Phosphonium ylide complexes as precursors for thin layers comprising metal elements

Abstract

Disclosed herein are methods and systems for forming a metal-containing layer on a semiconductor substrate using a metal precursor comprising a phosphonium ylide ligand. Also disclosed are compositions comprising the metal precursor and semiconductor device structures including the metal-containing layer.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Application 63 / 734,087, filed December 14, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure generally relates to the field of semiconductor devices. More specifically, the present invention relates to methods for forming a metal-containing layer on a semiconductor substrate, related devices, and apparatus for manufacturing the same. Background Technology

[0004] Currently, the selection of atomic layer deposition (ALD) and chemical vapor deposition (CVD) precursors for growing films containing certain metallic elements is limited to those containing only a few types of ligands, such as Cp, amidine, β-diketone, dialkylamide, alkoxide, alkyl, etc. Known examples have limitations that make them less than ideal for the growth of the desired layer (film). Limitations include a limited (and often insufficient) range of reactivity, low volatility of Cp and diketone complexes, or low thermal stability in the case of amidine, dialkylamide, alkoxide, and alkyl precursors, and low activation energy decomposition pathways leading to impurities and high resistivity. These drawbacks make the current chemical choices suboptimal for film growth in many applications. In particular, the reactivity of currently available ligands makes materials such as binary metal borides, carbides, and nitrides difficult to achieve.

[0005] In view of the above, there is a need to provide alternatives for precursors containing metallic elements that can overcome some of these drawbacks. Summary of the Invention

[0006] This synopsis is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the following detailed description of exemplary embodiments of this disclosure. This synopsis is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0007] Generally, the technology disclosed herein relates 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 yllide ligand; the metal precursor also comprises a metal element. Besides phosphonium yllides, the precursor may also comprise other common ligands. The metal deposition can be in the form of oxides, nitrides, carbides, borides, sulfides, phosphides, etc. This method is applicable to the fabrication of semiconductor devices.

[0008] The precursors according to the invention have one or more anionic carbon atoms bonded to a metal atom; this carbon-metal bond is highly reactive to many types of proton decomposition reactions, allowing for the easy acquisition of a wide range of binary metal / nonmetal materials, such as oxides, nitrides, carbides, sulfides, borides, phosphides, etc. Therefore, compared to the most well-known methods, the precursors according to the invention offer improved reactivity and also provide improvements in thermal stability, volatility, and the ability to approach difficult-to-find materials such as carbides, borides, and nitrides, making them highly advantageous for use in methods and apparatus for forming metal coatings on semiconductor substrates.

[0009] The advantages of using the precursor according to the invention compared to existing precursors are as follows:

[0010] 1) The precursor of the present invention provides a direct route to metal carbides, which is intended for use in back-to-end (BEOL) barrier / liner applications, since current methods typically do not provide carbon in pure carbide form.

[0011] 2) The precursors of the present invention constitute an alternative to oxides and sulfides, providing these materials with greater thermal stability and potentially improved reactivity.

[0012] 3) The precursors of this invention provide a potential route for preparing borides using diborane, triethylboron, boron trihalide, or other boron-containing co-reactants. Metal borides are challenging compounds to deposit via ALD, and there are very few methods available for obtaining them.

[0013] 4) Using NH3, hydrazine, or alkylhydrazine as co-reactants, the precursors of this invention provide a possible pathway for nitrides. Although known methods exist for these thin layers, the method according to this invention allows for metal-containing layers with better thermal stability and lower resistivity for BEOL applications.

[0014] 5) When the precursor is combined with a suitable reducing agent (e.g., H2, formic acid, formaldehyde, silane, etc.), the precursor of the present invention also provides a novel method for preparing metal-containing layers. Metal-containing layers of metals (e.g., molybdenum and tungsten) according to the present invention have a wide current range, which is highly advantageous for applications such as conductors in logic and memory devices. These metal-containing layers with low impurity levels are typically difficult to achieve without the use of plasma or metal halides because thermal organometallic methods introduce unacceptable levels of nitrogen and carbon impurities; therefore, the method according to the present invention allows for the acquisition of metal-containing layers with low impurity levels.

[0015] 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, thus allowing for the readily available acquisition of a wide range of binary metal / nonmetal materials, such as oxides, nitrides, carbides, sulfides, borides, phosphides, etc. It is also anticipated that, with suitable co-reactants, metal-containing layers can be formed. Furthermore, it is expected that co-reactants and conditions will be found in which the reaction of the precursor produces volatile phosphine or phosphine oxide as a byproduct, causing the breakage of one of the phosphorus-carbon bonds, thereby enabling the formation of a metal carbide layer.

[0016] Therefore, one aspect of this disclosure relates to an apparatus comprising:

[0017] The reaction chamber is constructed and arranged to at least hold the semiconductor substrate;

[0018] A metal precursor source, which is configured and arranged to provide vapor of at least one metal precursor;

[0019] A precursor distribution and removal system configured to supply vapors of metal precursors from a metal precursor source to a reaction chamber and to remove vapors of metal precursors from the reaction chamber; and

[0020] A sequence controller, operably connected to a precursor dispensing and removal system, includes a memory configured to control the flow of a metal precursor from a metal precursor source to a reaction chamber by activating the precursor dispensing and removal system during one or more cycles; thereby, as a result of the cycles, a metal-containing layer is formed on a semiconductor substrate in the reaction chamber.

[0021] At least one metal precursor comprises:

[0022] Selected from at least one of the following metals: 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;

[0023] At least one ligand of formula (I):

[0024] (I),

[0025] in,

[0026] R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0027] R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or

[0028] R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings;

[0029] R 3 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0030] R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0031] R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and

[0032] R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups.

[0033] In certain embodiments, the apparatus as disclosed herein further includes a reactant source configured and arranged to provide vapors of reactants; wherein a precursor distribution and removal system is further configured to provide vapors of reactants from the reactant source to a reaction chamber; and wherein a program stored in a memory is further configured to control the flow of reactants from the reactant source to the reaction chamber during one or more cycles.

[0034] In some embodiments, at least one reactant is selected from oxide reactants, nitride reactants, boride reactants, reducing agents, phosphide reactants, carbide reactants, sulfide reactants, and combinations thereof.

[0035] Another aspect of this disclosure relates to a method for forming a metal-containing layer on a semiconductor substrate, comprising the following steps:

[0036] a) Providing the semiconductor substrate into the reaction chamber;

[0037] b) Execute one or more loops, each loop consisting of:

[0038] Metal precursor pulse, wherein at least a portion of a semiconductor substrate is brought into contact with at least one metal precursor by introducing at least one metal precursor into a reaction chamber;

[0039] At least one metal precursor comprises:

[0040] Selected from at least one of the following metals: 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;

[0041] At least one ligand of formula (I):

[0042] (I),

[0043] in,

[0044] R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0045] R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or

[0046] R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings;

[0047] R 3Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0048] R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0049] R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and

[0050] R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups,

[0051] As a result of the cycle, a metal-containing layer is formed on the semiconductor substrate in the reaction chamber.

[0052] In some embodiments, at least one cycle further includes a reactant pulse, wherein at least a portion of the semiconductor substrate is contacted with the at least one reactant by introducing the at least one reactant into the reaction chamber; wherein the at least one reactant is selected from oxide reactants, nitride reactants, boride reactants, reducing agents, phosphide reactants, carbide reactants, sulfide reactants, and combinations thereof.

[0053] Another aspect of this disclosure relates to a semiconductor device structure. The semiconductor device structure according to the invention includes a metal-containing layer formed according to the method disclosed above.

[0054] Another aspect of this disclosure relates to a composition configured for forming a metal-containing film, the composition comprising a metal precursor as disclosed herein.

[0055] Another aspect of this disclosure relates to a container comprising a composition configured for forming a metal-containing film, the container comprising a composition containing a metal precursor as disclosed herein.

[0056] An overview of various other aspects of the technology disclosed herein is provided below, followed by a detailed description of specific embodiments. It should be understood that the foregoing objects and advantages also apply to various other aspects and features disclosed herein. Attached Figure Description

[0057] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated relative to other elements to aid in understanding the embodiments shown in this disclosure.

[0058] Figure 1 An exemplary embodiment of a method 100 for forming a metal layer on a semiconductor substrate, as disclosed herein, is illustrated schematically.

[0059] Figure 2 A device 600 according to another exemplary embodiment of the present disclosure is illustrated schematically. Detailed Implementation

[0060] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that this disclosure extends beyond the specific embodiments and / or uses disclosed herein, as well as their obvious modifications and equivalents. Therefore, it is intended that the scope of this disclosure should not be limited to the specific disclosed embodiments described below.

[0061] In the following detailed description, the technology upon which this disclosure is based will be described through various aspects of this disclosure. It will be readily understood that the aspects of this disclosure, as generally described herein and illustrated in the accompanying drawings, can be arranged, substituted, combined, and designed in a variety of different configurations, all of which are clearly contemplated and form part of this disclosure. This description is intended to assist the reader in a more readily understanding of 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 is to be considered illustrative in nature, not restrictive.

[0062] Throughout this specification, the reference to "an embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of this disclosure. Therefore, the phrases "in an embodiment" or "in one embodiment" appearing in various places throughout this specification do not necessarily refer to the same embodiment.

[0063] As used herein, the term "comprising" is synonymous with "including" or "containing" and is inclusive or open-ended, and does not exclude additional, unlisted members, elements, or method steps. When referring to listed members, elements, or method steps, the term "comprising" also includes embodiments that "consist of the listed members, elements, or method steps."

[0064] Unless the context clearly indicates otherwise, the singular forms “a,” “one,” and “the” include both singular and plural indicators.

[0065] The objects described in this document as “connected” or “linked” reflect the functional relationship between the objects being described. That is, the term indicates that the objects being described must be connected in a way that performs a specified function, which may be a direct or indirect connection, either electrical or non-electrical (i.e., physical), as appropriate for the use of the term.

[0066] As used herein, the term "basic" refers to the complete or near-complete extent or degree of an action, characteristic, property, state, structure, item, or result. For example, a "basic" closed object would mean that the object is completely or almost completely closed. In some cases, the exact permissible deviation from absolute completeness may depend on the specific circumstances. However, in general, near-completeness will have the same overall result as if absolute and completeness were achieved. When used negatively, the term "basic" is equally applicable to referring to the complete or near-complete absence of an action, characteristic, property, state, structure, item, or result.

[0067] As used herein, the term “about” is used to provide flexibility for the endpoints of a numerical value or range by specifying that a given value may be “slightly higher” or “slightly lower” depending on the specific circumstances. Unless otherwise stated, the use of the term “about” in relation to a particular number or range of numbers should also be understood to support such numerical terms or ranges for which the term “about” is not used. For example, the statement “about 30” should be interpreted as supporting not only values ​​slightly higher and slightly lower than 30, but also the actual value of 30.

[0068] The description of a numerical range by endpoints includes all integers and, where appropriate, fractions contained within that range (e.g., when referring to the quantity of, for example, elements, 1 to 5 may include 1, 2, 3, 4, and when referring to, for example, measures, may also include 1.5, 2, 2.75, and 3.80). This applies to numerical ranges, whether they are introduced by expressing "from…to…" or "between…and…" or other expressions. The description of endpoints also includes the endpoint values ​​themselves (e.g., 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range described herein is intended to include all subranges contained therein. Furthermore, unless otherwise stated, the terms first, second, third, etc., in the specification and claims are used to distinguish similar elements and are not necessarily used to describe an order or chronological order. It should be understood that the terms thus used are interchangeable where appropriate, and embodiments of this disclosure described herein can operate in orders other than those described or shown herein.

[0069] Reference may be made in this specification to devices, structures, apparatuses, systems, or methods that provide "improved" performance (e.g., increasing or decreasing results depending on the circumstances). It should be understood that, unless otherwise stated, such "improvement" is a measure of benefit obtained based on comparison with prior art devices, structures, apparatuses, systems, or methods. Furthermore, it should be understood that the degree of improved performance may vary among the disclosed embodiments, and the quantity, extent, or equivalence or consistency of the improved performance is not considered universally applicable.

[0070] In this disclosure, "gas" can include materials that are gaseous at normal temperature and pressure (NTP), evaporated solids and / or evaporated liquids, and may consist of a single gas or a mixture of gases, depending on the circumstances. Gases other than process gases, i.e., gases not introduced through gas distribution components, other gas distribution devices, etc., may be used, for example, to seal the reaction space, and may include sealing gases, such as rare gases.

[0071] In some cases, the term "precursor" can refer to a compound that participates in a chemical reaction that produces another compound, particularly a compound that forms a metal-layered matrix or a metal-layered backbone.

[0072] This specification describes techniques relating to methods and apparatus for fabricating metal-containing layers on semiconductor substrates. The inventors have surprisingly observed that precursors comprising phosphonium ylridinium ligands and metallic elements can be readily used to form metal-containing layers on semiconductor substrates. Advantageously, the precursors according to this specification exhibit high reactivity to many types of proton decomposition reactions, thereby allowing a wide variety of binary metal / nonmetal materials to be readily used to form metal-containing layers on semiconductor substrates.

[0073] Therefore, one aspect of this disclosure relates to an apparatus comprising:

[0074] The reaction chamber is constructed and arranged to at least hold the semiconductor substrate;

[0075] A metal precursor source, which is configured and arranged to provide vapor of at least one metal precursor;

[0076] A precursor distribution and removal system configured to supply vapors of metal precursors from a metal precursor source to a reaction chamber and to remove vapors of metal precursors from the reaction chamber; and

[0077] A sequence controller, operably connected to a precursor dispensing and removal system, includes a memory configured to control the flow of a metal precursor from a metal precursor source to a reaction chamber by activating the precursor dispensing and removal system during one or more cycles; thereby, as a result of the cycles, a metal-containing layer is formed on a semiconductor substrate in the reaction chamber.

[0078] At least one metal precursor comprises:

[0079] Selected from at least one of the following metals: 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;

[0080] At least one ligand of formula (I):

[0081] (I),

[0082] in,

[0083] R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0084] R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or

[0085] R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings;

[0086] R 3 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0087] R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0088] R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and

[0089] R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups.

[0090] As used herein, the term "substrate" can refer to any one or more underlying materials on which devices, circuits, or metal layers (films) can be formed or on which they are formed. A "substrate" can be continuous or discontinuous; rigid or flexible; solid or porous; and combinations thereof. A substrate can be in any form, such as powder, plate, or workpiece. Plate-type substrates can include wafers of various shapes and sizes. A substrate can include bulk materials (such as silicon (e.g., single-crystal silicon)), other group IV materials (e.g., germanium), or other semiconductor materials (e.g., group II-VI or III-V semiconductor materials), and may contain one or more layers overlying or underlying the bulk material. Furthermore, the substrate may include various features formed within or on at least a portion of the substrate layers, such as recesses, protrusions, etc.

[0091] Examples of suitable substrates include wafers, such as silicon, silicon dioxide, glass, or GaAs wafers. Wafers can have one or more different materials deposited thereon from previous manufacturing steps. For example, wafers may include silicon layers (crystalline, amorphous, porous, etc.), silicon oxide layers, silicon nitride layers, silicon oxynitride layers, carbon-doped silicon oxide (SiCOH) layers, or combinations thereof. Additionally, wafers may include copper layers or noble metal layers (e.g., platinum, palladium, rhodium, or gold). Wafers may include barrier layers, such as manganese, manganese oxide, etc. Plastic layers, such as poly(3,4-ethylenedioxythiophene)poly(styrene sulfonate), may also be used. These layers can be planar or patterned.

[0092] In certain embodiments, the substrate may include silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, or silicon carbide (as a bulk semiconductor material).

[0093] As used interchangeably herein, “film” or “layer” refers to a material extending in a direction perpendicular to the thickness direction to cover the entire target or related surface, or simply a layer covering the target or related surface. In certain embodiments, a film or layer refers to a structure or membrane or non-film structure of a certain thickness formed on a surface. A layer may comprise a continuous or discontinuous structure or material, such as a material deposited according to the present technology. A film or layer may consist of discrete single films or layers or multiple films or layers having certain properties, and the boundaries between adjacent films or layers may or may not be clear, and may or may not be based on the physical, chemical and / or any other properties, formation process or sequence and / or function or purpose of adjacent films or layers.

[0094] For example, films and / or layers may include two-dimensional materials, three-dimensional materials, nanoparticles, or even partial or complete molecular layers or partial or complete atomic layers or atomic and / or molecular clusters, or layers composed of separate atoms and / or molecules. Films or layers may include materials or layers with pinholes, which may be continuous or discontinuous.

[0095] Throughout this specification, references to substituents are intended to indicate that one or more hydrogen atoms on an atom indicated by "substitution" are replaced with a selection from the specified group detailed below, provided that the substitution does not exceed the normal valence of the specified atom, and that the substitution produces a chemically stable compound, i.e., a compound sufficiently robust to withstand separation from the reaction mixture.

[0096] The term "alkyl" as a group or part of a group refers to the formula C n H 2n+1 The alkyl group is a hydrocarbon group, where n is a number greater than or equal to 1. The alkyl group can be straight-chain or branched and can be substituted as shown herein. Typically, the alkyl groups of this disclosure contain 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. When a subscript is used herein following a carbon atom, the subscript indicates the number of carbon atoms that the named group may contain. For example, the term "C 1-10 "Alkyl", as a group or part of a group, refers to the formula -C n H 2n+1 The hydrocarbon group, where n is a number from 1 to 10. Therefore, for example, "C 1-8 "Alkyl" includes all straight-chain or branched alkyl groups having between 1 and 8 carbon atoms, and therefore includes methyl ("Me"), ethyl ("Et"), n-propyl ("nPr"), isopropyl ("iPr"), butyl and its isomers (e.g., n-butyl, isobutyl, and tert-butyl); pentyl and its isomers, hexyl and its isomers, etc. "Substituted alkyl" means an alkyl group that is substituted at any available attachment point with one or more substituents (e.g., 1 to 3 substituents, such as 1, 2, or 3 substituents).

[0097] Term "C" 1-6 "Alkoxy", as a group or part of a group, refers to a group having the formula -OR b The group, wherein R b It is C as defined above. 1-6 Alkyl group. Suitable C 1-6 Non-limiting examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, and hexoxy.

[0098] The term "cycloalkyl," as a group or part of a group, refers to a cycloalkyl group, i.e., a monovalent saturated hydrocarbon group having one or more ring structures and containing 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms; even more preferably 3 to 6 carbon atoms. Cycloalkyl includes all saturated hydrocarbon groups containing one or more rings, including monocyclic, bicyclic, or tricyclic groups. Other rings in polycyclic cycloalkyl groups may be fused, bridged, and / or linked by one or more spiro atoms. When a subscript is used herein following a carbon atom, the subscript indicates the number of carbon atoms that the named group may contain. For example, the term "C 3-10 "Cycloalkyl" is a cyclic alkyl group containing 3 to 10 carbon atoms. For example, the term "C 3-8 "Cycloalkyl" is a cyclic alkyl group containing 3 to 8 carbon atoms. For example, the term "C 3-6 "Cycloalkyl" is 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]hept-2-yl, (1S,4R)-norcamphen-2-yl, (1R,4R)-norcamphen-2-yl, (1S,4S)-norcamphen-2-yl, and (1R,4S)-norcamphen-2-yl.

[0099] The term "aryl," as a group or part of a group, refers to a polyunsaturated aromatic hydrocarbon group having multiple aromatic rings that are monocyclic (i.e., phenyl), fused together (e.g., naphthyl), or covalently linked, typically containing 6 to 12 carbon atoms, wherein at least one ring is aromatic. The aromatic ring may optionally include one or two additional rings (cycloalkyl, heterocyclic, or heteroaryl) fused with it. Examples of suitable aryl groups include C... 6-10 Aryl, more preferably C 6-8Aryl. Non-limiting examples of aryl include phenyl, biphenyl, biphenylene, or 1- or 2-naphthyl; 1-, 2-, 3-, 4-, 5-, or 6-tetrahydronaphthyl (also known as "1,2,3,4-tetrahydronaphthyl"); 1-, 2-, 3-, 4-, 5-, 6-, 7-, or 8-chamomilecycloyl; 4-, 5-, 6-, or 7-indenyl; 4- or 5-indenyl; 5-, 6-, 7-, or 8-tetrahydronaphthyl; 1,2, 3,4-tetrahydronaphthyl; and 1,4-dihydronaphthyl; 1-, 2-, 3-, 4-, or 5-pyrene. "Substituted aryl" means an aryl group having one or more substituents (e.g., 1, 2, or 3 substituents, or 1 to 2 substituents) at any available attachment site.

[0100] The terms "heterocyclic group," "heterocyclic alkyl group," or "heterocycle," as a group or part of a group, refer to a non-aromatic, fully saturated, or partially unsaturated cyclic group (e.g., a 3- to 7-membered monocyclic ring, a 7- to 11-membered bicyclic ring, or containing a total of 3 to 10 ring atoms) having at least one heteroatom in at least one carbon-containing ring; wherein said ring may be fused with an aryl, cycloalkyl, heteroaryl, or heterocyclic ring. Each ring of the heterocyclic group containing heteroatoms may have 1, 2, 3, or 4 heteroatoms selected from N, O, and / or S, wherein N and S heteroatoms may optionally be oxidized and N heteroatoms may optionally be quaternized; and wherein at least one carbon atom of the heterocyclic group may be oxidized to form at least one C=O. Where valence permits, the heterocyclic group may be attached to any heteroatom or carbon atom of the ring or ring system. The rings of polycyclic heterocycles may be fused, bridged, and / or linked by one or more spiro atoms.

[0101] Non-limiting exemplary heterocyclic groups include aziridinyl, ethylene oxide, thiocyclopropane, piperidinyl, aziridine, oxacyclobutane, pyrrolyl, thiocyclobutane, 2-imidazolinyl, pyrazolyl, imidazolinyl, isoxazolinyl, oxazolyl, isoxazolyl, thiazolinyl, isothiazolyl, succinimide, 3H-indolyl, dihydroindolyl, isodihydroindolyl, chromanyl (also known as 3,4-dihydrobenzo[b]pyranyl), 2H-pyrrolyl, 1-pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, 4H-quinazinyl, 2-oxopiperazinyl, piperazinyl, homopiperazinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydro-2H-pyranyl, 2H-pyranyl, 4H-pyranyl, 3 ,4-Dihydro-2H-pyranyl, 3-dioxopentyl, 1,4-dioxacyclohexyl, 2,5-dioxaimidazyl, 2-oxopiperidinyl, 2-oxopiperylyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopheneyl, tetrahydroquinolinyl, tetrahydroisoquinolin-1-yl, tetrahydroisoquinolin-2-yl, tetrahydroisoquinolin-3-yl, tetrahydroisoquinolin-4-yl, tetrahydroisoquinolin-4-yl, thiomorpholin-4-yl, thiomorpholin-4-yl sulfoxide, thiomorpholin-4-yl sulfone, 1,3-dioxopentyl, 1,4-oxothiocyclohexyl, 1,4-dithiaalkyl, 1,3,5-trioxacyclohexyl, 1H-pyrrolazinyl, tetrahydro-1,1-dioxothiopheneyl, N-formylpiperazinyl, and morpholin-4-yl. As used herein, the term "aziridinyl" includes aziridin-1-yl and aziridin-2-yl. As used herein, the term "ethylene oxide" includes ethylene oxide-2-yl. As used herein, the term "thiapropylcycloyl" includes thiapropylcycloyl-2-yl. As used herein, the term "azircyclobutane" includes azircyclobutane-1-yl, azircyclobutane-2-yl, and azircyclobutane-3-yl. As used herein, the term "oxacyclobutane" includes oxacyclobutane-2-yl and oxacyclobutane-3-yl. As used herein, the term "thiacyclobutane" includes thiacyclobutane-2-yl and thiacyclobutane-3-yl. As used herein, the term "pyrrolidinyl" includes pyrrolidin-1-yl, pyrrolidin-2-yl, and pyrrolidin-3-yl. As used herein, the term "tetrahydrofuranyl" includes tetrahydrofuran-2-yl and tetrahydrofuran-3-yl. As used herein, the term "tetrahydrothiophene" includes tetrahydrothiophene-2-yl and tetrahydrothiophene-3-yl. As used herein, the term "succinimide" includes succinimide-1-yl and succinimide-3-yl. As used herein, the term "dihydropyrrole" 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-pyrrole" includes 2H-pyrrole-2-yl, 2H-pyrrole-3-yl, 2H-pyrrole-4-yl, and 2H-pyrrole-5-yl. As used herein, the term "3H-pyrrole" 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 "dihydrothiophene" includes 2,3-dihydrothiophene-2-yl, 2,3-dihydrothiophene-3-yl, 2,3-dihydrothiophene-4-yl, 2,3-dihydrothiophene-5-yl, 2,5-dihydrothiophene-2-yl, 2,5-dihydrothiophene-3-yl, 2,5-dihydrothiophene-4-yl, and 2,5-dihydrothiophene-5-yl. As used herein, the term "imidazolidinyl" includes imidazolin-1-yl, imidazolin-2-yl, and imidazolin-4-yl. As used herein, the term "pyrazolylyl" includes pyrazollin-1-yl, pyrazollin-3-yl, and pyrazollin-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 "dioxolaneyl" (also known as "1,3-dioxolaneyl") includes dioxolane-2-yl, dioxolane-4-yl, and dioxolane-5-yl. As used herein, the term "dioxacyclopentenyl" (also known as "1,3-dioxacyclopentenyl") includes dioxacyclopenten-2-yl, dioxacyclopenten-4-yl, and dioxacyclopenten-5-yl. As used herein, the term "oxazolidinyl" includes oxazolidin-2-yl, oxazolidin-3-yl, oxazolidin-4-yl, and oxazolidin-5-yl. The term "isooxazolidinyl" as used herein includes isoxazolidin-2-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, and isoxazolidin-5-yl. The term "azolinyl" as used herein includes 2-azolinyl-2-yl, 2-azolinyl-4-yl, 2-azolinyl-5-yl, 3-azolinyl-2-yl, 3-azolinyl-4-yl, 3-azolinyl-5-yl, 4-azolinyl-2-yl, 4-azolinyl-3-yl, 4-azolinyl-4-yl, and 4-azolinyl-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 "thiazolinyl" includes thiazolinyl-2-yl, thiazolinyl-3-yl, thiazolinyl-4-yl, and thiazolinyl-5-yl. As used herein, the term "isothiazolinyl" includes isothiazolyl-2-yl, isothiazolyl-3-yl, isothiazolyl-4-yl, and isothiazolyl-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-isothiazolin-3-yl, 2-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-3-yl, 3-isothiazolin-4-yl, 3-isothiazolin-5-yl, 4-isothiazolin-2-yl, 4-isothiazolin-3-yl, 4-isothiazolin-4-yl, and 4-isothiazolin-5-yl. As used herein, the term "piperidinyl" is also called "piperidinyl" and includes piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, and piperidin-4-yl. As used herein, the term "dihydropyridyl" includes 1,2-dihydropyridin-1-yl, 1,2-dihydropyridin-2-yl, 1,2-dihydropyridin-3-yl, 1,2-dihydropyridin-4-yl, 1,2-dihydropyridin-5-yl, 1,2-dihydropyridin-6-yl, 1,4-dihydropyridin-1-yl, 1,4-dihydropyridin-2-yl, 1,4-dihydropyridin-3-yl, 1,4-dihydropyridin-4-yl, 2,3-dihydropyridin-2-yl, 2,3-dihydropyridin-3-yl 2,3-Dihydropyridin-4-yl, 2,3-Dihydropyridin-5-yl, 2,3-Dihydropyridin-6-yl, 2,5-Dihydropyridin-2-yl, 2,5-Dihydropyridin-3-yl, 2,5-Dihydropyridin-4-yl, 2,5-Dihydropyridin-5-yl, 2,5-Dihydropyridin-6-yl, 3,4-Dihydropyridin-2-yl, 3,4-Dihydropyridin-3-yl, 3,4-Dihydropyridin-4-yl, 3,4-Dihydropyridin-5-yl and 3,4-Dihydropyridin-6-yl.As used herein, the term "tetrahydropyridyl" includes 1,2,3,4-tetrahydropyridin-1-yl, 1,2,3,4-tetrahydropyridin-2-yl, 1,2,3,4-tetrahydropyridin-3-yl, 1,2,3,4-tetrahydropyridin-4-yl, 1,2,3,4-tetrahydropyridin-5-yl, 1,2,3,4-tetrahydropyridin-6-yl, 1,2,3,6-tetrahydropyridin-1-yl, and 1,2,3,6-tetrahydropyridin-2-yl. 1,2,3,6-Tetrahydropyridin-3-yl, 1,2,3,6-Tetrahydropyridin-4-yl, 1,2,3,6-Tetrahydropyridin-5-yl, 1,2,3,6-Tetrahydropyridin-6-yl, 2,3,4,5-Tetrahydropyridin-2-yl, 2,3,4,5-Tetrahydropyridin-3-yl, 2,3,4,5-Tetrahydropyridin-4-yl, 2,3,4,5-Tetrahydropyridin-5-yl, and 2,3,4,5-Tetrahydropyridin-6-yl. The term "tetrahydropyranyl" (also known as "oxacyclohexyl" 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-6-yl. As used herein, the term "3,6-dihydro-2H-pyranyl" includes 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, tetrahydrothiophen-3-yl, and tetrahydrothiophen-4-yl. As used herein, the term "2H-thiaranyl" includes 2H-thiaran-2-yl, 2H-thiaran-3-yl, 2H-thiaran-4-yl, 2H-thiaran-5-yl, and 2H-thiaran-6-yl. As used herein, the term "4H-thiaranyl" includes 4H-thiaran-2-yl, 4H-thiaran-3-yl, and 4H-thiaran-4-yl. As used herein, the term "3,4-dihydro-2H-thiaranyl" includes 3,4-dihydro-2H-thiaran-2-yl, 3,4-dihydro-2H-thiaran-3-yl, 3,4-dihydro-2H-thiaran-4-yl, 3,4-dihydro-2H-thiaran-5-yl, and 3,4-dihydro-2H-thiaran-6-yl.As used herein, the term "3,6-dihydro-2H-thiaranyl" includes 3,6-dihydro-2H-thiaran-2-yl, 3,6-dihydro-2H-thiaran-3-yl, 3,6-dihydro-2H-thiaran-4-yl, 3,6-dihydro-2H-thiaran-5-yl, and 3,6-dihydro-2H-thiaran-6-yl. As used herein, the term "piperazinyl" includes piperazin-1-yl and piperazin-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 "dioxane-hexyl" includes 1,2-dioxane-3-yl, 1,2-dioxane-4-yl, 1,3-dioxane-2-yl, 1,3-dioxane-4-yl, 1,3-dioxane-5-yl, and 1,4-dioxane-2-yl. As used herein, the term "dithiaalkyl" includes 1,2-dithiaalkyl-3-yl, 1,2-dithiaalkyl-4-yl, 1,3-dithiaalkyl-2-yl, 1,3-dithiaalkyl-4-yl, 1,3-dithiaalkyl-5-yl, and 1,4-dithiaalkyl-2-yl. As used herein, the term "oxothiacyclohexyl" includes oxothiacyclohexyl-2-yl and oxothiacyclohexyl-3-yl. As used herein, the term "trioxanehexyl" includes 1,2,3-trioxane-4-yl, 1,2,3-trioxane-5-yl, 1,2,4-trioxane-3-yl, 1,2,4-trioxane-5-yl, 1,2,4-trioxane-6-yl, and 1,3,4-trioxane-2-yl. As used herein, the term "azircycloheptyl" includes azircycloheptane-1-yl, azircycloheptane-2-yl, azircycloheptane-3-yl, and azircycloheptane-4-yl. As used herein, the term "homoperazinyl" includes holoperazin-1-yl, holoperazin-2-yl, holoperazin-3-yl, and holoperazin-4-yl. As used herein, the term "dihydroindolyl" includes dihydroindol-1-yl, dihydroindol-2-yl, dihydroindol-3-yl, dihydroindol-4-yl, dihydroindol-5-yl, dihydroindol-6-yl, and dihydroindol-7-yl. As used herein, the term "quinazinyl" includes quinazinalkyl-1-yl, quinazinalkyl-2-yl, quinazinalkyl-3-yl, and quinazinalkyl-4-yl. As used herein, the term "isoindololinyl" includes isoindololin-1-yl, isoindololin-2-yl, isoindololin-3-yl, isoindololin-4-yl, isoindololin-5-yl, isoindololin-6-yl, and isoindololin-7-yl. As used herein, the term "3H-indolyl" includes 3H-indolyl-2-yl, 3H-indolyl-3-yl, 3H-indolyl-4-yl, 3H-indolyl-5-yl, 3H-indolyl-6-yl, and 3H-indolyl-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. Similarly, the term "tetrahydroisoquinolinyl" as used herein 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 "benzodihydropyranyl" includes benzodihydropyran-2-yl, benzodihydropyran-3-yl, benzodihydropyran-4-yl, benzodihydropyran-5-yl, benzodihydropyran-6-yl, benzodihydropyran-7-yl, and benzodihydropyran-8-yl. As used herein, the term "1H-pyrrolizine" includes 1H-pyrrolizine-1-yl, 1H-pyrrolizine-2-yl, 1H-pyrrolizine-3-yl, 1H-pyrrolizine-5-yl, 1H-pyrrolizine-6-yl, and 1H-pyrrolizine-7-yl. As used herein, the term "3H-pyrrolizine" includes 3H-pyrrolizine-1-yl, 3H-pyrrolizine-2-yl, 3H-pyrrolizine-3-yl, 3H-pyrrolizine-5-yl, 3H-pyrrolizine-6-yl, and 3H-pyrrolizine-7-yl.

[0102] The term "heteroaryl" as a group or part of a group refers to, but is not limited to, an aromatic ring of 5 to 12 carbon atoms or a ring system containing one or two rings that may be fused together or covalently linked, typically containing 5 to 6 atoms; at least one of which is aromatic, wherein one or more carbon atoms in one or more of these rings may be replaced by N, O, and / or S atoms, wherein the N and S heteroatoms may optionally be oxidized and the N heteroatomium may optionally be quaternized, and wherein at least one carbon atom of the heteroaryl group may be oxidized to form at least one C=O. Such a ring may be fused with aryl, cycloalkyl, heteroaryl, or heterocyclic rings. Non-limiting examples of such heteroaryl groups include: pyrrole, furanyl, thiophene, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiazolyl, tetrazolyl, oxtriazolyl, thiazolyl, pyridinyl, pyrazinyl, pyridazinyl, oxazinyl, dioxazeneyl, thiazolyl, triazinyl, imidazo[2,1-b][1,3]thiazolyl, thiophene[3,2-b]furanyl Brønsyl, thieno[3,2-b]thienoyl, thieno[2,3-d][1,3]thiazolyl, thieno[2,3-d]imidazolyl, tetrazo[1,5-a]pyridyl, indole, indazinyl, isoindole, benzofuranyl, isobenzofuranyl, benzothienoyl, isobenzothienoyl, indazole, benzimidazolyl, 1,3-benzoxazolyl, 1,2-benzoisoxazolyl, 2,1-benzoisoxazolyl, 1,3 -Benzothiazolyl, 1,2-Benzisothiazolyl, 2,1-Benzisothiazolyl, benzotriazolyl, 1,2,3-Benzoxadiazolyl, 1,2,3-Benzothiadiazolyl, 2,1,3-Benzothiadiazolyl, benzo[d]azole-2(3H)-one, 2,3-dihydro-benzofuranyl, thienopyridyl, purine, imidazo[1,2-a]pyridyl, 6-oxo-pyridazin-1(6H)-yl, 2-oxo The heteroaryl group is selected from pyridinyl-1(2H)-yl, 1,3-benzodioxacyclopentenyl, quinolinyl, isoquinolinyl, cyclopentenyl, quinazolinyl, and quinoxalinyl; preferably, the heteroaryl group is selected from pyridinyl, 1,3-benzodioxacyclopentenyl, benzo[d]azole-2(3H)-one, 2,3-dihydro-benzofuranyl, pyrazinyl, pyrazolyl, pyrroleyl, isoxazolyl, thiophenyl, imidazoyl, benzimidazolyl, pyrimidinyl, triazolyl, and thiazolyl.

[0103] As a group or part of a group, the term "monoc, di, or tric" 1-6 "alkylamino" refers to the formula N(R) o (R) p (R) q ) groups, wherein R o R p and R q Each is independently selected from hydrogen or C. 1-6 Alkyl, wherein Ro R p or R q At least one of them is C 1-6 Alkyl. Therefore, alkylamino groups include monoalkylamino groups (e.g., mono-C). 1-6 Alkylamino, such as methylamino and ethylamino), dialkylamino (e.g., di-C) 1-6 Alkylamino groups, such as dimethylamino and diethylamino, and trialkylamino groups, such as tri-C 1-6 Alkylamino groups, such as trimethylamino and triethylamino. Suitable mono-, di-, and tri-C... 1-6 Non-limiting examples of alkylamino groups include n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, tert-butylamino, pentylamino, n-hexylamino, di-n-propylamino, diisopropylamino, ethylmethylamino, methyl-n-propylamino, methyl isopropylamino, n-butylmethylamino, isobutylmethylamino, tert-butylmethylamino, ethyl-n-propylamino, ethyl isopropylamino, n-butylethylamino, isobutylethylamino, tert-butylethylamino, di-n-butylamino, diisobutylamino, methylpentylamino, methylhexylamino, ethylpentylamino, ethylhexylamino, propylpentylamino, propylhexylamino, trimethylamino, triethylamino, tri-n-propylamino, triisopropylamino, tri-n-butylamino, triisobutylamino, etc.

[0104] In some embodiments, the apparatus may further include a reactant source configured and arranged to provide vapors of reactants; wherein a precursor distribution and removal system is further configured to provide vapors of reactants from the reactant source to a reaction chamber; wherein a program stored in a memory is further configured to control the flow of reactants from the reactant source to the reaction chamber during one or more cycles.

[0105] In some embodiments, one or more metal precursors and / or one or more optional reactants are supplied from a temperature-controlled container to a reaction chamber. In some embodiments, the temperature-controlled container is configured to cool the precursors and / or optional reactants.

[0106] In some embodiments, the reactants are selected from oxide reactants, nitride reactants, boride reactants, reducing agents, phosphide reactants, carbide reactants, sulfide reactants, and combinations thereof.

[0107] In some embodiments, the reactants are oxide reactants, wherein the oxide reactants are selected from H2O, O2, O3, H2O2, N2O, NO2, N2O4, pyridine N-oxide, and O2 plasma.

[0108] As used in this article, oxide reactants are reagents that can produce metal oxides when in contact with metal precursors.

[0109] In some embodiments, the reactants are nitride reactants, wherein the nitride reactants are selected from NH3, N2H4, hydrazine, alkylamine, N2 plasma, NH3 plasma and N2 / H2 plasma.

[0110] As used in this article, nitride reactants are reagents that can produce metal nitrides when in contact with metal precursors.

[0111] A suitable example of hydrazine is formula The compounds, in which,

[0112] R 24 Selected from H, C 1-8 Alkyl, C 3-10 cycloalkyl and aryl; preferably, R 24 Selected from H, C 1-6 Alkyl and aryl; preferably, R 24 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, cyclopentyl, cyclohexyl, phenyl, and naphthyl;

[0113] R 25 Selected from H, C 1-8 Alkyl, C 3-10 cycloalkyl and aryl; preferably, R 25 Selected from H, C 1-6 Alkyl and aryl; preferably, R 25 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, cyclopentyl, cyclohexyl, phenyl, and naphthyl;

[0114] R 26 Selected from H, C 1-8 Alkyl, C 3-10 cycloalkyl and aryl; preferably, R 26 Selected from H, C 1-6 Alkyl and aryl; preferably, R 26 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, cyclopentyl, cyclohexyl, phenyl, and naphthyl;

[0115] R 27 Selected from H, C 1-8 Alkyl, C 3-10 cycloalkyl and aryl; preferably, R 27 Selected from H, C 1-6 Alkyl and aryl; preferably, R 27 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, cyclopentyl, cyclohexyl, phenyl, and naphthyl.

[0116] Other non-limiting examples of suitable hydrazines include tert-butylhydrazine, 1,1-dimethylhydrazine, methylhydrazine, and phenylhydrazine.

[0117] A suitable example of an alkylamine is the formula... The compounds, in which,

[0118] R 28 It is C 1-8 Alkyl; preferably, R 28 It is C 1-6 Alkyl; preferably, R 28 It is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl.

[0119] R 28a Is it H or C? 1-8 Alkyl; preferably, R 28a Is it H or C? 1-6 Alkyl; preferably, R 28a Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl.

[0120] Other non-limiting examples of suitable alkylamines include tert-butylamine, isobutylamine, and tert-amylamine.

[0121] In some embodiments, the reactants are boride reactants, wherein the boride reactants are selected from BF3, BCl3, BBr3, BI3, boranes, and formulas... The compounds, in which,

[0122] R 50 Selected from halogens, C 1-8 Alkyl and aryl; preferably, R 50 Selected from halogens, C 1-6 Alkyl and aryl; preferably, R 50 Selected from halogens, C 1-4 Alkyl and aryl; preferably, R 50 Selected from F, Cl, Br, I, C 1-6 Alkyl and phenyl; preferably, R 50 Selected from F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and phenyl;

[0123] R 51 Selected from halogens, C 1-8 Alkyl and aryl; preferably, R 51 Selected from halogens, C 1-6 Alkyl and aryl; preferably, R51 Selected from halogens, C 1-4 Alkyl and aryl; preferably, R 51 Selected from F, Cl, Br, I, C 1-6 Alkyl and phenyl; preferably, R 51 Selected from F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and phenyl;

[0124] R 52 Selected from halogens, C 1-8 Alkyl and aryl; preferably, R 52 Selected from halogens, C 1-6 Alkyl and aryl; preferably, R 52 Selected from halogens, C 1-4 Alkyl and aryl; preferably, R 52 Selected from F, Cl, Br, I, C 1-6 Alkyl and phenyl; preferably, R 52 Selected from F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and phenyl;

[0125] R 53 Selected from halogens, C 1-8 Alkyl and aryl; preferably, R 53 Selected from halogens, C 1-6 Alkyl and aryl; preferably, R 53 Selected from halogens, C 1-4 Alkyl and aryl; preferably, R 53 Selected from F, Cl, Br, I, C 1-6 Alkyl and phenyl; preferably, R 53 Selected from F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and phenyl;

[0126] R 54 Selected from halogens, C 1-8 Alkyl and aryl; preferably, R 54 Selected from halogens, C 1-6 Alkyl and aryl; preferably, R 54 Selected from halogens, C 1-4 Alkyl and aryl; preferably, R 54 Selected from F, Cl, Br, I, C 1-6 Alkyl and phenyl; preferably, R 54 Selected from F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and phenyl; and

[0127] R 55 Selected from halogens, C 1-8 Alkyl and aryl; preferably, R 55 Selected from halogens, C 1-6 Alkyl and aryl; preferably, R 55 Selected from halogens, C 1-4 Alkyl and aryl; preferably, R 55 Selected from F, Cl, Br, I, C 1-6 Alkyl and phenyl; preferably, R 55 Selected from F, Cl, Br, I, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and phenyl.

[0128] As used in this article, boride reactants are reagents that can generate metal borides when in contact with metal precursors.

[0129] Suitable examples of cycloborazines are compounds such as cycloborazine, trichlorocycloborazine, tribromocycloborazine, and 1,3,5-trimethylcycloborazine.

[0130] Suitable examples of boranes are compounds selected from the following: 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 Compounds of BH3, among which...

[0131] R 29 Selected from NH3, single C 1-6 Alkylamino, diC 1-6 Alkylamino, tri-C 1-6 Alkylamino, -S(C 1-6 Alkyl)2, heterocyclic, heteroalkyl and C-shaped 1-4 Alkyl-substituted heteroaryl; preferably, R 29 Selected from NH3, single C 1-4 Alkylamino, diC 1-4 Alkylamino, tri-C 1-4 Alkylamino, -S(C 1-4 Alkyl)2, heterocyclic, heteroalkyl and C-shaped 1-4 Alkyl-substituted heteroaryl; preferably, R 29 Selected from NH3, trimethylamine, triethylamine, dimethylamine, diethylamine, di-tert-butylamine, methylamine, ethylamine, tert-butylamine, tetrahydrofuran, pyridine, and 2-methylpyridine.

[0132] Other non-limiting examples of suitable boranes include: BH3[S(CH3)2], ammonia-borane, trimethylamine-borane, triethylamine-borane, pyridine-borane, dimethylamine-borane, 2-methylpyridine-borane, tert-butylamine-borane, and tetrahydrofuran-borane.

[0133] In some embodiments, the reactant is a reducing agent, wherein the reducing agent is selected from H2, H2 plasma, N2 / H2 plasma, N2H4, hydrazine, formic acid, formalin, borane, SiH4, Si2H6, H2Si(SiH3)2, silane and cyclic dienes.

[0134] A suitable example of hydrazine is formula The compounds, in which,

[0135] R 24 Selected from H, C 1-8 Alkyl and aryl; preferably, R 24 Selected from H, C 1-6 Alkyl and aryl; preferably, R 24 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl;

[0136] R 25 Selected from H, C 1-8 Alkyl and aryl; preferably, R 25 Selected from H, C 1-6 Alkyl and aryl; preferably, R 25 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl;

[0137] R 26 Selected from H, C 1-8 Alkyl and aryl; preferably, R 26 Selected from H, C 1-6 Alkyl and aryl; preferably, R 26 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl;

[0138] R 27 Selected from H, C 1-8 Alkyl and aryl; preferably, R 27 Selected from H, C 1-6 Alkyl and aryl; preferably, R 27 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl.

[0139] Suitable examples of boranes are compounds selected from the following: 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 Compounds of BH3, among which...

[0140] R 29 Selected from NH3, single C 1-6 Alkylamino, diC 1-6 Alkylamino, tri-C 1-6 Alkylamino, -S(C 1-6 Alkyl)2, heterocyclic, heteroalkyl and C-shaped 1-4 Alkyl-substituted heteroaryl; preferably, R 29 Selected from NH3, single C 1-4 Alkylamino, diC 1-4 Alkylamino, tri-C 1-4 Alkylamino, -S(C 1-4 Alkyl)2, heterocyclic, heteroalkyl and C-shaped 1-4 Alkyl-substituted heteroaryl; preferably, R 29 Selected from NH3, trimethylamine, triethylamine, dimethylamine, diethylamine, di-tert-butylamine, methylamine, ethylamine, tert-butylamine, tetrahydrofuran, pyridine, and 2-methylpyridine.

[0141] Other non-limiting examples of suitable boranes include: BH3[S(CH3)2], ammonia-borane, trimethylamine-borane, triethylamine-borane, pyridine-borane, dimethylamine-borane, 2-methylpyridine-borane, tert-butylamine-borane, and tetrahydrofuran-borane.

[0142] A suitable example of a silane is formula [formula missing]. The compounds, in which,

[0143] R 30 Selected from H, halogens, C 1-6 Alkyl, mono-C 1-6 Alkylamino, diC 1-6 Alkylamino, tri-C 1-6 Alkylamino and SiH3; preferably, R 30 Selected from H, halogens, C 1-4 Alkyl mono-C 1-4 Alkylamino, diC 1-4 Alkylamino, tri-C 1-4 Alkylamino and SiH3; preferably, R 30 Selected from H, F, Cl, Br, I, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, methylamino, ethylamino, tert-butylamino, di-sec-butylamino and SiH3;

[0144] R 30a Selected from H, halogens, C 1-6 Alkyl, mono-C 1-6 Alkylamino, diC 1-6 Alkylamino, tri-C 1-6 Alkylamino and SiH3; preferably, R 30a Selected from H, halogens, C 1-4 Alkyl mono-C 1-4 Alkylamino, diC 1-4 Alkylamino, tri-C 1-4 Alkylamino and SiH3; preferably, R 30a Selected from H, F, Cl, Br, I, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, methylamino, ethylamino, tert-butylamino, di-sec-butylamino and SiH3;

[0145] R 31 Selected from H, halogens, C 1-6 Alkyl, mono-C 1-6 Alkylamino, diC 1-6 Alkylamino, tri-C 1-6 Alkylamino and SiH3; preferably, R 31 Selected from H, halogens, C 1-4 Alkyl mono-C 1-4 Alkylamino, diC 1-4 Alkylamino, tri-C 1-4 Alkylamino and SiH3; preferably, R 31 Selected from H, F, Cl, Br, I, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, methylamino, ethylamino, tert-butylamino, di-sec-butylamino, and SiH3; and

[0146] R 31a Selected from H, halogens, C 1-6 Alkyl, mono-C 1-6 Alkylamino, diC 1-6 Alkylamino, tri-C 1-6 Alkylamino and SiH3; preferably, R 31a Selected from H, halogens, C 1-4 Alkyl mono-C 1-4 Alkylamino, diC 1-4 Alkylamino, tri-C 1-4 Alkylamino and SiH3; preferably, R 31a Selected from H, F, Cl, Br, I, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, methylamino, ethylamino, tert-butylamino, di-sec-butylamino and SiH3.

[0147] In some embodiments, R 30 R30a R 31 or R 31a At least two of them are H.

[0148] A suitable example of a silane is Si. x H y Compounds, wherein 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 understand that formula Si... x H y Silanes include straight-chain, branched, and cyclic silanes.

[0149] Other non-limiting examples of suitable silanes include: bis(diethylamino)silane, diisopropylaminosilane, silane, diethylsilane, propane, cyclohexylsilane, neopentylsilane, and disec-butylaminosilane.

[0150] 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, even more preferably 3 to 6 carbon atoms; and may have at least one heteroatom selected from N, O, and S, preferably at least one N atom. The cyclic diene according to the invention may be substituted with one or more substituents selected from C. 1-6 Alkyl, halogen, C 1-6 Alkoxy, C 1-6 Alkylamino, diC 1-6 Alkylamino, phenyl and tri-C 1-6 Alkylsilyl. Other non-limiting examples of suitable 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.

[0151] In some embodiments, the reactants are phosphide reactants selected from phosphine, phosphorus halides, phosphorus oxyhalides, organophosphates, organophosphites, aminophosphine, alkylphosphine, and silylphosphine.

[0152] As used in this article, phosphide reactants are reagents that can generate metal phosphides when in contact with metal precursors.

[0153] Suitable examples of phosphorus halides include compounds of the formula PX3 or PX5, wherein X is fluorine, chlorine, bromine, 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).

[0154] Suitable examples of phosphorus halides include compounds of the formula POX3, where X is fluorine, chlorine, bromine, or iodine. Suitable, but non-limiting, examples of phosphorus halides include, for example, phosphorus chloride oxychloride (POCl3) and phosphorus bromine oxychloride (POBr3).

[0155] A suitable example of an organophosphate ester is formula [formula missing]. The compounds, in which,

[0156] R 32 Selected from H, C 1-8 Alkyl and aryl; preferably, R 32 Selected from H, C 1-6 Alkyl and aryl; preferably, R 32 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl;

[0157] R 33 Selected from H, C 1-8 Alkyl and aryl; preferably, R 33 Selected from H, C 1-6 Alkyl and aryl; preferably, R 33 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl;

[0158] R 34 Selected from H, C 1-8 Alkyl and aryl; preferably, R 34 Selected from H, C 1-6 Alkyl and aryl; preferably, R 34 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl;

[0159] Among them, R 32 R 33 or R 34 Only one of them is hydrogen.

[0160] Suitable, but not limiting, examples of organophosphates include trimethyl phosphate (PO[OMe3]) and triethyl phosphate (PO[OEt3]).

[0161] Suitable examples of organic phosphites include those of formula [formula missing]. The compounds, in which,

[0162] R 35 Selected from H, C 1-8 Alkyl, -SiR 35a and aryl, of which R 35a It is C 1-6 Alkyl; preferably, R 35 Selected from H, C 1-6 Alkyl, -SiR 35a and aryl, of which R 35a It is C 1-6 Alkyl; preferably, R 35 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, trimethylsilyl, phenyl, and naphthyl;

[0163] R 36 Selected from H, C 1-8 Alkyl, -SiR 36a and aryl, of which R 36a It is C 1-6 Alkyl; preferably, R 36 Selected from H, C 1-6 Alkyl, -SiR 37a and aryl, of which R 36a It is C 1-6 Alkyl; preferably, R 36 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, trimethylsilyl, phenyl, and naphthyl;

[0164] R 37 Selected from H, C 1-8 Alkyl, -SiR 37a and aryl, of which R 37a It is C 1-6 Alkyl; preferably, R 37 Selected from H, C 1-6 Alkyl, -SiR 37a and aryl, of which R 37a It is C 1-6 Alkyl; preferably, R 37 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, trimethylsilyl, phenyl, and naphthyl;

[0165] Among them, R 35 R 36 or R 37 Only one of them is hydrogen.

[0166] Suitable, but not limiting, examples of organic phosphites include trimethyl phosphite (P[OMe]3) and triethyl phosphite (P[OEt]3).

[0167] Suitable examples of aminophosphine include formula The compounds, in which,

[0168] Each R 38 Independently selected from H and C 1-8 Alkyl and aryl; preferably, each R 38 Independently selected from H and C 1-6 Alkyl and aryl; preferably, each R 35 It is independently selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl;

[0169] Each R 39 Independently selected from H and C 1-8 Alkyl and aryl; preferably, each R 39 Independently selected from H and C 1-6 Alkyl and aryl; preferably, each R 39 It is independently selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl;

[0170] Each R 40 Independently selected from H and C 1-8 Alkyl and aryl; preferably, each R 40 Independently selected from H and C 1-6 Alkyl and aryl; preferably, each R 40 It is independently selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl and naphthyl.

[0171] Suitable but non-limiting examples of aminophosphine include tris(dimethylamino)phosphine (P[NMe2]3), tris(ethylmethylamino)phosphine (P[NEtMe]3), and tris(diethylamino)phosphine (P[NEt2]3).

[0172] Suitable examples of alkylphosphine include those of the formula... The compounds, in which,

[0173] R 41 Selected from H and C 1-8 Alkyl; preferably, R 41 Selected from H and C 1-6 Alkyl; preferably, R 41Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl;

[0174] R 42 Selected from H and C 1-8 Alkyl; preferably, R 42 Selected from H and C 1-6 Alkyl; preferably, R 42 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl; and

[0175] R 43 Selected from H and C 1-8 Alkyl; preferably, R 43 Selected from H and C 1-6 Alkyl; preferably, R 43 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl;

[0176] Among them, R 41 R 42 and R 43 At least one of them is not hydrogen.

[0177] Suitable, but non-limiting, examples of alkylphosphines include tert-butylphosphine (C4H9PH2) and triethylphosphine (P[CH2CH3]3).

[0178] Suitable examples of silylphosphine include formula The compounds, in which,

[0179] R 44 Is it H or Si(R)? 44a )3, where each R 44a Independently selected from H, halogen, C 1-8 Alkyl and aryl; preferably, each R 44a Independently selected from H, halogen, C 1-6 Alkyl and aryl; preferably, each R 44a Independently selected from 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;

[0180] R 45 Is it H or Si(R)? 45a )3, where each R 45a Independently selected from H, halogen, C 1-8 Alkyl and aryl; preferably, each R 45a Independently selected from H, halogen, C 1-6Alkyl and aryl; preferably, each R 45a Independently selected from 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; and

[0181] R 46 Is it H or Si(R)? 46a )3, where each R 46a Independently selected from H, halogen, C 1-8 Alkyl and aryl; preferably, each R 46a Independently selected from H, halogen, C 1-6 Alkyl and aryl; preferably, each R 46a Independently selected from 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;

[0182] Among them, R 44 R 45 and R 46 At least one of them is not H.

[0183] In some embodiments, silylphosphine includes the formula... Compounds, wherein each R 44a R 45a and R 46a As defined above.

[0184] Suitable but non-limiting examples of silylphosphine include tris(trimethylsilyl)phosphine (P[SiMe3]3) and tris(silyl)phosphine (P[SiH3]3).

[0185] In some embodiments, the reactants are carbide reactants, wherein the carbide reactants are selected from alkyl iodine, aryl iodine, alkyl bromide, aryl bromide, acetylene, propargyl chloride, propargyl bromide, propargyl iodine, allyl chloride, allyl bromide, allyl iodine and cyclodiene.

[0186] As used in this article, carbide reactants are reagents that can produce metal carbides when in contact with metal precursors.

[0187] As used herein, the term "alkyl iodine" refers to C 1-8 Alkyl group, wherein one, two, or three hydrogen atoms are each replaced by an iodine atom; preferably C. 1-6 Alkyl; preferably C 1-4 Alkyl groups. Other non-limiting examples of suitable alkyl iodides include iodomethane, diiodomethane, iodoethane, 1,2-diiodoethane, and 1-iodobutane.

[0188] As used herein, the term "aryl iodine" refers to an aryl group in which one, two, three, four, five, or six hydrogen atoms are each replaced by an iodine atom; preferably three hydrogen atoms; preferably two hydrogen atoms; preferably one hydrogen atom. Other non-limiting examples of suitable aryl iodines 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.

[0189] As used herein, the term "alkyl bromide" refers to C 1-8 Alkyl group, wherein one, two, or three hydrogen atoms are each replaced by a bromine atom; preferably C 1-6 Alkyl; preferably C 1-4 alkyl.

[0190] 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 replaced by a bromine atom; preferably three hydrogen atoms; preferably two hydrogen atoms; preferably one hydrogen atom.

[0191] Other non-limiting examples of suitable alkyl bromides include bromoethane, 1,2-dibromoethane, and 1-bromobutane.

[0192] Other 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.

[0193] In some embodiments, the reactants are sulfide reactants, wherein the sulfide reactants are selected from H2S, S8, S2Cl2, thiols, dithiols, bis(trimethylsilyl) sulfides, CS2, and disulfides.

[0194] As used in this article, sulfide reactants are reagents that can produce metal sulfides when in contact with metal precursors.

[0195] Suitable examples of thiols include formula R 47 SH compounds, among which,

[0196] R 47 Selected from C 1-8 Alkyl and aryl; preferably, R 47 Selected from C 1-6 Alkyl and aryl; preferably, R 47It is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl.

[0197] Other non-limiting examples of suitable thiols include tert-butylthiols, 1-hexanethiols, tert-amylthiols, and thiophenols.

[0198] As used herein, the term "dithiol" refers to a C-type dithiol in which two hydrogen atoms are replaced by thiol (-SH) groups. 1-8 Alkyl; preferably C 1-6 Alkyl; preferably C 1-4 Alkyl groups. Other non-limiting examples of suitable dithiols include 1,2-ethanedithiol, 1,3-propanedithiol, and 1,4-butanedithiol.

[0199] Suitable examples of disulfides include formula R 47 -SSR 48 The compounds, in which,

[0200] R 47 Selected from C 1-8 Alkyl and aryl; preferably, each R 47 Selected from C 1-6 Alkyl and aryl; preferably, R 47 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl; and

[0201] R 48 Selected from C 1-8 Alkyl and aryl; preferably, each R 48 Selected from C 1-6 Alkyl and aryl; preferably, R 48 It is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, phenyl, and naphthyl.

[0202] Other non-limiting examples of suitable disulfides include: dimethyl disulfide, diethyl disulfide and di-tert-butyl disulfide.

[0203] In some embodiments, the temperature-controlled container is configured for heating the precursor and, optionally, the reactants. In some embodiments, the temperature-controlled container is maintained at a temperature of at least -50°C to at most 20°C, or at a temperature of at least 20°C to at most 250°C, or at a temperature of at least 100°C to at most 200°C.

[0204] In certain embodiments, the apparatus disclosed herein may be configured to manufacture semiconductor devices as disclosed herein or field-effect transistors (FETs) as disclosed herein.

[0205] In certain embodiments, the devices disclosed herein are configured to form at least a portion of a semiconductor device as disclosed herein or a field-effect transistor (FET) as disclosed herein.

[0206] In some embodiments, at least one metal precursor comprises:

[0207] The metal is selected from at least one of the following: 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 Cr, Mo, W, Sc, Y, La, Ce, Gd, Tb, Ho, Er, Ti, Zr, Hf, V, Nb, Ta, Co, Ni, Al, Ga, In, and Lu;

[0208] At least one ligand of formula (I):

[0209] (I),

[0210] in,

[0211] R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0212] R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or

[0213] R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings;

[0214] R 3 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0215] R 4 Selected from H, C1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0216] R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and

[0217] R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups.

[0218] In some embodiments, at least one metal precursor comprises at least one ligand of formula (I), wherein,

[0219] R 1 Selected from C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl; preferably, R 1 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 Cycloalkyl groups, C substituted with methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl. 3-6 cycloalkyl;

[0220] R 2 Selected from C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl; preferably, R 2 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 Cycloalkyl groups, C substituted with methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl. 3-6 cycloalkyl; or

[0221] R 1 and R2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9, or 10-membered rings; preferably R. 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 4, 5, 6, 7, or 8-membered rings; preferably R. 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 5, 6, or 7-membered rings;

[0222] R 3 Selected from H, C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl; preferably, R 3 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 Cycloalkyl groups, C substituted with methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl. 3-6 cycloalkyl;

[0223] R 4 Selected from H, C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl; preferably, R 4 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 Cycloalkyl groups, C substituted with methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl. 3-6 cycloalkyl;

[0224] R 5 Selected from H, C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl; preferably, R 5 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 Cycloalkyl groups, C substituted with methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl. 3-6 cycloalkyl;

[0225] R 6 Selected from H, C 1-6Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl; preferably, R 6 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, C 3-6 Cycloalkyl groups, C substituted with methyl, ethyl, n-propyl, n-butyl, sec-butyl, or isobutyl. 3-6 Cycloalkyl.

[0226] It should be understood that, within the scope of this disclosure, metal precursors may comprise any combination of the aforementioned types of ligands.

[0227] When forming the metal precursor of the present invention, the metal atom can interact with the ligand of formula (I) in two possible ways: in one way, the metal atom bonds to two carbon atoms of the ligand of formula (I) to form a bidentate ylitade (see structures (A) and (B) below). Alternatively, the metal atom bonds to one carbon atom of the ligand of formula (I) to form a monodentate ylitade (see structure (C) below).

[0228] .

[0229] In some embodiments, metal atoms bind ligands of formula (I) to form bidentate ylites.

[0230] As used herein, compounds in which the same ligands are attached to the same central metal atom are referred to in the art as homogeneous complexes.

[0231] In some embodiments, the metal precursor comprises one or more identical ligands of formula (I); these compounds may also be referred to as homogamic ylides. Some examples of homogamic ylides according to the invention are:

[0232] ,

[0233] Among them, R 1 R 2 R 3 R 4 R 5 and R 6 As described herein, some non-limiting examples of the equipotential ylide according to the invention are:

[0234] .

[0235] As used herein, compounds in which different ligands are attached to the same central metal atom are referred to in the art as heterocoordination complexes.

[0236] In some embodiments, the metal precursor comprises at least one ligand of formula (I) and one or more additional ligands selected from the following: cyclopentadienyl ligand, amide ligand, imide ligand, amidine ligand, halide ligand, alkyl ligand, alkoxide ligand, diketoate ligand, and 1,4-diazabutadiene ligand.

[0237] In some embodiments, one or more additional ligands are of the formula (1) Cyclopentadienyl ligand, wherein

[0238] R 7a Selected from H, C 1-8 Alkyl and -SiR 9a , where R 9a It is C 1-6 Alkyl; preferably, R 7a Selected from H, C 1-6 Alkyl and -SiR 9a , where R 9a It is C 1-4 Alkyl; preferably, R 7a Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and trimethylsilyl;

[0239] R 7b Selected from H, C 1-8 Alkyl and -SiR 9b , where R 9b It is C 1-6 Alkyl; preferably, R 7b Selected from H, C 1-6 Alkyl and -SiR 9a , where R 9b It is C 1-4 Alkyl; preferably, R 7b Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and trimethylsilyl;

[0240] R 7c Selected from H, C 1-8 Alkyl and -SiR 9c , where R 9c It is C 1-6 Alkyl; preferably, R 7c Selected from H, C 1-6 Alkyl and -SiR 9c , where R 9c It is C 1-4 Alkyl; preferably, R 7cSelected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and trimethylsilyl;

[0241] R 7d Selected from H, C 1-8 Alkyl and -SiR 9d , where R 9d It is C 1-6 Alkyl; preferably, R 7d Selected from H, C 1-6 Alkyl and -SiR 9d , where R 9d It is C 1-4 Alkyl; preferably, R 7d Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and trimethylsilyl; and

[0242] R 7e Selected from H, C 1-8 Alkyl and -SiR 9e , where R 9e It is C 1-6 Alkyl; preferably, R 7e Selected from H, C 1-6 Alkyl and -SiR 9e , where R 9e It is C 1-4 Alkyl; preferably, R 7e It is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl and trimethylsilyl.

[0243] In some embodiments, the cyclopentadienyl ligand is selected from cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, tert-butylcyclopentadienyl, trimethylsilylcyclopentadienyl, pentamethylcyclopentadienyl, 1,2,4-triisopropylcyclopentadienyl, and 1,2,4-tritert-butylcyclopentadienyl.

[0244] In some embodiments, the cyclopentadienyl ligand is bonded to the metal in an η-1, η-3, or η-5 coordination mode. The Greek letter η followed by a number indicates that the number of consecutive atoms of the same type in the ligand are simultaneously bonded to the metal atom. Preferably, the cyclopentadienyl ligand is bonded to the metal in an η-5 coordination mode.

[0245] In some embodiments, the metal precursor comprises at least one ligand of formula (I) and one or more cyclopentadienyl ligands, wherein the metal precursor has formula (II):

[0246] (II),

[0247] in,

[0248] R 1 R 2 R 3 R 4 R 5 and R 6 As described in this article;

[0249] R 7 Selected from H, C 1-8 Alkyl and -SiR 9 , where R 9 It is C 1-6 Alkyl; preferably, R 7 Selected from H, C 1-6 Alkyl and -SiR 9 , where R 9 It is C 1-4 Alkyl; preferably, R 7 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl, isobutyl, n-pentyl, tert-pentyl, isopentyl and trimethylsilyl;

[0250] R 8 Selected from H, C 1-8 Alkyl and -SiR 10 , where R 10 It is C 1-6 Alkyl; preferably, R 8 Selected from H, C 1-6 Alkyl and -SiR10, where R 10 It is C 1-4 Alkyl; preferably, R 8 The derivative is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and trimethylsilyl. In some of these examples, 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.

[0251] In some embodiments, one or more additional ligands are amide ligands of formula (2):

[0252] (2),

[0253] in,

[0254] R 11 Independently selected from H and C 1-8 Alkyl and -SiR 12 , where R 12 It is C1-6 Alkyl; preferably, R 11 Selected from H, C 1-6 Alkyl and -SiR 12, wherein R 12 It is C 1-4 Alkyl; preferably, R 11 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and trimethylsilyl; and

[0255] R 11a Independently selected from H and C 1-8 Alkyl and -SiR 12a , where R 12a It is C 1-6 Alkyl; preferably, R 11a Selected from H, C 1-6 Alkyl and -SiR 12a , where R 12a It is C 1-4 Alkyl; preferably, R 11a Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl, and trimethylsilyl;

[0256] Among them, R 11 and R 11a At least one of them is not H.

[0257] In some embodiments, the acylamino ligand is selected from dimethylacylamino, diethylacylamino, ethylmethylacylamino, diisopropylacylamino, tert-butylacylamino, and bis(trimethylsilyl)acylamino.

[0258] In some embodiments, one or more additional ligands are imide ligands of formula (3):

[0259] =NR 13 (3),

[0260] Among them, R 13 It is C 1-8 Alkyl; preferably, R 13 It is C 1-6 Alkyl; preferably, R 13 It is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, isopentyl and trimethylsilyl.

[0261] In some embodiments, the imino ligand is selected from ethylimino, isopropylimino, isobutylimino, tert-butylimino, and tert-pentylimino.

[0262] In some embodiments, the metal precursor comprises at least one ligand of formula (I) and one or more imino ligands, wherein the metal precursor has formula (III):

[0263] (III),

[0264] in,

[0265] R 1 R 2 R 3 R 4 R 5 and R 6 As described in this article;

[0266] R 7’ It is C 1-8 Alkyl; preferably, R 7’ It is C 1-6 Alkyl; preferably, R 7’ Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl; and

[0267] R 8’ It is C 1-8 Alkyl; preferably, R 8’ It is C 1-6 Alkyl; preferably, R 8’ The ligand is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl. In some of these embodiments, M is preferably selected from Cr, Mo, and W. In some embodiments, one or more additional ligands are amidine ligands of formula (4):

[0268] (4),

[0269] in,

[0270] R 14 It is C 1-8 Alkyl; preferably, R 14 It is C 1-6 Alkyl; preferably, R 14 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl;

[0271] R 15 It is C 1-8 Alkyl; preferably, R 15 It is C 1-6 Alkyl; preferably, R 15Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl; and

[0272] R 16 Selected from H, C 1-6 Alkyl, mono-C 1-6 Alkylamino and diC 1-6 Alkylamino; preferably, R 16 Selected from H, C 1-4 Alkyl, mono-C 1-4 Alkylamino and diC 1-4 Alkylamino; preferably, R 16 It is selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl, isobutyl, dimethylamine, diethylamine and ethylmethylamine.

[0273] In some embodiments, the amidoyl ligand is selected from N,N'-diethylacetamidine, N,N'-diisopropylacetamidine, N,N'-diisopropylmethylamidine, N,N'-di-tert-butylacetamidine, and N,N'-di-tert-butylmethylamidine.

[0274] In some embodiments, one or more additional ligands are alkoxide ligands of formula (5):

[0275] (5),

[0276] in,

[0277] R 17 Selected from H, C 1-8 Alkyl and aryl; preferably, R 17 Selected from H or C 1-6 Alkyl; preferably, R 17 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl;

[0278] R 18 Selected from H, C 1-8 Alkyl and aryl; preferably, R 18 Selected from H or C 1-6 Alkyl; preferably, R 18 Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl; and

[0279] R 19 Selected from H, C 1-8 Alkyl and aryl; preferably, R 19 Selected from H or C 1-6 Alkyl; preferably, R 19Selected from H, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, sec-butyl, isobutyl, n-pentyl, tert-pentyl, and isopentyl.

[0280] In some embodiments, the alkoxide ligand is selected from methanol salts, ethanol salts, isopropoxide salts, tert-butoxide salts, 1-methoxy-2-methyl-2-propoxide salts, 1-dimethylamino-2-propoxide salts, 1-dimethylamino-2-methyl-2-propoxide salts, 1-ethylmethylamino-2-methyl-2-propoxide salts, 1-diethylamino-2-methyl-2-propoxide salts, 1-dimethylamino-2-methyl-2-butoxide salts, 1-ethylmethylamino-2-methyl-2-butoxide salts, and 1-diethylamino-2-methyl-2-butoxide salts.

[0281] In some embodiments, one or more additional ligands are diketone ligands of formula (6):

[0282] (6),

[0283] in,

[0284] R 20 Selected from C 1-8 Alkyl groups, halogenated C 1-8 Alkyl and aryl; preferably, R 20 Selected from C 1-6 Alkyl groups, halogenated C 1-6 Alkyl and aryl; preferably, R 20 Selected from 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 tolueneyl; and

[0285] R 21 Selected from C 1-8 Alkyl groups, halogenated C 1-8 Alkyl and aryl; preferably, R 21 Selected from C 1-6 Alkyl groups, halogenated C 1-6 Alkyl and aryl; preferably, R 21 It is selected from 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.

[0286] In some embodiments, the diketone ligand is selected from acetylacetonate, 2,2,6,6-tetramethylheptane-3,5-diketone, and 1,1,1,5,5,5-hexafluoropentane-2,5-diketone.

[0287] In some embodiments, one or more additional ligands are diazabutadiene ligands of formula (7):

[0288] (7),

[0289] in,

[0290] R 22 It is C 1-8 Alkyl; preferably, R 22 It is C 1-6 Alkyl; preferably, R 22 Selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl; and

[0291] R 23 It is C 1-8 Alkyl; preferably, R 23 It is C 1-6 Alkyl; preferably, R 23 It is selected from methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, isobutyl, sec-butyl, n-pentyl, tert-pentyl, and isopentyl.

[0292] In some embodiments, the diazabutadiene ligand is selected from 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.

[0293] Some non-limiting examples of the heterozygous ylide according to the present invention are:

[0294] .

[0295] Figure 2 A device 600 according to another exemplary embodiment of the present disclosure is illustrated schematically. Device 600 may be used to perform the methods described herein and / or form a portion of a transistor or semiconductor device as described herein.

[0296] In the illustrated example, apparatus 600 includes one or more reaction chambers 602, a metal precursor gas source 604, a purge gas source 610, an exhaust device 612, and a controller 614. The reaction chamber 602 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber. Optionally, apparatus 600 includes additional gas sources, such as a reactant source 608 and a vacuum power supply (611).

[0297] Metal gas source 604 is configured to deliver metal precursors as described herein. Metal precursor gas source 604 may include a container and one or more metal precursors as described herein—either alone or mixed with one or more carrier gases (e.g., inert gases). Optional reactant source 608 may include a container and one or more reactants as described herein—either alone or mixed with one or more carrier gases (e.g., inert gases). Purge gas source 610 may include one or more inert gases, such as N2 or rare gases, as described herein. Apparatus 600 may include any suitable number of gas sources. Gas sources 604-611 may be coupled to reaction chamber 602 via lines 616-621, each of which may include a flow controller, valve, heater, etc. Exhaust device 612 may include one or more vacuum pumps.

[0298] Controller 614 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in apparatus 600. Such circuitry and components operate to introduce precursors, optional reactants, and purge gases from respective sources 604-611. Controller 614 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to provide appropriate operation of apparatus 600. Controller 614 may include control software to electrically or pneumatically control valves to control the inflow and outflow of precursors, optional reactants, and purge gases from reaction chamber 602. Controller 614 may include modules, such as software or hardware components like FPGAs or ASICs, to perform certain tasks. Modules may advantageously be configured to reside on addressable storage media of the control system and configured to perform one or more processes.

[0299] Other configurations of the apparatus 600 are possible, including different quantities and types of precursor and optional reactant sources, as well as purge gas sources. Furthermore, it should be understood that numerous arrangements of valves, conduits, precursor sources, optional reactant sources, and purge gas sources exist to achieve the objective of selectively feeding gas into the reaction chamber 602. Additionally, for the sake of simplicity, many components have been omitted in the schematic diagram of the apparatus, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0300] Additionally, embodiments of the controller may include a combination of hardware, software, and electronic components or modules, which may be depicted for the purposes of discussion as if implemented primarily in hardware. However, those skilled in the art will recognize from this detailed description that, in at least one embodiment, the electronic aspects of this disclosure may be implemented in software (e.g., instructions stored on a non-transitory computer-readable medium) executable by one or more processing units (e.g., microprocessors and / or application-specific integrated circuits).

[0301] During operation of reactor apparatus 600, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate processing system to reaction chamber 602. Once the substrate is transferred to reaction chamber 602, one or more gases (e.g., precursors, carrier gases, optional reactants, and / or purge gases) from gas sources 604-611 are introduced into reaction chamber 602.

[0302] Another aspect of this disclosure relates to a method for forming a metal-containing layer on a semiconductor substrate, comprising the following steps:

[0303] a) Providing the semiconductor substrate into the reaction chamber; and

[0304] b) Execute one or more loops, each loop consisting of:

[0305] Metal precursor pulse, wherein at least a portion of a semiconductor substrate is brought into contact with at least one metal precursor by introducing at least one metal precursor into a reaction chamber;

[0306] At least one metal precursor comprises:

[0307] Selected from at least one of the following metals: 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;

[0308] At least one ligand of formula (I):

[0309] (I),

[0310] in,

[0311] R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0312] R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or

[0313] R 1 and R 2Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings;

[0314] R 3 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0315] R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0316] R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and

[0317] R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups,

[0318] As a result of the cycle, a metal-containing layer is formed on the semiconductor substrate in the reaction chamber.

[0319] According to step b) of this method, and after the substrate is provided to the reaction chamber, one or more (deposition) cycles are performed to form a metal-containing layer on the semiconductor substrate.

[0320] Specifically, this (deposition) method can be a cyclic deposition process, preferably a combination of cyclic deposition processes, such as atomic layer deposition (ALD) or cyclic chemical vapor deposition (CVD). Each cyclic deposition process includes one or more different (deposition) cycles. In a particular embodiment, the method disclosed herein can be an ALD method. Compared to sputtering techniques commonly used in the prior art to deposit thin films and layers to fabricate various semiconductors and transistors, cyclic deposition processes such as ALD have been found to provide more uniform deposition on the substrate surface and / or (previously) deposited layers.

[0321] As used herein, the synonyms “deposition” or “cyclic deposition” or “cyclic deposition process” or “cyclic deposition process” refer to processing techniques that sequentially introduce precursors (and / or reactants) into a reaction chamber to deposit a layer or film on a substrate, and include, for example, ALD, CVD, and mixed cyclic deposition processes including ALD and CVD components. Typically, one 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 number and type of cycles and the available reaction sites on the substrate and / or previously deposited layers.

[0322] The term "atomic layer deposition" (ALD) refers to a vapor-phase deposition process performed in a processing chamber in a deposition cycle (typically multiple consecutive deposition cycles). As used herein, the term atomic layer deposition is also intended to include processes specified by related terms such as chemical vapor deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas-source MBE, organometallic MBE, and chemical beam epitaxy when performed using alternating pulses of precursor / reactive gases and purge gases (e.g., inert carrier gases).

[0323] In the ALD process, during each cycle, a precursor (e.g., a metal precursor) is typically introduced into the reaction chamber and chemisorbed onto the deposition surface (e.g., a substrate surface that may include previously deposited material from a previous ALD cycle or other materials), thereby forming a material, such as a monolayer or sub-monolayer, or several monolayers, or multiple monolayers, which does not readily react with the additional precursor (i.e., a self-limiting reaction). Subsequently, in some cases, reactants (e.g., another precursor or a reactive gas, such as oxygen reactant) may be introduced into the processing chamber. The reactants are capable of further reacting with the precursor. It should be noted that, as used herein, the ALD process does not necessarily involve a series of self-limiting surface reactions.

[0324] In some embodiments, step b) of the method according to this disclosure further includes a reactant pulse, wherein at least a portion of the semiconductor substrate is contacted with at least one reactant by introducing at least one reactant into the reaction chamber. The description of the reactant types provided in the apparatus section is adapted to the description of the method with necessary modifications.

[0325] The descriptions of the types of metal precursors and ligands provided in the apparatus section are modified as necessary to apply to the description of the method.

[0326] Optionally, during one or more repetitions, such as during each deposition step, a purging step may be used to remove any excess precursors from the processing chamber and / or any excess reactants and / or reaction byproducts from the reaction chamber.

[0327] As used herein, the term "purging" can refer to the process of supplying an inert or substantially inert gas to a reaction chamber between two pulses of reacting gases. For example, purging, for instance, using an inert gas (e.g., a rare gas), can be provided between subsequent pulses to avoid or at least minimize gas-phase interactions between precursors and / or reactants.

[0328] In certain embodiments, the methods disclosed herein provide purging of the reaction chamber before and / or after each precursor pulse. In certain embodiments, the methods disclosed herein provide purging of the reaction chamber before and / or after each metal precursor pulse and reactant pulse.

[0329] In some embodiments, the purging duration is greater than or equal to 0.1 seconds; preferably greater than or equal to 0.5 seconds; preferably greater than or equal to 1 second; preferably greater than or equal to 5 seconds; preferably greater than or equal to 10 seconds. In some embodiments, the duration is less than or equal to 60 seconds; preferably less than or equal to 45 seconds; preferably less than or equal to 35 seconds; preferably less than or equal to 20 seconds; preferably less than or equal to 10 seconds. In some embodiments, the duration is from 0.1 to 60 seconds; preferably 0.5 to 20 seconds; preferably 5 to 10 seconds; preferably 1 to 10 seconds.

[0330] Advantageously, the cyclic deposition process disclosed herein can be a thermal deposition process. In other words, in some embodiments, neither the pulses nor the purges in the cyclic deposition process employ plasma. In the case of a thermal cyclic deposition process, the duration of the steps of providing the metal precursor to the reaction chamber and / or providing the reactant to the reaction chamber can be relatively long to allow the precursor and / or reactant to the substrate surface and / or the previously deposited layer.

[0331] In some embodiments, the duration of the step of providing the metal precursor to the reaction chamber is greater than or equal to 0.1 seconds; preferably greater than or equal to 0.5 seconds; preferably greater than or equal to 1 second; preferably greater than or equal to 5 seconds; preferably greater than or equal to 10 seconds. In some embodiments, the duration is less than or equal to 60 seconds; preferably less than or equal to 45 seconds; preferably less than or equal to 35 seconds; preferably less than or equal to 20 seconds; preferably less than or equal to 10 seconds. In some embodiments, the duration is from 0.1 to 60 seconds; preferably 0.5 to 20 seconds; preferably 5 to 10 seconds; preferably 1 to 10 seconds.

[0332] In some embodiments, the duration of the step of providing reactants to the reaction chamber is greater than or equal to 0.1 seconds; preferably greater than or equal to 0.5 seconds; preferably greater than or equal to 1 second; preferably greater than or equal to 5 seconds; preferably greater than or equal to 10 seconds. In some embodiments, the duration is less than or equal to 60 seconds; preferably less than or equal to 45 seconds; preferably less than or equal to 35 seconds; preferably less than or equal to 20 seconds; preferably less than or equal to 10 seconds. In some embodiments, the duration is from 0.1 to 60 seconds; preferably 0.5 to 20 seconds; preferably 5 to 10 seconds; preferably 1 to 10 seconds.

[0333] In some embodiments, the cyclic deposition process employs plasma-enhanced deposition techniques. For example, the cyclic deposition process may include plasma-enhanced atomic layer deposition and / or plasma-enhanced chemical vapor deposition. In this case, any pulse in the cyclic deposition process may include the generation of plasma in the reaction chamber.

[0334] In some embodiments, the methods disclosed herein can be a continuous vacuum deposition process. In the case of a continuous vacuum deposition process, material is deposited onto a substrate in a reaction chamber without the introduction of atmosphere or any interruption that would disrupt the controlled vacuum environment. This process involves maintaining a consistent vacuum pressure within the reaction chamber.

[0335] In certain embodiments, the methods disclosed herein provide the ability to form a metal-containing layer without any intermediate vacuum disruption. The term "without any intermediate vacuum disruption" can mean no vacuum disruption, no interruption as a timeline, no intermediate material steps, no change in processing conditions, and / or immediately following such interruption.

[0336] In certain embodiments, the formation of the metal 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 step may be repeated from at least 1 cycle to at most 5000 cycles; preferably from at least 1 cycle to at most 1000 cycles; preferably from at least 2 cycles to at most 100 cycles; and preferably from at least 5 cycles to at most 50 cycles.

[0337] Each cycle may include one or more pulses. In some embodiments, at least one pulse relates to a self-limiting surface reaction. In some embodiments, all pulses relate to a self-limiting surface reaction. In the case of ALD, a self-limiting surface reaction refers to a chemical reaction that automatically stops or slows down once a certain threshold or coverage is reached on the surface, for example, once a complete monolayer or sub-monolayer is formed, the reaction stops by preventing further reaction with additional precursors. In some embodiments, a cycle includes one or more precursor pulses, and optionally one or more reactant pulses.

[0338] In a particular embodiment, the metal layer may have the following average thickness: between 10.0 nm and 100.0 nm, or between 1.0 nm and 100.0 nm, or between 5.0 nm and 20 nm, or between 1.0 nm and 10.0 nm, or between 0.05 nm and 2.0 nm, or between 0.10 nm and 2.0 nm, or between 0.10 nm and 1.75 nm, or between 0.10 nm and 1.50 nm, or between 0.10 nm and 1.25 nm, preferably between 0.10 nm and 1.0 nm, or between 0.20 nm and 1.0 nm, or between 0.25 nm and 1.0 nm. In certain embodiments, the method disclosed herein provides that the average thickness of the channel layer can be between 0.05 nm and 2.0 nm, or between 0.10 nm and 2.0 nm, or between 0.10 nm and 1.75 nm, or between 0.10 nm and 1.50 nm, or between 0.10 nm and 1.25 nm, preferably between 0.10 nm and 1.0 nm, or between 0.20 nm and 1.0 nm, or between 0.25 nm and 1.0 nm.

[0339] In some embodiments, the cycle for growing a metal-containing layer may include the following pulse sequence: a metal precursor pulse and an optional reactant pulse. In the metal precursor pulse, one or more metal precursors are provided to the reaction chamber and can be chemisorbed onto the substrate (i.e., atoms or molecules adhering to the surface of the substrate and / or a previously deposited layer or material and forming chemical bonds therewith). In the optional reactant pulse, one or more reactants are provided to the reaction chamber and can 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 total thickness of the deposited metal-containing layer.

[0340] The advantage of the cyclic deposition process disclosed herein is the precise control of the overall layer thickness.

[0341] Figure 1An exemplary embodiment of a method 100 for forming a metal-containing layer on a semiconductor substrate as disclosed herein is described. The method begins 111 after the substrate is provided to a reaction chamber. A cyclic deposition process includes providing one or more metal precursors (gases) as described herein to the reaction chamber in the form of metal precursor pulses 112. Optionally, the reaction chamber is purged 113 after the metal precursor pulses 112. The metal precursor pulses are configured to deliver the metal precursors as described herein. Optionally, one or more reactants are provided to the reaction chamber in the form of reactant pulses 114. Optionally, the reaction chamber may be purged 115 after the reactant pulses.

[0342] The metal precursor pulse 112, optional reactant pulse 114, and optional purges 113 and 115 can be repeated 116 any number of times to obtain a metal-containing layer 117 with the desired thickness. The method ends 118 when a metal-containing layer with the desired thickness has been deposited. Once the method ends, the substrate can be subjected to additional processes known in the art for forming device structures and / or devices (e.g., FETs) as disclosed herein.

[0343] It should be understood that the metal precursor pulse 112 and the optional reactant pulse 114 may overlap in a single cycle. Furthermore, the order of each method step (112 to 115) within each cycle may vary. For example, and in another exemplary embodiment, the cycle may include consecutive steps of the optional reactant pulse and the metal precursor pulse. Thus, the optional reactant pulse may precede the metal precursor pulse.

[0344] In certain embodiments, the methods disclosed herein provide that the metal precursor pulses and optional reactant pulses comprise multiple micropulses. As used herein, a “micropulse” is a short period of time that can introduce one or more metal precursors and optionally one or more reactants into the reaction chamber. Therefore, the methods disclosed herein offer a high degree of flexibility in pulse sequence and length compared to conventional metal-containing layer production processes known in the art, thus providing a cost-effective and more efficient approach.

[0345] In some embodiments, the metal precursor pulse and optionally one or more reactants can last for at least 0.01 s to at most 120 s, or at least 0.01 s to at most 0.1 s, or at least 0.01 s to at most 0.02 s, or at least 0.02 s to at most 0.05 s, or at least 0.05 s to at most 0.1 s, or at least 0.1 s to at most 20 s, or at least 0.1 s to at most 0.2 s, or at least 0.2 s to at most 0.5 s, or at least 0.5 s to at most 1.0 s, or at least 1.0 s to at most 2.0 s, or at least 2.0 s to at most 5.0 s, or at least 5.0 s to at most 10.0 s, or at least 10.0 s to at most 20.0 s.

[0346] It should be understood that any two steps and / or pulses and / or micropulses can be separated by purging. Therefore, in some embodiments, the metal precursor pulse and optionally the reactant pulse can be separated by purging. In some embodiments, subsequent cycles are separated by purging.

[0347] In certain embodiments, the reaction chamber may be purged before and / or after the metal precursor pulse and optional reactant pulse. The advantage of purging is that it prevents gas-phase reactions, which can inhibit / eliminate self-limiting surface reactions. Another advantage of purging the reaction chamber before and / or after each precursor pulse and / or optional reactant pulse is the removal of any residual precursors, reactants, and / or reaction byproducts, thereby avoiding cross-contamination between pulses and producing a film or layer with high purity and fewer harmful defects.

[0348] The methods disclosed herein can be performed at different temperatures and / or pressures. In specific embodiments, the methods disclosed herein provide temperatures that can heat the substrate to 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 can reduce the time required for material deposition, although lower or higher temperatures are still conceivable.

[0349] In certain embodiments, as provided by the methods disclosed herein, the pressure in the reaction chamber is between about 0.1 Torr and about 100.0 Torr, or between about 0.5 Torr and about 100.0 Torr, or between about 1.0 Torr and about 100.0 Torr, or between about 2.0 Torr and about 100.0 Torr, or between about 5.0 Torr and about 100.0 Torr, or between about 5.0 Torr and about 80.0 Torr, or preferably between about 5.0 Torr and about 50.0 Torr, or between about 10.0 Torr and about 50.0 Torr, or between 0.5 Torr and about 10.0 Torr. The listed pressures can reduce the time required for material deposition, although lower or higher pressures may still be considered.

[0350] In some embodiments, after the cyclic deposition process, the substrate is subjected to an annealing step in an environment including hydrogen and nitrogen. Suitably, the annealing step may be performed at a temperature of at least 300°C to at most 600°C. Alternatively, the annealing step may be performed at a temperature of at least 300°C to at most 1000°C.

[0351] In some embodiments, one or more metal precursors and / or optionally one or more reactants are supplied to the reaction chamber by means of a carrier gas. Exemplary carrier gases include nitrogen (N2) and rare gases such as He, Ne, Ar, Xe, or Kr.

[0352] The continuous substrate may extend beyond the boundary of the processing / reaction chamber where the deposition process occurs. In some processes, the continuous substrate may be moved through the processing chamber, allowing the process to continue until the end of the substrate is reached. The continuous substrate can be supplied from a continuous substrate supply system to allow the continuous substrate to be manufactured and output in any suitable form. Non-limiting examples of continuous substrates may include sheets or flexible materials. The continuous substrate may also include a carrier or sheet on which a non-continuous substrate is mounted.

[0353] Another aspect of the present invention relates to a semiconductor device structure formed according to the method described herein. The semiconductor device structure preferably includes a metal layer comprising a plurality of metal atoms selected from the following: 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.

[0354] In some embodiments, the semiconductor device structure includes a metal layer comprising at least one ligand of formula (I):

[0355] (I),

[0356] in,

[0357] R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0358] R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or

[0359] R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings;

[0360] R 3 Selected from H, C1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0361] R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0362] R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and

[0363] R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups.

[0364] Another aspect of this disclosure relates to a composition configured for forming a metal-containing film, the composition comprising at least one metal precursor, the at least one metal precursor comprising:

[0365] Selected from at least one of the following metals: 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;

[0366] At least one ligand of formula (I):

[0367] (I),

[0368] in,

[0369] R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0370] R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or

[0371] R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings;

[0372] R 3 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0373] R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0374] R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and

[0375] R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups.

[0376] Examples of metal precursors were discussed above.

[0377] The compositions disclosed herein may contain one or more impurities. The use of metal precursors for deposition requires relatively high purity. Impurities in the composition are undesirable because they can degrade the quality of the resulting film. For example, impurities in the composition may lead to the incorporation of impurity elements into the resulting film. Alternatively or concurrently, impurities in the composition may cause process drift due to differences in the vapor pressures of the various components of the composition. In some embodiments, the composition comprises at least about 95% by weight of a metal precursor, or 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% by weight of a metal precursor, or at least about 99.5% by weight of a metal precursor, or at least about 99.7% by weight of a metal precursor, or at least about 99.9% by weight of a metal precursor, or at least about 99.99% by weight of a metal precursor.

[0378] In some embodiments, the composition is used in the methods described herein. In some embodiments, the composition is used in a device as described herein.

[0379] Another aspect of this disclosure relates to a container comprising a composition configured for forming a metal-containing film, the composition comprising at least one metal precursor, the at least one metal precursor comprising:

[0380] Selected from at least one of the following metals: 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;

[0381] At least one ligand of formula (I):

[0382] (I),

[0383] in,

[0384] R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0385] R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or

[0386] R 1 and R2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings;

[0387] R 3 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0388] R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups;

[0389] R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and

[0390] R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups.

[0391] Examples of metal precursors were discussed above.

[0392] The container is configured to store a composition and provide 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 typically formed of a material that is not reactive with 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 of stainless steel (e.g., 316, 316L, 304, or an alloy of 304L). The configuration of the container may vary in different embodiments of this disclosure depending on the melting point and volatility of the metal precursor and other factors. However, the container typically includes an outer wall surrounding a cavity for storing the composition and a gas outlet for allowing vapors of the composition to exit the cavity. The gas outlet is located in the outer wall of the container and communicates with the cavity of the container, and has at least one valve located thereon for fluidly connecting or disconnecting the cavity from the external environment. In some embodiments, in addition to the gas outlet, the container includes one or more other fluid inlets or outlets. For example, the container may include a fluid inlet located in the outer wall of the container and communicating with the cavity of the container, and having at least one valve located thereon for filling the container with the composition. Alternatively, the container may include a fluid inlet located in the outer wall of the container and communicating with the cavity of the container, and having at least one valve thereon for allowing carrier gas to flow into the cavity of the container, over the surface of the composition, and / or through the composition. Some or all of the one or more valves disposed on the various inlets and outlets may be rated for high temperatures (e.g., typically up to 100°C, or up to 150°C, or up to 200°C, or up to 250°C) to withstand the temperatures that may be required to provide sufficient vapor pressure and / or mitigate condensation or adhesion of the composition within the valves and other components.

[0393] In some embodiments, the container further includes 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 include 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 within the container cavity are known in the art, including but not limited to capacitance-based sensors, conductivity-based sensors, float-switch level sensors, tuning fork sensors, and ultrasonic sensors.

[0394] In some embodiments, the container further includes one or more heat transfer elements, such as fins, rods, beads, etc., to facilitate heat transfer from the container walls to the composition within the cavity and vice versa. One or more heat transfer elements may include a series of bags or compartments for holding the composition within the cavity. One or more heat transfer elements may form a serpentine or radial path for holding the composition within the cavity and, in some cases, for guiding a carrier gas over or through the composition. This configuration is particularly useful for conveying vapors of low-volatility liquid and solid compositions.

[0395] In some embodiments, the container is used in the methods described herein. In some embodiments, the container is used in a device as described herein.

[0396] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of various processes, apparatuses, systems and configurations, as well as other features, functions, actions and / or properties disclosed herein, and any and all equivalents thereof.

[0397] The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of this disclosure.

[0398] The specific embodiments shown and described are illustrative of this disclosure and its best mode, and are not intended to limit the scope of aspects and embodiments in any way. In fact, for the sake of brevity, conventional manufacturing, connection, fabrication, and other functional aspects of the device may not be described in detail. Furthermore, the connecting lines shown in the figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in the actual device, and / or may not exist in some embodiments.

[0399] It should be understood that the configurations and / or methods described herein are exemplary in nature, and these specific embodiments or examples herein should not be considered limiting, as many variations are possible. The particular routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in a different order, or in some cases omitted.

Claims

1. An apparatus comprising: The reaction chamber is constructed and arranged to at least hold the semiconductor substrate; A metal precursor source, which is configured and arranged to provide vapor of at least one metal precursor; A precursor distribution and removal system configured to supply vapors of metal precursors from a metal precursor source to a reaction chamber and to remove vapors of metal precursors from the reaction chamber; as well as A sequence controller, operably connected to a precursor dispensing and removal system, includes a memory configured to control the flow of a metal precursor from a metal precursor source to a reaction chamber by activating the precursor dispensing and removal system during one or more cycles; thereby, as a result of the cycles, a metal-containing layer is formed on a semiconductor substrate in the reaction chamber. At least one metal precursor comprises: Selected from at least one of the following metals: 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; At least one ligand of formula (I): (I)， in, R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings; R 3 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups.

2. The device according to claim 1, wherein, R 1 Selected from C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 2 Selected from C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings; R 3 Selected from H, C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 4 Selected from H, C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 5 Selected from H, C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and R 6 Selected from H, C 1-6 Alkyl, C 3-6 cycloalkyl, C 1-6 Alkyl-substituted C 3-6 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups.

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

4. The device according to claim 3, wherein, The reactants are selected from oxide reactants, nitride reactants, boride reactants, reducing agents, phosphide reactants, carbide reactants, sulfide reactants, and combinations thereof.

5. The device according to claim 3, wherein, The reactants are oxide reactants, wherein the oxide reactants are selected from H2O, O2, O3, H2O2, N2O, NO2, N2O4, pyridine N-oxide and O2 plasma.

6. The device according to claim 3, wherein, The reactants are nitride reactants, wherein the nitride reactants are selected from NH3, N2H4, hydrazine, alkylamine, N2 plasma, NH3 plasma and N2 / H2 plasma.

7. The device according to claim 3, wherein, The reactants are boride reactants, wherein the boride reactants are selected from borazane, BF3, BCl3, BBr3, BI3 and borane.

8. The device according to claim 3, wherein, The reactant is a reducing agent, wherein the reducing agent is selected from H2, H2 plasma, N2 / H2 plasma, N2H4, hydrazine, formic acid, formalin, borane, silane and cyclodiene.

9. The device according to claim 3, wherein, The reactants are phosphide reactants, wherein the phosphide reactants are selected from phosphine, phosphorus halides, phosphorus oxyhalides, organophosphates, organophosphites, aminophosphine, alkylphosphine, and silylphosphine.

10. The device according to claim 3, wherein, The reactants are carbide reactants, wherein the carbide reactants are selected from alkyl iodine, iodobenzene, alkyl bromide, bromobenzene, acetylene, propargyl chloride, propargyl bromide, propargyl iodine, allyl chloride, allyl bromide, allyl iodine and cyclodiene.

11. The device according to claim 3, wherein, The reactants are sulfide reactants, wherein the sulfide reactants are selected from H2S, S8, S2Cl2, thiols, dithiols, bis(trimethylsilyl) sulfides, CS2 and disulfides.

12. The device according to claim 1, wherein, The at least one metal precursor further includes one or more additional ligands selected from cyclopentadienyl ligands, amide ligands, imide ligands, amidine ligands, halide ligands, alkyl ligands, alkoxide ligands, diketone ligands, and 1,4-diazabutadiene ligands.

13. The device according to claim 1, wherein, The at least one metal precursor further comprises one or more cyclopentadienyl ligands of formula (1): (1), in, R 7a Selected from H, C 1-8 Alkyl and -SiR 9a , where R 9a It is C 1-6 alkyl; R 7b Selected from H, C 1-8 Alkyl and -SiR 9b , where R 9b It is C 1-6 alkyl; R 7c Selected from H, C 1-8 Alkyl and -SiR 9c , where R 9c It is C 1-6 alkyl; R 7d Selected from H, C 1-8 Alkyl and -SiR 9d , where R 9d It is C 1-6 Alkyl; and R 7e Selected from H, C 1-8 Alkyl and -SiR 9e , where R 9e It is C 1-6 alkyl.

14. The device according to claim 1, wherein, The at least one metal precursor further comprises one or more amide ligands of formula (2): (2), in, R 11 Independently selected from H and C 1-8 Alkyl and -SiR 12 , where R 12 It is C 1-6 Alkyl; and R 11a Independently selected from H and C 1-8 Alkyl and -SiR 12a , where R 12a It is C 1-6 alkyl, Among them, R 11 and R 11a At least one of them is not H.

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

16. A method for forming a metal-containing layer on a semiconductor substrate, comprising the following steps: a) Providing the semiconductor substrate into the reaction chamber; and b) Execute one or more loops, each loop consisting of: Metal precursor pulse, wherein at least a portion of a semiconductor substrate is brought into contact with at least one metal precursor by introducing at least one metal precursor into a reaction chamber; At least one metal precursor comprises: Selected from at least one of the following metals: 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; At least one ligand of formula (I): (I)， in, R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings; R 3 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups, As a result of the cycle, a metal-containing layer is formed on the semiconductor substrate in the reaction chamber.

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

18. The method according to claim 16, wherein, At least one cycle further includes a reactant pulse, wherein at least a portion of the semiconductor substrate is in contact with the at least one reactant by introducing the at least one reactant into the reaction chamber; wherein the at least one reactant is selected from 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 for forming a metal-containing film, the composition comprising at least one metal precursor, the at least one metal precursor comprising: Selected from at least one of the following metals: 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 At least one ligand of formula (I): (I)， in, R 1 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 2 Selected from C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; or R 1 and R 2 Together with the phosphorus atoms to which they are attached, they form saturated or unsaturated 3, 4, 5, 6, 7, 8, 9 or 10-membered rings; R 3 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 4 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; R 5 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups; and R 6 Selected from H, C 1-10 Alkyl, C 3-10 cycloalkyl, C 1-6 Alkyl-substituted C 3-10 cycloalkyl, aryl and C-shaped 1-6 Alkyl-substituted aryl groups.

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