Method for forming a transition metal-containing film on a substrate by a cyclic deposition process, method for delivering a transition metal halide compound to a reaction chamber, and related vapor deposition apparatus

Abstract

To provide a method for forming a transition metal containing film onto a substrate by a cyclical deposition process.SOLUTION: A method includes steps of: bringing a substrate into contact with a first gas phase reactant containing a transition metal halide compound containing a bidentate nitrogen-containing addition ligand; and bringing the substrate into contact with a second gas phase reactant. A method for supplying a transition metal halide compound containing a bidentate nitrogen-containing ligand into a reaction chamber is provided together with a related vapor deposition apparatus.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This disclosure claims the benefit of U.S. patent application Ser. No. 15 / 897,578, filed Feb. 15, 2018, and entitled "A METHOD OF FORMING A TRANSITION METAL CONTAINING FILM ON A SUBSTRATE BY A CYCLICAL DEPOSITION PROCESS, A METHOD FOR SUPPLYING A TRANSITION METAL HALIDE COMPOUND TO A REACTION CHAMBER, AND RELATED VAPOR DEPOSITION APPARATUS," which is incorporated herein by reference.

[0002] Parties to the Joint Research Agreement The invention claimed in this application was made by, for, and / or in connection with a Joint Research Agreement between the University of Helsinki and ASM Microchemistry Oy, which was in effect on or before the date the claimed invention was made, and which resulted from activities undertaken within the scope of the Agreement.

[0003] The present disclosure relates generally to methods for forming transition metal-containing films, particularly cobalt-, copper-, and nickel-containing films, on substrates by a cyclic deposition process. The present disclosure also relates generally to methods for delivering transition metal halide compounds to vapor deposition tools and associated vapor deposition equipment. [Background technology]

[0004] Semiconductor device manufacturing processes at advanced technology nodes generally require state-of-the-art deposition methods to form transition metal-containing films, such as, for example, elemental transition metals, transition metal oxides, transition metal nitrides, transition metal silicides, transition metal phosphides, transition metal selenides, or transition metal borides.

[0005] A common requirement for the deposition of transition metal-containing films is that the deposition process be highly conformal. For example, conformal deposition is often required to uniformly deposit transition metal-containing films on three-dimensional structures including high aspect ratio features. Another common requirement for the deposition of transition metal-containing films is that the deposition process be capable of depositing continuous, ultra-thin films over large substrate areas. In certain cases where the transition metal-containing film is electrically conductive, the deposition process may need to be optimized to produce a film with low electrical resistance.

[0006] Cyclic deposition processes, such as atomic layer deposition (ALD) and cyclic chemical vapor deposition (CCVD), sequentially introduce one or more precursors (reactants) into a reaction chamber, where the precursors react with the surface of a substrate, one at a time, in a sequential, self-limiting manner. Cyclic deposition processes have been demonstrated to produce metal-containing films with excellent conformality and atomic-level thickness control.

[0007] Cyclic deposition processes may be utilized for the deposition of transition metal-containing films, such as copper-containing films, nickel-containing films, and particularly cobalt-containing films. However, suitable chemical precursors for the cyclic deposition of transition metal-containing films, and cobalt-containing films in particular, are uncommon and prohibitively expensive. For example, existing chemical precursors utilized for the cyclic deposition of cobalt-containing films may require the use of undesirable high-temperature and / or plasma-enhanced deposition processes. In addition, cyclic deposition processes utilizing existing cobalt chemical precursors may be undesirable due to the sensitivity of the deposition process to the underlying substrate material. Therefore, cyclic deposition methods, chemical precursors suitable for use in cyclic deposition processes, and associated vapor deposition equipment are desirable for the formation of transition metal-containing films, particularly cobalt-, copper-, and nickel-containing films. Summary of the Invention [Means for solving the problem]

[0008] This Summary is provided to introduce a selection of concepts in a simplified form. These concepts are described in more detail below in the Detailed Description of Exemplary Embodiments of this Disclosure. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0009] In some embodiments of the present disclosure, a method for forming a metal-containing film on a substrate by a cyclic deposition process is provided, which can include contacting the substrate with a first gas-phase reactant comprising a transition metal halide compound comprising a bidentate nitrogen-containing additional ligand, and contacting the substrate with a second gas-phase reactant.

[0010] In some embodiments of the present disclosure, additional methods are provided for forming a metal-containing film on a substrate by a cyclic deposition process. The method may include contacting the substrate with a first gas-phase reactant comprising a transition metal compound comprising an adduct-forming ligand, and contacting the substrate with a second gas-phase reactant, wherein the transition metal is selected from the group consisting of copper (Cu), nickel (Ni), and cobalt (Co).

[0011] In some embodiments of the present disclosure, a method for delivering a transition metal halide compound comprising a bidentate nitrogen-containing additional ligand to a reaction chamber is provided. The method may include providing a precursor source container configured to contain the transition metal halide compound, fluidly connecting the precursor source container to a reaction chamber, heating the transition metal halide compound contained within the precursor source container to a temperature greater than 150° C., generating a vapor pressure of the transition metal halide compound of at least 0.001 mbar, and delivering the transition metal halide compound to the reaction chamber.

[0012] Some embodiments of the present disclosure provide a vapor deposition apparatus that utilizes reactive volatile chemicals. The apparatus may include a reaction chamber, a substrate disposed within the reaction chamber, a precursor source vessel in fluid communication with the reaction chamber, and a transition metal halide compound comprising a bidentate nitrogen-containing additional ligand disposed within the precursor source vessel.

[0013] For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described hereinabove. It is, of course, to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner to achieve or optimize one advantage or group of advantages as taught or suggested herein, without necessarily achieving other objects or advantages that may be taught or suggested herein.

[0014] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments, taken in conjunction with the accompanying drawings, and the invention is not limited to any particular embodiment disclosed.

[0015] While this specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the present disclosure, the advantages of the presently disclosed embodiments may be more readily ascertained from the following description of certain specific examples of the presently disclosed embodiments when read in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 illustrates a process flow for an exemplary cyclic deposition method according to an embodiment of the present disclosure. [Figure 2] FIG. 2 shows a schematic diagram of an exemplary device structure including a deposited transition metal-containing film according to an embodiment of the present disclosure. [Figure 3]FIG. 3 shows examples of transition metal halide compounds utilized in the cyclic deposition process of the present disclosure. [Figure 4] FIG. 4 shows a schematic diagram of an exemplary deposition apparatus according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0017] Although certain specific embodiments and examples are disclosed below, it will be understood by those skilled in the art that the present invention extends beyond the specifically disclosed embodiments and / or uses of the invention, as well as obvious modifications and equivalents thereof. Therefore, it is not intended that the scope of the disclosed invention should be limited by the specific disclosed embodiments described below.

[0018] The figures shown herein are not meant to be actual illustrations of any particular materials, structures or devices, but merely idealized representations used to explain embodiments of the present disclosure.

[0019] As used herein, the term "cyclical deposition" refers to the sequential introduction of precursors (reactants) into a reaction chamber to deposit a film on a substrate, and includes deposition techniques such as atomic layer deposition and cyclic chemical vapor deposition.

[0020] As used herein, the term "cyclic chemical vapor deposition" can refer to any process in which a substrate is sequentially exposed to two or more volatile precursors that react and / or decompose on the substrate to produce a desired deposit.

[0021] As used herein, the term "substrate" may refer to any underlying material or materials that may be used or upon which a device, circuit, or film may be formed.

[0022] As used herein, the term "atomic layer deposition" (ALD) can refer to a vapor deposition process in which deposition cycles, preferably multiple consecutive deposition cycles, are performed in a process chamber. Typically, during each cycle, a precursor chemisorbs to a deposition surface (e.g., the surface of a substrate or a previously deposited underlying surface, such as a material deposited using a previous ALD cycle) to form a monolayer or submonolayer that does not readily react with additional precursors (i.e., a self-limiting reaction). If desired, a reactant (e.g., another precursor or reactant gas) can then be introduced into the process chamber for use in converting the chemisorbed precursor to the desired material on the deposition surface. Typically, this reactant can further react with the precursor. Additionally, a purge step can be utilized during each cycle to remove excess precursor from the process chamber after conversion of the chemisorbed precursor and / or to remove excess reactants and / or reaction by-products from the process chamber. Additionally, the term "atomic layer deposition" as used herein is also meant to include processes denoted by related terms, such as "chemical vapor deposition atomic layer deposition," "atomic layer epitaxy" (ALE), molecular beam epitaxy (MBE), gas source MBE, or metalorganic MBE, as well as chemical beam epitaxy when performed with alternating pulses of precursor compositions, reactive gases, and purge (e.g., inert carrier) gases.

[0023] As used herein, the terms "film," "thin film," "layer," and "thin layer" are intended to refer to any continuous or discontinuous structure and material deposited by the methods disclosed herein. "Film," "thin film," "layer," and "thin layer" can include, for example, 2D materials, nanorods, nanotubes, or nanoparticles, or partial or complete molecular layers, or partial or complete atomic layers, or clusters of atoms and / or molecules. "Film," "thin film," "layer," and "thin layer" can include materials or layers that have pinholes, but are still at least partially continuous.

[0024] As used herein, the term "transition metal-containing film" can refer to a film containing a transition metal species, including, but not limited to, elemental transition metals, transition metal oxides, transition metal nitrides, transition metal silicides, transition metal selenides, transition metal phosphides, transition metal borides, and mixtures thereof. Additionally, the term "transition metal-containing film" can refer to a film containing a transition metal species as well as a carbon- and / or hydrogen-containing film.

[0025] It should be noted that many exemplary materials are provided throughout the embodiments of this disclosure, and the chemical formulas provided for each of the exemplary materials should not be construed as limiting, nor should the non-limiting exemplary materials provided be limited by any exemplary stoichiometry.

[0026] The present disclosure includes methods for forming transition metal-containing films on substrates and particular methods for the cyclic deposition of transition metal-containing films on substrates. Embodiments of the present disclosure can include, for example, methods for the cyclic deposition of transition metal-containing films, such as copper-containing films, nickel-containing films, and particularly cobalt-containing films.

[0027] In certain embodiments of the present disclosure, cyclic deposition methods may be used to deposit cobalt-containing films, such as elemental cobalt, cobalt oxide, cobalt nitride, cobalt silicide, cobalt phosphide, cobalt selenide, or cobalt boride. In emerging semiconductor device fabrication processes, cobalt metal films may be important in applications such as liner and capping layers to suppress electromigration of copper interconnect materials into surrounding dielectric materials. Indeed, as device feature sizes decrease at advanced technology nodes, cobalt metal films may be used as interconnect materials, replacing commonly used copper interconnects. Cobalt metal films may also be of interest in giant magnetoresistance and magnetic memory applications. Furthermore, cobalt thin films can be deposited on silicon gate contacts in integrated circuits to form cobalt silicide upon annealing. Oxides of cobalt may have applications in emerging energy-related technologies, such as lithium-ion batteries and electrochemical water oxidation, and are also used as catalytic materials.

[0028] The deposition of elemental cobalt and cobalt-containing films has typically been achieved using sputtering techniques and CVD methods using organometallic precursors. However, such known methods for depositing cobalt-containing films may be unsuitable for advanced technology nodes due to their inherent non-conformality. Cyclic deposition methods, such as atomic layer deposition, are characteristically conformal deposition methods and are highly suitable for depositing conformal transition metal-containing films on three-dimensional structures, including high aspect ratio features. Therefore, a cyclic deposition method for depositing transition metal-containing films, particularly cobalt-containing films, is highly desirable.

[0029] Furthermore, the development of cyclic deposition methods for cobalt-containing films has been hindered by a lack of suitable and cost-effective chemical precursors. For example, cyclic deposition of cobalt-containing films using known chemical precursors can require undesirably high-temperature deposition processes, e.g., above 300°C. While plasma-enhanced atomic layer deposition processes may be used to deposit cobalt-containing films at lower deposition temperatures, the use of plasma-based processes may be undesirable for some device applications due to potential damage to underlying semiconductor device structures by high-energy plasma reactants. Therefore, chemical precursors suitable for the deposition of transition metal-containing films are desirable, and specific chemical precursors are desirable for the deposition of cobalt-containing films by cyclic deposition processes. Furthermore, methods and related apparatus for delivering chemical precursors to a suitable deposition system, e.g., an atomic layer deposition system, are needed.

[0030] Accordingly, embodiments of the present disclosure can include a method of forming a transition metal-containing film on a substrate by a cyclic deposition process, which can include contacting the substrate with a first vapor-phase reactant comprising a transition metal halide compound comprising a bidentate nitrogen-containing additional ligand, and contacting the substrate with a second vapor-phase reactant.

[0031] In some embodiments of the present disclosure, transition metal-containing layers (or films) can be deposited by a cyclic deposition process utilizing a transition metal halide compound as a metal precursor. Non-limiting exemplary embodiments of cyclic deposition processes include atomic layer deposition (ALD), which is based on a typically self-limiting reaction whereby sequential and alternating pulses of reactants are used to deposit approximately one atomic (or molecular) monolayer of material per deposition cycle. Deposition conditions and precursors are typically selected to provide a self-saturating reaction, such that an adsorbed layer of one reactant leaves a surface termination unreactive with the gas-phase reactant of the same reactant. The substrate is then contacted with a different reactant that reacts with the previous termination, allowing for continuous deposition. Thus, each cycle of alternating pulses typically leaves approximately one monolayer or less of the desired material. However, as noted above, one skilled in the art will recognize that more than one monolayer of material can be deposited in one or more ALD cycles, for example, if several gas-phase reactions occur despite the alternating nature of the process.

[0032] In an ALD-type process for depositing a transition metal-containing film, one deposition cycle can include contacting a substrate with a first reactant, removing any unreacted first reactant and reaction by-products from the reaction space, and contacting the substrate with a second reactant, followed by a second removing step. The first reactant can include a transition metal halide compound ("metal precursor"), and the second reactant can include 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.

[0033] The precursors can be separated by an inert gas, such as argon (Ar) or nitrogen (N), to prevent gas-phase reactions between the reactants and allow for self-saturating surface reactions. However, in some embodiments, the substrate can be moved to allow separate contact between the first and second gas-phase reactants. Because the reaction is self-saturating, strict temperature control of the substrate and precise dosage control of the precursor may not be necessary. However, the substrate temperature is preferably such that the incident gas species do not condense into a monolayer and decompose on the surface. Before contacting the substrate with the next reactive chemical, excess chemicals and reaction by-products, if any, are removed from the substrate surface, for example, by purging the reaction space or by moving the substrate. Undesired gas molecules can be effectively evacuated from the reaction space using an inert purge gas. A vacuum pump can be used to facilitate purging.

[0034] Any reactor that can be used to deposit transition metal-containing films can be used for deposition. Such reactors include ALD reactors equipped with appropriate devices and means for delivering precursors, as well as CVD reactors. In some embodiments, showerhead reactors can be used. In some embodiments, crossflow, batch, minibatch, or spatial ALD reactors can be used.

[0035] Examples of suitable reactors that can be used include commercially available single-substrate (or single-wafer) deposition equipment, such as Pulsar® reactors (e.g., Pulsar® 2000, Pulsar® 3000, and Pulsar® XP ALD, etc.), and EmerALD® XP and EmerALD® reactors, available from ASM America, Inc., Phoenix, Arizona, and ASM Europe BV, Almere, The Netherlands. Other commercially available reactors include those sold under the trade names Eagle® XP and XP8, manufactured by ASM Japan Co., Ltd. (Tokyo, Japan). In some embodiments, the reactor is a spatial ALD reactor in which the substrate moves or rotates during processing.

[0036] In some embodiments of the present disclosure, a batch reactor may be used. Suitable batch reactors include, but are not limited to, Advance® 400 series reactors commercially available from ASM Europe BV (Almere, The Netherlands) under the trade names A400 and A412PLUS. In some embodiments, the wafers are rotated during processing. In other embodiments, the batch reactor comprises a mini-batch reactor configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers, or 2 or fewer wafers. In some embodiments where a batch reactor is used, wafer-to-wafer non-uniformity is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

[0037] The deposition methods described herein can optionally be performed in reactors or reaction chambers connected to a cluster tool. In a cluster tool, each reaction chamber is dedicated to one type of process, allowing the temperature of the reaction chambers in each module to be kept constant, improving throughput compared to reactors that heat substrates to process temperatures before each run. Furthermore, a cluster tool can reduce the time it takes to evacuate a reaction chamber to a desired process pressure level between substrate runs. In some embodiments of the present disclosure, the deposition process can be performed in a cluster tool including multiple reaction chambers, each individual reaction chamber may be used to expose the substrate to a separate precursor gas, and the substrate may be transported between different reaction chambers to be exposed to multiple precursor gases, with the substrate transport being performed in a controlled ambient environment to avoid oxidation / contamination of the substrate. In some embodiments of the present disclosure, the deposition process can be performed in a cluster tool with multiple reaction chambers, each individual reaction chamber may be configured to heat the substrate to a different deposition temperature.

[0038] A stand-alone reactor is equipped with a load lock, in which case there is no need to cool the reaction space between runs. In some embodiments, a deposition process for depositing a transition metal-containing film can include multiple deposition cycles, such as ALD cycles or cyclic CVD cycles.

[0039] In some embodiments, a cyclical deposition process is used to form a transition metal-containing film on a substrate, and the cyclical deposition process can be an ALD-type process. In some embodiments, the cyclical deposition can be a hybrid ALD / CVD or cyclical CVD process. For example, in some embodiments, the growth rate of an ALD process can be low compared to a CVD process. One approach to increasing the growth rate is to operate at a higher substrate temperature than typically used in an ALD process, resulting in a chemical vapor deposition process, but further utilizing sequential introduction of precursors; such a process can be referred to as cyclical CVD.

[0040] According to some embodiments of the present disclosure, ALD processes can be used to deposit transition metal-containing films on substrates, such as partially fabricated semiconductor device structures. In some embodiments of the present disclosure, each ALD cycle includes two distinct deposition steps or phases. In the first phase of the deposition cycle (the "metal phase"), the surface of the substrate on which deposition is desired is contacted with a first gas-phase reactant that includes a metal precursor that chemisorbs onto the surface of the substrate and forms no more than about one monolayer of the reactant species on the surface of the substrate. In a second stage of deposition, the substrate surface on which deposition is desired is contacted with a second vapor-phase reactant comprising 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, and the second vapor-phase reactant can react with the transition metal species on the surface of the substrate to form a transition metal-containing film on the substrate, such as, for example, an elemental transition metal, a transition metal oxide, a transition metal nitride, a transition metal silicide, a transition metal selenide, a transition metal phosphide, a transition metal boride, and mixtures thereof, and a transition metal-containing film further comprising carbon and / or hydrogen.

[0041] In some embodiments of the present disclosure, the first vapor-phase reactant can comprise a metal-containing precursor, also referred to herein as a "metal compound." In some embodiments, the first vapor-phase reactant can comprise a transition metal compound having an adduct-forming ligand. In some embodiments, the first vapor-phase reactant can comprise a transition metal compound. In some embodiments, the first vapor-phase reactant can comprise a transition metal halide compound. In some embodiments, the first vapor-phase reactant can comprise a transition metal compound having an adduct-forming ligand, such as a monodentate, bidentate, or polydentate adduct-forming ligand. In some embodiments, the first vapor-phase reactant can comprise a transition metal halide compound having an adduct-forming ligand, such as a monodentate, bidentate, or polydentate adduct-forming ligand. In some embodiments, the first vapor-phase reactant can comprise a transition metal compound having a nitrogen-containing adduct-forming ligand, such as a nitrogen-containing monodentate, bidentate, or polydentate adduct-forming ligand. In some embodiments, the first vapor-phase reactant may include a transition metal compound having an adduct-forming ligand containing phosphorous, oxygen, or sulfur, such as a monodentate, bidentate, or polydentate adduct-forming ligand containing phosphorous, oxygen, or sulfur. For example, in some embodiments, the transition metal halide compound may include a transition metal chloride, transition metal iodide, transition metal fluoride, or transition metal bromide. In some embodiments of the present disclosure, the transition metal halide compound may include a transition metal species including, but not limited to, at least one of cobalt, nickel, or copper. In some embodiments of the present disclosure, the transition metal halide compound may include at least one of cobalt chloride, nickel chloride, or copper chloride. In some embodiments, the transition metal halide compound may include a bidentate nitrogen-containing adduct-forming ligand. In some embodiments, the transition metal halide compound may include an adduct-forming ligand containing two nitrogen atoms, where each of the nitrogen atoms is bonded to at least one carbon atom. In some embodiments of the present disclosure, the transition metal halide compound includes one or more nitrogen atoms bonded to a central transition metal atom, thereby forming a metal complex.

[0042] In some embodiments of the present disclosure, the first vapor phase reactant may include a transition metal compound having the following formula (I): (adduct) n -MX a (I) wherein each of the "adducts" is an adduct-forming ligand, which can be independently selected to be a monodentate, bidentate, or polydentate adduct-forming ligand or mixture thereof, where n is 1 to 4 for monodentate-forming ligands and n is 1 to 2 for bidentate or polydentate adduct-forming ligands, M is a transition metal such as, for example, cobalt (Co), copper (Cu), or nickel (Ni), and X a is another ligand, which can be independently selected to be a halide or other ligand, where a is 1 to 4, and in some examples, a is 2.

[0043] In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound, such as the transition metal halide compound, can include monodentate, bidentate, or polydentate adduct-forming ligands that coordinate to the transition metal atom of the transition metal compound through at least one of a nitrogen atom, a phosphorous atom, an oxygen atom, or a sulfur atom. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound can include cycloaddition ligands. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound can include a monoamine, a diamine, or a polyamine. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound can include a monoether, a diether, or a polyether. In some embodiments, the adduct-forming ligands in the transition metal compound can include a monophosphine, a diphosphine, or a polyphosphine. In some embodiments, the adduct-forming ligands in the transition metal compound can include carbon in addition to nitrogen, oxygen, phosphorous, or sulfur in the adduct-forming ligand.

[0044] In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include one monodentate adduct-forming ligand. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include two monodentate adduct-forming ligands. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include three monodentate adduct-forming ligands. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include four monodentate adduct-forming ligands. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include one bidentate adduct-forming ligand. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include two bidentate adduct-forming ligands. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include one polydentate adduct-forming ligand. In some embodiments of the present disclosure, the adduct-forming ligands in the transition metal compound may include two polydentate adduct-forming ligands.

[0045] In some embodiments of the present disclosure, the adduct-forming ligands include nitrogen, such as amine, diamine, or polyamine adduct-forming ligands. In such embodiments, the transition metal compound is selected from the group consisting of triethylamine (TEA), N,N,N',N'-tetramethyl-1,2-ethylenediamine (CAS: 110-18-9) (TMEDA), N,N,N',N'-tetraethylethylenediamine (CAS: 150-77-6) (TEEDA), N,N'-diethyl-1,2-ethylenediamine (CAS: 111-74-0) (DEEDA), N,N'-diisopropylethylenediamine (CAS: 4013-94-9), N,N,N',N'-tetramethyl-1,3-propanediamine (CAS: 110-95-2) (TMPDA), N,N,N',N'-tetramethylmethanediamine (CAS: 51-80-9) (TMMDA), N,N,N',N'',N''-pentamethyldiethylenetriamine (CAS: 3 030-47-5) (PMDETA), diethylenetriamine (CAS: 111-40-0) (DIEN), triethylenetetramine (CAS: 112-24-3) (TRIEN), tris(2-aminoethyl)amine (CAS: 4097-89-6) (TREN, TAEA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (CAS: 3083-10-1) ( 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).

[0046] In some embodiments of the present disclosure, the adduct-forming ligand comprises a phosphorous acid, such as a phosphine, diphosphine, or polyphosphine adduct-forming ligand. For example, the transition metal compound may comprise at least one of triethylphosphine (CAS: 554-70-1), trimethylphosphite (CAS: 121-45-), 1,2-bis(diethylphosphino)ethane (CAS: 6411-21-8) (BDEPE), or 1,3-bis(diethylphosphino)propane (CAS: 29149-93-7).

[0047] In some embodiments of the present disclosure, the adduct-forming ligand includes oxygen, such as an ether, diether, or polyether adduct-forming ligand. For example, the transition metal compound can 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-tetraoxacyclododecane (CAS: 294-93-9) (12-crown-4).

[0048] In some embodiments of the present disclosure, the adduct-forming ligand may comprise a thioether or mixed ether amine, such as, for example, at least one of 1,7-diaza-12-crown-4:1,7-dioxa-4,10-diazacyclododecane (CAS: 294-92-8), or 1,2-bis(methylthio)ethane (CAS: 6628-18-8).

[0049] In some embodiments, the transition metal halide compound can include cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl2(TMEDA)). In some embodiments, the transition metal halide compound can include cobalt bromide tetramethylethylenediamine (CoBr2(TMEDA)). In some embodiments, the transition metal halide compound can include cobalt iodide tetramethylethylenediamine (Col2(TMEDA)). In some embodiments, the transition metal halide compound can include cobalt chloride N,N,N',N'-tetramethyl-1,3-propanediamine (CoCl2(TMPDA)). In some embodiments of the present disclosure, the transition metal halide compound may include cobalt chloride N,N,N',N'-tetramethyl-1,2-ethylenediamine (CoCl(TMEDA)), nickel chloride tetramethyl-1,3-propanediamine (NiCl(TMPDA)), or nickel iodide tetramethyl-1,3-propanediamine (NiI(TMPDA)).

[0050] In some embodiments of the present disclosure, contacting the substrate with a first vapor-phase reactant comprising a transition metal halide compound, i.e., a transition metal halide comprising an adduct-forming ligand, can include exposing the substrate to the transition metal halide compound, i.e., contacting the substrate with the transition metal halide compound for about 0.01 seconds to about 60 seconds, about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5.0 seconds. Additionally, during pulse injection of the transition metal halide compound, the flow rate of the transition metal halide compound can be less than 2000 sccm, or less than 500 sccm, or even 100 sccm. Additionally, during pulse injection of the transition metal halide compound onto the substrate, the flow rate of the transition metal halide compound can vary from about 1 to 2000 sccm, from about 5 to 1000 sccm, or from about 10 to about 500 sccm.

[0051] If present, excess transition metal halide compound and reaction by-products may be removed from the surface, for example, by pumping with an inert gas. For example, in some embodiments of the present disclosure, the method may include a purge cycle in which the surface of the substrate is purged for a time period of less than about 2.0 seconds. Excess transition metal halide compound and reaction by-products may be removed using a vacuum generated by a pumping system in fluid communication with the reaction chamber.

[0052] In a second stage of the deposition cycle, the substrate can be contacted with a second gas-phase reactant comprising 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. In some embodiments, the second gas-phase reactant can comprise an oxygen precursor, and transition metal-containing films deposited by the cyclic deposition methods disclosed herein can comprise a transition metal oxide. In some embodiments, the second gas-phase reactant can comprise a reducing agent, described in more detail below, and transition metal-containing films deposited by the cyclic deposition methods disclosed herein can comprise an elemental transition metal. In some embodiments, the second gas-phase reactant can comprise a nitrogen precursor, and transition metal-containing films deposited by the cyclic deposition methods disclosed herein can comprise a transition metal nitride. In some embodiments, the second gas-phase reactant can comprise a silicon precursor, and transition metal-containing films deposited by the cyclic deposition methods disclosed herein can comprise a transition metal silicide. In some embodiments, the second gas-phase reactant may include a sulfur precursor, and the transition metal-containing films deposited by the cyclic deposition methods disclosed herein may include a transition metal sulfide. In some embodiments, the second gas-phase reactant may include a selenium precursor, and the transition metal-containing films deposited by the cyclic deposition methods disclosed herein may include a transition metal selenide. In some embodiments, the second gas-phase reactant may include a phosphorus precursor, and the transition metal-containing films deposited by the cyclic deposition methods disclosed herein may include a transition metal phosphide. In some embodiments, the second gas-phase reactant may include a boron precursor, and the transition metal-containing films deposited by the cyclic deposition methods disclosed herein may include a transition metal boride.

[0053] In embodiments of the present disclosure, the second vapor-phase reactant includes an oxygen precursor, which may include at least one of ozone (O), molecular oxygen (O), atomic oxygen (O), oxygen plasma, oxygen radicals, excited oxygen species, water (H2O), or hydrogen peroxide (H2O2). In embodiments of the present disclosure, the second vapor-phase reactant includes a nitrogen precursor, which may include at least one of ammonia (NH3), hydrazine (N2H4), triazane (N3H5), tert-butylhydrazine (C4H9N2H3), methylhydrazine (CH3NHNH2), dimethylhydrazine ((CH3)2N2H2), or nitrogen plasma, or the nitrogen plasma includes hydrogen.

[0054] In some embodiments, the second vapor-phase reactant can include a hydrocarbon-substituted hydrazine precursor. In the second stage of the deposition cycle (the "substituted hydrazine stage"), the substrate is contacted with a second vapor-phase reactant comprising a hydrocarbon-substituted hydrazine precursor. In some embodiments of the present disclosure, the method can further include selecting the substituted hydrazine to include an alkyl group having at least four carbon atoms, where "alkyl group" refers to a saturated or unsaturated hydrocarbon chain at least four carbon atoms in length, such as, but not limited to, butyl, pentyl, hexyl, heptyl, and octyl, and isomers thereof, such as n-, iso-, sec-, and tert-isomers thereof. The alkyl group can be linear or branched and can encompass all structural isomeric forms of the alkyl group. In some embodiments, the alkyl chain can be substituted. In some embodiments of the present disclosure, the alkyl hydrazine can include at least one hydrogen bonded to the nitrogen. In some embodiments of the present disclosure, the alkyl hydrazine can include at least two hydrogens bonded to the nitrogen. In some embodiments of the present disclosure, the alkylhydrazine may include at least one hydrogen bonded to the nitrogen and at least one alkyl chain bonded to the nitrogen. In some embodiments of the present disclosure, the second reactant may include an alkylhydrazine and may further include one or more of tert-butylhydrazine (C4H9N2H3), dimethylhydrazine, or diethylhydrazine. In some embodiments of the present disclosure, the substituted hydrazine has at least one hydrocarbon group bonded to the nitrogen. In some embodiments of the present disclosure, the substituted hydrazine has at least two hydrocarbon groups bonded to the nitrogen. In some embodiments of the present disclosure, the substituted hydrazine has at least three hydrocarbon groups bonded to the nitrogen. In some embodiments of the present disclosure, the substituted hydrazine has at least one C1-C3 hydrocarbon group bonded to the nitrogen. In some embodiments of the present disclosure, the substituted hydrazine has at least one C4-C10 hydrocarbon group bonded to the nitrogen. In some embodiments of the present disclosure, the substituted hydrazine has a straight-chain, branched-chain, cyclic, or aromatic hydrocarbon group bonded to the nitrogen.In some embodiments of the present disclosure, the substituted hydrazine comprises a substituted hydrocarbon group attached to the nitrogen.

[0055] In some embodiments of the present disclosure, the substituted hydrazine has the following formula II: R I R II -N-NR III R IV (II) In the formula, R I can be selected from hydrocarbon groups, such as linear, branched, cyclic, aromatic or substituted hydrocarbon groups, and R II , R III , R IV Each of the groups can be independently selected to be a hydrogen group or a hydrocarbon group, such as a straight-chain, branched-chain, cyclic, aromatic, or substituted hydrocarbon group.

[0056] In some embodiments, R of formula (II) I , R II , R III , R IV Each of R can be a C1-C10 hydrocarbon, a C1-C3 hydrocarbon, a C4-C10 hydrocarbon, such as a straight chain, branched chain, cyclic, aromatic, or substituted hydrocarbon group, or hydrogen. I , R II , R III , R IV At least one of the groups comprises an aromatic group, such as a phenyl group. In some embodiments, R I , R II , R III , R IV At least one of the groups comprises a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tert-butyl group, or a phenyl group. I , R II , R III , R IV At least two of the groups can be independently selected to include a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, tert-butyl group, or a phenyl group.II , R III and R IV In some embodiments, R II , R III and R IV At least one of the two groups is hydrogen. In some embodiments, R II , R III and R IV At least one of the groups is hydrogen. In some embodiments, R II , R III and R IV All of the groups are hydrogen.

[0057] In an embodiment of the present disclosure, the second vapor phase reactant comprises a silicon precursor, which may be silane (SiH), disilane (SiH), trisilane (SiH), tetrasilane (SiH), or a combination thereof. 10 ), isopentasilane (Si5H 12 ), or neopentasilane (Si5H 12 In embodiments of the present disclosure, the second vapor-phase reactant may include at least one of a silicon precursor, which may include a C1-C4 alkyl silane. In embodiments of the present disclosure, the second vapor-phase reactant may include a silicon precursor, which may include a precursor from the silane family.

[0058] In an embodiment of the present disclosure, the second vapor phase reactant comprises a boron precursor, the boron precursor being borane (BH), diborane (BH), or decaborane (B 10 H 14 ), and other boranes such as

[0059] In embodiments of the present disclosure, the second vapor phase reactant includes a hydrogen precursor, which may include at least one of H2, H atoms, H-ions, H-plasma, or H-radicals.

[0060] In some embodiments of the present disclosure, the second vapor-phase reactant includes a phosphorus precursor, a sulfur precursor, or a selenide precursor. In some embodiments, the sulfur precursor includes hydrogen and sulfur. In some embodiments, the sulfur precursor is an alkyl sulfur compound. In some embodiments, the second reactant includes one or more elemental sulfur, H2S, (CH3)2S, (NH4)2S, ((CH3)2SO), and H2S2. In some embodiments, the selenium precursor is an alkyl selenium compound. In some embodiments, the second reactant includes one or more of elemental selenium, H2Se, (CH3)2Se, and H2Se2. In some embodiments, the selenium precursor includes hydrogen and selenium. In some embodiments, the second reactant may include Te, Sb, Se, or an alkyl silyl compound such as (Me3Si)2Te, (Me3Si)2Se, or (Me3Si)3Sb. In some embodiments, the phosphorus precursor is an alkyl phosphorus compound. In some embodiments, the second reactant includes elemental phosphorus, PH 3、 or alkyl phosphines, such as methyl phosphine, hi some embodiments, the phosphorus precursor comprises hydrogen and phosphorus.

[0061] In embodiments of the present disclosure, the second vapor phase reactant may include an organic precursor, such as a reducing agent, and may utilize, for example, an alcohol, an aldehyde, or a carboxylic acid, or other organic compounds, such as organic compounds that do not contain a metal or metalloid but contain an -OH group. The alcohol may be a primary alcohol, a secondary alcohol, a tertiary alcohol, a polyhydroxy alcohol, a cyclic alcohol, an aromatic alcohol, or other derivatives of alcohol.

[0062] Primary alcohols have an -OH group attached to a carbon atom that is bonded to another carbon atom, in particular primary alcohols according to general formula (III). R1-OH (III) wherein R1 is a straight 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.

[0063] Secondary alcohols have an -OH group attached to a carbon atom that is bonded to two other carbon atoms. In particular, secondary alcohols have the following general formula (IV):

[0064] [ka]

[0065] wherein each R is independently selected from the group of straight or branched C-C alkyl and alkenyl groups, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of secondary alcohols include 2-propanol and 2-butanol.

[0066] Tertiary alcohols have an —OH group attached to a carbon atom that is bonded to three other carbon atoms. In particular, tertiary alcohols have the following general formula (V):

[0067] [ka]

[0068] wherein each R1 is independently selected from the group of straight or branched chain C1-C20 alkyl and alkenyl groups, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. An example of a tertiary alcohol is tert-butanol.

[0069] Polyhydroxy alcohols, 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.

[0070] A cyclic alcohol has an —OH group attached to at least one carbon atom that is part of a ring of 1 to 10 carbon atoms, such as 5 to 6 carbon atoms.

[0071] Aromatic alcohols have at least one -OH group attached to either a benzene ring or a carbon atom in a side chain.

[0072] The organic precursor may contain at least one aldehyde group (-CHO) selected from the group consisting of compounds having the general formula (VI), alkanediol compounds having the general formula (VII), halogenated aldehydes, and other derivatives of aldehydes.

[0073] Thus, in one embodiment, the organic precursor is an aldehyde having the general formula (VI): R3-CHO (VI) wherein R3 is selected from the group consisting of hydrogen and straight or branched C1-C20 alkyl and alkenyl groups, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. In some embodiments, R3 is selected from the group consisting of methyl or ethyl. Exemplary compounds according to formula (VI) include, but are not limited to, formaldehyde, acetaldehyde, and butyraldehyde.

[0074] In another embodiment, the organic precursor is an aldehyde having the general formula (VII). OHC-R4-CHO (VII) wherein R4 is a straight or branched chain C1-C20 saturated or unsaturated hydrocarbon. Alternatively, the aldehyde groups may be directly bonded to each other (R4 is null).

[0075] The organic precursor containing at least one -COOH group may be selected from the group consisting of compounds of general formula (VIII), polycarboxylic acids, halogenated carboxylic acids and other derivatives of carboxylic acids.

[0076] Thus, in one embodiment, the organic precursor is a carboxylic acid having the general formula (VIII): R5-COOH (VIII) wherein R5 is hydrogen or a straight or branched chain C1-C20 alkyl or alkenyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl, e.g., methyl or ethyl. In some embodiments, R5 is a straight or branched chain C1-C3 alkyl or alkenyl group. Examples of compounds according to formula (VII) are formic acid, propanoic acid, and acetic acid, and in some embodiments, formic acid (HCOOH).

[0077] In some embodiments of the present disclosure, exposing or contacting the substrate with the second gas-phase reactant comprises pulsing the second gas-phase reactant over the substrate for a time period of 0.1 seconds to 2.0 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 pulsing of the second gas-phase reactant over the substrate, the flow rate of the second gas-phase reactant can be less than 50 sccm, or less than 25 sccm, or less than 15 sccm, or even less than 10 sccm.

[0078] For example, excess second gas-phase reactant and reaction by-products, if any, may be removed from the surface of the substrate by pulses of purge gas and / or a vacuum created by an evacuation system. The purge gas is preferably any inert gas, such as, but not limited to, argon (Ar), nitrogen (N), helium (He), or, in some cases, hydrogen (H). One stage is generally considered to immediately follow another stage if a purge (i.e., purge gas pulse) or other reactant removal step intervenes.

[0079] The deposition cycle of alternately contacting the substrate with a first gas-phase reactant (i.e., a metal halide compound) and a second gas-phase reactant (e.g., an oxygen precursor) may be repeated one or more times until a transition metal-containing film of a desired thickness is deposited. It should be understood that in some embodiments of the present disclosure, the order of contacting the substrate with the first and second gas-phase reactants may be such that the substrate is first contacted with the second gas-phase reactant followed by the first gas-phase reactant. Furthermore, in some embodiments, the cyclic deposition process may include contacting the substrate one or more times with the first gas-phase reactant before contacting the substrate one or more times with the second gas-phase reactant, or equivalently, contacting the substrate one or more times with the second gas-phase reactant before contacting the substrate one or more times with the first gas-phase reactant.

[0080] Additionally, some embodiments of the present disclosure may be free of plasma reactants, e.g., the first and second gas-phase reactants are substantially free of ionized reactive species. In some embodiments, the first and second gas-phase reactants are substantially free of ionized reactive species, excited species, and radical species. For example, both the first and second gas-phase reactants may be free of plasma reactants to prevent ionization damage to the underlying substrate and the associated defects generated thereby. The use of non-plasma reactants may be particularly useful when the underlying substrate includes fragile fabricated or at least partially fabricated semiconductor device structures, as energetic plasma species may damage and / or degrade device performance characteristics.

[0081] In some embodiments of the present disclosure, the exemplary cyclic deposition method of the present disclosure can include an additional process step including contacting the substrate with a third gas-phase reactant comprising a reducing agent. In some embodiments, the reducing agent is hydrogen (H), hydrogen (H) plasma, ammonia (NH), ammonia (NH) plasma, hydrazine (NH), silane (SiH), disilane (SiH), trisilane (SiH), germane (GeH), digermane (GeH), borane (BH), diborane (BH), tertiary butylhydrazine (CH), or the like. 12 The reactant may include at least one of N2, a selenium precursor, a boron precursor, a phosphorous precursor, a sulfur precursor, an organic precursor (e.g., an alcohol, an aldehyde, or a carboxylic acid), or a hydrogen precursor. In some embodiments of the present disclosure, an exemplary cyclic deposition method of the present disclosure may include contacting the substrate with a second gas-phase reactant that is a reducing agent (without any additional precursor / reactant contacting step).

[0082] A third gas-phase reactant, including a reducing agent, may be introduced into the reaction chamber and contacted with the substrate during some process stages of the exemplary cyclic deposition method. In some embodiments of the present disclosure, the reducing agent may be introduced into the reaction chamber and contacted with the substrate separately from the first gas-phase reactant and separately from the second gas-phase reactant. For example, the reducing agent may be introduced into the reaction chamber and contacted with the substrate before contacting the substrate with the first gas-phase reactant, after contacting the substrate with the first gas-phase reactant and before contacting the substrate with the second gas-phase reactant, and / or after contacting the substrate with the second gas-phase reactant. In some embodiments of the present disclosure, the reducing agent may be introduced into the reaction chamber and contacted with the substrate simultaneously with the first gas-phase reactant and / or simultaneously with the second gas-phase reactant. For example, the reducing agent and the first gas-phase reactant may flow into the reaction chamber simultaneously and contact the substrate simultaneously, and / or the reducing agent and the second gas-phase reactant may flow into the reaction chamber simultaneously and contact the substrate simultaneously.

[0083] In some embodiments of the present disclosure, the first gas-phase reactant may include a transition metal halide compound, and the second gas-phase reactant may include an oxygen precursor. In such embodiments, the cyclic deposition process may deposit a transition metal oxide on a substrate. As a non-limiting example, the first gas-phase reactant may include CoCl (TMEDA), the second gas-phase reactant may include water (HO), and the film deposited on the substrate may include cobalt oxide. In some embodiments, the transition metal oxide may be further treated 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 including forming gas (H + N), ammonia (NH), hydrazine (NH), molecular hydrogen (H), atomic hydrogen (H), hydrogen plasma, hydrogen radicals, excited hydrogen species, alcohols, aldehydes, carboxylic acids, boranes, or amines.

[0084] In some embodiments, exposing the transition metal oxide to a reducing agent can reduce the transition metal oxide to elemental transition metal. As a non-limiting example, using the cyclic deposition process of the present disclosure, a cobalt oxide film can be deposited to a thickness of 50 nanometers and exposed to 10% forming gas at a pressure of 1000 mbar and a temperature of about 250° C. to reduce the cobalt oxide film to elemental cobalt. In some embodiments of the present disclosure, the transition metal oxide can have a thickness of less than 500 nanometers, or less than 100 nanometers, or less than 50 nanometers, or less than 25 nanometers, or less than 20 nanometers, or less than 10 nanometers, or even less than 5 nanometers. In some embodiments, the transition metal oxide can be exposed to the 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 even less than 1 minute. In some embodiments, the transition metal oxide may be exposed to the reducing agent at a substrate temperature of less than 500° C., or less than 400° C., or less than 300° C., or less than 250° C., or less than 200° C., or even less than 150° C. In some embodiments, the transition metal oxide may be exposed to the reducing agent in a reducing atmosphere, and the pressure may be from about 0.001 mbar to about 10 bar, or from about 1 mbar to about 1000 mbar.

[0085] The cyclic deposition processes described herein, which utilize a first gas-phase reactant comprising a transition metal halide compound and a second gas-phase reactant for depositing a transition metal-containing film, can be carried out in an ALD or CVD deposition system using a heated substrate. For example, in some embodiments, the method can include heating the substrate to a temperature of about 80°C to about 150°C, or further heating the substrate to a temperature of about 80°C to about 120°C. Of course, the appropriate temperature window for any given cyclic deposition process, such as an ALD reaction, will depend on the surface termination and reactant species involved. Here, the temperature varies depending on the precursors used and is generally about 700°C or less. In some embodiments, for vapor deposition processes, the deposition temperature is generally about 100°C or greater; in some embodiments, the deposition temperature is about 100°C to about 300°C; in some embodiments, the deposition temperature is about 120°C to about 200°C. In some embodiments, the deposition temperature is less than about 500°C, or less than about 400°C, or less than about 350°C, or less than about 300°C. In some cases, the deposition temperature may be less than about 300° C., less than about 200° C., or less than about 100° C. In some cases, the deposition temperature may be greater than about 20° C., greater than about 50° C., and greater than about 75° C. In some embodiments of the present disclosure, the deposition temperature, i.e., the temperature of the substrate during deposition, is about 275° C.

[0086] In some embodiments, the growth rate of the transition metal-containing film is between about 0.005 Å / cycle and about 5 Å / cycle, or between about 0.01 Å / cycle and about 2.0 Å / cycle. In some embodiments, the growth rate of the transition metal-containing film 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 film 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 0.2 Å / cycle. In some embodiments of the present disclosure, the growth rate of the transition metal-containing film can be about 0.4 Å / cycle.

[0087] Embodiments of the present disclosure can include cyclic deposition, which can be illustrated in more detail by the exemplary cyclic deposition method 100 of FIG. 1 . Method 100 can begin by process block 110, which includes providing at least one substrate into a reaction chamber and heating the substrate to a deposition temperature. For example, the substrate can include one or more partially fabricated semiconductor device structures, the reaction chamber can comprise an atomic layer deposition reaction chamber, and the substrate can be heated to a deposition temperature of less than about 275° C. Additionally, the pressure within the reaction chamber can be controlled to reduce the atmosphere within the reaction chamber. For example, the pressure within the reaction chamber during the cyclic deposition process can be less than 1000 mbar, or less than 100 mbar, or less than 10 mbar, or less than 5 mbar, or even, in some cases, less than 1 mbar.

[0088] The method 100 may continue with process block 120, which includes contacting the substrate with a transition metal halide compound, for example, contacting the substrate with the transition metal halide compound for about 1 second. In some embodiments of the present disclosure, the transition metal compound may contact the substrate for about 0.01 seconds to about 60 seconds, about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5 seconds. Furthermore, during pulse injection of the transition metal precursor onto the substrate, the flow rate of the transition metal precursor can 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.

[0089] Once the substrate is contacted with the transition metal halide compound, excess metal precursor and any reaction by-products can be removed from the reaction chamber by a purge / evacuation process.

[0090] The method 100 can continue at process block 130, which includes contacting the substrate with a second vapor-phase reactant, such as, for example, an oxygen precursor, a nitrogen precursor, a silicon precursor, a phosphorus precursor, a selenium precursor, a boron precursor, or a reducing agent. The second vapor-phase reactant, e.g., water, can contact the substrate for approximately 4 seconds. In some embodiments of the present disclosure, the second vapor-phase reactant can contact the substrate for 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 5.0 seconds. Furthermore, while pulsing the second vapor-phase reactant on the substrate, the flow rate of the second vapor-phase reactant can 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.

[0091] Once the substrate has been contacted with the second vapor phase reactant precursor, excess second vapor phase reactant and any reaction by-products can be removed from the reaction chamber by a purge / evacuation process.

[0092] The exemplary cyclic deposition method 100, in which the substrate is alternately and sequentially contacted with a transition metal halide compound (process block 120) and a second vapor-phase reactant (process block 130), may constitute one deposition cycle. In some embodiments of the present disclosure, a method for depositing a transition metal-containing film may include repeating the deposition cycle one or more times. For example, the method 100 may continue with a decision gate 140, which determines whether the cyclic deposition method 100 continues or terminates via process block 150. The decision gate 140 is determined based on the thickness of the deposited transition metal-containing film; for example, if the thickness of the transition metal-containing film is insufficient for the desired device structure, the method 100 may return to process block 120 and repeat the process of contacting the substrate with a transition metal halide compound and contacting the substrate with a second vapor-phase reactant one or more times. Once the transition metal-containing film is deposited to the desired thickness, the method terminates via process block 150, and the transition metal-containing film and the underlying semiconductor structure may undergo additional processing to form one or more device structures.

[0093] A film or layer comprising a transition metal deposited according to some embodiments described herein may be a continuous thin film. In some embodiments, a film comprising a transition metal deposited according to some embodiments described herein may be continuous at a thickness of less than about 100 nanometers, or less than about 60 nanometers, or less than about 50 nanometers, or less than about 40 nanometers, or less than about 30 nanometers, or less than about 25 nanometers, or less than about 20 nanometers, or less than about 15 nanometers, or less than about 10 nanometers, or less than about 5 nanometers, or even less. Continuity, as referred to herein, can be physical continuity or electrical continuity. In some embodiments, the thickness at which a film can be physically continuous may not be the same as the thickness at which the film is electrically continuous, and the thickness at which a film can be electrically continuous may not be the same as the thickness at which the film is physically continuous.

[0094] In some embodiments, transition metal-containing films deposited according to some embodiments described herein can have a thickness of about 20 nanometers to about 100 nanometers. In some embodiments, transition metal-containing films deposited according to some embodiments described herein can have a thickness of about 20 nanometers to about 60 nanometers. In some embodiments, transition metal-containing films deposited according to some embodiments described herein can have a thickness of greater than about 20 nanometers, or greater than about 30 nanometers, or greater than about 40 nanometers, or greater than about 50 nanometers, or greater than about 60 nanometers, or greater than about 100 nanometers, or greater than about 250 nanometers, or greater than about 500 nanometers, or even greater. In some embodiments, transition metal-containing films deposited according to some embodiments described herein can have a thickness of less than about 50 nanometers, less than about 30 nanometers, less than about 20 nanometers, less than about 15 nanometers, less than about 10 nanometers, less than about 5 nanometers, less than about 3 nanometers, less than about 2 nanometers, or less than about 1 nanometer.

[0095] In some embodiments of the present disclosure, transition metal-containing films may be deposited on three-dimensional structures, such as non-planar substrates containing high aspect ratio features. In some embodiments, the step coverage of the transition metal-containing film may be about 50% or greater, or about 80% or greater, or about 90% or greater, or about 95% or greater, or about 98% or greater, or about 99% or greater, or greater, in structures with aspect ratios (height / width) greater than about 2, greater than about 5, greater than about 10, greater than about 25, greater than about 50, or even greater than about 100.

[0096] In some embodiments of the present disclosure, transition metal-containing films deposited according to embodiments of the present disclosure may contain less than about 50 atomic percent oxygen, less than about 25 atomic percent oxygen, less than about 10 atomic percent oxygen, less than about 5 atomic percent oxygen, less than about 2 atomic percent oxygen, or even less than about 1 atomic percent oxygen. In other embodiments, the transition metal-containing films may contain less than about 5 atomic percent hydrogen, or less than about 2 atomic percent hydrogen, or less than about 1 atomic percent hydrogen, or even less than about 0.5 atomic percent hydrogen. In yet other embodiments, the transition metal-containing films may contain less than about 5 atomic percent carbon, or less than about 2 atomic percent carbon, or less than about 1 atomic percent carbon, or even less than about 0.5 atomic percent carbon. In yet other embodiments, the transition metal-containing films may contain less than about 5 atomic percent halide species, or less than about 2 atomic percent halide species, or less than about 1 atomic percent halide species, or even less than about 0.5 atomic percent halide species. In some embodiments, the atomic percent of a transition metal-containing material may be determined using time-of-flight elastic recoil detection (ToF-ERDA).

[0097] In some embodiments of the present disclosure, the cyclic deposition process of the present disclosure can be used to deposit transition metal oxides, such as cobalt oxide. Because cobalt precursors, prior to their use in cyclic deposition processes such as atomic layer deposition, have proven unreactive with water (HO), ozone (O) has typically been used as the oxygen precursor. However, the use of ozone for cyclic deposition of cobalt oxide typically results in the formation of cobalt(II,III) oxide (CoO) rather than cobalt(II) oxide (CoO). In some embodiments, it may be beneficial to deposit CoO rather than CoO; for example, lower oxidation states of cobalt in the form of CoO may be more easily reduced to cobalt metal. Thus, in some embodiments of the present disclosure, the cyclic deposition process of the present disclosure can be used to deposit substantially cobalt(II) oxide (CoO) films, i.e., with a cobalt-to-oxygen ratio substantially equal to 1:1. In some embodiments of the present disclosure, the deposition temperature during the cyclic deposition process can affect the stoichiometry of the deposited film. For example, when depositing a cobalt oxide film using the cyclic deposition process disclosed herein, the substrate temperature can affect the cobalt-to-oxygen (Co:O) ratio in the deposited film. Thus, as a non-limiting exemplary embodiment of the present disclosure, a cobalt oxide film can be deposited using CoCl (TMEDA) as the cobalt precursor and water (HO) as the oxygen precursor. During such a cyclic deposition process, the substrate temperature can be controlled at about 275°C, resulting in the deposition of cobalt(II) oxide (CoO) with a cobalt-to-oxygen (Co:O) ratio of about 1:1.

[0098] Transition metal-containing films deposited by the cyclic deposition processes disclosed herein may be utilized in a variety of contexts, such as, for example, liner layers, capping layers, gap fill layers, trench fill layers, seed layers, contact layers / contact fill layers, electromigration improvement layers, conductive interconnects in back-end (BEOL) applications, and silicide forms of semiconductor device contacts. In some embodiments, the transition metal-containing films of the present disclosure may be utilized as an electrode, or at least a portion of an electrode, configured to provide electrical current to one or more device structures. In some embodiments of the present disclosure, the transition metal-containing films of the present disclosure may be utilized in CMOS device applications as at least a portion of an electrode to one or more CMOS devices.

[0099] As a non-limiting exemplary embodiment, as shown in FIG. 2 , a transition metal-containing film, such as cobalt, may be utilized as a barrier material and / or capping layer in back-end (BEOL) metallization applications. More specifically, FIG. 2 illustrates a partially fabricated semiconductor device structure 200 comprising a substrate 202, which may comprise partially fabricated and / or fabricated semiconductor device structures, such as transistors and memory elements (not shown). The partially fabricated semiconductor device structure 200 may include a dielectric material 204 formed on the substrate 202, which may include a low-k material, i.e., a low-k dielectric, such as a silicon-containing dielectric or a metal oxide. A trench may be formed in the dielectric material 204, and a barrier material 206 may be disposed on a surface of the trench that prevents or substantially prevents diffusion of a metal interconnect material 208 into the surrounding dielectric material 204. In some embodiments of the present disclosure, the barrier material 206 may include cobalt deposited by the cyclic deposition processes described herein. In some embodiments of the present disclosure, the cobalt film may have a thickness of less than 35 angstroms, or less than 25 angstroms, or even less than 15 angstroms. The partially fabricated semiconductor structure 200 may also include a metal interconnect material 208 for electrically interconnecting multiple device structures disposed within the substrate 202. In some embodiments, the metal interconnect material 208 may include one or more of copper or cobalt. In addition to using cobalt as a barrier material, cobalt may also be utilized as a capping layer. Thus, with reference to FIG. 2 , the partially fabricated semiconductor device structure 200 may also include a capping layer 210 disposed directly on the top surface of the metal interconnect material 208. The capping layer 210 may be utilized to prevent oxidation of the metal interconnect material 208 and, importantly, to prevent diffusion of the metal interconnect material 208 into additional dielectric materials formed over the partially fabricated semiconductor structure 200 in subsequent manufacturing processes, i.e., for multi-level interconnect structures. In some embodiments of the present disclosure, the capping layer 210 may also include cobalt having a thickness of less than 20 angstroms, or less than 15 angstroms, or even less than 10 angstroms.In some embodiments, the metal interconnect material 208 , the barrier material 206 , and the capping layer 210 may collectively form electrodes for electrical interconnection of multiple semiconductor devices disposed within the substrate 202 .

[0100] Embodiments of the present disclosure may also be utilized to synthesize chemical precursors useful in vapor deposition processes, such as atomic layer deposition, chemical vapor deposition, and cyclic chemical vapor deposition. Accordingly, embodiments of the present disclosure may include methods for synthesizing transition metal halide compounds containing adduct-forming ligands, as described hereinabove, such as transition metal halides containing bidentate nitrogen-containing adduct ligands. In some embodiments, the methods of the present disclosure may be utilized to synthesize one or more of cobalt(II) chloride (TMEDA), nickel(II) chloride (TMEDA), or copper(II) chloride (TMEDA). In some embodiments, the methods of the present disclosure may be utilized to synthesize one or more of cobalt(II) iodide (TMEDA), nickel(II) iodide (TMEDA), or copper(II) iodide (TMEDA). In some embodiments, the methods of the present disclosure may be utilized to synthesize one or more of cobalt(II) bromide (TMEDA), nickel(II) bromide (TMEDA), or copper(II) bromide (TMEDA). Additionally, in some embodiments, the methods of the present disclosure may be utilized to synthesize cobalt(II) chloride (TMPDA), nickel(II) chloride (TMPDA), and copper(II) chloride (TMPDA).

[0101] The following description discloses a method for synthesizing CoCl(TMEDA), and it should be understood that the methods disclosed for the synthesis of CoCl(TMEDA) are equally applicable to the methods for synthesizing additional transition metal halide compounds disclosed herein and should not be construed as limiting.

[0102] The drug precursor synthesis method can be carried out using standard Schlenk techniques and an inert gas (e.g., N or Ar) glovebox, with all handling and manipulations performed with strict exclusion of air and moisture. Anhydrous CoCl (99%) and N,N,N',N'-tetramethylethylenediamine (TMEDA) (99%) were used as reactants. Additionally, dichloromethane (CHCl) was used as a suitable solvent, and the process included deoxygenating and drying the CHCl over molecular sieves of 4 Å or greater.

[0103] In some embodiments of the present disclosure, a certain amount of CoCl can be weighed and added to a suitable container, such as a Schlenk flask. A certain amount of CHCl can be added to CoCl. A stoichiometric amount of TMEDA can then be added dropwise to the solution. In some embodiments, the adduct-forming ligand, e.g., TMEDA, can be added in excess of the halide compound, e.g., 2-fold, 5-fold, or even 10-fold greater than the amount of the halide compound. The resulting suspension can be stirred at room temperature for about 1 hour. As a non-limiting example, 6.00 g (46.211 mmol) of CoCl can be weighed and added to a Schlenk flask along with 100 ml of CHCl. 5.37 g (46.211 mmol) of TMEDA can be added to the solution and stirred at room temperature for 1 hour. The resulting blue solution can be evaporated to dryness to yield a blue product. The resulting product can be transferred to a sublimator and sublimated at a temperature of about 150-200°C, thereby producing CoCl(TMEDA). In some embodiments of the present disclosure, the resulting volatile transition metal halide compound, e.g., CoCl(TMEDA), can have an impurity concentration of less than 5 at%, or less than 2 at%, or less than 1 at%, or less than 0.1 at%, or even less than 0.01 at%. In some embodiments of the present disclosure, the volatile transition metal halide compound can have a higher decomposition temperature compared to the organotransition metal precursor. For example, the transition metal halide compound of the present disclosure can have a decomposition temperature greater than 150°C or even greater than 200°C.

[0104] Thus, in some embodiments of the present disclosure, transition metal halide compounds can be synthesized that can be used in the deposition of transition metal-containing films. In some embodiments, the metal halide compounds including adduct-forming ligands can be synthesized using a one-step synthesis process that includes combining a transition metal halide compound and an adduct-forming ligand at a temperature of less than about 50° C., or less than about 30° C., or even less than about 15° C., and the entire synthesis process can be completed in less than 5 hours, or less than 2 hours, or less than 1 hour, or even less than 30 minutes.

[0105]

[0009] Embodiments of the present disclosure may also include a vapor deposition apparatus including one or more precursor source vessels configured to contain a transition metal halide compound and to deliver the transition metal halide compound to a reaction chamber. Accordingly, some embodiments of the present disclosure provide a vapor deposition apparatus that utilizes reactive volatile chemicals. The apparatus may include a reaction chamber, a substrate disposed within the reaction chamber, a precursor source vessel in fluid communication with the reaction chamber, and a transition metal halide compound including a bidentate nitrogen-containing ligand disposed within the precursor source vessel.

[0106] More specifically, Figure 4 schematically illustrates a deposition apparatus 400, including a reaction chamber 402. It should be noted that Figure 4 is a simplified schematic version of the deposition apparatus 400 and does not include any and all elements that may be utilized in the deposition apparatus 400 of the present disclosure, including, but not limited to, valves, electrical connections, mass flow controllers, seals, and gas conduits. In some embodiments of the present disclosure, the reaction chamber 402 may include a susceptor 404 configured to hold a substrate 406 within the reaction chamber. Also disposed within the reaction chamber is a showerhead gas distributor 408 that is utilized to selectively expose the substrate to various gases.

[0107] In some embodiments of the present disclosure, the precursor source vessel 410A may be fluidly connected to the reaction chamber 402 via a conduit or other suitable means 412A and may be further coupled to a manifold, valve control system, mass flow control system, or mechanism to control the gaseous precursor from the precursor source vessel 410A. The precursor source vessel 410A may be configured to store a transition metal halide compound including a bidentate nitrogen-containing ligand. In some embodiments, the precursor source vessel 410A may include a quartz material, which may be substantially chemically inert to the transition metal halide compound stored in the precursor source vessel 410A. In alternative embodiments of the present disclosure, the precursor source vessel 410A may be fabricated from a corrosion-resistant metal or metal alloy, such as, for example, Hastelloy, Monel, or a combination thereof.

[0108] In some embodiments of the present disclosure, the precursor source vessel 410A may further comprise one or more heating sections 414 configured to heat the transition metal halide compound stored in the precursor source vessel 410A. In some embodiments, the one or more heating sections 414 may be utilized to heat the transition metal halide compound to a temperature greater than about 0° C., or greater than about 20° C., or greater than about 100° C., or greater than about 150° C., or greater than about 200° C., or greater than about 200° C., or greater than about 300° C., or even greater than about 400° C. In some embodiments, the one or more heating sections 414 may be configured to heat the transition metal halide compound stored in the precursor source vessel 410A to a temperature of about 170° C.

[0109] In some embodiments, one or more heaters 414 associated with the precursor source vessel 410A are configured to convert the transition metal halide compound from a solid to either a liquid or a gas. In some embodiments, one or more heaters 414 associated with the precursor source vessel 410A may be utilized to control the viscosity of the transition metal halide compound stored in the precursor storage vessel 410A. In some embodiments, one or more heaters 414 associated with the precursor source vessel 410A may be configured to control the vapor pressure generated by the transition metal halide compound stored in the precursor source vessel. In some embodiments of the present disclosure, the transition metal halide compound may have a vapor pressure greater than 0.01 mbar at temperatures greater than 25°C, greater than 50°C, or even greater than 100°C. In some embodiments of the present disclosure, the transition metal halide compound may have a vapor pressure greater than 0.01 mbar at temperatures less than 350°C, or less than 250°C, or less than 200°C, or even less than 150°C. In some embodiments of the present disclosure, the transition metal halide compound may have a vapor pressure of greater than 0.1 mbar at temperatures greater than 25° C., or even greater than 100° C. In some embodiments of the present disclosure, the transition metal halide compound may have a vapor pressure of greater than 0.1 mbar at temperatures less than 400° C., or less than 200° C., or even less than 100° C. In some embodiments of the present disclosure, the transition metal halide compound may have a vapor pressure of greater than 1 mbar at temperatures greater than 25° C., or even greater than 100° C. For example, the transition metal halide compound may be heated to a temperature greater than 150° C. to generate a vapor pressure of greater than 0.001 mbar.

[0110] In some embodiments, the transition metal halide 416 stored in the precursor source container 410A can include at least one of cobalt chloride (TMEDA) or nickel chloride (TMEDA). In some embodiments, the transition metal halide 416 stored in the precursor source container 410A can include cobalt iodide (TMEDA). In some embodiments, the transition metal halide 416 stored in the precursor source container 410A can include. Further, in some embodiments, the transition metal halide 416 stored in the precursor source container 410A can include cobalt chloride (TMEDA) and nickel chloride (TMEDA).

[0111] In some embodiments of the present disclosure, vapor passage 418 may be connected to precursor source vessel 410A such that one or more carrier gases may be transferred from a carrier gas storage vessel (not shown) into the precursor source vessel via vapor passage 418. In some embodiments, a mass flow controller (not shown) may be disposed on vapor passage 418 and located proximate to precursor source vessel 410A. For example, the mass flow controller may be calibrated to control the mass flux of the carrier gas entering precursor source vessel 410A, thereby allowing greater control over the subsequent flow of transition metal halide compound vapor from precursor source vessel 410A into reaction chamber 402.

[0112] In some embodiments, a carrier gas (e.g., hydrogen, nitrogen, helium, argon, and mixtures thereof) can flow over the exposed surface of the transition metal halide compound 416, thereby picking up a portion of the vapor from the transition metal halide compound 416 and transporting the transition metal halide compound, along with the carrier gas, to the reaction chamber 402. In alternative embodiments of the present disclosure, the carrier gas can be "bubbled" through the transition metal halide compound 416, for example, by optional vapor passage 418', thereby agitating and picking up a portion of the transition metal halide compound 416 and transporting the transition metal halide compound to the reaction chamber 402 via gas conduit 412A.

[0113] In some embodiments of the present disclosure, the deposition apparatus 400 may include one or more source containers for additional precursor source containers and inert purge gases. For example, the precursor source container 410B may be configured to contain a second vapor-phase reactant, such as one or more of an oxygen precursor, a nitrogen precursor, a sulfur precursor, a selenium precursor, a phosphorus precursor, a boron precursor, a silicon precursor, or a reducing agent. The second vapor-phase reactant contained in the precursor source container 410B may be transferred to the reaction chamber 402 via a gas conduit 412B. In some embodiments, the precursor source container 410B may further include an associated heater 414 for controlling the temperature of the precursor stored in the precursor source container 410B. Furthermore, the source container 410C may be utilized to contain an inert purge gas, such as, but not limited to, argon (Ar), nitrogen (N), or helium (He). Although deposition system 400 includes three source vessels, it should be understood that additional source vessels containing additional chemical precursors can be configured for use in reaction chamber 402 .

[0114] In some embodiments of the present disclosure, the deposition apparatus 400 may further include a system operation and control mechanism 420, which provides electronic circuitry and mechanical components for selectively operating valves, manifolds, pumps, and other equipment associated with the deposition apparatus 400. Such circuitry and components operate to introduce precursor and purge gases from the respective precursor source vessels 410A, 410B, and purge gas vessel 410C. The system operation and control mechanism 420 may also control the timing of gas pulse sequences, substrate and reaction chamber temperatures, reaction chamber pressure, and various other operations necessary to provide proper operation of the deposition apparatus 400. The operation and control mechanism 420 may include control software and electrical or pneumatic control valves for controlling the flow of precursor, reactant, and purge gases into and out of the reaction chamber 402. The control system may include software and / or hardware components, such as modules, such as FPGAs or ASICs, that perform specific tasks. Modules may typically be configured to reside on addressable storage media in the control system and to perform one or more processes.

[0115] Those skilled in the relevant art will appreciate that other configurations of the deposition apparatus are possible, including different numbers and types of precursor reactant sources and purge gas sources. Furthermore, such skilled artisans will also appreciate that there are many arrangements of valves, conduits, precursor sources, and purge gas sources that can be used to achieve the goal of selectively delivering gases into the reaction chamber 402. Furthermore, as a simplified diagram of the deposition apparatus, many components are omitted for ease of illustration. Such components may include, for example, various valves, manifolds, purifiers, heaters, reservoirs, vents, and / or bypasses.

[0116] The vapor deposition apparatus 400 of FIG. 4 can be utilized to deliver a transition metal halide compound comprising a bidentate nitrogen-containing additional ligand to a vapor deposition tool. The method can include providing a precursor source container configured to contain the transition metal halide compound, fluidly connecting the precursor source container to a reaction chamber, heating the transition metal halide compound contained within the precursor source container to a temperature greater than 150° C., generating a vapor pressure of the transition metal halide compound of at least 0.001 mbar, and delivering the transition metal halide compound to the reaction chamber. In some embodiments of the present disclosure, the transition metal halide compound can have a vapor pressure greater than 0.01 mbar at temperatures greater than 25° C., greater than 50° C., or even greater than 100° C. In some embodiments of the present disclosure, the transition metal halide compound can have a vapor pressure greater than 0.01 mbar at temperatures less than 350° C., less than 250° C., less than 200° C., or even less than 150° C. In some embodiments of the present disclosure, the transition metal halide compound may have a vapor pressure of greater than 0.1 mbar at temperatures greater than 25° C., or even greater than 100° C. In some embodiments of the present disclosure, the transition metal halide compound may have a vapor pressure of greater than 0.1 mbar at temperatures less than 400° C., or less than 200° C., or even less than 100° C. In some embodiments of the present disclosure, the transition metal halide compound may have a vapor pressure of greater than 1 mbar at temperatures greater than 25° C., or even greater than 100° C.

[0117] In some embodiments, the transition metal halide compound can include at least one of cobalt chloride (TMEDA) or nickel chloride (TMPDA).

[0118] The exemplary embodiments of the present disclosure described above are merely examples of embodiments of the present invention, as defined by the appended claims and their legal equivalents, and therefore do not limit the scope of the present invention. Any equivalent embodiments are intended to be within the scope of the present invention. Indeed, various modifications of the present disclosure in addition to those shown and described herein may become apparent to those skilled in the art from the description, including alternative useful combinations of the described elements. Such modifications and embodiments are also intended to fall within the scope of the appended claims. [Explanation of symbols]

[0119] 200 Semiconductor Device Structure 202 Base material 204 Dielectric Materials 206 Barrier Materials 208 Metallic Interconnect Materials 210 Capping Layer 400 Vapor deposition equipment 402 Reaction Chamber 404 Susceptor 406 Base material 408 Shower Head Gas Distributor 410A, 410B Precursor Source Vessel 410C Purge Gas Cylinder 412A, 412B conduit 414 Heating section 416 Transition Metal Halides 418 Steam Passage 420 System Operation and Control Mechanism

Claims

1. 1. A method for forming a transition metal-containing film on a substrate by a cyclic deposition process, comprising: contacting the substrate with a first vapor phase reactant comprising a transition metal halide compound comprising a bidentate nitrogen-containing additional ligand, wherein the bidentate nitrogen-containing additional ligand is N,N,N',N'-tetramethyl-1,2-ethylenediamine (TMEDA) or N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA), the transition metal halide compound is cobalt halide (TMEDA) or cobalt halide (TMPDA), and the bidentate nitrogen-containing additional ligand coordinates with a transition metal atom of the transition metal halide compound, such that a halogen atom is bonded to the metal atom; contacting the substrate with a second gas phase reactant comprising an oxygen precursor; The method wherein the transition metal-containing film is cobalt oxide.

2. 2. The method of claim 1, wherein the additional ligand comprises two nitrogen atoms, each nitrogen atom being bonded to at least one carbon atom.

3. The method of claim 1 , wherein the transition metal halide compound comprises cobalt chloride.

4. The second gas phase reactant is ozone (O ３ ), molecular oxygen (O ２ ), oxygen atoms (O), oxygen plasma, oxygen radicals, oxygen excited species, water (H ２ O), and hydrogen peroxide (H ２ O ２ 10. The method of claim 1, comprising an oxygen precursor selected from the group consisting of:

5. 2. The method of claim 1, wherein the cobalt oxide substantially comprises cobalt (II) oxide (CoO).

6. 10. The method of claim 1, further comprising contacting the cobalt oxide with a reducing agent precursor, thereby forming an elemental transition metal.

7. The reducing agent precursor is a forming gas (H ２ +N ２ ), ammonia (NH ３ ), hydrazine (N ２ H ４ ), hydrogen molecule (H ２ 7. The method of claim 6, wherein the reactant comprises at least one of: atomic hydrogen (H), hydrogen plasma, hydrogen radicals, excited hydrogen species, alcohols, aldehydes, carboxylic acids, boranes, or amines.

8. Tertiary butylhydrazine (C ４ H １２ N ２ ), hydrogen (H ２ ), hydrogen (H ２ ) plasma, ammonia (NH ３ ), ammonia (NH ３ ) plasma, hydrazine (N ２ H ４ ), silane (SiH ４ ), disilane (Si ２ H ６ ), trisilane (Si ３ H ８ ), Germanium (GeH ４ ), Zigelmane (Ge ２ H ６ ), Borane (BH ３ ), and diborane (B ２ H ６ 10. The method of claim 1, further comprising contacting the substrate with a third vapor phase reactant comprising a reducing agent precursor selected from the group consisting of:

9. The method of claim 1 , wherein the transition metal-containing film comprises elemental cobalt.

10. The method of claim 1 , wherein the cyclical deposition process comprises an atomic layer deposition process.

11. The method of claim 1 , wherein the cyclic deposition process comprises a cyclic chemical vapor deposition process.

12. 1. A method for forming a transition metal-containing film on a substrate by a cyclic deposition process, comprising: contacting the substrate with a first vapor phase reactant comprising a transition metal compound comprising an adduct-forming ligand coordinated to the transition metal of the transition metal compound and having a halide bonded to the transition metal, wherein the adduct-forming ligand is N,N,N',N'-tetramethyl-1,2-ethylenediamine (TMEDA) or N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA), and the transition metal compound is cobalt halide (TMEDA) or cobalt halide (TMPDA); contacting the substrate with a second gas phase reactant comprising an oxygen precursor; A method of forming a transition metal-containing film on a substrate by a cyclic deposition process, wherein the transition metal-containing film is cobalt oxide.

13. 13. The method of claim 12, wherein the transition metal compound comprising an adduct-forming ligand is synthesized using a one-step synthesis process comprising combining a transition metal halide compound and an adduct-forming ligand at a temperature below 50°C.

14. 1. A method for supplying a first vapor phase reactant comprising a transition metal halide compound comprising a bidentate nitrogen-containing additional ligand to a reaction chamber, wherein the bidentate nitrogen-containing additional ligand is N,N,N',N'-tetramethyl-1,2-ethylenediamine (TMEDA) or N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA), and the transition metal halide compound is cobalt halide (TMEDA) or cobalt halide (TMPDA); providing a precursor source container configured to contain the transition metal halide compound, the transition metal halide compound comprising a halide atom bonded to a transition metal atom; fluidly connecting the precursor source vessel to the reaction chamber; heating the transition metal halide compound contained within the precursor source vessel to a temperature greater than 50°C; generating a vapor pressure of said transition metal halide compound of at least 0.001 mbar; providing said transition metal halide compound to said reaction chamber.

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