Precursors comprising enolate salt ligands

Abstract

The present invention relates to compositions, precursor vessels, methods, and systems for depositing metals from Group 4, Group 5, Group 6, or Group 13, as well as methods for synthesizing metal precursors. The compositions of the present invention include a coordination compound comprising a metal from Group 5, Group 6, or Group 13 and at least one enamine alkoxide ligand.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application 63 / 726,357, filed November 29, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of film deposition comprising metals from Groups 4, 5, 6, or 13. In particular, this invention relates to precursors for said deposition. Background Technology

[0004] Deposition techniques, such as chemical vapor deposition (CVD), and more specifically, atomic layer deposition (ALD), are essential in the fabrication of semiconductor devices, enabling the controlled formation of thin films at the atomic level. These processes are crucial for producing materials with the precise composition and properties required for advanced electronic applications.

[0005] Metals from Groups 4, 5, 6, and 13 of the periodic table are commonly used for depositing metal, metal oxide, and metal nitride films. When provided as pure metals or nitrides of these metals, they are valued for their thermal, chemical, and mechanical stability, as well as their excellent electrical conductivity. These properties make them suitable for back-end process (BEOL) applications in semiconductor device fabrication. Meanwhile, oxides of these metals are typically dielectrics with good thermal, chemical, and mechanical stability, and several can be used in high-k applications in transistor devices such as MOSFETs.

[0006] However, depositing these metals presents several challenges. A major challenge is achieving high-purity films. Impurities in the deposited film can adversely affect electrical and physical properties, leading to compromised device performance. Controlling impurity levels is critical but difficult due to the potential introduction of contaminants from precursors or the deposition environment.

[0007] Another challenge is the preference for low-temperature deposition processes. High deposition temperatures can be detrimental to the underlying layers and materials in multilayer device architectures, especially in BEOL processes where temperature-sensitive components may be present. Therefore, there is a need for deposition methods that can operate effectively at lower temperatures without sacrificing film quality.

[0008] Furthermore, the oxidation state of the metal plays a crucial role during deposition. Depositing metals in lower oxidation states can be advantageous because it facilitates subsequent processing steps to achieve the desired metallic state or specific material phase with optimal properties. However, stabilizing low-oxidation-state metal precursors suitable for vapor deposition is often challenging. These materials may be unstable or insufficiently volatile, making their use in CVD or ALD processes less practical.

[0009] Given the aforementioned challenges, selecting appropriate chemical precursors for the deposition of these metals is a complex task. The precursors must exhibit suitable physical and chemical properties, such as volatility, thermal stability, and reactivity, to enable precise control over the deposition process. Finding compounds that meet these criteria, while also addressing issues related to purity, deposition temperature, and oxidation state, remains a significant challenge in this field.

[0010] Therefore, further progress is still needed in this field to address at least some of these challenges. Summary of the Invention

[0011] The object of this invention is to provide a composition that solves at least some of the above-mentioned problems.

[0012] The above-mentioned objectives are achieved by the composition according to the invention, the precursor container containing the composition, and the deposition method and apparatus using the composition.

[0013] The advantage of embodiments of the present invention is that they provide precursors suitable for advanced deposition techniques such as chemical vapor deposition and atomic layer deposition, which can be used to deposit thin films in a controlled manner at the atomic level.

[0014] The advantage of the embodiments of the present invention is that the enaminolate ligand of the precursor is universal and can attach to various metal atoms in a series of oxidation states, thereby enhancing the stability of the low oxidation state metal complex and the precursor properties.

[0015] An advantage of embodiments of the present invention is that enamine alkoxide ligands can be used to stabilize low-oxidation-state metal precursors from metals of groups 4, 5, 6 and 13.

[0016] The advantage of embodiments of the present invention is that it enables the good deposition of metal, metal oxide and metal nitride films comprising metals from Groups 4, 5, 6 and 13, which are important for downstream process applications due to their good thermal stability, chemical stability and mechanical stability as well as excellent conductivity.

[0017] In one aspect, the present invention relates to a composition comprising a precursor containing a coordination compound, the coordination compound comprising:

[0018] Metals from Groups 4, 5, 6, or 13, and

[0019] At least one enamine ol salt ligand.

[0020] In another aspect, the present invention relates to a precursor container comprising a composition containing a precursor, the precursor comprising a coordination compound comprising:

[0021] Metals from Groups 4, 5, 6, or 13, and

[0022] At least one enamine ol salt ligand,

[0023] The container is configured to supply vapor of the coordination compound to the reaction chamber of the vapor deposition system, preferably to the reaction chamber of a semiconductor processing device.

[0024] In another aspect, the present invention relates to a method for depositing a material comprising a metal from Group 4, Group 5, Group 6 or Group 13 on a substrate, the method comprising:

[0025] A substrate is provided in the reaction chamber, and then,

[0026] A gas-phase composition comprising a precursor containing a coordination compound is provided to the reaction chamber, the coordination compound comprising:

[0027] Metals, and

[0028] At least one enamine ol salt ligand,

[0029] This forms a metal-containing layer on a portion of the substrate surface.

[0030] In another aspect, a method for synthesizing precursors for vapor deposition is disclosed. In embodiments, the method comprises reacting a potassium salt of an enamine of the following formula with a halide of a Group 4, Group 5, Group 6, or Group 13 metal:

[0031] .

[0032] In another embodiment of the method for synthesizing precursors for vapor deposition, the method includes reacting a free ligand of the following formula with an alkali metal compound of a Group 4, Group 5, Group 6, or Group 13 metal:

[0033] .

[0034] In some embodiments, the basic metal compound of a Group 4, Group 5, Group 6 or Group 13 metal is selected from homocoordinated metal alkyl, homocoordinated dialkylamide, and homocoordinated alkoxide compounds.

[0035] In another aspect, the present invention relates to a system for depositing a material comprising a metal from Group 4, Group 5, Group 6 or Group 13 on a substrate, the system comprising:

[0036] Reaction chamber for receiving substrate

[0037] A first source for providing a gaseous composition comprising a precursor containing a coordination compound, wherein the first source is in communication with a reaction chamber gas via a first valve, and the coordination compound comprises:

[0038] Metals, and

[0039] At least one enamine ol salt ligand,

[0040] A controller operably connected to the first valve, wherein the controller is configured and programmed to open the first valve to provide a flow of composition into the reaction chamber, and to close the first valve to stop the flow of composition into the reaction chamber.

[0041] Specific and preferred aspects of the invention are set forth in the appended independent and dependent claims. Features from the dependent claims may be suitably combined with features of the independent claims and other dependent claims, and are not limited to those expressly set forth in the claims.

[0042] Despite the ongoing improvements, changes, and evolutions in equipment in this field, this concept is considered to represent a substantially new and novel improvement, including deviations from existing practices, resulting in more efficient, stable, and reliable equipment of this nature.

[0043] The above and other features, characteristics, and advantages of the present invention will become apparent from the following detailed description taken in conjunction with the accompanying drawings, which illustrate the principles of the invention by way of example. This description is given for illustrative purposes only and does not limit the scope of the invention. The references to the drawings cited below refer to the accompanying drawings. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of a deposition system according to an embodiment of the present invention.

[0045] Figure 2 Is Figure 1 A schematic diagram of the film formed on the substrate in the reaction chamber of the deposition system.

[0046] In different figures, the same reference numerals denote the same or similar elements. Detailed Implementation

[0047] The invention will be described with reference to specific embodiments and certain accompanying drawings, but is not limited thereto; rather, it is limited only by the claims. The described drawings are illustrative only and not restrictive. In the drawings, the dimensions of some elements may be exaggerated and not drawn to scale for illustrative purposes. Dimensions and relative dimensions do not correspond to actual reductions in practice of the invention.

[0048] Furthermore, the terms first, second, third, etc., used in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequence in time, space, order, or any other way. It should be understood that the terms thus used are interchangeable where appropriate, and the embodiments of the invention described herein can operate in orders other than those described or shown herein.

[0049] Furthermore, the terms top, bottom, above, below, etc., used in the specification and claims are for descriptive purposes and are not necessarily used to describe relative positions. It should be understood that such terms are interchangeable where appropriate, and the embodiments of the invention described herein can operate in orientations other than those described or shown herein.

[0050] It should be noted that the term "comprising" should not be construed as limited to the devices listed thereafter; it does not exclude other elements or steps. Therefore, it should be interpreted as specifying the presence of the stated feature, integer, step, or component, but not excluding the presence or addition of one or more other features, integers, steps, or components, or groups thereof. Thus, the term "comprising" covers both the presence of only the stated feature and the presence of these features plus one or more other features. Therefore, the term "comprising" according to the invention also includes the absence of other components as an example. Therefore, the scope of the expression "device comprising devices A and B" should not be construed as limited to a device consisting only of components A and B. This means that, with respect to the invention, the only relevant components of the device are A and B.

[0051] Similarly, it should be noted that the term "connection" should not be interpreted as limited to direct connection. The terms "connection" and "linkage" and their derivatives may be used. It should be understood that these terms are not intended to be synonyms with each other. Therefore, the scope of the expression "device A connected to device B" should not be limited to devices or systems where the output of device A is directly connected to the input of device B. This implies that there is a path between the output of A and the input of B, which may include other devices or apparatuses. "Connection" can mean two or more elements in direct physical or electrical contact, or two or more elements that are not in direct contact with each other but still cooperate or interact with each other.

[0052] In this disclosure, the term "alkyl" includes all straight-chain, branched, and cyclic isomers of alkyl groups. For example, the term "C1 to C6 alkyl" may mean any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0053] Throughout this specification, the reference to "an embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the invention. Therefore, the phrases "in an embodiment" or "in one embodiment" appearing in various places throughout this specification do not necessarily refer to the same embodiment, but may refer to the same embodiment. Furthermore, in one or more embodiments, particular features, structures, or characteristics may be combined in any suitable manner as will be apparent to those skilled in the art based on this disclosure.

[0054] Similarly, it should be understood that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, drawing, or description therein in order to simplify the disclosure and aid in understanding one or more of the various aspects of the invention. However, this method of disclosure should not be construed as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as reflected in the following claims, inventive aspects lie in fewer than all features of a single foregoing disclosed embodiment. Therefore, the claims following the detailed description are expressly incorporated herein, wherein each claim is independently a separate embodiment of the invention.

[0055] Furthermore, while some embodiments described herein include features that are not included in other embodiments, combinations of features from different embodiments are intended to be within the scope of the invention and form different embodiments, as will be understood by those skilled in the art. For example, in the following claims, any claimed embodiment may be used in any combination.

[0056] Furthermore, some of the embodiments described herein are methods or combinations of method elements that can be implemented by a processor of a computer system or by other means of performing functions. Therefore, a processor having the necessary instructions for performing such methods or method elements forms means for performing such methods or method elements. Moreover, the elements of the apparatus embodiments described herein are examples of means for performing the functions performed by the elements, for the purposes of this invention.

[0057] Numerous specific details are set forth in the description provided herein. However, it should be understood that embodiments of the invention can be practiced without these specific details. In other instances, well-known methods, structures, and techniques have not been shown in detail so as not to obscure the understanding of this specification.

[0058] In the context of this invention, the terms "precursor" and "co-reactant" can refer to a molecule (compound, or molecule containing a single element such as O2 or O3) that participates in a chemical reaction to produce another compound or element. A precursor typically contains a portion at least partially bound to the compound or element produced by the chemical reaction in question. The resulting compound or element can then be deposited on a substrate. In some cases, the co-reactant is a precursor. In other cases, the compound or element produced by the chemical reaction does not contain a portion of the co-reactant (an element or group within the co-reactant), and therefore the co-reactant is not a precursor. In some embodiments, the precursor or co-reactant is provided as a mixture of two or more compounds. In the mixture, the compounds other than the precursor may be inert compounds or elements. In some embodiments, the precursor or co-reactant is provided in a composition. The composition may be a solution or a gas under standard conditions.

[0059] In the context of this invention, the terms "layer" and / or (thin) "film" can refer to any continuous or discontinuous material, such as materials deposited by the methods disclosed herein, and these terms are used interchangeably. For example, layers and / or films can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partial or complete molecular layers or partial or complete atomic layers or atomic and / or molecular clusters. Films or layers can include materials or layers with pinholes, which can be at least partially continuous. In some embodiments, layers according to this disclosure are substantially continuous. In embodiments, layers or films can have a thickness of 0.1 nm to 1 μm, for example, 0.5 nm to 200 nm.

[0060] As used herein, "substrate" refers to one or more underlying materials on which devices, circuits, materials, or material layers can be formed or on which they are formed. Substrates can be continuous or discontinuous; rigid or flexible; solid or porous; and combinations thereof. Substrates can be in any form, such as powder, sheet, plate, or workpiece. Sheet-form substrates can extend beyond the boundaries of the reaction space or processing / reaction chamber where the deposition process occurs, and in some cases, move through the chamber so that the process continues until the end of the substrate is reached. Plate-form substrates can include wafers of various shapes and sizes. Substrates can be made of semiconductor materials, including, for example, Mo, Mo germanium, Mo oxide, gallium arsenide, gallium nitride, and Mo carbide. Substrates can include one or more layers covering a bulk material, such as nitrides (e.g., TiN), oxides, insulating materials, dielectric materials, conductive materials, metals (e.g., tungsten, ruthenium, Group 6 metals, cobalt, aluminum, or copper) or other metallic materials, crystalline materials, epitaxial, heteroepitaxial, and / or single-crystal materials. The substrate may include various topologies, such as gaps, grooves, lines, trenches, vias, holes, or spaces between protrusions (e.g., fins) formed in or on at least a portion of the layers of the substrate.

[0061] The present invention will now be described in detail through several embodiments thereof. It is clear that other embodiments of the invention can be configured based on the knowledge of those skilled in the art without departing from the technical teachings of the invention, which is limited only by the terms of the appended claims.

[0062] In a first aspect, the present invention relates to a composition comprising a precursor containing a coordination compound, the coordination compound comprising:

[0063] Metals from Groups 4, 5, 6, or 13, and

[0064] At least one enamine ol salt ligand.

[0065] In a preferred embodiment, the composition includes a precursor comprising a coordination compound, the coordination compound comprising:

[0066] Metals from Group 5, Group 6, or Group 13, and

[0067] At least one enamine ol salt ligand.

[0068] Such preferred embodiments provide improved deposition of metals from Group 5, Group 6 or Group 13.

[0069] In the embodiments, each enamine alkoxide ligand may be independently monodentate or bidentate bonded to the metal. In the embodiments, each enamine alkoxide ligand may be independently monodentately bonded to the metal. In the embodiments, each enamine alkoxide ligand may be bidentately bonded to the metal. Specifically, the enamine alkoxide ligand comprises both oxygen and nitrogen atoms, one or both of which may be bonded to the metal. Typically, each enamine alkoxide ligand carries a single negative charge, which may be located on the oxygen atom.

[0070] In some embodiments, the coordination compound comprises a single metal atom. In some embodiments, the coordination compound comprises more than one metal atom. In some embodiments, the enamine alkoxide ligand is bonded to two metal atoms. In such embodiments, the enamine alkoxide can be monodentately bonded to the first metal atom via oxygen and monodentately bonded to the second metal atom via nitrogen. In some embodiments, the first metal atom and the second metal atom can be the same chemical element. In some embodiments, the first metal atom and the second metal atom can be different chemical elements.

[0071] Enaminolate ligands are known in the art and have been previously used in atomic layer deposition. However, they have only served as precursors for some rare earth elements, including Y, La, Er, and Lu (Jayakodiarachchi, N., Evans, PG, Ward, CL, & Winter, CH (2021). Evaluation of volatility and thermalstability in monomeric and dimeric lanthanide (III) complexes containing enaminolate ligands. Organometallics, 40(9), 1270-1283). In the case of these rare earth elements, oxidation and reduction are not issues.

[0072] The inventors of this invention have recognized that these enamine alkoxide ligands can attach to a variety of metal atoms in various oxidation states. Indeed, as typical bidentate monoanionic ligands with good alkyl substituent tunability, enamine alkoxide ligands are considered excellent in stabilizing monomeric coordination compounds containing metals in low oxidation states. Furthermore, enamine alkoxides can be used to provide coordination compounds with good precursor properties because their structures can be tuned to optimize their precursor properties. Therefore, enamine alkoxide ligands allow metals to be deposited in any oxidation state desired for a specific purpose, including deposition in low oxidation states, which is typically difficult when using ligands of the prior art.

[0073] An advantage of embodiments of the present invention is that the enamine alkoxide ligands can be thermally stable. Their high thermal stability leads to good and predictable deposition and prevents the deposited material from being contaminated by the decomposition products of the ligands.

[0074] In some embodiments, the metal is in an oxidation state lower than the metal's highest common oxidation state. The highest common oxidation state for Group 5 metals is typically +5. The highest common oxidation state for Group 6 metals is typically +6. The highest common oxidation state for Group 4 metals is typically +4. The highest common oxidation state for Group 13 metals is typically +3. In an embodiment, the metal may be Ti. 2+ Ti 3 + Zr 3+ , Hf 2+ , Hf 3+ , Cr 2+ , Cr 3+ Mo 3+ W 3+ V 2+ V 3+ , Ta3+ , Nb 3+ Ga 1+ In 1+ Mo 2+ Mo 4 + W 2+ W 4+ V 4+ , Ta 2+ , Ta 4+ , Nb 2+ or Nb 4+ In some preferred embodiments, the metal may be Cr. 2+ , Cr 3+ Mo 3+ W 3+ V 2+ V 3+ , Ta 3+ , Nb 3+ Ga 1+ In 1+ Mo 2+ Mo 4+ W 2+ W 4+ V 4+ , Ta 2+ , Ta 4+ , Nb 2+ or Nb 4+ The advantage of these embodiments is that the low-oxidation-state precursors exhibit higher reactivity and provide an easier pathway to reduction to the zero oxidation state during the deposition process.

[0075] However, this is not necessary. In some embodiments, the metal is in its highest common oxidation state. In some embodiments, the metal may be Ti. 4+ Zr 4+ , Hf 4+ V +5 , Nb +5 W 6+ Mo +6 Al 3+ In 3+ or Ga 3+ In some preferred embodiments, the metal may be V. +5 , Nb +5 W 6+ Mo +6 Al 3+ In 3+ or Ga 3+ .

[0076] In some embodiments, the metal is from Group 5 or Group 6. In some embodiments, the metal is selected from vanadium (V), niobium (Nb), and tantalum (Ta). In some of these embodiments, the metal is selected from chromium (Cr), molybdenum (Mo), and tungsten (W).

[0077] In some embodiments, the metal is from Group 4. In some embodiments, the metal is selected from titanium (Ti), zirconium (Zr), and hafnium (Hf). In other embodiments, the metal is not a Group 4 metal.

[0078] In some embodiments, the metal is from Group 13. In one embodiment, the metal is aluminum (Al). In some embodiments, the metal is gallium (Ga). In one embodiment, the metal is indium (In).

[0079] In the embodiments, each enamine ol salt ligand has the following chemical formula I:

[0080] .

[0081] In some embodiments, R1 may be hydrogen or a C1 to C8 alkyl or alkylsilyl. In some embodiments, R1 may be hydrogen or a C1 to C8 alkyl. In some embodiments, R1 is a C3 or C4 alkyl. In some embodiments, R1 is butyl. In some embodiments, R1 is tert-butyl. In some embodiments, R1 may be an alkylsilyl containing silicon atoms bonded to three alkyl groups, wherein each of the three alkyl groups is independently selected from C1 to C8 alkyl, preferably C1 to C4 alkyl, more preferably C1 to C2 alkyl. In some embodiments, R1 is SiMe3 or SiEt3. In embodiments where R1 is an alkylsilyl, the silicon atom may be directly bonded to the carbon atom bonded to R1. In embodiments where R1 is an alkylsilyl, the silicon atom may be bonded to the carbon atom bonded to R1 via a C1 to C4 chain, preferably a C1 to C2 chain, more preferably a C1 chain.

[0082] In embodiments, R2 and R3 may each be independently selected from C1 to C8 alkyl or alkylsilyl groups. In some embodiments, R2 and R3 may each be independently selected from C1 to C8 alkyl groups. In some embodiments, R2 and R3 are the same alkyl group. For example, in some embodiments, R2 and R3 are methyl groups. In some embodiments, R2 and R3 are ethyl groups. In some embodiments, R2, R3, and the N atoms to which they are bonded may together form a four- to nine-membered ring. In some embodiments, R2 may be an alkylsilyl group containing silicon atoms bonded to three alkyl groups, wherein each of the three alkyl groups is independently selected from C1 to C8 alkyl groups, preferably C1 to C4 alkyl groups, more preferably C1 to C2 alkyl groups. In some embodiments, R2 may be SiMe3 or SiEt3. In embodiments where R2 is an alkylsilyl group, the silicon atom may be directly bonded to the nitrogen atom bonded to R2. In embodiments where R2 is an alkylsilyl group, the silicon atom may be bonded to the nitrogen atom bonded to R2 via a C1 to C4 chain, preferably a C1 to C2 chain, more preferably a C1 chain. In some embodiments, R3 may be an alkylsilyl group containing silicon atoms bonded to three alkyl groups, wherein each of the three alkyl groups is independently selected from C1 to C8 alkyl groups, preferably C1 to C4 alkyl groups, and more preferably C1 to C2 alkyl groups. In some embodiments, R3 may be SiMe3 or SiEt3. In some embodiments where R3 is an alkylsilyl group, the silicon atom may be directly bonded to the nitrogen atom bonded to R3. In embodiments where R3 is an alkylsilyl group, the silicon atom may be bonded to the nitrogen atom bonded to R3 via a C1 to C4 chain, preferably a C1 to C2 chain, and more preferably a C1 chain.

[0083] In some embodiments, R4 may be hydrogen or a C1 to C8 alkyl or alkylsilyl. In some embodiments, R4 may be hydrogen or a C1 to C8 alkyl. In some embodiments, R2, R4, the carbon atom bonded to R4, and the N atom bonded to R2 may together form a four- to nine-membered ring. In some embodiments, R1, R4, the carbon atom bonded to R1, and the carbon atom bonded to R4 together form a four- to nine-membered ring. Each of the mentioned rings may be substituted independently. Each of the rings is preferably composed of carbon atoms, except for the nitrogen atoms to which R2 and R3 may be attached. In some embodiments, R4 may be an alkylsilyl containing silicon atoms bonded to three alkyl groups, wherein each of the three alkyl groups is independently selected from C1 to C8 alkyl groups, preferably C1 to C4 alkyl groups, more preferably C1 to C2 alkyl groups. In some embodiments, R4 may be SiMe3 or SiEt3. In embodiments where R4 is an alkylsilyl, the silicon atom may be directly bonded to the carbon atom bonded to R4. In embodiments where R4 is an alkylsilyl group, the silicon atom can be bonded to the carbon atom bonded to R4 via a C1 to C4 chain, preferably a C1 to C2 chain, more preferably a C1 chain.

[0084] In some embodiments, R4 may be hydrogen or a C1 to C6 alkyl group, preferably hydrogen or a C1 to C4 alkyl group. In a preferred embodiment, R4 is hydrogen.

[0085] Preferably, the conjugate acid of the enamine alkoxide has a high pKa, in which case the enamine alkoxide can have a high affinity for the metal, which can produce a stable coordination compound. Simultaneously, the high pKa leads to the easy protonation of the enamine alkoxide, making it highly reactive to proton co-reactants such as H₂O. Specifically, through this protonation, the enamine alkoxide can be converted into an (uncharged) α-amino ketone. The α-amino ketone can be readily released from the metal. This can facilitate the vapor deposition of the coordination compound of the embodiments of the present invention on the substrate, followed by the release of the enamine alkoxide from the substrate.

[0086] In some embodiments, R4 is hydrogen. In these embodiments, each enamine alkoxide ligand has the following chemical formula (II):

[0087] .

[0088] Each of R1, R2, and R3 can be selected independently as described accordingly above. In some embodiments, R1 is hydrogen or a C1 to C8 alkyl group. In some embodiments, R2 and R3 can each be independently selected from C1 to C8 alkyl groups. In some embodiments, R1 is a C3 or C4 alkyl group. In some embodiments, R1 is butyl. In some embodiments, R1 is tert-butyl. In some embodiments, R2 and R3 are the same alkyl group. For example, in some embodiments, R2 and R3 are methyl. In some embodiments, R2 and R3 are ethyl. In some embodiments, R2 and R3 can form optionally substituted rings having 4 to 9 atoms, preferably 4 to 7 atoms, together with the nitrogen atom to which they are attached. The ring is preferably composed of carbon atoms, except for the nitrogen atom to which R2 and R3 are attached. In embodiments in which the ring is substituted, the substitution can be with a C1 to C8 alkyl group, preferably with a C1 to C6 alkyl group. In certain embodiments, the coordination compound according to this disclosure comprises at least one enamine alkoxide ligand, wherein R1 is tert-butyl, R2 and R3 are methyl, and R4 is H. In some embodiments, R1 is hydrogen or a C1 to C6 alkyl group, and R2 and R3 are each independently selected from C1 to C6 alkyl groups. In some embodiments, R1 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl, and R2 and R3 are each independently selected from methyl, ethyl, and isopropyl.

[0089] In embodiments where the coordination compound comprises more than one enamine alkoxide ligand, each enamine alkoxide ligand of the coordination compound may have the same structure. In embodiments where the coordination compound comprises more than one enamine alkoxide ligand, the different enamine alkoxide ligands of the coordination compound may have different structures.

[0090] In some embodiments, the coordination compounds are homocoordinated.

[0091] In some embodiments, the coordination compound has the chemical formula ML3, wherein M is selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, Ga, and In, and wherein each L is an enamine alkoxide ligand. Each L may be the same enamine alkoxide ligand, in which case the coordination compound is homocoordinated, but the invention is not limited thereto. In some of these embodiments, the coordination compound is AlL3, GaL3, or InL3, wherein L is an enamine alkoxide ligand according to the present disclosure. In some embodiments, the coordination compound is heterocoordinated.

[0092] In some embodiments, the coordination compound further comprises at least one ligand selected from the group consisting of cyclopentadienyl ligands, amidation ligands, alkyl ligands, alkylamide ligands, imino ligands, alkoxide ligands, halide ligands, guanidinyl ligands, and β-diketone ligands.

[0093] In some embodiments, the coordination compound has the chemical formula MO2L2, wherein M is Cr, Mo, or W, and wherein each L is an enamine ol salt ligand.

[0094] In some embodiments, the coordination compound has the chemical formula MOL3, wherein M is V, Nb, or Ta, and wherein each L is an enamine ol salt ligand.

[0095] In some embodiments, the coordination compound has the chemical formula M(NR). x L y In some of these embodiments, M is V, Nb, Ta, Cr, Mo, or W, each R is an alkyl or trialkylsilyl group, each L is an enamine alkoxide ligand, and each of x and y is an integer equal to or greater than 1, and x+y is an integer from 2 to 6. In some of these embodiments, each R is independently selected from C1 to C8 alkyl groups, preferably C1 to C6 alkyl groups, more preferably C1 to C4 alkyl groups. In some of these embodiments, each R is independently selected from ethyl, isopropyl, sec-butyl, tert-butyl, and tert-pentyl, preferably isopropyl, sec-butyl, tert-butyl, and tert-pentyl. In some embodiments, the trialkylsilyl group may comprise silicon bonded to three alkyl groups, each alkyl group being independently selected from C1 to C8 alkyl groups, preferably C1 to C4 alkyl groups, more preferably C1 to C2 alkyl groups. In some of these embodiments, each R is independently selected from trimethylsilyl and triethylsilyl. In some embodiments, x is 1 to 5, y is 1 to 5, and x+y is 2 to 6.

[0096] In some embodiments, the coordination compound has the chemical formula ML x L' y, wherein M is Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W, wherein each L is an enamine olite ligand, and wherein each L' is a ligand selected from the following: dimethylamino, diethylamino, ethylmethylamino, methoxy, ethoxy, isopropoxy, tert-butoxy, tert-pentoxy, trimethylsilyloxy or triethylsilyloxy, N,N'-diisopropylacetamidine, N,N'-di-tert-butylacetamidine, N,N'-diisopropylformamidine, N,N'-di-tert-butylformamidine, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, tert-butylcyclopentadienyl, trimethylsilylcyclopentadienyl, and pentamethylcyclopentadienyl, and wherein each of x and y is an integer equal to or greater than 1, and wherein x+y is an integer from 2 to 6. In the embodiments, x is 1 to 5, y is 1 to 5, and x+y is 2 to 6.

[0097] In some embodiments, the coordination compound has the chemical formula ML x L' y , where M is Al, Ga or In, where each L is an enamine ol salt ligand, and where each L' is a ligand selected from the following: cyclopentadienyl ligand, amidation ligand, alkyl ligand, aryl ligand, alkylamide ligand, imide ligand, alkoxy ligand, halide ligand, guanidinyl ligand and β-diketone ligand, where each of x and y is an integer equal to or greater than 1, and x+y is 3.

[0098] In some embodiments, the coordination compound is AlR'2L, GaR'2L, or InR'2L, wherein L is an enamine alkoxide ligand according to the present disclosure, and wherein each R' is independently selected from C1 to C4 alkyl and aryl groups. In some embodiments, the coordination compound is AlR'L2, GaR'L2, or InR'L2, wherein each L is an enamine alkoxide ligand according to the present disclosure, and R' is independently selected from C1 to C4 alkyl and aryl groups. In some embodiments, at least one alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl. In some embodiments, at least one R' is an aryl group, such as phenyl. In a particular embodiment, the coordination compound comprises an enamine alkoxide ligand, wherein R1 is tert-butyl, R2 and R3 are methyl, and R4 is H; and each R' is a methyl ligand, and the metal atom is selected from Al, Ga, and In. In another embodiment, the coordination compound comprises an enamine alkoxide ligand, wherein R1 is tert-butyl, R2 and R3 are ethyl, and R4 is H; and each R' is a methyl ligand, and the metal atom is selected from Al, Ga, and In.

[0099] In some embodiments, the coordination compound is AlL(NRR')2, GaL(NRR')2, or InL(NRR')2, wherein L is an enamine alkoxide ligand according to the present disclosure, and wherein R and R' are independently selected from H, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trimethylsilyl, and triethylsilyl. In some embodiments, the coordination compound is AlL2(NRR'), GaL2(NRR'), or InL2(NRR'), wherein each L is an enamine alkoxide ligand according to the present disclosure, and wherein R and R' are independently selected from H, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trimethylsilyl, and triethylsilyl.

[0100] In some embodiments, the coordination compound is AlL(OR)2, GaL(OR)2, or InL(OR)2, wherein L is an enamine alkoxide ligand according to the present disclosure, and wherein R is selected from H, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trimethylsilyl, and triethylsilyl. In some embodiments, the coordination compound is AlL2(OR), GaL2(OR), or InL2(OR), wherein each L is an enamine alkoxide ligand according to the present disclosure, and wherein R is selected from H, methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, tert-butyl, trimethylsilyl, and triethylsilyl.

[0101] The compositions disclosed herein are generally stable enough to allow for storage and use over extended periods, such as several months. The compositions are generally adapted to withstand deposition conditions that allow vapor transfer into the reaction chamber. Furthermore, the evaporation rate of the composition under predetermined conditions is preferably kept constant. Some compositions may be subject to evaporation of more than one substance. If the substances have different volatility, the composition may become richer in the less volatile substance over time. This can lead to a phenomenon known as process drift: one or more of the deposition process parameters gradually change over time as the chemical composition changes. The consequences of process drift can be detrimental in sensitive applications, and adjusting the process to compensate for drift can be costly, difficult, or even impossible.

[0102] In the embodiments, the purity of the composition (e.g., the coordination compound) is at least 95% by weight, preferably at least 99% by weight, more preferably at least 99.9% by weight, even more preferably at least 99.99% by weight, even more preferably at least 99.999% by weight, and even more preferably at least 99.9999% by weight. This high purity is generally strongly preferred for chemical vapor deposition, particularly for atomic layer deposition. Preferably, the composition contains no more than about 5% by weight, or no more than about 4% by weight, or no more than about 3% by weight, or no more than about 2% by weight, or no more than about 1% by weight, or no more than about 0.5% by weight, or no more than about 0.1% by weight, or no more than about 100 ppm, or no more than about 10 ppm of halogenated impurities, such as halogenated impurities. Preferably, the composition contains no more than about 1% by weight, or no more than about 0.1% by weight, or no more than about 100 ppm, or no more than about 10 ppm, or no more than about 1 ppm, or no more than about 100 ppb, or no more than about 10 ppb of metallic impurities, such as metallic impurities. The metallic impurities may be metals not included in the coordination compounds of the embodiments of the present invention. Metallic impurities may include, for example, alkali metals (e.g., Li, Na, K) and / or alkaline earth metals (e.g., Mg, Ca).

[0103] Any feature of any embodiment of the first aspect may be independently described as in any embodiment of any other aspect of the invention.

[0104] In a second aspect, the present invention relates to a precursor container comprising a composition containing a precursor, the precursor comprising a coordination compound comprising:

[0105] Metals from Groups 4, 5, 6, or 13, and

[0106] At least one enamine ol salt ligand,

[0107] The container is configured to supply the vapor of the precursor to the reaction chamber of the vapor deposition system, preferably to the reaction chamber of the semiconductor processing equipment. The reaction chamber of the vapor deposition system, i.e., the vapor deposition system reaction chamber, can be a chemical vapor deposition system reaction chamber. The chemical vapor deposition system reaction chamber can be an atomic layer deposition system reaction chamber.

[0108] A composition comprising a precursor containing a coordination compound is described in the first aspect of this disclosure. The precursor container may be made of a suitable container material, such as stainless steel, aluminum, copper, nickel, silver, alloys thereof, graphite, boron nitride, ceramic materials, or combinations or mixtures of said materials. The container material may be a thermally conductive material. The container material may be a coating or covering material.

[0109] The precursor container includes a shell defining an internal volume of the precursor container. The internal volume is adapted to contain a composition comprising a precursor, which includes a coordination compound according to embodiments of the invention. In some embodiments, the internal volume has a generally circular cylindrical shape, such that the internal volume has a generally circular base plate. However, the internal volume of the precursor container can have any shape that facilitates uniform flow of the precursor vapor and, optionally, a carrier gas through the internal volume. In embodiments, the precursor container can have a height-to-width ratio in the range of about 0.5 to 4, for example, 1 to 2 or 1 to 3. The height of the precursor container is the dimension of the portion of the precursor container outside the cap to the shell furthest from the cap. The width of the precursor container is the maximum dimension spanning the precursor container perpendicular to its height.

[0110] In some embodiments, the precursor container includes a lid for isolating the internal volume from the surrounding atmosphere. In some of these embodiments, the lid may include an inlet for feeding a generally inert carrier gas (e.g., N2, He, or Ar) into the internal volume of the precursor container. The inlet for feeding the carrier gas may include an inlet valve for introducing the carrier gas when the inlet valve is open and for preventing the carrier gas from being fed into the precursor container when the inlet valve is closed. The lid may include an outlet for feeding the precursor and optionally the carrier gas into the reaction chamber. The outlet may include an outlet valve for providing the vapor of the precursor and optionally the carrier gas into the reaction chamber when the outlet valve is open, and for preventing the chemical precursor and optionally the carrier gas from being fed into the reaction chamber when the outlet valve is closed.

[0111] The precursor container may be equipped with gas lines extending from the inlet and outlet, isolation valves on the lines, and fittings on the valves, the fittings being configured to connect to gas flow lines for other components of the chemical vapor deposition system. The isolation valves isolate the contents of the precursor container from external fluids. One isolation valve may be located upstream of the precursor container inlet, and another isolation valve may be located downstream of the precursor container outlet.

[0112] A deposition system in which a precursor container or precursor container may be a part may include a heater, such as a radiant heat lamp or a resistance heater. In some embodiments, the heater may be adapted to heat the precursor container to a temperature of 40°C to 200°C, for example to 70°C, 85°C, 90°C, 110°C, 120°C, 140°C, 160°C, or 180°C. In particular, during the use of a precursor container in a vapor deposition method, the heater may be configured to heat the precursor container to a temperature above the volatilization temperature of the precursor under pressure within the precursor container.

[0113] In some embodiments, the pressure within the precursor container can be from 10 Pa to 1000 Pa, but the invention is not limited thereto. In particular, the precursor container is typically subjected to such low pressures during use in chemical vapor deposition methods. The precursor container may include, or may be coupled to, a pressure control system for monitoring the pressure within the precursor container. The precursor container may include a valve for coupling the precursor container to a vacuum pump.

[0114] In some embodiments, the precursor container may include precursor distribution means for achieving efficient precursor evaporation, such as a precursor holding structure or carrier gas guiding means within the internal volume of the precursor container. The precursor container may include features for filtering solid particles to prevent their presence in the gas phase flow, such as filters or other interception structures. Additionally, the inlet and outlet of the precursor container and the gas lines extending therefrom may include heaters for heating the valves and gas lines between the precursor container and the reaction chamber to prevent reactant vapors from condensing and depositing on any components.

[0115] Any feature of any embodiment of the second aspect may be independently described as in any embodiment of any other aspect of the invention.

[0116] In a third aspect, the present invention relates to a method for depositing a material comprising a metal from Group 4, Group 5, Group 6 or Group 13 on a substrate, the method comprising:

[0117] A substrate is provided in the reaction chamber, and then,

[0118] A gaseous composition comprising a precursor is provided to the reaction chamber. The precursor comprises a coordination compound, which comprises:

[0119] Metals, and

[0120] At least one enamine ol salt ligand,

[0121] This forms a layer or thin film containing metal on a portion of the substrate surface.

[0122] A composition comprising a precursor containing a coordination compound is described in the first aspect of this disclosure.

[0123] In the embodiments, the deposition method can be any type of vapor deposition process, including physical vapor deposition and chemical vapor deposition processes, such as atomic layer deposition.

[0124] In some embodiments, the chemical vapor deposition process may be characterized by vapor deposition, which is not self-limiting. In embodiments, the chemical vapor deposition process may involve a vapor-phase reaction between a precursor according to the invention and another precursor or co-reactant. The precursor and another precursor or co-reactant according to the invention may be provided simultaneously to the reaction chamber or substrate, or provided in partially or completely separate pulses. In some embodiments, the precursor according to the invention or another precursor or co-reactant, or the precursor according to the invention and another precursor or co-reactant simultaneously, are provided until a layer of desired thickness is deposited.

[0125] In some embodiments, a cyclic chemical vapor deposition process can be used in conjunction with multiple cycles to deposit a thin film of a desired thickness. In a cyclic chemical vapor deposition process, such as atomic layer deposition, precursors and / or any co-reactants can be supplied to the reaction chamber in non-overlapping or partially or completely overlapping pulses.

[0126] In a preferred embodiment, the present invention relates to a cyclic deposition process, such as atomic layer deposition. In a cyclic deposition process, during each cycle, a precursor is introduced into a reaction chamber, and a coordination compound may be deposited on or chemisorbed onto a substrate surface (wherein the substrate surface may be a bare substrate, or may include previously deposited material from a previous deposition cycle, or another material). In some embodiments, the coordination compound on the substrate surface does not readily react with itself, such that the deposition of the coordination compound may be partially or completely self-limiting. Subsequently, a co-reactant may be introduced into the reaction chamber to convert the chemisorbed precursor into the desired material on the surface. The co-reactant may be able to further react with the precursor. A purging step may be used to remove any excess precursor from the processing chamber and / or any excess co-reactant and / or reaction byproducts from the reaction chamber. Therefore, in some embodiments, the cyclic deposition process includes purging the reaction chamber after the coordination compound has been provided into it.

[0127] In some embodiments, the method further includes performing the following cyclically after the layer is formed:

[0128] Optionally, the reaction chamber is purged, and then,

[0129] A gaseous co-reactant is supplied to the reaction chamber, and then...

[0130] Optionally, the reaction chamber is purged, and then,

[0131] The precursor is provided to the reaction chamber.

[0132] In some embodiments, the method further includes at least one cycle of performing a cyclic deposition process, each cycle comprising:

[0133] A gaseous composition comprising a precursor containing a coordination compound is provided into the reaction chamber;

[0134] The reaction chamber may be purged.

[0135] Provide gaseous co-reactants to the reaction chamber; and

[0136] The reaction chamber can be purged optionally.

[0137] In some embodiments, the co-reactant is an oxygen precursor, and the deposited material can be an oxide of a metal coordination compound. The oxygen precursor can provide oxygen for forming the metal oxide. The oxygen precursor can be a gas or a material that can be converted into a gaseous state and can be represented by a chemical formula including oxygen.

[0138] In some of these embodiments, the oxygen precursor is selected from water, molecular oxygen, hydrogen peroxide, ozone, and reactive oxygen species. In some embodiments, the oxygen precursor comprises hydrogen and oxygen. In some embodiments, the oxygen precursor does not contain carbon, i.e., it is carbon-free. In some embodiments, the oxygen precursor does not contain silicon, i.e., it is silicon-free. In some embodiments, the oxygen precursor comprises water. In some embodiments, the oxygen precursor is water. In some embodiments, the oxygen precursor is molecular oxygen. In some embodiments, the oxygen precursor includes hydrogen peroxide. In some embodiments, the oxygen precursor is hydrogen peroxide. In some embodiments, the oxygen precursor is ozone. Depending on the selected oxygen precursor, the oxygen precursor may be liquid or gaseous in the precursor container. However, the invention is not limited thereto, and solid precursors may be used.

[0139] In some embodiments, the co-reactant is a nitrogen precursor, and the deposited material may be a metal nitride of a coordination compound. The nitrogen precursor can provide nitrogen for forming the metal nitride. The term nitrogen precursor can refer to a gas or a material that can be converted into a gaseous state and can be represented by a chemical formula including nitrogen. In some embodiments, the chemical formula includes nitrogen and hydrogen. In some embodiments, the nitrogen precursor does not include diatomic nitrogen. In embodiments, the nitrogen precursor may be selected from ammonia (NH3), hydrazine (N2H4), and one or more other compounds containing nitrogen and hydrogen or composed thereof. For example, a mixture of nitrogen and hydrogen gas can be used. In embodiments, the nitrogen precursor does not include diatomic nitrogen, i.e., the nitrogen precursor is a non-diatomic precursor.

[0140] In some embodiments, the nitrogen precursor is selected from molecular nitrogen (N2), ammonia (NH3), hydrazine (NH2NH2), and hydrazine derivatives (e.g., tert-butylhydrazine). In some embodiments, the nitrogen precursor does not contain carbon, i.e., the nitrogen precursor may be carbon-free. In some embodiments, the nitrogen precursor does not contain silicon, i.e., the nitrogen precursor may be silicon-free. Depending on the nitrogen precursor selected, the nitrogen precursor may be liquid or gaseous in the precursor container upon evaporation. However, the invention is not limited thereto, and the nitrogen precursor may be solid.

[0141] In some embodiments, the nitrogen precursor comprises ammonia. In some embodiments, the nitrogen precursor consists of or is substantially composed of ammonia. In some embodiments, the nitrogen precursor comprises alkylamines. In some embodiments, the nitrogen precursor consists of or is substantially composed of alkylamines. Examples of alkylamines include dimethylamine, n-butylamine, and tert-butylamine.

[0142] In some embodiments, the nitrogen precursor comprises hydrazine. In some embodiments, the nitrogen precursor consists of or is substantially composed of hydrazine. In some embodiments, the nitrogen precursor comprises hydrazine substituted with one or more alkyl or aryl substituents. In some embodiments, the nitrogen precursor consists of or is substantially composed of hydrazine substituted with one or more alkyl or aryl substituents. In some embodiments, the hydrazine derivative comprises alkyl-hydrazine, including at least one of the following: tert-butylhydrazine (C4H9N2H3), methylhydrazine (CH3NHNH2), 1,1-dimethylhydrazine ((CH3)2NNH2), 1,2-dimethylhydrazine (CH3NHNHCH3), ethylhydrazine, 1,1-diethylhydrazine, 1-ethyl-1-methylhydrazine, isopropylhydrazine, phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, N-aminopiperidine, N-amino Pyrrole, N-aminopyrrolidine, N-methyl-N-phenylhydrazine, 1-amino-1,2,3,4-tetrahydroquinoline, 1-amino-1,2,3,4-tetrahydroquinoline, 1,1-dibenzylhydrazine, 1,2-dibenzylhydrazine, 1-ethyl-1-phenylhydrazine, 1-aminoazacycloheptane, 1-methyl-1-(m-tolyl)hydrazine, 1-ethyl-1-(p-tolyl)hydrazine, 1-aminoimidazolium, 1-amino-2,6-dimethylpiperidine, N-aminoaziridine, or azo-tert-butane.

[0143] In some embodiments, the co-reactant is a reducing agent, and the deposited material may be a (pure or metallic) metal of the coordination compound. The term "reducing agent" may refer to a gas or a material that can be converted to a gaseous state and can reduce the deposited coordination compound to a metal. The reducing agent may be provided to the reaction chamber in a gaseous or vapor phase. The reducing agent may be in contact with a substrate containing a coordination compound chemisorbed onto the substrate. The reduction of the coordination compound to a metal may occur at the substrate surface. In some embodiments, the reduction may occur at least partially in the gaseous phase. The introduction of the coordination compound and the reducing agent into the reaction chamber may at least partially overlap. In some embodiments, the introduction of the coordination compound and the reducing agent into the reaction chamber may be simultaneous. However, in some embodiments, the introduction of the coordination compound and the reducing agent into the reaction chamber may be at least partially separate.

[0144] In some embodiments, the reducing agent may comprise hydrogen. In some embodiments, the reducing agent may comprise molecular hydrogen (H2) or plasma derived from H2.

[0145] In some embodiments, the reducing agent may comprise boron. In some embodiments, the reducing agent comprises, or is substantially composed of, a neutral ligand adduct of diborane (B2H6) or borane (BH3).

[0146] In some embodiments, the reducing agent comprises nitrogen gas. In some embodiments, the reducing agent may comprise, or consist substantially of, hydrazine or a derivative thereof. In some embodiments, the reducing agent may comprise alkylhydrazine or dialkylhydrazine. In some embodiments, the reducing agent may comprise a diazepine compound. The diazepine compound may be azo-tert-butane. In some embodiments, the reducing agent may comprise, consist of, or consist essentially of: 1,1-diethylhydrazine, 1-ethyl-1-methylhydrazine, isopropylhydrazine, phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, N-aminopiperidine, N-aminopyrrole, N-aminopyrrolidine, N-methyl-N-phenylhydrazine, 1-amino-1,2,3,4-tetrahydroquinoline, N-aminopiperazine, 1,1-dibenzylhydrazine, 1,2-dibenzylhydrazine, 1-ethyl-1-phenylhydrazine, 1-aminoazacycloheptane, 1-methyl-1-(m-tolyl)hydrazine, 1-ethyl-1-(p-tolyl)hydrazine, 1-aminoimidazolium, 1-amino-2,6-dimethylpiperidine, N-aminoaziridine, or azo-tert-butane.

[0147] In some embodiments, the reducing agent may comprise, or consist of essentially, one or more hydrocarbon-substituted hydrazine reducing agents. In some embodiments, the substituted hydrazine may comprise one or more alkyl groups. Each alkyl group may comprise one or more, for example, two, three, four, five, six, seven, or eight carbon atoms. The number of alkyl groups in the substituted hydrazine reducing agent may be one, two, three, or four. For the purposes of this disclosure, the alkyl group may be aryl. Thus, the reducing agent according to this disclosure may comprise, for example, phenylhydrazine or diphenylhydrazine.

[0148] In some embodiments, the co-reactant may comprise boron. In these embodiments, the material formed on the surface portion may be a boride of a metal. In these embodiments, the co-reactant may comprise an adduct of B₂H₆, BH₃, or a compound of formula B. x H y More advanced boranes.

[0149] In some embodiments, the co-reactant may be a hydrocarbon. In these embodiments, the material formed on the surface portion may be a metal carbide. The hydrocarbon may be aliphatic or aromatic. The hydrocarbon may be saturated or unsaturated, straight-chain or branched, cyclic or acyclic. The hydrocarbon may include, for example, alkyl halides, alkenes, alkynes, or alkyl metals.

[0150] In some embodiments, the process includes one or more non-cyclic (i.e., continuous) stages. In some embodiments, the deposition process includes a continuous flow of precursors and / or co-reactants. In such embodiments, the process may include a continuous flow of precursors.

[0151] In some embodiments, at least one of the precursor and co-reactant is provided to the reaction chamber in a pulsed manner. In some embodiments, the precursor is supplied in a pulsed manner and the co-reactant is supplied in a pulsed manner, and the reaction chamber is purged between consecutive pulses of the precursor and the co-reactant. The duration for which the precursor and co-reactant are provided to the reaction chamber (i.e., the pulse time of the precursor and the pulse time of the co-reactant, respectively) may each be independently of, for example, about 0.01 s to about 60 s, for example, about 0.01 s to about 5 s, or about 1 s to about 20 s, or about 0.5 s to about 10 s, or about 5 s to about 15 s, or about 10 s to about 30 s, or about 10 s to about 60 s, or about 20 s to about 60 s. The pulse times of the precursor and the co-reactants can each be independently, for example, 0.03s, 0.1s, 0.5s, 1s, 1.5s, 2s, 2.5s, 3s, 4s, 5s, 8s, 10s, 12s, 15s, 25s, 30s, 40s, 50s, or 60s. In some embodiments, the pulse time of the precursor can be at least 5 seconds or at least 10 seconds. In some embodiments, the pulse time of the precursor can be at most 5 seconds, at most 10 seconds, at most 20 seconds, or at most 30 seconds. In some embodiments, the pulse time of the co-reactants can be at least 5 seconds, at least 10 seconds, or at least 20 seconds. In some embodiments, the pulse time of the co-reactants can be at most 5 seconds, at most 10 seconds, at most 20 seconds, or at most 30 seconds.

[0152] In some embodiments, providing the precursor and / or co-reactant into the reaction chamber may include pulsed the precursor and / or pulsed the co-reactant into the reaction chamber above the substrate. In some embodiments, the precursor may be pulsed more than once, such as two, three, or four times, before the co-reactant is pulsed into the reaction chamber. Similarly, more than one pulse of the co-reactant may be present, such as two, three, or four pulses, before the precursor is pulsed (i.e., provided) into the reaction chamber.

[0153] In some embodiments, the method includes one or more purging steps to remove any precursors and / or co-reactants and / or gaseous byproducts from the reaction chamber. Purging may include evacuating the reaction chamber with a vacuum pump and / or replacing the gas in the reaction chamber with an inert or substantially inert gas (e.g., argon or nitrogen). Purging can limit or prevent interactions between precursors and co-reactants, for example, in the gas phase. Purging may be performed temporally, spatially, or both. In embodiments, the purging step may include supplying a purge gas to the reaction chamber while simultaneously pumping gas from the reaction chamber, wherein the substrate on which the layer is deposited remains stationary. The purging step may be performed for about 0.01 seconds to about 20 seconds, about 0.05 seconds to about 20 seconds, or about 1 second to about 20 seconds, or about 0.5 seconds to about 10 seconds, or about 1 second to about 7 seconds, such as 5 seconds, 6 seconds, or 8 seconds, but other purging times may be utilized if desired. In an embodiment, the purging step may include moving the substrate from a first position for continuous supply of precursors to a second position for continuous supply of co-reactants by purging an air curtain or by another means of separating the first position from the second position.

[0154] The provision of a substrate in a reaction chamber typically means that the substrate is in a space where deposition conditions can be controlled. The reaction chamber can be a single-wafer reactor. Alternatively, the reaction chamber can be a batch reactor. The reaction chamber can form part of a vapor deposition assembly for fabricating semiconductor devices. The processing assembly can include one or more multi-station processing chambers. In some embodiments, the substrate moves between processing stations within a multi-station processing chamber. The reaction chamber can be part of a cluster tool where different processes are performed to form integrated circuits. The various stages of a vapor deposition method can be performed in a single reaction chamber, or they can be performed in multiple reaction chambers, such as the reaction chamber of a cluster tool, or the deposition stations of a multi-station processing chamber.

[0155] A reaction chamber is typically a semiconductor processing apparatus reaction chamber. In some embodiments, the reaction chamber may be a flow reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber may be a spray head reactor. In some embodiments, the reaction chamber may be a spatially partitioned reactor. In some embodiments, the reaction chamber may be a single-wafer atomic layer deposition reactor. In some embodiments, the reaction chamber may be a high-capacity single-wafer atomic layer deposition reactor. In some embodiments, the reaction chamber may be a batch reactor for simultaneously fabricating multiple substrates.

[0156] The reaction chamber may be part of a vapor deposition system. The reaction chamber may be part of a chemical vapor deposition system. In some embodiments, the chemical vapor deposition is atomic layer deposition. The reaction chamber may be part of an atomic layer deposition system. In some embodiments, the system or reaction chamber may be equipped with a heater to activate the reaction by raising the temperature of one or more of the substrate, precursor, and co-reactants.

[0157] The substrate can be a semiconductor wafer, such as a silicon wafer, gallium arsenide wafer, silicon carbide wafer, germanium wafer, or indium phosphide wafer, although the invention is not limited thereto. In embodiments, portions of the substrate surface are reactive to the coordination compound. In embodiments, portions of the substrate surface may be functionalized to promote the chemisorption (or chemical adsorption) of the coordination compound. In some embodiments, portions of the surface may be functionalized with groups selected from hydroxyl, amino, carboxyl, thiol, silyl groups, or combinations thereof. However, this is not necessary; instead, the coordination compound may be deposited without reacting with the surface.

[0158] Any feature of any embodiment of the third aspect may be independently described as in any embodiment of any other aspect of the invention.

[0159] In a fourth aspect, a method for synthesizing a composition comprising a precursor containing a coordination compound, the coordination compound comprising:

[0160] Metals from Groups 4, 5, 6, or 13, and

[0161] At least one enamine ol salt ligand.

[0162] A composition comprising a precursor containing a coordination compound is described in the first aspect of this disclosure.

[0163] The precursors according to this disclosure are applicable to vapor deposition processes, such as ALD or CVD.

[0164] Synthetic route 1: Reaction of alkali metal salts of enamine ol salt ligands with metal halides

[0165] In some embodiments, the synthesis is carried out by reacting an alkali metal salt of an enamine with a halide of a desired Group 4, Group 5, Group 6, or Group 13 metal.

[0166] In some embodiments, the synthesis of coordination compounds comprising a metal from Group 4, Group 5, Group 6, or Group 13 and at least one enamine alkali ligand is carried out by reacting a potassium salt of an enamine (or another alkali metal salt) with a halide of the desired Group 4, Group 5, Group 6, or Group 13 metal. In some embodiments, the synthesis is carried out by reacting a sodium salt of an enamine with a halide of the desired Group 4, Group 5, Group 6, or Group 13 metal.

[0167] In some embodiments, the alkali metal salt of enamine includes compounds of formula (III):

[0168] ,

[0169] In this formula, R1 is hydrogen or a C1 to C8 alkyl group, and R2 and R3 are each independently selected from C1 to C8 alkyl groups, or R2, R3 and the N group to which they are bonded together form a four- to nine-membered ring, and R4 is hydrogen or a C1 to C8 alkyl group. The alkali metal salt shown in formula (III) is a potassium salt; however, the alkali metal salt may contain another alkali metal, such as Na or Li.

[0170] In some embodiments, the halides of Group 4, Group 5, Group 6, or Group 13 metals are chlorides. In some embodiments, the halides of Group 4, Group 5, Group 6, or Group 13 metals are iodides. In some embodiments, the halides of Group 4, Group 5, Group 6, or Group 13 metals are bromides. In some embodiments, the halides of Group 4, Group 5, Group 6, or Group 13 metals are fluorides.

[0171] In embodiments where the metal in the coordination compound is titanium, the metal halide is selected from titanium(II) chloride (TiCl2), titanium(III) chloride (TiCl3), and titanium(IV) chloride (TiCl4). In some embodiments, the metal halide is TiCl4.

[0172] In embodiments where the metal in the coordination compound is zirconium, the metal halide is selected from zirconium(II) chloride (ZrCl2), zirconium(III) chloride (ZrCl3), and zirconium(IV) chloride (ZrCl4). In some embodiments, the metal halide is ZrCl4.

[0173] In embodiments where the metal in the coordination compound is hafnium, the metal halide is selected from hafnium(II) chloride (HfCl2), hafnium(III) chloride (HfCl3), and hafnium(IV) chloride (HfCl4). In some embodiments, the metal halide is HfCl4.

[0174] In embodiments where the metal in the coordination compound is vanadium, the metal halide is selected from vanadium(II) chloride (VCl2), vanadium(III) chloride (VCl3), and vanadium(IV) chloride (VCl4). In some embodiments, the metal halide is VCl4. In some embodiments, the metal halide is VCl3.

[0175] In embodiments where the metal in the coordination compound is niobium, the metal halide is selected from niobium(III) chloride (NbCl3), niobium(IV) chloride (NbCl4), and niobium(V) chloride (NbCl5). In some embodiments, the metal halide is NbCl5.

[0176] In embodiments where the metal in the coordination compound is tantalum, the metal halide is selected from tantalum chloride (V) (TaCl5), tantalum bromide (V) (TaBr5), and tantalum iodide (V) (TaI5). In some embodiments, the metal halide is TaCl5.

[0177] In embodiments where the metal in the coordination compound is chromium, the metal halide is selected from chromium(II) chloride (CrCl2), chromium(III) chloride (CrCl3), chromium(II) bromide (CrBr2), chromium(III) bromide (CrBr3), chromium(II) iodide (CrI2), and chromium(III) iodide (CrI3). In some embodiments, the metal halide is CrCl3.

[0178] In embodiments where the metal in the coordination compound is molybdenum, the metal halide is selected from molybdenum(III) chloride (MoCl3), molybdenum(IV) chloride (MoCl4), molybdenum(V) chloride (MoCl5), and molybdenum(VI) chloride (MoCl6). In some embodiments, the metal halide is MoCl6. In some embodiments, the metal halide is MoCl5.

[0179] In embodiments where the metal in the coordination compound is tungsten, the metal halide is selected from tungsten chloride (IV) (WCl4), tungsten chloride (V) (WCl5), and tungsten chloride (VI) (WCl6). In some embodiments, the metal halide is WCl5.

[0180] In embodiments where the metal in the coordination compound is aluminum, the metal halide is selected from aluminum chloride (AlCl3), aluminum bromide (AlBr3), and aluminum iodide (AlI3).

[0181] In embodiments where the metal in the coordination compound is gallium, the metal halide is selected from gallium chloride (GaCl3), gallium bromide (GaBr3), and gallium iodide (GaI3).

[0182] In embodiments where the metal in the coordination compound is indium, the metal halide is selected from indium chloride (InCl3), indium bromide (InBr3), and indium iodide (InI3).

[0183] Synthetic Route 2: Free Ligands Reacting with Alkali Metal Compounds

[0184] In some embodiments, the synthesis of coordination compounds comprising a metal from Group 4, Group 5, Group 6 or Group 13 and at least one enamine alkoxide ligand according to the present disclosure is carried out by reacting a free ligand precursor (i.e., a protonated form of the ligand) with a basic compound of the desired Group 4, Group 5, Group 6 or Group 13 metal to form a metal enamine alkoxide coordination complex.

[0185] In some embodiments, the free ligand precursor is a compound of formula (IV):

[0186] ,

[0187] Wherein, R1 is hydrogen or a C1 to C8 alkyl group, and wherein R2 and R3 are each independently selected from C1 to C8 alkyl groups, or wherein R2, R3 and the N group to which they are bonded together form a four- to nine-membered ring, and wherein R4 is hydrogen or a C1 to C8 alkyl group.

[0188] In some embodiments, the basic compound of a Group 4, Group 5, Group 6, or Group 13 metal is a homopolymeric dialkylamide compound. In some embodiments, the basic compound is a homopolymeric dialkylamide compound comprising a Group 4 metal. In some embodiments, the basic compound is a homopolymeric dialkylamide compound comprising a Group 5 metal. In some embodiments, the basic compound is a homopolymeric dialkylamide compound comprising a Group 6 metal. In some embodiments, the basic compound is a homopolymeric dialkylamide compound comprising a Group 13 metal.

[0189] In some embodiments, the homogeneous dialkylamide compound may comprise aluminum and have the formula (V):

[0190] ,

[0191] R1 and R2 are selected from C1 to C6 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, and tert-butyl. Although usually described as monomers, such compounds can exist as dimers, as illustrated in formula (VI):

[0192] .

[0193] For the purposes of this disclosure, descriptions of any particular molecule (both monomeric and dimer forms) are contemplated, whether or not explicitly mentioned.

[0194] As a non-limiting example, the homogeneous dialkylamide compound may be selected from tetra(ethylmethylamido)zirconium, tetra(ethylmethylamido)hafnium, tetra(dimethylamido)vanadium, hexa(dimethylamido)aluminum, hexa(dimethylamido)tungsten, hexa(dimethylamido)gallium or hexa(dimethylamido)molybdenum.

[0195] In some embodiments, the basic compound of a Group 4, Group 5, Group 6, or Group 13 metal is a homozygous alkoxide compound. In some embodiments, the basic compound is a homozygous alkoxide compound comprising a Group 4 metal. In some embodiments, the basic compound is a homozygous alkoxide compound comprising a Group 5 metal. In some embodiments, the basic compound is a homozygous alkoxide compound comprising a Group 6 metal. In some embodiments, the basic compound is a homozygous alkoxide compound comprising a Group 13 metal. In some embodiments, the homozygous alkoxide compound has the formula M(OR). x In this formula, M is a group 4, 5, 6, or 13 metal atom, each R is a C1 to C6 alkyl or phenyl group, and x is an integer corresponding to the oxidation state of M. In some embodiments, M is a group 4 metal, such as Ti, Zr, or Hf. In some embodiments, M is a group 5 metal, such as V, Nb, or Ta. In some embodiments, M is a group 6 metal, such as Cr, Mo, or W. In some embodiments, M is a group 13 metal, such as Al, Ga, or In. In some embodiments, the isotropic alkoxide compound is aluminum triethoxy (Al(OEt)3), gallium triethoxy (Ga(OEt)3), indium triethoxy (In(OEt)3), or aluminum isopropoxide (Al(iPr)3). In some embodiments, the isotropic alkoxide compound is V(OR)4, where R can be various alkyl groups. Examples of such molecules are V(OMe)4, V(OEt)4, and V(OtBu)4. In some embodiments, the homopolymeric alkoxide compound is selected from Nb(OEt)5, Nb(OMe)5, Ta(OMe)5, Ta(OEt)5, Cr(OtBu)4, Mo(OEt)6, Mo(OtBu)6, and W2(OtBu)6. In the formula, Et represents ethyl, iPr represents isopropoxide, and tBu represents tert-butyl.

[0196] In some embodiments, the basic compound is a trialkyl metal compound comprising a Group 13 metal. In some embodiments, the trialkyl metal compound comprises three C1 to C6 alkyl groups. The alkyl groups may be the same or different. In some embodiments, the trialkyl metal compound is a trimethyl metal compound. In some embodiments, the trialkyl metal compound is a triethyl metal compound. In some embodiments, the trialkyl metal compound is a tripropyl metal compound. In some embodiments, the basic compound is a trialkylaluminum compound. In some embodiments, the basic compound is a trialkylindium compound. In some embodiments, the basic compound is a trialkylgallium compound. In some embodiments, the trialkyl metal compound is trimethylaluminum. In some embodiments, the trialkyl metal compound is trimethylindium. In some embodiments, the trialkyl metal compound is trimethylgallium. In some embodiments, the trialkyl metal compound is triethylaluminum. In some embodiments, the trialkyl metal compound is triethylindium. In some embodiments, the trialkyl metal compound is triethylgallium.

[0197] The synthesis of the coordination compounds according to this disclosure can be carried out in the liquid phase using conventional solvents such as tetrahydrofuran or toluene. The synthesis can be carried out at temperatures between 0°C and 150°C, for example, between 15°C and 115°C, or, for example, between 20°C and 66°C. The duration of the reaction of the components in the synthesis reaction is selected by the reactivity of the specific molecule, the temperature, and other factors known in the art that influence reaction rates in the field of chemical synthesis.

[0198] In some embodiments, the obtained coordination compound is purified. Purification can be performed to obtain a purity that meets the requirements of the semiconductor industry. In some embodiments, the coordination compound according to this disclosure is a liquid at room temperature. In some embodiments, the coordination compound according to this disclosure is a solid at room temperature. The purification method selected may depend on the phase of the coordination complex. In embodiments where the coordination complex is a liquid, it can be purified by distillation. In embodiments where the coordination complex according to this disclosure is a solid, it can be purified by recrystallization. In embodiments where the coordination complex according to this disclosure is a solid, it can be purified by sublimation.

[0199] Any feature of any embodiment of the fourth aspect may be independently described as in any embodiment of any other aspect of the invention.

[0200] In a fifth aspect, the present invention relates to a system, such as a semiconductor processing apparatus, for depositing on a substrate a material comprising a metal from Group 4, Group 5, Group 6, or Group 13. The system includes a reaction chamber for receiving or comprising the substrate. The system also includes a first source for providing a gaseous composition comprising a precursor containing a coordination compound, wherein the first source is in gas communication with the reaction chamber via a first valve. The coordination compound comprises a metal and at least one enamine alkoxide ligand.

[0201] A composition comprising a precursor containing a coordination compound is described in the first aspect of this disclosure.

[0202] The system also includes a controller operatively connected to the first valve, wherein the controller is configured and programmed to open the first valve to provide composition flow into the reaction chamber, and to close the first valve to stop composition flow into the reaction chamber. The first source may include a precursor container according to an embodiment of the second aspect of the invention.

[0203] In one embodiment, the system further includes a second source in gas communication with the reaction chamber via a second valve. The second source may include a co-reactant container. The second source may include any source suitable for providing co-reactants, such as a compressed gas cylinder in which the co-reactants may be contained as a pressurized gas, or a co-reactant generator, such as an ozone generator. The second source may be used to provide gaseous co-reactants. In these embodiments, the system may also include a controller operatively connected to the second valve, wherein the controller is configured and programmed to open the second valve to provide co-reactant flow into the reaction chamber and to close the second valve to stop co-reactant flow into the reaction chamber. The controller operatively connected to the first valve may be the same as the controller operatively connected to the second valve, but the invention is not limited thereto.

[0204] In one embodiment, the system is a semiconductor processing apparatus. In another embodiment, the reaction chamber includes a substrate. The first source may include a precursor container according to an embodiment of a second aspect of the invention.

[0205] The precursor container may have an inlet fluidly connected to a carrier gas source. The carrier gas may be an inert gas, such as N2, He, or Ar. The carrier gas can purge the precursor vapor along with the precursor through the precursor container outlet into the reaction chamber.

[0206] The system may include a heater, which can be operated by a controller, for maintaining the gaseous composition at or above the evaporation temperature of the precursor to prevent unwanted condensation in valves, filters, conduits, and other components associated with delivering the gaseous composition to the reaction chamber. In addition to the heater for heating the precursor container, as described elsewhere in this specification, additional heaters may be provided for heating various valves and gas flow lines between the precursor container and the reaction chamber to prevent condensation and deposition of the gaseous composition on these components. Gas delivery components between the precursor container and the reaction chamber may be provided, wherein the temperature is maintained above the evaporation temperature of the precursor (i.e., the "hot zone").

[0207] In one embodiment, the system further includes means for purging the reaction chamber, such as means for purging the reaction chamber with an inert gas or means for vacuum pumping the reaction chamber. The system may also include a controller for activating the purging means to purge the reaction chamber. The controller may be configured and programmed to purge the reaction chamber after the first valve is closed and before the second valve is opened, and / or after the second valve is closed and before the first valve is opened.

[0208] Any feature of any embodiment of the fifth aspect may be independently described as in any embodiment of any other aspect of the invention.

[0209] Example: Deposition of materials containing transition metals or lanthanides

[0210] Figure 1 A schematic diagram of a deposition system 1 according to an embodiment of the present invention is shown.

[0211] The deposition system 1 includes a reaction chamber 2 for receiving a substrate 3 on which a thin film is to be formed.

[0212] The deposition system 1 further includes: a first source 41 comprising a precursor container according to an embodiment of the invention, connected at the container's outlet via a first valve 410 to the reaction chamber 2 to provide a gaseous precursor; and a controller 5 operatively connected to the first valve 410. The controller 5 is configured and programmed to open and close the first valve 410 to control the inflow of the gaseous precursor into the reaction chamber 2. The gaseous precursor comprises a coordination compound containing a metal from Group 4, Group 5, Group 6, or Group 13 and at least one enamine olite ligand.

[0213] The deposition system 1 also includes a second source 42, which is connected to the reaction chamber 2 via a second valve 420 at its outlet to provide co-reactants. Although the second source 42 is... Figure 1The first source is depicted as a container, but the second source 42 can include any source suitable for providing the co-reactant. In embodiments, the co-reactant can be, for example, NH3 or O2, and the second source can include a compressed gas cylinder containing the co-reactant as a compressed gas. In embodiments, the co-reactant can be ozone, and the second source can be an ozone generator suitable for producing ozone from O2, which can then be delivered in the gaseous phase to the reaction chamber. The co-reactant can include an oxygen source, a nitrogen source, a reducing agent, or any other type of co-reactant; the invention is not limited to any type of co-reactant. The deposition system 1 also includes a controller 5 operatively connected to the second valve 420. The controller 5 is configured and programmed to open and close the second valve 420 to control the flow of the co-reactant into the reaction chamber 2.

[0214] The deposition step cycle is now described according to an embodiment of the invention. A first valve 410 is opened by a controller 5. An inert carrier gas 411 is supplied to the precursor container 41 via its inlet to cause the precursor to flow through the outlet of the precursor container 41 and into the reaction chamber 2 via the first valve 410. Alternatively, or otherwise, the precursor can be caused to flow from the precursor container 41 into the reaction chamber 2 by providing a pressure difference between the precursor container 41 and the reaction chamber 2.

[0215] Therefore, as Figure 2 As schematically shown, a thin film comprising a deposited coordination compound is formed on substrate 3, the deposited coordination compound being a chemisorbed coordination compound. The chemisorbed coordination compound may contain a portion of a gas-phase coordination compound, although another portion of the gas-phase coordination compound may have already been reacted in the reaction used to chemisorb the coordination compound. In this example, the metal M of the chemisorbed coordination compound may be bonded to the surface of substrate 3. In embodiments of the invention, the chemisorbed coordination compound may contain a metal from the coordination compound, which may be bonded to one or more enamine alkoxide ligands and / or one or more optional other ligands from the coordination compound.

[0216] Next, the first valve 410 can be closed via controller 5. Undeposited gaseous precursors can then be purged from reaction chamber 2.

[0217] Subsequently, the second valve 420 can be opened via the controller 5, and the gaseous co-reactant can be introduced into the reaction chamber 2 above the substrate surface 3. For this purpose, an inert carrier gas 421 can be introduced into the second source 42 through the inlet of the second source 42 to provide the carrier gas, along with the co-reactant, to flow through the second valve 420 into the reaction chamber 2 via the outlet of the second source 42. The co-reactant can react with the deposited coordination compound. For example, water can be provided as a co-reactant, which can react with any enamine alkoxide ligands of the chemisorbed coordination compound to remove the enamine alkoxide ligands from the chemisorbed coordination compound.

[0218] Next, the second valve 420 can be closed via controller 5. Unreacted gaseous co-reactants can then be purged from reaction chamber 2.

[0219] The above steps can be repeated to form a thin film 31 of deposited material, the chemical composition of which depends on the type of co-reactants and typically includes at least a metal of a coordination compound.

[0220] Although the cyclic chemical vapor deposition method in this embodiment includes cyclically supplying the coordination compounds and co-reactants of the embodiments of the present invention into the reaction chamber, the invention is not limited thereto. Any type of vapor deposition process, including non-cyclic and non-chemical processes, can be performed according to embodiments of the present invention.

[0221] It should be understood that although preferred embodiments, specific constructions and configurations, and materials have been discussed herein with respect to the apparatus according to the invention, various changes or modifications in form and detail may be made without departing from the scope of the invention. Steps may be added to or removed from the methods described within the scope of the invention.

Claims

1. A composition comprising a coordination compound, the coordination compound comprising: Metals from Group 5, Group 6, or Group 13, and At least one enamine ol salt ligand.

2. The composition according to claim 1, wherein, The metal is from Group 5 or Group 6.

3. The composition according to claim 2, wherein, The metal is selected from vanadium, niobium and tantalum.

4. The composition according to claim 2, wherein, The metal is selected from chromium, molybdenum and tungsten.

5. The composition according to claim 1, wherein, Each enamine ol salt ligand has the following chemical formula: ， Wherein, R1 is hydrogen or C1 to C8 alkyl or alkylsilyl, R2 and R3 are each independently selected from C1 to C8 alkyl or alkylsilyl groups, or Among them, R2, R3, and the N they are bonded to form four- to nine-membered rings, and R4 is hydrogen or C1 to C8 alkyl or alkylsilyl.

6. The composition according to claim 5, wherein, R1 is hydrogen or a C1 to C6 alkyl group, and R2 and R3 are each independently selected from C1 to C6 alkyl groups.

7. The composition according to claim 6, wherein, R1 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl, and R2 and R3 are each independently selected from methyl, ethyl and isopropyl.

8. The composition according to claim 1, wherein, The metal is in an oxidation state lower than the highest common oxidation state of the metal.

9. The composition according to claim 1, wherein, The coordination compounds are homocoordinated.

10. The composition according to claim 9, wherein, The coordination compound has the chemical formula ML3, wherein M is selected from V, Nb, Ta, Cr, Mo, W, Al, Ga and In, and wherein each L is an enamine olate ligand.

11. The composition according to claim 1, wherein, The coordination compound is heterocoordinated.

12. The composition according to claim 11, wherein, The coordination compound further comprises at least one ligand selected from the following: cyclopentadienyl ligand, amidine ligand, amide ligand, alkyl ligand, alkylamide ligand, imino ligand, alkoxide ligand, halide ligand, guanidinyl ligand, and β-diketone ligand.

13. The composition according to claim 11, wherein, The coordination compound has the chemical formula MO2L2, wherein M is Cr, Mo or W, and wherein each L is an enamine ol salt ligand.

14. The composition according to claim 11, wherein, The coordination compound has the chemical formula MOL3, wherein M is V, Nb, or Ta, and wherein each L is an enamine ol salt ligand.

15. The composition according to claim 11, wherein, The coordination compound has the chemical formula M(NR). x L y Where M is V, Nb, Ta, Cr, Mo, or W. Each R is an alkyl or trialkylsilyl group. Each L is an enamine alcohol ligand, and Each of x and y is an integer equal to or greater than 1, and x+y is an integer from 2 to 6.

16. The composition according to claim 11, wherein, The coordination compound has the chemical formula ML x L' y Where M is V, Nb, Ta, Cr, Mo, or W. Each L is an enamine olate ligand, and each L' is a ligand selected from: dimethylamino, diethylamino, ethylmethylamino, methoxy, ethoxy, isopropoxy, tert-butoxy, tert-pentoxy, trimethylsilyloxy or triethylsilyloxy, N,N'-diisopropylacetamidine, N,N'-di-tert-butylacetamidine, N,N'-diisopropylformamidinium, N,N'-di-tert-butylformamidinium, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, tert-butylcyclopentadienyl, trimethylsilylcyclopentadienyl and pentamethylcyclopentadienyl, and Each of x and y is an integer equal to or greater than 1, and x+y is an integer from 2 to 6.

17. A precursor container comprising the composition according to claim 1, in, The precursor container is configured to supply vapor of the coordination compound to the reaction chamber of the vapor deposition system.

18. A method for depositing a material comprising a metal from Group 4, Group 5, Group 6 or Group 13 on a substrate, the method comprising: A substrate is provided in the reaction chamber, and then, A gas-phase composition comprising a precursor containing a coordination compound is provided to the reaction chamber, the coordination compound comprising: Metals, and At least one enamine ol salt ligand, This forms a metal-containing layer on a portion of the substrate surface.

19. The method of claim 18, further comprising at least one cycle of performing a cyclic deposition process, each cycle comprising: The gaseous composition is supplied to the reaction chamber; The reaction chamber may be purged. Provide gaseous co-reactants to the reaction chamber; as well as The reaction chamber can be purged optionally.

20. A system for depositing a material comprising a metal from Group 4, Group 5, Group 6, or Group 13 on a substrate, the system comprising: Reaction chamber for receiving substrate A first source for providing a gaseous composition comprising a precursor containing a coordination compound, wherein the first source is in communication with a reaction chamber gas via a first valve, and the coordination compound comprises: Metals, and At least one enamine ol salt ligand, A controller operably connected to the first valve, wherein the controller is configured and programmed to open the first valve to provide a flow of composition into the reaction chamber, and to close the first valve to stop the flow of composition into the reaction chamber.

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