Method of selectively depositing transition metal-containing material on substrate by cyclic deposition process and vapor deposition assembly for depositing the same

Abstract

This invention relates to a method and apparatus for manufacturing semiconductor devices. In this invention, a transition metal-containing material is selectively deposited on a substrate by a cyclic deposition process. The deposition method includes providing a substrate in a reaction chamber, wherein the substrate includes a first surface comprising a first material and a second surface comprising a second material. A transition metal precursor comprising a transition metal halide compound is provided in the reaction chamber in the gas phase to deposit the transition metal-containing material on the first surface relative to the second surface. The transition metal compound may include an adduct forming a ligand. Furthermore, a deposition assembly for depositing a transition metal-containing material is disclosed.

Description

Technical Field

[0001] This invention relates to methods and apparatus for manufacturing semiconductor devices. More specifically, the invention relates to a method for selectively depositing a metal-containing material on a surface of a substrate, to a layer and structure comprising the metal-containing material, and to a vapor deposition apparatus for depositing the metal-containing material. Prior Technology

[0002] The deposition of metallic materials can be used to manufacture various devices, such as semiconductor devices, flat panel display devices, and photovoltaic devices. For many applications, it is generally desirable to deposit the metallic material on a substrate with a surface that may contain different compositions.

[0003] Advances in semiconductor manufacturing have highlighted the need for new processing methods. Patterning in semiconductor processing is conventionally known to involve subtractive processes, where a blanket layer is deposited, masked using photolithography, and etched through openings in the mask. Additive patterning is also known, where a masking step is performed before the desired material is deposited, such as patterning using lift-off techniques or damascene processes. In most cases, expensive multi-step photolithography techniques are applied to patterning. Selective deposition offers an alternative to patterning and has gained increasing interest from semiconductor manufacturers. Selective deposition can be highly advantageous in various aspects. Notably, it allows for fewer photolithography steps, reducing processing costs. One challenge of selective deposition is that the selectivity of the deposition process is often not high enough to achieve the desired selectivity. Surface pretreatment can sometimes be used to suppress or promote deposition on a given surface, but such treatments themselves often require photolithography to be performed or remain only on the surface to be treated.

[0004] Therefore, there is a need in the art for a more general selective deposition scheme to deposit different materials on various combinations of surface materials used in semiconductor structures.

[0005] Any discussion presented in this section, including discussions of problems and solutions, is included in this invention solely for the purpose of providing background context. Such discussions should not be construed as an admission that any or all information was known at the time of completion of this invention or otherwise constituted prior art. Summary of the Invention

[0006] This invention may be presented in a simplified form, and may be described in detail below. The content of this invention is not intended to necessarily identify the key or essential technical features of the claimed substance, nor is it intended to limit the scope of the claimed substance.

[0007] In one embodiment, the present invention discloses a method for selectively depositing a transition metal-containing material onto a substrate using a cyclic deposition process. The method includes providing a substrate in a reaction chamber, wherein the substrate includes a first surface comprising a first material and a second surface comprising a second material; providing a transition metal precursor comprising a transition metal halide compound in the gas phase in the reaction chamber; and providing a second precursor in the gas phase in the reaction chamber, to deposit a transition metal-containing material on the first surface relative to the second surface.

[0008] In some embodiments, the transition metal halide compound comprises a transition metal chloride, a transition metal iodide, or a transition metal fluoride.

[0009] In some embodiments, the transition metal in the transition metal halide compound is selected from the group consisting of manganese, iron, cobalt, nickel and copper.

[0010] In some embodiments, the transition metal halide compound comprises at least one of cobalt chloride, nickel chloride or copper chloride, cobalt bromide, nickel bromide or copper bromide, cobalt iodide, nickel iodide or copper iodide.

[0011] In some embodiments, the method according to the invention further includes contacting the transition metal-containing material with a reducing agent to form an elemental transition metal.

[0012] In one embodiment, a method for selectively depositing a transition metal-containing material on a substrate via a cyclic deposition process is disclosed. The method includes providing a substrate in a reaction chamber, wherein the substrate includes a first surface comprising a first material and a second surface comprising a second material; providing a transition metal precursor comprising a transition metal compound in the gas phase in the reaction chamber; and providing a second precursor in the gas phase in the reaction chamber; and depositing the transition metal-containing material on the first surface relative to the second surface, wherein the transition metal compound comprises an adduct-forming ligand.

[0013] In some embodiments, the adduct forming ligand comprises at least one of nitrogen, phosphorus, oxygen, or sulfur.

[0014] In some embodiments, the second precursor comprises at least one of an oxygen precursor, a nitrogen precursor, a silicon precursor, a sulfur precursor, a selenium precursor, a phosphorus precursor, a boron precursor, or a reducing agent.

[0015] In semiconductor device manufacturing, layers of elemental cobalt are crucial for applications such as substrates and capping layers, suppressing electromigration of copper interconnect materials or improving copper adhesion and wetting. In fact, as device feature sizes shrink in advanced technology nodes, cobalt layers can be used as interconnect materials or in contact vias to replace commonly used copper interconnects. Cobalt layers are also gaining attention in large magnetoresistive applications and magnetic memory applications. Furthermore, thin cobalt layers can be deposited on silicon gate or source-drain contacts in integrated circuits to form a cobalt silicate during annealing. Many applications benefit from the ability to deposit elemental transition metal layers.

[0016] Accordingly, there is a high demand for cyclic deposition methods for the selective deposition of transition metal layers, particularly cobalt-containing layers. Therefore, in another embodiment, the present invention discloses a method for depositing a transition metal layer on a substrate using a cyclic deposition process. The method includes providing a substrate in a reaction chamber, wherein the substrate comprises a first surface including a first material and a second surface including a second material; providing a transition metal precursor comprising a transition metal halide compound in the gas phase in the reaction chamber; and providing a second precursor comprising a carboxylic acid in the gas phase in the reaction chamber, to deposit a transition metal layer on the first surface relative to the second surface. In some embodiments, a transition metal layer may mean a layer of material having less than 10 at.% of elements other than the transition metal in question.

[0017] In some embodiments, the carboxylic acid contains 1 to 7 carbon atoms in addition to the carboxylic acid carbon.

[0018] In some embodiments, the carboxylic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, benzoic acid and oxalic acid.

[0019] In some embodiments, a substantially continuous transition metal layer system having a thickness of at least 20 nm may be deposited on a first surface, and substantially no deposition may be made on the second surface.

[0020] In some embodiments, the transition metal precursor and the second precursor are provided to the reaction chamber in an alternating and sequential manner.

[0021] In some embodiments, the selectivity of the method is at least 80%.

[0022] In some embodiments, after a transition metal precursor and / or a second precursor are provided in the reaction chamber, the reaction chamber is purged.

[0023] In another embodiment, a device structure is disclosed, comprising the transition metal material formed according to the method disclosed herein.

[0024] In another embodiment, a vapor deposition assembly for depositing a transition metal material on a substrate is disclosed. The vapor deposition assembly includes one or more reaction chambers configured and arranged to hold a substrate comprising a first surface and a second surface, the first surface comprising a first material and the second surface comprising a second material. The vapor deposition assembly further includes a precursor injector system configured and arranged to provide a transition metal precursor and a second precursor in the reaction chambers, a transition metal precursor source container configured and arranged to hold a transition metal precursor, and a second precursor source container configured and arranged to hold a second precursor. The transition metal precursor source container and the second precursor source container are in fluid communication with the reaction chambers, and the transition metal precursor comprises a transition metal halide compound and / or an adduct forming ligand according to the invention.

[0025] In this invention, any two numbers of a variable can constitute the working range of that variable, and any indicated range may include or exclude those endpoints. Furthermore, any numerical value of the indicated variable (whether or not it is expressed as "about") may refer to an exact value or an approximate value and includes equivalent values, and may refer to an average, median, representative value, multi-value, etc. Further, in some embodiments of this invention, the terms "including," "constituted by," and "having" independently mean "typically or broadly comprising," "comprising," "consisting essentially of," or "consisting of." In some embodiments of this invention, any definition does not necessarily exclude the general and conventional meaning. Simple Explanation of the Diagram

[0026] The accompanying drawings, which provide a further understanding of the invention and form part of this specification, schematically illustrate several exemplary embodiments and, in conjunction with the description, explain the principles of the invention. In the drawings... [Figures 1A and 1B] illustrate an exemplary embodiment of a method for depositing a transition metal material on a substrate according to one of the present invention. [Figure 2] is a schematic diagram of an exemplary embodiment of a method for depositing a transition metal material on a substrate according to one of the present invention. [Figure 3] shows a process flow diagram of an exemplary embodiment of a method for selectively depositing a transition metal layer on a substrate according to one of the present invention. [Figure 4] is a schematic diagram of a vapor deposition apparatus according to one of the present invention. Implementation

[0027] The following descriptions of various exemplary embodiments of methods, structures, apparatuses, and devices are merely illustrative and for purposes of explanation. The following descriptions are not intended to limit the scope of the invention or the claims. Furthermore, the description of various embodiments having specified features is not intended to exclude other embodiments having additional features, or other embodiments including different combinations of said features. For example, various embodiments are illustrated by way of multiple exemplary embodiments and may be listed in multiple appendices. Unless otherwise stated, multiple exemplary embodiments or components thereof may be combined or applied separately.

[0028] 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 the embodiments disclosed herein.

[0029] In various methods according to the invention, a substrate is provided in a reaction chamber. In other words, the substrate is introduced into a space where deposition conditions can be controlled. The reaction chamber may be part of a clustering tool in which various different processes are performed to form an integrated circuit. In some embodiments, the reaction chamber may be a flow reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber may be a spray head reactor. In some embodiments, the reaction chamber may be a space-divided reactor. In some embodiments, the reaction chamber may be a single-wafer ALD reactor. In some embodiments, the reaction chamber may be a high-capacity single-wafer ALD reactor. In some embodiments, the reaction chamber may be a batch reactor for simultaneously fabricating multiple substrates. substrate

[0030] When used herein, the term "substrate" can refer to any underlying material(s) on which devices, circuits, materials, or material layers can be formed or on which they are formed. A substrate can include a host material, 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). A substrate can include one or more layers overlying a host material. A substrate can include various topologies, such as gaps, including spaces between grooves, lines, trenches, or raised portions (e.g., fins) formed within or above at least a portion of a layer of the substrate, and the like. A substrate can include nitrides, such as TiN, oxides, thermally insulating materials, dielectric materials, conductive materials, metals such as tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper, or metallic materials, crystalline materials, epitaxial materials, heteroepilithographic materials, and / or single-crystal materials. In some embodiments of the invention, the substrate comprises silicon. As described above, in addition to silicon, the substrate may comprise other materials. These other materials may form multiple layers.

[0031] The substrate according to the invention comprises two surfaces, and the transition metal material and the transition metal layer system according to the invention are deposited on the first surface relative to the second surface. The substrate may include any number of additional surfaces. The first and second surfaces may be arranged in any suitable pattern. For example, the first and second surfaces may be alternating columns, or one surface may surround the other in a planar view. The first and second surfaces may be coplanar, the first surface may be convex relative to the second surface, or the second surface may be convex relative to the first surface. The first and second surfaces may be formed using one or more reaction chambers. The patterned structure may be provided on any suitable substrate.

[0032] The first surface and the second surface may have different material properties. In some embodiments, the first surface and the second surface are adjacent to each other. The first surface and the second surface may be located at the same level, or one of the surfaces may be lower than the other. In some embodiments, the first surface is lower than the second surface. For example, in some embodiments, the first surface may be etched to be positioned lower than the second surface. In some embodiments, the second surface may be etched to be positioned lower than the first surface. Alternatively or additionally, the materials of the first surface and the second surface may be deposited to position the first surface and the second surface at different levels.

[0033] In addition to the first and second surfaces, the substrate may include additional material or surfaces. This additional material may be positioned between the first surface and the substrate, or between the second surface and the substrate, or between both the first and second surfaces and the substrate. This additional material may form additional surfaces on the substrate.

[0034] In some embodiments, the first surface is a metal or a metallic surface. In some embodiments, the first surface comprises a metal or a metallic material. In some embodiments, the metal or metallic surface may comprise a metal, a metal oxide, and / or a mixture thereof. In some embodiments, the metal or metallic surface may comprise a surface oxide. In some embodiments, the first surface is substantially composed of or made of a metal or a metallic material. In some embodiments, one of the metal or metallic surfaces of a substrate comprises an elemental metal or a metal alloy, while one of the second, different surfaces of the substrate comprises a dielectric material, such as an oxide. In embodiments where the first surface comprises a metal but the second surface does not, unless otherwise indicated, a surface referred to herein as a metallic surface may be either a metallic surface or a metallic surface.

[0035] In some embodiments, the metal or metallic surface may comprise a metal, a metal oxide, and / or a mixture thereof. In some embodiments, the metal or metallic surface may comprise a surface oxide. In some embodiments, the metal or metallic material of the metal or metallic surface is conductive with or without surface oxide. In some embodiments, the metal or metallic surface may be any surface that is acceptable or compatible with the first or second precursor used in a selective deposition process as described herein.

[0036] In some embodiments, the metal in or on the first surface is a transition metal. In some embodiments, the first surface includes a transition metal. In some embodiments, the first surface is substantially composed of or composed of at least one transition metal. For example, one of the metals in or on the first surface may be a group 4-6 transition metal. One of the metals in or on the first surface may be a group 4-7 transition metal. In some embodiments, one of the metals in or on the first surface may be a group 8-12 transition metal. In some embodiments, one of the metals in or on the first surface is selected from the group consisting of vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), cobalt (Co), iridium (Ir), nickel (Ni), copper (Cu), aluminum (Al), gallium (Ga), indium (In), and tin (Sb). In some embodiments, the metal in or on the first surface is selected from the group consisting of Nb, W, Fe, Co, Ni, Cu, and Al. In some embodiments, the first surface contains vanadium. In some embodiments, the first surface is substantially composed of or composed of vanadium. In some embodiments, the first surface comprises niobium. In some embodiments, the first surface is substantially composed of or composed of niobium. In some embodiments, the first surface comprises iron. In some embodiments, the first surface is substantially composed of or composed of iron. In some embodiments, the first surface comprises iridium. In some embodiments, the first surface is substantially composed of or composed of iridium. In some embodiments, the first surface comprises gallium. In some embodiments, the first surface is substantially composed of or composed of gallium. In some embodiments, the first surface comprises indium. In some embodiments, the first surface is substantially composed of or composed of indium. In some embodiments, the first surface comprises tin. In some embodiments, the first surface is substantially composed of or composed of tin. In some embodiments, the first surface comprises copper. In some embodiments, the first surface is substantially composed of or composed of copper. In some embodiments, the first surface comprises tungsten. In some embodiments, the first surface is substantially composed of or composed of tungsten. In some embodiments, the first surface comprises ruthenium. In some embodiments, the first surface is substantially composed of or composed of ruthenium. In some embodiments, the first surface comprises cobalt. In some embodiments, the first surface is substantially composed of or composed of cobalt. In some embodiments, the first surface comprises molybdenum. In some embodiments, the first surface is substantially composed of or composed of molybdenum. In some embodiments, the first surface comprises tantalum. In some embodiments, the first surface is substantially composed of or composed of tantalum. In some embodiments, the first surface comprises aluminum. In some embodiments, the first surface is substantially composed of or made of aluminum. In some embodiments, the first surface comprises nickel. In some embodiments, the first surface is substantially composed of or made of nickel. In some embodiments, the metal in or on the first surface is a group 8-12 transition metal or a post-transition metal.In some embodiments, the metal in or on the first surface is selected from the group consisting of aluminum, gallium, indium, thallium, tin, and lead. In some embodiments, the metal or metallic surface comprises one or more noble metals, such as Ru, Ir, or palladium (Pd). In some embodiments, the metal or metallic surface may comprise zinc (Zn), Fe, Mn, or Mo.

[0037] In some embodiments, the transition metal-containing material comprises Co, and the first material comprises Cu, is substantially composed of Cu, or is composed of Cu. In some embodiments, the transition metal-containing material comprises Co, and the first material comprises Mo, is substantially composed of Mo, or is composed of Mo. In some embodiments, the transition metal-containing material comprises Ni, and the first material comprises Cu, is substantially composed of Cu, or is composed of Cu. In some embodiments, the transition metal-containing material comprises Ni, and the first material comprises Co, is substantially composed of Co, or is composed of Co.

[0038] In some embodiments, the first surface comprises in-situ grown transition metal nitrides. In some embodiments, the first surface is substantially composed of or composed of in-situ grown transition metal nitrides. In some embodiments, the first surface comprises in-situ grown titanium nitride. In some embodiments, the first surface is substantially composed of or composed of in-situ grown titanium nitride. In some embodiments, the first surface comprises in-situ grown tantalum nitride. In some embodiments, the first surface is substantially composed of or composed of in-situ grown tantalum nitride. "In-situ grown transition metal nitride" herein means that the transition metal nitride was not exposed to the ambient atmosphere prior to the selective deposition according to the invention. In some embodiments, "in-situ grown transition metal nitride" means that the transition metal nitride has been grown in the same cluster tool or even in the reaction chamber where the selective deposition according to the invention is performed without removing the substrate from the tool.

[0039] In some embodiments, the metal or metallic surface comprises a conductive metal oxide, nitride, carbide, boride, or a combination thereof. For example, the metal or metallic surface may comprise one or more of RuOx, NbCx, NbBx, NiOx, CoOx, NbOx, WNCx, TaN, or TiN.

[0040] In some embodiments, the metal or metallic material of the metal or metallic surface is conductive with or without surface oxidation. In some embodiments, the first surface may comprise a conductive material. In some embodiments, the metal or metallic surface comprises one or more transition metals. In some embodiments, the first surface may be substantially composed of or composed of a conductive material. "Conductive material" herein means a material having conductivity equivalent to that of materials generally conductive in semiconductor device manufacturing techniques. In some embodiments, the resistivity of the conductive material may vary from about 2 μOhm cm to about 5 mOhm cm.

[0041] In some embodiments, the metal surface may be doped with nonmetallic or semimetallic elements to affect its electrical properties. In some embodiments, the first surface includes a doped metal surface. In some embodiments, the first surface is substantially composed of or consists of a doped metal surface.

[0042] The second surface may include a dielectric material. Possible examples of dielectric materials include silicon oxide-based materials, including grown or deposited silicon dioxide, doped and / or porous oxides, native oxides on silicon, etc. In some embodiments, the dielectric material includes a metal oxide. In some embodiments, the dielectric material includes a low-k (dielectric constant) material.

[0043] In some embodiments, the second surface comprises a dielectric material. In some embodiments, the second surface is substantially composed of or composed of a dielectric material. In some embodiments, the dielectric material is silicon oxide, such as primary oxide, thermal oxide, or silicon carbide. In some embodiments, the dielectric material comprises a metal oxide. In some embodiments, the dielectric material comprises a high-k material. The high-k material is selected from the group consisting of HfO2, ZrO2, HfSiO4, ZrSiO4, Ta2O5, SiCN, and SiN. In some embodiments, the dielectric material comprises a low-k material, such as SiOC.

[0044] In some embodiments, the second surface may contain –OH groups. In some embodiments, the second surface may be a SiO2 surface or a SiO2-based surface. In some embodiments, the second surface may contain Si-O bonds. In some embodiments, the second surface may contain a SiO2-based low-k material. In some embodiments, the second surface may contain more than about 30%, preferably more than about 50%, of SiO2. In some embodiments, the second surface may contain GeO2. In some embodiments, the second surface may contain Ge-O bonds. In some embodiments, a transition metal material is selectively deposited on a first metallic or metallic surface relative to a second Si or Ge surface (e.g., an HF-deposited Si or HF-deposited Ge surface).

[0045] In some embodiments, the first surface may comprise a silicon dioxide surface, and the second dielectric surface may comprise a second, different silicon dioxide surface. For example, in some embodiments, the first surface may comprise a native or chemically grown silicon dioxide surface. In some embodiments, the second surface may comprise a thermally grown silicon dioxide surface. In other embodiments, the second surface may be replaced by a deposited silicon dioxide layer.

[0046] In one embodiment, a semiconductor device structure is disclosed, comprising material deposited according to the method presented herein. As used herein, "structure" may refer to or may include a substrate as described herein. The structure may include one or more layers overlying the substrate, such as one or more layers formed according to a method according to the invention. Selective

[0047] By appropriately selecting deposition conditions, transition metal-containing materials can be selectively deposited on the first surface relative to the second surface. The method according to the invention can be performed without pretreatment (such as passivation or other surface treatments that introduce selectivity). Therefore, in some embodiments of the method presented in this invention, deposition is inherently selective. However, as those skilled in the art will understand, selectivity can be improved by processes such as cleaning the substrate surface, selective etching, or similar techniques.

[0048] Selectivity can be given as a percentage calculated as [(deposition on the first surface) - (deposition on the second surface)] / (deposition on the first surface). Deposition can be measured in any of a variety of ways. In some embodiments, deposition can be given as a measurement of the thickness of the deposited material. In some embodiments, deposition can be given as a measurement of the amount of deposited material.

[0049] In some embodiments, the selectivity is greater than about 30%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99%, or even greater than about 99.5%. In embodiments, the selectivity may vary with the duration or thickness of the deposition.

[0050] In some embodiments, deposition occurs only on the first surface and not on the second surface. In some embodiments, the deposition system on the first surface of the substrate relative to the second surface of the substrate has at least about 80% selectivity, which may be sufficient for some specific applications. In some embodiments, the deposition system on the first surface of the substrate relative to the second surface of the substrate has at least about 50% selectivity, which may be sufficient for some specific applications. In some embodiments, the deposition system on the first surface of the substrate relative to the second surface of the substrate has at least about 10% selectivity, which may be sufficient for some specific applications.

[0051] In some embodiments, the transition metal-containing material deposited on the first surface of the substrate may have a thickness of less than about 50 nm, less than about 20 nm, less than about 10 nm, less than about 5 nm, less than about 3 nm, less than about 2 nm, or less than about 1 nm. Meanwhile, the ratio of the transition metal-containing material deposited on the first surface of the substrate relative to the second surface of the substrate may be greater than or equal to about 2:1, greater than or equal to about 20:1, or greater than or equal to about 200:1. For example, the ratio of the transition metal-containing material deposited on the first surface of the substrate relative to the second surface of the substrate may be about 150:1, about 100:1, about 50:1, about 20:1, about 15:1, about 10:1, about 5:1, about 3:1, or about 2:1.

[0052] In some embodiments, the selectivity of the selective deposition process described herein may depend on the materials constituting the first and / or second surfaces. For example, in some embodiments, when the first surface comprises a Cu surface and the second surface comprises a silicon dioxide surface, the selectivity may be greater than about 10:1 or greater than about 20:1. In some embodiments, when the first surface comprises a metal or metal oxide and the second surface comprises a silicon dioxide surface, the selectivity may be greater than about 5:1. vapor deposition

[0053] A transition metal material is deposited using a cyclic deposition process. As used herein, the term "cyclic deposition" can refer to the sequential introduction of precursors (reactants) into a reaction chamber to deposit a layer over a substrate, and includes processing techniques such as atomic layer deposition (ALD) and cyclic chemical vapor deposition (cyclic CVD). CVD processes typically involve a gas-phase reaction between two or more precursors. These precursors may be simultaneously provided to a reaction chamber containing a substrate to which a material is to be deposited. The precursors may be provided by partially or completely separate pulses. The substrate and / or reaction chamber may be heated to promote the reaction between the gaseous precursors. In some embodiments, the precursors are provided until a layer of the desired thickness has been deposited. In some embodiments, a cyclic CVD process may employ multiple cycles to deposit a thin material of the desired thickness. In a cyclic CVD process, the precursors may be provided to the reaction chamber by non-overlapping pulses, partially or completely overlapping pulses.

[0054] ALD-type processes are based on the controlled and typically self-limiting surface reactions of these precursors. Gas-phase reactions can be avoided by feeding these precursors alternately and sequentially into the reaction chamber. The gas-phase precursors are separated within the reaction chamber, for example, by removing excess precursors and / or precursor byproducts from the reaction chamber between precursor pulses. This can be achieved by a vacuuming step and / or an inert gas pulse or blowing. In some embodiments, the substrate is contacted with a blowing gas (such as an inert gas). For example, the substrate may be contacted with the blowing gas between precursor pulses to remove excess precursors and reaction byproducts.

[0055] In some embodiments, the reactions are self-limiting and achieve monolayer-by-monolayer growth. These may be referred to as "true ALD" reactions. In some such embodiments, a transition metal precursor may be adsorbed onto the substrate surface in a self-limiting manner. A second precursor may then react with the adsorbed transition metal precursor to form a transition metal-containing material on the substrate. In some embodiments, up to one monolayer containing transition metal material may be formed in a single deposition cycle. A reducing agent may be introduced to reduce a transition metal to an elemental transition metal.

[0056] In some embodiments, the deposition process containing transition metal materials has one or more non-self-limiting stages. For example, in some embodiments, at least one of the precursors is at least partially decomposed on the substrate surface. Therefore, in some embodiments, the process can be operated under process condition mechanisms close to CVD conditions, or in some cases, entirely under CVD conditions.

[0057] The method according to the invention can also be used in a space atomic layer deposition apparatus. In a space ALD, the precursors and reactants are continuously supplied in different solid sections, and the substrate moves between the sections. At least two sections can be provided, wherein a half-reaction can occur in the presence of the substrate. If the substrate is present in this half-reaction section, a monolayer can be formed from the first or second precursor. The substrate then moves to a second half-reaction zone, where the ALD cycle is completed using the first or second precursor to form the target material. Alternatively, the position of the substrate can be fixed, and the gas supply can be moved, or some combination of both. To obtain a thicker layer, this sequence can be repeated.

[0058] Blowing refers to the removal of gaseous precursors and / or gaseous byproducts from the substrate surface, for example, by evacuating the reaction chamber using a vacuum pump and / or by replacing the gas in the reaction chamber with an inert gas (such as argon or nitrogen). Blowing can be performed between two precursor pulses. Typical blowing times range from about 0.05 seconds to 20 seconds, and can be about 0.2 and 10 seconds, or between about 0.5 seconds and 5 seconds. However, other blowing times can be used if necessary, such as in cases requiring high conformal step coverage on structures with very high aspect ratios or other structures with complex surface morphologies, or when different reactor types (e.g., batch reactors) can be used. As described above for ALD, blowing can be performed in either time or space modes.

[0059] In this invention, "gas" may include materials that are gases, vaporized solids, and / or vaporized liquids at normal temperature and pressure (NTP), and may consist of a single gas or a mixture of gases depending on the context. The term "inert gas" may refer to a gas that does not participate in a chemical reaction to a perceptible degree. Exemplary inert gases include He and Ar, and any combination thereof. In some cases, nitrogen and / or hydrogen may be inert gases. Gases other than process gases, i.e., gases not introduced through a gas distribution assembly, other gas distribution device, or the like, may be used, for example, to seal a reaction space and may comprise a sealed gas such as a rare gas.

[0060] The term "precursor" can refer to a compound that participates in a chemical reaction that produces another compound, especially a compound that constitutes the deposited material. The term "reactant" can be used interchangeably with the term "precursor." However, reactants can be used to modify the chemical properties of the deposited material. For example, a reducing agent that reduces a transition metal to an elemental metal can be called a reactant.

[0061] In some embodiments, the method according to this disclosure is a thermal deposition method. A thermal deposition method should be understood as a method that does not involve plasma activation of a transition metal precursor or a second precursor. However, in some embodiments, the method may include one or more plasma activation steps. Such a process may be referred to as a plasma process, although it may also include thermal deposition steps. Deposited materials

[0062] Transition metal-containing materials can be deposited using the method according to the present invention. In some embodiments, the transition metal is a first-order transition metal. In other words, the transition metal is selected from the group consisting of scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn). In some embodiments, the transition metal is manganese. In some embodiments, the transition metal can be selected from the group consisting of manganese, iron, cobalt, nickel, and copper. In some embodiments, the transition metal can be selected from the group consisting of cobalt, nickel, and copper. In some embodiments, the transition metal is iron. In some embodiments, the transition metal is cobalt. In some embodiments, the transition metal is nickel. In some embodiments, the transition metal is copper. The transition metal-containing material may contain one or more transition metals.

[0063] The transition metal-containing material may contain a second element. The transition metal-containing material may contain a transition metal oxide. In some embodiments, the transition metal-containing material may contain oxygen in a form other than an oxide. The transition metal-containing material may contain a transition metal nitride. In some embodiments, the transition metal-containing material may contain nitrogen in a form other than a nitride. The transition metal-containing material may contain a transition metal sulfide. In some embodiments, the transition metal-containing material may contain sulfur in a form other than a sulfide. The transition metal-containing material may contain a transition metal silicate. The transition metal-containing material may contain a transition metal phosphide. The transition metal-containing material may contain a transition metal selenide. The transition metal-containing material may contain a transition metal boride.

[0064] In some embodiments, the cyclic deposition method can be used to selectively deposit cobalt-containing layers, such as, for example, elemental cobalt, cobalt oxide, cobalt nitride, cobalt silicate, cobalt phosphide, cobalt selenide, cobalt sulfide, or cobalt boride.

[0065] In some embodiments, the cyclic deposition method can be used to selectively deposit nickel-containing layers, such as, for example, elemental nickel, nickel oxide, nickel nitride, nickel silicate, nickel phosphide, nickel selenide, nickel sulfide, or nickel boride.

[0066] In some embodiments, the cyclic deposition method can be used to selectively deposit copper-containing layers, such as, for example, elemental copper, copper oxide, copper nitride, copper silicate, copper phosphide, copper selenide, copper sulfide, or copper boride.

[0067] In some embodiments, the cyclic deposition method can be used to selectively deposit manganese-containing layers, such as, for example, elemental manganese, manganese oxide, manganese nitride, manganese silicate, manganese phosphide, manganese selenide, manganese sulfide, or manganese boride.

[0068] In some embodiments, the cyclic deposition method can be used to selectively deposit iron-containing layers, such as, for example, elemental iron, iron oxide, iron nitride, iron silicate, iron phosphide, iron selenide, iron sulfide, or iron boride.

[0069] In some embodiments, a transition metal-containing material may comprise, for example, about 70 to about 99.5 at.% of transition metal-containing material, or about 80 to about 99.5 at.% of transition metal-containing material, or about 90 to about 99.5 at.% of transition metal-containing material. A transition metal-containing layer deposited by the method according to the invention may comprise, for example, about 80 at.%, about 83 at.%, about 85 at.%, about 87 at.%, about 90 at.%, about 95 at.%, about 97 at.%, or about 99 at.% of transition metal-containing material. In some embodiments, the transition metal-containing material deposited according to the invention contains less than about 3 at.% or less than about 1 at.% of chlorine. In some embodiments, the transition metal-containing material deposited according to the invention contains less than about 2 at.%, less than about 1 at.%, or less than about 0.5 at.% of oxygen. In some embodiments, the transition metal-containing material deposited according to the present invention contains less than about 5 at.%, or less than about 2 at.%, or less than about 1 at.%, or less than about 0.5 at.%. In some embodiments, the transition metal-containing material deposited according to the present invention contains less than about 0.5 at.%, or less than about 0.2 at.%, or less than about 0.1 at.%. In some embodiments, the transition metal-containing material deposited according to the present invention contains less than about 1.5 at.%, or less than about 1 at.%.

[0070] In some embodiments, the transition metal-containing material is substantially composed of or consists of a transition metal-containing material. In some embodiments, the transition metal-containing material is substantially composed of or consists of cobalt sulfide. In some embodiments, the transition metal-containing material is substantially composed of or consists of nickel sulfide. In some embodiments, the transition metal-containing material is substantially composed of or consists of copper sulfide. In some embodiments, the transition metal-containing material is substantially composed of or consists of cobalt selenide. In some embodiments, the transition metal-containing material is substantially composed of or consists of nickel selenide. In some embodiments, the transition metal-containing material is substantially composed of or consists of copper selenide. In some embodiments, the transition metal-containing material is substantially composed of or consists of cobalt telluride. In some embodiments, the transition metal-containing material is substantially composed of or consists of nickel telluride. In some embodiments, the transition metal-containing material is substantially composed of or consists of copper telluride.

[0071] In some embodiments, the transition metal-containing material deposited according to the present invention may form a layer. As used herein, the terms "layer" and / or "thin film" may refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, layers and / or thin films 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. A thin film or layer may comprise a material or layer having at least partially continuous pinholes. A seed layer may be a discontinuous layer for increasing the nucleation rate of another material. However, the seed layer may also be substantially or completely continuous. Transition metal precursors

[0072] In some embodiments, a transition metal material or a transition metal layer may be deposited by a cyclic deposition process using a transition metal precursor comprising a transition metal halide compound. In some embodiments, a transition metal material or a transition metal layer may be deposited by a cyclic deposition process using a transition metal precursor, wherein the transition metal compound comprises an adduct forming a ligand.

[0073] In some embodiments, the transition metal precursor may comprise a transition metal compound having an adduct-forming ligand (such as a monodentate, bidate, or multidentate adduct-forming ligand). In some embodiments, the transition metal precursor may comprise a transition metal halide compound having an adduct-forming ligand (such as a monodentate, bidate, 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, bidate, or multidentate adduct-forming ligand). In some embodiments, the adduct-forming ligand comprises at least one of nitrogen, phosphorus, oxygen, or sulfur.

[0074] In some embodiments, the transition metal in the transition metal halide compound is selected from the group consisting of manganese, iron, cobalt, nickel and copper.

[0075] In some embodiments, the transition metal halide compound comprises a transition metal chloride, a transition metal iodide, or a transition metal fluoride. Specifically, the transition metal halide compound may comprise at least one of cobalt chloride, nickel chloride or copper chloride, cobalt bromide, nickel bromide or copper bromide, cobalt iodide, nickel iodide or copper iodide.

[0076] In some embodiments, the transition metal precursor may comprise a transition metal compound having adduct-forming ligands comprising phosphorus, oxygen, or sulfur (such as monodentate, didentate, or polydentate adduct-forming ligands comprising phosphorus, oxygen, or sulfur). For example, in some embodiments, the transition metal halide compound may comprise a transition metal chloride, a transition metal iodide, a transition metal fluoride, or a transition metal bromide. In some embodiments of the invention, the transition metal halide compound may comprise a transition metal species, including, but not limited to, at least one of manganese, iron, cobalt, nickel, or copper. In some embodiments of the invention, the transition metal halide compound may comprise at least one of manganese chloride, ferric chloride, cobalt chloride, nickel chloride, or copper chloride. In some embodiments of the invention, the transition metal halide compound may comprise at least one of manganese bromide, ferric bromide, cobalt bromide, nickel bromide, or copper bromide. In some embodiments of the present invention, the transition metal halide compound may comprise at least one of manganese monofluoride, iron monofluoride, cobalt monofluoride, nickel monofluoride, or copper monofluoride. In some embodiments, the transition metal halide compound comprises a bidentate nitrogen-containing ligand. In some embodiments, the transition metal halide compound may comprise a bidentate nitrogen-containing adduct forming ligand. In some embodiments, the transition metal halide compound may comprise an adduct forming ligand comprising two nitrogen atoms, wherein each of the nitrogen atoms is bonded to at least one carbon atom. In some embodiments of the present invention, the transition metal halide compound comprises nitrogen atoms bonded to one or more central transition metal atoms to form a metal complex.

[0077] In some embodiments, the bidentate nitrogen adduct forms a coordination system comprising two nitrogen atoms, each of which is bonded to at least one carbon atom.

[0078] In some embodiments of the present invention, the transition metal precursor may comprise a transition metal compound having the molecular formula (I): (Adduct)nM-Xa (I)

[0079] Each of the “adducts” is an adduct-forming ligand and may be independently selected as a monodentate, a bidentate, or a multidentate adduct-forming ligand or a mixture thereof: n is from 1 to 4 in the case of a monodentate adduct-forming ligand, and from 1 to 2 in the case of a bidentate or multidentate adduct-forming ligand; M is a transition metal, such as, for example, cobalt (Co), copper (Cu), or nickel (Ni); each of the Xa is another ligand and may be independently selected as a halide or other ligand; a is from 1 to 4, and in some cases a is 2.

[0080] In some embodiments of the invention, the adduct-forming ligand in the transition metal compound (such as a transition metal halide compound) may comprise a monodentate, bidentate, or polydentate adduct-forming ligand coordinated to the transition metal atom of the transition metal compound via at least one of a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom. In some embodiments of the invention, the adduct-forming ligand in the transition metal compound may comprise a cyclic adduct ligand. In some embodiments of the invention, the adduct-forming ligand in the transition metal compound may comprise a monoamine, diamine, or polyamine. In some embodiments of the invention, the adduct-forming ligand in the transition metal compound may comprise a monoether, diether, or polyether. In some embodiments, the adduct-forming ligand in the transition metal compound may comprise a monophosphine, diphosphine, or polyphosphine. Phosphine may be particularly advantageous in embodiments where the transition metal includes copper. In some embodiments, in addition to nitrogen, oxygen, phosphorus or sulfur in the adduct forming ligand, the adduct forming ligand in the transition metal compound may also / or may contain carbon.

[0081] In some embodiments of the present invention, the adduct-forming ligand in the transition metal compound may comprise one monodentate adduct-forming ligand. In some embodiments of the present invention, the adduct-forming ligand in the transition metal compound may comprise two monodentate adduct-forming ligands. In some embodiments of the present invention, the adduct-forming ligand in the transition metal compound may comprise three monodentate adduct-forming ligands. In some embodiments of the present invention, the adduct-forming ligand in the transition metal compound may comprise four monodentate adduct-forming ligands. In some embodiments of the present invention, the adduct-forming ligand in the transition metal compound may comprise one bidentate adduct-forming ligand. In some embodiments of the present invention, the adduct-forming ligand in the transition metal compound may comprise two bidentate adduct-forming ligands. In some embodiments of the present invention, the adduct-forming ligand in the transition metal compound may comprise one multidentate adduct-forming ligand. In some embodiments of the present invention, the adduct forming ligand in the transition metal compound may comprise two multidentate adduct forming ligands.

[0082] In some embodiments, the adduct forming ligand comprises nitrogen, such as a monoamine, monodiamine, or monopolyamine adduct forming ligand. In such embodiments, the transition metal compound may comprise at least one of the following: triethylamine (TEA), N,N,N',N'-tetramethyl-1,2-ethylenediamine (CAS: 110-18-9, TMEDA), N,N,N',N'-tetraethylethylenediamine (CAS: 150-77-6, TMEDA), 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-propanediamine (CAS: 110-95-2, TMPDA), N,N,N',N'-tetramethylmethyldiamine (CAS: 51-80-9, TMPDA), N,N,N',N'',N''-pentamethyldiethyl Triethylenetriamine (CAS: 3030-47-5, PMDETA), diethylenetriamine (CAS: 111-40-0, DIEN), triethylenetetramine (CAS: 112-24-3, TRIEN), tri(2-aminoethyl)amine (CAS: 4097-89-6, TREN, TAEA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (CAS: 3083-10-1, 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.

[0083] In some embodiments, the adduct forming ligand comprises phosphorus, such as a monophosphine, a diphosphine, or a polyphosphine adduct forming ligand. For example, the transition metal compound may include at least one of triethylphosphine (CAS: 554-70-1), trimethyl phosphite (CAS: 121-45-9), 1,2-bis(diethylphospho)ethane (CAS: 6411-21-8, BDEPE), or 1,3-bis(diethylphospho)propane (CAS: 29149-93-7).

[0084] In some embodiments of the invention, the adduct forming ligand comprises oxygen, such as a monoether, diether, or polyether adduct forming ligand. For example, the transition metal compound may include 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-tetraoxane-dodecane (CAS: 294-93-9, 12-Crown-4).

[0085] In some embodiments, the adduct forming ligand may include a monothione or a mixture of etheramines, such as at least one of 1,7-diaza-12-crown ether-4:1,7-dioxa-4,10-diazacyclododecane (CAS: 294-92-8) or 1,2-bis(methylthio)ethane (CAS: 6628-18-8).

[0086] In some embodiments, the transition metal halide compound may comprise cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)). In some embodiments, the transition metal halide compound may comprise cobalt bromide tetramethylethylenediamine (CoBr2(TMEDA)). In some embodiments, the transition metal halide compound may comprise cobalt iodide tetramethylethylenediamine (CoI2(TMEDA)). In some embodiments, the transition metal halide compound may comprise cobalt chloride N,N,N',N'-tetramethyl-1,3-propanediamine (CoCl2(TMPDA)). In some embodiments, the transition metal halide compound may comprise at least one of cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)), nickel chloride tetramethyl-1,3-propanediamine (NiCl2(TMPDA)), or nickel iodide tetramethyl-1,3-propanediamine (NiI2(TMPDA)). In some embodiments, the transition metal compound or the transition metal halide compound comprises at least one of CoCl2 (TMEDA), CoBr2 (TMEDA), CoI2 (TMEDA), CoCl2 (TMPDA), or NiCl2 (TMPDA).

[0087] In some embodiments of the invention, contacting the substrate with a transition metal precursor may include providing the transition metal precursor in the reaction chamber for a duration between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, between about 0.1 seconds and about 5.0 seconds, between 0.5 seconds and 10 seconds, or between 1 second and 30 seconds. For example, the transition metal precursor may be provided in the reaction chamber for about 0.5 seconds, about 1 second, about 1.5 seconds, about 2 seconds, or about 3 seconds. Furthermore, during the pulse of the transition metal precursor, the flow rate of the transition metal precursor may be less than 2000 sccm, or less than 500 sccm, or even less than 100 sccm. Furthermore, during the period when the metal precursor is provided over the substrate, the flow rate of the transition metal precursor may range from about 1 to 2000 sccm, from about 5 to 1000 sccm, or from about 10 to about 500 sccm.

[0088] Excess transition metal precursors and reaction byproducts (if any) can be removed from the surface, for example, by suction using an inert gas. For example, in some embodiments of the invention, the method may include a blow-through cycle in which the substrate surface is blown for a period of less than about 2 seconds. Excess metal source precursors and any reaction byproducts can be removed by means of a vacuum generated by a suction system in fluid communication with the reaction chamber.

[0089] In some embodiments, a transition metal halide compound comprises a bidentate nitrogen-containing ligand. In some embodiments, the bidentate nitrogen-containing ligand comprises a bidentate nitrogen-containing adduct forming ligand. Second precursor

[0090] The transition metal precursor may comprise a transition metal halide compound, and a second precursor may comprise at least one of an oxygen precursor, a nitrogen precursor, a silicon precursor, a sulfur precursor, a selenium precursor, a phosphorus precursor, a boron precursor, or a reducing agent. The selection of the second precursor will depend on the type of material to be deposited. For a transition metal oxide material, an oxygen precursor may be selected. For a transition metal nitride material, a nitrogen precursor may be selected. For a transition metal silicate material, a silicon precursor may be selected. For a transition metal sulfide material, a sulfur precursor may be selected. For a transition metal selenide material, a selenium precursor may be selected. For a transition metal phosphide material, a phosphorus precursor may be selected. For a transition metal boride material, a boron precursor may be selected. For an elemental transition metal material, a reducing agent may be selected.

[0091] In some embodiments of the invention, each deposition cycle comprises two distinct deposition stages. In a first stage ("metal stage") of a deposition cycle, the substrate is contacted with a first gaseous reactant containing a metal precursor by providing a transition metal precursor in a reaction chamber. The transition metal precursor is adsorbed onto the substrate surface. The term adsorption is intended to be non-limiting in terms of a specific interaction mode between the precursor and the substrate. Without limiting the invention to any particular theory of molecular interactions, in some embodiments, the transition metal precursor may be chemisorbed onto the substrate surface.

[0092] In a second stage of deposition, the substrate is contacted with a second precursor by providing a second precursor in the reaction chamber. The second precursor may comprise at least one of an oxygen precursor, a nitrogen precursor, a silicon precursor, a sulfur precursor, a selenium precursor, a phosphorus precursor, a boron precursor, or a reducing agent. The second precursor may react with a transition metal species on one surface of the substrate to form a transition metal-containing material on the substrate, such as, for example, an elemental transition metal, a transition metal oxide, a transition metal nitride, a transition metal silicate, a transition metal selenide, a transition metal phosphide, a transition metal boride, and mixtures thereof, and the transition metal-containing material further comprises carbon and / or hydrogen.

[0093] In some embodiments, the second precursor comprises an oxygen precursor. In some embodiments, the oxygen precursor is selected from the group consisting of ozone (O3), molecular oxygen (O2), oxygen atom (O), oxygen plasma, oxygen free radical, oxygen excited species, water (H2O), and hydrogen peroxide (H2O2). In some embodiments, the transition metal-containing material comprises a transition metal oxide. In some embodiments, the transition metal oxide comprises cobalt(II) oxide (CoO), is substantially composed of cobalt(II) oxide (CoO), or is composed of cobalt(II) oxide (CoO).

[0094] In some embodiments, the second precursor comprises a nitrogen precursor. In some embodiments, the nitrogen precursor comprises an NH bond. The nitrogen precursor may comprise at least one of ammonia (NH3), ammonia plasma, hydrazine (N2H4), triazine (N3H5), hydrazine derivatives, tri-butane (C4H9N2H3), methylhydrazine (CH3NHNH2), dimethylhydrazine ((CH3)2N2H2), or a nitrogen plasma or a hydrogen-containing nitrogen plasma.

[0095] In some embodiments, the transition metal-containing material comprises a transition metal nitride. However, in some embodiments, the transition metal-containing material may comprise a transition metal and nitrogen, but the material may be at least to some extent another material that is not a transition metal nitride. For example, the transition metal-containing material may be a nitrogen-doped transition metal.

[0096] In some embodiments, the second precursor may comprise a hydrocarbon-substituted hydrazine precursor. In a second stage of the deposition cycle, the substrate may be contacted with a second precursor comprising a hydrocarbon-substituted hydrazine precursor. In some embodiments, the method according to the invention may further comprise selecting the substituted hydrazine to comprise an alkyl group having at least four (4) carbon atoms. In this invention, "alkyl" refers to a saturated or unsaturated hydrocarbon chain having a length comprising at least four (4) carbon atoms, such as, but not limited to, butyl, pentyl, hexyl, heptyl, and octyl, and their isomers, such as normal, iso, secondary, and tertiary isomers. Alkyl groups may be straight-chain or branched and may include all structural isomers of alkyl groups. In some embodiments, the alkyl chain may be substituted. In some embodiments, the alkyl-hydrazine may comprise at least one hydrogen atom bonded to nitrogen. In some embodiments, the alkyl-hydrazine may comprise at least two hydrogen atom bonds to nitrogen. In some embodiments, the alkyl-hydrazine may comprise at least one hydrogen atom bonded to nitrogen and at least one alkyl chain bonded to nitrogen. In some embodiments of the present invention, the second precursor may comprise an alkyl hydrazine and may further comprise one or more of tert-butylhydrazine (TBH, C4H9N2H3), dimethylhydrazine, or diethylhydrazine. In some embodiments, the substituted hydrazine has at least one hydrocarbon group attached to nitrogen. In some embodiments, the substituted hydrazine has at least two hydrocarbon groups attached to nitrogen. In some embodiments, the substituted hydrazine has at least three hydrocarbon groups attached to nitrogen. In some embodiments, the substituted hydrazine has at least one C1 to C3 hydrocarbon group attached to nitrogen. In some embodiments, the substituted hydrazine has at least one C4 to C10 hydrocarbon group attached to nitrogen. In some embodiments, the substituted hydrazine has a straight-chain, branched-chain, cyclic, or aromatic hydrocarbon group attached to nitrogen. In some embodiments, the substituted hydrazine comprises a substituted hydrocarbon group attached to nitrogen.

[0097] In some embodiments, the substituted hydrazine has the following molecular formula (II): RIRII-N-NRIIIRIV, (II)

[0098] RI can be selected from hydrocarbon groups, such as straight-chain, branched-chain, cyclic, aromatic or substituted hydrocarbon groups, and each of the RII, RIII, and RIV groups can be independently selected as hydrogen or hydrocarbon groups, such as straight-chain, branched-chain, cyclic, aromatic or substituted hydrocarbon groups.

[0099] In some embodiments, in formula (II), each of the RI, RII, RIII, and RIV groups may be a C1-C10 hydrocarbon, a C1-C3 hydrocarbon, a C4-C10 hydrocarbon, or hydrogen, such as a straight-chain, branched-chain, cyclic, aromatic, or substituted hydrocarbon group. In some embodiments, at least one of the RI, RII, RIII, and RIV groups comprises an aromatic group, such as a phenyl group. In some embodiments, at least one of the RI, RII, RIII, and RIV groups comprises methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, or phenyl. In some embodiments, at least two of each of the RI, RII, RIII, and RIV groups may be independently selected to comprise methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, or phenyl. In some embodiments, the RII, RIII, and RIV groups are hydrogen. In some embodiments, at least two of the RII, RIII, and RIV groups are hydrogen. In some embodiments, at least one of the RII, RIII, and RIV groups is hydrogen. In some embodiments, all of the RII, RIII, and RIV groups are hydrocarbons.

[0100] In embodiments where the second precursor comprises a silicon precursor, the silicon precursor may comprise at least one of silane (SiH4), disylane (Si2H6), trisilane (Si3H8), tetrasilane (Si4H10), isopentylsilane (Si5H12), or neopentylsilane (Si5H12). In embodiments where the second precursor comprises a silicon precursor, the silicon precursor may comprise a C1-C4 alkylsilane. In embodiments of the invention, wherein the second precursor comprises a silicon precursor, the silicon precursor may comprise a precursor from a silane family.

[0101] In embodiments where the second precursor comprises a boron precursor, the boron precursor may comprise at least one of borane (BH3), diborane (B2H6), or other boranes (such as decaborane (B10H14)).

[0102] In an embodiment where the second precursor comprises a hydrogen precursor, the hydrogen precursor may comprise at least one of H2, H atoms, H-ions, H-plasma, or H-radicals.

[0103] In some embodiments, the second precursor comprises a phosphorus precursor, a sulfur precursor, or a selenide precursor. In some embodiments, the sulfur precursor comprises hydrogen and sulfur. In some embodiments, the sulfur precursor is an alkylsulfur compound. In some embodiments, the second precursor comprises one or more of elemental sulfur, H₂S, (CH₃)₂S, (NH₄)₂S, (CH₃)₂SO, and H₂S₂. In some embodiments, the selenium precursor is an alkylselenium compound. In some embodiments, the second precursor comprises one or more of elemental selenium, H₂Se, (CH₃)₂Se, and H₂Se₂. In some embodiments, the selenium precursor comprises hydrogen and selenium. In some embodiments, the second precursor may comprise an alkylsilane compound of Te, Sb, or Se, such as (Me₃Si)₂Te, (Me₃Si)₂Se, or (Me₃Si)₃Sb, where Me represents methyl. In some embodiments, the phosphorus precursor is an alkylphosphorus compound. In some embodiments, the second precursor comprises one or more of elemental phosphorus, PH3, or alkylphosphine (such as methylphosphine). In some embodiments, the phosphorus precursor comprises hydrogen and phosphorus.

[0104] In an embodiment, the second precursor comprises an organic precursor, such as a reducing agent, for example, an alcohol, aldehyde, or carboxylic acid, or other available organic compound. For example, an organic compound that does not have a metal or half-metal but contains a -OH group. The alcohol can be a primary alcohol, secondary alcohol, tertiary alcohol, polyhydroxy alcohol, cyclic alcohol, aromatic alcohol, and other derivatives of alcohols.

[0105] Primary alcohols have a -OH group attached to a carbon atom bonded to another carbon atom, especially primary alcohols according to general formula (III): R1-OH (III)

[0106] R1 is a straight-chain or branched C1-C20 alkyl or alkenyl group, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of primary alcohols include methanol, ethanol, propanol, butanol, 2-methylpropanol, and 2-methylbutanol.

[0107] Secondary alcohols have -OH groups attached to carbon atoms bonded to two other carbon atoms. Specifically, secondary alcohols have the general formula (IV): (IV)

[0108] R1 and R2 are independently selected from the group consisting of straight-chain or branched C1-C20 alkyl and alkenyl groups, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of secondary alcohols include 2-propanol and 2-butanol.

[0109] Tertiary alcohols have -OH groups attached to carbon atoms bonded to three other carbon atoms. Specifically, tertiary alcohols have the general formula (V): (V)

[0110] R1, R2, and R3 are independently selected from the group consisting of straight-chain or branched C1-C20 alkyl and alkenyl groups, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. An example of a tertiary alcohol is tertiary butanol.

[0111] Polyols, such as diols and triols, have primary, secondary, and / or tertiary alcohol groups as described above. Examples of polyhydroxy alcohols are ethylene glycol and glycerol.

[0112] Cyclic alcohols have a -OH group attached to at least one carbon atom of a ring having 1 to 10 (such as 5 to 6 carbon atoms).

[0113] Aromatic alcohols have at least one -OH group attached to a carbon atom in a benzene ring or side chain.

[0114] Organic precursors may contain at least one aldehyde group (-CHO), and are selected from the group consisting of compounds having general formula (VI), alkanedialdehyde compounds having general formula (VII), haloaldehydes and other derivatives of aldehydes.

[0115] Therefore, in one embodiment, the organic precursor system has an aldehyde of general formula (VI): R1-CHO, (VI)

[0116] R1 is selected from the group consisting of hydrogen and straight-chain or branched C1-C20 alkyl and alkenyl groups, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. In some embodiments, R1 is selected from the group consisting of methyl or ethyl groups. Exemplary compounds according to, but not limited to, formula (VI) are formaldehyde, acetaldehyde, and butyraldehyde.

[0117] In some embodiments, the organic precursor system has an aldehyde of general formula (VII): OHC-R1-CHO, (VII)

[0118] R1 is a straight-chain or branched C1-C20 saturated or unsaturated hydrocarbon. Alternatively, aldehyde groups may be directly bonded to each other (R1 is not present).

[0119] Organic precursors containing at least one -COOH group may be selected from the group consisting of compounds of free general formula (VIII), polycarboxylic acids, halogenated carboxylic acids and derivatives of other carboxylic acids.

[0120] Therefore, in one embodiment, the organic precursor system has a carboxylic acid of general formula (VIII): R1-COOH (VIII)

[0121] R1 is hydrogen or a straight-chain or branched C1-C20 alkyl or alkenyl group, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl, for example, methyl or ethyl. In some embodiments, R1 is a straight-chain or branched C1-C3 alkyl or alkenyl group. Examples of compounds according to formula (VIII) are formic acid, propionic acid, and acetic acid; in some embodiments, formic acid (HCOOH) is used.

[0122] In some embodiments, trimethylaluminum can be used as a second precursor to deposit a carbon-containing transition metal material. The carbon content of such material can vary from about 20 at.% to about 60 at.%. Furthermore, TBGeH (tributylgermanium hydride) and TBTH (tributyltin hydride) can be used to selectively deposit a transition metal layer according to the present invention.

[0123] In some embodiments, the second precursor may be a carbonyl-containing precursor. In some embodiments, the second precursor may be a hydroxyl-containing organic precursor.

[0124] In some embodiments, exposing (i.e., contacting) the substrate with the second precursor includes pulsating the second precursor over the substrate for a period of time between 0.1 seconds and 2 seconds, or from about 0.01 seconds to about 10 seconds, or less than about 20 seconds, less than about 10 seconds, or less than about 5 seconds. During the pulsation of the second precursor over the substrate, the flow rate of the second precursor may be less than 50 sccm, or less than 25 sccm, or less than 15 sccm, or even less than 10 sccm.

[0125] Excess secondary precursors and reaction byproducts (if present) may be removed from the substrate surface, for example, by a purge gas pulse and / or a vacuum generated by a pumping system. The purge gas is preferably any inert gas, such as, but not limited to, argon (Ar), nitrogen (N2), or helium (He), or in some instances, hydrogen (H2). One stage is generally considered to follow immediately after another if a purge (i.e., a purge gas pulse) or other precursor, reactant, or byproduct removal step is inserted.

[0126] A deposition cycle system, in which a substrate is alternately contacted with a transition metal precursor (i.e., containing a metal halide compound) and a second precursor by providing a precursor in a reaction chamber, can be repeated one or more times until a desired thickness of transition metal-containing material has been deposited. It should be understood that, in some embodiments, the sequence of contact between the substrate and the transition metal precursor and the second precursor may be that the substrate first contacts the second precursor, and then contacts the transition metal precursor. Furthermore, in some embodiments, the cyclic deposition process may include contacting the substrate with the transition metal precursor one or more times before contacting the substrate with the second precursor one or more times, and similarly, alternatively, may include contacting the substrate with the second precursor one or more times before contacting the substrate with the transition metal precursor one or more times.

[0127] Furthermore, some embodiments of the present invention may include plasma-free precursors, for example, the transition metal precursor and the second precursor being substantially non-ionizable reactive species. In some embodiments, the transition metal precursor and the second precursor are substantially non-ionizable reactive species, non-excited-state species, or non-radical species. For example, both the transition metal precursor and the second precursor may include plasma-free precursors to prevent ionization damage to the underlying substrate and the resulting associated defects. The use of plasma-free precursors may be particularly useful when the underlying substrate comprises a fragile or at least partially fabricated semiconductor device structure, as high-energy plasma species can impair and / or degrade device performance characteristics. reducing agent

[0128] In some embodiments, the cyclic deposition method according to the present invention includes an additional process step comprising contacting the substrate with a reducing agent. The reducing agent may be provided in the gas phase within the reaction chamber. In some embodiments, the reducing agent may comprise at least one of hydrogen (H2), hydrogen (H2) plasma, ammonia (NH3), ammonia (NH3) plasma, hydrazine (N2H4), silane (SiH4), disylane (Si2H6), trisilane (Si3H8), germanane (GeH4), digermanane (Ge2H6), borane (BH3), diborane (B2H6), tributylhydrazine (TBH, C4H12N2), a selenium precursor, a boron precursor, a phosphorus precursor, a sulfur precursor, an organic precursor (e.g., an alcohol, an aldehyde, or a carboxylic acid, such as formic acid), aluminum hydride, or a hydrogen precursor. In some embodiments, the method includes contacting the substrate with a second precursor that serves as a reducing agent (without any additional precursor / reactant introduction step).

[0129] In some embodiments, the method further includes contacting the substrate with a third precursor comprising a reducing agent precursor selected from the group consisting of tert-butylhydrazine (C4H12N2), hydrogen (H2), monohydrogen (H2) plasma, ammonia (NH3), monoammonium (NH3) plasma, hydrazine (N2H4), silane (SiH4), disylane (Si2H6), trisilane (Si3H8), germanane (GeH4), digermanane (Ge2H6), borane (BH3), and diborane (B2H6).

[0130] The reducing agent can be introduced into the reaction chamber in a cyclic deposition method according to one invention and contact the substrate at various process stages. In some embodiments, the reducing agent can be provided in the reaction chamber and contact the substrate separately from the transition metal precursor and separately from the second precursor. For example, the reducing agent can be provided into the reaction chamber and contact the substrate before contacting the transition metal precursor, after contacting the substrate with the transition metal precursor, and before and / or after contacting the substrate with the second precursor. In some embodiments, the reducing agent can be introduced into the reaction chamber and contact the substrate simultaneously with the transition metal precursor and / or simultaneously with the second precursor. For example, the reducing agent and the transition metal precursor can co-flow into the reaction chamber and simultaneously contact the substrate, and / or the reducing agent and the second precursor can co-flow into the reaction chamber and simultaneously contact the substrate.

[0131] In some embodiments, the transition metal precursor may comprise a transition metal halide compound, and the second precursor may comprise an oxygen precursor. In such embodiments, a cyclic deposition process may deposit a transition metal oxide on the substrate. As a non-limiting example, the transition metal precursor may comprise CoCl2 (TMEDA), the second precursor may comprise water (H2O), and the material deposited on the substrate may comprise cobalt monoxide. As a non-limiting example, the transition metal precursor may comprise CoCl2 (TMEDA), the second precursor may comprise TBH, and the material deposited on the substrate may comprise nitrogen-doped cobalt. In some embodiments, the transition metal oxide may be further processed by exposing the transition metal oxide to a reducing agent. In some embodiments, the transition metal oxide may be exposed to at least one reducing agent comprising a forming gas (H2+N2), ammonia (NH3), hydrazine (N2H4), molecular hydrogen (H2), hydrogen atoms (H), a hydrogen plasma, hydrogen radicals, hydrogen excited species, alcohols, aldehydes, carboxylic acids, boron, or amines.

[0132] In some embodiments, exposing the transition metal oxide or the transition metal nitride to a reducing agent can reduce the transition metal oxide to an elemental transition metal. As a non-limiting example, the cyclic deposition process according to the present invention can be used to deposit cobalt oxide material to a thickness of 50 nanometers (nm), and the cobalt oxide material can be exposed to 10% forming gas at a pressure of 1000 mbar and a temperature of about 250 °C to reduce the cobalt oxide material to elemental cobalt. In some embodiments, the transition metal oxide may have a thickness of less than 500 nm, or less than 100 nm, or less than 50 nm, or less than 25 nm, or less than 20 nm, or less than 10 nm, or less than 5 nm. In some embodiments, the transition metal oxide may be exposed to a reducing agent for less than 5 hours, or less than 1 hour, or less than 30 minutes, or less than 15 minutes, or less than 10 minutes, or less than 5 minutes, or at least 1 minute. In some embodiments, the transition metal oxide may be exposed to the reducing agent at a substrate temperature below 500 °C, or below 400 °C, or below 300 °C, or below 250 °C, or below 200 °C, or even below 150 °C. In some embodiments, the transition metal oxide may be exposed to the reducing agent under reduced pressure, wherein the pressure may be from about 0.001 mbar to about 10 bar or from about 1 mbar to about 1000 mbar.

[0133] The cyclic deposition process described herein, which utilizes a transition metal precursor comprising a transition metal halide compound and a second precursor to deposit a transition metal material, can be performed in an ALD or CVD deposition system with a heated substrate. For example, in some embodiments, the method may include heating the substrate to a temperature between about 80°C and about 150°C, or even to a temperature between about 80°C and about 120°C. Of course, the appropriate temperature window for any given cyclic deposition process (such as in the case of an ALD reaction) will depend on the surface termination and reactant species involved. Here, the temperature varies depending on the precursor used and is generally equal to or below about 700°C. In some embodiments, for vapor deposition processes, the deposition temperature is typically about 100°C or higher; in some embodiments, the deposition temperature is between about 100°C and about 300°C; and in some embodiments, the deposition temperature is between about 120°C and about 200°C. In some embodiments, the deposition temperature is below about 500°C, or below about 400°C, or below about 350°C, or below about 300°C. In some instances, the deposition temperature may be below about 300°C, below about 200°C, or below about 100°C. In some instances, the deposition temperature may be above about 20°C, above about 50°C, or above about 75°C. In some embodiments, the deposition temperature (i.e., the temperature of the substrate during deposition) is about 275°C.

[0134] In some embodiments, the growth rate of the transition metal-containing material is from about 0.005 Å / cycle to about 5 Å / cycle or from about 0.01 Å / cycle to about 2.0 Å / cycle. In some embodiments, the growth rate of the transition metal-containing material is greater than about 0.05 Å / cycle, greater than about 0.1 Å / cycle, greater than about 0.15 Å / cycle, greater than about 0.20 Å / cycle, greater than about 0.25 Å / cycle, or greater than about 0.3 Å / cycle. In some embodiments, the growth rate of the transition metal-containing material is less than about 2.0 Å / cycle, less than about 1.0 Å / cycle, less than about 0.75 Å / cycle, less than about 0.5 Å / cycle, or less than about 0.2 Å / cycle. In some embodiments, the growth rate of the transition metal-containing material may be about 0.4 Å / cycle. Clean the substrate surface

[0135] In some embodiments, the method includes cleaning the substrate prior to providing the transition metal precursor in the reaction chamber. In some embodiments, cleaning the substrate includes contacting the substrate with a cleaning agent. In some embodiments, the cleaning agent comprises a chemical substance selected from β-diketones, cyclopentadienyl compounds, carbonyl compounds, carboxylic acids, and hydrogen.

[0136] Therefore, various cleaning agents may be suitable. For example, the cleaning agent may contain a β-diketonate. Examples of β-diketonate cleaning agents are hexafluoroacetylacetone (Hfac), acetylacetone (Hacac), or ditrimethylacetylmethane, namely 2,2,6,6-tetramethyl-3,5-heptanedione (Hthd). In some embodiments, the β-diketonate contains hexafluoroacetylacetone (Hfac). In some embodiments, the β-diketonate contains acetylacetone (Hacac). In some embodiments, the β-diketonate contains ditrimethylacetylmethane (Hthd).

[0137] Alternatively, the cleaning agent may contain a cyclopentadienyl group, such as a substituted or unsubstituted cyclopentadienyl group. Exemplary substituted cyclopentadienyl groups include alkyl-substituted cyclopentadienyl groups, such as methyl-substituted cyclopentadienyl, ethyl-substituted cyclopentadienyl, isopropyl-substituted cyclopentadienyl, and isobutyl-substituted cyclopentadienyl. Alternatively, the cleaning agent may contain a carbonyl group. In some embodiments, the cleaning agent contains carbon monoxide. In some embodiments, the cleaning agent comprises a cyclopentadienyl group. In some embodiments, the cleaning agent comprises a mixture of one or more cyclopentadienyl-containing compounds. In some embodiments, the cleaning agent comprises one or more carbonyl-containing compounds. In some embodiments, the cleaning agent consists of a mixture of cyclopentadiene and carbon monoxide.

[0138] In some embodiments, the cleaner contains β-ketoamines, such as acetoacetone amine or 4-amino-1,1,1,5,5,5-hexafluoropentane-2-one.

[0139] In some embodiments, the cleaning agent comprises β-dithione or β-dithione. An example of β-dithione is 1,1,1,5,5,5-hexafluoropentane-2,4-dithione.

[0140] In some embodiments, the cleaning agent comprises β-diimide. An example of β-diimide is 1,1,1,5,5,5-hexafluoropentene-2,4-diimide.

[0141] In some embodiments, the cleaning agent comprises an aminothiol, for example, a compound containing a thiol group and an amino group at the β position. Exemplary aminothiols include 4-amino-3-penten-2-mercapto and 4-amino-1,1,1,5,5,5-hexafluoropentane-2-mercapto.

[0142] In some embodiments, the cleaning agent comprises β-thioimide. In some embodiments, the cleaning agent comprises β-thioneimide. Suitable β-thioimide includes 1,1,1,5,5,5-hexafluoropentane-2-mercapto-4-imide.

[0143] In some embodiments, the cleaning agent contains a carboxylic acid. Suitable carboxylic acids include formic acid.

[0144] In some embodiments, the cleaning agent contains a cyclopentadienyl group.

[0145] In some embodiments, the cleaning agent contains carbon monoxide.

[0146] In some embodiments, the cleaning agent contains a carboxylic acid.

[0147] In some embodiments, the cleaning agent contains formic acid.

[0148] In some embodiments, the cleaning agent may be provided to the reaction chamber as a mixture containing the cleaning agent and H2. For example, the cleaning agent may be provided to the reaction chamber in a gas stream containing at least 10 vol.% H2 to at most 90 vol.% H2, or at least 10 vol.% H2 to at most 30 vol.% H2, or at least 30 vol.% H2 to at most 50 vol.% H2, or at least 50 vol.% H2 to at most 70 vol.% H2, or at least 70 vol.% H2 to at most 90 vol.% H2.

[0149] In some embodiments, the cleaning agent may be provided to the reaction chamber as a mixture containing the cleaning agent and CO2. For example, the cleaning agent may be provided to the reaction chamber in a gas stream containing at least 10 vol.% CO2 to at most 90 vol.% CO2, or at least 10 vol.% CO2 to at most 30 vol.% CO2, or at least 30 vol.% CO2 to at most 50 vol.% CO2, or at least 50 vol.% CO2 to at most 70 vol.% CO2, or at least 70 vol.% CO2 to at most 90 vol.% CO2.

[0150] In some embodiments, the cleaning agent may be supplied to the reaction chamber in a gas stream comprising from at least 10 vol.% to at most 90 vol.% cleaning agent, or from at least 10 vol.% to at most 30 vol.% cleaning agent, or from at least 30 vol.% to at most 50 vol.% cleaning agent, or from at least 50 vol.% to at most 70 vol.% cleaning agent, or from at least 70 vol.% to at most 90 vol.% cleaning agent. The remainder of the gas stream may comprise an additional gas. Exemplary additional gases include H2 and CO2.

[0151] Providing the cleaning agent, mixed with another gas (such as H2 and CO2), to the reaction chamber can advantageously prevent the redeposition of metallic impurities after they have been removed from the substrate using the cleaning agent. This other gas may be a decomposition product of the cleaning agent. Without being limited to any particular theory or mode of operation, it is believed that when formic acid is used as a cleaning agent, for example, at a temperature of at least 150°C to at most 275°C or at a temperature of at least 170°C to at most 230°C, formic acid can naturally decompose into H2 and / or CO2 during the cleaning step. By mixing formic acid with one or more of its decomposition products (i.e., H2 and CO2), it is believed that the decomposition of formic acid can be slowed or prevented, thereby improving cleaning uniformity.

[0152] The present invention will be further explained by way of the exemplary embodiments illustrated in the following figures. The figures presented herein are not intended to represent actual views of any particular material, structure, or device, but are merely schematic diagrams illustrating embodiments of the invention. It should be understood that the elements in the figures are shown for simplicity and clarity and are not necessarily shown to scale. For example, the dimensions of some elements in the figures may be particularly enlarged relative to other elements to aid in understanding the illustrated embodiments of the invention. The various structures and devices shown in the figures may include additional elements and details, which have been omitted for clarity. Figures 1A and 1B

[0153] Figures 1A and 1B illustrate a process flow diagram of an exemplary embodiment of a method for depositing a transition metal material on a substrate by means of a cyclic vapor deposition method 100 according to the present invention.

[0154] The method 100 may begin with process block 102, which includes providing a substrate to a reaction chamber. The substrate is heated to a deposition temperature. For example, the substrate may include one or more partially fabricated semiconductor device structures, the reaction chamber may include an atomic layer deposition reaction chamber, and the substrate may be heated to a deposition temperature of approximately 175°C to approximately 300°C. The deposition temperature may be, for example, from approximately 200°C to approximately 275°C, such as 225°C or 250°C. Furthermore, the pressure in the reaction chamber may be controlled. For example, the pressure in the reaction chamber during the cyclic deposition process may be less than 1000 mbar, or less than 100 mbar, or less than 10 mbar, or less than 5 mbar, or even less than 1 mbar in some instances.

[0155] The method 100 can proceed to process block 104, wherein a transition metal precursor is provided to the reaction chamber. When a transition metal precursor is provided to the reaction chamber, the transition metal precursor may contact the substrate for a period of time (pulse time) of about 0.05 seconds to about 60 seconds. In some embodiments, the transition metal compound may contact the substrate for a period of time between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds. Furthermore, during the time the transition metal precursor is provided to the reaction chamber, the flow rate of the transition metal precursor may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or even less than 100 sccm.

[0156] The method 100 can proceed to process block 106, which includes contacting the substrate with a second precursor, such as an oxygen precursor, a nitrogen precursor, a silicon precursor, a phosphorus precursor, a selenium precursor, a boron precursor, a sulfur precursor, or a reducing agent. In some embodiments of the invention, the second precursor may contact the substrate for a period of time between about 0.01 seconds and about 60 seconds, or between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds. Furthermore, during the pulse of the second gaseous reactant over the substrate, the flow rate of the second precursor may be less than 2000 sccm, or less than 1000 sccm, or less than 500 sccm, or less than 200 sccm, or even less than 100 sccm.

[0157] In the reaction chamber, a transition metal precursor (block 104) and a second precursor (block 106) are provided and brought into contact with the substrate, resulting in the deposition of a transition metal-containing material (block 108) on the first surface. Although depicted as separate blocks, the transition metal-containing material can be deposited continuously as the second precursor is provided in the reaction chamber. The actual deposition rate and its kinetics can vary depending on process details. The process selectivity can be altered depending on the specific material being deposited and the composition of the first and second surfaces.

[0158] An exemplary cyclic deposition method 100 may constitute a deposition cycle in which a transition metal-containing material is selectively deposited on the first surface of the substrate relative to the second surface of the substrate by alternately and sequentially contacting the substrate with the transition metal precursor (process block 104) and the second precursor (process block 106). In some embodiments, the method of depositing a transition metal-containing material may include repeating the deposition cycle one or more times (process block 110). The repetition of the deposition cycle is determined based on the thickness of the deposited transition metal-containing material. For example, if the thickness of the transition metal-containing material is insufficient for the desired device structure, method 100 may return to process block 104, and the processes of contacting the substrate with the transition metal precursor 104 and contacting the substrate with the second precursor 106 may be repeated one or more times (block 110). Once the transition metal material has been deposited to the required thickness, the process can be stopped, and the transition metal material and the underlying semiconductor structure can withstand further processes to form one or more device structures.

[0159] In some embodiments, a material comprising a transition metal deposited according to the method described herein may have a thickness on the first surface that is continuously less than about 100 nm, or less than about 60 nm, or less than about 50 nm, or less than about 40 nm, or less than about 30 nm, or less than about 25 nm, or less than about 20 nm, or less than about 15 nm, or less than about 10 nm, or less than about 5 nm or lower. The continuity mentioned herein may be physical continuity or electrical continuity. In some embodiments, the thickness of the material when it is physically continuous may not be the same as the thickness of the material when it is electrically continuous, and the thickness of the material when it is electrically continuous may not be the same as the thickness of the material when it is physically continuous.

[0160] In some embodiments, a transition metal-containing material deposited according to some embodiments described herein may have a thickness from about 10 nm to about 100 nm. In some embodiments, a transition metal-containing material deposited according to some embodiments described herein may have a thickness from about 1 nm to about 10 nm. In some embodiments, the transition metal-containing material may have a thickness of less than 10 nm. In some embodiments, a transition metal-containing material deposited according to some embodiments described herein may have a thickness from about 10 nm to about 50 nm. In some embodiments, a transition metal-containing material deposited according to some embodiments described herein may have a thickness greater than about 20 nm, or greater than about 40 nm, or greater than about 50 nm, or greater than about 60 nm, or greater than about 100 nm, or greater than about 250 nm or greater than about 500 nm. In some embodiments, a transition metal-containing material deposited according to some embodiments described herein may have a thickness of less than about 50 nm, less than about 30 nm, less than about 20 nm, less than about 15 nm, less than about 10 nm, less than about 5 nm, less than about 3 nm, less than about 2 nm or even less than about 1 nm.

[0161] After a transition metal material has been sufficiently deposited, the deposited material can be selectively restored in block 112. Alternatively, the deposited material can be restored during the deposition process (not shown). In some embodiments, restoring the deposited material by removing any possible deposited material from the second surface can also improve process selectivity. Figure 1B

[0162] Figure 1B is a process flow diagram of an exemplary embodiment of a method for depositing a transition metal-containing material on a substrate according to one of the present invention. The process follows the overview depicted in Figure 1A, but includes blowing the reaction chamber (block 105) after a transition metal precursor (104) has been provided in the reaction chamber. In other words, after the substrate comes into contact with the transition metal precursor at block 104, excess transition metal-containing precursor and any reaction byproducts can be removed from the reaction chamber by a blowing process.

[0163] After the second precursor is provided to the reaction chamber, the reaction chamber can also be blown (block 109). If the cyclic deposition process is repeated (block 110), the transition metal precursor (104) can then be provided in the reaction chamber after the second blow (109). In other words, after the substrate is brought into contact with the second precursor (block 106), excess second precursor and any reaction byproducts can be removed from the reaction chamber by a blow process.

[0164] As a non-limiting example, by pulsed CoCl2 (TMEDA) and TBH into a reaction chamber in an alternating and sequential manner, co-contained materials can be selectively deposited on in-situ deposited TiN relative to native silicon oxide. The substrate can be pre-cleaned at the deposition temperature using H2 flowing into the reaction chamber. This deposition temperature (referring to the substrate temperature in this embodiment) can be 275°C. The transition metal precursors can be pulsed (i.e., provided) in the reaction chamber for 2 seconds, followed by a 2-second blow-out of the reaction chamber. Subsequently, TBH can be pulsed in the reaction chamber for 0.3 seconds, followed by a 2-second blow-out step. This cycle can be repeated 75 to 1,500 times to obtain a cobalt-containing material layer. The deposited cobalt-containing material can contain between 60 and 80 at.% cobalt and between 10 and 30 at.% nitrogen. The resistivity of such a material can be between 15 and 85 μΩ cm. The methods described herein may be used to deposit transition metal materials of up to 10 nm, or up to 20 nm, or up to 30 nm on a metal (such as on copper) without growing on a dielectric material. Figure 2

[0165] Figure 2 illustrates a semiconductor device structure 200 fabricated as part of a simplified schematic diagram. The structure 200 includes a substrate 202 and a dielectric material 204 formed above the substrate 202. The dielectric material may comprise a low dielectric constant material, i.e., a low-k dielectric. A trench may be formed in the dielectric material 204, and a metal interconnect material 206 may be formed in the trench to electrically interconnect a plurality of device structures disposed on the substrate 202. In some embodiments, a barrier material (not shown in Figure 2) may be disposed on the surface of the trench to prevent diffusion of the metal interconnect material. In some embodiments, the metal interconnect material 206 may comprise one or more of copper, cobalt, or molybdenum.

[0166] In addition to using cobalt as a barrier material, cobalt can also be used as a capping layer. Therefore, referring to FIG. 2b, the structure 200 may also include a capping layer 208 directly disposed on the surface above the metal interconnect material 206. The capping layer 208 serves to prevent oxidation of the metal interconnect material 206 and, importantly, to prevent the metal interconnect material 206 from diffusing into additional materials formed on the structure 200 in subsequent manufacturing processes. In some embodiments of the invention, the capping layer 208 may also include cobalt. The thickness of a capping layer can vary from less than 1 nm to several nm. In some embodiments, the metal interconnect material 206, the barrier material, and the capping layer 208 may collectively form an electrode for the electrical interconnection of a plurality of semiconductor devices disposed in the substrate 202. Figure 3

[0167] Figure 3 illustrates an exemplary embodiment of a method for selectively depositing a transition metal layer on a substrate according to one aspect of the present invention. In blocks 302 and 304, as explained in Figure 1, a substrate is provided in a reaction chamber, and a transition metal precursor is provided in the reaction chamber, respectively. After a transition metal precursor is provided to the reaction chamber (304), excess precursor and / or any reaction byproducts can be removed by blowing the reaction chamber (block 305).

[0168] When a transition metal layer (308) is to be deposited on the substrate, a reducing agent (block 306) may be provided in the reaction chamber after providing the transition metal precursor (304) and optionally blowing (305). In some embodiments, the reducing agent does not contain nitrogen. In some embodiments, the reducing agent may be a carboxylic acid. In some embodiments, the carboxylic acid may be formic acid. Method 300 may also include a blowing step 309 and a repeating loop 310.

[0169] As a non-limiting example, elemental cobalt can be deposited on a substrate comprising a copper surface as a first surface and a thermally oxidized silicon surface as a second surface. The transition metal precursor may comprise CoCl2 (TMEDA), and the second precursor may be formic acid. In some embodiments, the formic acid may have a purity of at least 95%, such as 99%. Prior to deposition, the substrate may be cleaned by repeatedly pulsed formic acid into the reaction chamber at a temperature of 275°C. Co can be deposited by pulsed transition metal precursor in the reaction chamber for 8 seconds, blown out of the reaction chamber for 5 seconds, and pulsed second precursor in the reaction chamber for 3 seconds, followed by blown out of the reaction chamber for 5 seconds. This deposition cycle can be repeated 500 to 1000 times. The carbon content of the deposited Co layer may be less than 4 at.%, the oxygen content less than 2 at.%, and the nitrogen content less than the detection limit (less than 0.5 at.%). The deposition rate of Co may be between about 0.1 and about 0.2 Å / cycle. The methods described herein can be used to deposit transition metal layers of up to 10 nm, up to 20 nm, or up to 30 nm on metals (such as copper) without growing on dielectric materials.

[0170] In another non-limiting example, Co can be similarly deposited on Ru, while no deposition occurs on thermally heated silicon oxide. At temperatures ranging from 225 °C to 275 °C, a transition metal precursor can be pulsed again for 8 seconds, and a second precursor for 3 seconds, and this cycle can be repeated 400 times. This process can result in the deposition of 5 to 10 nm of elemental cobalt on the Ru surface. Without limiting the invention to any particular theory, the deposition temperature of Co on Ru can be lower than that on Cu. Figure 4

[0171] Figure 4 is a schematic diagram of a vapor deposition assembly 40 according to the present invention. The deposition assembly 40 can be used to perform the methods described herein and / or to form a structure or device or part thereof as described herein.

[0172] In the illustrated example, the deposition assembly 40 includes one or more reaction chambers 42, a precursor injector system 43, a transition metal precursor container 431, a second precursor container 432, a blow-through gas source 433, an exhaust source 44, and a controller 45.

[0173] Reaction chamber 42 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber.

[0174] The transition metal precursor container 431 may include a container and one or more transition metal precursors—alone or mixed with one or more carrier (e.g., inert) gases, as described herein. The second precursor container 432 may include a container and a second precursor according to the invention—alone or mixed with one or more carrier gases. The purge gas source 433 may include one or more inert gases as described herein. Although three source containers 431-433 are illustrated, the deposition assembly 40 may include any suitable number of source containers. Source containers 431-433 may be coupled to the reaction chamber 42 via lines 434-436, each of which may include a flow controller, valve, heater, and the like. In some embodiments, the transition metal precursor in the precursor container may be heated. In some embodiments, the container is heated such that the transition metal precursor reaches a temperature between about 150 °C and about 200 °C, such as between about 160 °C and about 185 °C, for example, 165 °C, 170 °C, 175 °C or 180 °C.

[0175] The exhaust source 44 may include one or more vacuum pumps.

[0176] Controller 45 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in the deposition assembly 40. These circuitry and components operate to introduce precursors, reactants, and purge gases from respective sources 431-433. Controller 45 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber 42, the pressure within the reaction chamber 42, and various other operations to provide suitable operation of the deposition assembly 40. Controller 45 may include control software to electrically or pneumatically control valves, thereby controlling the flow of precursors, reactants, and purge gases into and out of the reaction chamber 42. Controller 45 may include modules, such as software or hardware components, that perform certain operations. A module may be configured to reside on an addressable storage medium of the control system and configured to perform one or more processes.

[0177] Other configurations of the deposition assembly 40 are also possible, including different numbers and types of precursor sources and purge gas sources. Furthermore, it will be understood that various arrangements of valves, conduits, precursor sources, and purge gas sources exist, which can be used to achieve the goal of selectively and coordinately feeding gas into the reaction chamber 42. Moreover, as illustrated in the schematic diagram of the deposition assembly, many components have been omitted for simplicity, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypass pipes.

[0178] During the operation of the deposition assembly 40, a substrate, such as a semiconductor wafer (not shown), is transported from, for example, a substrate processing system to the reaction chamber 42. Once the substrate(s) have been transferred to the reaction chamber 42, one or more gases (such as precursors, reactants, carrier gases, and / or purge gases) from gas sources 431-433 are introduced into the reaction chamber 42 to implement the method according to the invention.

[0179] The foregoing exemplary embodiments of the present invention do not limit the scope of the invention, as these embodiments are merely examples of a plurality of embodiments of the invention, defined by the claims and their legal equivalents appended below. Any equivalent embodiments are intended to be within the scope of the invention. In fact, in addition to what is shown and described herein, those skilled in the art will understand from this specification various modifications to the invention (such as alternatives to the described elements that may be combined). Such modifications and embodiments are also intended to fall within the scope of the appended claims.

[0180] 100: Method 102, 104, 105, 106, 108, 109, 110, 112: Process blocks, blocks 200: Semiconductor device structure, structure 202:Substrate 204: Dielectric material 206: Metal interconnect materials 208: Overlay 300: Method 302, 304, 305, 306, 308, 309, 310: Process blocks, blocks 40: Vapor deposition assembly, deposition assembly 42: Reaction Chamber 43: Precursor Injector System 44: Exhaust source 45: Controller 431: Transition metal precursor container, source container 432: Second precursor container, source container 433: Blowing gas source, source container 434~436: Pipelines

Claims

1. A method for selectively depositing a transition metal-containing material on a substrate by a cyclic deposition process, the method comprising: providing a substrate in a reaction chamber, wherein the substrate includes a first surface comprising a first material and a second surface comprising a second material; providing a transition metal precursor comprising a transition metal halide compound in the reaction chamber in the gas phase; and providing a second precursor in the reaction chamber in the gas phase to deposit a transition metal-containing material on the first surface relative to the second surface, wherein the first material comprises a conductive metal oxide, a metal nitride, a metal carbide, a metal boride, or a combination thereof, or a doped metal surface.

2. The method of claim 1, wherein the transition metal halide compound comprises a bidentate nitrogen-containing ligand.

3. The method of claim 1, wherein the transition metal halide compound comprises a transition metal chloride, a transition metal iodide, or a transition metal fluoride.

4. The method of claim 1, wherein one of the transition metals in the transition metal halide compound is selected from the group consisting of manganese, iron, cobalt, nickel and copper.

5. The method of claim 1, wherein the first surface comprises a metal or a metallic material.

6. The method of claim 5, wherein the metal is a transition metal.

7. The method of claim 1, wherein the first surface comprises a conductive material.

8. The method of claim 1, wherein the second surface comprises a dielectric material.

9. The method of claim 1, wherein the second precursor comprises an oxygen precursor.

10. The method of any one of claims 1 to 8, wherein the second precursor comprises a nitrogen precursor.

11. A method for selectively depositing a transition metal-containing material on a substrate by a cyclic deposition process, the method comprising: providing a substrate in a reaction chamber, wherein the substrate includes a first surface comprising a first material and a second surface comprising a second material; providing a transition metal precursor comprising a transition metal compound in the gas phase in the reaction chamber; and providing a second precursor in the gas phase in the reaction chamber to deposit the transition metal-containing material on the first surface relative to the second surface; wherein the transition metal compound includes an adduct forming ligand, and wherein the first material comprises a conductive metal oxide, a metal nitride, a metal carbide, a metal boride, or a combination thereof, or a doped metal surface.

12. The method of claim 11, wherein the transition metal compound comprises at least one of CoCl2 (TMEDA), CoBr2 (TMEDA), CoI2 (TMEDA), CoCl2 (TMPDA), or NiCl2 (TMPDA).

13. A method for selectively depositing a transition metal layer on a substrate by a cyclic deposition process, the method comprising: providing a substrate in a reaction chamber, wherein the substrate includes a first surface comprising a first material and a second surface comprising a second material; providing a transition metal precursor comprising a transition metal halide compound in the gas phase in the reaction chamber; and providing a second precursor in the gas phase in the reaction chamber, wherein the second precursor comprises a nitrogen-free compound, for depositing a transition metal layer on the first surface relative to the second surface, wherein the first material comprises a conductive metal oxide, a metal nitride, a metal carbide, a metal boride, or a combination thereof, or a doped metal surface.

14. The method of claim 13, wherein the second precursor comprises a carboxylic acid.

15. The method of claim 14, wherein the carboxylic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, benzoic acid and oxalic acid.

16. The method of claim 13 or 14, wherein a substantially continuous transition metal layer having a thickness of at least 20 nm is deposited on the first surface, and there is substantially no deposition on the second surface.

17. The method of claim 13, wherein the transition metal precursor and the second precursor are provided in the reaction chamber in an alternating and sequential manner.

18. The method of claim 13, wherein the selectivity of the method is at least 80%.

19. The method of claim 13, wherein the method is a thermal deposition method.

20. The method of claim 13, wherein a transition metal material or the transition metal layer is formed at a temperature of about 175°C to about 350°C.

21. The method of claim 13, wherein the reaction chamber is blown after the transition metal precursor and / or the second precursor are provided in the reaction chamber.

22. A vapor deposition assembly for depositing a transition metal material on a substrate, the vapor deposition assembly comprising: one or more reaction chambers configured and arranged to hold a substrate including a first surface and a second surface, the first surface including a first material and the second surface including a second material; a precursor injector system configured and arranged to provide a transition metal precursor and a second precursor in the reaction chambers; a transition metal precursor source container configured and arranged to hold the transition metal precursor and in fluid communication with the reaction chambers; a second precursor source container configured and arranged to hold the second precursor and in fluid communication with the reaction chambers; wherein the transition metal precursor includes a transition metal halide compound and / or an adduct forming a ligand, and wherein the first material includes a conductive metal oxide, a metal nitride, a metal carbide, a metal boride or a combination thereof, or a doped metal surface.

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