Liquid molybdenum bis(arene) compositions for the deposition of molybdenum-containing films

Abstract

The disclosed and claimed subject matter relates to a mixture of Mo(arene)2 compounds and its use for depositing Mo-containing films. The arene ligands are selected to provide a mixture of Mo(arene)2 compounds that is liquid at temperatures between about 20°C and about 35°C, with little or no difference in boiling points between the different components of the mixture.

Description

[Technical Field]

[0001] technology

[0002] The disclosed and claimed subject matter relates to compositions comprising a mixture of Mo(arene)2 complexes and their use for depositing Mo-containing films. The arene ligands are selected to provide a mixture of Mo(arene)2 compositions that is liquid at temperatures between about 20°C and about 35°C, with little or no difference in boiling points between the different components of the mixture. In some embodiments, all of the arene ligands have substantially the same or the same molecular weight. In other embodiments, all of the arene ligands have the same number of carbons. [Background technology]

[0003] Related technologies

[0004] Transition metal-containing films are used in semiconductor and electronics applications. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been applied as the primary deposition techniques for producing thin films for semiconductor devices. These methods enable the realization of conformal films (metals, metal oxides, metal nitrides, metal silicides, etc.) through the chemical reaction of metal-containing compounds (precursors). The chemical reaction occurs on surfaces that may include metals, metal oxides, metal nitrides, metal silicides, and other surfaces. In CVD and ALD, precursor molecules play a key role in obtaining high-quality films with high conformality and low impurities. The substrate temperature in CVD and ALD processes is an important consideration when selecting precursor molecules. Higher substrate temperatures, in the range of 150–500 degrees Celsius (°C), promote higher film growth rates. Preferred precursor molecules must be stable in this temperature range. Preferred precursors can be delivered to the reaction vessel in the liquid phase. Liquid-phase delivery of precursors generally provides more uniform delivery of precursors to the reaction vessel than solid-phase precursors.

[0005] CVD and ALD processes are increasingly being used because they offer the advantages of enhanced compositional control, high film uniformity, and effective control of doping. Furthermore, CVD and ALD processes provide excellent conformal step coverage over the highly non-planar geometries associated with modern microelectronic devices.

[0006] CVD is a chemical process that uses precursors to form thin films on a substrate surface. In a typical CVD process, precursors are passed over the surface of a substrate (e.g., a wafer) in a low-pressure or ambient-pressure reaction chamber. The precursors react and / or decompose on the substrate surface to produce a thin film of deposited material. Plasma can be used to assist the precursor reaction or to improve material properties. Volatile byproducts are removed by gas flow through the reaction chamber. Deposition film thickness can be difficult to control because it depends on adjusting many parameters, such as temperature, pressure, gas flow rate and uniformity, chemical depletion effects, and time.

[0007] ALD is a chemical method for the deposition of thin films. It is a unique, self-limiting, sequential film growth technique based on surface reactions that provides precise thickness control and can deposit conformal thin films of precursor-provided materials onto substrates of various compositions. In ALD, precursors are separated during the reaction. The first precursor is passed over the substrate surface, producing a monolayer on the surface. Excess unreacted precursor is pumped out of the reaction chamber. A second precursor or co-reactant is then passed over the substrate surface and reacts with the first precursor to form a second monolayer on the substrate surface. Plasma can be used to support the precursor or co-reactant reaction or to improve material quality. This cycle is repeated to form a film of the desired thickness.

[0008] Thin films, especially metal-containing thin films, have a variety of important applications in nanotechnology and semiconductor device fabrication, including capacitor electrodes, gate electrodes, adhesive diffusion barriers, and integrated circuits.

[0009] Molybdenum-containing thin films have attracted attention due to their low resistivity and thermal stability compared to other metals such as tungsten and cobalt. As a result, molybdenum (Mo) has become an increasingly popular material in the electronics industry for forming Mo-containing thin films using CVD or ALD techniques in next-generation devices. There is a continuing need for halogen-free molybdenum precursors that are liquid at room or low temperatures and have relatively high vapor pressure, high thermal stability, and reactivity. Most known molybdenum precursors contain molybdenum in a high oxidation state of 4-6, which typically results in high-resistivity molybdenum-containing films. For the deposition of low-resistivity molybdenum-containing films, molybdenum complexes with low oxidation states of 0-4 are desirable.

[0010] Molybdenum bis(arene) precursors are a series of organometallic compounds of the formula Mo(arene)2, where the arenes are the same or different unsubstituted or substituted benzenes, such as benzene, toluene, mesitylene, ethylbenzene, diethylbenzene, and xylene. Such precursors typically have relatively high vapor pressures, making them good candidates for CVD or ALD to produce Mo thin films with low resistivity and low amounts of carbon and nitrogen contamination. Commercially available mixtures containing Mo(EtBz)2 have been used for the deposition of molybdenum-containing films such as MoO, MoC seed layers, and Mo metal films.

[0011] For example, U.S. Patent Application Publication No. 2022 / 0139713(A1) describes a method for depositing elemental molybdenum thin films on a substrate using a liquid precursor containing molybdenum bis(ethylbenzene). In this method, a molybdenum thin film containing carbon as a contaminant is deposited on the substrate by a cyclic deposition process, followed by oxidation to remove the carbon. The method includes providing a substrate to a deposition chamber, providing a molybdenum precursor in the vapor phase to the chamber, and providing reactants in the vapor phase to the reaction chamber to form a molybdenum film on the substrate. The molybdenum precursor is provided in a mixture, and the reactant is a halogen (I2) or a halogenated hydrocarbon (ICH2CH2I), where at least two halogen atoms are bonded to different carbon atoms of the hydrocarbon.

[0012] U.S. Patent Application Publication No. 2021 / 0047726(A1) describes a method for forming molybdenum thin films by oxidation and reduction using zero-valent halide-free organometallic molybdenum precursors [Mo(EtBz)2, CpMo(Co)2(NO) and MeCPMo(Co)2(NO)]. The first step is the formation of a molybdenum oxide film by CVD or ALD, but the film contains a small amount of carbon as a contaminant. As a result, the molybdenum oxide film requires additional processing (i.e., oxidation) to remove the carbon, followed by reduction to remove oxygen, ultimately forming a high-purity molybdenum thin film. The molybdenum thin film has low resistivity and bulk-molybdenum-like properties.

[0013] U.S. Patent Application Publication No. 2020 / 0115798 describes a deposition method for depositing molybdenum or tungsten metal films or layers on a substrate, which involves an organometallic molybdenum or tungsten precursor, such as Mo(EtBz)2 or W(EtBz)2, containing only the metal, carbon, and hydrogen. The deposited metal layer contains carbon as a contaminant from the precursor. As a result, additional processing is required to remove the carbon. Specifically, hydrogen gas is flowed into the deposition chamber to expose the deposited metal to hydrogen, and then an oxidizing agent is introduced to react with the carbon contaminants, removing them from the deposited metal layer and resulting in a high-quality metal film or layer.

[0014] US Patent Application Publication No. 2019 / 226086 describes a chemical vapor deposition method for depositing molybdenum films on titanium nitride surfaces (3D NAND devices with vertical walls) using a bis(alkyl-arene)molybdenum composition containing Mo(EtBz)2 as a precursor to form a MoC seed layer (Mo:C=40:60-99:1, thickness: 6-100 Å) or a Mo-containing metal film at a pressure of 10-50 Torr and below 300°C.

[0015] Deposition of molybdenum-containing films has been demonstrated using a liquid Mo(arene)2 composition containing Mo(EtBz)2; however, this commercially available composition contains a mixture of molybdenum arene complexes with different ligands. Specifically, the mixture contains less than 60 mol% ethylbenzene ligands, more than 10 mol% benzene ligands, more than 30 mol% diethylbenzene ligands, and more than 1 mol% triethylbenzene. Without being bound by theory, it is believed that this composition contains various molybdenum arene complexes, such as Mo(Bz)2, Mo(EtBz)(Bz), Mo(EtBz)2, Mo(EtBz)(Et2Bz), Mo(Et2Bz)2, and Mo(Et3Bz)2. These complexes have sufficiently different molecular weights, thermal stabilities, and vapor pressures to result in inconsistent chemical delivery to the tool and inreproducible deposition of molybdenum-containing films. It is highly desirable to have a liquid composition in which the arene ligand contains a higher concentration of ethylbenzene in order to reduce the difference in boiling points of the different mixture components.

[0016] U.S. Patent Application Publication No. 2022 / 0372053(A1) describes a method for forming a metal-containing film on a substrate, the method comprising exposing the substrate to vapor of a film-forming composition containing a metal-containing precursor and depositing at least a portion of the metal-containing precursor on the substrate to form a metal-containing film on the substrate by a vapor deposition process. The metal-containing precursor is said to be pure Mo(arene)2, such as Mo(toluene)2, Mo(m-xylene)2, or Mo(mesitylene)2, as opposed to the commercially available "Mo(EtBz)2" mixture of pure Mo(EtBz)2 and metalloarene compositions. However, no data are provided establishing the purity of the Mo(arene)2. Additionally, the allegedly pure material is prepared by previously reported methods (discussed below) without additional purification steps known to impart impurities. Thus, while this reference states that it is desirable to use "pure" materials in the disclosed methods, it does not describe how to obtain such pure materials. Therefore, the present invention addresses the continuing need for high purity molybdenum arene complexes that are substantially free of impurities that affect the quality of deposited molybdenum-containing films.

[0017] The preparation of compositionally pure Mo(EtBz)2 complexes is not directly possible by the Fischer-Hafner method. The Fischer-Hafner method is affected by the isomerization of alkylbenzenes with alkyl groups larger than methyl. Therefore, such molybdenum arene complexes contain a mixture of various arenes with different molecular weights. For example, when ethylbenzene is used in the synthesis of a Mo(arene)2 complex, the arene ligand contains a mixture of benzene, ethylbenzene, diethylbenzene, and triethylbenzene, where the amount of ethylbenzene is less than 60 mol%. On the other hand, relatively pure Mo(arene)2 complexes could be prepared using benzene, methylbenzene (toluene), dimethylbenzene (xylene), and trimethylbenzene (mesitylene). However, all these complexes are solids with melting points above 80 °C: Mo(benzene)2 (mp = 115 °C), Mo(toluene)2 (mp = 82 °C), Mo(m-xylene)2 (mp = 104 °C), Mo(mesitylene)2 (mp = 110 °C).

[0018] MTAshby et al., in Organometallics, 20, 1687-1688 (2001), reported that arene metathesis with Mo(benzene) complexes was used to obtain Mo(RC6H5)2 (R=Et, i Pr, t Molybdenum arene compositions have been developed that are substantially free of Mo(benzene)2. However, all complexes are solids produced in low yields due to the thermal instability of Mo(benzene)2. In addition, these compositions still contain residual Mo(benzene)2, which has a different vapor pressure and low thermal stability. Therefore, there remains a need for molybdenum arene compositions that are substantially free of Mo(benzene)2.

[0019] It is highly desirable to have a mixture of Mo(arene)2 compounds that are liquid at room temperature, as this makes it much easier to transport the liquid from a bulk container to an on-board container on a semiconductor tool. Typically, compositions with a melting point below 35°C are preferred.

[0020] It is also desirable to obtain liquid mixtures of Mo(arene)2 compounds in which all of the arene ligands have the same or substantially the same molecular weight. Without being bound by theory, it is believed that all of the components of these mixtures have similar boiling points and accordingly maintain their composition during evaporation from the ampoule on the semiconductor tool.

[0021] The disclosed and claimed subject matter provides a Mo(Ar) compound with a consistent vapor pressure that is particularly well suited for use in CVD and ALD applications. 1 )(Ar 2 The present invention overcomes the above drawbacks by providing a liquid mixture of the compounds. Summary of the Invention

[0022] The disclosed and claimed subject matter is a Mo(Ar)2O3 prepared via arene metathesis in which the ethylbenzene ligand ("EtBz") content in the composition is increased from about 54% (commercial grade) to about 60 mol % to about 95 mol %, while the undesired ligands, i.e., benzene ligand ("Bz"), diethylbenzene ligand ("EtBz"), and triethylbenzene ligand ("EtBz"), are simultaneously reduced. 1 )(Ar 2 ) for a mixture of compounds. Importantly, this compositional change still provides a liquid composition at room temperature with a much more consistent vapor pressure during evaporation.

[0023] In one embodiment, for example, Mo(Ar 1 )(Ar 2 In a further aspect of this embodiment, the liquid mixture of Mo(Ar) compounds comprises (i) about 60 mol % to about 95 mol % EtBz, and (ii) reduced amounts of other undesirable ligands. 1 )(Ar 2The liquid mixture of Mo(Ar) compounds contains (i) about 60 mol % to about 95 mol % EtBz, (iia) about 0.25 mol % to about 13 mol % Bz, (iib) about 6.75 mol % to about 44.5 mol % EtBz, and (iic) about 0.75 mol % to about 7 mol % EtBz. These compositions are liquid at room temperature, for example, Mo(Ar) containing greater than about 97% EtBz, about 0.48% Bz, and about 2.35% EtBz. 1 )(Ar 2 This is highly unexpected given that the mixture of compounds is solid below 37° C. (melting point). Thus, the disclosed and claimed compositions contain significantly increased amounts of desired ligands (e.g., ethylbenzene ligands) while also unexpectedly remaining liquid at room temperature.

[0024] In one embodiment, Mo(Ar 1 )(Ar 2 ) The liquid mixture of compounds contains greater than 60 mole % EtBz and less than about 1 mole % each of Bz and EtBz.

[0025] In one embodiment, Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains less than about 1 mol % of each of Bz and / or EtBz. In one embodiment, 1 )(Ar 2 ) compounds contain less than about 0.5 mol % each of Bz and / or EtBz. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds contain less than about 0.1 mol % each of Bz and / or EtBz. In one embodiment, Mo(Ar 1 )(Ar 2 ) The liquid mixture of compounds does not contain each of Bz and / or Et3Bz.

[0026] In another embodiment, the disclosed and claimed subject matter provides a Mo(Ar)-based zeolite comprising (i) about 60 mol % to about 95 mol % EtBz, and (ii) at least 5 mol % dimethylbenzene ligands (“Me2Bz”). 1 )(Ar 2) compounds. Liquid Mo(Ar) containing both EtBz and Me2Bz 1 )(Ar 2 ) compounds are more attractive because Mo(EtBz)2 and Mo(Me2Bz)2 and Mo(EtBz)(Me2Bz) have the same MW and the same expected boiling point or vapor pressure.

[0027] In one embodiment, the special mixture is Mo(Ar 1 )(Ar 2 ) compounds, comprising: (i) Ar 1 and Ar 2 are different arenes, and (ii) Ar 1 and Ar 2 each have the same number of carbons, and (iii) the composition is liquid within a temperature range of about 20°C to about 35°C. 1 )(Ar 2 ) compounds.

[0028] In another embodiment, the special mixture is Mo(Ar 1 )(Ar 2 ) compounds, comprising: (i) Ar 1 and Ar 2 are different arene structures, and (ii) Ar 1 and Ar 2 each have substantially the same or the same molecular weight, and (iii) the composition is liquid within a temperature range of about 20°C to about 35°C. 1 )(Ar 2 ) compounds.

[0029] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter, and which are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and, together with the detailed description, serve to explain the principles of the disclosed subject matter. [Brief explanation of the drawings]

[0030] [Figure 1] 1 shows the H NMR of greater than 97% compositionally pure Mo(EtBz)2 of Example 6.

[0031] [Figure 2] 1 shows the DSC of greater than 97% compositionally pure Mo(EtBz)2 from Example 6.

[0032] [Figure 3] 1 shows the TGA of greater than 97% compositionally pure Mo(EtBz)2 from Example 6.

[0033] [Figure 4] 1 shows the H NMR of the composition of Example 10, which contains a mixture of 60% Mo(EtBz), 30% Mo(EtBz)(m-xylene), and 10% Mo(m-xylene). DETAILED DESCRIPTION OF THE INVENTION

[0034] All references cited in this specification, including publications, patent applications, and patents, are herein incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0035] In the context of describing the disclosed and claimed subject matter (particularly in the context of the claims below), the use of the terms "a," "an," and "the," and similar references, should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better elucidate the disclosed and claimed subject matter and does not impose limitations on the scope of the disclosed and claimed subject matter unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed and claimed subject matter. The use of the terms "comprising" or "including" in the specification and claims includes the narrower language of "consisting essentially of" and "consisting of."

[0036] Embodiments of the disclosed and claimed subject matter are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed subject matter. Variations of these embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors anticipate that skilled artisans will employ such variations as appropriate, and the inventors intend for the disclosed and claimed subject matter to be practiced otherwise than as specifically described herein. Accordingly, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Furthermore, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosed and claimed subject matter unless otherwise indicated herein or clearly contradicted by context.

[0037] It will be understood that the term "silicon" deposited as a material on a microelectronic device includes polysilicon.

[0038] For ease of reference, "microelectronic device" or "semiconductor device" corresponds to semiconductor wafers having integrated circuits, memory, and other electronic structures fabricated for use in microelectronic, integrated circuit, or computer chip applications, as well as other products including flat panel displays, phase change memory devices, solar panels and solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS). Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. It should be understood that the terms "microelectronic device" or "semiconductor device" are not intended to be limiting in any way and include any substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0039] As defined herein, the term "barrier material" corresponds to any material used in the art to encapsulate metal lines, e.g., copper interconnects, to minimize the diffusion of the metal, e.g., copper, into dielectric materials. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals, as well as their nitrides and silicides.

[0040] As used herein, the term "arene" refers to a cyclic hydrocarbon (i.e., aromatic ring) having alternating double and single bonds between carbon atoms, and also includes heteroarenes in which one or more carbon atoms forming such an aromatic ring are replaced by a heteroatom (e.g., oxygen, sulfur, nitrogen, silicon, germanium, phosphorus). Examples of arenes include, for example, benzene, substituted benzene, naphthalene, anthracene, etc. Examples of heteroarenes include, for example, pyridine, furan, indole, benzimidazole, thiophene, benzothiazole, etc.

[0041] "Substantially free" is defined herein as less than 0.001% by weight. The term "free" means 0.000% by weight. As used herein, "about" or "approximately" is intended to correspond to ±5% of the stated value. The terms "substantially free" and "free" may also relate to halide ions (or halides), such as, for example, chloride, fluoride, bromide, and iodide. The level of halide impurities is less than 100 ppm (by weight) as measured by ion chromatography (IC), preferably less than 25 ppm as measured by IC, more preferably less than 5 ppm as measured by IC, and most preferably 0 ppm as measured by IC. Furthermore, the terms "substantially free" or "free" refer to the presence or absence of Li as an impurity in the molybdenum arene compound. + , Na + , K. + , Mg 2+ , Ca 2+ , Al 3+ , Fe 2+ , Fe3+ , Ni 2+ and Cr 3+ It can also be said that the material is substantially free of metal ions such as Li, Na, K, Mg, Ca, Al, Fe, Ni, and Cr. As used herein, the term "substantially free" refers to less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably 0.1 ppm of each of these metals as measured by ICP-MS or other analytical method for measuring the metal.

[0042] In all such compositions where a particular component of a composition is discussed with reference to a weight percent (or wt. %) range including a lower limit of zero, it will be understood that such component may or may not be present in various specific embodiments of the composition, and that when present, such component may be present in concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such component is used. Note that all percentages of components are weight percents and are based on the total weight of the composition, i.e., 100%. References to "one or more" or "at least one" include "two or more" and "three or more," etc.

[0043] Where applicable, all weight percentages are "neat" unless otherwise indicated, meaning that they do not include the aqueous solution present when added to the composition. For example, "neat" refers to the weight percent amount of undiluted acid or other material (i.e., a 100g inclusion of 85% phosphoric acid consists of 85g of acid and 15 grams of diluent).

[0044] Furthermore, when referring to compositions described herein in terms of weight percent, it is understood that the weight percent of all components, including non-essential components such as impurities, never exceeds 100 weight percent. In a composition "consisting essentially of" listed components, such components may add up to 100 weight percent of the composition, or may add up to less than 100 weight percent. Where components add up to less than 100 weight percent, such compositions may contain small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 weight percent or less of impurities. In another embodiment, the formulation may contain less than 1 weight percent of impurities. In a further embodiment, the formulation may contain less than 0.05 weight percent of impurities. In other such embodiments, the components may form at least 90 weight percent, more preferably at least 95 weight percent, more preferably at least 99 weight percent, more preferably at least 99.5 weight percent, and most preferably at least 99.9 weight percent, and may include other components that do not significantly affect the performance of the wet etchant. Otherwise, it is understood that the composition of all essential components essentially totals 100% by weight in the absence of significant non-essential impurity components.

[0045] As will be appreciated by those skilled in the art, in the disclosed and claimed subject matter, the Mo compositions include arene (Ar) ligands, or simply “arenes.” The following abbreviations are used herein for these arene ligands: [Table 1] Unless a particular isomer of a given arene is specified, it is understood that recitation of an arene that may contain multiple isomers can include any single or mixture of such isomers. Thus, for example, when the abbreviation "Me2Bz" is used, it is understood to include any one of o-Me2Bz, m-Me2Bz, and p-Me2Bz, a mixture of two or more of o-Me2Bz, m-Me2Bz, and p-Me2Bz, or all three of o-Me2Bz, m-Me2Bz, and p-Me2Bz.

[0046] The headings used herein are not intended to be limiting; rather, they are included for organizational purposes only.

[0047] Disclosed and claimed Mo(Ar 1 )(Ar 2 )composition

[0048] I. Improved Mo(Ar 1 )(Ar 2 )composition

[0049] As disclosed above, in one aspect, the disclosed and claimed subject matter provides a Mo(Ar)-based ion exchange copolymer, comprising (i) about 60 mole % to about 95 mole % ethylbenzene ligand (“EtBz”), and (ii) reduced amounts of other undesirable ligands, wherein the mixture of compounds is a liquid below 35° C. 1 )(Ar 2 In a further embodiment, a mixture of liquid Mo(Ar 1 )(Ar 2 ) the composition further comprises (iii) at least 5 mole % dimethylbenzene ligands (“Me2Bz”).

[0050] In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds, the liquid mixture includes (i) about 60 mol % to about 95 mol % EtBz, (iia) about 0.25 mol % to about 13 mol % Bz, (iib) about 6.75 mol % to about 44.5 mol % EtBz, and (iic) about 0.75 mol % to about 7 mol % EtBz. In a further aspect of this embodiment, Mo(Ar 1 )(Ar 2 ) the liquid mixture of compounds further comprises (iii) at least 5 mol % Me2Bz.

[0051] In one embodiment, Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds is liquid within a temperature range of about 20° C. to about 35° C. In one embodiment, 1 )(Ar 2The liquid mixture of Mo(Ar) compounds is liquid at temperatures below about 35° C. In one embodiment, 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds is liquid at temperatures below about 30° C. In one embodiment, 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds is liquid at temperatures below about 25° C. In one embodiment, 1 )(Ar 2 ) The liquid mixture of compounds is liquid at temperatures below about 20°C.

[0052] In one embodiment, Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds has a viscosity of about 500 cP or less. 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds has a viscosity of about 250 cP or less. 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds has a viscosity of about 100 cP or less. 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds has a viscosity of about 50 cP or less. 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds has a viscosity of about 25 cP or less. 1 )(Ar 2 ) The liquid mixture of compounds has a viscosity of about 15 cP or less.

[0053] Ligand content

[0054] (i) Ethylbenzene (“EtBz”) ligand

[0055] As noted above, in one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 60 mol % to about 95 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2The liquid mixture of Mo(Ar) compounds contains 60 mol % to about 90 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains 65 mol % to about 85 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar) 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains 70 mol % to about 80 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains 60 mol % to about 65 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar) 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains 65 mol % to about 70 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar) 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains 70 mol % to about 75 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar) 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains 75 mol % to about 80 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar) 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains 80 mol % to about 85 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains 85 mol % to about 90 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains 85 mole % to about 95 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar) 1 )(Ar 2 The liquid mixture of compounds contains 90 mole % to about 95 mole % EtBz.

[0056] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2) compounds comprises about 60 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 65 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 70 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 75 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 80 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 85 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 90 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 91 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 92 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 93 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 94 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of compounds contains about 95 mole % EtBz.

[0057] (ii) Undesirable ligand content

[0058] As noted above, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains reduced amounts of undesired ligands, namely, (1) benzene ligand (Bz), (2) diethylbenzene ligand (EtBz, three isomers), and (3) triethylbenzene ligand (EtBz, three isomers). As will be appreciated by those skilled in the art, the liquid mixture of Mo(Ar) compounds contains reduced amounts of undesired ligands, namely, (1) benzene ligand (Bz), (2) diethylbenzene ligand (EtBz, three isomers), and (3) triethylbenzene ligand (EtBz, three isomers). 1 )(Ar 2 ) The total amount of EtBz and any one or more undesirable ligands in a given liquid mixture of compounds does not exceed 100 mole %.

[0059] (iia) benzene ligand (“Bz”)

[0060] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 0.25 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 0.5 mol % to about 10 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 1 mol % to about 10 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 0.25 mol % to about 5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 0.75 mol % to about 5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 1 mol % to about 5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2The liquid mixture of Mo(Ar) compounds contains about 2.5 mol % to about 5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 5 mol % to about 10 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 5 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 6 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 7 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 7.5 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of compounds contains about 10 mol % to about 13 mol % of Bz.

[0061] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds include about 0.25 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 0.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 0.75 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 1 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2) compounds contains about 1.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 2.0 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 2.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 3 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 3.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 4 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 4.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 5.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 6 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 6.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 7 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2) compounds contains about 7.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 8 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 8.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 9 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 9.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 10 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 10.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 11 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 11.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 12 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 12.5 mole % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of compounds contains about 13 mole % Bz.

[0062] (iib) Diethylbenzene Ligand (“Et2Bz”)

[0063] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 6.75 mol % to about 44.5 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 6.75 mol % to about 10 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 10 mol % to about 15 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 15 mol % to about 20 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 20 mol % to about 25 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 25 mol % to about 30 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 30 mol % to about 35 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 35 mol % to about 40 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) The liquid mixture of compounds contains about 40 mol % to about 44.5 mol % Et2Bz.

[0064] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 6.75 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2) compounds contains about 7 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 8 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 9 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 10 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 15 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 20 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 25 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 30 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 35 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 40 mole % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) The liquid mixture of compounds contains about 44.5 mole % Et2Bz.

[0065] (iic) Triethylbenzene Ligand ("Et3Bz")

[0066] In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar2 ) composition comprises about 0.75 mol % to about 7 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 1 mol % to about 7 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar) 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 1.5 mol % to about 6.5 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 2 mol % to about 6 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar) 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 3 mol % to about 5 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 1 mol % to about 3 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 1 mol % to about 5 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar) 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 1 mol % to about 4 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds contains about 1 mol % to about 3 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) The liquid mixture of compounds contains about 1 mol % to about 2 mol % Et3Bz.

[0067] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds includes about 0.75 mole % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar2 ) compounds contains about 1 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 1.5 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 2 mole % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 2.5 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 3 mole % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 3.5 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 4 mole % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 4.5 mole % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 5 mole % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 5.5 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 6 mole % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 6.5 mol % Et3Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2) The liquid mixture of compounds contains about 7 mole % Et3Bz.

[0068] combination

[0069] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds includes EtBz and one or more of (1) benzene ligand (Bz), (2) diethylbenzene ligand (EtBz), and (3) triethylbenzene ligand (EtBz), with the total Ar ligand not exceeding 100 mole percent. In this regard, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of Mo(Ar) compounds includes the EtBz ligand and any combination of one or more of the above-mentioned ligands, and amounts thereof. For example, in one embodiment, Mo(Ar) 1 )(Ar 2 ) The liquid mixture of compounds comprises: (i) about 0.25 mol % to about 13 mol % Bz ligand, (ii) about 6.75 mol % to about 44.5 mol % EtBz ligand, and (iii) about 0.75 mol % to about 7 mol % EtBz, the total amount of ligands not exceeding 100 mol %.

[0070] II. Special Mo(Ar 1 )(Ar 2 )composition

[0071] In another aspect, the disclosed and claimed subject matter provides a compound comprising Mo(Ar 1 )(Ar 2 ) a specific mixture of compounds, comprising: (i) Ar 1 and Ar 2 are different, and (ii) Ar 1 and Ar 2 The ligand comprises more than 95 mol% of the arene ligands present, such as Mo(Ar 1 )(Ar 2 In another aspect, the disclosed and claimed subject matter relates to a specific mixture of Mo(Ar) compounds. 1 )(Ar 2 ) a specific mixture of compounds, comprising: (i) Ar 1 and Ar2 are different, and (ii) Ar 1 and Ar 2 The ligand comprises more than about 97 mol % of the arene ligands present. 1 )(Ar 2 In another aspect, the disclosed and claimed subject matter relates to a specific mixture of Mo(Ar) compounds. 1 )(Ar 2 ) a specific mixture of compounds, comprising: (i) Ar 1 and Ar 2 are different, and (ii) Ar 1 and Ar 2 The ligand comprises at least about 97 mole % of the arene ligands present. 1 )(Ar 2 In another aspect, the disclosed and claimed subject matter relates to a specific mixture of Mo(Ar) compounds. 1 )(Ar 2 ) a specific mixture of compounds, comprising: (i) Ar 1 and Ar 2 are different, and (ii) Ar 1 and Ar 2 The ligand comprises at least about 99 mole % of the arene ligands present. 1 )(Ar 2 ) relating to a special mixture of compounds.

[0072] In another aspect, the disclosed and claimed subject matter provides a compound comprising Mo(Ar 1 )(Ar 2 ) a specific mixture of compounds, comprising: (i) Ar 1 and Ar 2 are different, and (ii) Ar 1 and Ar 2 The ligand comprises more than 95 mol% of the arene ligands present, such as Mo(Ar 1 )(Ar 2 In another aspect, the disclosed and claimed subject matter relates to a specific mixture of Mo(Ar) compounds. 1 )(Ar 2 ) a specific mixture of compounds, comprising: (i) Ar 1 and Ar 2 are different, and (ii) Ar 1 and Ar2 (iii) the compound is a liquid, Mo(Ar 1 )(Ar 2 In another aspect, the disclosed and claimed subject matter relates to a specific mixture of Mo(Ar) compounds. 1 )(Ar 2 ) a specific mixture of compounds, comprising: (i) Ar 1 and Ar 2 are different, and (ii) Ar 1 and Ar 2 The ligand comprises at least about 97 mole % of the arene ligands present. 1 )(Ar 2 In another aspect, the disclosed and claimed subject matter relates to a specific mixture of Mo(Ar) compounds. 1 )(Ar 2 ) a specific mixture of compounds, comprising: (i) Ar 1 and Ar 2 are different, and (ii) Ar 1 and Ar 2 The ligand comprises at least about 99 mole % of the arene ligands present. 1 )(Ar 2 ) relating to a special mixture of compounds.

[0073] In one embodiment, Mo(Ar 1 )(Ar 2 The special mixture of Mo(Ar) compounds has a viscosity of about 500 cP or less. 1 )(Ar 2 The special mixture of Mo(Ar) compounds has a viscosity of about 250 cP or less. 1 )(Ar 2 The special mixture of Mo(Ar) compounds has a viscosity of about 100 cP or less. 1 )(Ar 2 The special mixture of Mo(Ar) compounds has a viscosity of about 50 cP or less. 1 )(Ar 2 The special mixture of Mo(Ar) compounds has a viscosity of about 25 cP or less. 1 )(Ar2 ) The particular mixture of compounds has a viscosity of about 15 cP or less.

[0074] Specific embodiment 1

[0075] In one embodiment, the special mixture is Mo(Ar 1 )(Ar 2 ) compounds, comprising: (i) Ar 1 and Ar 2 are different arenes, and (ii) Ar 1 and Ar 2 each have the same number of carbons, Mo(Ar 1 )(Ar 2 In one embodiment, the specific mixture includes Mo(Ar 1 )(Ar 2 ) compounds, comprising: (i) Ar 1 and Ar 2 are different arenes, and (ii) Ar 1 and Ar 2 each have the same number of carbons, and (iii) the compound is liquid within a temperature range of about 20°C to about 35°C. 1 )(Ar 2 ) compounds.

[0076] In one aspect of this embodiment, Ar 1 and Ar 2 At least one of Ar contains one or more substituents selected from an unsubstituted linear C1-C6 alkyl group, a linear C1-C6 alkyl group substituted with a halogen, a linear C1-C6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, or a branched C3-C6 alkyl group substituted with an amino group, an unsubstituted amine, or a substituted amine. 1 and Ar 2 At least one of Ar contains one or more substituents that are C1-C6 alkyl groups. 1 and Ar 2 At least one of Ar includes one or more substituents that are linear C1-C6 alkyl groups substituted with halogen. 1 and Ar2 At least one of Ar contains one or more substituents that are linear C1-C6 alkyl groups substituted with amino groups. 1 and Ar 2 At least one of Ar includes one or more substituents that are unsubstituted branched C3-C6 alkyl groups. 1 and Ar 2 At least one of Ar includes one or more substituents that are branched C3-C6 alkyl groups substituted with halogen. 1 and Ar 2 At least one of Ar contains one or more substituents that are branched C3-C6 alkyl groups substituted with amino groups. 1 and Ar 2 In one embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 At least one of the groups contains two substituents.

[0077] In one aspect of this embodiment, Ar 1 and Ar 2each of Ar includes one or more different substituents selected from an unsubstituted linear C1-C6 alkyl group, a linear C1-C6 alkyl group substituted with a halogen, a linear C1-C6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, or a branched C3-C6 alkyl group substituted with an amino group, an unsubstituted amine, or a substituted amine. 1 and Ar 2 Each of Ar includes one or more substituents that are C1-C6 alkyl groups. 1 and Ar 2 Each of Ar includes one or more substituents that are linear C1-C6 alkyl groups substituted with halogen. 1 and Ar 2 Each of Ar includes one or more substituents that are linear C1-C6 alkyl groups substituted with amino groups. 1 and Ar 2 Each of Ar includes one or more substituents that are unsubstituted branched C3-C6 alkyl groups. 1 and Ar 2 Each of Ar includes one or more substituents that are branched C3-C6 alkyl groups substituted with halogen. 1 and Ar 2 Each of Ar includes one or more substituents that are branched C3-C6 alkyl groups substituted with amino groups. 1 and Ar 2 Each of Ar contains one or more substituents that are unsubstituted amines. 1 and Ar 2 Each of Ar contains one or more substituents that are substituted amines. 1 and Ar 2 Each of Ar contains one or more substituents that are C1-C3 alkyl groups. 1 and Ar 2 Each of Ar contains one or more substituents that are methyl groups. 1 and Ar 2 Each of Ar contains one or more substituents that are ethyl groups. 1and Ar 2 Each of Ar contains one or more substituents that are propyl groups. 1 and Ar 2 Each of Ar contains one substituent. 1 and Ar 2 Each of the groups contains two substituents.

[0078] In one aspect, Ar 1 and Ar 2 At least one of Ar is a five-membered arene. 1 and Ar 2 At least one of Ar is a six-membered arene. 1 and Ar 2 At least one of Ar is a five-membered heterocyclic arene. 1 and Ar 2 At least one of Ar is a 6-membered heterocyclic arene. 1 and Ar 2 is a five-membered cyclic arene. 1 and Ar 2 is a six-membered cyclic arene. 1 and Ar 2 is a five-membered heterocyclic arene. 1 and Ar 2 is a 6-membered heterocyclic arene. 1 and Ar 2 At least one of Ar is a substituted benzene, pyridine, pyrrole, furan, and thiophene. 1 and Ar 2 are substituted benzenes, pyridines, pyrroles, furans, and thiophenes, respectively.

[0079] B. Special Embodiment 2

[0080] In another embodiment, the special mixture is Mo(Ar 1 )(Ar 2 ) compounds, comprising: (i) Ar 1 and Ar 2are different arene structures, and (ii) Ar 1 and Ar 2 each having substantially the same or the same molecular weight, Mo(Ar 1 )(Ar 2 In another embodiment, the specific mixture includes Mo(Ar 1 )(Ar 2 ) compounds, comprising: (i) Ar 1 and Ar 2 are different arene structures, and (ii) Ar 1 and Ar 2 each have substantially the same or the same molecular weight, and (iii) the compound is liquid within a temperature range of about 20°C to about 35°C. 1 )(Ar 2 As one skilled in the art will appreciate, in these embodiments, Bz does not have isomers, and therefore Ar 1 Also Ar 2 This is also impossible in Bz.

[0081] In one aspect of this embodiment, Ar 1 and Ar 2 At least one of Ar contains one or more substituents selected from an unsubstituted linear C1-C6 alkyl group, a linear C1-C6 alkyl group substituted with a halogen, a linear C1-C6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, or a branched C3-C6 alkyl group substituted with an amino group, an unsubstituted amine, or a substituted amine. 1 and Ar 2 At least one of Ar contains one or more substituents that are C1-C6 alkyl groups. 1 and Ar 2 At least one of Ar includes one or more substituents that are linear C1-C6 alkyl groups substituted with halogen. 1 and Ar 2 At least one of Ar contains one or more substituents that are linear C1-C6 alkyl groups substituted with amino groups. 1 and Ar 2At least one of Ar includes one or more substituents that are unsubstituted branched C3-C6 alkyl groups. 1 and Ar 2 At least one of Ar includes one or more substituents that are branched C3-C6 alkyl groups substituted with halogen. 1 and Ar 2 At least one of Ar contains one or more substituents that are branched C3-C6 alkyl groups substituted with amino groups. 1 and Ar 2 In one embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 In one preferred embodiment, at least one of Ar 1 and Ar 2 At least one of the groups contains two substituents.

[0082] In one aspect of this embodiment, Ar 1 and Ar 2each of Ar includes one or more different substituents selected from an unsubstituted linear C1-C6 alkyl group, a linear C1-C6 alkyl group substituted with a halogen, a linear C1-C6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, or a branched C3-C6 alkyl group substituted with an amino group, an unsubstituted amine, or a substituted amine. 1 and Ar 2 Each of Ar includes one or more substituents that are C1-C6 alkyl groups. 1 and Ar 2 Each of Ar includes one or more substituents that are linear C1-C6 alkyl groups substituted with halogen. 1 and Ar 2 Each of Ar includes one or more substituents that are linear C1-C6 alkyl groups substituted with amino groups. 1 and Ar 2 Each of Ar includes one or more substituents that are unsubstituted branched C3-C6 alkyl groups. 1 and Ar 2 Each of Ar includes one or more substituents that are branched C3-C6 alkyl groups substituted with halogen. 1 and Ar 2 Each of Ar includes one or more substituents that are branched C3-C6 alkyl groups substituted with amino groups. 1 and Ar 2 Each of Ar contains one or more substituents that are unsubstituted amines. 1 and Ar 2 Each of Ar contains one or more substituents that are substituted amines. 1 and Ar 2 Each of Ar contains one or more substituents that are C1-C3 alkyl groups. 1 and Ar 2 Each of Ar contains one or more substituents that are methyl groups. 1 and Ar 2 Each of Ar contains one or more substituents that are ethyl groups. 1and Ar 2 Each of Ar contains one or more substituents that are propyl groups. 1 and Ar 2 Each of Ar contains one substituent. 1 and Ar 2 Each of the groups contains two substituents.

[0083] In one aspect, Ar 1 and Ar 2 At least one of Ar is a five-membered arene. 1 and Ar 2 At least one of Ar is a six-membered arene. 1 and Ar 2 At least one of Ar is a five-membered heterocyclic arene. 1 and Ar 2 At least one of Ar is a 6-membered heterocyclic arene. 1 and Ar 2 is a five-membered cyclic arene. 1 and Ar 2 is a six-membered cyclic arene. 1 and Ar 2 is a five-membered heterocyclic arene. 1 and Ar 2 is a 6-membered heterocyclic arene. 1 and Ar 2 At least one of Ar is a substituted benzene, pyridine, pyrrole, furan, and thiophene. 1 and Ar 2 are substituted benzenes, pyridines, pyrroles, furans, and thiophenes, respectively.

[0084] Representative specific embodiments

[0085] In the above embodiment, preferred arene ligands include: [Table 2]

[0086] As one of ordinary skill in the art will appreciate, in some embodiments, some arenes may comprise mixtures of isomers. Unless a particular isomer of a given arene is specified, it is understood that the recitation of an arene that may comprise multiple isomers may include any single or mixture of such isomers. Thus, for example, when the abbreviation "Me2Bz" is used, it is understood to include any one of o-Me2Bz, m-Me2Bz, and p-Me2Bz, a mixture of two or more of o-Me2Bz, m-Me2Bz, and p-Me2Bz, or all three of o-Me2Bz, m-Me2Bz, and p-Me2Bz.

[0087] In the above embodiment, the preferred Mo(Ar 1 )(Ar 2 ) compounds include the following: [Table 3]

[0088] Mo(Ar 1 )(Ar 2 ): ethylbenzene (EtBz) and dimethylbenzene ("Me2Bz") ligands

[0089] A preferred embodiment of the special mixture is Mo(Ar 1 )(Ar 2 ) compounds, comprising: (i) Ar 1 and Ar 2 One of them is ethylbenzene ("EtBz"), and the other is Ar 1 and Ar 2 The other is dimethylbenzene ("Me2Bz"), Mo(Ar 1 )(Ar 2 ) compounds. As mentioned above, these Mo(Ar 1 )(Ar 2 ) compounds, Ar 1 and Ar 2The ligands constitute 100 mol % of the arene ligands present. Thus, in this embodiment, the arene ligands other than EtBz and Me2Bz are Mo(Ar 1 )(Ar 2 ) is not present in the compound (i.e., the mole % of EtBz + the mole % of Me2Bz equals 100 mole % of the arene ligands present).

[0090] In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2 ) compound contains up to about 95 mol % EtBz and at least about 5 mol % MeBz. In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2 ) compound contains about 95 mol % to about 60 mol % EtBz and about 5 mol % to about 40 mol % MeBz. In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2 ) compound contains about 95 mol % to about 90 mol % EtBz and about 5 mol % to about 10 mol % MeBz. In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2 ) compound contains about 90 mol % to about 85 mol % EtBz and about 10 mol % to about 15 mol % MeBz. In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2 ) compound contains about 85 mol % to about 80 mol % EtBz and about 15 mol % to about 20 mol % MeBz. In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2 ) compound contains about 80 mol % to about 75 mol % EtBz and about 20 mol % to about 25 mol % MeBz. In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2 ) compound contains about 75 mol % to about 70 mol % EtBz and about 25 mol % to about 30 mol % MeBz. In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2) compound contains about 70 mol % to about 65 mol % EtBz and about 30 mol % to about 35 mol % MeBz. In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2 ) The compound contains about 65 mol % to about 60 mol % EtBz and about 35 mol % to about 40 mol % Me2Bz.

[0091] How to use

[0092] The disclosed and claimed subject matter provides a method for depositing Mo(Ar) films using any chemical vapor deposition process known to those skilled in the art. 1 )(Ar 2 As used herein, the term "chemical vapor deposition process" refers to any process in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface to produce the desired deposition.

[0093] In one embodiment, the method includes depositing a molybdenum-containing film using an atomic layer deposition process (ALD) using Mo(Ar 1 )(Ar 2 ) compound mixtures. As used herein, the term "atomic layer deposition process" or ALD refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant) sequential surface chemistry that deposits films of materials on substrates of various compositions. While the precursors, reagents, and sources used herein may be described as "gaseous," it is understood that the precursors may be either liquids or solids that are transported into the reactor by direct vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, the vaporized precursor may be passed through a plasma generator. As used herein, the term "reactor" includes, but is not limited to, a reaction chamber, reaction vessel, or deposition chamber.

[0094] Mo(Ar 1 )(Ar 2Chemical vapor deposition processes that can utilize the above mixture of compounds include, but are not limited to, those used in the manufacture of semiconductor-type microelectronic devices, such as ALD and plasma-enhanced ALD (PEALD). In one embodiment, for example, a metal-containing film is deposited using an ALD process. In another embodiment, for example, a metal-containing film is deposited using a plasma-enhanced ALD (PEALD) process.

[0095] Mo(Ar 1 )(Ar 2 Suitable substrates onto which the mixture of SiO2 and SiO2 compounds can be deposited are not particularly limited and vary depending on the intended end use. For example, the substrate may be selected from oxides such as HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, or nitride-based films. Other substrates may include solid substrates such as metal substrates (e.g., Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt, and metal silicides (e.g., TiSi2, CoSi2, and NiSi2), metal nitride-containing substrates (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN), semiconductor materials (e.g., Si, SiGe, GaAs, InP, diamond, GaN, and SiC), insulators (e.g., SiO2, Si3N4, SiON, HfO2, Ta2O5, ZrO2, TiO2, Al2O3, and barium strontium titanate), and combinations thereof.

[0096] Such deposition methods and processes may utilize an oxidizing agent, which is typically introduced in gaseous form. Examples of suitable oxidizing agents include, but are not limited to, oxygen gas, water vapor, ozone, oxygen plasma, or mixtures thereof.

[0097] Deposition methods and processes may also involve the use of one or more purge gases. Purge gases, used to purge away unconsumed reactants and / or reaction by-products, are inert gases that do not react with the precursors. Exemplary purge gases include argon (Ar), nitrogen (N), helium (He), neon, and mixtures thereof. For example, a purge gas, such as Ar, is supplied into the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 10,000 seconds, thereby purging unreacted materials and any by-products that may remain in the reactor.

[0098] Deposition methods and processes require the addition of energy to the molybdenum arene precursor to induce a reaction and form a metal-containing film or coating on the substrate. Such energy can be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma, and combinations thereof. In some processes, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. When utilizing plasma, the plasma generation process can include a direct plasma generation process in which the plasma is generated directly within the reactor, or a remote plasma generation process in which the plasma is generated outside the reactor and fed into the reactor.

[0099] When utilized in such deposition methods and processes, Mo(Ar 1 )(Ar 2 The above mixture of compounds can be delivered to a reaction chamber, such as an ALD reactor, in a variety of ways. In some instances, a liquid delivery system can be utilized. In other instances, a combined liquid delivery and flash evaporation process unit, such as a turbo-vaporizer manufactured by MSP Corporation (Shoreview, MN), can be used to enable volumetric delivery of low-volatility materials, resulting in reproducible transport and deposition without thermal decomposition of the precursors.

[0100] When used in these deposition methods and processes, Mo(Ar 1 )(Ar 2 Formulations of mixtures of ZnO and ZnO compounds are particularly desirable because they can be mixed with or contain hydrocarbon solvents, which can be dried to sub-ppm levels of water. Exemplary hydrocarbon solvents that can be used with the precursors include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decalin). The disclosed and claimed precursors can also be stored and used in stainless steel containers. In certain embodiments, the hydrocarbon solvent is a high-boiling solvent or has a boiling point of 100°C or higher. The disclosed and claimed precursors can also be mixed with other suitable metal precursors, and the mixture used to simultaneously deliver both metals for the growth of bimetallic films.

[0101] A flow of argon and / or other gases was used as a carrier gas to measure Mo(Ar) during precursor pulsing. 1 )(Ar 2 ) into the reaction chamber. 1 )(Ar 2 ) When delivering the above mixture of compounds, the reaction chamber process pressure is 1 to 50 Torr, preferably 5 to 20 Torr.

[0102] Substrate temperature can be an important process variable in the deposition of high-quality metal-containing films. Typical substrate temperatures range from about 150°C to about 550°C. Higher temperatures can promote higher film growth rates.

[0103] In view of the above, one skilled in the art would understand that the disclosed and claimed subject matter is a compound capable of reacting Mo(Ar) in a chemical vapor deposition process such as 1 )(Ar 2It will be appreciated that the present invention further includes the use of mixtures of compounds.

[0104] In one embodiment, the disclosed and claimed subject matter includes a method for forming a Mo-containing film on at least one surface of a substrate, the method comprising: a. providing at least one surface of a substrate in a reaction vessel; b. Mo(Ar) as the metal source compound for the deposition process 1 )(Ar 2 ) forming a transition metal-containing film on at least one surface by a thermal chemical vapor deposition (CVD) or atomic layer deposition (ALD) process using one or more of the mixture of compounds. In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel. In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from the group consisting of water, diatomic oxygen, oxygen plasma, ozone, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from the group consisting of hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, a boron-containing compound, a silicon-containing compound, and combinations thereof.

[0105] In one embodiment, the disclosed and claimed subject matter includes a method of forming a Mo-containing film via a cyclic chemical vapor deposition (CCVD) process at a temperature greater than 300° C., the method comprising: a. providing a substrate to a reaction vessel; b. Add Mo(Ar) to the reaction vessel.1 )(Ar 2 ) introducing one of a mixture of compounds and a source gas; c. purging the reaction vessel with a second purge gas; d. sequentially repeating steps b to c until a transition metal-containing film of a desired thickness is obtained. In a further aspect of this embodiment, the source gas is one or more oxygen-containing source gases selected from water, diatomic oxygen, oxygen plasma, ozone, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the source gas is one or more nitrogen-containing source gases selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof. In a further aspect of this embodiment, the method further comprises applying energy to the one or more precursors, source gas, substrate, and combinations thereof, the energy being one or more of thermal, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma, and combinations thereof. In a further aspect of this embodiment, step b of the method further comprises introducing the precursor into the reaction vessel using a carrier gas flow to deliver vapor of the precursor to the reaction vessel. In a further aspect of this embodiment, step b of the method further comprises using a solvent medium comprising one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyltoluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene, and combinations thereof.

[0106] In one embodiment, the disclosed and claimed subject matter includes a method of forming a Mo-containing film via a thermal atomic layer deposition (ALD) process or a thermal ALD-like process, the method comprising: a. providing a substrate to a reaction vessel; b. Add Mo(Ar) to the reaction vessel. 1 )(Ar 2 ) introducing one of the mixtures of compounds; c. purging the reaction vessel with a first purge gas; d. introducing a source gas into the reaction vessel; e. purging the reaction vessel with a second purge gas; f. sequentially repeating steps b to e until a transition metal-containing film of a desired thickness is obtained. In a further aspect of this embodiment, the source gas is one or more oxygen-containing source gases selected from water, diatomic oxygen, ozone, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the source gas is one or more nitrogen-containing source gases selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof. In a further aspect of this embodiment, the method further comprises applying energy to the one or more precursors, source gases, substrate, and combinations thereof, the energy being one or more of thermal, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma, and combinations thereof. In a further aspect of this embodiment, step b of the method further comprises introducing the precursor into the reaction vessel using a carrier gas flow to deliver vapor of the precursor to the reaction vessel. In a further aspect of this embodiment, step b of the method further comprises using a solvent medium comprising one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyltoluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene, and combinations thereof. [Example]

[0107] Example

[0108] Reference will now be made to more specific embodiments of the present disclosure, as well as experimental results supporting such embodiments. The examples are provided below to more fully explain the disclosed and claimed subject matter, and should not be construed as in any way limiting the disclosed subject matter.

[0109] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and the specific examples provided herein without departing from the spirit and scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the description provided by way of example below, is intended to cover modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.

[0110] Materials and Methods:

[0111] All reactions and manipulations described in the examples were carried out under a nitrogen atmosphere in an inert atmosphere glove box or using standard Schlenk techniques. All chemicals were received from Millipore-Sigma and Strem.

[0112] Comparative Example 1: Synthesis of Mo(EtBz)2 compound

[0113] 5.4 g of MoCl5 was slowly added to a suspension of 0.3 g of AlCl3 and 2.1 g of Al in 30 mL of anhydrous, deoxygenated ethylbenzene with stirring under nitrogen. The mixture was heated to 135°C, maintained at that temperature for 24 hours, and then cooled to room temperature. 20 mL of deoxygenated THF was then slowly added to the reaction. The mixture was heated to 100°C for 8 hours. After cooling to room temperature, volatiles were removed under vacuum. 60 mL of pentane was added, and the mixture was stirred for 1 hour. The dark green solution was slowly decanted into 25 mL of deoxygenated KOH solution in a 250 mL flask below 0°C. The green organic solution was separated from the mixture and washed with 25 mL of water. The green solution was dried over 10 g of anhydrous MgSO4. The solvent was removed to yield 3.7 g of a dark green liquid. Distillation at 130-170°C / 0.075-0.1 mmHg gave 1.65 g (30% yield) of pure product.

[0114] Comparative Example 2: Synthesis of Mo(EtBz)2 compound

[0115] 5.4 g of MoCl5 was slowly added to a suspension of 0.3 g of AlCl3 and 2.1 g of Al in 30 mL of anhydrous, deoxygenated ethylbenzene with stirring under nitrogen. The mixture was heated to 135°C, maintained at that temperature for 24 hours, and then cooled to room temperature. 20 mL of deoxygenated THF was then slowly added to the reaction. The mixture was heated to 100°C for 8 hours. After cooling to room temperature, volatiles were removed under vacuum. 60 mL of pentane was then added, and the mixture was stirred for 1 hour to form a suspension. The suspension was slowly added to 25 mL of deoxygenated KOH solution below 0°C. The green organic solution was separated from the mixture and washed with 25 mL of water. The green solution was dried over 10 g of anhydrous MgSO4. The solvent was removed to yield 4.0 g of a dark green liquid. Distillation at 130-170°C / 0.075-0.1 mmHg gave 2.2 g (40% yield) of pure product.

[0116] Example 3: Compositional analysis of comparative Mo(EtBz)2 compounds

[0117] The following analytical method was developed to analyze the Mo(EtBz)2 compound. A 50 mg sample was dissolved in 4 mL of toluene to form a green solution, which was oxidized with oxygen to yield a colorless solution containing the arene ligand and a brown solid (MoO species) after filtration. The colorless solution was used directly for GC-FID analysis. Results for the commercially available product from Strem and materials prepared as in Comparative Examples 1 and 2 are summarized in Table 1. GC analysis shows that the sample from Comparative Example 1 has a similar composition to the commercially available product from Strem. However, the sample from Comparative Example 2, when prepared by a different synthetic route, shows that the compound contains more than 40% Et2Bz and more than 6% Et3Bz. Thus, all of these samples contained less than 60 mol% EtBz in the mixture of arenes utilized in the Mo(arene)2 complex. [Table 4]

[0118] Comparative Example 4: Vacuum evaporation of commercial Mo(EtBz)

[0119] A 10.2 g sample from Strem was distilled under vacuum at different temperatures (135-153 °C). Three fractions (6.5 wt%, 68.6 wt%, and 18.6 wt%) were collected and analyzed by GC-FID. The results are summarized in Table 2. GC analysis indicates that the three fractions contain different components, which may result in inconsistent delivery during vacuum evaporation. [Table 5]

[0120] Example 5: Liquid Mo(Ar 1 )(Ar 2 ) compound (more than 60 mol% EtBz)

[0121] A mixture of Mo(EtBz)2 compounds (4.5 g) containing approximately 7.06% Bz, 41.52% EtBz, 44.48% Et2Bz, and 6.93% Et3Bz was dissolved in ethylbenzene (22.5 g) to form a green solution. The green solution was heated under nitrogen at 120°C, 125°C, and 135°C for 18 hours. After cooling the solution to room temperature, the black solid was filtered off, and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum below 90°C to yield a green residue (4.0 g). Distillation at 130-170°C and 0.1 mmHg yielded 3.2 g of product (80% yield). The product was analyzed by the GC-FID method described in Example 3, and the results are summarized in Table 3. [Table 6]

[0122] GC analysis shows that arene metathesis significantly altered the composition of the Mo(EtBz)2 mixture. Based on the data in Table 3, EtBz in the mixture increases from 41.5 mol % to over 64 mol % at 120 °C, 75 mol % at 125 °C, and 92 mol % at 135 °C. While the product remains liquid, the other ligands decrease to less than 0.5 mol % for Bz, less than 1 mol % for Et3Bz, and less than 8 mol % for Et2Bz at 135 °C.

[0123] Example 6: Mo(Ar) with a melting point below 50°C 1 )(Ar 2 Preparation of a mixture of the .sup.3) compound with more than 97 mol% EtBz The liquid product from Example 5c was purified by recrystallization to give a green solid. 3.5 g of the product was dissolved in 20 mL of hexane at room temperature. The dark green solution was cooled to -78 °C under dry ice / acetone to give a green solid. After filtration, 1.95 g of a green solid was isolated (55.7% yield). 1 The H NMR is shown in Figure 1: 1H NMR (CD, 500 MHz, 20 °C) δ 4.64 (d, 4 H, CHCHCH), 4.59 (t, 10 H, CHCHCH), 4.54 (t, 2 H, CHCHCH), 2.10 (q, 4 H, CHCHCH), 1.07 (t, 6 H, CHCHCH); the green solid was also analyzed by DSC and GC-FID as described in Example 3. DSC indicates that the green solid melts at 36.9 °C (Figure 2). TGA indicates a residue of 0.23% (Figure 3), and GC analysis as described in Example 3 indicates that the sample composition contains 97.17 mol% EtBz, 2.35 mol% EtBz, 0.48 mol% Bz, and less than 0.01 mol% EtBz.

[0124] Example 7: Preparation of a Substantially Chloride-Free Mo Arene Composition

[0125] Commercially available molybdenum arenes or those prepared by literature methods contain at least 27 ppm chloride, as measured by ion chromatography. Residual chloride can cause corrosion in stainless steel containers containing the molybdenum arenes and / or lead to unwanted chloride contamination of molybdenum-containing films deposited from the molybdenum arenes. The following procedure was effective in reducing chloride to less than 5 ppm. A sample of commercially available molybdenum arenes (5 g) was dissolved in hexane (100 mL) or MTBE (methyl tert-butyl ether) (100 mL) to form a green solution. The solution was washed twice with 50 mL of 10% KOH / HO solution. After separation, the organic solution was dried over anhydrous sodium sulfate. After filtration, the solution was passed through an adsorbent to yield a deep green solution. The volatiles were removed under vacuum to yield 4.8 g of a green liquid. The liquid was analyzed by ion chromatography. The results show that chloride was reduced from 27 ppm to less than 1 ppm.

[0126] Example 8: Viscosity of Mo Arene Compositions

[0127] The viscosity of a commercially available molybdenum arene composition (13.1% benzene, 54.0% ethylbenzene, 31.1% diethylbenzene, and 1.9% triethylbenzene) containing a mixture of various arene ligands and described in Example 3 was measured using capillary viscometer tubing and an ISO 17025 standard set available from Paragon Scientific Ltd. The viscosity was 15 cP at 20°C. The viscosity of the molybdenum arene composition with high amounts of diethylbenzene and triethylbenzene ligands from Example 2 was 20.5 cP. We found that the improved composition of the present invention (Sample 5c from Table 3 in Example 5) had a substantially lower viscosity of 11 cP at 20°C. This example suggests that reducing the amount of diethylbenzene and triethylbenzene ligands is important for reducing the viscosity of molybdenum arene compositions based on Mo(EtBz)2. A viscosity below 15 cP is important for effective delivery of precursors to a deposition tool by direct liquid injection.

[0128] Example 9: Preparation of Mo(m-Me2Bz)2 compound

[0129] Under nitrogen, 5.4 g of MoCl5 was slowly added to a stirring suspension of 2.6 g of AlCl3 and 1.0 g of Al in 30 mL of anhydrous, deoxygenated m-xylene. The mixture was heated to 135 °C for 20 h and cooled to room temperature. 60 mL of MTBE was then slowly added to the reaction mixture at room temperature. Next, 100 mL of cold 30% KOH solution was slowly added (dropwise at first) to the flask below 0 °C. After the addition of KOH, the flask was stirred for 4 h. The green organic fraction was then separated from the aqueous fraction and washed with water (100 mL). All volatiles were evaporated, and the residue was extracted with hexane / MTBE (100 / 100 mL) to give a dark green solution, which was dried over 10 g of Na2SO4 in a glovebox. After filtration in the glovebox, all volatiles were removed under vacuum to give a green solid. The green solid was washed with 10 mL of hexane to give 1.95 g of product (32% yield). The solid was analyzed by TGA and DSC. The melting point of the complex was found to be 104°C.

[0130] Example 10: Mo(Ar 1 )(Ar 2 Preparation of a liquid mixture of compounds (Ar 1 and Ar 2 are independently selected arenes, and Mo(EtBz)2 is approximately 60%.

[0131] A sample (10 g) of Mo(m-xylene)2 from Example 9 was dissolved in anhydrous ethylbenzene (80 g) to form a green suspension. The green suspension was heated to 120°C under nitrogen for 18 hours. After the solution was cooled to room temperature, the black solid was filtered off through silica gel and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum below 90°C to give a green liquid residue. After distillation at 130-150°C and 0.1 mmHg, 8.5 g of product was obtained in 85% yield. 1The product was characterized by H NMR spectroscopy (FIG. 4). The product is a liquid containing 60% Mo(EtBz)2, 30% Mo(EtBz)(m-xylene), and 10% Mo(m-xylene)2 based on NMR analysis. The TGA residue was 0.3%, and DSC showed an exothermic event at 272 °C. Mo(EtBz)2: 1 H NMR(C6D6,500MHz,20℃)δ 4.60(d,4 H,C6H5CH2CH3),4.54(t,10 H,C6H5CH2CH3),4.50(m,2 H,C6H5CH2CH3),2.09(q,4 H,C6H5CH2CH3),1.07(t,6 H,C6H5CH2CH3);Mo(EtBz)(m-xylene): 1 H NMR(C6D6,500MHz,20℃)δ 4.72(s,1 H,C6H5(CH3)2),4.54(m,1 H,C6H5(CH3)2),4.42(m,2 H,C6H5(CH3)2),2.01(q,2 H,C6H5CH2CH3),1.93(s,6 H,C6H5(CH2)2),1.09(t,3 H,C6H5CH2CH3);Mo(m-xylene)2: 1 H NMR(C6D6,500MHz,20℃)δ 4.54(s,2 H,C6H5(CH3)2),4.50(m,6 H,C6H5(CH3)2),1.84(s,12 H,C6H5(CH2)2)

[0132] Example 11: Mo(Ar 1 )(Ar 2 Preparation of a liquid mixture of compounds (Ar 1 and Ar 2 are each independently selected arenes, and Mo(EtBz)2 is approximately 80%.

[0133] A sample of Mo(m-xylene)2 (27 g) from Example 9 was dissolved in anhydrous ethylbenzene (135 g) to form a green suspension. The green suspension was heated to 120 °C under nitrogen for 24 hours. After cooling the solution to room temperature, the black solid was filtered off through silica gel, and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum to yield a green liquid residue. After distillation at 130-142 °C and 0.1 mmHg, 25 g of product was obtained in 92% yield. The product was characterized by NMR spectroscopy, and the composition was analyzed based on the peak integration described in Example 10. Based on NMR analysis, the product contains 80.5% Mo(EtBz)2, 18% Mo(EtBz)(m-xylene), and 1.5% Mo(m-xylene). The TGA residue was 0.013%, and DSC showed an exothermic event at 278 °C.

[0134] Example 12: Mo(Ar 1 )(Ar 2 Preparation of a liquid mixture of compounds (Ar 1 and Ar 2 are each independently selected arenes, and Mo(EtBz)2 is approximately 80%.

[0135] A sample of Mo(m-xylene)2 (69 g) from Example 9 was dissolved in anhydrous ethylbenzene (420 g) to form a green suspension. The green suspension was heated to 130 °C under nitrogen for 24 hours. After cooling the solution to room temperature, the black solid was filtered off through silica gel, and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum to yield a green liquid residue. After distillation at 130-140 °C and 0.15-0.2 mmHg, 61.5 g of product was obtained in 89% yield. The product was characterized by NMR spectroscopy, and the composition was analyzed based on the peak integration described in Example 10. Based on NMR analysis, the product contains 80% Mo(EtBz)2, 18% Mo(EtBz)(m-xylene), and 2% Mo(m-xylene). The TGA residue was 0.05%, and DSC showed an exothermic event at 280 °C.

[0136] Example 13: Mo(Ar 1 )(Ar2 Preparation of a liquid mixture of compounds (Ar 1 and Ar 2 are each independently selected arenes, and Mo(m-xylene)2 is greater than 15%.

[0137] A sample of Mo(m-xylene)2 (52 g) from Example 9 was dissolved in anhydrous ethylbenzene (290 g) to form a green suspension. The green suspension was heated to 132 °C under nitrogen for 24 hours. After cooling the solution to room temperature, the black solid was filtered through silica gel, and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum to yield a green liquid residue. After distillation at 130-140 °C and 0.15-0.2 mmHg, 47 g of product was obtained in 90% yield. The product was characterized by NMR spectroscopy, and the composition was analyzed based on the peak integration described in Example 10, and the results are summarized in Table 4. Based on NMR analysis, the product contained 65% Mo(EtBz)2, 19% Mo(EtBz)(m-xylene), and 16% Mo(m-xylene). After overnight, a solid formed in the flask. The TGA residue was 1% and the DSC showed an exothermic event at 272 ° C. This experiment indicates that the amount of residual Mo(m-xylene) should be less than 15 mol % to avoid the formation of solids in the desired liquid formulation.

[0138] Example 14: Mo(Ar 1 )(Ar 2 ) Viscosity of liquid mixtures of compounds (Ar 1 and Ar 2 are each independently selected arenes, and Mo(EtBz)2 is approximately 80%.

[0139] A sample of Mo(m-xylene)2 (55 g) from Example 9 was dissolved in anhydrous ethylbenzene (250 g) to form a green suspension. The green suspension was heated to 139.7 °C under nitrogen for 24 hours. After cooling the solution to room temperature, the black solid was filtered through silica gel, and the remaining green filtrate was collected. After filtering through silica gel, mirror Mo metal was found on top of the silica gel. All volatiles were removed from the green filtrate under vacuum to yield a green liquid residue. 50 g of product was obtained in 90% yield. The product was characterized by NMR spectroscopy, and the composition was analyzed based on the peak integrations described in Example 10, and the results are summarized in Table 4. Based on NMR analysis, the product contained 81% Mo(EtBz)2, 17.4% Mo(EtBz)(m-xylene), and 1.6% Mo(m-xylene). The viscosity of this sample was 10 MPa·s, substantially lower than that of commercially available compositions containing Mo(EtBz)2. Trace metal analysis by ICP-MS indicates that the composition contains less than 3 ppm aluminum. Ion chromatography also shows that the amount of residual chloride has been reduced to less than 1 ppm.

[0140] The compositions of the molybdenum arene mixtures from Examples 10-14 are summarized in Table 4. [Table 7]

[0141] Example 15: Mo(Ar 1 )(Ar 2 Preparation of a liquid mixture of compounds (Ar 1 and Ar 2 are independently selected arenes, and Mo(EtBz)2 is over 90%.

[0142] 110 g of the composition from Example 12 was dissolved in anhydrous ethylbenzene (120 g) to form a green suspension. The suspension was heated to 137° C. under nitrogen for 24 hours. After the solution was cooled to room temperature, the black solid was filtered through silica gel and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum to yield a green liquid residue. The product was characterized by NMR spectroscopy, and the composition was analyzed based on the peak integration described in Example 10. Based on NMR analysis, the product contains 90% Mo(EtBz)2, 9.5% Mo(EtBz)(m-xylene), and 0.5% Mo(m-xylene)2.

[0143] Example 16: Hot Hydrogen and Mo(Ar 1 )(Ar 2 Deposition of Mo-containing films using a liquid mixture of compounds (Ar 1 and Ar 2 are each independently selected arenes, and Mo(EtBz)2 is approximately 70%.

[0144] In the deposition process, a molybdenum arene compound containing 70.6% Mo(EtBz)2, 22.0% Mo(EtBz)(m-xylene), and 7.4% Mo(m-xylene)2 was delivered to the deposition reactor chamber by passing 50 sccm of argon through a stainless steel vessel filled with the compound and heated to 110°C. The chamber pressure was 20 Torr. The substrates were TiN, Cu, Pt, and SiO2. The Mo-containing films were deposited by a cyclic chemical vapor deposition (CCVD) process at 400°C. a. providing a substrate to a deposition reactor chamber; b. introducing molybdenum arene vapor into the deposition reactor chamber for 10 seconds; c. purging the deposition reactor chamber with argon purge gas for 30 seconds; d. introducing hydrogen gas into the deposition reactor chamber at 1000 sccm for 10 seconds; e. purging the deposition reactor chamber with an argon purge for 10 seconds; f. Repeating steps b to e consecutively 100 times. The film thicknesses of the molybdenum-containing films on different substrates are summarized in Table 5. [Table 8] The examples demonstrate the selective deposition of Mo-containing films onto Cu substrates.

[0145] Example 17: Diiodobutane and Mo(Ar 1 )(Ar 2 Deposition of Mo-containing films using a liquid mixture of compounds (Ar 1 and Ar 2 are each independently selected arenes, and Mo(EtBz)2 is approximately 70%.

[0146] In the deposition process, a molybdenum arene compound containing 70.6% Mo(EtBz)2, 22.0% Mo(EtBz)(m-xylene), and 7.4% Mo(m-xylene)2 was delivered to the deposition reactor chamber by passing 50 sccm of argon through a stainless steel vessel filled with the compound and heated to 110°C. The chamber pressure was 10 Torr. The substrates were TiN, Cu, Pt, and SiO2. A separate pulse of diiodobutane was also delivered to the deposition reaction chamber by passing 50 sccm of argon through a stainless steel vessel filled with diiodobutane and heated to 50°C. The Mo-containing films were deposited by a cyclic chemical vapor deposition (CCVD) process at 400°C. a. providing a substrate to a deposition reactor chamber; b. introducing molybdenum arene vapor into the deposition reactor chamber for 20 seconds; c. purging the deposition reactor chamber with argon purge gas for 30 seconds; d. introducing diiodobutane vapor into the deposition reactor chamber for 20 seconds; e. purging the deposition reactor chamber with an argon purge for 42 seconds; f. Repeating steps b to e consecutively 100 times. The film thicknesses of the molybdenum-containing films on different substrates are summarized in Table 6. [Table 9] The resistivity of the Mo-containing film deposited on silicon oxide was measured by the four-point probe method and was found to be 260 μOhm cm.

[0147] Example 18: Diiodobutane and Mo(Ar 1 )(Ar 2 Deposition of Mo-containing films using a liquid mixture of compounds (Ar 1 and Ar 2 are each independently selected arenes, and Mo(EtBz)2 is approximately 70%.

[0148] In the deposition process, a molybdenum arene compound containing 70.6% Mo(EtBz)2, 22.0% Mo(EtBz)(m-xylene), and 7.4% Mo(m-xylene)2 was delivered to the deposition reactor chamber by passing 50 sccm of argon through a stainless steel vessel filled with the compound and heated to 110°C. The chamber pressure was 10 Torr. The substrates were TiN, Cu, Pt, and SiO2. A separate pulse of diiodobutane was also delivered to the deposition reactor chamber by passing 50 sccm of argon through a stainless steel vessel filled with diiodobutane and heated to 50°C. The Mo-containing films were deposited by a cyclic chemical vapor deposition (CCVD) process at 300°C. a. providing a substrate to a deposition reactor chamber; b. introducing molybdenum arene vapor into the deposition reactor chamber for 20 seconds; c. purging the deposition reactor chamber with argon purge gas for 30 seconds; d. introducing diiodobutane vapor into the deposition reactor chamber for 2 seconds; e. purging the deposition reactor chamber with an argon purge for 42 seconds; f. Repeating steps b to e consecutively 100 times. The film thicknesses of the molybdenum-containing films on different substrates are summarized in Table 7. [Table 10] The resistivity of the Mo-containing film deposited on silicon oxide was measured by a four-point probe method and was found to be 131 μOhm cm. The examples demonstrate the deposition of Mo-containing films with resistivities of less than 150 μOhm cm. It is expected that further process optimization can reduce the film resistivity to less than 50 μOhm cm.

[0149] It is anticipated that the method of the present invention can be used with deposition tools commonly found in semiconductor manufacturing sites to produce molybdenum-containing layers for logic applications and other potential functions.

[0150] The foregoing description has been primarily for purposes of illustration. While the disclosed and claimed subject matter has been shown and described with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in form and detail thereof may be made without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. Mo(Ar) containing about 60 mol % to about 95 mol % EtBz ligands １ ) (Ar ２ ) compounds, wherein Ar １ and Ar ２ is an arene ligand, and the mole percentage is Ar １ and Ar ２ and the compound is a liquid. １ ) (Ar ２ ) A mixture of compounds.

2. 2. The Mo(Ar) of claim 1, wherein the mixture comprises about 60 mol % to about 90 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

3. 10. The Mo(Ar) of claim 1, wherein the mixture comprises about 65 mol % to about 85 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

4. 2. The Mo(Ar) of claim 1, wherein the mixture comprises about 70 mol % to about 80 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

5. 10. The Mo(Ar) of claim 1, wherein the mixture comprises about 60 mol % to about 65 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

6. 10. The Mo(Ar) of claim 1, wherein the mixture comprises about 65 mol % to about 70 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

7. 10. The Mo(Ar) of claim 1, wherein the mixture comprises about 70 mol % to about 75 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

8. 2. The Mo(Ar) of claim 1, wherein the mixture comprises about 75 mol % to about 80 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

9. 10. The Mo(Ar) of claim 1, wherein the mixture comprises about 80 mol % to about 85 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

10. 2. The Mo(Ar) of claim 1, wherein the mixture comprises about 85 mol % to about 90 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

11. 10. The Mo(Ar) of claim 1, wherein the mixture comprises about 90 mol % to about 95 mol % EtBz ligands. １ ) (Ar ２ ) A mixture of compounds.

12. 10. The Mo(Ar) of claim 1, wherein the mixture further comprises about 0.25 mol % to about 13 mol % of a Bz ligand, the total amount of ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

13. 10. The Mo(Ar) of claim 1, wherein the mixture further comprises about 5 mol % to about 13 mol % Bz ligand, the total amount of ligand not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

14. 10. The Mo(Ar) of claim 1, wherein the mixture further comprises about 5 mol % to about 10 mol % of a Bz ligand, the total amount of ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

15. 10. The Mo(Ar) of claim 1, wherein the mixture further comprises about 10 mol % to about 13 mol % of a Bz ligand, the total amount of ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

16. % of Et ２ 10. The Mo(Ar) of claim 1 further comprising a Bz ligand, the total amount of the ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

17. The mixture is from about 6.75 mol % to about 10 mol % Et ２ 10. The Mo(Ar) of claim 1 further comprising a Bz ligand, the total amount of the ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

18. The mixture is from about 10 mol % to about 15 mol % Et ２ 10. The Mo(Ar) of claim 1 further comprising a Bz ligand, the total amount of the ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

19. The mixture is from about 15 mol % to about 20 mol % Et ２ 10. The Mo(Ar) of claim 1 further comprising a Bz ligand, the total amount of the ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

20. The mixture comprises from about 0.75 mol % to about 7 mol % Et ３ 10. The Mo(Ar) of claim 1 further comprising a Bz ligand, the total amount of the ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

21. The mixture comprises from about 1 mol % to about 3 mol % Et ３ 10. The Mo(Ar) of claim 1 further comprising a Bz ligand, the total amount of the ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

22. The mixture is from about 3 mol % to about 7 mol % Et ３ 10. The Mo(Ar) of claim 1 further comprising a Bz ligand, the total amount of the ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

23. The mixture comprises about 1 mol % to about 2 mol % Et ３ 10. The Mo(Ar) of claim 1 further comprising a Bz ligand, the total amount of the ligands not exceeding 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

24. The mixture comprises: (i) about 0.25 mol % to about 13 mol % of a Bz ligand; (ii) about 6.75 mol % to about 44.5 mol % of an Et ２ Bz ligand, and (iii) about 0.75 mol % to about 7 mol % of Et ３ 2. The Mo(Ar) of claim 1 further comprising Bz, wherein the total amount of the ligands does not exceed 100 mol %. １ ) (Ar ２ ) A mixture of compounds.

25. The Mo(Ar １ ) (Ar ２ 10. The Mo(Ar) ion exchange composition of claim 1, wherein the mixture of Mo(Ar) ions has a viscosity of about 500 cP or less. １ ) (Ar ２ ) A mixture of compounds.

26. The Mo(Ar １ ) (Ar ２ 10. The Mo(Ar) ion exchange composition of claim 1, wherein the mixture of Mo(Ar) ions has a viscosity of about 250 cP or less. １ ) (Ar ２ ) A mixture of compounds.

27. The Mo(Ar １ ) (Ar ２ 10. The Mo(Ar) ion exchange composition of claim 1, wherein the mixture of Mo(Ar) ions has a viscosity of about 100 cP or less. １ ) (Ar ２ ) A mixture of compounds.

28. The Mo(Ar １ ) (Ar ２ 10. The Mo(Ar) ion exchange composition of claim 1, wherein the mixture of Mo(Ar) ions has a viscosity of about 50 cP or less. １ ) (Ar ２ ) A mixture of compounds.

29. The Mo(Ar １ ) (Ar ２ 10. The Mo(Ar) ion exchange composition of claim 1, wherein the mixture of Mo(Ar) ions has a viscosity of about 25 cP or less. １ ) (Ar ２ ) A mixture of compounds.

30. The Mo(Ar １ ) (Ar ２ 10. The method of claim 1, wherein the mixture of Mo(Ar) compounds has a viscosity of about 10 cP or less. １ ) (Ar ２ ) A mixture of compounds.

31. Mo(Ar １ ) (Ar ２ ) compounds, (i) Ar １ and Ar ２ each containing a different arene structure, (ii) Ar １ and Ar ２ each having the same number of carbon atoms, Mo(Ar １ ) (Ar ２ ) A mixture containing compounds.

32. 32. The mixture of claim 31, wherein the compound is liquid within a temperature range of about 20°C to about 35°C.

33. Ar １ and Ar ２ At least one of the following is an unsubstituted linear C １ ~C ６ Alkyl group, halogen-substituted linear C １ ~C ６ Linear C substituted with alkyl or amino groups １ ~C ６ Alkyl group, unsubstituted branched C ３ ~C ６ Alkyl group, branched C substituted with halogen ３ ~C ６ Branched C substituted with an alkyl group, an amino group, an unsubstituted amine or a substituted amine ３ ~C ６ 32. The mixture of claim 31, comprising one or more substituents selected from alkyl groups.

34. Ar １ and Ar ２ Each of the groups is an unsubstituted linear C １ ~C ６ Alkyl group, halogen-substituted linear C １ ~C ６ Linear C substituted with alkyl or amino groups １ ~C ６ Alkyl group, unsubstituted branched C ３ ~C ６ Alkyl group, branched C substituted with halogen ３ ~C ６ Branched C substituted with an alkyl group, an amino group, an unsubstituted amine or a substituted amine ３ ~C ６ 32. The mixture of claim 31, comprising one or more different substituents selected from alkyl groups.

35. Ar １ and Ar ２ At least one of the following is an unsubstituted linear C １ ~C ３ 32. The mixture of claim 31, comprising one or more substituents that are alkyl groups.

36. Ar １ and Ar ２ Each of the groups is an unsubstituted linear C １ ~C ３ 32. The mixture of claim 31, comprising one or more substituents that are alkyl groups.

37. Ar １ and Ar ２ Each of the １ ~C ３ 32. The mixture of claim 31, comprising one or more substituents that are alkyl groups.

38. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein each of comprises one or more substituents that are methyl groups.

39. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein each of comprises one or more substituents that are ethyl groups.

40. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein each of comprises one or more substituents that are propyl groups.

41. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein each of comprises one substituent or two substituents.

42. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein at least one of is a five-membered arene.

43. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein at least one of is a six-membered arene.

44. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein at least one of is a five-membered heterocyclic arene.

45. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein at least one of is a six-membered heterocyclic arene.

46. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein each of is a five-membered cyclic arene.

47. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein each of is a six-membered cyclic arene.

48. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein each of is a five-membered heterocyclic arene.

49. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein each of is a six-membered heterocyclic arene.

50. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein at least one of is a substituted benzene, pyridine, pyrrole, furan, or thiophene.

51. Ar １ and Ar ２ 32. The mixture of claim 31 , wherein each of is a substituted benzene, pyridine, pyrrole, furan, or thiophene.

52. Ar １ and Ar ２ One of the groups is EtBz, and Ar １ and Ar ２ The other is Me ２ 32. The mixture of claim 31, wherein the compound is Bz.

53. Ar １ and Ar ２ One of the groups is EtBz, and Ar １ and Ar ２ The other is meta-Me ２ 32. The mixture of claim 31, wherein the compound is Bz.

54. Mo(Ar １ ) (Ar ２ 32. The mixture of claim 31, wherein the mixture containing the .) compound has a viscosity of about 500 cP or less.

55. Mo(Ar １ ) (Ar ２ 32. The mixture of claim 31, wherein the mixture containing the .) compound has a viscosity of about 250 cP or less.

56. Mo(Ar １ ) (Ar ２ 32. The mixture of claim 31, wherein the mixture containing the .) compound has a viscosity of about 100 cP or less.

57. Mo(Ar １ ) (Ar ２ 32. The mixture of claim 31, wherein the mixture containing the .) compound has a viscosity of about 50 cP or less.

58. Mo(Ar １ ) (Ar ２ 32. The mixture of claim 31, wherein the mixture containing the .) compound has a viscosity of about 25 cP or less.

59. Mo(Ar １ ) (Ar ２ 32. The mixture of claim 31, wherein the mixture containing the .) compound has a viscosity of about 10 cP or less.

60. Mo(Ar １ ) (Ar ２ ) compounds, (i) Ar １ and Ar ２ each containing a different arene structure, (ii) Ar １ and Ar ２ each having substantially the same molecular weight, Mo(Ar １ ) (Ar ２ ) A mixture containing compounds.

61. 61. The mixture of claim 60, wherein the compound is liquid within a temperature range of about 20°C to about 35°C.

62. Ar １ and Ar ２ 61. The mixture of claim 60, wherein:

63. Ar １ and Ar ２ At least one of the following is an unsubstituted linear C １ ~C ６ Alkyl group, halogen-substituted linear C １ ~C ６ Linear C substituted with alkyl or amino groups １ ~C ６ Alkyl group, unsubstituted branched C ３ ~C ６ Alkyl group, branched C substituted with halogen ３ ~C ６ Branched C substituted with an alkyl group, an amino group, an unsubstituted amine or a substituted amine ３ ~C ６ 61. The mixture of claim 60, comprising one or more substituents selected from alkyl groups.

64. Ar １ and Ar ２ Each of the groups is an unsubstituted linear C １ ~C ６ Alkyl group, halogen-substituted linear C １ ~C ６ Linear C substituted with alkyl or amino groups １ ~C ６ Alkyl group, unsubstituted branched C ３ ~C ６ Alkyl group, branched C substituted with halogen ３ ~C ６ Branched C substituted with an alkyl group, an amino group, an unsubstituted amine or a substituted amine ３ ~C ６ 61. The mixture of claim 60, comprising one or more different substituents selected from alkyl groups.

65. Ar １ and Ar ２ At least one of the following is an unsubstituted linear C １ ~C ３ 61. The mixture of claim 60, comprising one or more substituents that are alkyl groups.

66. Ar １ and Ar ２ Each of the groups is an unsubstituted linear C １ ~C ３ 61. The mixture of claim 60, comprising one or more substituents that are alkyl groups.

67. Ar １ and Ar ２ Each of the １ ~C ３ 61. The mixture of claim 60, comprising one or more substituents that are alkyl groups.

68. Ar １ and Ar ２ 61. The mixture of claim 60, wherein each of comprises one or more substituents that are methyl groups.

69. Ar １ and Ar ２ 61. The mixture of claim 60, wherein each of comprises one or more substituents that are ethyl groups.

70. Ar １ and Ar ２ 61. The mixture of claim 60, wherein each of comprises one or more substituents that are propyl groups.

71. Ar １ and Ar ２ 61. The mixture of claim 60, wherein each of comprises one substituent or two substituents.

72. Ar １ and Ar ２ 61. The mixture of claim 60, wherein at least one of is a five-membered arene.

73. Ar １ and Ar ２ 61. The mixture of claim 60, wherein at least one of is a six-membered arene.

74. Ar １ and Ar ２ 61. The mixture of claim 60, wherein at least one of is a five-membered heterocyclic arene.

75. Ar １ and Ar ２ 61. The mixture of claim 60, wherein at least one of is a six-membered heterocyclic arene.

76. Ar １ and Ar ２ 61. The mixture of claim 60, wherein each of is a five-membered cyclic arene.

77. Ar １ and Ar ２ 61. The mixture of claim 60, wherein each of is a six-membered cyclic arene.

78. Ar １ and Ar ２ 61. The mixture of claim 60, wherein each of is a five-membered heterocyclic arene.

79. Ar １ and Ar ２ 61. The mixture of claim 60, wherein each of is a six-membered heterocyclic arene.

80. Ar １ and Ar ２ 61. The mixture of claim 60, wherein at least one of is a substituted benzene, pyridine, pyrrole, furan, or thiophene.

81. Ar １ and Ar ２ 61. The mixture of claim 60, wherein each of is a substituted benzene, pyridine, pyrrole, furan, or thiophene.

82. Ar １ and Ar ２ One of the groups is EtBz, and Ar １ and Ar ２ The other is Me ２ 61. The mixture of claim 60, wherein the compound is Bz.

83. Ar １ and Ar ２ One of the groups is EtBz, and Ar １ and Ar ２ The other is meta-Me ２ 61. The mixture of claim 60, wherein the compound is Bz.

84. Mo(Ar １ ) (Ar ２ 61. The mixture of claim 60, wherein the mixture containing the .) compound has a viscosity of about 500 cP or less.

85. Mo(Ar １ ) (Ar ２ 61. The mixture of claim 60, wherein the mixture containing the .) compound has a viscosity of about 250 cP or less.

86. Mo(Ar １ ) (Ar ２ 61. The mixture of claim 60, wherein the mixture containing the .) compound has a viscosity of about 100 cP or less.

87. Mo(Ar １ ) (Ar ２ 61. The mixture of claim 60, wherein the mixture containing the .) compound has a viscosity of about 50 cP or less.

88. Mo(Ar １ ) (Ar ２ 61. The mixture of claim 60, wherein the mixture containing the .) compound has a viscosity of about 25 cP or less.

89. Mo(Ar １ ) (Ar ２ 61. The mixture of claim 60, wherein the mixture containing the .) compound has a viscosity of about 15 cP or less.

90. 10. The Mo(Ar) of claim 1, wherein the mixture is substantially free of halide ions. １ ) (Ar ２ ) A mixture of compounds.

91. 10. The Mo(Ar) of claim 1, wherein the mixture is substantially free of chloride ions. １ ) (Ar ２ ) A mixture of compounds.

92. 32. The mixture of claim 31 , wherein the mixture is substantially free of halide ions.

93. 32. The mixture of claim 31 , wherein the mixture is substantially free of chloride ions.

94. 61. The mixture of claim 60, wherein the mixture is substantially free of halide ions.

95. 61. The mixture of claim 60, wherein the mixture is substantially free of chloride ions.

96. 1. A method for forming a transition metal-containing film on at least one surface of a substrate, comprising: a. providing the at least one surface of the substrate in a reaction vessel; b) forming a transition metal-containing film on said at least one surface by a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process using one or more of the mixtures of any one of claims 1 to 95.

97. 97. The process of claim 96, wherein forming the transition metal-containing film comprises chemical vapor deposition (CVD).

98. 97. The process of claim 96, wherein forming the transition metal-containing film comprises thermal chemical vapor deposition (CVD).

99. 97. The process of claim 96, wherein forming the transition metal-containing film comprises cyclic chemical vapor deposition (CCVD).

100. 97. The process of claim 96, wherein forming the transition metal-containing film comprises atomic layer deposition (ALD).

101. 1. A method for forming a transition metal-containing film on at least one surface of a substrate, comprising: a. providing a substrate to a reaction vessel; b. introducing one or more precursors into the reaction vessel, the precursor comprising one or more of the mixtures of any one of claims 1 to 95; c. purging the reaction vessel with a first purge gas; d. introducing a source gas into the reaction vessel; e. purging the reaction vessel with a second purge gas; f. sequentially repeating steps b through e until a Mo-containing film of a desired thickness is obtained.

102. The source gas may be water, diatomic oxygen, oxygen plasma, ozone, NO, N ２ O, NO ２ 102. The method of claim 101, wherein the oxygen-containing source gas is one or more selected from the group consisting of carbon monoxide, carbon dioxide, and combinations thereof.

103. 102. The method of claim 101, wherein the source gas is one or more nitrogen-containing source gases selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof.

104. 102. The method of claim 101, wherein the first and second purge gases are each independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof.

105. 102. The method of claim 101, further comprising applying energy to the one or more precursors, the source gas, the substrate, or combinations thereof, wherein the energy is one or more of thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma, and combinations thereof.

106. 102. The method of claim 101, wherein step b further comprises introducing the one or more precursors into the reaction vessel using a carrier gas flow to deliver vapors of the one or more precursors to the reaction vessel.

107. 102. The method of claim 101, wherein step b further comprises using a solvent medium comprising one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyltoluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, decahydronaphthalene, and combinations thereof.

108. A precursor supply package comprising a container and one or more of the mixtures of any one of claims 1 to 95, said container adapted to contain and dispense said mixtures.

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