Phosphonium ylide complexes as precursors for thin layers containing metallic elements

Abstract

The precursor of the present invention provides a direct pathway to metal carbides, which is expected to have applications in back-end (BEOL) barrier / liner layers, as current methods often do not provide carbon in pure carbide form. [Solution] This specification discloses a method and system for forming a metal-containing layer on a semiconductor substrate using a metal precursor containing a phosphonium ylide ligand. Also disclosed are a composition containing the metal precursor and a semiconductor device structure containing the metal-containing layer.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the interests of U.S. Provisional Patent Application No. 63 / 734,087, filed on 14 December 2024, the contents of which are incorporated herein by reference in their entirety.

[0002] This disclosure relates in general to the field of semiconductor devices. More specifically, the present invention relates to a method for forming a metal-containing layer on a semiconductor substrate, related devices, and apparatus for manufacturing a metal-containing layer. [Background technology]

[0003] Currently, the selection of atomic layer deposition (ALD) and chemical vapor deposition (CVD) precursors for growing films containing specific metal elements is limited to those containing only a few types of ligands, such as Cp, amidinates, beta-diketonates, dialkylamides, alkoxides, and alkyls. Known examples have limitations and are not ideal for growing the desired layer (film). Limitations include a limited (and often insufficient) range of reactivity, low volatility of Cp and diketonate complexes, or low thermal stability in the case of amidinates, dialkylamides, alkoxides, and alkyl precursors, as well as low activation energy decomposition pathways that result in impurities and high electrical resistivity. Due to these drawbacks, the current chemical options are not optimal for film growth for many applications. In particular, the reactivity of currently available ligands makes it difficult to achieve materials such as binary metal borides, carbides, and nitrides.

[0004] Considering the above, there is a need to provide alternatives to thin-layer precursors containing metallic elements that can overcome some of these drawbacks. [Overview of the project]

[0005] This summary is provided to introduce some concepts in a simplified form. These concepts are described in more detail below in the detailed description of the exemplary embodiments of this disclosure. This summary is not intended to identify any major or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. [Means for solving the problem]

[0006] In general, the techniques disclosed herein relate to the field of semiconductor devices, and more specifically, to a method for forming a metal-containing layer on a semiconductor substrate using a novel metal precursor comprising a phosphonium ylide ligand, wherein the metal precursor also comprises a metal element. The precursor may contain other common ligands in addition to the phosphonium ylide. The metal deposition may be in the form of oxides, nitrides, carbides, borides, sulfides, phosphides, etc. This method is applicable to the manufacture of semiconductor devices.

[0007] The precursor according to the present invention has one or more anionic carbon atoms bonded to a metal atom, and this carbon-metal bond is highly reactive to many types of proton decomposition reactions, allowing easy access to a wide range of binary metal / nonmetal materials, such as oxides, nitrides, carbides, sulfides, borides, phosphides, etc. Therefore, the precursor according to the present invention has improved reactivity compared to the most well known methods currently available, as well as improved thermal stability, volatility, and ability to access difficult materials such as carbides, borides, and nitrides, which greatly favors their use in methods and apparatus for forming metal coating layers on semiconductor substrates.

[0008] The advantages of using the precursor according to the present invention compared to existing precursors are as follows:

[0009] 1) The precursor of the present invention provides a direct pathway to metal carbides, which is expected to have applications in back-end (BEOL) barrier / liner layers, as current methods often do not provide carbon in pure carbide form.

[0010] 2) The precursors of the present invention constitute an alternative method for oxides and sulfides, providing higher thermal stability and potentially improved reactivity for these materials.

[0011] 3) The precursors of the present invention use diborane, triethylboron, boron trihalide, or other boron-containing co-reactants to provide a potential route to borides. Metal borides are compounds that are difficult to target for deposition by ALD, and few methods are available to obtain them.

[0012] 4) The precursors of the present invention use NH3, hydrazine, or alkyl hydrazine as co-reactants to provide a possible route to nitrides. Although there are known methods for these thin layers, the method according to the present invention enables better thermal stability and low resistivity metal-containing layers for BEOL applications.

[0013] 5) The precursors of the present invention also provide a new method for forming metal-containing layers when the precursor is combined with a suitable reducing agent, such as H2, formic acid, formaldehyde, disilane, or others. Metal-containing layers of metals according to the present invention, such as molybdenum and tungsten, conduct a wide current and are very advantageous for use, such as conductors in logic devices and memory devices. Forming these metal-containing layers is often difficult because unacceptable levels of nitrogen and carbon impurities are introduced in the thermal metal-organic process. Therefore, the method according to the present invention makes it possible to obtain metal-containing layers with low impurity levels.

[0014] Compounds containing this ligand have one or more anionic carbon atoms bonded to a metal atom. This carbon-metal bond is expected to be highly reactive to many types of proton decomposition reactions, allowing easy access to a wide range of binary metal / nonmetal materials, such as oxides, nitrides, carbides, sulfides, borides, and phosphides. It is also expected that a metal-containing layer can be formed using suitable co-reactants. Furthermore, it is anticipated that co-reactants and conditions will be found in which volatile phosphine or phosphine oxide is produced as a byproduct by the reaction of the reaction precursor, thereby cleaving one of the phosphorus-carbon bonds and enabling the formation of a metal carbide layer. Therefore, one aspect of this disclosure is, A reaction chamber configured and positioned to hold at least a semiconductor substrate, A metal precursor source constructed and arranged to supply vapor of at least one metal precursor, A precursor distribution and removal system configured to supply metal precursor vapor from a metal precursor source to a reaction chamber and remove metal precursor vapor from the reaction chamber, A sequence controller operably connected to a precursor distribution system and a removal system, the sequence controller having a memory containing a program configured to control the flow of a metal precursor from a metal precursor source to a reaction chamber by operating the precursor distribution and removal system during one or more cycles, thereby causing a metal-containing layer to be formed on a semiconductor substrate in the reaction chamber as a result of the cycles, the sequence controller having a memory containing a program configured to control the flow of a metal precursor from a metal precursor source to a reaction chamber metal-containing layer formed on a semiconductor substrate in the reaction chamber as a result of the cycles, At least one metal precursor, At least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu, Equation (I): [ka] (In the formula, R 1 is C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 cycloalkyl substituted with alkyl, C 3-10 cycloalkyl, aryl, and C 1-6 aryl substituted with alkyl, and is selected from the group consisting of R 2 is C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 cycloalkyl substituted with alkyl, C 3-10 cycloalkyl, aryl, and C 1-6 aryl substituted with alkyl, or is selected from the group consisting of R 1 and R 2 together with the phosphorus atom to which they are attached form a saturated or unsaturated 3-, 4-, 5-, 6-, 7-, 8-, 9-, or 10-membered ring R 3 is H, C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 cycloalkyl substituted with alkyl, C 3-10 cycloalkyl, aryl, and C 1-6 aryl substituted with alkyl, and is selected from the group consisting of R 4 is H, C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 cycloalkyl substituted with alkyl, C 3-10 cycloalkyl, aryl, and C 1-6 aryl substituted with alkyl, and is selected from the group consisting of R 5 is H, C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 cycloalkyl substituted with alkyl, C 3-10 cycloalkyl, aryl, and C 1-6 aryl substituted with alkyl, and is selected from the group consisting of R 6 is H, C 1-10 alkyl, C 3-10Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 The present invention relates to an apparatus comprising at least one ligand (selected from the group including alkyl-substituted aryls).

[0015] In certain embodiments, the apparatus disclosed herein further comprises a reactant source configured and positioned to supply reactant vapors, a precursor distribution and removal system further configured to supply reactant vapors from the reactant source to a reaction chamber, and a program stored in memory further configured to control the flow of reactants from the reactant source to the reaction chamber during one or more cycles.

[0016] In some embodiments, at least one reactant is selected from the group including oxide reactants, nitride reactants, boride reactants, reducing agents, phosphide reactants, carbide reactants, sulfide reactants, and combinations thereof.

[0017] Another aspect of this disclosure is a method for forming a metal-containing layer on a semiconductor substrate, a) A step of supplying a semiconductor substrate into a reaction chamber, b) A process that performs one or more cycles, where each cycle is A metal precursor pulse comprising a step of which at least a portion of a semiconductor substrate comes into contact with at least one metal precursor by introducing at least one metal precursor into a reaction chamber, At least one metal precursor, At least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu, Equation (I): [ka] (In the formula, R 1 C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 2 C 1-10 Alkyl, C 3-10 Cycloalkyl, C1-6 alkyl substituted C 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, or R 1 and R 2 Together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings. R 3 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 4 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 5 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 6 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 It comprises at least one ligand (selected from the group including alkyl-substituted aryls), The present invention relates to a method by which, as a result of the cycle, a metal-containing layer is formed on a semiconductor substrate in a reaction chamber.

[0018] In some embodiments, at least one cycle further comprises a reactant pulse, by introducing at least one reactant into the reaction chamber, thereby bringing at least a portion of the semiconductor substrate into contact with at least one reactant, the at least one reactant being selected from the group including oxide reactants, nitride reactants, boride reactants, reducing agents, phosphide reactants, carbide reactants, sulfide reactants, and combinations thereof.

[0019] Another aspect of this disclosure relates to semiconductor device structures. A semiconductor device structure according to the present invention includes a metal-containing layer formed according to a method disclosed herein.

[0020] A further aspect of this disclosure relates to a composition configured to form a metal-containing film, wherein the composition comprises a metal precursor disclosed herein.

[0021] A further aspect of this disclosure relates to a container comprising a composition configured to form a metal-containing film, wherein the container comprises a composition comprising a metal precursor disclosed herein.

[0022] This specification outlines various aspects of the technology disclosed herein, followed by a more detailed description of specific embodiments. It should be understood that the objectives and advantages described above also apply to various other aspects and features disclosed herein. [Brief explanation of the drawing]

[0023] It should be understood that the elements in the figures are illustrated for simplification and clarity and are not necessarily drawn to actual size. For example, the dimensions of some elements in the figures may be exaggerated relative to others to help improve understanding of the illustrated embodiments of this disclosure.

[0024] [Figure 1] This figure schematically illustrates an exemplary embodiment of a method (100) for forming a metal layer on a semiconductor substrate disclosed herein. [Figure 2] This figure schematically illustrates an apparatus (600) according to an additional exemplary embodiment of the present disclosure. [Modes for carrying out the invention]

[0025] While certain embodiments and examples are disclosed below, it will be understood by those skilled in the art that this disclosure extends beyond the specifically disclosed embodiments and / or uses thereof, as well as their obvious modifications and equivalents. Therefore, the scope of this disclosure is not intended to be limited by the specific disclosed embodiments described below.

[0026] In the following detailed description, the underlying technology of this disclosure will be described in different embodiments. The embodiments of this disclosure may be arranged, substituted, combined, and designed in a wide variety of different configurations, as generally described herein and as shown in the figures, all of which are clearly intended to form part of this disclosure. This description is intended to assist the reader in more easily understanding the technical concepts, but is not intended to limit the scope of this disclosure, which is limited only by the claims. Therefore, the following description should be considered essentially illustrative and not restrictive.

[0027] Throughout this Spec., any reference to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in relation to an embodiment is included in at least one embodiment of this disclosure. Therefore, the use of the phrase “in one embodiment” or “in an embodiment” in various places throughout this Spec.

[0028] As used herein, the terms “comprising,” “comprises,” and “comprised of” are synonymous with “including,” “includes,” or “containing,” and are comprehensive or open-ended, and do not exclude additional, undescribed components, elements, or process steps. When the terms “comprising,” “comprises,” and “comprised of” refer to a described component, element, or process step, they also include embodiments that “consist of” the described component, element, or process step.

[0029] The singular forms "a," "an," and "the" refer to both singular and plural objects unless otherwise explicitly indicated by the context.

[0030] In this specification, objects described as “connected” or “joined” reflect a functional relationship between the objects described. That is, the term indicates that the objects described must be connected to perform a specified function, where appropriate to the context in which the term is used, and this may be a direct or indirect connection in an electrical or non-electrical (i.e., physical) manner.

[0031] As used herein, the term “substantially” refers to the complete or near-complete range or extent of a function, feature, characteristic, state, structure, item, or result. For example, an object “substantially” enclosed means that the object is completely enclosed or nearly completely enclosed. The exact acceptable degree of deviation from absolute completeness may, in some cases, depend on the specific context. However, generally speaking, near-complete means having the same overall result as if absolute and complete completeness had been achieved. The use of “substantially” is equally applicable when used in a negative sense to refer to the complete or near-complete absence of a function, feature, characteristic, state, structure, item, or result.

[0032] Where used herein, the term “about” is used to provide flexibility to the endpoints of a number or range by specifying, depending on the particular context, that a given value may be “slightly above” or “slightly below” this value or endpoint. Unless otherwise stated, the use of the term “about” in accordance with a particular number or range of numbers should also be understood to support such a number term or range without the term “about.” For example, the statement “about 30” should be interpreted not only as supporting values ​​slightly above and slightly below 30, but also as supporting the actual number 30.

[0033] Enumerations of numerical ranges by endpoint include all integers and, where appropriate, fractions within that range (for example, 1-5 may include 1, 2, 3, 4 if referring to the number of elements, and 1.5, 2, 2.75, 3.80 if referring to measured values). This applies to numerical ranges whether they begin with expressions such as "from... to...", "between... and...", or other expressions. Enumerations of endpoints also include the endpoint values ​​themselves (for example, 1.0-5.0 includes both 1.0 and 5.0). Any numerical range enumerated herein is intended to include all subranges contained within it. Furthermore, terms such as first, second, third, etc., in this description and claims are used to distinguish between similar elements unless otherwise specified, and are not necessarily used to describe order or chronological order. It should be understood that terms used in this way are interchangeable under appropriate circumstances, and that embodiments of the disclosures described herein may operate in any order other than those described or illustrated herein.

[0034] References herein may be made to devices, structures, apparatus, systems, or methods that “improve” performance (e.g., increase or decrease results, depending on the context). Unless otherwise stated, such “improvement” should be understood to be a measure of benefit obtained based on comparison with devices, structures, apparatus, systems, or methods in the prior art. Furthermore, it should be understood that the degree of performance improvement may vary among the disclosed embodiments, and that the quantity, degree, or uniformity or consistency in the realization of performance improvement should not be assumed to be universally applicable.

[0035] In this disclosure, “gas” can encase materials that are gaseous at room temperature and pressure (NTP), vaporized solids and / or vaporized liquids, and may consist of a single gas or a mixture of gases, depending on the context. Gases other than process gases, i.e., gases introduced without passing through gas distribution assemblies, other gas distribution devices, etc., can be used, for example, to seal reaction spaces, and include sealing gases, such as noble gases.

[0036] In some cases, the term "precursor" may refer to a compound involved in a chemical reaction that produces another compound, particularly a compound that constitutes the matrix or main skeleton of a metal-containing layer.

[0037] This specification describes techniques relating to methods and apparatus for manufacturing metal-containing layers on semiconductor substrates. The inventors have surprisingly observed that precursors comprising phosphonium ylide ligands and metal elements can be readily used to form metal-containing layers on semiconductor substrates. Advantageously, the precursors described herein are highly reactive to many types of proton decomposition reactions, allowing for easy access to a wide range of binary metal / nonmetal materials for forming metal-containing layers on semiconductor substrates.

[0038] Therefore, one aspect of this disclosure is, A reaction chamber configured and positioned to hold at least a semiconductor substrate, A metal precursor source constructed and arranged to supply vapor of at least one metal precursor, A precursor distribution and removal system configured to supply metal precursor vapor from a metal precursor source to a reaction chamber and remove metal precursor vapor from the reaction chamber, A sequence controller operably connected to a precursor dispensing system and a removal system, comprising a memory having a program configured to control the flow of a metal precursor from a metal precursor source to a reaction chamber by operating the precursor dispensing and removal systems one or more times, whereby, as a result of the cycle, a metal-containing layer is formed on a semiconductor substrate within the reaction chamber, the sequence controller, and the apparatus comprising: At least one metal precursor is at least one metal selected from the group consisting of Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu; Formula (I):

Chemical formula

[0039] As used herein, the term “substrate” may refer to any underlying material or material that can be used to form a device, circuit, or film, or on which a device, circuit, or metal-containing layer (film) can be formed. A “substrate” may be continuous or discontinuous, rigid or flexible, solid or porous, or a combination thereof. A substrate may be in any form, such as powder, plate, or workpiece. Examples of substrates in plate form include wafers of various shapes and sizes. A substrate may consist of a bulk material such as silicon (e.g., single-crystal silicon), another Group IV material such as germanium, or another semiconductor material such as Group II-VI or Group III-V semiconductor materials, and may consist of one or more layers on or beneath the bulk material. Furthermore, a substrate may have various shapes, such as recesses, protrusions, and the like, formed in or on at least a portion of the layers of the substrate.

[0040] Examples of suitable substrates include wafers made of silicon, silica, glass, or GaAs. The wafer may have one or more layers of different materials deposited thereon, which differ from those in the previous manufacturing process. For example, the wafer may include a silicon layer (crystalline, amorphous, porous, etc.), a silicon oxide layer, a silicon nitride layer, a silicon oxynitride layer, a carbon-doped silicon oxide (SiCOH) layer, or a combination thereof. Furthermore, the wafer may include a copper layer or a noble metal layer (e.g., platinum, palladium, rhodium, or gold). The wafer may also include a barrier layer such as manganese or manganese oxide. Plastic layers such as poly(3,4-ethylenedioxythiophene)poly(styrene sulfonate) can also be used. The layers may be planar or patterned.

[0041] In certain embodiments, the substrate may include silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, or silicon carbide (as a bulk semiconductor material).

[0042] As used herein, the terms “film” and “layer” are interchangeable and refer to a material that extends perpendicular to the thickness direction and covers an entire object or related surface, or simply a layer covering an object or related surface. In certain embodiments, film or layer refers to a structure of a certain thickness formed on a surface, or a synonym for film, or a non-film structure. Layers can include continuous or discontinuous structures or materials, such as materials deposited according to this Art. Films or layers may consist of a single film or layer having certain properties, or a plurality of films or layers, and boundaries between adjacent films or layers may or may not be defined and may or may not be established based on physical, chemical, and / or any other properties, formation process or sequence, and / or function or purpose of adjacent films or layers.

[0043] For example, films and / or layers may consist of two-dimensional materials, three-dimensional materials, nanoparticles, or partial or complete molecular layers, or partial or complete atomic layers, or clusters of atoms and / or molecules, or layers consisting of solitary atoms and / or solitary molecules. Films or layers may include materials or layers having continuous or discontinuous pinholes.

[0044] Throughout this specification, references to substituents mean that one or more hydrogen atoms on an atom indicated by the expression "substituted" are substituted with substituents selected from the group detailed below, provided that the substitution does not exceed the normal valence of the atom and that the substitution results in a chemically stable compound, i.e., a compound robust enough to withstand separation from the reaction mixture.

[0045] The term "alkyl" refers to a group or part of a group of the formula C n H 2n+1This refers to the hydrocarbyl group, where n is a number of 1 or more. The alkyl group may be linear or branched and may be substituted as shown herein. Generally, the alkyl groups of this disclosure contain 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Where a subscript is used after a carbon atom in this specification, the subscript indicates the number of carbon atoms that the group may contain. For example, "C 1-10 The term "alkyl" refers to a group or part of a group of the formula -C n H 2n+1 This refers to the hydrocarbyl group, where n is a number in the range of 1 to 10. Therefore, for example, "C 1-8 "Alkyl" includes all linear or branched alkyl groups having 1 to 8 carbon atoms, and therefore includes methyl ("Me"), ethyl ("Et"), n-propyl ("nPr"), i-propyl ("iPr"), butyl and its isomers (e.g., n-butyl, i-butyl, and t-butyl), pentyl and its isomers, hexyl and its isomers, etc. "Substitutive alkyl" refers to an alkyl group in which one or more substituents (e.g., 1 to 3 substituents, e.g., 1, 2, or 3 substituents) are attached at any bondable position.

[0046] "C 1-6 The term "alkoxy" refers to a group or part of a group, in the formula -OR b This refers to a group having R, in the formula b This is the C defined above. 1-6 It is alkyl. Preferred C 1-6 Non-limiting examples of alkoxys include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, and hexyloxy.

[0047] The term "cycloalkyl" refers to a cyclic alkyl group, either as a group or as part of a group, having one or more cyclic structures and containing 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms, and is a monovalent saturated hydrocarbyl group. Cycloalkyls include all saturated hydrocarbon groups containing one or more rings, including monocyclic, bicyclic, or tricyclic groups. Further rings in polycyclic cycloalkyls may be condensed, crosslinked, and / or bonded via one or more spiro atoms. Where a subscript is used after a carbon atom in this specification, the subscript indicates the number of carbon atoms that the group may contain. For example, "C 3-10 The term "cycloalkyl" refers to a cyclic alkyl group containing 3 to 10 carbon atoms. For example, "C 3-8 The term "cycloalkyl" refers to a cyclic alkyl group containing 3 to 8 carbon atoms. For example, "C 3-6 The term "cycloalkyl" refers to a cyclic alkyl group containing 3 to 6 carbon atoms. 3-10 Examples of cycloalkyl groups include, but are not limited to, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptan-2yl, (1S,4R)-norbornan-2-yl, (1R,4R)-norbornan-2-yl, (1S,4S)-norbornan-2-yl, and (1R,4S)-norbornan-2-yl.

[0048] The term "aryl" refers to a polyunsaturated aromatic hydrocarbyl group, which consists of a single ring (i.e., phenyl) or multiple aromatic rings fused together (e.g., naphthyl) or covalently linked, typically containing 6 to 12 carbon atoms, with at least one ring being aromatic. The aromatic ring may optionally contain one or two additional rings fused to it (either cycloalkyl, heterocyclyl, or heteroaryl). A suitable example of an aryl is C 6-10 Aryl, more preferably C 6-8Examples of aryls include phenyl, biphenylyl, biphenylenyl, or 1 or 2-naphthalenyl, 1-, 2-, 3-, 4-, 5-, or 6-tetralinyl (also known as 1,2,3,4-tetrahydronaphthalene), 1-, 2-, 3-, 4-, 5-, 6-, 7-, or 8-azlenyl, 4-, 5-, 6-, or 7-indenyl, 4- or 5-indanyl, 5-, 6-, 7-, or 8-tetrahydronaphthyl, 1,2,3,4-tetrahydronaphthyl, and 1,4-dihydronaphthyl, 1-, 2-, 3-, 4-, or 5-pyrenyl. A "substituted aryl" refers to an aryl group having one or more substituents (e.g., 1, 2, or 3 substituents, or 1 to 2 substituents) at any available bond site.

[0049] The terms “heterocyclyl,” “heterocycloalkyl,” or “heterocyclo” refer to a non-aromatic, fully saturated or partially unsaturated cyclic group (e.g., 3- to 7-membered monocyclic, 7- to 11-membered bicyclic, or having a total of 3 to 10 ring atoms) having at least one heteroatom in a ring containing at least one carbon atom. Here, the ring may be fused with an aryl ring, a cycloalkyl ring, a heteroaryl ring, or a heterocyclyl ring. Each ring of a heterocyclyl group containing a heteroatom may have one, two, three, or four heteroatoms selected from N, O, and / or S, the N heteroatom and S heteroatom may optionally be oxidized, the N heteroatom may optionally be quaternized, and at least one carbon atom of the heterocyclyl can be oxidized to form at least one C=O. The ring may be fused with an aryl ring, a cycloalkyl ring, a heteroaryl ring, or a heterocyclyl ring. The rings in a polycyclic heterocycle may be fused, bridged, and / or bonded via one or more spiro atoms.

[0050] Examples of non-restrictive exemplary heterocyclic groups include azilidinyl, oxyranyl, tyranyl, piperidinyl, azetidinyl, oxetanyl, pyrrolidinyl, thietanyl, 2-imidazolinyl, pyrazolidinyl, imidazolidinyl, isoxazolidinyl, oxazolidinyl, isoxazolidinyl, thiazolidinyl, isothiazolidinyl, succinimidyl, 3H-indolyl, indolinyl, and Soindlinyl, Chromanil (also known as 3,4-dihydrobenzo[b]pyranil), 2H-pyrrolyl, 1-pyrrolinil, 2-pyrrolinil, 3-pyrrolinil, 4H-quinolidinyl, 2-oxopiperazinyl, piperazinyl, homopiperazinyl, 2-pyrazolinyl, 3-pyrazolinyl, tetrahydro-2H-pyranil, 2H-pyranil, 4H-pyranil, 3,4-dihydro-2H- Examples include pyranyl, 3-dioxolanil, 1,4-dioxanil, 2,5-dioxymidazolidinyl, 2-oxopiperidinyl, 2-oxopyrrodinyl, tetrahydropyranil, tetrahydrofuranil, tetrahydrothiophenyl, tetrahydroquinolinil, tetrahydroisoquinoline-1-yl, tetrahydroisoquinoline-2-yl, tetrahydroisoquinoline-3-yl, tetrahydroisoquinoline-4-yl, thiomorpholine-4-yl, thiomorpholine-4-yl sulfoxide, thiomorpholine-4-yl sulfone, 1,3-dioxolanil, 1,4-oxathianil, 1,4-dithianil, 1,3,5-trioxanil, 1H-pyrrolidinil, tetrahydro-1,1-dioxothiophenyl, N-formylpiperazinyl, and morpholine-4-yl. As used herein, the term "aziridinyl" includes aziridinyl-1-yl and aziridinyl-2-yl. As used herein, the term "oxyranil" includes oxyranyl-2-yl. As used herein, the term "tyranil" includes tyranyl-2-yl. As used herein, the term "azetidinyl" includes azetidine-1-yl, azetidine-2-yl, and azetidine-3-yl. As used herein, the term "oxetanyl" includes oxetan-2-yl and oxetan-3-yl.As used herein, the term "thietanyl" includes thietan-2-yl and thietan-3-yl. As used herein, the term "pyrrolidinyl" includes pyrrolidine-1-yl, pyrrolidine-2-yl, and pyrrolidine-3-yl. As used herein, the term "tetrahydrofuranyl" includes tetrahydrofuran-2-yl and tetrahydrofuran-3-yl. As used herein, the term "tetrahydrothiophenyl" includes tetrahydrothiophene-2-yl and tetrahydrothiophene-3-yl. As used herein, the term "succinimidyl" includes succinimido-1-yl and succinimido-3-yl. As used herein, the term “dihydropyrrolyl” includes 2,3-dihydropyrrole-1-yl, 2,3-dihydro-1H-pyrrole-2-yl, 2,3-dihydro-1H-pyrrole-3-yl, 2,5-dihydropyrrole-1-yl, 2,5-dihydro-1H-pyrrole-3-yl, and 2,5-dihydropyrrole-5-yl. As used herein, the term “2H-pyrrolyl” includes 2H-pyrrole-2-yl, 2H-pyrrole-3-yl, 2H-pyrrole-4-yl, and 2H-pyrrole-5-yl. As used herein, the term “3H-pyrrolyl” includes 3H-pyrrole-2-yl, 3H-pyrrole-3-yl, 3H-pyrrole-4-yl, and 3H-pyrrole-5-yl. As used herein, the term “dihydrofuranyl” includes 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,3-dihydrofuran-4-yl, 2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 2,5-dihydrofuran-4-yl, and 2,5-dihydrofuran-5-yl.As used herein, the term “dihydrothiophenyl” includes 2,3-dihydrothiophen-2-yl, 2,3-dihydrothiophen-3-yl, 2,3-dihydrothiophen-4-yl, 2,3-dihydrothiophen-5-yl, 2,5-dihydrothiophen-2-yl, 2,5-dihydrothiophen-3-yl, 2,5-dihydrothiophen-4-yl, and 2,5-dihydrothiophen-5-yl. As used herein, the term “imidazolidinyl” includes imidazolidin-1-yl, imidazolidin-2-yl, and imidazolidin-4-yl. As used herein, the term “pyrazolidinyl” includes pyrazolidine-1-yl, pyrazolidine-3-yl, and pyrazolidine-4-yl. As used herein, the term "imidazolinyl" includes imidazolin-1-yl, imidazolin-2-yl, imidazolin-4-yl, and imidazolin-5-yl. As used herein, the term "pyrazolinyl" includes 1-pyrazolin-3-yl, 1-pyrazolin-4-yl, 2-pyrazolin-1-yl, 2-pyrazolin-3-yl, 2-pyrazolin-4-yl, 2-pyrazolin-5-yl, 3-pyrazolin-1-yl, 3-pyrazolin-2-yl, 3-pyrazolin-3-yl, 3-pyrazolin-4-yl, and 3-pyrazolin-5-yl. As used herein, the term "dioxolanil," also known as "1,3-dioxolanil," includes dioxolan-2-yl, dioxolan-4-yl, and dioxolan-5-yl. As used herein, the term “dioxolyl,” also known as “1,3-dioxolyl,” includes dioxol-2-yl, dioxol-4-yl, and dioxol-5-yl. As used herein, the term “oxazolidinyl” includes oxazolidine-2-yl, oxazolidine-3-yl, oxazolidine-4-yl, and oxazolidine-5-yl. As used herein, the term “isoxazolidinyl” includes isoxazolidine-2-yl, isoxazolidine-3-yl, isoxazolidine-4-yl, and isoxazolidine-5-yl.As used herein, the term "oxazolinyl" includes 2-oxazolinyl-2-yl, 2-oxazolinyl-4-yl, 2-oxazolinyl-5-yl, 3-oxazolinyl-2-yl, 3-oxazolinyl-4-yl, 3-oxazolinyl-5-yl, 4-oxazolinyl-2-yl, 4-oxazolinyl-3-yl, 4-oxazolinyl-4-yl, and 4-oxazolinyl-5-yl. As used herein, the term "isoxazolinyl" includes 2-isoxazolinyl-3-yl, 2-isoxazolinyl-4-yl, 2-isoxazolinyl-5-yl, 3-isoxazolinyl-3-yl, 3-isoxazolinyl-4-yl, 3-isoxazolinyl-5-yl, 4-isoxazolinyl-2-yl, 4-isoxazolinyl-3-yl, 4-isoxazolinyl-4-yl, and 4-isoxazolinyl-5-yl. As used herein, the term "thiazolidinyl" includes thiazolidinyl-2-yl, thiazolidinyl-3-yl, thiazolidinyl-4-yl, and thiazolidinyl-5-yl. As used herein, the term "isothiazolidinyl" includes thiazolidinyl-2-yl, thiazolidinyl-3-yl, thiazolidinyl-4-yl, and thiazolidinyl-5-yl. As used herein, the term "thiazolinyl" includes 2-thiazolinyl-2-yl, 2-thiazolinyl-4-yl, 2-thiazolinyl-5-yl, 3-thiazolinyl-2-yl, 3-thiazolinyl-4-yl, 3-thiazolinyl-5-yl, 4-thiazolinyl-2-yl, 4-thiazolinyl-3-yl, 4-thiazolinyl-4-yl, and 4-thiazolinyl-5-yl. As used herein, the term "isothiazolinyl" includes 2-isothiazolinyl-3-yl, 2-isothiazolinyl-4-yl, 2-isothiazolinyl-5-yl, 3-isothiazolinyl-3-yl, 3-isothiazolinyl-4-yl, 3-isothiazolinyl-5-yl, 4-isothiazolinyl-2-yl, 4-isothiazolinyl-3-yl, 4-isothiazolinyl-4-yl, and 4-isothiazolinyl-5-yl.As used herein, the term “piperidyl,” also known as “piperidinyl,” includes piperidyl-1-yl, piperido-2-yl, piperido-3-yl, and piperido-4-yl. As used herein, the term “dihydropyridinyl” includes 1,2-dihydropyridine-1-yl, 1,2-dihydropyridine-2-yl, 1,2-dihydropyridine-3-yl, 1,2-dihydropyridine-4-yl, 1,2-dihydropyridine-5-yl, 1,2-dihydropyridine-6-yl, 1,4-dihydropyridine-1-yl, 1,4-dihydropyridine-2-yl, 1,4-dihydropyridine-3-yl, 1,4-dihydropyridine-4-yl, 2,3-dihydropyridine-2-yl, and 2,3-dihydropyridine-3-yl. This includes -yl, 2,3-dihydropyridine-4-yl, 2,3-dihydropyridine-5-yl, 2,3-dihydropyridine-6-yl, 2,5-dihydropyridine-2-yl, 2,5-dihydropyridine-3-yl, 2,5-dihydropyridine-4-yl, 2,5-dihydropyridine-5-yl, 2,5-dihydropyridine-6-yl, 3,4-dihydropyridine-2-yl, 3,4-dihydropyridine-3-yl, 3,4-dihydropyridine-4-yl, 3,4-dihydropyridine-5-yl, and 3,4-dihydropyridine-6-yl.As used herein, the term "tetrahydropyridinyl" refers to 1,2,3,4-tetrahydropyridine-1-yl, 1,2,3,4-tetrahydropyridine-2-yl, 1,2,3,4-tetrahydropyridine-3-yl, 1,2,3,4-tetrahydropyridine-4-yl, 1,2,3,4-tetrahydropyridine-5-yl, 1,2,3,4-tetrahydropyridine-6-yl, 1,2,3,6-tetrahydropyridine-1-yl, 1,2,3,6-tetrahydropyridine-2-yl This includes tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydropyran-5-yl, tetrahydropyran-6-yl, 2,3,4,5-tetrahydropyran-2-yl, 2,3,4,5-tetrahydropyran-3-yl, 2,3,4,5-tetrahydropyran-4-yl, 2,3,4,5-tetrahydropyran-5-yl, and 2,3,4,5-tetrahydropyran-6-yl. The term "tetrahydropyranyl," also known as "oxanyl" or "tetrahydro-2H-pyranyl" as used herein, includes tetrahydropyran-2-yl, tetrahydropyran-3-yl, and tetrahydropyran-4-yl. As used herein, the term "2H-pyranyl" includes 2H-pyran-2-yl, 2H-pyran-3-yl, 2H-pyran-4-yl, 2H-pyran-5-yl, and 2H-pyran-6-yl. As used herein, the term "4H-pyranyl" includes 4H-pyran-2-yl, 4H-pyran-3-yl, and 4H-pyran-4-yl. As used herein, the term "3,4-dihydro-2H-pyranyl" includes 3,4-dihydro-2H-pyran-2-yl, 3,4-dihydro-2H-pyran-3-yl, 3,4-dihydro-2H-pyran-4-yl, 3,4-dihydro-2H-pyran-5-yl, and 3,4-dihydro-2H-pyran. Includes 3,6-dihydro-2H-pyran-6-yl. As used herein, the term "3,6-dihydro-2H-pyran-2-yl," 3,6-dihydro-2H-pyran-3-yl, 3,6-dihydro-2H-pyran-4-yl, 3,6-dihydro-2H-pyran-5-yl, and 3,6-dihydro-2H-pyran-6-yl. As used herein, the term "tetrahydrothiophenyl" includes tetrahydrothiophen-2-yl, tetrahydrothiophenyl-3-yl, and tetrahydrothiophenyl-4-yl. As used herein, the term "2H-thiopyran-2-yl," 2H-thiopyran-3-yl, 2H-thiopyran-4-yl, 2H-thiopyran-5-yl, and 2H-thiopyran-6-yl. As used herein, the term "4H-thiopyranyl" includes 4H-thiopyran-2-yl, 4H-thiopyran-3-yl, and 4H-thiopyran-4-yl. As used herein, the term "3,4-dihydro-2H-thiopyranyl" includes 3,4-dihydro-2H-thiopyran-2-yl, 3,4-dihydro-2H-thiopyran-3-yl, 3,4-dihydro-2H-thiopyran-4-yl, 3,4-dihydro-2H-thiopyran-5-yl, and 3,4-dihydro-2H-thiopyran-6-yl. As used herein, the term "3,6-dihydro-2H-thiopyranyl" includes 3,6-dihydro-2H-thiopyran-2-yl, 3,6-dihydro-2H-thiopyran-3-yl, 3,6-dihydro-2H-thiopyran-4-yl, 3,6-dihydro-2H-thiopyran-5-yl, and 3,6-dihydro-2H-thiopyran-6-yl. As used herein, the term "piperazinyl," also known as "piperazinyl," includes piperazine-1-yl and piperazine-2-yl. As used herein, the term "morpholinyl" includes morpholin-2-yl, morpholin-3-yl, and morpholin-4-yl. As used herein, the term "thiomorpholinyl" includes thiomorpholin-2-yl, thiomorpholin-3-yl, and thiomorpholin-4-yl.As used herein, the term “dioxanyl” includes 1,2-dioxan-3-yl, 1,2-dioxan-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, and 1,4-dioxan-2-yl. As used herein, the term “dithianyl” includes 1,2-dithian-3-yl, 1,2-dithian-4-yl, 1,3-dithian-2-yl, 1,3-dithian-4-yl, 1,3-dithian-5-yl, and 1,4-dithian-2-yl. As used herein, the term “oxathianyl” includes oxathian-2-yl and oxathian-3-yl. As used herein, the term “trioxanyl” includes 1,2,3-trioxan-4-yl, 1,2,3-trioxan-5-yl, 1,2,4-trioxan-3-yl, 1,2,4-trioxan-5-yl, 1,2,4-trioxan-6-yl, and 1,3,4-trioxan-2-yl. As used herein, the term “azepanyl” includes azepan-1-yl, azepan-2-yl, azepan-3-yl, and azepan-4-yl. As used herein, the term “homopiperazinyl” includes homopiperazin-1-yl, homopiperazin-2-yl, homopiperazin-3-yl, and homopiperazin-4-yl. As used herein, the term "indolinyl" includes indolin-1-yl, indolin-2-yl, indolin-3-yl, indolin-4-yl, indolin-5-yl, indolin-6-yl, and indolin-7-yl. As used herein, the term "quinolidinyl" includes quinolidin-1-yl, quinolidin-2-yl, quinolidin-3-yl, and quinolidin-4-yl. As used herein, the term "isoindolinyl" includes isoindolin-1-yl, isoindolin-2-yl, isoindolin-3-yl, isoindolin-4-yl, isoindolin-5-yl, isoindolin-6-yl, and isoindolin-7-yl.As used herein, the term “3H-indolyl” includes 3H-indole-2-yl, 3H-indole-3-yl, 3H-indole-4-yl, 3H-indole-5-yl, 3H-indole-6-yl, and 3H-indole-7-yl. As used herein, the term “tetrahydroquinolinyl” includes tetrahydroquinolin-1-yl, tetrahydroquinolin-2-yl, tetrahydroquinolin-3-yl, tetrahydroquinolin-4-yl, tetrahydroquinolin-5-yl, tetrahydroquinolin-6-yl, tetrahydroquinolin-7-yl, and tetrahydroquinolin-8-yl. As used herein, the term "tetrahydroisoquinolinyl" includes tetrahydroisoquinolin-1-yl, tetrahydroisoquinolin-2-yl, tetrahydroisoquinolin-3-yl, tetrahydroisoquinolin-4-yl, tetrahydroisoquinolin-5-yl, tetrahydroisoquinolin-6-yl, tetrahydroisoquinolin-7-yl, and tetrahydroisoquinolin-8-yl. As used herein, the term "chromanil" includes chroman-2-yl, chroman-3-yl, chroman-4-yl, chroman-5-yl, chroman-6-yl, chroman-7-yl, and chroman-8-yl. As used herein, the term "1H-pyrrolidine" includes 1H-pyrrolidine-1-yl, 1H-pyrrolidine-2-yl, 1H-pyrrolidine-3-yl, 1H-pyrrolidine-5-yl, 1H-pyrrolidine-6-yl, and 1H-pyrrolidine-7-yl. As used herein, the term "3H-pyrrolidine" includes 3H-pyrrolidine-1-yl, 3H-pyrrolidine-2-yl, 3H-pyrrolidine-3-yl, 3H-pyrrolidine-5-yl, 3H-pyrrolidine-6-yl, and 3H-pyrrolidine-7-yl.

[0051] The term "heteroaryl" refers to, but is not limited to, an aromatic ring containing 5 to 12 carbon atoms as a group or part of a group, or a ring system in which one or two rings are linked by condensation or covalent bonds, typically containing 5 to 6 atoms, at least one of which is aromatic, and in one or more of these rings one or more carbon atoms may be substituted with N, O, and / or S atoms, the N and S heteroatoms may optionally be oxidized, and the N heteroatom may optionally be quaternized, and furthermore, at least one carbon atom of the heteroaryl may be oxidized to form at least one C=O, and such rings may be condensed into aryl, cycloalkyl, heteroaryl, or heterocyclyl rings.Non-exclusive examples of such heteroaryls include pyrrolyl, furanyl, thiophenyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, oxatriazolyl, thiatriazolyl, pyridinyl, pyrimidyl, pyrazinyl, pyridadinyl, oxazinyl, dioxynyl, thiadinyl, triazinyl, imidazo[2,1-b][1,3]thiazolyl, and thieno[3,2-b] ]Furanil, thieno[3,2-b]thiophenyl, thieno[2,3-d][1,3]thiazolyl, thieno[2,3-d]imidazolyl, tetrazolo[1,5-a]pyridinyl, indolyl, indolidinyl, isoindolyl, benzofuranil, isobenzofuranil, benzothiophenyl, isobenzothiophenyl, indazolyl, benzimidazolyl, 1,3-benzoxazolyl, 1,2-benzisoxazolyl, 2,1-benzisoxazolyl, 1,3-benzothiazolyl , 1,2-benzoisothiazolyl, 2,1-benzoisothiazolyl, benzotriazol, 1,2,3-benzoxadiazolyl, 2,1,3-benzoxadiazolyl, 1,2,3-benzothiadiazolyl, 2,1,3-benzothiadiazolyl, benzo[d]oxazole-2(3H)-one, 2,3-dihydro-benzofuranyl, thienopyridinyl, purinyl, imidazo[1,2-a]pyridinyl, 6-oxopyridazine-1(6H)-yl, 2-oxopyridine-1(2H Examples include )-yl, 1,3-benzodioxolyl, quinolinyl, isoquinolinyl, sinnolinyl, quinazolinyl, and quinoxalinyl, and preferably the heteroaryl group is selected from the group consisting of pyridyl, 1,3-benzodioxolyl, benzo[d]oxazole-2(3H)-one, 2,3-dihydro-benzofuranyl, pyrazinyl, pyrazolyl, pyrrolyl, isoxazolyl, thiophenyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl, and thiazolyl.

[0052] "Mono-, di-, or tri-C" as a base or part of a base 1-6 The term "alkylamino" is derived from the formula -N(R o )(R p )(Rq ) refers to the base, and in the formula, R o , R p , and R q Each is independently hydrogen, or C 1-6 Selected from alkyl groups, in the formula, R o , R p , or R q At least one of them is C 1-6 It is alkyl. Therefore, alkylamino groups include monoalkylamino groups (for example, mono-C such as methylamino and ethylamino). 1-6 Alkylamino group), dialkylamino group (e.g., di-C such as dimethylamino and diethylamino) 1-6 Alkylamino groups, and trialkylamino groups (e.g., tri-C trimethylamino and triethylamino). 1-6 Examples include alkylamino groups. Preferred mono-, di-, and tri-C groups. 1-6 Non-limiting examples of alkylamino groups include n-propylamino, isopropylamino, n-butylamino, i-butylamino, sec-butylamino, t-butylamino, pentylamino, n-hexylamino, di-n-propylamino, di-i-propylamino, ethylmethylamino, methyl-n-propylamino, methyl-i-propylamino, n-butylmethylamino, i-butylmethylamino, t-butylmethylamino, ethyl-n-propylamino, ethyl-i-propylamino, n-butylethylamino, i-butylethylamino, t-butylethylamino, di-n-butylamino, di-i-butylamino, methylpentylamino, methylhexylamino, ethylpentylamino, ethylhexylamino, propylpentylamino, propylhexylamino, trimethylamino, triethylamino, tri-n-propylamino, tri-isopropylamino, tri-n-butylamino, and tri-i-butylamino.

[0053] In some embodiments, the apparatus may further include a reactant source configured and positioned to supply reactant vapors, a precursor distribution and removal system further configured to supply reactant vapors from the reactant source to the reaction chamber, and a program stored in memory further configured to control the flow of reactants from the reactant source to the reaction chamber during one or more cycles.

[0054] In some embodiments, one or more metal precursors and / or one or more optional reactants are supplied to the reaction chamber from a temperature-controlled vessel. In some embodiments, the temperature-controlled vessel is configured to cool the precursors and / or optional reactants.

[0055] In some embodiments, the reactant is selected from the group including oxide reactants, nitride reactants, boride reactants, reducing agents, phosphide reactants, carbide reactants, sulfide reactants, and combinations thereof.

[0056] In some embodiments, the reactant is an oxide reactant, which is selected from the group including H2O, O2, O3, H2O2, N2O, NO2, N2O4, pyridine N-oxide, and O2 plasma.

[0057] As used herein, an oxide reactant is a reagent that, upon contact with a metal precursor, can produce a metal oxide.

[0058] In some embodiments, the reactant is a nitride reactant, which is selected from the group including NH3, N2H4, hydrazine, alkylamine, N2 plasma, NH3 plasma, and N2 / H2 plasma.

[0059] As used herein, a nitride reactant is a reagent that, upon contact with a metal precursor, can produce a metal nitride. A suitable example of hydrazine is: [ka] It is a compound of, R 24 H, C 1-8 Alkyl, C 3-10 Selected from the group including cycloalkyl and aryl, preferably R 24 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 24 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, cyclopentyl, cyclohexyl, phenyl, and naphthyl. R 25 H, C 1-8 Alkyl, C 3-10 Selected from the group including cycloalkyl and aryl, preferably R 25 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 25 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, cyclopentyl, cyclohexyl, phenyl, and naphthyl. R 26 H, C 1-8 Alkyl, C 3-10 Selected from the group including cycloalkyl and aryl, preferably R 26 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 26 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, cyclopentyl, cyclohexyl, phenyl, and naphthyl. R 27 H, C 1-8 Alkyl, C 3-10 Selected from the group including cycloalkyl and aryl, preferably R27 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 27 The group is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, cyclopentyl, cyclohexyl, phenyl, and naphthyl.

[0060] Further non-limiting examples of suitable hydrazines include tert-butyl-hydrazine, 1,1-dimethylhydrazine, methylhydrazine, and phenylhydrazine. A suitable example of an alkylamine is: [ka] It is a compound of, R 28 is C 1-8 It is alkyl, preferably R 28 is C 1-6 It is alkyl, preferably R 28 The group is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl.

[0061] R 28a is H or C 1-8 It is alkyl, preferably R 28a is H or C 1-6 It is alkyl, preferably R 28a The group is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl.

[0062] Further non-limiting examples of suitable alkylamines include tert-butylamine, isobutylamine, and tert-pentylamine.

[0063] In some embodiments, the reactant is a boride reactant, and the boride reactant is BF3, BCl3, BBr3, BI3, borane, and formula [ka] Selected from the group including the compounds, R 50 is halogen, C 1-8 Selected from the group including alkyl and aryl, preferably R 50 is halogen, C 1-6 Selected from the group including alkyl and aryl, preferably R 50 is halogen, C 1-4 Selected from the group including alkyl and aryl, preferably R 50 F, Cl, Br, I, C 1-6 Selected from the group including alkyl and phenyl, preferably R 50 This is selected from the group comprising F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and phenyl. R 51 is halogen, C 1-8 Selected from the group including alkyl and aryl, preferably R 51 is halogen, C 1-6 Selected from the group including alkyl and aryl, preferably R 51 is halogen, C 1-4 Selected from the group including alkyl and aryl, preferably R 51 F, Cl, Br, I, C 1-6 Selected from the group including alkyl and phenyl, preferably R 51 This is selected from the group comprising F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and phenyl. R 52 is halogen, C1-8 Selected from the group including alkyl and aryl, preferably R 52 is halogen, C 1-6 Selected from the group including alkyl and aryl, preferably R 52 is halogen, C 1-4 Selected from the group including alkyl and aryl, preferably R 52 F, Cl, Br, I, C 1-6 Selected from the group including alkyl and phenyl, preferably R 52 This is selected from the group comprising F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and phenyl. R 53 is halogen, C 1-8 Selected from the group including alkyl and aryl, preferably R 53 is halogen, C 1-6 Selected from the group including alkyl and aryl, preferably R 53 is halogen, C 1-4 Selected from the group including alkyl and aryl, preferably R 53 F, Cl, Br, I, C 1-6 Selected from the group including alkyl and phenyl, preferably R 53 This is selected from the group comprising F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and phenyl. R 54 is halogen, C 1-8 Selected from the group including alkyl and aryl, preferably R 54 is halogen, C 1-6 Selected from the group including alkyl and aryl, preferably R 54 is halogen, C 1-4 Selected from the group including alkyl and aryl, preferably R 54 F, Cl, Br, I, C 1-6Selected from the group including alkyl and phenyl, preferably R 54 This is selected from the group comprising F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and phenyl. R 55 is halogen, C 1-8 Selected from the group including alkyl and aryl, preferably R 55 is halogen, C 1-6 Selected from the group including alkyl and aryl, preferably R 55 is halogen, C 1-4 Selected from the group including alkyl and aryl, preferably R 55 F, Cl, Br, I, C 1-6 Selected from the group including alkyl and phenyl, preferably R 55 The group is selected from F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and phenyl.

[0064] As used herein, a boride reactant is a reagent that, upon contact with a metal precursor, can produce a metal boride.

[0065] Appropriate examples of borazines include compounds such as borazine, trichloroborazine, tribromoborazine, and 1,3,5-trimethylborazine.

[0066] A suitable example of volan is BH3, B2H6, B 10 H 14 , B(CH3)3, B(CH2CH3)3, B(OCH3)3, B[N(CH3)2]3, pinacolborane, and formula R 29 A compound selected from the group consisting of BH3 compounds, R 29 NH3, Mono-C 1-6 Alkylamino, di-C 1-6Alkylamino, Tri-C 1-6 Alkylamino, -S(C 1-6 Alkyl)2, heterocyclyl, heteroalkyl, and C 1-4 Selected from the group including alkyl-substituted heteroaryls, preferably R 29 NH3, Mono-C 1-4 Alkylamino, di-C 1-4 Alkylamino, Tri-C 1-4 Alkylamino, -S(C 1-4 Alkyl)2, heterocyclyl, heteroalkyl, and C 1-4 Selected from the group including alkyl-substituted heteroaryls, preferably R 29 The group is selected from NH3, trimethylamine, triethylamine, dimethylamine, diethylamine, di-tert-butylamine, methylamine, ethylamine, tert-butylamine, tetrahydrofuran, pyridine, and 2-picoline.

[0067] Further non-limiting examples of suitable boranes include BH3[S(CH3)2], ammonia-borane, trimethylamine-borane, triethylamine-borane, pyridine-borane, dimethylamine-borane, 2-picoline-borane, tert-butylamine-borane, and tetrahydrofuran-borane.

[0068] In some embodiments, the reactant is a reducing agent, which is selected from the group including H2, H2 plasma, N2 / H2 plasma, N2H4, hydrazine, formic acid, formalin, borane, SiH4, Si2H6, H2Si(SiH3)2, silane, and cyclic dienes. A suitable example of hydrazine is:

[0069] [ka] It is a compound of, R 24 H, C 1-8 Selected from the group including alkyl and aryl, preferably R 24 H, C1-6 Selected from the group including alkyl and aryl, preferably R 24 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. R 25 H, C 1-8 Selected from the group including alkyl and aryl, preferably R 25 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 25 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. R 26 H, C 1-8 Selected from the group including alkyl and aryl, preferably R 26 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 26 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. R 27 H, C 1-8 Selected from the group including alkyl and aryl, preferably R 27 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 27 The group is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl.

[0070] A suitable example of volan is BH3, B2H6, B 10 H 14, B(CH3)3, B(CH2CH3)3, B(OCH3)3, B[N(CH3)2]3, pinacolborane, and formula R 29 A compound selected from the group consisting of BH3 compounds, R 29 NH3, Mono-C 1-6 Alkylamino, di-C 1-6 Alkylamino, Tri-C 1-6 Alkylamino, -S(C 1-6 Alkyl)2, heterocyclyl, heteroalkyl, and C 1-4 Selected from the group including alkyl-substituted heteroaryls, preferably R 29 NH3, mono-amino acid C 1-4 Alkyl, di-amino C 1-4 Alkyl, Tri-amino C 1-4 Alkyl, -S(C 1-4 Alkyl)2, heterocyclyl, heteroalkyl, and C 1-4 Selected from the group including alkyl-substituted heteroaryls, preferably R 29 The group is selected from NH3, trimethylamine, triethylamine, dimethylamine, diethylamine, di-tert-butylamine, methylamine, ethylamine, tert-butylamine, tetrahydrofuran, and pyridine, 2-picoline.

[0071] Further non-limiting examples of suitable boranes include BH3[S(CH3)2], ammonia-borane, trimethylamine-borane, triethylamine-borane, pyridine-borane, dimethylamine-borane, 2-picoline-borane, tert-butylamine-borane, and tetrahydrofuran-borane.

[0072] A suitable example of silane is: [ka] It is a compound of which, in the formula, R 30 H, halogen, C 1-6 Alkyl, Mono-C 1-6 Alkylamino, di-C 1-6Alkylamino, Tri-C 1-6 Selected from the group comprising alkylamino and SiH3, preferably R 30 H, halogen, C 1-4 Alkyl mono-C 1-4 Alkylamino, di-C 1-4 Alkylamino, Tri-C 1-4 Selected from the group comprising alkylamino and SiH3, preferably R 30 This is selected from the group comprising H, F, Cl, Br, I, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, methylamino, ethylamino, tert-butylamino, di-sec-butylamino, and SiH3. R 30a H, halogen, C 1-6 Alkyl, Mono-C 1-6 Alkylamino, di-C 1-6 Alkylamino, Tri-C 1-6 Selected from the group comprising alkylamino and SiH3, preferably R 30a H, halogen, C 1-4 Alkyl mono-C 1-4 Alkylamino, di-C 1-4 Alkylamino, Tri-C 1-4 Selected from the group comprising alkylamino and SiH3, preferably R 30a This is selected from the group comprising H, F, Cl, Br, I, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, methylamino, ethylaminotert-butylamino, di-sec-butylamino, and SiH3. R 31 H, halogen, C 1-6 Alkyl, Mono-C 1-6 Alkylamino, di-C 1-6 Alkylamino, Tri-C 1-6 Selected from the group comprising alkylamino and SiH3, preferably R 31 H, halogen, C 1-4 Alkyl mono-C 1-4 Alkylamino, di-C 1-4 Alkylamino, Tri-C 1-4Selected from the group comprising alkylamino and SiH3, preferably R 31 This is selected from the group comprising H, F, Cl, Br, I, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, methylamino, ethylamino, tert-butylamino, di-sec-butylamino, and SiH3. R 31a H, halogen, C 1-6 Alkyl, Mono-C 1-6 Alkylamino, di-C 1-6 Alkylamino, Tri-C 1-6 Selected from the group comprising alkylamino and SiH3, preferably R 31a H, halogen, C 1-4 Alkyl mono-C 1-4 Alkylamino, di-C 1-4 Alkylamino, Tri-C 1-4 Selected from the group comprising alkylamino and SiH3, preferably R 31a The group is selected from H, F, Cl, Br, I, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, methylamino, ethylamino, tert-butylamino, di-sec-butylamino, and SiH3.

[0073] In some embodiments, R 30 R30 a , R 31 , or R 31a At least two of them are H.

[0074] A suitable example of a silane is the formula Si x H y The compound is such that x is an integer selected from 1, 2, 3, 4, 5, or 6, and y is an integer selected from 0, 2x+2, or 2x. Those skilled in the art will know that the formula Si x H y You will understand that silanes include linear, branched, and cyclic silanes.

[0075] Further non-limiting examples of suitable silanes include bis(diethylamino)silane, diisopropylaminosilane, silane, disilane, trisilane, cyclohexasilane, neopentasilane, and di-sec-butylaminosilane.

[0076] As used herein, the term “cyclic diene” refers to a cyclic group having two double bonds, comprising 3 to 12 carbon atoms, preferably 3 to 9 carbon atoms, more preferably 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms, and potentially having at least one heteroatom selected from N, O, and S, preferably at least one N atom. The cyclic diene according to the present invention is C 1-6 Alkyl, halogen, C 1-6 Alkoxy, C 1-6 Alkylamino, di-C 1-6 Alkylamino, phenyl, and tri-C 1-6 They may be substituted with one or more substituents selected from the group including alkylsilyls. Further non-limiting examples of preferred cyclic dienes include 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1-methyl-1,4-cyclohexadiene, 1-methyl-1,3-cyclohexadiene, 2-methyl-1,3-cyclohexadiene, 3,6-bis(trimethylsilyl)-1,4-cyclohexadiene, 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene, 9,10-dihydroanthracene, and 1,4-dihydro-1,4-bis(trimethylsilyl)pyrazine.

[0077] In some embodiments, the reactant is a phosphine reactant selected from the group comprising phosphine, phosphorus halogens, phosphorus oxyhalides, organophosphates, organophosphates, aminophosphines, alkylphosphines, and silylphosphines.

[0078] As used herein, a phosphide reactant is a reagent that, upon contact with a metal precursor, can produce a metal phosphide.

[0079] Suitable examples of phosphorus halides include compounds of formula PX3 or PX5, where X is fluoro, chloro, bromo, or iodine. Suitable but non-limiting examples of phosphorus halides include, for example, phosphorus trichloride (PCl3), phosphorus pentachloride (PCl5), phosphorus tribromide (PBr3), and phosphorus pentabromide (PBr5).

[0080] A suitable example of phosphorus oxyhalides is a compound of formula POX3, where X is fluoro, chloro, bromo, or iodine. Suitable but not limited examples of phosphorus oxyhalides include, for example, phosphorus oxychloride (POCl3) and phosphorus oxybromide (POBr3).

[0081] A suitable example of an organophosphate is the formula [ka] Examples of compounds include: R 32 H, C 1-8 Selected from the group including alkyl and aryl, preferably R 32 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 32 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. R 33 H, C 1-8 Selected from the group including alkyl and aryl, preferably R 33 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 33 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. R 34 H, C 1-8Selected from the group including alkyl and aryl, preferably R 34 H, C 1-6 Selected from the group including alkyl and aryl, preferably R 34 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. In the formula, R 32 , R 33 , or R 34 Only one of them is hydrogen.

[0082] Appropriate but not limited examples of organophosphates include trimethyl phosphate (PO[OMe3]) and triethyl phosphate (PO[OEt3]).

[0083] A suitable example of an organic phosphate is the formula [ka] Examples of compounds include: R 35 H, C 1-8 Alkyl, -SiR 35a Selected from the group including aryl, R 35a is C 1-6 It is alkyl, preferably R 35 H, C 1-6 Alkyl, -SiR 35a Selected from the group including aryl, R 35a C 1-6 It is alkyl, preferably R 35 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, trimethylsilyl, phenyl, and naphthyl. R 36 H, C 1-8 Alkyl, -SiR 36a Selected from the group including aryl, R 36a is C1-6 It is alkyl, preferably R 36 H, C 1-6 Alkyl, -SiR 37a Selected from the group including aryl, R 36a C 1-6 It is alkyl, preferably R 36 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, trimethylsilyl, phenyl, and naphthyl. R 37 H, C 1-8 Alkyl, -SiR 37a Selected from the group including aryl, R 37a is C 1-6 It is alkyl, preferably R 37 H, C 1-6 Alkyl, -SiR 37a Selected from the group including aryl, R 37a C 1-6 It is alkyl, preferably R 37 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, trimethylsilyl, phenyl, and naphthyl. In the formula, R 35 , R 36 , or R 37 Only one of them is hydrogen.

[0084] Appropriate but not limited examples of organic phosphates include trimethyl phosphate (P[OMe]3) and triethyl phosphate (P[OEt]3).

[0085] A suitable example of an aminophosphine is the formula [ka] Examples of compounds include: Each R 38 H, C1-8 A group independently selected from alkyl and aryl, preferably each R 38 H, C 1-6 A group independently selected from alkyl and aryl, preferably each R 35 This is independently selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. Each R 39 H, C 1-8 A group independently selected from alkyl and aryl, preferably each R 39 H, C 1-6 A group independently selected from alkyl and aryl, preferably each R 39 This is independently selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. Each R 40 H, C 1-8 A group independently selected from alkyl and aryl, preferably each R 40 H, C 1-6 A group independently selected from alkyl and aryl, preferably each R 40 The compound is independently selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl.

[0086] Appropriate but not limited examples of aminophosphines include tris(dimethylamino)phosphine (P[NMe2]3), tris(ethylmethylamino)phosphine (P[NEtMe]3), and tris(diethylamino)phosphine (P[NEt2]3).

[0087] A suitable example of an alkylphosphine is the formula [ka] Examples of compounds include: R 41 H and C 1-8 Selected from alkyl groups, preferably R 41 H and C 1-6 Selected from alkyl groups, preferably R 41 It is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl. R 42 H and C 1-8 Selected from alkyl groups, preferably R 42 H and C 1-6 Selected from alkyl groups, preferably R 42 It is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl. R 43 H and C 1-8 Selected from alkyl groups, preferably R 43 H and C 1-6 Selected from alkyl groups, preferably R 43 It is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl. In the formula, R 41 , R 42 , and R 43 At least one of them is not hydrogen.

[0088] Suitable but not limited examples of alkylphosphines include tert-butylphosphine (C4H9PH2) and triethylphosphine (P[CH2CH3]3).

[0089] A suitable example of silylphosphine is formula [ka] Examples of compounds include: R 44 is H or Si(R 44a )3, and in the formula, each R 44a These are independently H, halogen, and C. 1-8 A group independently selected from alkyl and aryl, preferably each R 44a H, halogen, C 1-6 A group independently selected from alkyl and aryl, preferably each R 44a These are independently selected from the group comprising H, F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. R 45 is H or Si(R 45a )3, and in the formula, each R 45a H, halogen, C 1-8 A group independently selected from alkyl and aryl, preferably each R 45a H, halogen, C 1-6 A group independently selected from alkyl and aryl, preferably each R 45a These are independently selected from the group comprising H, F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. R 46 is H or Si(R 46a )3, and in the formula, each R 46a H, halogen, C 1-8 A group independently selected from alkyl and aryl, preferably each R 46a H, halogen, C 1-6 A group independently selected from alkyl and aryl, preferably each R 46aThese are independently selected from the group comprising H, F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl. In the formula, R 44 , R 45 , and R 46 At least one of them is not H.

[0090] In some embodiments, the silylphosphine is the formula [ka] Examples of compounds include the following, in the formula, each R 44a , R 45a , and R 46a This is as defined above.

[0091] Appropriate but not limited examples of silylphosphine include tris(trimethylsilyl)phosphine (P[SiMe3]3) and tri(silyl)phosphine (P[SiH3]3).

[0092] In some embodiments, the reactant is a carbide reactant, which is selected from the group comprising alkyl iodides, aryl iodides, alkyl bromides, aryl bromides, acetylene, propargyl chloride, propargyl bromide, propargyl iodide, allyl chloride, allyl bromide, allyl iodide, and cyclic dienes.

[0093] As used herein, a carbide reactant is a reagent that, upon contact with a metal precursor, can produce a metal carbide.

[0094] As used herein, the term "alkyl iodide" refers to a C150 compound in which one, two, or three hydrogen atoms are each replaced by an iodine atom. 1-8 Alkyl alkyl group, preferably C 1-6 Alkyl alkyl group, preferably C 1-4This refers to an alkyl group. Further non-limiting examples of suitable alkyl iodides include iodomethane, diiodomethane, iodoethane, 1,2-diiodoethane, and 1-iodobutane.

[0095] As used herein, the term “aryl iodide” refers to an aryl group in which one, two, three, four, five, or six hydrogen atoms are each substituted with iodine atoms, preferably three hydrogen atoms, preferably two hydrogen atoms, and preferably one hydrogen atom. Further non-limiting examples of suitable aryl iodides include iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4-triiodobenzene, 1,3,5-triiodobenzene, 1,2,3,4-tetraiodobenzene, 1,2,3,5-tetraiodobenzene, 1,2,4,5-tetraiodobenzene, and pentaiodobenzene and hexaiodobenzene.

[0096] As used herein, the term "alkyl bromide" refers to a C13 compound in which one, two, or three hydrogen atoms are each replaced by bromine atoms. 1-8 Alkyl alkyl group, preferably C 1-6 Alkyl alkyl group, preferably C 1-4 This refers to an alkyl group.

[0097] As used herein, the term "aryl bromide" refers to an aryl group in which one, two, three, four, five, or six hydrogen atoms are each substituted with bromine atoms, preferably three hydrogen atoms, preferably two hydrogen atoms, and preferably one hydrogen atom.

[0098] Further non-limiting examples of suitable alkyl bromides include bromoethane, 1,2-dibromoethane, and 1-bromobutane.

[0099] Further non-limiting examples of suitable aryl bromides include bromobenzene, 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromobenzene, 1,2,3-tribromobenzene, 1,2,4-tribromobenzene, 1,3,5-tribromobenzene, 1,2,3,4-tetrabromobenzene, 1,2,3,5-tetrabromobenzene, 1,2,4,5-tetrabromobenzene, pentabromobenzene, and hexabromobenzene.

[0100] In some embodiments, the reactant is a sulfide reactant, which is selected from the group including H2S, S8, S2Cl2, thiols, dithiols, bis(trimethylsilyl) sulfide, CS2, and disulfide.

[0101] As used herein, a sulfide reactant is a reagent that, upon contact with a metal precursor, can produce a metal sulfide.

[0102] A suitable example of a thiol is the formula R 47 Examples of SH compounds include, in the formula, R 47 C 1-8 Selected from alkyl and aryl, preferably R 47 C 1-6 Selected from alkyl and aryl, preferably R 47 The compounds are selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl.

[0103] Further non-limiting examples of suitable thiols include tert-butylthiol, 1-hexanethiol, tert-pentylthiol, and thiophenol.

[0104] As used herein, the term "dithiol" refers to a C atom in which two hydrogen atoms are substituted with a thiol (-SH) group. 1-8 Alkyl alkyl group, preferably C1-6 Alkyl alkyl group, preferably C 1-4 This refers to an alkyl group. Further non-limiting examples of suitable dithiols include 1,2-ethanedithiol, 1,3-propanedithiol, and 1,4-butanedithiol.

[0105] A suitable example of a disulfide is the formula R 47 -SSR 48 Examples of compounds include, in the formula, R 47 C 1-8 Selected from alkyl and aryl, preferably each R 47 C 1-6 Selected from alkyl and aryl, preferably R 47 It is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl. R 48 C 1-8 Selected from alkyl and aryl, preferably each R 48 C 1-6 Selected from alkyl and aryl, preferably R 48 The compounds are selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, phenyl, and naphthyl.

[0106] Further non-limiting examples of suitable disulfides include dimethyl disulfide, diethyl disulfide, and di-tert-butyl disulfide.

[0107] In some embodiments, the temperature-controlled vessel is configured to heat the precursor and any reactants. In some embodiments, the temperature-controlled vessel is maintained at a temperature of at least -50°C and at most 20°C, or at least 20°C and at most 250°C, or at least 100°C and at most 200°C.

[0108] In certain embodiments, the apparatus disclosed herein may be configured to manufacture a semiconductor device disclosed herein, or a field-effect transistor (FET) disclosed herein.

[0109] In certain embodiments, the apparatus disclosed herein is configured to form at least a portion of a semiconductor device or a field-effect transistor (FET) disclosed herein.

[0110] In some embodiments, at least one metal precursor is At least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu, preferably at least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Gd, Tb, Ho, Er, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, and Lu, Equation (I) [ka] (In the formula, R 1 C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 2 C 1-10 Alkyl, C 3-10 Cycloalkyl, C1-6 alkyl substituted C 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, or R 1 and R 2Together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings. R 3 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 4 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 5 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 6 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 It comprises at least one ligand (selected from the group including alkyl-substituted aryls).

[0111] In some embodiments, at least one metal precursor comprises at least one ligand of formula (I), where, R 1 C 1-6 Alkyl, C 3-6 Cycloalkyl, C1 -6 C substituted with alkyl 3-6 Cycloalkyl, aryl, and C 1-6Selected from the group including alkyl-substituted aryls, preferably R 1 These are methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 C substituted with cycloalkyl, methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl 3-6 Selected from the group including cycloalkyl, R 2 C 1-6 Alkyl, C 3-6 Cycloalkyl, C1 -6 C substituted with alkyl 3-6 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, preferably R 2 These are methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 C substituted with cycloalkyl, methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl 3-6 Selected from the group including cycloalkyl groups, or R 1 and R 2 These, together with the phosphorus atoms to which they are bonded, form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings, preferably R 1 and R 2 These, together with the phosphorus atoms to which they are bonded, form saturated or unsaturated 4-membered, 5-membered, 6-membered, 7-membered, or 8-membered rings, preferably R 1 and R 2 Together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 5-membered, 6-membered, or 7-membered rings. R 3 H, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 C substituted with alkyl 3-6 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, preferably R 3H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 C substituted with cycloalkyl, methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl 3-6 Selected from the group including cycloalkyl, R 4 H, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Cycloalkyl-substituted C 3-6 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, preferably R 4 H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 C substituted with cycloalkyl, methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl 3-6 Selected from the group including cycloalkyl, R 5 H, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Cycloalkyl-substituted C 3-6 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, preferably R 5 H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 C substituted with cycloalkyl, methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl 3-6 Selected from the group including cycloalkyl, R 6 H, C 1-6 Alkyl, C 3-6 Cycloalkyl, C 1-6 Cycloalkyl-substituted C 3-6 Cycloalkyl, aryl, and C 1-6Selected from the group including alkyl-substituted aryls, preferably R 6 H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 C substituted with cycloalkyl, methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl 3-6 Selected from the group including cycloalkyl groups.

[0112] Within the scope of this disclosure, it should be understood that the metal precursor may include any combination of ligands of the aforementioned types.

[0113] When forming the metal precursor of the present invention, the metal atom can interact with the ligand of formula (I) in two ways: firstly, the metal atom bonds to two carbon atoms of the ligand of formula (I) to form a bidentate ylide (see structures (A) and (B) below); or secondly, the metal atom bonds to one carbon atom of the ligand of formula (I) to form a monodentate ylide (see structure (C) below). [ka]

[0114] In some embodiments, the metal atom binds to the ligand of formula (I) to form a bidentate ylide.

[0115] As used herein, compounds in which the same ligand is linked to the same central metal atom are known in the art as homoreptic complexes.

[0116] In some embodiments, the metal precursor comprises one or more identical ligands of formula (I), and these compounds may also be referred to as homoreptic ylides. Some examples of homoreptic ylides according to the present invention are: [ka] And in the formula, R 1 , R 2 , R3 , R 4 , R 5 , and R 6 These are as described herein. Some non-limiting examples of homoreptic ylides according to the present invention are [ka] That is the case.

[0117] As used herein, compounds in which different ligands are linked to the same central metal atom are known in the art as heteroreptic complexes.

[0118] In some embodiments, the metal precursor comprises at least one ligand of formula (I) and one or more further ligands selected from the group consisting of cyclopentadienyl ligands, amide ligands, imide ligands, amidinates, halogen ligands, alkyl ligands, alkoxide ligands, diketonate ligands, and 1,4-diazabutadiene ligands.

[0119] In some embodiments, one or more further ligands are cyclopentadienyl ligands of formula (1), [ka] During the ceremony, R 7a H, C 1-8 Alkyl and -SiR 9a Selected from the group including, in the formula, R 9a is C 1-6 It is alkyl, preferably R 7a H, C 1-6 Alkyl and -SiR 9a Selected from the group including R 9a is C 1-4 It is alkyl, preferably R 7aThis is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and trimethylsilyl. R 7b H, C 1-8 Alkyl and -SiR 9b Selected from the group including, in the formula, R 9b is C 1-6 It is alkyl, preferably R 7b H, C 1-6 Alkyl and -SiR 9a Selected from the group including R 9b is C 1-4 It is alkyl, preferably R 7b This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and trimethylsilyl. R 7c H, C 1-8 Alkyl and -SiR 9c Selected from the group including, in the formula, R 9c is C 1-6 It is alkyl, preferably R 7c H, C 1-6 Alkyl and -SiR 9c Selected from the group including R 9c is C 1-4 It is alkyl, preferably R 7c This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and trimethylsilyl. R 7d H, C 1-8 Alkyl and -SiR 9d Selected from the group including, in the formula, R 9d is C 1-6 It is alkyl, preferably R 7d H, C 1-6 Alkyl and -SiR 9dSelected from the group including R 9d is C 1-4 It is alkyl, preferably R 7d This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and trimethylsilyl. R 7e H, C 1-8 Alkyl and -SiR 9e Selected from the group including, in the formula, R 9e is C 1-6 It is alkyl, preferably R 7e H, C 1-6 Alkyl and -SiR 9e Selected from the group including R 9e is C 1-4 It is alkyl, preferably R 7e The group is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and trimethylsilyl.

[0120] In some embodiments, the cyclopentadienyl ligand is selected from the group comprising cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, tert-butylcyclopentadienyl, trimethylsilylcyclopentadienyl, pentamethylcyclopentadienyl, 1,2,4-triisopropylcyclopentadienyl, and 1,2,4-tri-tert-butylcyclopentadienyl.

[0121] In some embodiments, the cyclopentadienyl ligand binds to the metal in η-1, η-3, or η-5 coordination modes. The number following the Greek letter eta (η) indicates the number of consecutive atoms of the same type in the ligand that are simultaneously bound to the metal atom. The cyclopentadienyl ligand is preferably bound to the metal in η-5 coordination mode.

[0122] In some embodiments, the metal precursor comprises at least one ligand of formula (I) and one or more cyclopentadienyl ligands, wherein the metal precursor is of formula (II): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 This is as described herein, R 7 H, C 1-8 Alkyl and -SiR 9 Selected from the group including, in the formula, R 9 is C 1-6 It is alkyl, preferably R 7 H, C 1-6 Alkyl and -SiR 9 Selected from the group including, in the formula, R 9 is C 1-4 It is alkyl, preferably R 7 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl, isobutyl, n-pentyl, tert-pentyl, iso-pentyl, and trimethylsilyl. R 8 H, C 1-8 Alkyl and -SiR 10 Selected from the group including, in the formula, R 10 is C 1-6 It is alkyl, preferably R 8 H, C 1-6 Alkyl and -SiR 10 Selected from the group including, in the formula, R 10 is C 1-4 It is alkyl, preferably R 8M is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and trimethylsilyl. In some of these embodiments, M is selected from Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, preferably selected from Sc, Y, La, and Ce.

[0123] In some embodiments, one or more additional ligands are expressed in formula (2) [ka] (In the formula, R 11 H, C 1-8 Alkyl and -SiR 12 Independently selected from the group containing, in the formula, R 12 is C 1-6 It is alkyl, preferably R 11 H, C 1-6 Alkyl and -SiR 12 Selected from the group including R 12 is C 1-4 It is alkyl, preferably R 11 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and trimethylsilyl. R 11a H, C 1-8 Alkyl and -SiR 12a Independently selected from the group containing, in the formula, R 12a is C 1-6 It is alkyl, preferably R 11a H, C 1-6 Alkyl and -SiR 12a Selected from the group including R 12a C 1-4 It is alkyl, preferably R 11aThis is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and trimethylsilyl. In the formula, R 11 and R 11a At least one of them is an amide ligand (not H).

[0124] In some embodiments, the amide ligand is selected from the group comprising dimethylamide, diethylamide, ethylmethylamide, diisopropylamide, tert-butylamide, and bis(trimethylsilyl)amide. In some embodiments, one or more additional ligands are expressed in formula (3) =NR 13 (3) (In the formula, R 13 is C 1-8 It is alkyl, preferably R 13 is C 1-6 It is alkyl, preferably R 13 The ligand is an imide ligand selected from the group including methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, iso-pentyl, and trimethylsilyl.

[0125] In some embodiments, the imide ligand is selected from the group comprising ethylimide, isopropylimide, isobutylimide, tert-butylimide, and tert-pentylimide. In some embodiments, the metal precursor comprises at least one ligand of formula (I) and one or more imide ligands, wherein the metal precursor is of formula (III): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , and R6 This is as described herein, R 7’ is C 1-8 It is alkyl, preferably R 7’ is C 1-6 It is alkyl, preferably R 7’ This is selected from the group comprising methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and iso-pentyl. R 8’ is C 1-8 It is alkyl, preferably R 8’ is C 1-6 It is alkyl, preferably R 8’ (is selected from the group comprising methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and iso-pentyl). In some of these embodiments, M is preferably selected from Cr, Mo, and W. In some embodiments, one or more further ligands are of formula (4) [ka] (In the formula, R 14 is C 1-8 It is alkyl, preferably R 14 is C 1-6 It is alkyl, preferably R 14 This is selected from the group including methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl. R 15 is C 1-8 It is alkyl, preferably R 15 is C 1-6 It is alkyl, preferably R 15 This is selected from the group comprising methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and iso-pentyl. R16 H, C 1-6 Alkyl, Mono-C 1-6 Alkylamino and di-C 1-6 Selected from the group including alkylaminos, preferably R 16 H, C 1-4 Alkyl, Mono-C 1-4 Alkylamino and di-C 1-4 Selected from the group including alkylaminos, preferably R 16 This is an amidinate ligand (selected from the group including H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl, isobutyl, dimethylamine, diethylamine, and ethylmethylamine).

[0126] In some embodiments, the amidinate ligand is selected from the group comprising N,N'-diethylacetamidinate, N,N'-diisopropylacetamidinate, N,N'-diisopropylformamidinate, N,N'-di-tert-butylacetamidinate, and N,N'-di-tert-butylformamidinate.

[0127] In some embodiments, one or more additional ligands are expressed in formula (5) [ka] (In the formula, R 17 H, C 1-8 Selected from the group including alkyl and aryl, preferably R 17 is H or C 1-6 Selected from alkyl groups, preferably R 17 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl. R 18 H, C 1-8 Selected from the group including alkyl and aryl, preferably R 18 is H or C 1-6Selected from alkyl groups, preferably R 18 This is selected from the group comprising H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl. R 19 H, C 1-8 Selected from the group including alkyl and aryl, preferably R 19 is H or C 1-6 Selected from alkyl groups, preferably R 19 This is an alkoxide ligand (selected from the group including H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl, isobutyl, n-pentyl, tert-pentyl, and isopentyl).

[0128] In some embodiments, the alkoxide ligand is selected from the group comprising methoxide, ethoxide, isopropoxide, tert-butoxide, 1-methoxy-2-methyl-2-propoxide, 1-dimethylamino-2-propoxide, 1-dimethylamino-2-methyl-2-propoxide, 1-ethylmethylamino-2-methyl-2-propoxide, 1-diethylamino-2-methyl-2-propoxide, 1-dimethylamino-2-methyl-2-butoxide, 1-ethylmethylamino-2-methyl-2-butoxide, and 1-diethylamino-2-methyl-2-butoxide. In some embodiments, one or more additional ligands are expressed in formula (6). [ka] (In the formula, R 20 C 1-8 C substituted with alkyl or halogen 1-8 Selected from the group including alkyl and aryl, preferably R 20 C 1-6 C substituted with alkyl or halogen 1-6 Selected from the group including alkyl and aryl, preferably R 20This is selected from the group comprising methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, phenyl, and toluyl. R 21 C 1-8 C substituted with alkyl or halogen 1-8 Selected from the group including alkyl and aryl, preferably R 21 C 1-6 C substituted with alkyl or halogen 1-6 Selected from the group including alkyl and aryl, preferably R 21 This is a diketonate ligand (selected from the group including methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, phenyl, and toluyl).

[0129] In some embodiments, the diketonate ligand is selected from the group comprising acetylacetonate, 2,2,6,6-tetramethylheptane-3,5-dione, and 1,1,1,5,5,5-hexafluoropentane-2,5-dione.

[0130] In some embodiments, one or more additional ligands are expressed in formula (7) [ka] (In the formula, R 22 is C 1-8 It is alkyl, preferably R 22 is C 1-6 It is alkyl, preferably R 22This is selected from the group comprising methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and iso-pentyl. R 23 is C 1-8 It is alkyl, preferably R 23 is C 1-6 It is alkyl, preferably R 23 This is a diazabutadiene ligand (selected from the group including methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl).

[0131] In some embodiments, the diazabutadiene ligand is selected from the group comprising 1,4-di-tert-butyl-1,4-diaza-1,3-butadiene, 1,4-diisopropyl-1,4-diaza-1,3-butadiene, 1,4-di-sec-butyl-1,4-diaza-1,3-butadiene, and 1,4-di-tert-pentyl-1,4-diaza-1,3-butadiene.

[0132] Some non-limiting examples of heteroreptic ylides according to the present invention are: [ka] That is the case.

[0133] Figure 2 schematically shows apparatus (600) according to an additional exemplary embodiment of the present disclosure. Apparatus (600) may be used to carry out the methods described herein and / or to form (a portion of) a transistor or semiconductor device described herein.

[0134] In the illustrated embodiment, the apparatus (600) comprises one or more reaction chambers (602), a metal precursor gas source (604), a purge gas source (610), an exhaust system (612), and a controller (614). The reaction chamber (602) may include any suitable reaction chamber, such as an ALD or CVD reaction chamber. Optionally, the apparatus (600) may include further gas sources, such as a reactant source (608) and a vacuum source (611).

[0135] A metal gas source (604) is configured to deliver a metal precursor as described herein. The metal precursor gas source (604) may comprise a container and one or more metal precursors as described herein, which are used alone or in combination with one or more carrier (e.g., inert) gases. An optional reactant source (608) may comprise a container and one or more reactants as described herein, alone or in combination with one or more carrier (e.g., inert) gases. A purge gas source (610) may comprise one or more inert gases as described herein, e.g., N2 or noble gases. The apparatus (600) may comprise any suitable number of gas sources. The gas sources (604) to (611) may be connected to the reaction chamber (602) via lines (616) to (621), each of which may comprise a flow controller, valves, heaters, etc. The exhaust system (612) may comprise one or more vacuum pumps.

[0136] The controller (614) includes electronic circuits and software for selectively operating valves, manifolds, heaters, pumps, and other components contained in the apparatus (600). Such circuits and components operate to introduce precursors, optional reactants, and purge gases from their respective sources (604) to (611). The controller (614) can control the timing of the gas pulse sequence, the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to provide proper operation of the apparatus (600). The controller (614) includes control software that can electrically or pneumatically control the valves to control the inflow and outflow of precursors, optional reactants, and purge gases into and from the reaction chamber (602). The controller (614) may include modules, such as software or hardware components, that perform specific tasks, e.g., FPGAs or ASICs. The modules may be advantageously configured to reside on an addressable storage medium of the control system and may be configured to perform one or more processes.

[0137] Other configurations of the apparatus 600 are possible, including different numbers and types of precursor sources, optional reactant sources, and purge gas sources. Furthermore, it will be understood that there are numerous arrangements of valves, conduits, precursor sources, optional reactant sources, and purge gas sources that can be used to achieve the objective of selectively supplying gas to the reaction chamber (602). In addition, many components have been omitted from the schematic diagram of the apparatus for the sake of simplicity of explanation. Such components include, for example, various valves, manifolds, purifiers, heaters, vessels, vents, and / or bypasses.

[0138] Furthermore, embodiments of the controller may include a combination of hardware, software, and electronic components or modules, which may be described for the purposes of consideration as being primarily implemented in hardware. However, those skilled in the art will recognize, by reading this detailed description, that in at least one embodiment, the electronic-based aspects of the present disclosure may be implemented in software (e.g., instructions stored on a non-temporary computer-readable medium) executable by one or more processing units, such as a microprocessor and / or application-specific integrated circuit.

[0139] During the operation of the reaction apparatus (600), a substrate such as a semiconductor wafer (not shown) is transferred, for example, from a substrate handling system to the reaction chamber (602). Once the substrate is transferred to the reaction chamber (602), one or more gases from gas sources (604) to (611), such as a precursor, carrier gas, any reactants, and / or purge gas, are introduced into the reaction chamber (602).

[0140] Another aspect of this disclosure is a method for forming a metal-containing layer on a semiconductor substrate, a) A step of supplying a semiconductor substrate into a reaction chamber, b) A process that performs one or more cycles, where each cycle is A metal precursor pulse comprising a step of which at least a portion of a semiconductor substrate comes into contact with at least one metal precursor by introducing at least one metal precursor into a reaction chamber, At least one metal precursor, At least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu, Equation (I) [ka] (In the formula, R 1 C 1-10 Alkyl, C 3-10 Cycloalkyl, C1-6 alkyl substituted C 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 2 C 1-10 Alkyl, C 3-10 Cycloalkyl, C1-6 alkyl substituted C 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, or R 1 and R 2 Together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings. R 3 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 4 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 5 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 6 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 It comprises at least one ligand (selected from the group including alkyl-substituted aryls), The present invention relates to a method by which, as a result of the cycle, a metal-containing layer is formed on a semiconductor substrate in a reaction chamber.

[0141] Following step b) of this method, and after supplying the substrate to the reaction chamber, one or more (deposition) cycles are performed to form a metal-containing layer on the semiconductor substrate.

[0142] In particular, the (deposition) method may be a combination of periodic deposition processes, preferably atomic layer deposition (ALD) processes or periodic chemical vapor deposition (CVD) processes. Each periodic deposition process comprises one or more separate (deposition) cycles. In a more specific embodiment, the method disclosed herein may be an ALD method. In contrast to sputtering techniques commonly used in the art for the deposition of thin films and layers for the manufacture of various semiconductors and transistors, periodic deposition processes such as ALD have been found to provide more uniform deposition across the surface of the substrate and / or across (previously) deposited layers.

[0143] As used herein, the synonyms “cyclic deposition process” or “cyclical deposition process” can refer to a process in which precursors (and / or reactants) are continuously introduced into a reaction chamber to deposit layers or films on a substrate, and include processing techniques such as ALD components and hybrid cyclical deposition processes containing ALD components. Typically, a single deposition cycle can form a film or layer of about 0.10 nm to about 0.2 nm. However, experimental thicknesses can vary depending on the quantity and type of cycle, as well as the available reaction sites on the substrate and / or previously deposited layers.

[0144] The term "atomic layer deposition" (ALD) may refer to a deposition process in which a deposition cycle, typically multiple consecutive deposition cycles, are carried out within a process chamber. As used herein, the term atomic layer deposition also means processes specified by related terms such as atomic layer chemical deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas-source MBE, organometallic MBE, and chemical beam epitaxy, when carried out using alternating pulses of precursor / reactive gas and purge (e.g., inert carrier) gas(s).

[0145] In the ALD process, during each cycle, a precursor (e.g., a metal precursor) is typically introduced into the reaction chamber and chemically adsorbed onto the deposition surface (e.g., a substrate surface, which may contain pre-deposited material from a previous ALD cycle or other materials), thereby forming a material that does not readily react with other precursors (i.e., exhibits self-controlled reactions), such as a monolayer or sub-monolayer of the material, several monolayers of the material, or multiple monolayers of the material. Subsequently, in some cases, a reactant (e.g., another precursor or a reaction gas such as an oxygen reactant) may be introduced into the process chamber. The reactant can then react further with the precursor. It should be noted that, as used in this disclosure, the ALD process does not necessarily consist of a sequence of self-controlled surface reactions.

[0146] In some embodiments, step b) of the method according to the present disclosure further comprises a reactant pulse, wherein at least a portion of the semiconductor substrate is brought into contact with at least one reactant by introducing at least one reactant into a reaction chamber. The description of the types of reactants provided in the Apparatus section is applied mutatis mutandis to the description of the Method.

[0147] The descriptions of the types of metal precursors and ligands provided in the apparatus section shall be applied mutatis mutandis to the description of the method.

[0148] If necessary, a purging step can be utilized during one or more iterations (e.g., during each deposition step in each cycle) to remove any excess precursors from the process chamber and / or any excess reactants and / or reaction byproducts from the reaction chamber.

[0149] As used herein, the term "purge" may refer to a procedure in which an inert or substantially inert gas is supplied to the reaction chamber between two pulses of reacting gases. By purging with an inert gas, such as a noble gas, between subsequent pulses, gas-phase interactions between precursors and / or reactants can be avoided or at least minimized.

[0150] In certain embodiments, the method disclosed herein provides that the reaction chamber is purged before and / or after each precursor pulse. In certain embodiments, the method disclosed herein provides that the reaction chamber is purged before and / or after each metal precursor pulse and reactant pulse.

[0151] In some embodiments, the duration of the purge is 0.1 seconds or more, preferably 0.5 seconds or more, preferably 1 second or more, preferably 5 seconds or more, preferably 10 seconds or more. In some embodiments, the duration is 60 seconds or less, preferably 45 seconds or less, preferably 35 seconds or less, preferably 20 seconds or less, preferably 10 seconds or less. In some embodiments, the duration o is 0.1 seconds to 60 seconds, preferably 0.5 seconds to 20 seconds, preferably 5 seconds to 10 seconds, preferably 1 second to 10 seconds.

[0152] Advantageously, the periodic deposition processes disclosed herein may be thermal deposition processes. In other words, in some embodiments, neither pulsed nor purged plasma is employed in the periodic deposition process. In the case of thermal periodic deposition processes, the duration of the step of providing the metal precursor to the reaction chamber, and / or the duration of the step of providing the reactant to the reaction chamber, may be relatively long to allow the precursor and / or reactant to react with the surface of the substrate and / or previously deposited layers.

[0153] In some embodiments, the duration of the step of supplying the metal precursor to the reaction chamber is 0.1 seconds or more, preferably 0.5 seconds or more, preferably 1 second or more, preferably 5 seconds or more, preferably 10 seconds or more. In some embodiments, the duration is 60 seconds or less, preferably 45 seconds or less, preferably 35 seconds or less, preferably 20 seconds or less, preferably 10 seconds or less. In some embodiments, the duration is 0.1 seconds to 60 seconds, preferably 0.5 seconds to 20 seconds, preferably 5 seconds to 10 seconds, preferably 1 second to 10 seconds.

[0154] In some embodiments, the duration of the step of supplying the reactant to the reaction chamber is 0.1 seconds or more, preferably 0.5 seconds or more, preferably 1 second or more, preferably 5 seconds or more, and preferably 10 seconds or more. In some embodiments, the duration is 60 seconds or less, preferably 45 seconds or less, preferably 35 seconds or less, preferably 20 seconds or less, and preferably 10 seconds or less. In some embodiments, the duration is 0.1 seconds to 60 seconds, preferably 0.5 seconds to 20 seconds, preferably 5 seconds to 10 seconds, and preferably 1 second to 10 seconds.

[0155] In some embodiments, the periodic deposition process employs plasma-enhanced deposition techniques. For example, the periodic deposition process may include plasma-enhanced atomic layer deposition and / or plasma-enhanced chemical vapor deposition. In such cases, one of the pulses in the periodic deposition process may include generating plasma within the reaction chamber.

[0156] In some embodiments, the methods disclosed herein may be continuous vacuum deposition processes. In a continuous vacuum deposition process, the material is deposited onto a substrate in a reaction chamber without introducing air or interrupting the controlled vacuum environment. This process involves maintaining a consistent vacuum pressure within the reaction chamber.

[0157] In certain embodiments, the methods disclosed herein provide that a metal-containing layer can be formed without any intervening vacuum breaking. The term “without vacuum breaking” may mean without breaking the vacuum, without interruption as a timeline, without material intermediate steps, without changing processing conditions, and / or immediately thereafter.

[0158] In certain embodiments, the formation of the metal-containing layer may include at least 1 cycle, at least 2 cycles, at least 5 cycles, at least 10 cycles, at least 20 cycles, at least 40 cycles, at least 100 cycles, at least 200 cycles, at least 400 cycles, at least 600 cycles, or at least 1000 cycles. In some embodiments, the process may be repeated for at least 1 to a maximum of 5000 cycles, preferably at least 1 to a maximum of 1000 cycles, preferably at least 2 to a maximum of 100 cycles, and preferably at least 5 to a maximum of 50 cycles.

[0159] Each cycle may include one or more pulses. In some embodiments, at least one pulse is accompanied by a self-controlled surface reaction. In some embodiments, all pulses are accompanied by a self-controlled surface reaction. In the context of ALD, a self-controlled surface reaction refers to a chemical reaction that automatically stops or slows down when a certain threshold or coverage is achieved on the surface, for example, when a complete monolayer or sub-monolayer is formed, stopping the reaction by preventing further reaction with additional precursors. In some embodiments, a cycle includes one or more precursor pulses and any one or more reactant pulses.

[0160] In certain embodiments, the metal-containing layer may have an average thickness of 10.0 nm to 100.0 nm, or 1.0 nm to 100.0 nm, or 5.0 nm to 20 nm, or 1.0 nm to 10.0 nm, or 0.05 nm to 2.0 nm, or 0.10 nm to 2.0 nm, or 0.10 nm to 1.75 nm, or 0.10 nm to 1.50 nm, or 0.10 nm to 1.25 nm, preferably 0.10 nm to 1.0 nm, or 0.20 nm to 1.0 nm, or 0.25 nm to 1.0 nm. In certain embodiments, the methods disclosed herein provide that the channel layer may have an average thickness of 0.05 nm to 2.0 nm, or 0.10 nm to 2.0 nm, or 0.10 nm to 1.75 nm, or 0.10 nm to 1.50 nm, or 0.10 nm to 1.25 nm, preferably 0.10 nm to 1.0 nm, or 0.20 nm to 1.0 nm, or 0.25 nm to 1.0 nm.

[0161] In some embodiments, a cycle for growing a metal-containing layer may include a sequence of pulses of a metal precursor pulse and an optional reactant pulse. In the metal precursor pulse, one or more metal precursors are supplied into the reaction chamber and may chemisorb onto the substrate (i.e., adhere to atoms or molecules on the substrate surface and / or previously deposited layers or materials, forming chemical bonds). In the optional reactant pulse, one or more reactants are supplied into the reaction chamber and react with the chemisorbed metal to form a metal-containing layer on at least a portion of the substrate. The number of cycles determines the overall thickness of the deposited metal-containing layer.

[0162] The advantage of the periodic deposition process described herein is precise control over the entire thickness of the layer.

[0163] Figure 1 illustrates an exemplary embodiment of a method (100) for forming a metal-containing layer on a semiconductor substrate disclosed herein. The method begins by providing the substrate to a reaction chamber (111). The periodic deposition process includes supplying one or more metal precursors (gases) described herein into the reaction chamber in a metal precursor pulse (112). Optionally, the reaction chamber is purged after the metal precursor pulse (112) (113). The metal precursor pulse is configured to deliver the metal precursor as described herein. Optionally, one or more reactants are supplied to the reaction chamber in a reactant pulse (114). Optionally, the reaction chamber may be purged after the reactant pulse (115).

[0164] The metal precursor pulse (112), the optional reactant pulse (114), and the optional purge (113, 115) can be repeated any number of times (116) to obtain a metal-containing layer (117) having the desired thickness. The method is completed when a metal-containing layer of the desired thickness has been deposited (118). Once the method is completed, the substrate can be subjected to additional processes known in the art for forming device structures and / or devices (e.g., FETs) disclosed herein.

[0165] Naturally, it should be noted that the metal precursor pulse (112) and the optional reactant pulse (114) may overlap within a single cycle. Furthermore, the order of each method step (112-115) within each cycle can vary. For example, in and another exemplary embodiment, a cycle may include a sequence of optional reactant pulses and metal precursor pulses. Thus, there may be an optional reactant pulse preceding the metal precursor pulse.

[0166] In certain embodiments, the methods disclosed herein specify that the metal precursor pulse and optional reactant pulse comprise a plurality of micropulses. As used herein, a “micropulse” is a short duration in which one or more metal precursors and one or more optional reactants can be introduced into the reaction chamber. Thus, the methods disclosed herein offer high flexibility in pulse sequence and length, thereby providing a more cost-effective and efficient method compared to conventional metal-containing layer manufacturing processes known in the prior art.

[0167] In some embodiments, the metal precursor pulse, any one or more reactants may be sustained for at least 0.01 seconds to a maximum of 120 seconds, or at least 0.01 seconds to a maximum of 0.1 seconds, or at least 0.01 seconds to a maximum of 0.02 seconds, or at least 0.02 seconds to a maximum of 0.05 seconds, or at least 0.05 seconds to a maximum of 0.1 seconds, or at least 0.1 seconds to a maximum of 20 seconds, or at least 0.1 seconds to a maximum of 0.2 seconds, or at least 0.2 seconds to a maximum of 0.5 seconds, or at least 0.5 seconds to a maximum of 1.0 seconds, or at least 1.0 seconds to a maximum of 2.0 seconds, or at least 2.0 seconds to a maximum of 5.0 seconds, or at least 5.0 seconds to a maximum of 10.0 seconds, or at least 10.0 seconds to a maximum of 20.0 seconds.

[0168] Naturally, it will be understood that any two processes and / or pulses and / or micropulses can be separated by purging. Therefore, in some embodiments, the metal precursor pulse and, optionally, the reactant pulse may be separated by purging. In some embodiments, subsequent cycles are separated by purging.

[0169] In certain embodiments, the reaction chamber may be purged before and / or after the metal precursor pulse and any reactant pulse. The advantage of purging is to prevent gas-phase reactions that can prevent / eliminate self-controlled surface reactions. Another advantage of purging the reaction chamber before and / or after each precursor pulse and / or any reactant pulse is to remove any residual precursors, reactants and / or reaction byproducts, thereby avoiding cross-contamination between pulses and resulting in a highly pure film or layer with fewer harmful defects.

[0170] The methods disclosed herein may be carried out at different temperatures and / or pressures. In certain embodiments, the methods disclosed herein provide that the substrate may be heated to a temperature of about 80°C to about 500°C, or about 80°C to about 400°C, or about 100°C to about 400°C, or about 125°C to about 400°C, preferably about 150°C to about 400°C, or about 175°C to about 400°C, preferably about 200°C to about 400°C, or about 200°C to about 300°C, or about 250°C to about 400°C, or about 300°C to about 400°C. The listed temperatures may reduce the time required for material deposition, but lower or higher temperatures may still be considered.

[0171] In certain embodiments, the methods disclosed herein provide that the pressure in the reaction chamber is about 0.1 Torr to about 100.0 Torr, or about 0.5 Torr to about 100.0 Torr, or about 1.0 Torr to about 100.0 Torr, or about 2.0 Torr to about 100.0 Torr, or about 5.0 Torr to about 100.0 Torr, or about 5.0 Torr to about 80.0 Torr, or preferably about 5.0 Torr to about 50.0 Torr, or about 10.0 Torr to about 50.0 Torr, or 0.5 to about 10.0 Torr. The listed pressures can reduce the time required for material deposition, but lower or higher pressures may still be considered.

[0172] In some embodiments, the substrate is subjected to an annealing process in an environment containing hydrogen and nitrogen after a periodic deposition process. Preferably, the annealing process can be carried out at a temperature of at least 300°C to a maximum of 600°C. Alternatively, the annealing process can be carried out at a temperature of at least 300°C to a maximum of 1000°C.

[0173] In some embodiments, one or more metal precursors and / or any one or more reactants are supplied to the reaction chamber by a carrier gas. Exemplary carrier gases include nitrogen (N2) and noble gases such as He, Ne, Ar, Xe, or Kr.

[0174] Continuous substrates may extend beyond the boundary of the process / reaction chamber on which the deposition process is carried out. In some processes, the continuous substrate may move through the process chamber, thereby allowing the process to continue until the edge of the substrate is reached. Continuous substrates may be supplied from a continuous substrate supply system to enable the manufacture and production of continuous substrates in any suitable form. Non-limiting examples of continuous substrates include sheets or flexible materials. Continuous substrates may also include carriers or sheets on which discontinuous substrates are placed.

[0175] Another aspect of this disclosure relates to a semiconductor device structure formed according to the method described herein. The semiconductor device structure preferably includes a metal-containing layer comprising a plurality of metal atoms selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu.

[0176] In some embodiments, the semiconductor device structure is given by equation (I): [ka] (In the formula, R 1 C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 2 C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, or R 1 and R 2 Together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings. R 3 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 4 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 5 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 6 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 The metal layer comprises at least one ligand (selected from the group including alkyl-substituted aryls).

[0177] Another aspect of this disclosure relates to a composition configured to form a metal-containing film, wherein the composition is At least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu, and formula (I): [ka] (In the formula, R 1 C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 2 C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, or R 1 and R 2 Together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings. R 3 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 4 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 5 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 6 H, C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 The present invention comprises at least one metal precursor, which includes at least one ligand (selected from the group including alkyl-substituted aryls).

[0178] Embodiments of the metal precursor are discussed above.

[0179] The compositions disclosed herein may contain one or more impurities. The use of metal precursors for deposition requires relatively high purity. Impurities in the compositions are undesirable because they may degrade the quality of the resulting film. For example, impurities in the compositions may lead to the incorporation of impurity elements into the resulting film. Additionally, or instead, impurities in the compositions may cause process drift due to differences in the vapor pressures of the various components of the composition. In some embodiments, the compositions contain at least about 95% by weight of a metal precursor, at least about 97% by weight of a metal precursor, or at least about 98% by weight of a metal precursor, or at least about 99% by weight of a metal precursor, or at least about 99.5% by weight of a metal precursor, at least about 99.7% by weight of a metal precursor, at least about 99.9% by weight of a metal precursor, or at least about 99.99% by weight of a metal precursor.

[0180] In some embodiments, the composition is used in the method described herein. In some embodiments, the composition is used in the apparatus described herein.

[0181] Another aspect of the present disclosure relates to a container comprising a composition configured to form a metal-containing film, wherein the composition is At least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu, Equation (I): [ka] (In the formula, R 1 C 1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 Selected from the group including alkyl-substituted aryls, R 2 C1-10 Alkyl, C 3-10 Cycloalkyl, C 1-6 C substituted with alkyl 3-10 Cycloalkyl, aryl, and C 1-6 selected from the group consisting of alkyl-substituted aryl, or R 1 and R 2 together with the phosphorus atom to which they are attached form a saturated or unsaturated 3-, 4-, 5-, 6-, 7-, 8-, 9-, or 10-membered ring, R 3 is H, C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 C substituted with alkyl 3-10 cycloalkyl, aryl, and C 1-6 selected from the group consisting of alkyl-substituted aryl, R 4 is H, C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 C substituted with alkyl 3-10 cycloalkyl, aryl, and C 1-6 selected from the group consisting of alkyl-substituted aryl, R 5 is H, C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 C substituted with alkyl 3-10 cycloalkyl, aryl, and C 1-6 selected from the group consisting of alkyl-substituted aryl, R 6 is H, C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 C substituted with alkyl 3-10 cycloalkyl, aryl, and C 1-6 selected from the group consisting of alkyl-substituted aryl) and at least one ligand, and comprises at least one metal precursor.

[0182] Embodiments of the metal precursor are discussed above.

[0183] The container is configured to store a composition and supply a vapor stream of the composition from the container to an external environment, such as a substrate processing system or semiconductor processing apparatus for forming a metal-containing film. The container is generally formed from a material that is non-reactive to the composition and, in some embodiments, may comply with U.S. Department of Transportation (DOT) regulations such as 49 CFR §178 (2021). In some embodiments, the container is formed from stainless steel (e.g., 316, 316L, 304, or 304L alloy). In various embodiments of the present invention, the configuration of the container may vary depending on the melting point and volatility of the metal precursor and other factors. However, the container generally comprises an outer wall enclosing a cavity for storing the composition and a gas outlet for discharging the vapor of the composition from the cavity. The gas outlet is installed on the outer wall of the vapor delivery container and has at least one valve that communicates with the cavity of the container and is arranged to fluidically connect or disconnect the cavity to the external environment. In some embodiments, the container has one or more other fluid inlets or outlets in addition to the gas outlet. For example, a container may have a fluid inlet on its outer wall that communicates with the container's cavity, and at the inlet may be fitted with at least one valve for filling the container with the composition. Additionally, or alternatively, a container may have a fluid inlet on its outer wall that communicates with the container's cavity, and at the inlet may be fitted with at least one valve for allowing a carrier gas to flow into the container's cavity through the surface of the composition and / or through the composition. Some or all of the valves fitted at various inlets and outlets may be designed to withstand high temperatures (e.g., typically up to 100°C, or 150°C, or 200°C, or 250°C) in order to supply sufficient vapor pressure and / or to withstand temperatures that may be necessary to reduce condensation or solidification of the composition within the valves and other components.

[0184] In some embodiments, the container may further comprise one or more probe members, which may include one or more temperature sensors and / or one or more pressure sensors and / or one or more level sensors or solid sensors. In these embodiments, the container may comprise probe member ports configured such that the probe members can be removably inserted into the cavity of the container. Various sensors for measuring the amount of composition in the cavity of the container are known in the art and include, but are not limited to, capacitive sensors, conductivity sensors, float switch level sensors, tuning fork sensors, ultrasonic sensors, and the like.

[0185] In some embodiments, the container further comprises one or more heat transfer elements, such as fins, rods, or beads, to facilitate heat transfer from the container wall to the film-forming composition within the cavity, or vice versa. One or more heat transfer elements may include a series of pockets or compartments for holding the composition within the cavity. One or more heat transfer elements may form meandering or radial paths for holding the composition within the cavity and, optionally, covering the film-forming composition or directing the flow of a carrier gas through the film-forming composition. Such configurations are particularly useful for delivering vapors of low-volatility liquid and solid compositions.

[0186] In some embodiments, the container is used in the method described herein. In some embodiments, the container is used in the apparatus described herein.

[0187] The subject matter of this disclosure includes all novel and non-obvious combinations and partial combinations of the various processes, apparatus, systems, and configurations disclosed herein, as well as other features, functions, operations, and / or characteristics, and any and all equivalents thereof.

[0188] The examples presented herein are not intended to represent the actual appearance of any particular material, structure, or device, but are merely idealized representations used to illustrate embodiments of the disclosure.

[0189] The specific embodiments illustrated and described are illustrative of the best mode of this disclosure and are not intended to limit the scope of the aspects and embodiments in any way. Furthermore, for the sake of brevity, prior manufacturing, related, preparation, and other functional aspects of the apparatus may not be described in detail. Additionally, the connecting lines shown in various figures are intended to represent illustrative functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships and physical connections may exist in actual apparatuses, although they may not be present in some embodiments.

[0190] It will be understood that the configurations and / or approaches described herein are essentially illustrative, and these particular embodiments or examples should not be considered limiting, as numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various operations illustrated may be performed in the order illustrated, or in other orders, or, in some cases, omitted.

Claims

1. A reaction chamber configured and positioned to hold at least a semiconductor substrate, A metal precursor source constructed and arranged to supply vapor of at least one metal precursor, A precursor distribution system and a removal system configured to supply vapor of the metal precursor from the metal precursor source to the reaction chamber and to remove the vapor of the metal precursor from the reaction chamber, A sequence controller operably connected to the precursor distribution system and removal system, comprising a memory containing a program configured to control the flow of the metal precursor from the metal precursor source to the reaction chamber by operating the precursor distribution system and removal system during one or more cycles, thereby forming a metal-containing layer on the semiconductor substrate in the reaction chamber as a result of the cycle, The at least one metal precursor is At least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu, Equation (I): 【Chemistry 1】 (In formula (I), R １ C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ２ is selected from the group consisting of C １－１０ alkyl, C ３－１０ cycloalkyl, C1- ６ cycloalkyl substituted with alkyl, aryl, and C ３－１０ aryl substituted with alkyl, or １－６ is selected from the group consisting of C R １ and R ２ Together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings. R ３ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ４ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ５ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ６ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ An apparatus comprising at least one ligand (selected from the group including alkyl-substituted aryls).

2. R １ However, C １－６ Alkyl, C ３－６ Cycloalkyl, C １－６ C substituted with alkyl ３－６ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ２ However, C １－６ Alkyl, C ３－６ Cycloalkyl, C １－６ C substituted with alkyl ３－６ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, or R １ and R ２ However, together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings. R ３ However, H, C １－６ Alkyl, C ３－６ Cycloalkyl, C １－６ C substituted with alkyl ３－６ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ４ However, H, C １－６ Alkyl, C ３－６ Cycloalkyl, C １－６ C substituted with alkyl ３－６ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ５ However, H, C １－６ Alkyl, C ３－６ Cycloalkyl, C １－６ C substituted with alkyl ３－６ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ６ However, H, C １－６ Alkyl, C ３－６ Cycloalkyl, C １－６ C substituted with alkyl ３－６ Cycloalkyl, aryl, and C １－６ The apparatus according to claim 1, selected from the group comprising alkyl-substituted aryls.

3. The apparatus according to claim 1, further comprising a reactant source configured and positioned to supply vapor of reactants, wherein the precursor distribution system and removal system are further configured to supply vapor of reactants from the reactant source to the reaction chamber, and the program stored in the memory is configured to control the flow of reactants from the reactant source to the reaction chamber during the one or more cycles.

4. The apparatus according to claim 3, wherein the reactant is selected from the group including oxide reactants, nitride reactants, boride reactants, reducing agents, phosphide reactants, carbide reactants, sulfide reactants, and combinations thereof.

5. The reactant is an oxide reactant, and the oxide reactant is H ２ O, O ２ , O ３ , H ２ O ２ , N ２ O, NO ２ , N ２ O ４、 Pyridine N-oxide and O ２ The apparatus according to claim 3, selected from the group including plasma.

6. where the reactant is a nitride reactant, and the nitride reactant is NH ３ , N ２ H ４ , hydrazine, alkylamine, N ２ plasma, NH ３ plasma, and N ２ / H ２ plasma, and the apparatus according to claim 3, which is selected from the group consisting of

7. The reactant is a boride reactant, and the boride reactant is selected from the group consisting of borazine, BF ３ , BCl ３ , BBr ３ , BI ３ , and borane. The apparatus according to claim 3

8. The reactant is a reducing agent, and the reducing agent is H ２ , H ２ Plasma, N ２ / H ２ Plasma, N ２ H ４ The apparatus according to claim 3, selected from the group comprising hydrazine, formic acid, formalin, borane, silane, and cyclic diene.

9. The apparatus according to claim 3, wherein the reactant is a phosphide reactant, and the phosphide reactant is selected from the group comprising phosphine, phosphorus halogen, phosphorus oxyhalogen, organic phosphate, organic phosphate, aminophosphine, alkylphosphine, and silylphosphine.

10. The apparatus according to claim 3, wherein the reactant is a carbide reactant, and the carbide reactant is selected from the group comprising alkyl iodide, iodobenzene, alkylbromobenzene bromide, acetylene, propargyl chloride, propargyl bromide, propargyl iodide, allyl chloride, allyl bromide, allyl iodide, and cyclic dienes.

11. The reactant is a sulfide reactant, and the sulfide reactant is H ２ S, S ８ S ２ Cl ２ , thiol, dithiol, bis(trimethylsilyl) sulfide, CS ２ The apparatus according to claim 3, selected from the group including and disulfides.

12. The apparatus according to claim 1, wherein the at least one metal precursor comprises one or more further ligands selected from the group comprising cyclopentadienyl ligand, amide ligand, imide ligand, amidinate ligand, halogen ligand, alkyl ligand, alkoxide ligand, diketonate ligand, and 1,4-diazabutadiene ligand.

13. The at least one metal precursor is given by formula (1): 【Chemistry 2】 (In formula (1), R ７ａ H, C １－８ Alkyl and -SiR ９ａ Selected from the group including, in the formula, R ９ａ is C １－６ It is alkyl, R ７ｂ H, C １－８ Alkyl and -SiR ９ｂ Selected from the group including, in the formula, R ９ｂ is C １－６ It is alkyl, R ７ｃ H, C １－８ Alkyl and -SiR ９ｃ Selected from the group including, in the formula, R ９ｃ is C １－６ It is alkyl, R ７ｄ H, C １－８ Alkyl and -SiR ９ｄ Selected from the group including, in the formula, R ９ｄ is C １－６ It is alkyl, R ７ｅ H, C １－８ Alkyl and -SiR ９ｅ Selected from the group including, in the formula, R ９ｅ is C １－６ The apparatus according to claim 1, further comprising one or more cyclopentadienyl ligands (which are alkyl).

14. The at least one metal precursor is given by formula (2): 【Transformation 3】 (In formula (2), R １１ H, C １－８ Alkyl and -SiR １２ Independently selected from the group including, in the formula, R １２ is C １－６ It is alkyl, R １１ａ H, C １－８ Alkyl and -SiR １２ａ Independently selected from the group including, in the formula, R １２ａ is C １－６ It is alkyl, In the formula, R １１ and R １１ａ The apparatus according to claim 1, further comprising one or more amide ligands (at least one of which is not H).

15. The apparatus according to claim 1, wherein the at least one metal precursor comprises only the ligand of formula (I).

16. A method for forming a metal-containing layer on a semiconductor substrate, a) A step of supplying a semiconductor substrate into a reaction chamber, b) A process that performs one or more cycles, where each cycle is A step of performing a metal precursor pulse, wherein at least a portion of the semiconductor substrate comes into contact with at least one metal precursor by introducing at least one metal precursor into the reaction chamber, The at least one metal precursor is At least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu, Equation (I): 【Chemistry 4】 (In formula (I), R １ C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ２ C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, or R １ and R ２ Together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings. R ３ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ４ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ５ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ６ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ It comprises at least one ligand (selected from the group including alkyl-substituted aryls), A method wherein, as a result of the cycle, the metal-containing layer is formed on the semiconductor substrate in the reaction chamber.

17. The method according to claim 16, comprising a periodic deposition process which is part of atomic layer deposition (ALD).

18. The method according to claim 16, wherein at least one cycle further comprises a reactant pulse, and by introducing at least one reactant into the reaction chamber, at least a portion of the semiconductor substrate comes into contact with at least one reactant, the at least one reactant is selected from the group including oxide reactants, nitride reactants, boride reactants, reducing agents, phosphide reactants, carbide reactants, sulfide reactants, and combinations thereof.

19. A semiconductor device structure comprising a metal-containing layer formed according to the method of claim 16.

20. A composition configured to form a metal-containing film, wherein the composition is At least one metal selected from the group including Cr, Mo, W, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, Tl, and Lu, Equation (I): 【Transformation 5】 (In formula (I), R １ C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ２ C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, or R １ and R ２ Together with the phosphorus atoms to which they are bonded, they form saturated or unsaturated 3-membered, 4-membered, 5-membered, 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered rings. R ３ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ４ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ５ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ Selected from the group including alkyl-substituted aryls, R ６ H, C １－１０ Alkyl, C ３－１０ Cycloalkyl, C １－６ C substituted with alkyl ３－１０ Cycloalkyl, aryl, and C １－６ A composition comprising at least one metal precursor, which comprises at least one ligand (selected from the group comprising alkyl-substituted aryls).

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