected from alkyl, R’ is independently selected from monoamine ligands having one nitrogen atom, and the nitrogen atom in R’ coordinates with the transition metal atom M.

[0052] For the selection range of R1 to R8, please refer to the above description in this application. For the selection range of R1’ and R2’, please refer to the above description regarding R1 and R2.

[0053] It should be noted that the two groups R’ in formula (II) may be the same monoamine ligand or different monoamine ligands. In some embodiments of this application, R’ is independently selected from monoalkylamine or nitrogen heterocyclic ligands. For the selection range of monoalkylamine or nitrogen heterocyclic ligands, please refer to the above description in this application. Details will not be repeated here.

[0054] In some embodiments of this application, the metal compound is a lanthanide coordination complex, and specifically may contain any one of the following substances.

Chemical formula

[0055] One embodiment of the present application includes the following steps: obtaining a coordination compound containing a transition metal atom and at least one β-diketone ligand; performing a coordination reaction between a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent to obtain a reaction solution; and removing the organic solvent from the reaction solution to obtain a metal compound. The transition metal atom in the metal compound coordinates with the oxygen atom in the β-diketone ligand and coordinates with two nitrogen atoms in one diamine ligand or coordinates with two nitrogen atoms in two monoamine ligands. The present application further provides a method for preparing a metal compound.

[0056] In some implementation forms of the present application, the step of "performing a coordination reaction on a diamine ligand or a monoamine ligand and a coordination compound in an organic solvent" specifically includes (1) dispersing the coordination compound in an organic solvent to obtain a first solution, and dissolving a diamine ligand or a monoamine ligand in the organic solvent to obtain a second solution; (2) dropping the second solution into the first solution and performing a coordination reaction under stirring conditions; and includes.

[0057] The above-mentioned addition mode helps the diamine ligand or the monoamine ligand to completely coordinate with the transition metal atom in the coordination compound. The step of "dropping the second solution into the first solution" may be performed at room temperature. Optionally, the stirring speed under stirring conditions may be 200 to 1000 revolutions per minute. The coordination reaction may take 1 to 4 hours, for example, 2 to 4 hours. The organic solvent can dissolve the monoamine ligand or the diamine ligand. The organic solvent includes one or more of toluene, tetrahydrofuran, chloroform, n-hexane, etc., but is not limited thereto. In some implementation forms, the organic solvent is toluene. In this case, the coordination compound formed by the transition metal atom and the β-diketone ligand and the diamine ligand or the monoamine ligand have relatively high solubility in toluene.

[0058] In another implementation form of the present application, it can be understood that the diamine ligand or monoamine ligand, and the coordination compound may be directly dispersed in an organic solvent to carry out the coordination reaction.

[0059] The preparation method of the above metal compound has a simple process, is easy to operate, has a low cost, and the obtained metal compound has high structural stability.

[0060] One embodiment of the present application further provides the application of a metal compound when preparing a film containing a transition metal element.

[0061] The material of the film containing a transition metal element may be a compound containing a transition metal element (for example, a metal oxide, nitride, carbide, or carbonitride), or a simple substance containing a transition metal element. The metal oxide may be a single transition metal 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, for example, one or more transition metal elements.

[0062] In some implementations of the present application, when the compound containing a transition metal element is a La-containing oxide, the compound may specifically be lanthanum oxide (La2O3), a lanthanum-containing bimetallic or polymetallic oxide (e.g., 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. When La2O3 is prepared, the raw materials required to prepare the La2O3 film based on the vapor deposition method should include a metal compound with a central atom being a La atom and an oxygen source. Also, when a lanthanum-containing bimetallic or polymetallic oxide is prepared, the required raw materials further include a precursor corresponding to another metal element, specifically, it may be a metal compound with a central atom not being a La atom, or it may be a well-known or future-developed metal precursor, which can be understood. The oxygen source may include one or more of oxygen (O2), ozone (O3), water vapor (H2O), and hydrogen peroxide (H2O2). The oxygen source has high reactivity with the metal compound and can minimize the intrusion of impurities. In some implementations, the oxygen source is ozone.

[0063] By using a metal compound based on the vapor deposition method, a film containing a transition metal element is prepared. The vapor deposition method may specifically be a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method. CVD may be a conventional CVD or a modified vapor deposition process of CVD, for example, plasma-enhanced CVD (PECVD), low-pressure CVD (LPCVD), atmospheric pressure CVD (APCVD), pulsed CVD (P-CVD), or hot-wire CVD (HWVCD, i.e., the energy source in the hot-wire charged deposition process). ALD may be a conventional ALD or a modified vapor deposition process of ALD, for example, plasma-enhanced ALD (PEALD), spatial ALD, or thermal ALD (Thermal ALD).

[0064] When a film containing a transition metal element is deposited based on the CVD method or the ALD method, a metal compound may be used as a raw material for the transition metal element. The metal compound has a low melting point, high volatility, good vaporizability, can smoothly reach the surface of the substrate to be deposited, and is less likely to undergo thermal decomposition until it reaches the substrate. Particularly when the ALD method is used for deposition, the thickness of the film containing the transition metal element can be accurate and controllable, and the film can be guaranteed to be of higher quality and more conformal.

[0065] One embodiment of the present application further provides the application of a metal compound in preparing an electronic device. Specifically, the metal compound may be used to prepare a film containing a transition metal element in an electronic device. The electronic device may specifically be a semiconductor device.

[0066] The prepared electronic device generally includes a substrate and a film containing a transition metal element located on the substrate. As described above, the film containing a transition metal element may be prepared by using a metal compound based on the CVD method or the ALD method, and the film containing a transition metal element may be an oxide, nitride, carbide, carbonitride, etc. containing a transition metal element. In addition, the substrate may be a pure substrate such as silicon, quartz, SiC, SiGe, GaAs, GaN, sapphire, etc., or a substrate having a film of other materials on its surface.

[0067] The metal compound is used as a transition metal precursor to prepare a film containing a transition metal element in an electronic device. The metal compound has a low melting point, good vaporizability, can smoothly reach the surface of the substrate to be deposited, and has high reactivity for performing a vapor deposition reaction. The morphology and deposition thickness of the prepared film may be accurately adjusted, the film has higher quality, and helps to ensure the stable and continuous operation of the electronic device. When the film containing a transition metal element is prepared based on the ALD method, almost no thermal decomposition occurs until it reaches the substrate, the film thickness can be accurately controlled, and it is highly conformal and uniform.

[0068] One embodiment of the present application further provides a film containing a transition metal element, and the film is prepared by using the metal compound in the embodiment of the present application. For specific preparation methods, please refer to the following description of the present application.

[0069] Before introducing the method for preparing a film containing a transition metal element, first, the apparatus for preparing a film containing a transition metal element is introduced.

[0070] The apparatus for preparing a film containing a transition metal element provided in this embodiment of the present application may include a container chamber and a deposition chamber that communicate with each other. The container chamber is configured to store the metal compound in the embodiment of the present application. The substrate is disposed in the deposition chamber. The metal compound can be transported to the deposition chamber and deposited on the surface of the substrate to form a film containing a transition metal element.

[0071] Specifically, the apparatus may be a CVD device or an ALD device. For the specific structure of the apparatus, please refer to the entire description of FIG. 1 of the present application.

[0072] Specifically, at least one material storage container 11 may be disposed in the container chamber 10 of the apparatus, and the metal compound in the embodiment of the present application may be disposed in the corresponding material storage container 11. A heating device (not shown in FIG. 1) may be disposed outside each material storage container 11 and configured to heat the material storage container to transport the metal compound to the deposition chamber 20 in a gaseous form. Valves may be disposed in each transfer pipeline communicating with each material storage container 11 and the deposition chamber 20. A heating component 22 is disposed outside the deposition chamber 20 and configured to enable the temperature in the deposition chamber 20 to reach the deposition reaction temperature.

[0073] By using this apparatus, a high-quality film containing a transition metal element can be prepared.

[0074] Next, a method for depositing a film containing a transition metal element will be described. The method for depositing a film containing a transition metal element provided in one embodiment of the present application includes the following steps: Introducing the vaporized metal compound into a deposition chamber of a deposition device in which a substrate is disposed to form a film containing a transition metal element, and depositing the vaporized metal compound on the surface of the substrate. It includes.

[0075] The substrate on which the film containing the transition metal element is deposited may be determined based on the predicted purpose. In some implementation forms of the present application, the substrate may include, but is not limited to, silicon (Si), quartz (SiO2), SiC, SiGe, GaAs, GaN, sapphire, glass, plastic, metal, a substrate having a film of another material on the surface, etc. In the case of a semiconductor device, the film of another material on the substrate may be a metal layer (for example, Pd, Pt, Au, Al, W, or Ti), a nitride (for example, TaN, TiN, TiSN, or Si3N4), an oxide (for example, SiO2, SiON, HfO2, ZrO2, or Al2O3), or a combination of a metal layer, a nitride, and an oxide.

[0076] The substrate 21 in the deposition chamber 20 may be heated to a sufficient temperature so that the vaporized metal compound reacts on the surface of the substrate to obtain a necessary film containing a transition metal element. In the deposition process, it is necessary to make the temperature in the deposition chamber 20 higher than the vaporization temperature of the metal compound, and in order to avoid condensation in the transfer process, the stability of the metal compound material in the transfer process from the container chamber 10 to the deposition chamber 20 needs to be further ensured. In addition, when ALD is performed, the temperature in the deposition chamber needs to be even lower than the decomposition temperature of the metal compound. In this case, when the reaction temperature of the metal compound is reached, non-uniform film formation due to thermal decomposition of the metal compound can be avoided.

[0077] The metal compound may be introduced above the substrate 21 in the form of vapor, and the vapor may be formed by a solid or liquid metal compound realized, for example, by sublimation or evaporation of the metal compound. In some implementation forms, the solid metal compound may be heated to reach the liquid phase temperature, and there is a vapor pressure temperature sufficient for vaporization. In some other implementation forms, in order to facilitate the vaporization of the metal compound, a carrier gas (such as argon, helium, or nitrogen) may be conveyed to the container storing the metal compound. In some other implementation forms, the metal compound is mixed with an organic solvent to form a solution, and then the solution is heated and vaporized, as a result, the metal compound may enter the deposition chamber 20, and the carrier gas may be further bubbled into the solution.

[0078] In some implementation forms of the present application, the deposition method further includes a step of introducing a reaction species into the deposition chamber. The reaction species may be a source of a constituent element (such as an oxygen element) of the film to be prepared, or may be other gases necessary for the deposition reaction. The reaction species may be a vapor of a gaseous reagent or a liquid reagent.

[0079] In some embodiments, when the film containing a transition metal element is specifically a transition metal alone (such as Cu), the reaction species may be a reducing gas, such as hydrogen (H2). In this case, the deposition chamber 20 may be equipped with a hydrogen generator for generating hydrogen.

[0080] In some other embodiments, when the film containing a transition metal element further contains an oxygen (O) element, in this case, the film containing a transition metal element may specifically be a metal oxide (such as La2O3). The reaction species may include an oxygen source, and the oxygen source may be one or more of the following, O 2、 O 3、 H2O, H2O2, etc. In some implementation forms, the oxygen source is ozone (O3). The deposition chamber 20 may be equipped with an ozone generator for generating ozone.

[0081] In some other embodiments, when the film containing a transition metal element further contains a nitrogen (N) element, for example, when the film containing a transition metal element is lanthanum nitride or lanthanum carbonitride, the reaction species may include a nitrogen source. The nitrogen source may include one or more of nitrogen (N2), ammonia (NH3), hydrazine (N2H4), etc., but is not limited thereto.

[0082] In some other embodiments, when the film containing a transition metal element further contains a carbon (C) element, for example, when the film containing a transition metal element is lanthanum carbide or lanthanum carbonitride, the reaction species may include a carbon source. The carbon source may include one or more of methane (CH4), ethane (C2H6), ethylene (C2H4), propylene (C3H6), etc., but is not limited thereto.

[0083] The deposition method for forming the film containing a transition metal element may be a CVD method. In this case, the reaction species may be introduced into the deposition chamber 20 in which the substrate 21 is disposed, together with the metal compound. The deposition method for forming the film containing a transition metal element may also be an ALD method. In this case, the reaction species and the metal compound are alternately introduced into the deposition chamber 20 in which the substrate 21 is disposed, and as a result, the substrate 21 is alternately exposed to the reaction species and the metal compound.

[0084] For example, a La2O3 film is prepared by deposition. First, a metal compound (abbreviated as a La coordination complex) having a lanthanum atom as a central atom and an oxygen source may be disposed in a material storage container 11 different from the container chamber 10 of the deposition device 100 in FIG. 1. By heating the material storage container 11, the metal compound and the oxygen source may be vaporized separately. When a La2O3 film is prepared by deposition based on the CVD method, the vaporized La coordination complex and the oxygen source may be transported together to the deposition chamber 20 of the deposition device 100. When a La2O3 film is prepared by deposition based on the ALD method, the vaporized La coordination complex and the gaseous oxygen source or oxygen source vapor are alternately transported to the deposition chamber 20 of the deposition device 100. Specifically, the vaporized La coordination complex is first transported to the deposition chamber 20, and excess coordination complex that has not adsorbed on the surface of the substrate 21 is removed by purging using an inert gas. Then, the gaseous oxygen source is transported to the deposition chamber 20. The La coordination complex adsorbed on the substrate reacts with the oxygen source diffused on the substrate surface (the ALD process depends on a self-limiting saturated surface reaction). Next, the excess oxygen source on the surface of the substrate 21 is removed by purging using an inert gas. So far, this is one cycle. This cycle is repeated a plurality of times to perform atomic layer deposition having self-limiting characteristics on the surface of the substrate 21. Due to the surface controllability of the ALD process, a highly conformal and uniform La2O3 film is deposited with accurate thickness control.

[0085] In some implementations of the present application, the deposition method further includes a step of introducing another metal source into the deposition chamber 20 in which the substrate 21 is disposed. In this case, the film containing a transition metal element to be prepared may contain two types of metal elements (for ease of understanding, the transition metal element may be considered a metal element in a broad sense).

[0086] Another metal source may contain a metal element other than the transition metal atom in the metal compound, for example, another transition metal atom or a main group metal atom. One or more other metal sources may be present. For example, when a lanthanum-containing bimetallic or polymetallic oxide is prepared, in addition to the metal compound whose central atom is a lanthanum atom, the required metal source further includes a precursor corresponding to another metal element. Another metal source can still be the metal compound defined above in the present application or an existing metal coordination complex well-known in the art. Another metal source may be introduced into the deposition chamber together with the metal compound. For example, another metal source may be mixed with the metal compound and vaporized before being introduced into the deposition chamber. Of course, another metal source and the metal compound may alternatively be introduced into the deposition chamber alternately. For example, in the present application, the lanthanum metal compound is designated as raw material A, the hafnium precursor is designated as raw material B, and ozone is designated as raw material C. When lanthanum hafnium oxide is prepared by using the ALD method, the lanthanum metal compound, the hafnium precursor, and ozone may be alternately exposed to the surface of the substrate 21 in the order of A, B, C, and purging is performed by using an inert gas at intervals for transporting different materials into the deposition chamber.

[0087] One embodiment of the present application further provides a film containing a transition metal element, and the film is prepared by using the metal compound in the embodiment of the present application.

[0088] In the process of preparing a film containing a transition metal element, it can be understood that the reaction raw materials used may further include reaction species, another metal source, etc. in addition to the metal compound. The prepared film containing a transition metal element has been described above in the present application, and the details will not be repeated here.

[0089] One embodiment of the present application further provides an electronic device. The electronic device has a film containing a transition metal element in the embodiment of the present application.

[0090] The electronic device includes a substrate and a film containing a transition metal element located on the substrate. For the substrate and the film containing the transition metal element, refer to the foregoing description of this application.

[0091] Hereinafter, the technical solutions in the embodiments of this application will be further described by using specific embodiments.

[0092] Embodiment 1 Lanthanum-containing compound: La(thd)3(DMEDA), where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and DMEDA represents N,N'-dimethylethylenediamine.

[0093] The synthesis route of the lanthanum-containing compound is as follows.

Chemical formula

[0094] The preparation method of the lanthanum-containing compound is as follows: Weigh 41.3 g of the hexacoordinate lanthanum-containing compound La(thd)3 (English name: tris(2,2,6,6-tetramethyl-3,5-heptanedione)lanthanum(III)) into a 1 L flask, add 500 mL of toluene, stir the mixture to obtain a turbid La(thd)3 dispersion. Weigh 5.3 g of N,N'-dimethylethylenediamine (DMEDA) into another 100 mL beaker, add 50 mL of toluene, stir and dissolve the mixture to obtain a DMEDA solution. At room temperature, drop the DMEDA solution into the La(thd)3 dispersion, stir the mixture for 4 hours for a coordination reaction. Then, distill off toluene from the obtained reaction solution under reduced pressure to obtain 46.5 g of La(thd)3(DMEDA).

[0095] The nuclear magnetic resonance spectrum of the lanthanum-containing compound La(thd)3(DMEDA) is shown in Figure 2. Specifically, the available nuclear magnetic resonance data are as follows. 1 H-NMR(400 MHz,C6D6):δ5.86(s,3H,O=C-C H-C=O), 2.41 (s, 6H, N-C H 3), 2.24 (s, 4H, -C H 2-N), 1.28 (s, 54H, -C H 3). These nuclear magnetic resonance results indicate that the lanthanum-containing compound having the above general structural formula was successfully prepared in this application.

[0096] Thermal performance analysis was performed on the lanthanum-containing compound La(thd)3(DMEDA). As shown in Figure 3, thermogravimetric analysis (abbreviated as TG or TGA) curves and differential scanning calorimetry (abbreviated as DSC) curves were obtained. The curve diagram of the saturated vapor pressure of the lanthanum-containing compound with respect to temperature is shown in Figure 4. From Figure 3 and Figure 4, it can be seen that the lanthanum-containing compound has a low melting point (about 135 °C) and high thermal stability (decomposition temperature higher than 300 °C). Under the same vapor pressure, the lower the volatilization temperature of the material, the higher the volatility of the material. The lanthanum-containing compound in Embodiment 1 has a volatilization temperature of 130 °C at a saturated vapor pressure of 0.1 torr, which is lower than the volatilization temperature of La(thd)3 (exceeding about 200 °C) at a saturated vapor pressure of 0.1 torr, indicating that it has high volatility.

[0097] The lanthanum-containing compound La(thd)3(DMEDA) is used to prepare La2O3 film through deposition. La(thd)3(DMEDA) is used as the lanthanum precursor material, ozone O3 is used as the oxidant, a quartz (SiO2) plate is used as the substrate, and a La2O3 film is deposited on the substrate based on the ALD method. The evaporation temperature of the lanthanum-containing compound is controlled at 150 °C (i.e., the material storage container 11 in the container chamber 10 of Figure 1 is heated to 150 °C to vaporize the lanthanum-containing compound), and by controlling the temperature of the connection pipeline between the container chamber 10 and the deposition chamber 20 at 170 °C, it is ensured that the lanthanum-containing compound does not condense in the process of being transported to the deposition chamber 20. The lanthanum-containing compound and O3 are periodically and alternately transported to the deposition chamber 20, and during the interval between transporting the two vaporized substances to the deposition chamber, the excess precursor raw material is purged by using argon.

[0098] Relevant data of the La2O3 film obtained through deposition are shown in Figure 5. From the four sub-figures (a) to (d) in Figure 5, it can be seen that the La2O3 film obtained by ALD using La(thd)3(DMEDA) as the raw material conforms to the ALD characteristics. The saturation pulse time of La(thd)3(DMEDA) is 7 s, the saturation pulse time of O3 is 90 s, the ALD temperature window is 210 to 250 °C, the thickness of the La2O3 film increases proportionally to the number of cycles, and the deposition rate of the La2O3 film can be calculated to be 0.45 Å per cycle.

[0099] Figures 6 and 7 respectively show a scanning electron microscope (SEM) photograph and an XRD graph of a La2O3 film prepared by using La(thd)3(DMEDA) based on the ALD method. From Figure 6, it can be seen that a continuous and uniform La2O3 film can be deposited by using La(thd)3(DMEDA). Since the deposition rate per cycle of the La2O3 film is 0.45 Å, a La2O3 film with a thickness of 23.8 nm can be calculated to correspond to approximately 529 deposition cycles. From Figure 7, it can be seen that the formed La2O3 film is specifically hexagonal h-La2O3, and a sharp diffraction peak of the crystal plane of h-La2O3(101) can be seen in the figure.

[0100] Embodiment 2 Lanthanum-containing compound: La(ibpm)3(DMEDA), where ibpm represents 2,2,6-trimethyl-3,5-heptanedione, and DMEDA represents N,N’-dimethylethylenediamine.

[0101] The synthesis route of the lanthanum-containing compound is as follows. [Chemical formula]

[0102] The preparation method of the lanthanum-containing compound is as follows: Weigh 48.5 g of the hexa-coordinated lanthanum coordination complex La(ibpm)3 (English name: tris(2,2,6-trimethyl-3,5-heptanedione)lanthanum(III)) into a 1 L flask, add 500 mL of toluene, stir the mixture to obtain a turbid La(ibpm)3 dispersion; Weigh 8.5 g of N,N’-dimethylethylenediamine (DMEDA) into another 100 mL beaker, add 50 mL of toluene, stir and dissolve the mixture to obtain a DMEDA solution; At room temperature, drop the DMEDA solution into the La(ibpm)3 dispersion, stir the mixture for 3 hours for a coordination reaction; Then, distill off toluene from the obtained reaction solution by vacuum distillation to obtain 55.4 g of La(ibpm)3(DMEDA).

[0103] The nuclear magnetic resonance spectrum of the lanthanum-containing compound La(ibpm)3(DMEDA) is shown in Figure 8. Specifically, the available nuclear magnetic resonance data are as follows. 1 H 1 H-NMR(400 MHz,CDCl3)δ5.37(s,3H,O=CC H C=O),2.72(s,4H,C H 2N),2.48(s,6H,NC H 3),2.29(3H,m,C H (CH3)2),1.06(s,27H,C(C H 3)3).1.01(d,18H,C H (C H 3)2). These nuclear magnetic resonance results indicate that the lanthanum-containing compound La(ibpm)3(DMEDA) with the above general structural formula is successfully prepared in this application.

[0104] Thermal performance analysis was performed on the lanthanum-containing compound La(ibpm)3(DMEDA), and TG-DSC curves as shown in Figure 9 were obtained. A curve diagram of the saturated vapor pressure of the lanthanum-containing compound with respect to temperature is shown in Figure 10. From Figures 9 and 10, it can be seen that the lanthanum-containing compound La(ibpm)3(DMEDA) has a low melting point (about 57 °C), high thermal stability (decomposition temperature higher than 300 °C), and high volatility. The evaporation temperature of the lanthanum-containing compound at a saturated vapor pressure of 0.1 torr is 116 °C. Therefore, the lanthanum-containing compound La(ibpm)3(DMEDA) is suitable for preparing a film containing a lanthanum element by deposition based on the ALD method or the CVD method.

[0105] Embodiment 3 Lanthanum-containing compound: La(tmod)3(DMEDA), where tmod represents 2,2,6,6-tetramethyl-3,5-octanedione, and DMEDA represents N,N'-dimethylethylenediamine.

[0106] The preparation method of the lanthanum-containing compound is as follows: Weigh 50 g of the hexa-coordinated lanthanum coordination complex La(tmod)3 (English name: tris(2,2,6,6-tetramethyl-3,5-octanedionato)lanthanum(III)) into a 1 L flask, add 500 mL of toluene, stir the mixture to obtain a turbid La(tmod)3 dispersion. Weigh 8.8 g of N,N’-dimethylethylenediamine (DMEDA) into another 100 mL beaker, add 50 mL of toluene, stir and dissolve the mixture to obtain a DMEDA solution. At room temperature, drop the DMEDA solution into the La(tmod)3 dispersion, and stir the mixture for 2 hours to carry out the coordination reaction. Then, remove toluene from the obtained reaction solution by vacuum distillation to obtain 56.3 g of La(tmod)3DMEDA.

[0107] The synthesis route of the lanthanum-containing compound is as follows.

Chemical formula

[0108] The nuclear magnetic resonance spectrum of the lanthanum-containing compound La(tmod)3(DMEDA) is shown in Figure 11. Specifically, the available nuclear magnetic resonance data are as follows. 1 H 1 H-NMR(400 MHz,CDCl3)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 2CH3),1.078(s,27H,C(C H 3)3),1.02(s.18H,C(C H 3)2),0.74(t,9H,CH2C H 3). These nuclear magnetic resonance results indicate that the lanthanum-containing compound La(tmod)3(DMEDA) having the above general structural formula is successfully prepared in this application.

[0109] Thermal performance analysis was carried out on the lanthanum-containing compound La(tmod)3(DMEDA), and TG-DSC curves as shown in Figure 12 were obtained. The curve diagram of the saturated vapor pressure of the lanthanum-containing compound with respect to temperature is shown in Figure 13. From the TG curve in Figure 12, it is shown that for the lanthanum-containing compound La(tmod)3(DMEDA), T50 is 266 °C, the end temperature of volatilization is 286.6 °C, the residual mass is 1.35%, it has high volatility, high thermal stability, and the thermal decomposition temperature exceeds 300 °C. From the DSC curve in Figure 12, the peak value at 74 °C indicates the crystal phase transition of the compound La(tmod)3(DMEDA), and the endothermic peak at 166 °C indicates the melting of the compound. From Figure 13, it can be seen that for La(tmod)3(DMEDA), the volatilization temperature at a saturated vapor pressure of 0.1 torr is 154 °C, indicating high volatility. Therefore, the lanthanum-containing compound La(tmod)3(DMEDA) is suitable for preparing a film containing a lanthanum element by deposition based on the ALD method or CVD method.

[0110] Embodiment 4 Lanthanum-containing compound: La(thd)3(Py)2, where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione and Py represents pyridine.

[0111] The synthesis route of the lanthanum-containing compound is as follows.

Chemical formula

[0112] The preparation method of the lanthanum-containing compound is as follows: Weigh 13.8 g of La(thd)3 into a 1 L flask, add 100 mL of toluene, dropwise add a mixture of 1.8 g of pyridine and 5 mL of toluene, heat and reflux the mixture at 120 °C for 3 hours to carry out a coordination reaction. Then, after returning the flask temperature to room temperature, remove volatile substances from the obtained reaction solution under reduced pressure to obtain a pale yellow powder of La(thd)3(Py)2.

[0113] The nuclear magnetic resonance spectrum of the lanthanum-containing compound La(thd)3(Py)2 is shown in Fig. 14. Specifically, the available nuclear magnetic resonance data are as follows. 1 1H-NMR: δ8.66 (d, 6H, py), 7.68 (t, 3H, py), 7.27 (m, 6H, py), 5.68 (s, 3H, O=C-C H -C=O), 1.09 (s, 54H, -C H 3). These nuclear magnetic resonance results indicate that the lanthanide coordination complex La(thd)3(Py)2 having the above general structural formula is successfully prepared in this application.

[0114] Thermal performance analysis was performed on the lanthanum-containing compound La(thd)3(Py)2, and a TG-DSC curve as shown in Fig. 15 was obtained. From Fig. 12, it can be seen that the TG curve of La(thd)3(Py)2 has two steps before 300 °C. The weight loss of about 16% before 100 °C corresponds to the desorption of the neutral ligand pyridine, indicating that the bond strength between pyridine and the lanthanum atom is slightly weak. The thermal stability of this lanthanum-containing compound is slightly lower than that of the lanthanum-containing compounds of Embodiments 1 to 3. Therefore, the lanthanum-containing compound La(thd)3(Py)2 is suitable for preparing a compound film or a lanthanide film containing a lanthanum element by deposition based on the CVD method (however, it is not suitable for deposition based on the ALD method).

[0115] Embodiment 5 Lanthanum-containing compound: La(thd)3(DPA)2, where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione, and DPA represents diisopropylamine. The synthesis route of the lanthanum-containing compound is as follows.

Chemical formula

[0116] The preparation method of the lanthanum-containing compound is as follows: Weigh 45 g of La(thd)3 into a 1 L flask, add 100 mL of n-hexane, and stir the mixture to obtain a turbid La(thd)3 dispersion. Weigh 10.1 g of diisopropylamine (DPA) into another 100 mL beaker, add 50 mL of n-hexane, and stir and dissolve the mixture to obtain a DPA solution. At room temperature, drop the DPA solution into the La(thd)3 dispersion, and stir the mixture for 2 hours for a coordination reaction. Then, remove n-hexane from the obtained reaction solution by vacuum distillation to obtain 51.7 g of La(thd)3(DPA)2.

[0117] The nuclear magnetic resonance spectrum of the lanthanum-containing compound La(thd)3(DPA)2 is shown in Figure 16. Specifically, the available nuclear magnetic resonance data are as follows. 1 H-NMR: δ 5.64 (s, 3H, O=C-C H -C=O), 2.57 (t, 8H, N-C H 2-C H 2-CH3), 1.63 - 1.40 (m, 6H, N-CH2-CH2-C H 3), 1.09 (s, 54H, -C(C H 3)3). These nuclear magnetic resonance results indicate that the lanthanum-containing compound La(thd)3(DPA)2 having the above general structural formula is successfully prepared in this application.

[0118] Thermal performance analysis was carried out on the lanthanum-containing compound La(thd)3(DPA)2, and the results as shown in Figure 17 were obtained. Based on the TG curve, the coordination complex has two weight loss steps before 300 °C. The first step has a weight loss of about 21.82%, which corresponds to the separation of two molecules of diisopropylamine. The second step has a weight loss of about 77.89%, which is the weight loss step of La(thd)3. The residual mass percentage is about -0.06%, indicating that the compound La(thd)3(DPA)2 has high volatility. From the endothermic peaks of the DSC curve, it can be seen that 38 °C is the melting point peak of La(thd)3(DPA)2, 77 °C and 105 °C are the desorption weight loss peaks of two molecules of diisopropylamine, 176 °C is the crystal phase transition peak of La(thd)3, and 263 °C is the melting point peak of La(thd)3.

[0119] The thermal performance data indicate that the aforementioned lanthanum-containing compound La(thd)3(DPA)2 has a much lower melting point (the melting point is about 38 °C) than La(thd)3, can be transported in a liquid state, and helps to reduce the transport energy. After being transported to the deposition chamber at a higher temperature, the lanthanum-containing compound La(thd)3(DPA)2 becomes more volatile, and the monoamine ligand preferentially dissociates from the lanthanum-containing compound La(thd)3(DPA)2 after the temperature rises. The lanthanum-containing compound La(thd)3(DPA)2 is particularly suitable for preparing a film containing a lanthanum element by deposition based on the CVD method (however, it is not suitable for film formation based on the ALD method).

[0120] Embodiment 6 Cerium-containing compound: Ce(thd)3(DMEDA), where thd represents 2,2,6,6-tetramethyl-3,5-heptanedione, and DMEDA represents N,N'-dimethylethylenediamine.

[0121] The preparation method of the cerium-containing compound is as follows: Weigh 40 g of Ce(thd)3 into a 1 L flask, add 100 mL of toluene, stir the mixture to obtain a turbid Ce(thd)3 dispersion. Weigh 5.4 g of N,N’-dimethylethylenediamine (DMEDA) into another 100 mL beaker, add 50 mL of toluene, stir and dissolve the mixture to obtain a DMEDA solution. At room temperature, drop the DMEDA solution into the Ce(thd)3 dispersion and stir for 2 hours to carry out a coordination reaction. Then, distill off toluene from the obtained reaction solution under reduced pressure to obtain 45.2 g of Ce(thd)3(DMEDA).

[0122] Thermal performance analysis is performed on the cerium-containing compound Ce(thd)3(DMEDA)2 obtained in Embodiment 6. This compound has a low melting point (less than 135 °C), high thermal stability (decomposition temperature exceeds 300 °C), and high volatility. The evaporation temperature of the cerium-containing compound at a saturated vapor pressure of 0.1 torr is 140 °C, which is lower than that of La(thd)3 at 0.1 torr.

[0123] The foregoing description is only some exemplary implementations of the present application. Although the description is relatively specific and detailed, it cannot be construed as a limitation to the patent scope of the present application. It should be noted that those skilled in the art can make some improvements and modifications without departing from the concept of the present application, and the improvements and modifications shall fall within the protection scope of the present application. Therefore, the protection scope of the present application shall follow the protection scope of the claims.

Explanation of Signs

[0124] 10 Container chamber 11 Material storage container 20 Deposition chamber 21 Substrate 22 Heating component 100 Deposition device

Claims

1. A metal compound comprising a transition metal atom and at least one β-diketone ligand coordinated with the transition metal atom, further comprising one diamine ligand coordinated with the transition metal atom or two monoamine ligands coordinated with the transition metal atom, wherein the transition metal atom coordinates with two oxygen atoms in the β-diketone ligand and coordinates with two nitrogen atoms in the diamine ligand or coordinates with the nitrogen atom in the monoamine ligand, the metal compound.

2. The metal compound according to claim 1, wherein the transition metal atom comprises a lanthanide element, 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. The metal compound according to claim 1 or 2, wherein the metal compound comprises three β-diketone ligands.

4. The general structural formula of the β-diketone ligand is R 1 -C(=O)-CH 2 -C(=O)-R 2 and is represented as R 1 and R 2 are independently selected from alkyls, the metal compound according to any one of claims 1 to 3.

5. The metal compound according to any one of claims 1 to 4, wherein the diamine ligand comprises a dialkylamine.

6. The general structural formula of the dialkylamine is N(R 3 )(R 4 )-C(R 7 )-C(R 8 )-N(R 5 )(R 6 ), and R 3 to R 8 are independently selected from a hydrogen atom or an alkyl group. The metal compound according to claim 5.

7. The metal compound according to claim 6, wherein the number of carbon atoms of the alkyl is in the range of 1 to 6.

8. The metal compound according to any one of claims 1 to 4, wherein the monoamine ligand comprises a monoalkylamine containing one nitrogen atom or a nitrogen heterocyclic ligand.

9. The general structural formula of the monoalkylamine is N(R 3 ’)(R 4 ’)(R 5 ’), where R 3 ’, R 4 ’ and R 5 ’ are independently selected from a hydrogen atom or an alkyl group, and at least one of R 3 ’ to R 5 ’ is an alkyl group, and the N-heterocyclic carbene ligand contains pyridine, piperidine, pyrrole or derivatives thereof. The metal compound according to claim 8.

10. The metal compound has a general structural formula represented by formula (I) or formula (II), 【Chemical 1】 or [Chemical Formula 2] having, M represents a transition metal atom, in formula (I), R 1 and R 2 are independently selected from alkyl, R 3 to R 8 are independently selected from a hydrogen atom or alkyl, in formula (II), R 1 ’ and R 2 ’ are independently selected from alkyl, R' is independently selected from monoamine ligands having one nitrogen atom, and the nitrogen atom in R' coordinates with the atom M. The metal compound according to any one of claims 1 to 9.

11. A preparation method for a metal compound, comprising the following steps: obtaining a coordination compound comprising a transition metal atom and at least one β-diketone ligand; performing a coordination reaction between a diamine ligand or a monoamine ligand and the coordination compound in an organic solvent to obtain a reaction solution; and removing the organic solvent from the reaction solution to obtain a metal compound, wherein the transition metal atom in the metal compound coordinates with the oxygen atom in the β-diketone ligand and coordinates with two nitrogen atoms in one diamine ligand or coordinates with two nitrogen atoms in two monoamine ligands, the preparation method.

12. The application of the metal compound according to any one of claims 1 to 10 when preparing a film containing a transition metal element.

13. Application of the metal compound according to any one of claims 1 to 10 when preparing an electronic device.

14. A film containing a transition metal element, which is prepared by using the metal compound according to any one of claims 1 to 10.

15. The film containing a transition metal element according to claim 14, wherein the film containing a transition metal element is prepared by using a chemical vapor deposition method or an atomic layer deposition method.

16. The film containing a transition metal element according to claim 14 or 15, wherein the film containing a transition metal element contains an oxide, a nitride, a carbide, or a carbonitride containing a transition metal element.

17. An electronic device having a film containing a transition metal element according to any one of claims 14 to 16.

18. A preparation apparatus for a film containing a transition metal element, comprising a container chamber and a deposition chamber communicating with each other, wherein the container chamber is configured to store the metal compound according to any one of claims 1 to 10, a substrate is disposed in the deposition chamber, the metal compound is transported to the deposition chamber and deposited on the surface of the substrate to form a film containing a transition metal element.

19. A deposition method for a film containing a transition metal element, comprising the following steps: Introducing the vaporized metal compound according to any one of claims 1 to 10 into a deposition chamber of a deposition device in which a substrate is disposed to form a film containing a transition metal element, and depositing the metal compound on the surface of the substrate. Including the deposition method.

20. The deposition method according to claim 19, further comprising the step of introducing a reaction species into the deposition chamber.

21. The film containing the transition metal element further contains an oxygen element, the reaction species includes an oxygen source, and the oxygen source includes one or more of oxygen, ozone, H 2 O, and H 2 O 2 The deposition method according to claim 20, comprising one or more of these.

22. The deposition according to any one of claims 19 to 21 is specifically a chemical vapor deposition process or an atomic layer deposition process.

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