Molybdenum(0) precursors for molybdenum film deposition

Abstract

A molybdenum(0) precursor and a method for forming a molybdenum-containing film on a substrate surface are described. The molybdenum(0) precursor has a purity of 90% or more molybdenum (Mo) on a molar basis. The substrate is exposed to the molybdenum(0) precursor and a reactant to form a molybdenum-containing film having 80% or more molybdenum (Mo) on an atomic basis. In some embodiments, the molybdenum-containing film has 80% or more molybdenum (Mo) on a molar basis. The exposure can be sequential or simultaneous.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate to molybdenum precursors and methods for depositing molybdenum-containing films. More particularly, embodiments of the present disclosure are directed to bis(arene)molybdenum(0) precursors and methods of using the same. [Background technology]

[0002] The semiconductor processing industry continues to strive to increase production yields while improving the uniformity of layers deposited on substrates with larger surface areas. These same factors, combined with new materials, also result in higher integration of circuits per unit area of ​​substrate. As circuit integration increases, the need for greater uniformity and process control over layer thickness increases. As a result, various techniques have been developed to deposit layers on substrates in a cost-effective manner while maintaining control over the layer's properties.

[0003] Chemical vapor deposition (CVD) is one of the most common deposition processes used to deposit layers on substrates. CVD is a flux-dependent deposition technique that requires precise control of substrate temperature and precursors introduced into the processing chamber to produce a desired layer of uniform thickness. These requirements become more important as substrate size increases, creating the need for greater sophistication in chamber design and gas flow techniques to maintain adequate uniformity.

[0004] A variant of CVD that demonstrates excellent step coverage is cyclic deposition, or atomic layer deposition (ALD). ALD uses chemisorption techniques to deliver precursor molecules onto a substrate surface in successive cycles. For example, a cycle involves exposing the substrate surface to a first precursor, a purge gas, a second precursor, and a purge gas. The first and second precursors react to form a product compound as a film on the substrate surface. This cycle is repeated to form a layer of the desired thickness.

[0005] The increasing complexity of advanced microelectronic devices places stringent demands on currently used deposition techniques. Unfortunately, the number of practical chemical precursors available that possess the necessary properties of robust thermal stability, high reactivity, and favorable vapor pressure for film growth is limited. In addition, precursors that meet these requirements often still result in thin films that have poor long-term stability and contain high concentrations of contaminants such as oxygen, nitrogen, and / or halides, which are often detrimental to the target film's application.

[0006] Molybdenum and molybdenum-based films have attractive material and conductive properties. These films have been proposed and tested for applications ranging from front-end to back-end components of semiconductor and microelectronic devices. Processing of molybdenum precursors often involves the use of halogen and carbonyl-based substituents. The presence of halogens in the structure of molybdenum (Mo) precursors is thought to present challenges because halogen contamination can affect device performance and therefore require additional removal procedures. Furthermore, the presence of halogens in the structure of molybdenum (Mo) precursors can undesirably etch other metal films. For example, carbonyl-based substituents have poor thermal stability and typically require lower temperatures.

[0007] Therefore, there is a need in the art for halogen-free molybdenum precursors that react to form molybdenum metal and molybdenum-based films. Summary of the Invention

[0008] One or more embodiments of the present disclosure include a compound represented by Formula (I), Formula (II), Formula (III), Formula (IV), Formula (V), Formula (VI), Formula (VII), or Formula (VIII): [ka] In some embodiments, the molybdenum(0) precursor has a purity of 90% or greater molybdenum (Mo) on a molar basis.

[0009] Additional embodiments of the present disclosure are directed to methods of forming a molybdenum-containing film. In one or more embodiments, the methods include exposing a substrate surface to a molybdenum(0) precursor and exposing the substrate surface to a reactant to form a molybdenum-containing film on the substrate surface.

[0010] Further embodiments of the present disclosure are directed to methods of forming molybdenum-containing films. In one or more embodiments, the methods include performing a process cycle that includes sequentially exposing a substrate surface to a molybdenum(0) precursor, a purge gas, a reactant, and a purge gas.

[0011] So that the above-recited features of the present disclosure may be understood in detail, a more particular description of the present disclosure briefly summarized above can be had by reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the accompanying drawings illustrate only typical embodiments of the present disclosure and are therefore not to be considered as limiting the scope of the present disclosure, since other equally effective embodiments may be recognized. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a process flow diagram illustrating a method according to one or more embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0013] Before describing several exemplary embodiments of the invention, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description. The invention is capable of other embodiments and of being practiced or being carried out in various ways.

[0014] As used herein, "substrate" refers to any substrate or material surface formed on a substrate upon which film processing occurs during a manufacturing process. For example, substrate surfaces upon which processing may occur include, depending on the application, materials such as silicon, silicon oxide, strained silicon, silicon-on-insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials, such as metals, metal oxides, metal nitrides, metal alloys, and other conductive materials. Substrates include, but are not limited to, semiconductor wafers. Substrates may be subjected to pretreatment processes that polish, etch, reduce, oxidize, hydroxylate, anneal, and / or bake the substrate surface. In addition to direct film processing on the surface of the substrate itself, the present invention also allows any of the disclosed film processing steps to be performed on an underlying layer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include such underlying layers as the context indicates. Thus, for example, if a film / layer or partial film / layer is deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface.

[0015] According to one or more embodiments, the method uses an atomic layer deposition (ALD) process. In such embodiments, the substrate surface is continuously or substantially continuously exposed to the precursor (or reactive gas). As used throughout this specification, "substantially continuously" means that the majority of the period of precursor exposure does not overlap with exposure to the co-reagent, although there may be some overlap.

[0016] As used herein and in the appended claims, terms such as "precursor," "reactant," and "reactive gas" are used interchangeably and refer to any gaseous species capable of reacting with the substrate surface.

[0017] As used herein, "atomic layer deposition" or "cyclic deposition" refers to the sequential exposure of two or more reactive compounds to deposit a layer of material on a substrate surface. As used herein and in the appended claims, terms such as "reactive compound," "reactive gas," "reactive species," "precursor," and "process gas" are used interchangeably to refer to a substance having species capable of reacting with the substrate surface or materials on the substrate surface in a surface reaction (e.g., chemisorption, oxidation, reduction). A substrate or a portion of a substrate is sequentially exposed to two or more reactive compounds introduced into a reaction zone of a processing chamber. In a time-domain ALD process, exposure to each reactive compound is separated by a time delay to allow each compound to adhere and / or react with the substrate surface. In a spatial ALD process, different portions of the substrate surface, or materials on the substrate surface, are simultaneously exposed to two or more reactive compounds, thereby preventing any given point on the substrate from being substantially simultaneously exposed to two or more reactive compounds. As used herein and in the appended claims, the term "substantially" as used in this regard means that, as will be understood by those skilled in the art, small portions of the substrate may be exposed to multiple reactive gases simultaneously due to diffusion, and that such simultaneous exposure is not intended.

[0018] In one aspect of a time-domain ALD process, a first reactive gas (i.e., a first precursor or compound A) is pulsed into the reaction zone, followed by a first time delay. Then, a second precursor or compound B is pulsed into the reaction zone, followed by a second delay. During each time delay, a purge gas, such as argon, is introduced into the processing chamber to purge the reaction zone or otherwise remove any residual reactive compounds or by-products from the reaction zone. Alternatively, the purge gas may flow continuously throughout the deposition process, such that only the purge gas flows during the time delay between pulses of reactive compounds. Alternatively, the reactive compounds are pulsed until the desired film or film thickness is formed on the substrate surface. In either scenario, an ALD process that pulses compound A, purge gas, compound B, and purge gas is one cycle. The cycle can begin with either compound A or compound B, and continues in that order until a film having the desired thickness is achieved. In some embodiments, there may be two reactants, A and B, that are alternately pulsed and purged. In other embodiments, there may be three or more reactants, A, B and C, that are alternately pulsed and purged.

[0019] In one embodiment of a spatial ALD process, a first reactive gas and a second reactive gas (e.g., hydrogen radicals) are simultaneously supplied to a reaction zone but separated by an inert gas curtain and / or a vacuum curtain. The substrate is moved relative to the gas supply system, thereby exposing any given point on the substrate to both the first reactive gas and the second reactive gas.

[0020] Current molybdenum precursors for ALD of metal films use halogen and carbonyl-based substituents, which provide sufficient stability at the expense of reduced reactivity and increased process temperatures. For example, halogen substituents such as chloride offer good thermal stability and reactivity. Halogen substituents do not impose temperature constraints, and stability at higher process temperatures can be beneficial in some cases (e.g., for metal films). However, without intending to be bound by theory, it is believed that the presence of halogens in the structure of molybdenum (Mo) precursors can present challenges because halogen contamination can affect device performance, necessitating additional removal steps. Furthermore, the presence of halogens in the structure of molybdenum (Mo) precursors can undesirably etch other metal films. For example, carbonyl-based substituents have poor thermal stability and typically require lower temperatures. Other molybdenum precursors contain anionic nitrogen ligands, which can lead to the formation of nitride impurities.

[0021] Embodiments of the present disclosure advantageously provide molybdenum(0) precursors that can be used to form molybdenum-containing films on semiconductor substrates. In one or more embodiments, the molybdenum(0) precursor is a liquid precursor that does not contain heteroatoms.

[0022] The molybdenum precursors described herein have been proposed for vapor-phase deposition of molybdenum-containing films due to their low molecular weight, higher vapor pressure, and higher thermal stability, and have either several gaseous or volatile liquid ligands. All precursors exist in the zero oxidation state, and no external reducing agent is required during precursor preparation. The molybdenum(0) precursors can advantageously be prepared as a single compound in a single step via a ligand exchange reaction starting from a commercially available molybdenum(0) precursor. In one or more embodiments, the commercially available molybdenum(0) precursor may be formed from any known molybdenum-containing compound, such as molybdenum chloride (MoCl), and the commercially available molybdenum(0) precursor may be used to prepare the molybdenum(0) precursors described herein as a single compound in a single step via a ligand exchange reaction.

[0023] The molybdenum(0) precursor of one or more embodiments advantageously avoids an additional process for metal reduction, is halogen-free, oxygen-free, and molybdenum-oxygen (Mo-O) bond-free, thermally stable to delivery, has a high vapor pressure, can be delivered by a gas-phase method, and is reactive to ALD processes at low temperatures (below 400°C), achieving successful synthesis of a single-compound precursor in high yield and purity in one step starting from a commercially available molybdenum(0) precursor. The zero oxidation state molybdenum complex advantageously provides a molybdenum(0) precursor with improved thermal stability while retaining high volatility.

[0024] The molybdenum(0) precursor of one or more embodiments advantageously has a molar purity of 90% or more molybdenum (Mo), 95% or more molybdenum (Mo), 99% or more molybdenum (Mo), or 99.9% or more molybdenum (Mo). Stated differently, for example, a purity of 90% or more molybdenum (Mo), 95% or more molybdenum (Mo), 99% or more molybdenum (Mo), or 99.9% or more molybdenum (Mo) means that 90% or more, 95% or more, 99% or more, or 99.9% or more of the molecules in the described molybdenum(0) precursor contain molybdenum (Mo) species. Advantageously, the molybdenum(0) precursor can be prepared as a single compound in a single step starting from a commercially available molybdenum(0) precursor and has a molar purity of 90% or more molybdenum (Mo). The purity of the molybdenum(0) precursor, on a molar basis, is believed to increase after subsequent reaction cycles.

[0025] Without intending to be bound by theory, it is believed that precursors containing multiple compounds or mixtures of compounds, such as, for example, commercially available bis(ethylbenzene)molybdenum, may be prone to processing and / or film quality issues.

[0026] In some embodiments, the molybdenum(0) precursor is halogen-free. In some embodiments, the molybdenum(0) precursor is oxygen-free and molybdenum-oxygen (Mo-O) bond-free. In one or more embodiments, the molybdenum(0) precursor is halogen-free, oxygen-free, and molybdenum-oxygen (Mo-O) bond-free. In one or more embodiments, the molybdenum(0) precursor is substantially halogen-free, oxygen-free, and molybdenum-oxygen (Mo-O) bond-free.

[0027] As used herein, the term "substantially free" means that less than about 5%, e.g., less than about 4%, less than about 3%, less than about 2%, less than about 1%, and less than about 0.5% of halogen is present in the molybdenum-containing film on an atomic basis. In some embodiments, the molybdenum-containing film is substantially free of oxygen, and less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, e.g., less than about 4%, less than about 3%, less than about 2%, less than about 1%, and less than about 0.5% of oxygen is present in the molybdenum-containing film on an atomic basis. In some embodiments, the molybdenum-containing film is substantially free of molybdenum-oxygen (Mo-O) bonds, where there are less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, e.g., less than about 4%, less than about 3%, less than about 2%, less than about 1%, and less than about 0.5% molybdenum-oxygen (Mo-O) bonds on an atomic basis.

[0028] The process of various embodiments uses vapor deposition techniques, such as atomic layer deposition (ALD) or chemical vapor deposition (CVD), to provide molybdenum-containing films. The molybdenum(0) precursors of one or more embodiments are volatile and thermally stable, and therefore suitable for vapor deposition.

[0029] Molybdenum (Mo) can be grown by atomic layer deposition (ALD) or chemical vapor deposition (CVD) for many applications. One or more embodiments of the present disclosure advantageously provide processes for atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form molybdenum-containing films.

[0030] As used herein, the term "molybdenum-containing film" refers to a film that contains molybdenum atoms and has about 1 atomic % or more molybdenum, about 2 atomic % or more molybdenum, about 3 atomic % or more molybdenum, about 4 atomic % or more molybdenum, about 5 atomic % or more molybdenum, about 10 atomic % or more molybdenum, about 15 atomic % or more molybdenum, about 20 atomic % or more molybdenum, about 25 atomic % or more molybdenum, about 30 atomic % or more molybdenum, about 35 atomic % or more molybdenum, about 40 atomic % or more molybdenum, about 45 atomic % or more molybdenum, about 50 atomic % or more molybdenum, about 60 atomic % or more molybdenum, about 70 atomic % or more molybdenum, about 80 atomic % or more molybdenum, about 90 atomic % or more molybdenum, or about 95 atomic % or more molybdenum.

[0031] In one or more embodiments, the molybdenum-containing film comprises, on a molar basis, 90% or more molybdenum (Mo), 95% or more molybdenum (Mo), 99% or more molybdenum (Mo), or 99.9% or more molybdenum (Mo). Stated differently, for example, a molybdenum-containing film comprising 90% or more molybdenum (Mo), 95% or more molybdenum (Mo), 99% or more molybdenum (Mo), or 99.9% or more molybdenum (Mo) means that 90% or more, 95% or more, 99% or more, or 99.9% or more of the molecules in the described molybdenum-containing film comprise molybdenum (Mo) species.

[0032] In some embodiments, the molybdenum-containing film may be made of metallic molybdenum (elemental molybdenum), molybdenum carbide (MoC x ), molybdenum carbonitride (MoC x N y ), molybdenum silicide (MoSi x ), molybdenum carbosilicide (MoC x Si y ), molybdenum sulfide (MoS x ), molybdenum carbosulfide (MoC x S y ), molybdenum nitride (MoN x ), molybdenum phosphide (MoP x ), or molybdenum carbon phosphide (MoCx P y ) containing one or more of the following.

[0033] Those skilled in the art will recognize the molecular formula, e.g., molybdenum carbide (MoC x ), molybdenum carbonitride (MoC x N y ), molybdenum silicide (MoSi x ), molybdenum carbosilicide (MoC x Si y ), molybdenum sulfide (MoS x ), molybdenum carbosulfide (MoC x S y ), molybdenum nitride (MoN x ), molybdenum phosphide (MoP x ), or molybdenum carbon phosphide (MoC x P y It will be appreciated that the use of the term "MoC" does not imply any particular stoichiometric relationship between elements, but simply an identification of the major components of the film. For example, MoC x refers to a film whose predominant composition includes molybdenum (Mo) atoms and carbon (C) atoms. In some embodiments, the predominant composition of the specified film (i.e., the sum of the atomic percentages of the specified atoms) is greater than or equal to about 95%, 98%, 99%, or 99.5% of the film on an atomic basis.

[0034] 1 , one or more embodiments of the present disclosure are directed to a method 100 for depositing a molybdenum-containing film. The method illustrated in FIG. 1 is representative of an atomic layer deposition (ALD) process in which a substrate or substrate surface is sequentially exposed to reactive gases in a manner that prevents or minimizes gas-phase reaction of the reactive gases. In some embodiments, the method comprises a chemical vapor deposition (CVD) process in which the reactive gases are mixed in a processing chamber to allow gas-phase reaction of the reactive gases and deposition of a thin film.

[0035] In some embodiments, method 100 may include a pretreatment operation 105. The pretreatment can be any suitable pretreatment known to those skilled in the art. Suitable pretreatments include, but are not limited to, preheating, cleaning, soaking, removing native oxides, or depositing an adhesion layer (e.g., titanium nitride (TiN)). In one or more embodiments, an adhesion layer, such as titanium nitride, is deposited in operation 105. In other embodiments, no adhesion layer is deposited.

[0036] In deposition 110, a process is performed to deposit a molybdenum-containing film on a substrate (or substrate surface). The deposition process can include one or more operations to form a molybdenum-containing film on the substrate. In operation 112, the substrate (or substrate surface) is exposed to a molybdenum precursor to deposit a film on the substrate (or substrate surface). The molybdenum precursor can be any suitable molybdenum-containing compound that can react with (i.e., adsorb or chemisorb onto) the substrate surface to leave behind molybdenum-containing species on the substrate surface.

[0037] In one or more embodiments, the molybdenum(0) precursor is represented by Formula (I), Formula (II), Formula (III), Formula (IV), Formula (V), Formula (VI), Formula (VII), or Formula (VIII): [ka] Includes the structure of

[0038] In other embodiments, the molybdenum(0) precursor is represented by Formula (IX), Formula (X), Formula (XI), or Formula (XII): [ka] (wherein n is in the range of 0 to 10, and m is in the range of 0 to 10) In one or more embodiments, n ranges from 1 to 9, 2 to 8, 3 to 7, or 4 to 6, and m ranges from 1 to 9, 2 to 8, 3 to 7, or 4 to 6. In one or more specific embodiments, the molybdenum(0) precursor comprises a compound of formula (XII-A) or (XII-B): [ka] Includes the structure of

[0039] As used herein, "substrate surface" refers to any substrate surface upon which a layer can be formed. The substrate surface may have one or more features formed thereon, one or more layers formed thereon, and combinations thereof. The substrate (or substrate surface) may be pretreated, for example, by polishing, etching, reduction, oxidation, halogenation, hydroxylation, annealing, calcination, etc., prior to deposition of the molybdenum-containing layer.

[0040] The substrate may be any substrate on which a material can be deposited, such as a silicon substrate, a III-V compound substrate, a silicon germanium (SiGe) substrate, an epitaxial substrate, a silicon-on-insulator (SOI) substrate, a display substrate such as a liquid crystal display (LCD), a plasma display, or an electroluminescent (EL) lamp display, a solar array, a solar panel, a light-emitting diode (LED) substrate, or a semiconductor wafer. In some embodiments, one or more additional layers may be deposited on the substrate such that a molybdenum-containing layer can be at least partially formed thereon. For example, in some embodiments, a layer including a metal, nitride, oxide, or the like, or a combination thereof, may be deposited on the substrate, and a molybdenum-containing layer may be formed on such layer or layers.

[0041] In operation 114, the processing chamber may be purged to remove unreacted molybdenum precursor, reaction products, and by-products. As used in this technique, the term "processing chamber" also includes a portion of the processing chamber adjacent to the substrate surface, rather than the entire internal volume of the processing chamber. For example, in spatially separated processing chamber sectors, the molybdenum precursor is purged from the portion of the processing chamber adjacent to the substrate surface by any suitable technique, including, but not limited to, moving the substrate through a gas curtain to a portion or sector of the processing chamber that does not contain or substantially does not contain the molybdenum precursor. In one or more embodiments, purging the processing chamber includes applying a vacuum. In some embodiments, purging the processing chamber includes flowing a purge gas over the substrate. In some embodiments, the portion of the processing chamber refers to a micro-volume or small-volume process station within the processing chamber. The term "adjacent" referring to the substrate surface refers to the physical space adjacent to the surface of the substrate that can provide sufficient space for surface reactions (e.g., precursor adsorption) to occur. In one or more embodiments, the purge gas is selected from one or more of nitrogen (N), helium (He), and argon (Ar).

[0042] In operation 116, the substrate (or substrate surface) is exposed to a reactant to form a molybdenum-containing film on the substrate. The reactant can react with molybdenum-containing species on the substrate surface to form a molybdenum-containing film. In some embodiments, the reactant includes a reducing agent. In one or more embodiments, the reducing agent can include any reducing agent known to those skilled in the art. In one or more embodiments, the reducing agent includes one or more of tetrahydrofuran (THF), acetonitrile (MeCN), triethylamine (NEt), pyridine (CHN), dimethyl sulfide ((CHS), dimethyl disulfide (CHS), trimethylphosphine (PMe), hydrogen sulfide (HS), ammonia (NH), 1-azabicyclo[2.2.2]octane (quinuclidine), or 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0043] In some embodiments, the reactants are selected from one or more of 1,1-dimethylhydrazine (DMH), alkylamines, hydrazine, alkylhydrazine, allylhydrazine, hydrogen (H), ammonia (NH), and plasmas thereof. In some embodiments, the alkylamine is selected from one or more of tert-butylamine (tBuNH), isopropylamine (iPrNH), ethylamine (CHCHNH), diethylamine ((CHCH)NH), or butylamine (BuNH). In some embodiments, the reactants include one or more of compounds having the formula R'NH, R'NH, R'N, R'SiNH, (R'Si)NH, (R'Si)N, where each R' is independently H or an alkyl group having 1 to 12 carbon atoms. In some embodiments, the alkylamine consists essentially of one or more of tert-butylamine (tBuNH2), isopropylamine (iPrNH2), ethylamine (CH3CH2NH2), diethylamine ((CH3CH2)2NH), butylamine (BuNH2).

[0044] Molybdenum(0) precursors comprising the structure of Formula (I), (II), (III), (IV), (V), (VI), (VII), or (VIII) can be advantageously prepared as a single compound in a single step via a ligand exchange reaction starting from a commercially available molybdenum(0) precursor.

[0045] In other embodiments, the molybdenum(0) precursor is represented by Formula (IX), Formula (X), Formula (XI), or Formula (XII): [ka] (wherein n is in the range of 0 to 4, and m is in the range of 0 to 4) In one or more embodiments, n ranges from 1 to 9, 2 to 8, 3 to 7, or 4 to 6, and m ranges from 1 to 9, 2 to 8, 3 to 7, or 4 to 6. In one or more specific embodiments, the molybdenum(0) precursor comprises a compound of formula (XII-A) or (XII-B): [ka] Includes the structure of

[0046] In certain embodiments where the molybdenum(0) precursor comprises a structure of Formula (IX), Formula (X), Formula (XI), or Formula (XII) (including Formulas (XII-A) and (XII-B)), a two-step reaction is carried out to form the described molybdenum(0) precursor. In one or more embodiments, the two-step reaction involves starting with a commercially available molybdenum(0) precursor and using a co-reagent to form a molybdenum(0) precursor comprising a structure of Formula (IX), Formula (X), Formula (XI), or Formula (XII) (including Formulas (XII-A) and (XII-B)). In one or more embodiments, the co-reagent is a reducing agent comprising one or more of tetrahydrofuran (THF), acetonitrile (MeCN), triethylamine (NEt), pyridine (CHN), dimethyl sulfide ((CHS), dimethyl disulfide (CHS), trimethylphosphine (PMe), hydrogen sulfide (HS), ammonia (NH), 1-azabicyclo[2.2.2]octane (quinuclidine), or 1,4-diazabicyclo[2.2.2]octane (DABCO). In one or more embodiments, the two-step reaction forms a molybdenum(0) precursor comprising a structure of Formula (IX), Formula (X), Formula (XI), or Formula (XII) (including Formulas (XII-A) and (XII-B)) in the form of a black precipitate having a molybdenum (Mo) purity of 80% or greater on a molar basis.

[0047] In operation 118, after exposure to the reactants, the processing chamber may be purged. Purging the processing chamber in operation 118 can be the same process or a different process than purging in operation 114. Purging the processing chamber, a portion of the processing chamber, an area adjacent to the substrate surface, etc., removes unreacted reactants, reaction products, and by-products from the area adjacent to the substrate surface.

[0048] Decision 120 considers the thickness of the deposited film or the number of cycles of the molybdenum(0) precursor and reactants. If the deposited film reaches a predetermined thickness or a predetermined number of process cycles has been performed, method 100 proceeds to optional post-treatment operation 130. If the deposited film thickness or number of process cycles has not reached a predetermined threshold, method 100 returns to operation 110 and continues by again exposing the substrate surface to the molybdenum precursor in operation 112.

[0049] In certain embodiments, the method 100 includes introducing a molybdenum(0) precursor pulse for about 3 seconds using a carrier gas including a mixture of argon (Ar) and hydrogen (H), purging the substrate with a purge gas including a mixture of argon (Ar) and hydrogen (H), introducing a reactant pulse for about 1 second including hydrogen sulfide (H2S) using a carrier gas including a mixture of argon (Ar), hydrogen (H2), and hydrogen sulfide (H2S), and purging the substrate with a purge gas including a mixture of argon (Ar) and hydrogen (H2). In some embodiments, the molybdenum(0) precursor ampoule is maintained at a temperature of about 130°C. It has been advantageously found that performing the method 100 according to one or more embodiments, such as certain embodiments, results in a molybdenum-containing film that is selectively formed on metal surfaces relative to dielectric surfaces.

[0050] The optional post-treatment operation 130 can be, for example, a process that alters film properties (e.g., annealing) or a further film deposition process (e.g., an additional ALD or CVD process) to grow an additional film. In some embodiments, the optional post-treatment operation 130 can be a process that alters the properties of the deposited film. In some embodiments, the optional post-treatment operation 130 includes annealing the as-deposited film. In some embodiments, the annealing is performed at a temperature in the range of about 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C, or 1000°C. The annealing environment in some embodiments includes one or more of an inert gas (e.g., molecular nitrogen (N), argon (Ar)), or a reducing gas (e.g., molecular hydrogen (H) or ammonia (NH)), or an oxidizing agent, such as, but not limited to, oxygen (O), ozone (O), or peroxide. The annealing can be performed for any suitable length of time. In some embodiments, the film is annealed for a predetermined time ranging from about 15 seconds to about 90 minutes, or from about 1 minute to about 60 minutes. In some embodiments, annealing the as-deposited film increases the film's density, decreases its resistivity, and / or increases its purity.

[0051] Method 100 can be performed at any suitable temperature, depending, for example, on the thermal history of the molybdenum precursor, reactants, or device. In one or more embodiments, the use of high temperature processing may be undesirable for temperature-sensitive substrates, such as logic devices. In some embodiments, exposure to the molybdenum precursor (operation 112) and reactants (operation 116) occurs at the same temperature. In some embodiments, the substrate is maintained at a temperature ranging from about 20°C to about 400°C, or from about 50°C to about 650°C.

[0052] In some embodiments, the exposure to the molybdenum(0) precursor (operation 112) is performed at a different temperature than the exposure to the reactants (operation 116). In some embodiments, the substrate is maintained at a first temperature in a range from about 20° C. to about 400° C., or from about 50° C. to about 650° C. for the exposure to the molybdenum(0) precursor, and at a second temperature in a range from about 20° C. to about 400° C., or from about 50° C. to about 650° C. for the exposure to the reactants.

[0053] In the embodiment shown in FIG. 1 , the substrate (or substrate surface) is sequentially exposed to the molybdenum(0) precursor and reactants in deposition operation 110. In another embodiment not shown, the substrate (or substrate surface) is simultaneously exposed to the molybdenum(0) precursor and reactants in a CVD reaction. In a CVD reaction, the substrate (or substrate surface) is exposed to a gaseous mixture of the molybdenum precursor and reactants to deposit a molybdenum-containing film having a predetermined thickness. In a CVD reaction, the molybdenum-containing film can be deposited in a single exposure to the reactive gas mixture, or by multiple exposures to the reactive gas mixture with purging in between.

[0054] In some embodiments, the formed molybdenum-containing film comprises elemental molybdenum. Stated another way, in some embodiments, the molybdenum-containing film comprises a metal film comprising molybdenum. In some embodiments, the metal film consists essentially of molybdenum. As used in this manner, the term "consisting essentially of molybdenum" means that the molybdenum-containing film is greater than or equal to about 80%, 85%, 90%, 95%, 98%, 99%, or 99.5% molybdenum on an atomic basis. Measurements of the composition of molybdenum-containing films refer to the bulk of the film, excluding interfacial regions where diffusion of elements from adjacent films may occur.

[0055] Deposition operation 110 can be repeated to form a molybdenum-containing film having a predetermined thickness. In some embodiments, deposition operation 110 can be repeated to form a molybdenum-containing film, such as molybdenum metal (elemental molybdenum), molybdenum carbide (MoC), or a molybdenum-containing film having a thickness ranging from about 0.3 nm to about 100 nm, or from about 30 Å to about 10 μm. x ), molybdenum carbonitride (MoC x N y ), molybdenum silicide (MoSi x ), molybdenum carbosilicide (MoC x Si y ), molybdenum sulfide (MoS x ), molybdenum carbosulfide (MoC x S y ), molybdenum nitride (MoN x ), molybdenum phosphide (MoP x ), or molybdenum carbon phosphide (MoC x P y ) to provide one or more of the following.

[0056] One or more embodiments of the present disclosure are directed to a method of depositing a molybdenum-containing film on a high aspect ratio feature. The high aspect ratio feature is a trench, via, or pillar having a height-to-width ratio of about 10, 20, or 50 or more. In some embodiments, the molybdenum-containing film is conformally deposited on the high aspect ratio feature. As used in this technique, the conformal film has a thickness near the top of the feature that is in the range of about 80-120% of the thickness at the bottom of the feature.

[0057] Some embodiments of the present disclosure are directed to methods for bottom-up gap filling of features. A bottom-up gap filling process fills a feature from the bottom, as opposed to a conformal process that fills the feature from the bottom and the sides. In some embodiments, the feature has a first material (e.g., nitride) on the bottom and a second material (e.g., oxide) on the sidewalls. A molybdenum-containing film is deposited selectively on the first material relative to the second material, thereby causing the molybdenum film to fill the feature in a bottom-up manner.

[0058] According to one or more embodiments, the substrate is subjected to processing before and / or after forming a layer. This processing can occur in the same chamber or in one or more separate processing chambers. In some embodiments, the substrate is moved from the first chamber to a separate second chamber for further processing. The substrate can be moved directly from the first chamber to the separate processing chamber, or from the first chamber to one or more transfer chambers and then to the separate processing chambers. Thus, the processing equipment may include multiple chambers in communication with a transfer station. This type of equipment may be referred to as a "cluster tool" or "cluster system," among other terms.

[0059] Generally, a cluster tool is a modular system with multiple chambers that perform various functions, such as substrate centering and orientation, degassing, annealing, deposition, and / or etching. According to one or more embodiments, a cluster tool includes at least a first chamber and a central transfer chamber. The central transfer chamber may house a robot capable of shuttling substrates between processing chambers and load lock chambers, as well as between the multiple chambers. The transfer chamber is typically maintained under vacuum and provides an intermediate stage for shuttling substrates from one chamber to another and / or to a load lock chamber located at the front end of the cluster tool. Two well-known cluster tools that are applicable to the present disclosure are the Centura® and Endura®, both available from Applied Materials, Inc. of Santa Clara, Calif. However, the exact arrangement and combination of chambers may be varied for the purpose of performing specific steps of the processes described herein. Other processing chambers that may be used include, but are not limited to, cyclic layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-clean, chemical cleaning, thermal treatments such as RTP, plasma nitridation, degassing, alignment, hydroxylation, and other substrate processes. By performing processes in chambers on a cluster tool, surface contamination of the substrate from atmospheric impurities can be avoided without oxidation prior to depositing subsequent films.

[0060] According to one or more embodiments, the substrate is continuously under vacuum or "load-lock" conditions and is not exposed to the atmosphere when moving from one chamber to the next. The transfer chamber is therefore under vacuum and is "pumped down" under vacuum pressure. An inert gas may be present in the processing chamber or the transfer chamber. In some embodiments, an inert gas is used as a purge gas to remove some or all of the reactants (e.g., a certain reactant). According to one or more embodiments, a purge gas is injected at the outlet of the deposition chamber to prevent the transfer of reactants (e.g., a certain reactant) from the deposition chamber to the transfer chamber and / or additional processing chambers. Thus, the flow of inert gas forms a curtain at the outlet of the chamber.

[0061] Substrates can be processed in a single substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. Substrates can also be processed in a continuous manner, similar to a conveyor system, where multiple substrates are individually loaded into a first portion of the chamber, moved through the chamber, and unloaded from a second portion of the chamber. The geometry of the chamber and associated conveyor system can form a linear or curved path. Additionally, the processing chamber can be a carousel, where multiple substrates are moved about a central axis and exposed to processes such as deposition, etching, annealing, and cleaning throughout the carousel path.

[0062] During processing, the substrate may be heated or cooled. Such heating or cooling can be achieved by any suitable means, including, but not limited to, changing the temperature of the substrate support or flowing heated or cooled gas over the substrate surface. In some embodiments, the substrate support includes a controllable heater / cooler that conductively changes the substrate temperature. In one or more embodiments, the gas being used (either a reactive gas or an inert gas) is heated or cooled to locally change the substrate temperature. In some embodiments, the heater / cooler is positioned in the chamber adjacent to the substrate surface to convectively change the substrate temperature.

[0063] The substrate can also be stationary or rotating during processing. A rotating substrate can be rotated continuously (about the substrate axis) or in discrete increments. For example, the substrate may be rotated throughout the entire process, or the substrate can be rotated in small increments between exposures to different reactive or purge gases. Rotating the substrate (either continuously or in steps) during processing can help produce more uniform deposition or etching, for example, by minimizing the effects of local variations in gas flow profiles.

[0064] The present disclosure will now be described with reference to the following examples. Before describing certain exemplary embodiments of the present disclosure, it is to be understood that the present disclosure is not limited to the details of construction or process steps set forth in the following description. The present disclosure is capable of other embodiments and of being practiced or carried out in various ways. [Example]

[0065] Example 1 Preparation of Formula (I) A molybdenum(0) precursor containing the structure of formula (I) was prepared by reacting commercially available bis(ethylbenzene)molybdenum with 30 equivalents of toluene at 170°C for 3 days. Removal of volatile materials under vacuum afforded the target precursor containing the structure of formula (I) as a single solid compound with a purity of 90% and a melting point of 67°C in 88% yield. As used herein, the term "removal of volatile materials" refers to the removal of any compounds other than the target precursor, unreacted precursor, and / or by-products from the described reaction. As used herein, the described purity is expressed on a percentage (%) molar basis, which refers to the percentage of molecules in the described molybdenum(0) precursor (e.g., the target precursor) that contain a molybdenum (Mo) species.

[0066] 1 H NMR (C6D6, 500MHz, ppm): δ4.65~4.58(m, 8H, CH), 4.52(t, 2H, CH J HH =4Hz), 1.86(s, 6H, CH3)

[0067] 13 C NMR (C6D6, 500MHz, ppm): δ89.5, 78.4, 75.7, 74.8, 21.3

[0068] Example 2A Preparation of Formula (II) using Formula (I) A molybdenum(0) precursor containing the structure of formula (II) was prepared by reacting a molybdenum(0) precursor containing the structure of formula (I) with 70 equivalents of ethylbenzene at 170°C for 4 days. Removal of volatile materials under vacuum afforded the target precursor containing the structure of formula (II) as a single compound semi-liquid with a purity of 99% and a melting point ranging from 28°C to 31°C in 78% yield.

[0069] 1 H NMR (C6D6, 500MHz, ppm): δ4.66~4.52(m, 10H, CH), 2.10(q, 4H, CH2J HH =7Hz), 1.07(t, 6H, CH3, JHH =7Hz)

[0070] 13 C NMR (C6D6, 500MHz, ppm): δ97.5, 77.1, 75.4, 74.7, 29.0, 16.3

[0071] Example 2B Preparation of formula (II) using commercially available bis(ethylbenzene)molybdenum A molybdenum(0) precursor containing the formula (II) was prepared by reacting commercially available bis(ethylbenzene)molybdenum with 76 equivalents of ethylbenzene at 170°C for 3 days. This reaction resulted in the formation of an intermediate compound containing a mixture of the molybdenum(0) precursor containing the formula (II) and unreacted compounds from the commercially available bis(ethylbenzene)molybdenum. The mixture of the molybdenum(0) precursor containing the formula (II) and unreacted compounds from the commercially available bis(ethylbenzene)molybdenum was reacted with 76 equivalents of ethylbenzene at 170°C for 2 days to form a molybdenum(0) precursor containing the formula (II). Removal of volatile materials under vacuum afforded the target precursor containing the formula (II) as a single semi-liquid compound with a purity of 99% and a melting point ranging from 28°C to 31°C in 84% yield.

[0072] 1 H NMR (C6D6, 500MHz, ppm): δ4.66~4.52(m, 10H, CH), 2.10(q, 4H, CH2J HH =7Hz), 1.07(t, 6H, CH3, J HH =7Hz)

[0073] 13 C NMR (C6D6, 500MHz, ppm): δ97.5, 77.1, 75.4, 74.7, 29.0, 16.3

[0074] Example 3A Preparation of Formula (III) using Formula (I) A molybdenum(0) precursor containing the structure of formula (III) was prepared by reacting a molybdenum(0) precursor containing the structure of formula (I) with n-propylbenzene at 195°C for 2 days. This reaction yielded the target precursor containing the structure of formula (III) as a single solid compound with a purity of 95% and a melting point of 36°C in a 64% yield.

[0075] 1 H NMR (C6D6, 500MHz, ppm): δ4.69~4.50(m, 10H, CH), 2.02(t, 4H, CH2J HH =7Hz), 1.49(h, 4H, CH2J HH =7Hz), 0.91(t, 6H, CH3, J HH =7Hz)

[0076] 13 C NMR (C6D6, 500MHz, ppm): δ95.0, 77.8, 75.7, 74.9, 38.1, 26.1, 13.2

[0077] Example 3B Preparation of formula (III) using commercially available bis(ethylbenzene)molybdenum A molybdenum(0) precursor containing the structure of formula (III) was prepared by reacting commercially available bis(ethylbenzene)molybdenum with 30 equivalents of n-propylbenzene at 170°C for 3 days. Removal of volatile materials under vacuum afforded the target precursor containing the structure of formula (III) as a single solid compound with a purity of 95% and a melting point of 36°C in 64% yield.

[0078] 1 H NMR (C6D6, 500MHz, ppm): δ4.69~4.50(m, 10H, CH), 2.02(t, 4H, CH2J HH =7Hz), 1.49(h, 4H, CH2J HH =7Hz), 0.91(t, 6H, CH3, J HH =7Hz)

[0079] 13C NMR (C6D6, 500MHz, ppm): δ95.0, 77.8, 75.7, 74.9, 38.1, 26.1, 13.2

[0080] Example 4 Preparation of formula (IV) A molybdenum(0) precursor containing the structure of formula (IV) was prepared by reacting commercially available bis(ethylbenzene)molybdenum with 30 equivalents of n-butylbenzene at 170°C for 3 days. Removal of volatile materials under vacuum afforded the target precursor containing the structure of formula (IV) as a single liquid compound with a purity of 95% in 60% yield.

[0081] 1 H NMR (C6D6, 500MHz, ppm): δ4.70~4.54(m, 10H, CH), 2.10(t, 4H, CH2J HH =7Hz), 1.52~1.44(m, 4H, CH2), 1.36~1.26(m, 4H, CH2), 0.87(t, 6H, CH3, J HH =7Hz)

[0082] 13 C NMR (C6D6, 500MHz, ppm): δ95.2, 77.8, 75.6, 74.8, 36.2, 35.1, 22.6, 13.9

[0083] Example 5 Preparation of formula (V) A molybdenum(0) precursor containing the structure of formula (V) was prepared by reacting commercially available bis(ethylbenzene)molybdenum with n-pentylbenzene at 170°C for 3 days. By removing volatile materials under vacuum, the target precursor containing the structure of formula (V) was obtained as a single compound liquid with a purity of 95% in 61% yield.

[0084] 1 H NMR (C6D6, 500MHz, ppm): δ4.72~4.54(m, 10H, CH), 2.12(t, 4H, CH2J HH=7Hz), 1.55~1.49(m, 4H, CH2), 1.35~1.23(m, 8H, CH2), 0.88(t, 6H, CH3, J HH =7Hz)

[0085] 13 C NMR (C6D6, 500MHz, ppm): δ95.2, 77.8, 75.6, 74.8, 36.5, 32.6, 31.7, 22.7, 14.0

[0086] Example 6 Preparation of formula (VI) A molybdenum(0) precursor containing the structure of formula (VI) was prepared by reacting commercially available bis(ethylbenzene)molybdenum with 30 equivalents of t-butylbenzene at 170°C for 3 days. Removal of volatile materials under vacuum afforded the target precursor containing the structure of formula (VI) as a solid in 88% yield with a purity of 95% and a melting point of 96°C.

[0087] 1 H NMR (C6D6, 500MHz, ppm): δ4.74~4.66(m, 4H, CH), 4.58~4.54(m, 2H, CH), 4.54~4.49(m, 4H, CH), 1.16(s, 18H, CH3)

[0088] 13 C NMR (C6D6, 500MHz, ppm): δ73.8, 73.7, 73.6, 33.0, 30.7

[0089] Example 7 Preparation of formula (VII) A molybdenum(0) precursor containing the structure of formula (VII) was prepared by reacting commercially available bis(ethylbenzene)molybdenum with 10 equivalents of (trimethylsilyl)benzene at 170°C for 3 days. Removal of volatile materials under vacuum afforded the target precursor containing the structure of formula (VII) as a single solid compound with a purity of 95% and a melting point of 85°C in 81% yield.

[0090] 1H NMR (C6D6, 500MHz, ppm): δ4.72~4.65(m, 2H, CH), 4.59~4.53(m, 4H, CH), 4.50~4.44(m, 4H, CH), 0.16(s, 18H, CH3)

[0091] 13 C NMR (C6D6, 500MHz, ppm): δ79.4, 77.3, 75.0, -0.9

[0092] Example 8 Preparation of formula (VIII) A molybdenum(0) precursor containing the structure of formula (VIII) was prepared by reacting a molybdenum(0) precursor containing the structure of formula (I) with 3.5 equivalents of 6,6-dimethylfulvene in the presence of toluene at 50°C for 3 days. This reaction afforded the target precursor containing the structure of formula (VIII) in 90% yield as a solid with a purity of 95% and a melting point of 70°C.

[0093] 1 H NMR (Toluene-d8, 500MHz, ppm): δ4.98(s, 2H, C5H4), 4.54(s, 2H, C5H4), 3.93(m, 1H, C6H 5), 3.83(m, 2H, C6H5), 3.80(m, 2H, C6H5), 1.78(s, 3H, C6H5CH3), 1.68(s, 6H, CMe2).

[0094] 13 C NMR (toluene-d8, 500 MHz, ppm): δ 90.1, 82.3, 78.3, 76.1, 75.9, 75.6, 74.7, 24.8, 20.8

[0095] Example 9 Atomic Layer Deposition (ALD) of Molybdenum-Containing Films General Procedure: A semiconductor substrate was placed in a processing chamber. A molybdenum (0) precursor with a molar purity of 90% or greater was flowed into the processing chamber in a nitrogen (N2) gas atmosphere onto the semiconductor substrate, leaving a molybdenum-precursor-terminated surface. Unreacted precursor and by-products were then purged from the chamber. A co-reactant that reacts with the surface-bound molybdenum species was then introduced into the chamber. Again, excess co-reactant and by-products were removed from the chamber. The resulting material on the substrate was a molybdenum-containing film containing 80% or greater molybdenum (Mo) on an atomic basis.

[0096] Spatially relative terms, such as "beneath," "below," "lower," "above," "upper," etc., may be used herein for ease of description to describe the relationship of one element or feature to another, as shown in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation shown in the figures. For example, if the device in the figures were inverted, an element described as "below" or "below" the other element or feature would then be oriented "above" the other element or feature. Thus, the exemplary term "below" may encompass both an above and below orientation. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptions used herein shall be interpreted accordingly.

[0097] The use of the terms "a," "an," and "the" and similar reference words in the context of describing the materials and methods discussed herein (particularly in the context of the claims below) is intended to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand means of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if set forth individually herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. All examples provided herein, or the use of illustrative language (e.g., "such as"), are intended merely to further clarify the materials and methods and do not limit the scope unless otherwise claimed. No language herein should be construed as indicating any non-claimed element as essential to the practice of the disclosed materials and methods.

[0098] Throughout this specification, references to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with an embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of phrases such as "in one or more embodiments," "in a particular embodiment," "in one embodiment," or "in an embodiment" in various places throughout this specification do not necessarily refer to the same embodiment of the present disclosure. In one or more embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner.

[0099] Although the disclosure herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed method and apparatus without departing from the spirit and scope of the disclosure. Therefore, the present disclosure is intended to cover modifications and variations that come within the scope of the appended claims and their equivalents.

Claims

1. A molybdenum(0) precursor comprising a structure of formula (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XII-A), or (XII-B), having a molybdenum (Mo) purity of 90% or more on a molar basis. 【Chemistry 1-1】 【Chemistry 1-2】 (wherein n is in the range of 0 to 10, and m is in the range of 0 to 10)

2. 2. The molybdenum(0) precursor of claim 1, which is substantially free of halogens, oxygen, and Mo—O bonds.

3. 1. A method of forming a molybdenum-containing film, comprising: exposing the substrate surface to a molybdenum(0) precursor; exposing the substrate surface to a reactant to form the molybdenum-containing film on the substrate surface; A method comprising:

4. 4. The method of claim 3, wherein the molybdenum(0) precursor has a structure of Formula (I), (II), (III), (IV), (V), (VI), (VII), (VII), (VIII), (IX), (X), (XI), (XII), (XII-A), or (XII-B), and the molybdenum(0) precursor has a molybdenum (Mo) purity of 90% or greater on a molar basis. 【Chemistry 2-1】 【Chemistry 2-2】 (wherein n is in the range of 0 to 10, and m is in the range of 0 to 10)

5. 5. The method of claim 4, wherein the molybdenum(0) precursor is a liquid precursor.

6. The reactants include a reducing agent, and the reducing agent is selected from the group consisting of tetrahydrofuran (THF), acetonitrile (MeCN), triethylamine (NEt 3 ), pyridine (C 5 H 5 N), dimethyl sulfide ((CH 3 ) 2 S), dimethyl disulfide (C 2 H 6 S 2 ), trimethylphosphine (PMe 3 ), hydrogen sulfide (H 2 S), ammonia (NH 3 4. The method of claim 3, wherein the compound comprises one or more of: 1-azabicyclo[2.2.2]octane (quinuclidine), 1-azabicyclo[2.2.2]octane (quinuclidine), or 1,4-diazabicyclo[2.2.2]octane (DABCO).

7. The molybdenum-containing film may be made of metal molybdenum (elemental molybdenum), molybdenum carbide (MoC x ), molybdenum carbonitride (MoC x N y ), molybdenum silicide (MoSi x ), molybdenum carbosilicide (MoC x Si y ), molybdenum sulfide (MoS x ), molybdenum carbosulfide (MoC x S y ), molybdenum nitride (MoN x ), molybdenum phosphide (MoP x ), or molybdenum carbonitride (MoC x P y 4. The method of claim 3, comprising one or more of:

8. 4. The method of claim 3, wherein the substrate surface is exposed sequentially to the molybdenum(0) precursor and the reactant.

9. The method of claim 3 , wherein the substrate surface is exposed to the molybdenum(0) precursor and the reactant simultaneously.

10. 4. The method of claim 3, further comprising purging the molybdenum(0) precursor from the substrate surface before exposing the substrate surface to the reactant.

11. The method of claim 10 , wherein purging comprises one or more of applying a vacuum on the substrate surface or flowing a purge gas over the substrate surface.

12. The purge gas is nitrogen (N 2 12. The method of claim 11 , wherein the gas comprises one or more of: nitrogen (N), helium (He), or argon (Ar).

13. The method of claim 3 , wherein the molybdenum-containing film comprises at least 80% molybdenum (Mo) on an atomic basis.

14. 1. A method of forming a molybdenum-containing film, comprising: performing a process cycle comprising sequential exposure of the substrate surface to a molybdenum(0) precursor, a purge gas, a reactant, and a purge gas; A method comprising:

15. 15. The method of claim 14, wherein the molybdenum(0) precursor has a structure of Formula (I), (II), (III), (IV), (V), (VI), (VII), (VII), (VIII), (IX), (X), (XI), (XII), (XII-A), or (XII-B), and the molybdenum(0) precursor has a molybdenum (Mo) purity of 90% or greater on a molar basis. 【Chemistry 3-1】 【Chemistry 3-2】 (wherein n is in the range of 0 to 10, and m is in the range of 0 to 10)

16. 16. The method of claim 15, wherein the molybdenum(0) precursor is substantially free of halogens, oxygen, and Mo—O bonds.

17. The reactants include a reducing agent, and the reducing agent is selected from the group consisting of tetrahydrofuran (THF), acetonitrile (MeCN), triethylamine (NEt 3 ), pyridine (C 5 H 5 N), dimethyl sulfide ((CH 3 ) 2 S), dimethyl disulfide (C 2 H 6 S 2 ), trimethylphosphine (PMe 3 ), hydrogen sulfide (H 2 S), ammonia (NH 3 15. The method of claim 14, wherein the compound comprises one or more of: 1-azabicyclo[2.2.2]octane (quinuclidine), 1-azabicyclo[2.2.2]octane (quinuclidine), or 1,4-diazabicyclo[2.2.2]octane (DABCO).

18. The purge gas is nitrogen (N 2 15. The method of claim 14, wherein the gas comprises one or more of: helium (He), and argon (Ar).

19. The molybdenum-containing film may be made of metal molybdenum (elemental molybdenum), molybdenum carbide (MoC x ), molybdenum carbonitride (MoC x N y ), molybdenum silicide (MoSi x ), molybdenum carbosilicide (MoC x Si y ), molybdenum sulfide (MoS x ), molybdenum carbosulfide (MoC x S y ), molybdenum nitride (MoN x ), molybdenum phosphide (MoP x ), or molybdenum carbonitride (MoC x P y 15. The method of claim 14, comprising one or more of:

20. 15. The method of claim 14, wherein the molybdenum-containing film comprises 80% or more molybdenum (Mo) on an atomic basis.

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