Gas deposition process

Abstract

The present disclosure relates to methods for depositing an elemental metal- or semimetal-containing material on a substrate via a cyclic deposition process, to layers containing the elemental metal or semimetal, to semiconductor structures and devices, and to deposition assemblies for depositing the elemental metal- or semimetal-containing material on a substrate. The methods according to the present disclosure include providing a substrate in a reaction chamber, providing a metal or semimetal precursor to the reaction chamber in a vapor phase, and providing a reducing agent to the reaction chamber in a vapor phase to form the elemental metal- or semimetal-containing material on the substrate. The reducing agent according to the methods includes a cyclohexadiene compound selected from compounds containing germanium-containing substituents.

Description

Technical Field

[0001] The present disclosure relates to methods and apparatus for fabricating semiconductor devices. More particularly, the present disclosure relates to methods and apparatus for depositing metals or semi-metals on substrates, and layers containing metals or semi-metals. Background Art

[0002] Semiconductor device manufacturing at advanced technology nodes requires the uniform deposition of high-quality thin films over large areas and complex 3D structures. Cyclic deposition processes can be used to deposit metallic and semi-metallic materials. However, reducing agents suitable for cyclic deposition of such materials, especially at low deposition temperatures, are uncommon and cost-prohibitive.

[0003] In vapor deposition techniques, thermal treatment is sought because plasmas can damage the underlying substrate material or compromise the conformality of the process. However, ALD deposition of metals and semimetals has been hampered by a lack of effective reducing agents combined with suitable precursors. The most commonly used reducing agents, such as H2 and NH3, typically require deposition temperatures exceeding 200°C to achieve sufficient reactivity. Other reducing agents may have drawbacks related to corrosiveness or the inclusion of unwanted elements in the deposited material.

[0004] Therefore, there is a need in the art for new reducing agents for depositing metallic and semi-metallic materials at low temperatures.

[0005] Any discussion set forth in this section (including discussion of problems and solutions) has been included in this disclosure solely to provide context for the disclosure. Such discussion should not be construed as an admission that any or all of the information was known at the time the present invention was made, or otherwise constitutes prior art. Summary of the Invention

[0006] This summary may introduce some concepts in a simplified form that are further described below. This summary is not intended to necessarily identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0007] Various embodiments of the present disclosure relate to methods of depositing elemental metal or semi-metal containing materials on substrates, elemental metal or semi-metal containing layers, semiconductor structures and devices, and deposition assemblies for depositing elemental metal or semi-metal containing materials on substrates.

[0008] In one aspect, a method for depositing an elemental metal or semimetal-containing material on a substrate via a cyclic deposition process is disclosed. The method comprises providing the substrate in a reaction chamber, providing a metal or semimetal precursor to the reaction chamber in a vapor phase, and providing a reducing agent to the reaction chamber in a vapor phase to form the elemental metal or semimetal-containing material on the substrate. The reducing agent according to the method comprises a cyclohexadiene compound selected from the group consisting of compounds of formula (I).

[0009]

[0010] In formula (I), Z 1 and Z 2 Each of which is independently selected from CR 11 and N, R 1 to R 11 Each of R is independently H, C1 to C7 linear or branched alkyl, C6 to C10 aryl, or C6 to C14 heteroaryl. 11 is H. In some embodiments, R 7 to R 10 Each of R is independently selected from the group consisting of H, C1 to C4 straight and branched alkyl groups, and phenyl groups. 7 to R 10 It’s H.

[0011] However, in some aspects, the reducing agent comprises a bicyclic bis(trialkylgermanyl) molecule. For example, two molecules according to formula (I) can be coupled to each other through their Z 1 and / or Z 2 Positional fusion. In this molecule, each bond Z 1 or Z 2 It's CR 11 , and the bonds between the rings replace R 11 In some embodiments, the reducing agent includes 4,4'-bis(trialkylgermanyl)-1,1',4,4'-tetrahydro-4,4'-bipyridine, such as 4,4'-bis(trimethylgermanyl)-1,1',4,4'-tetrahydro-4,4'-bipyridine.

[0012] In some embodiments, R 1 to R 6 Each of R is independently selected from the group consisting of H, methyl, ethyl, n-propyl and isopropyl. 1 to R 6 In some embodiments, all R 1 to R 6is methyl. In some embodiments, the cyclohexadiene compound is 1,4-bis(trialkylgermanyl)-1,4-dihydropyrazine. In some embodiments, the cyclohexadiene compound is 1,4-bis(trimethylgermanyl)-1,4-dihydropyrazine. In some embodiments, the metal or semi-metal precursor is a metal precursor, and the elemental metal is deposited on the substrate. In some embodiments, the metal or semi-metal precursor is a transition metal precursor, and the elemental transition metal is deposited on the substrate. In some embodiments, the transition metal is a 4th row transition metal. In some embodiments, the 4th row transition metal is selected from Co, Ni, Cu and Zn. In some embodiments, the transition metal is a Group 11 transition metal. In some embodiments, the transition metal is a noble metal. In some embodiments, the noble metal is selected from silver and gold. In some embodiments, the noble metal is gold. In some embodiments, the metal precursor comprises a metal halide. In some embodiments, the metal halide is selected from the group consisting of CoCl2, NiCl2, CuCl2, ZnCl2, AuCl, CoBr2, NiBr2, CuBr2, ZnBr2, AuBr, CoI2, NiI2, CuI2, ZnI2 and AuI. In some embodiments, the transition metal of the transition metal halide is a noble metal. In some embodiments, the metal precursor comprises an adduct ligand. In some embodiments, the adduct ligand is a monodentate adduct ligand. In some embodiments, the metal or semimetal precursor comprises a metal or semimetal atom in the +1, +2, +3 or +4 formal oxidation state.

[0013] In one aspect, a method for depositing a metal layer on a substrate is disclosed. The method comprises contacting the substrate with a vapor-phase metal precursor, wherein the metal precursor comprises metal atoms in an oxidation state of +1 or higher, and contacting the substrate with a vapor-phase reducing agent to reduce the metal atoms in the metal precursor, thereby forming the metal layer on the substrate. In the method, the reducing agent comprises a cyclohexadiene compound selected from the compounds of formula (I),

[0014]

[0015] Among them, Z 1 and Z 2 Each of which is independently selected from CR 11 and N, R 1 to R 11 Each of the groups is independently H, C1 to C7 linear or branched alkyl, C6 to C10 aryl, or C6 to C14 heteroaryl.

[0016] In another aspect, a metal or semi-metal layer produced by a cyclic deposition method is disclosed. The method includes providing a substrate in a reaction chamber, providing a metal or semi-metal precursor to the reaction chamber in a vapor phase, and providing a reducing agent to the reaction chamber in a vapor phase to form an elemental metal or semi-metal material on the substrate. The reducing agent comprises a cyclohexadiene compound selected from the group consisting of compounds of formula (I),

[0017]

[0018] Among them, Z 1 and Z 2 Each of which is independently selected from CR 11 and N, R 1 to R 11 Each of the groups is independently H, C1 to C7 linear or branched alkyl, C6 to C10 aryl, or C6 to C14 heteroaryl.

[0019] In another aspect, a semiconductor structure comprising an elemental metal or semimetal deposited by a cyclic deposition method is disclosed. The method comprises providing a substrate in a reaction chamber, providing a metal or semimetal precursor to the reaction chamber in a vapor phase, and providing a reducing agent to the reaction chamber in a vapor phase to form a material comprising the elemental metal or semimetal on the substrate. The reducing agent used to deposit the elemental metal or semimetal comprises a cyclohexadiene compound selected from the group consisting of compounds of formula (I),

[0020]

[0021] Among them, Z 1 and Z 2 Each of which is independently selected from CR 11 and N, R 1 to R 11 Each of the groups is independently H, C1 to C7 linear or branched alkyl, C6 to C10 aryl, or C6 to C14 heteroaryl.

[0022] In another aspect, a semiconductor device comprising an elemental metal or semimetal deposited by a cyclic deposition method is disclosed. The method comprises providing a substrate in a reaction chamber, providing a metal or semimetal precursor to the reaction chamber in a vapor phase, and providing a reducing agent to the reaction chamber in a vapor phase to form a material comprising the elemental metal or semimetal on the substrate. The reducing agent in the deposited elemental metal or semimetal comprises a cyclohexadiene compound selected from the group consisting of compounds of formula (I),

[0023]

[0024] Among them, Z 1 and Z 2 Each of which is independently selected from CR 11 and N, R 1 to R11 Each of the groups is independently H, C1 to C7 linear or branched alkyl, C6 to C10 aryl, or C6 to C14 heteroaryl.

[0025] In another aspect, a reducing agent for a vapor deposition process is disclosed, comprising an effective amount of a cyclohexadiene compound of formula (I).

[0026]

[0027] In the cyclohexadiene compound of the reducing agent, Z 1 and Z 2 Each of which is independently selected from CR 11 and N, R 1 to R 11 Each of is independently H, C1 to C7 linear or branched alkyl, C6 to C10 aryl or C6 to C14 heteroaryl. In an embodiment of the reducing agent according to the present disclosure, R 11 is H, all R 1 to R 6 is methyl or ethyl, and all R 7 to R 10 is H, methyl, ethyl, propyl or isopropyl.

[0028] In yet another aspect, a deposition assembly for depositing an elemental metal or semimetal on a substrate is disclosed. The deposition assembly includes one or more reaction chambers constructed and arranged to hold a substrate; and a precursor injector system constructed and arranged to provide a metal or semimetal precursor and a reducing agent to the reaction chambers in a vapor phase. The deposition assembly also includes a precursor vessel constructed and arranged to hold the metal or semimetal precursor, and the assembly is constructed and arranged to provide the metal or semimetal precursor and the reducing agent to the reaction chambers via the precursor injector system to deposit a metal or semimetal-containing material on the substrate.

[0029] In the present disclosure, any two numbers of a variable may constitute a feasible range for the variable, and any range indicated may include or exclude endpoints. In addition, any values of the variables indicated (regardless of whether they are expressed as "about") may refer to exact values or approximate values, and include equivalents, and may refer to average values, median values, representative values, majority values, etc. In addition, in the present disclosure, the terms "comprising," "consisting of," and "having" independently refer in some embodiments to "generally or broadly including," "including," "essentially consisting of," or "consisting of." In the present disclosure, the meaning of any definition does not necessarily exclude common and customary meanings in some embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The accompanying drawings, which are included to provide a further understanding of the disclosure and constitute a part of this specification, illustrate exemplary embodiments and together with the description help to explain the principles of the disclosure. In the drawings:

[0031] Panels A to C in FIG1 are block diagrams of exemplary embodiments of methods according to the present disclosure.

[0032] Figure 2 is a schematic diagram of a deposition assembly according to the present invention. DETAILED DESCRIPTION

[0033] The descriptions of exemplary embodiments of methods, layers, structures, devices, and deposition assemblies provided below are merely exemplary and are for illustrative purposes only. The following descriptions are not intended to limit the scope of the present disclosure or the claims. In addition, the recitation of multiple embodiments having the features illustrated is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the features. For example, various embodiments are set forth as exemplary embodiments and may be recited in dependent claims. Unless otherwise indicated, the exemplary embodiments or components thereof may be combined or may be applied separately from each other. The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the claimed invention.

[0034] Overall process

[0035] In the deposition methods according to the present invention, a material comprising an elemental metal or semimetal is deposited. Thus, the material deposited according to the present invention comprises elemental metal, elemental semimetal, or both. Elemental metal or semimetal, as used herein, refers to a metal or semimetal in an oxidation state of zero. The metal or semimetal deposited according to the present invention may include elemental metal or semimetal as well as other forms of the metal or semimetal. For example, the metal or semimetal deposited according to the present invention may have an oxidation state of 0, +1, +2, +3, +4, +5, and / or +6, as may be characteristic of the element in question. In some embodiments, the material deposited according to the present invention consists essentially of or consists of elemental metal. In some embodiments, the material deposited according to the present invention consists essentially of or consists of elemental semimetal. In some embodiments, the deposited metal or semimetal is at least partially oxidized. In some embodiments, at least 60% of the metal or semimetal is deposited as elemental metal or semimetal. In some embodiments, at least 80% or at least 90% of the metal or semimetal is deposited as elemental metal or semimetal. In some embodiments, at least 93% or 95% of the metal or semimetal is deposited as elemental metal or semimetal.

[0036] The elemental composition of the material deposited according to the present invention can vary depending on the process. In some embodiments, the material deposited according to the present invention includes at least one or more elements other than the target metal or semimetal. Such materials may have properties different from metals useful in certain applications. In some embodiments, the material may include two or more metals or semimetals. In such embodiments, at least one metal or semimetal is deposited according to the method of the present disclosure. In some embodiments, the material containing metal or semimetal may include, for example, at least about 60 atomic percent (atomic %) or at least about 75 atomic % of the target metal or semimetal, or about 75 to about 95 atomic % of the target metal or semimetal, or about 75 to about 89 atomic % of the target metal or semimetal. The material containing metal or semimetal deposited by the method according to the present disclosure may include, for example, at least about 80 atomic %, about 85 atomic %, about 87 atomic %, about 90 atomic %, about 95 atomic %, about 97 atomic % or about 99 atomic % of the target metal or semimetal. In some embodiments, the material containing metal or semimetal may be essentially composed of or composed of the target metal or semimetal. Materials composed of metals or semimetals may contain acceptable amounts of impurities, such as oxygen, carbon, chlorine or other halogens, and / or hydrogen, which may originate from one or more precursors used to deposit the metal- or semimetal-containing material.

[0037] In some embodiments, the metal- or semi-metal-containing material may include less than about 30 atomic %, less than about 20 atomic %, less than about 10 atomic %, less than about 8 atomic %, less than about 7 atomic %, less than about 5 atomic %, or less than about 2 atomic % oxygen. In some embodiments, the metal- or semi-metal-containing material may include less than about 20 atomic %, less than about 15 atomic %, less than about 10 atomic %, less than about 8 atomic %, less than about 6 atomic %, less than about 5 atomic %, less than 4.5 atomic %, or less than about 3 atomic % carbon.

[0038] In some embodiments, the material containing the elemental metal or semi-metal can form a layer. In such embodiments, the metal or semi-metal forms a metal or semi-metal layer. As used herein, a "metal or semi-metal layer" can be a layer of material containing a metal or semi-metal. As used herein, the terms "layer" and / or "film" can refer to any continuous or discontinuous structure and material, such as a material deposited by the methods disclosed herein. For example, a layer and / or film can include a two-dimensional material, a three-dimensional material, nanoparticles, or even a partial or complete molecular layer or a partial or complete atomic layer or clusters of atoms and / or molecules. A film or layer can include a material or layer having pinholes, which can be at least partially continuous. A seed layer can be a discontinuous layer used to increase the nucleation rate of another material. However, the seed layer can also be substantially or completely continuous.

[0039] substrate

[0040] As used herein, the term "substrate" may refer to any one or more underlying materials that can be used to form or on which a device, circuit, material, or layer of material can be formed. The substrate may include a bulk material, such as silicon (such as single crystal silicon), other Group IV materials, such as germanium, or other semiconductor materials, such as Group II-VI or Group III-V semiconductor materials. The substrate may include one or more layers overlying the bulk material. The substrate may include various topological structures, such as gaps, including recesses, lines, grooves, or spaces between raised portions (such as fins) formed within or on at least a portion of a layer of the substrate. The substrate may include nitrides such as TiN, oxides, insulating materials, dielectric materials, conductive materials, metals such as tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper, or metallic materials, crystalline materials, epitaxial materials, heteroepitaxial materials, and / or single crystal materials. In some embodiments of the present disclosure, the substrate includes silicon. As described above, the substrate may include other materials in addition to silicon. Other materials may form layers.

[0041] Vapor deposition process

[0042] The present disclosure relates to the deposition of materials from the gas phase. Thus, in the method according to the present disclosure a gaseous metal or semi-metal precursor and a reducing agent are used.

[0043] In the present disclosure, "gas" may include materials that are gaseous at normal temperature and pressure (NTP), evaporated solids and / or evaporated liquids, and may be composed of a single gas or a gas mixture, depending on the circumstances. A metal or semi-metal precursor may be provided to the reaction chamber in a gas phase. A reducing agent may be provided to the reaction chamber in a gas phase. The term "inert gas" may refer to a gas that does not participate in a chemical reaction and / or does not become part of a layer to any appreciable extent. Exemplary inert gases include He and Ar and any combination thereof. In some cases, molecular nitrogen and / or hydrogen may be an inert gas. Gases other than process gases, i.e., gases that are not introduced through a precursor injector system, other gas distribution devices, etc., may be used, for example, to seal the reaction space and may include sealing gases.

[0044] In the present disclosure, a deposition process may include a cyclic deposition process, such as an atomic layer deposition (ALD) process or a cyclic chemical vapor deposition (CVD) process. The term "cyclic deposition process" may refer to the sequential introduction of precursors and / or reactants into a reaction chamber to deposit a material, such as a metal- or semi-metal-containing material, on a substrate. Cyclic deposition includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and a hybrid cyclic deposition process including an ALD component and a cyclic CVD component. The process may include a purge step between providing precursors or between providing precursors and reactants in the reaction chamber.

[0045] The process may include one or more cyclic phases. For example, the pulses of the metal or semi-metal precursor and the reducing agent may be repeated. In some embodiments, the process includes one or more non-cyclic phases. In some embodiments, the deposition process includes a continuous flow of at least one precursor. In some embodiments, a reactant may be provided continuously in the reaction chamber. In such embodiments, the process includes a continuous flow of a precursor or reactant. In some embodiments, one or more precursors and / or reactants are provided continuously in the reaction chamber. In some embodiments, an auxiliary reactant may be provided continuously in the reaction chamber.

[0046] The term "atomic layer deposition" (ALD) may refer to a vapor deposition process in which deposition cycles (e.g., multiple consecutive deposition cycles) are performed in a reaction chamber. Typically, for an ALD process, during each cycle, a precursor is introduced into the reaction chamber and chemically adsorbed onto the deposition surface (e.g., a substrate surface that may include previously deposited material from a previous ALD cycle or other material), forming a monolayer or sub-monolayer of material that does not readily react with additional precursors (i.e., a self-limiting reaction). Thereafter, in some cases, another precursor or reactant may be subsequently introduced into the process chamber to convert the chemically adsorbed precursor into the desired material on the deposition surface. The second precursor or reactant is capable of further reacting with the precursor. During one or more cycles, for example, during each step of each cycle, a purge step may be utilized to remove any excess precursor from the process chamber and / or any excess reactant and / or reaction byproducts from the reaction chamber. Thus, in some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the metal or semi-metal precursor to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing a reducing agent to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing any precursors or reactants into the reaction chamber.

[0047] CVD type process generally involves a gas phase reaction between two or more precursors and / or reactants. Precursors and reactants can be provided to the reaction space or substrate simultaneously, or provided in partially or completely separated pulses. The substrate and / or reaction space can be heated to promote the reaction between the gaseous precursors and / or reactants. In certain embodiments, precursors and reactants are provided until a layer with a desired thickness is deposited. In certain embodiments, a cyclic CVD process can use multiple cycles to deposit a film with a desired thickness. In the cyclic CVD process, precursors and / or reactants can be provided to the reaction chamber in non-overlapping or partially or completely overlapping pulses.

[0048] Without limiting the present disclosure to any particular theory, in some embodiments, layers with low resistivity can be produced, particularly when depositing elemental metals. The resistivity of a metal layer according to the present disclosure can be less than 300 μΩcm, or less than 100 μΩcm, or less than 50 μΩcm. For example, the resistivity of a metal layer according to the present disclosure can be from about 5 μΩcm to about 300 μΩcm, or from about 5 μΩcm to about 100 μΩcm, or from about 5 μΩcm to about 50 μΩcm, such as about 10 μΩcm, 15 μΩcm, 30 μΩcm, or 40 μΩcm.

[0049] After deposition, the metal or semimetal may be at least partially in elemental form. Thus, the oxidation state of the metal or semimetal may be zero. In some embodiments, the metal or semimetal is substantially completely in elemental form after deposition. The metal or semimetal layer may include additional elements, such as nitrogen, carbon, and / or oxygen. Other additional or alternative elements are possible. In some embodiments, the metal or semimetal layer may include a significant proportion of other elements in addition to the target metal or semimetal. However, in some embodiments, the metal or semimetal layer may essentially only contain the metal or semimetal. Thus, the metal or semimetal layer may include, essentially consist of, or consist of the metal or semimetal. In some embodiments, the metal or semimetal layer may be a seed layer. The seed layer may be used to enhance the deposition of another layer. In some embodiments, two or more metals or semimetals may be deposited by the methods disclosed herein. In such embodiments, the method may include providing at least two different metal or semimetal precursors to the reaction chamber.

[0050] In some embodiments, after providing a metal or semi-metal precursor and / or a reducing agent in the reaction chamber, the reaction chamber is purged. As used herein, the term "purging" may refer to a process of removing gaseous precursors and / or gaseous byproducts from the substrate surface, such as by evacuating the reaction chamber with a vacuum pump and / or by replacing the gas in the reaction chamber with an inert or substantially inert gas such as argon or nitrogen. Purge can be performed between two gas pulses that react with each other. However, purge can be performed between two gas pulses that do not react with each other. For example, purge can be provided between pulses of two precursors or between a precursor and a reactant. Purge can avoid or at least reduce the gas phase interaction between the two gases that react with each other. It should be understood that purge can be performed in time or space, or both. For example, in the case of time purge, the purge step can be used, for example, in the time sequence of providing a first precursor to the reaction chamber, providing a purge gas to the reaction chamber, and providing a second precursor to the reaction chamber, wherein the substrate of the deposited layer does not move. For example, in the case of space purge, the purge step can take the following form: the substrate is moved from a first position where the first precursor is continuously supplied to a second position where the second precursor is continuously supplied through a purge gas curtain. The purge time can be, for example, from about 0.01 seconds to about 20 seconds, from about 0.05 seconds to about 20 seconds, or from about 1 second to about 20 seconds, or from about 0.5 seconds to about 10 seconds, or between about 1 second and about 7 seconds, such as 5 seconds, 6 seconds or 8 seconds. However, if desired, other purge times can be used, such as when a highly conformal step coverage on an extremely high aspect ratio structure or other structure with a complex surface morphology is required, or can be used for specific reactor types such as batch reactors.

[0051] In some embodiments, the cyclic deposition process according to the present disclosure includes a thermal deposition process. In thermal deposition, the temperature is increased relative to the ambient temperature to promote the chemical reaction. Typically, in the absence of other external energy sources (such as plasma, free radicals or other forms of radiation), the temperature increase provides the energy required to form the material containing the elemental metal or semi-metal. In some embodiments, the cyclic deposition process according to the present disclosure is a completely thermal process, that is, it does not include a plasma step. However, in some embodiments, the method includes at least one plasma enhancement step. In some embodiments, the method according to the present disclosure is a plasma enhanced deposition method, such as PEALD or PECVD.

[0052] The terms "precursor" and "reactant" may refer to molecules (compounds or molecules containing a single element) that participate in a chemical reaction to produce another compound. A precursor typically contains a moiety that at least partially incorporates into the compound or element produced by the chemical reaction. The resulting compound or element can be deposited on a substrate. A reactant can be an element or compound that is not incorporated to a significant extent into the resulting compound or element. However, in certain embodiments, a reactant may also contribute to the production of the compound or element, or it may alter the properties of the deposited material.

[0053] As used herein, a "metal or semimetal precursor" includes a gas or a material that can be converted to a gaseous state and can be represented by a chemical formula including a target metal or semimetal. The target metal or semimetal refers to the element to be deposited. Examples of target metals include transition metals such as early transition metals, late transition metals, lanthanide metals, and late transition metals. Examples of target semimetals include boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), bismuth (Bi), and tellurium (Te).

[0054] In some embodiments, the metal precursor comprises a transition metal for depositing an elemental transition metal on a substrate. In some embodiments, the transition metal precursor comprises a Group 4 to 6 transition metal for depositing an elemental Group 4 to 6 transition metal on a substrate. In some embodiments, the transition metal precursor comprises a Group 11 transition metal for depositing an elemental Group 11 transition metal on a substrate. In some embodiments, the metal precursor comprises a Row 4 transition metal for depositing an elemental Row 4 transition metal on a substrate. In some embodiments, the Row 4 transition metal is selected from cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn). In some embodiments, the transition metal in the transition metal precursor is selected from scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd). In some embodiments, the transition metal in the transition metal precursor is selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd. In some embodiments, the transition metal in the transition metal precursor is selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Co, Rh, Ir, Ni, Cu, and Zn. In some embodiments, the transition metal is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. In some embodiments, the metal precursor comprises a lanthanide metal for depositing an elemental lanthanide metal on a substrate.

[0055] In some embodiments, the metal precursor is a metal organic precursor or an organometallic precursor. Many different types of such precursors are used in the field of cyclic vapor deposition. The precursor should be gaseous at a suitable temperature and pressure to allow deposition according to the present disclosure. The metal precursor can be, for example, a β-diketone group, a cyclopentadienyl group, a carbonyl group, or an alkoxide.

[0056] In some embodiments, the metal precursor comprises a metal atom with an oxidation state of +1. In some embodiments, the metal precursor comprises a metal atom with an oxidation state of +2. In some embodiments, the metal precursor comprises a metal atom with an oxidation state of +1 or +2. In some embodiments, the metal precursor comprises a metal atom with an oxidation state of +2 or higher, such as +3, +4, +5, or +6. In some embodiments, the metal precursor comprises a metal halide. In some embodiments, the metal precursor comprises a metal halide and an adduct ligand. In some embodiments, the adduct ligand comprises a phosphine. In some embodiments, the adduct ligand comprises an amine. In some embodiments, the adduct ligand is a bidentate adduct ligand. In some embodiments, the adduct ligand is a monodentate adduct ligand.

[0057] In some embodiments, the metal precursor is a transition metal precursor for depositing a transition metal-containing material on a substrate. In some embodiments, the transition metal precursor comprises a transition metal halide. In some embodiments, the transition metal in the transition metal halide is selected from manganese, iron, cobalt, nickel, copper, and gold. In some embodiments, the transition metal is selected from Co, Ni, and Cu.

[0058] In some embodiments, the transition metal precursor may comprise a transition metal compound having an adduct-forming ligand, such as a monodentate, bidentate, or multidentate adduct-forming ligand. In some embodiments, the transition metal precursor may comprise a transition metal halide having an adduct-forming ligand, such as a monodentate, bidentate, or multidentate adduct-forming ligand. In some embodiments, the transition metal precursor may comprise a transition metal compound having a nitrogen-containing adduct-forming ligand, such as a nitrogen-containing monodentate, bidentate, or multidentate adduct-forming ligand. In some embodiments, the adduct-forming ligand comprises at least one of nitrogen, phosphorus, oxygen, or sulfur.

[0059] In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound, such as a transition metal halide, may comprise a monodentate, bidentate, or polydentate adduct-forming ligand coordinated to the transition metal atom of the transition metal compound through at least one of a nitrogen atom, a phosphorus atom, an oxygen atom, a carbon atom, or a sulfur atom. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may comprise a cyclic adduct-forming ligand. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may comprise a monoamine, a diamine, or a polyamine. In some embodiments of the present disclosure, the adduct-forming ligand in the transition metal compound may comprise a mono-, di-, or polyether. In some embodiments, the adduct-forming ligand in the transition metal compound may comprise a mono-, di-, or polyphosphine. Phosphine may be particularly advantageous in embodiments where the transition metal comprises copper. In some embodiments, the adduct-forming ligand in the transition metal compound may comprise carbon and / or in addition to nitrogen, oxygen, phosphorus, or sulfur in the adduct-forming ligand.

[0060] In some embodiments, the adduct-forming ligands in the transition metal compound may include one monodentate-forming adduct ligand. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include two monodentate-forming adduct ligands. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include three monodentate-forming adduct ligands. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include four monodentate-forming adduct ligands. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include one bidentate-forming adduct ligand. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include two bidentate-forming adduct ligands. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include one multidentate-forming adduct ligand. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include two multidentate-forming adduct ligands.

[0061] In some embodiments, the transition metal halide includes a transition metal bromide, a transition metal chloride, a transition metal iodide, or a transition metal fluoride. Specifically, the transition metal halide may include at least one of cobalt chloride, nickel chloride, copper chloride, gold chloride, cobalt bromide, nickel bromide, copper bromide, gold bromide, cobalt iodide, nickel iodide, copper iodide, or gold iodide.

[0062] In some embodiments of the present disclosure, the transition metal halide may include a transition metal species, including but not limited to at least one of manganese, iron, cobalt, nickel, copper, and gold. In some embodiments of the present disclosure, the transition metal halide may include at least one of manganese chloride, iron chloride, cobalt chloride, nickel chloride, copper chloride, and gold chloride. In some embodiments of the present disclosure, the transition metal halide may include at least one of manganese bromide, iron bromide, cobalt bromide, nickel bromide, copper bromide, and gold bromide. In some embodiments of the present disclosure, the transition metal halide may include at least one of manganese fluoride, iron fluoride, cobalt fluoride, nickel fluoride, copper fluoride, and gold fluoride. In some embodiments, the transition metal halide includes a bidentate nitrogen-containing ligand. In some embodiments, the transition metal halide may include a bidentate nitrogen-containing adduct-forming ligand. In some embodiments, the transition metal halide may include an adduct-forming ligand comprising two nitrogen atoms, each nitrogen atom being bonded to at least one carbon atom. In some embodiments of the present disclosure, the transition metal halide includes one or more nitrogen atoms bonded to a central transition metal atom, thereby forming a metal complex.

[0063] In some embodiments, the bidentate nitrogen-containing adduct-forming ligand comprises two nitrogen atoms, each nitrogen atom bonded to at least one carbon atom.

[0064] In some embodiments of the present disclosure, the transition metal precursor may include a transition metal compound having formula (III):

[0065] (Adduct) n -MX a (III)

[0066] wherein each “adduct” is an adduct-forming ligand and can be independently selected to form a monodentate, bidentate or polydentate adduct ligand or a mixture thereof: in the case of forming a monodentate adduct ligand, n is 1 to 4, in the case of forming a bidentate or polydentate adduct ligand, n is 1 to 2; M is a transition metal, such as cobalt (Co), copper (Cu) or nickel (Ni); wherein each X a is another ligand and can be independently selected as a halide or other ligand; wherein a is 1 to 4, and in some cases a is 2.

[0067] In some embodiments, the adduct-forming ligand comprises nitrogen, for example, forming an amine, diamine, or polyamine adduct ligand. In such an embodiment, the transition metal compound may include at least one of triethylamine (TEA), N,N,N',N'-tetramethylethylenediamine (CAS: 110-18-9, TMEDA), N,N,N',N'-tetraethylethylenediamine (CAS: 150-77-6, TEEDA), N,N'-diethyl-1,2-ethylenediamine (CAS: 111-74-0, DEEDA), N,N'-diisopropylethylenediamine (CAS: 4013-94-9), N,N,N',N'-tetramethyl-1,3-propylenediamine (CAS: 110-95-2, TMPDA), N,N,N',N'-tetramethylmethanediamine (CAS: 51-80-9, TMMDA), N,N,N',N",N"-pentamethyldiethylenetriamine amine (CAS: 3030-47-5, PMDETA), diethylenetriamine (CAS: 111-40-0, DIEN), triethylenetetramine (CAS: 112-24-3, TRIEN), tris(2-aminoethyl)amine (CAS: 4097-89-6, TREN, TAEA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (CAS: 3083-101, HMTETA), 1,4,8,11-tetraazacyclotetradecane (CAS: 295-37-4, Cyclam), 1,4,7-trimethyl-1,4,7-triazacyclononane (CAS: 96556-05-7) or 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (CAS: 41203-22-9). In some embodiments, the adduct-forming ligand comprises TMEDA or TMPDA.

[0068] In some embodiments, the transition metal halide may include cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)). In some embodiments, the transition metal halide may include cobalt bromide tetramethylethylenediamine (CoBr2(TMEDA)). In some embodiments, the transition metal halide may include cobalt iodide tetramethylethylenediamine (CoI2(TMEDA)). In some embodiments, the transition metal halide may include cobalt chloride N,N,N',N'-tetramethyl-1,3-propylenediamine (CoCl2(TMPDA)). In some embodiments, the transition metal halide may include at least one of cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)), nickel chloride tetramethyl-1,3-propylenediamine (NiCl2(TMPDA)), or nickel iodide tetramethyl-1,3-propylenediamine (NiI2(TMPDA)). In some embodiments, the transition metal compound or transition metal halide includes at least one of CoCl2(TMEDA), CoBr2(TMEDA), CoI2(TMEDA), CoCl2(TMPDA), or NiCl2(TMPDA).

[0069] In some embodiments, the adduct forming ligand comprises phosphorus, for example, to form a phosphine, diphosphine, or polyphosphine adduct ligand. For example, the transition metal compound may include triethylphosphine (CAS: 554-70-1), trimethyl phosphite (CAS: 121-45-9), 1,2-bis(diethylphosphino)ethane (CAS: 6411-21-8, BDEPE), 1,2-bis(dimethylphosphino)ethane (CAS: 23936-60-9), 1,3-bis(diethylphosphino)propane (CAS: 29149-93-7), or 1,3-bis(dimethylphosphino)propane (CAS: 39564-18-6).

[0070] In some embodiments, the metal precursor is a transition metal precursor and includes a transition metal halide containing an organophosphine adduct ligand.

[0071] In some embodiments, the transition metal of the transition metal halide is a Group 4 transition metal. In some embodiments, the transition metal may be selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. In some embodiments, the transition metal is selected from Co, Ni, and Cu. In some embodiments, the transition metal of the transition metal halide is a Group 11 transition metal. In some embodiments, the transition metal may be selected from Cu, Ag, and Au.

[0072] In some embodiments, the transition metal of the transition metal halide has an oxidation state of +2. In some embodiments, the transition metal of the transition metal halide has an oxidation state of +1. The halogen of the transition metal halide can be selected from fluorine (F), chlorine (Cl), bromine (Br) and iodine (I). In some embodiments, the halogen of the transition metal halide is selected from Cl and Br. In some embodiments, the transition metal halide is selected from CoCl2, CoBr2, NiCl2, NiBr2, CuCl2, CuBr2, AuCl, AuBr and AuI. In some embodiments, the transition metal halide is selected from NiCl2 and NiBr2. In some embodiments, the transition metal halide is AuCl.

[0073] Transition metal halides according to the present disclosure include organophosphine adduct ligands. The organophosphine adduct ligand comprises a phosphorus (P) atom bonded to one or more organic ligands. In some embodiments, the phosphorus atom of the organophosphine adduct ligand is bonded to at least one organic group. In some embodiments, the phosphorus atom of the organophosphine adduct ligand is bonded to at least two organic groups. In some embodiments, the phosphorus atom of the organophosphine adduct ligand is bonded to three organic groups. In some embodiments, the organic group is an alkyl group. In some embodiments, all organic groups bonded to the phosphorus atom are alkyl groups. In some embodiments, the alkyl group is a straight or branched alkyl group. In some embodiments, the alkyl group is not an aromatic alkyl group. In some embodiments, the alkyl group is not a cyclic alkyl group.

[0074] In some embodiments, the alkyl group is a C1 to C4 alkyl group. In some embodiments, the alkyl group is selected from methyl, ethyl, n-propyl, and isopropyl. In some embodiments, the phosphine adduct ligand is trimethylphosphine. In some embodiments, the phosphine adduct ligand is triethylphosphine. In some embodiments, the phosphine adduct ligand is tri-n-propylphosphine. In some embodiments, the phosphine adduct ligand is triisopropylphosphine. In some embodiments, the transition metal halide comprises two organic phosphine adduct ligands. In some embodiments, all organic ligands, such as C1 to C4 alkyl ligands, in the phosphine adduct ligand are the same. In some embodiments, the two organic phosphine adduct ligands are the same.

[0075] In some embodiments, the transition metal halide has formula (IV):

[0076] MX y (PRR'R") z (IV),

[0077] wherein M is a transition metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, and Au; x is a halogen selected from F, Cl, Br, and I; R, R', and R" are each independently selected from C1 to C4 alkyl, y is an integer from 1 to 5, and z is an integer from 1 to 4. In some embodiments, y is 2 and z is 2. In some embodiments, y is 3 and z is 2. In some embodiments, y is 3 and z is 3. In some embodiments, at least one of R, R', and R" is trimethylphosphine. In some embodiments, at least one of R, R', and R" is triethylphosphine. In some embodiments, at least one of R, R', and R" is tri-n-propylphosphine. In some embodiments, at least one of R, R', and R" is triisopropylphosphine. In some embodiments, R' and R" are the same. In some embodiments, all R, R', and R" are the same. In such embodiments, the transition metal halide may be represented by formula (V).

[0078] In some embodiments, the transition metal halide has Formula (Va):

[0079] MX2(PR3)2 (Va),

[0080] wherein M is a transition metal selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn; X is a halogen selected from F, Cl, Br, and I; and R is a C1 to C4 alkyl group. In some embodiments, M is selected from Ni, Cu, and Co. In some embodiments, X is selected from Cl and Br. In some embodiments, R is selected from methyl and ethyl. In some embodiments, M is Ni, X is Cl, and R is methyl. In some embodiments, M is Ni, X is Cl, and R is ethyl. In some embodiments, M is Ni, X is Br, and R is methyl. In some embodiments, M is Ni, X is Br, and R is ethyl. In some embodiments, M is Cu, X is Cl, and R is methyl. In some embodiments, M is Cu, X is Cl, and R is ethyl. In some embodiments, M is Cu, X is Br, and R is methyl. In some embodiments, M is Cu, X is Br, and R is ethyl. In some embodiments, M is Co, X is Cl, and R is methyl. In some embodiments, M is Co, X is Cl, and R is ethyl. In some embodiments, M is Co, X is Br, and R is methyl. In some embodiments, M is Co, X is Br, and R is ethyl.

[0081] In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dichlorobis(trimethylphosphine)nickel. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dichlorobis(triethylphosphine)nickel. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dibromo-bis(trimethylphosphine)nickel. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dibromo-bis(triethylphosphine)nickel. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dichlorobis(trimethylphosphine)copper. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dichloro-bis(triethylphosphine)copper. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dibromo-bis(trimethylphosphine)copper. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dibromobis(triethylphosphine)copper. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dichloro-bis(trimethylphosphine)cobalt. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dichloro-bis(triethylphosphine)cobalt. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dibromobis(trimethylphosphine)cobalt. In some embodiments, the transition metal halide comprises, consists essentially of, or consists of dibromo-bis(triethylphosphine)cobalt.

[0082] In some embodiments, the transition metal halide has Formula (Vb):

[0083] MX(PR3) (Vb),

[0084] wherein M is a transition metal selected from Co, Ag, and Au; X is a halogen selected from F, Cl, Br, and I; and R is a C1 to C4 alkyl group. In some embodiments, M is Au. In some embodiments, X is selected from Cl, Br, and I. In some embodiments, R is selected from methyl and ethyl. In some embodiments, M is Au, X is Cl, and R is methyl. In some embodiments, M is Au, X is Cl, and R is ethyl. In some embodiments, M is Au, X is Br, and R is methyl. In some embodiments, M is Au, X is Br, and R is ethyl. In some embodiments, M is Ni, X is I, and R is methyl. In some embodiments, M is Au, X is I, and R is ethyl. In some embodiments, M is Ag, X is Cl, and R is methyl. In some embodiments, M is Ag, X is Cl, and R is ethyl. In some embodiments, M is Ag, X is Br, and R is methyl. In some embodiments, M is Ag, X is Br, and R is ethyl. In some embodiments, M is Ag, X is I, and R is methyl. In some embodiments, M is Ag, X is I, and R is ethyl.

[0085] In some embodiments, the transition metal precursor is provided as a mixture of two or more compounds. In the mixture, other compounds except the transition metal precursor can be inert compounds or elements. In some embodiments, the transition metal precursor is provided in a composition. A composition suitable for use as a composition can include a transition metal compound and an effective amount of one or more stabilizers. The composition can be a solution or a gas under standard conditions. In some embodiments, a mixture of at least two transition metals can be deposited. In such embodiments, the transition metal precursor can include two different transition metal-containing compounds, one or more of which are transition metal halides according to the present disclosure.

[0086] In some embodiments of the present disclosure, the adduct-forming ligand comprises oxygen, such as an ether, diether, or polyether adduct-forming ligand. For example, the transition metal compound may comprise at least one of 1,4-dioxane (CAS: 123-91-1), 1,2-dimethoxyethane (CAS: 110-71-4, DME, monoglyme), diethylene glycol dimethyl ether (CAS: 111-96-6, diglyme), triethylene glycol dimethyl ether (CAS: 112-49-2, triglyme), or 1,4,7,10-tetraoxacyclododecane (CAS: 294-93-9,12-Crown-4).

[0087] In some embodiments, the adduct-forming ligand may comprise a thioether or mixed etheramine, such as at least one of 1,7-diaza-12-crown-4, 1,7-dioxa-4,10-diazacyclododecane (CAS: 294-92-8), or 1,2-bis(methylthio)ethane (CAS: 6628-18-8).

[0088] In some embodiments, the metal or semi-metal precursor is provided as a mixture of two or more compounds. In the mixture, the other compounds besides the metal or semi-metal precursor can be an inert compound or element. In some embodiments, the metal or semi-metal precursor is provided in the form of a composition. Compositions suitable for use as compositions can include a transition metal compound and an effective amount of one or more stabilizers. The composition can be a solution or a gas under standard conditions.

[0089] Reducing agents according to the present disclosure include cyclohexadiene compounds, which include two germanium atoms attached to a ring. In some embodiments, the germanium atom is directly bonded to the ring structure. In some embodiments, one or two germanium atoms are bonded to the ring structure by replacing one carbon atom in the ring with a nitrogen heteroatom. In some embodiments, the germanium atom is bonded to the adjacent position of the ring (1,2 configuration). In some embodiments, the germanium atom is bonded to the relative position of the ring (1,4 configuration).

[0090] To simplify nomenclature, the term cyclohexadiene includes ring structures containing only carbon as well as ring structures containing one or two nitrogen atoms. Therefore, in addition to the germanyl group, the cyclohexadiene ring may have additional substituents. In some embodiments, one or more ring carbons have an alkyl substituent. The alkyl substituent may be straight or branched. In some embodiments, one ring carbon has a C1 to C7 alkyl substituent. In some embodiments, two ring carbons have C1 to C7 alkyl substituents. In some embodiments, three ring carbons have C1 to C7 alkyl substituents. In some embodiments, four ring carbons have C1 to C7 alkyl substituents. If the germanium atom is attached to the cyclohexadiene ring via a carbon atom, the same carbon atom may have additional alkyl substituents. In some embodiments, all additional substituents on the ring carbons are C1 to C4 alkyl groups. In some embodiments, all additional substituents are methyl or ethyl groups. In some embodiments, all additional substituents are methyl groups. In some embodiments, all additional substituents are ethyl groups. In some embodiments, the cyclohexadiene compound has one additional substituent, and that additional substituent is a methyl group. In some embodiments, the cyclohexadiene compound has one additional substituent, and that additional substituent is an ethyl group. In some embodiments, the methyl group is attached to a carbon adjacent to the carbon atom to which the germanium group is bonded. However, in some embodiments, no ring carbon has additional substituents.

[0091] Increasing the molecular weight of a cyclohexadiene compound generally has a detrimental effect on its volatility. Thus, the more substituents a cyclohexadiene ring contains, the smaller it needs to be to maintain sufficient volatility.

[0092] In some embodiments, the two germanium groups of the cyclohexadiene compound are trialkylgermanium groups. In some embodiments, the two trialkylgermanium groups include C1 to C7 alkyl groups. The alkyl group can be straight or branched. In some embodiments, the two germanium groups of the cyclohexadiene compound are trimethylgermanium groups. In some embodiments, the two germanium groups of the cyclohexadiene compound are triethylgermanium groups.

[0093] In some embodiments, the cyclohexadiene compound according to the present disclosure has a structure according to formula (VI). In some embodiments, the cyclohexadiene compound according to the present disclosure has a structure according to formula (VII). In some embodiments, the cyclohexadiene compound according to the present disclosure has a structure according to formula (VIII). In some embodiments, the cyclohexadiene compound according to the present disclosure has a structure according to formula (IX). In some embodiments, the cyclohexadiene compound according to the present disclosure has a structure according to formula (X). In some embodiments, the cyclohexadiene compound according to the present disclosure has a structure according to formula (XII).

[0094]

[0095] In some aspects, the reducing agent comprises a bicyclic structure in which the two cyclohexadiene rings are connected by a bond between the rings (i.e., the rings do not share ring atoms). For example, a bicyclic bis(trialkylgermanyl) molecule can be used. The two rings can be dihydropyridine rings. For example, two molecules according to formula (I) can be connected by their Z 1 and / or Z 2 Positional fusion. In this molecule, each bond Z 1 or Z 2 It's CR 11 , and the bonds between the rings replace R 11 In some embodiments, the reducing agent includes 4,4'-bis(trialkylgermanyl)-1,1',4,4'-tetrahydro-4,4'-bipyridine, such as 4,4'-bis(trimethylgermanyl)-1,1',4,4'-tetrahydro-4,4'-bipyridine.

[0096] Attached photos

[0097] The present disclosure is further explained by the following exemplary embodiments depicted in the accompanying drawings. The illustrations presented herein are not meant to be actual views of any particular material, structure, device, or apparatus, but are merely schematic representations of embodiments of the present disclosure. It should be understood that the elements in the 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 help improve understanding of the illustrated embodiments of the present disclosure. The structures and devices depicted in the drawings may contain additional elements and details, which may be omitted for clarity.

[0098] FIG. 1 is a block diagram of an exemplary embodiment of a method 100 .

[0099] In the first stage 102, a substrate is provided to a reaction chamber. The substrate according to the present disclosure may include, for example, an oxide, such as silicon oxide (e.g., thermal silicon oxide or natural silicon oxide), aluminum oxide, or a transition metal oxide, such as hafnium oxide. The substrate may include a nitride such as silicon nitride or titanium nitride, a metal such as copper, cobalt, or tungsten, or a chalcogenide material such as molybdenum sulfide. A material containing an elemental metal or a semi-metal according to the present disclosure may be deposited on the surface. The deposited material may form a layer that can be used to manufacture electronic devices. Depending on the application in question, the layer properties may be different. For example, layers of different thicknesses may be deposited. In addition, the material containing an elemental metal or a semi-metal may be doped with another material (metal, semi-metal, or non-metal) to change its properties.

[0100] The reaction chamber may form part of an atomic layer deposition (ALD) assembly. The reaction chamber may form part of a chemical vapor deposition (CVD) assembly. The assembly may be a single wafer reactor. Alternatively, the reactor may be a batch reactor. The assembly may include one or more multi-station deposition chambers. The various stages of method 100 may be performed in a single reaction chamber, or may be performed in multiple reaction chambers, such as reaction chambers of a combination tool. In some embodiments, method 100 is performed in a single reaction chamber of a combination tool, but other, previous or subsequent manufacturing steps of the structure or device are performed in additional reaction chambers of the same combination tool. Optionally, the assembly including the reaction chamber may be provided with a heater to activate the reaction by raising the temperature of one or more substrates and / or reactants and / or precursors. The metal- or semi-metal-containing material according to the present disclosure may be deposited in a cross-flow reaction chamber. The metal- or semi-metal-containing material according to the present disclosure may be deposited in a cross-flow reaction chamber.

[0101] In stage 104, a metal precursor or a semi-metal precursor is provided in a reaction chamber containing a substrate. Without limiting the present disclosure to any particular theory, in the process of providing the metal or semi-metal precursor to the reaction chamber, the metal or semi-metal precursor can be chemically adsorbed on the substrate. For example, the duration (metal or semi-metal precursor pulse time) for providing the metal or semi-metal precursor to the reaction chamber can be from about 0.1 second to about 15 seconds, from about 0.5 second to about 10 seconds, from about 0.5 second to about 5 seconds, or from about 0.5 second to about 3 seconds. For example, the metal or semi-metal pulse time can be about 0.5 second, 1 second, 1.5 seconds, 2 seconds, 3 seconds, 3.5 seconds, 5 seconds, 7 seconds, or 10 seconds. In some embodiments, the metal or semi-metal precursor pulse time can be shorter than 25 seconds, shorter than 15 seconds, shorter than 8 seconds, shorter than 5 seconds, or shorter than 2 seconds. For example, the duration depends on the precursor used and the application. In some embodiments, a saturated pulse is used. In some embodiments, an unsaturated pulse mode is used.

[0102] When a reducing agent is provided in the reaction chamber at stage 106, the reducing agent can react with the chemically adsorbed metal precursor or semi-metal precursor or its derivative to form an elemental metal or semi-metal. The duration of providing the reducing agent in the reaction chamber (reducing agent pulse time) can be, for example, about 0.1 to about 15 seconds, about 0.5 to about 10 seconds, about 0.5 to about 5 seconds, or about 0.5 to about 3 seconds. For example, the metal or semi-metal pulse time can be about 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 3 seconds, 3.5 seconds, 5 seconds, 7 seconds, or 10 seconds. For example, the duration depends on the reducing agent, the metal or semi-metal precursor used, and the application. In some embodiments, the reducing agent pulse time can be shorter than 25 seconds, shorter than 15 seconds, shorter than 8 seconds, shorter than 5 seconds, or shorter than 2 seconds.

[0103] In some embodiments, the metal or semi-metal precursor is heated before being provided to the reaction chamber. In some embodiments, the reducing agent is heated before being provided to the reaction chamber. In some embodiments, the metal or semi-metal precursor is maintained at ambient temperature before being provided to the reaction chamber. In some embodiments, the reducing agent is maintained at ambient temperature before being provided to the reaction chamber.

[0104] Stages 104 and 106, performed in any order, can form a deposition cycle that results in the deposition of an elemental metal or semi-metallic material on the substrate surface. In some embodiments, the two stages of deposition of the elemental metal or semi-metallic material, i.e., providing a metal or semi-metallic precursor and a reducing agent (104 and 106) in the reaction chamber, can be repeated (cycle 108). Such embodiments include multiple deposition cycles. The thickness of the deposited metal or semi-metallic material can be adjusted by adjusting the number of deposition cycles. The deposition cycle (cycle 108) can be repeated until the desired thickness of the transition metal or semi-metallic material is obtained. For example, about 50, 100, 200, 300, 400, 500, 700, 800, 1000, 1200, 1500, or 2000 deposition cycles can be performed.

[0105] Figure 1B A similar deposition process as described above is shown. Figure 1B In the embodiment of the present invention, the process includes purging the reaction chamber after providing the metal or semi-metal precursor in the reaction chamber 105 and after providing the reducing agent in the reaction chamber 107. However, in some embodiments, only one of the purge phases 105 and 107 is performed. In some embodiments, both the purge phases 105 and 107 are performed. The duration of the purge phases 105 and 107 can be the same or different. The selection of an appropriate purge phase length depends on the properties of the precursor and reducing agent, as well as the topology of the substrate and other parameters of the deposition process.

[0106] Figure 1C One aspect of the present disclosure is shown, wherein a method 101 according to the present disclosure includes contacting a substrate with a vapor-phase metal precursor 110, wherein the metal precursor includes metal atoms in an oxidation state of +1 or higher. Thereafter, according to the present disclosure, the substrate is contacted with a vapor-phase reducing agent 112. This at least partially reduces the metal atoms in the metal precursor to deposit elemental metal 114 on the substrate. Although depicted as a separate stage 114, the deposition of the elemental metal can occur simultaneously with at least one of the other stages 110 and / or 112.

[0107] Stages 110 and 112, performed in any order, can form a deposition cycle that results in elemental metal being deposited on the substrate surface. In some embodiments, the two stages of elemental metal deposition can be repeated, i.e., contacting the substrate with a metal precursor 110 and contacting the substrate with a reducing agent 112 (loop 116). Such embodiments include multiple deposition cycles. The thickness of the deposited metal can be adjusted by adjusting the number of deposition cycles. The deposition cycle (loop 116) can be repeated until the desired metal thickness is obtained. For example, approximately 50, 100, 200, 300, 400, 500, 700, 800, 1000, 1200, 1500, or 2000 deposition cycles can be performed.

[0108] although Figure 1C An aspect of the present disclosure is shown in which an elemental metal is deposited on a substrate, but alternatively, an elemental semi-metal can be similarly deposited. Thus, a method according to the present disclosure can include contacting a substrate with a vapor-phase semi-metal precursor, wherein the semi-metal precursor includes semi-metal atoms in an oxidation state of +1 or higher. Thereafter, according to the present disclosure, the substrate is contacted with a vapor-phase reducing agent. This at least partially reduces the semi-metal atoms in the semi-metal precursor, thereby depositing the elemental semi-metal on the substrate. Although described as a separate stage, the deposition of the elemental semi-metal can occur simultaneously with at least one other stage.

[0109] The stages of contacting the substrate with a vapor-phase semi-metal precursor and contacting the substrate with a vapor-phase reducing agent, performed in any order, can form a deposition cycle, resulting in the deposition of the elemental semi-metal on the substrate surface. In some embodiments, the two stages of elemental semi-metal deposition, namely contacting the substrate with a semi-metal precursor and contacting the substrate with a reducing agent, can be repeated. Such embodiments include multiple deposition cycles. The thickness of the deposited semi-metal can be adjusted by adjusting the number of deposition cycles. The deposition cycles can be repeated until the desired semi-metal thickness is achieved. For example, approximately 50, 100, 200, 300, 400, 500, 700, 800, 1000, 1200, 1500, or 2000 deposition cycles can be performed.

[0110] Figure 2 A deposition assembly 200 according to the present disclosure is shown in schematic form. The deposition assembly 200 can be used to perform the methods described herein and / or form layers, structures, or devices described herein, or portions thereof.

[0111] In the example shown, the deposition assembly 200 includes one or more reaction chambers 202, a precursor injector system 201, a metal or semi-metal precursor container 204, a reducing agent container 206, an exhaust source 210, and a controller 212. The deposition assembly 200 may include one or more additional gas sources (not shown), such as an inert gas source, a carrier gas source, and / or a purge gas source. In addition, in the case of depositing materials containing additional elements, the deposition assembly may further include additional precursor and / or reactant containers.

[0112] Reaction chamber 202 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber as described herein.

[0113] The metal or semi-metal precursor container 204 may include a container and one or more metal or semi-metal precursors as described herein, either alone or mixed with one or more carrier gases (e.g., an inert gas). The reducing agent container 206 may include a container and a reducing agent as described herein, either alone or mixed with one or more carrier gases. Although two source containers 204 and 206 are shown, the deposition assembly 200 may include any suitable number of source containers. The source containers 204 and 206 may be coupled to the reaction chamber 202 via lines 214 and 216, which may each include a flow controller, a valve, a heater, etc. In some embodiments, the metal or semi-metal precursor in the metal or semi-metal precursor container 204 and / or the reducing agent in the reducing agent container 206 may be heated. In some embodiments, the temperature of the reducing agent container is adjusted so that it is between X°C and approximately Y°C. In some embodiments, the temperature of the reducing agent container is adjusted so that it is between X°C and approximately Y°C.

[0114] The exhaust source 210 may include one or more vacuum pumps.

[0115] The controller 212 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in the deposition assembly 200. Such circuitry and components operate to introduce precursors, reactants, and purge gases from their respective sources. The controller 212 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber 202, the pressure within the reaction chamber 202, and various other operations to provide proper operation of the deposition assembly 200. The controller 212 can include control software to control the flow of precursors, reactants, and purge gases into and out of the reaction chamber 202 using electrically or pneumatically controlled valves. The controller 212 can include modules, such as software or hardware components, that perform specific tasks. The modules can be configured to reside on an addressable storage medium of the control system and to execute one or more processes.

[0116] Other configurations of the deposition assembly 200 are possible, including different numbers and types of precursor and reactant sources. Furthermore, it should be understood that many arrangements of valves, conduits, precursor sources, and auxiliary reactant sources can be used to achieve the goal of selectively and in a coordinated manner supplying gases to the reaction chamber 202. Furthermore, as a schematic representation of the deposition assembly, many components have been omitted for simplicity of illustration, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0117] During operation of deposition assembly 200, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate handling system to reaction chamber 202. Once the substrate is transferred to reaction chamber 202, one or more gases, such as precursors, reactants, reducing agents, carrier gases, and / or purge gases, are introduced into reaction chamber 202 from a gas source.

[0118] In some embodiments, the metal or semi-metal precursor is supplied in pulses, the reducing agent is supplied in pulses, and the reaction chamber is purged between successive pulses of the metal or semi-metal precursor and the reducing agent.

[0119] Example

[0120] Example 1: Deposition of elemental nickel

[0121] In an exemplary deposition process, elemental (i.e., metallic) nickel is deposited using dichlorobis(triethylphosphine)nickel as a metal precursor and 1,4-bis(trimethylgermanyl)1,4-dihydropyrazine (GeDHP) as a reducing agent. In this example, the reducing agent is capable of reducing nickel to elemental metal. In this example, a flow-type (i.e., cross-flow) ALD reactor is used. In this process, the pressure within the reactor is from about 0.5 torr to about 10 torr. The deposition process is carried out at a temperature of from about 95°C to about 135°C, for example, from about 100°C to about 130°C. In an exemplary deposition process, a temperature of 110°C is used. The nickel precursor is provided (i.e., pulsed) in the reaction chamber for from about 0.5 seconds to about 2 seconds, for example, for about 1 second. The reducing agent can be provided to the reaction chamber over a period of from about 0.5 seconds to about 3 seconds, for example, for about 1.5 seconds. The process includes a purge phase after each precursor pulse phase.

[0122] N2 (5.0) was used as carrier gas and purge gas. The nickel precursor was evaporated at a temperature of 100°C and the reducing agent at a temperature of 35°C. Deposition was carried out on soda-lime glass, on silicon substrates with a native oxide layer, on copper and on titanium nitride. The growth rate of the elemental metal-containing material (in this case essentially only elemental nickel) was about After the deposited material forms a substantially pinhole-free layer, the growth rate of the material may decrease. As a non-limiting example, the growth rate may decrease to about A layer containing nickel metal can be obtained by this method, and the thickness of the layer depends on the number of pulse cycles. For example, a layer with a thickness of at least 15 nm, such as at least 20 nm, can be obtained.

[0123] In an exemplary process, the deposited metal-containing material included cubic nickel metal, as analyzed by XRD measurements. The resistivity of the nickel-containing layer was approximately 40 μΩcm. Conductive layers were obtained with a layer thickness of approximately 7.7 nm, and when the thickness exceeded 20 nm, these layers were substantially free of pinholes. Based on SEM imaging, the grain size was found to be small, and the layers were relatively smooth.

[0124] The deposited metal-containing material contained approximately 87 atomic percent nickel and approximately 7 atomic percent carbon. Raman spectroscopy indicated that all carbon in the layer was carbide. Only minor amounts of other elements were present. The material also contained less than 0.2 atomic percent chlorine, indicating efficient reduction. The majority of the oxygen was present only on the surface of the material, likely due to oxidation of the nickel metal surface caused by exposure to the ambient atmosphere after deposition.

[0125] Example 2: Deposition of elemental cobalt

[0126] In another set of experiments, elemental cobalt was deposited using a metal precursor comprising a cobalt halide and a diamine adduct ligand and a reducing agent in accordance with the present invention. Elemental cobalt was successfully deposited using CoBr2(N,N,N',N'-tetramethyl-1,2-ethylenediamine) [CoBr2(tmeda)], CoBr2(N,N,N',N'-tetramethyl-1,3-propylenediamine) [CoBr2(tmpda)], CoCl2(N,N,N',N'-tetramethyl-1,3-propylenediamine) [CoCl2(tmpda)], and CoI2(N,N,N',N'-tetramethyl-1,3-propylenediamine) [CoI2(tmpda)]. GeDHP was used as the reducing agent and deposition was performed at temperatures ranging from 180°C to 240°C. The materials deposited using CoBr2(tmeda) and GeDHP were studied to gain a preliminary understanding of the material properties. It was observed that an increase in temperature increased the deposition rate of the material, which increased from about 1.5 to 2.5 wt%. Arrive at the appointment At higher deposition temperatures, the resistivity of the deposited layer also increases, ranging from about 60 μΩcm to about 120 μΩcm. Even without process optimization, cobalt constitutes about 80 atomic percent of the material, carbon is less than 13 atomic percent, nitrogen is less than 2.5 atomic percent, and Ge and Br together are less than 3.5 atomic percent.

[0127] Example 3: Deposition of elemental gold

[0128] In another exemplary deposition process, as described above, elemental (i.e., metallic) gold is deposited using triethylphosphine gold (I) chloride (AuCl (TEP)) as a transition metal precursor and 1,4-bis (trimethylgermanyl) -1,4-dihydropyrazine (DHPGE) as a second precursor using a flow-type ALD reactor and a pressure of less than 10 Torr. The deposition process is performed multiple times at a temperature of about 160 ° C to about 180 ° C, and the higher deposition temperature significantly increases the growth rate of the layer. The transition metal precursor is provided (i.e., pulsed) in the reaction chamber for about 1 second to about 6 seconds, for example, about 3 or 4 seconds. The second precursor can be provided to the reaction chamber for about 0.2 seconds to about 3 seconds, for example, about 0.5 seconds. Similar to the above, the process includes a purge stage after each precursor pulse stage.

[0129] The transition metal precursor was evaporated at a temperature of 160° C. and the second precursor was evaporated at a temperature of 45° C. Deposition was carried out on soda-lime glass and silicon substrates with a native oxide layer. The growth rate of the transition metal-containing material (in this case essentially only elemental gold) was about to A gold-containing metal layer can be obtained through this process, and the thickness of the layer depends on the number of pulse cycles. For example, a layer with a thickness of at least about 50 nm, such as at least about 60 nm, 110 nm, or at least about 135 nm, can be obtained. The resistivity of the gold-containing layer was measured to be less than 2.5 μΩcm, for example, about 2.44 μΩcm, indicating very pure elemental gold material.

[0130] Example 4: Synthesis of GeDHP

[0131] GeDHP is synthesized by weighing lithium particles into a Schlenk flask, adding THF, and cooling the reaction vessel to -15°C. Magnetic stirring is applied. (CH3)3GeCl and pyrazine, dissolved in tetrahydrofuran at a molar ratio of 2:1, are slowly added to the mixture via a dropping funnel. The solution is stirred at -15°C overnight, after which unreacted lithium is filtered off. The filtrate is evaporated to dryness, and the resulting material is sublimed at approximately 80–100°C and 0.05 mbar. The yield of this process is approximately 86% of the theoretical yield.

[0132] The (CH3)3GeCl used in this process is synthesized via a high-pressure synthesis route from GeCl4 and Me4Si using AlBr3 as a catalyst. GeCl4 and Me4Si are added to an autoclave in a 1:2 molar ratio along with AlBr3. The reaction mixture is mixed at 200°C for 18 hours, and the product is distilled from the mixture at a temperature of approximately 53°C to 62°C and a pressure of 140 mmHg. The yield is approximately 80% of theoretical yield.

[0133] The exemplary embodiments disclosed above do not limit the scope of the present invention, as these embodiments are merely examples of embodiments of the present invention, and the scope of the present invention is defined by the appended claims and their legal equivalents. Any equivalent embodiments are within the scope of the present invention. Various modifications of the present disclosure, such as alternative and useful combinations of the described elements, in addition to those shown and described herein, will become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method for depositing an elemental metal or semi-metallic material on a substrate by a cyclic deposition process, the method comprising: providing a substrate in a reaction chamber; Providing a metal or semi-metal precursor to the reaction chamber in a gas phase; as well as providing a reducing agent in a gas phase into a reaction chamber to form an elemental metal or semi-metallic material on a substrate; wherein the reducing agent comprises a cyclohexadiene compound selected from the compounds of formula (I), Among them, Z 1 and Z 2 Each of which is independently selected from CR 11 and N, R 1 to R 11 Each of the groups is independently H, C1 to C7 linear or branched alkyl, C6 to C10 aryl, or C6 to C14 heteroaryl, wherein the two germanium atoms are bonded to the ring structure through a nitrogen heteroatom replacing one of the carbon atoms in the ring.

2. The method according to claim 1, wherein R 11 It’s H.

3. The method according to claim 1, wherein Z 1 and Z 2 It's N.

4. The method according to claim 1, wherein R 7 to R 10 Each of the groups is independently selected from the group consisting of H, C1 to C4 linear and branched alkyl groups, and phenyl groups.

5. The method according to claim 1, wherein All R 7 to R 10 It’s H.

6. The method according to claim 1, wherein R 1 to R 6 Each of the groups is independently selected from the group consisting of H, methyl, ethyl, n-propyl, and isopropyl.

7. The method according to claim 1, wherein All R 1 to R 6 It is a methyl or ethyl group.

8. The method according to claim 1, wherein The cyclohexadiene compound is 1,4-bis(trimethylgermanyl)-1,4-dihydropyrazine.

9. The method according to claim 1, wherein The metal or semi-metal precursor is a metallic precursor, and the elemental metal is deposited on the substrate.

10. The method according to claim 9, wherein: The metal precursor includes a metal halide.

11. The method according to claim 10, wherein: The metal halide is selected from the group consisting of CoCl2, NiCl2, CuCl2, ZnCl2, CoBr2, NiBr2, CuBr2, ZnBr2, CoI2, NiI2, CuI2 and ZnI2.

12. The method according to claim 10, wherein: The metal precursor includes an adduct ligand.

13. The method according to claim 12, wherein: The adduct ligand is a monodentate adduct ligand.

14. The method according to claim 1, wherein The metal or semimetal precursor is a transition metal precursor, and the elemental transition metal is deposited on the substrate.

15. The method according to claim 14, wherein The transition metal is a row 4 transition metal.

16. The method according to claim 15, wherein The row 4 transition metal is selected from Co, Ni, Cu and Zn.

17. The method according to claim 1, wherein The metal or semimetal precursor comprises a metal or semimetal atom in the +1, +2, +3 or +4 formal oxidation state.

18. The method according to claim 1, wherein Z 1 and Z 2 At least one of them is CR 11 .

19. A method for depositing a metal layer on a substrate, the method comprising: contacting the substrate with a vapor-phase metal precursor, wherein the metal precursor comprises metal atoms in an oxidation state of +1 or greater, contacting the substrate with a vapor-phase reducing agent to reduce metal atoms in the metal precursor to form a metal layer on the substrate, wherein The reducing agent comprises a cyclohexadiene compound selected from the compounds of formula (I), Among them, Z 1 and Z 2 Each of which is independently selected from CR 11 and N, R 1 to R 11 Each of the groups is independently H, C1 to C7 linear or branched alkyl, C6 to C10 aryl, or C6 to C14 heteroaryl, wherein the two germanium atoms are bonded to the ring structure through a nitrogen heteroatom replacing one of the carbon atoms in the ring.

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