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

Abstract

The disclosed and claimed subject matter relates to mixtures of Mo (arene) 2 compounds and their use for depositing Mo-containing films. The aromatic ligands are selected to provide a mixture of Mo (aromatic) 2 compounds that are liquid at a temperature of about 20 DEG C to about 35 DEG C, wherein the boiling point differences between the different components of the mixture are very small or no.

Description

background Field of the Invention

[0002] The disclosed and claimed subject matter relates to a compound comprising Mo(aromatic) 2 The invention relates to a composition of a mixture of composites and their use for depositing a Mo-containing film. The aromatic hydrocarbon ligand is selected to provide a Mo (aromatic hydrocarbon) that is liquid at a temperature of about 20° C. to about 35° C. 2 A mixture of compositions wherein the boiling point differences between the different components of the mixture are small or no difference. In some embodiments, all of the aromatic ligands have substantially the same or the same molecular weight. In other embodiments, all of the aromatic ligands have the same number of carbons.

[0003] Related technologies

[0004] Transition metal-containing films are used in semiconductor and electronic applications. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been used as the main deposition techniques for producing thin films for semiconductor devices. These methods enable conformal films (metals, metal oxides, metal nitrides, metal silicides, etc.) to be obtained by chemical reactions of metal-containing compounds (precursors). The chemical reactions occur 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 in selecting precursor molecules. Higher substrate temperatures in the range of 150 to 500 degrees Celsius (°C) promote higher film growth rates. Preferred precursor molecules must be stable within this temperature range. Preferred precursors can be delivered to the reaction vessel in a liquid phase. Liquid phase delivery of precursors generally provides more uniform precursor delivery to the reaction vessel than solid phase precursors.

[0005] CVD and ALD processes are increasingly being used because of their advantages of enhanced composition control, high film uniformity, and effective doping control. In addition, CVD and ALD processes provide excellent conformal step coverage on highly non-planar geometries associated with modern microelectronic devices.

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

[0007] ALD is a chemical process for depositing thin films. It is a self-limiting, sequential, unique thin film growth technology based on surface reactions that can provide precise thickness control and deposition of conformal material films provided by precursors onto the surfaces of substrates of different compositions. In ALD, the precursors are separated during the reaction process. The first precursor passes over the substrate surface, thereby producing a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction chamber. The second precursor or co-reactant is then passed over the substrate surface and reacts with the first precursor, thereby forming a second film monolayer on the first film monolayer formed on the substrate surface. Plasma can be used to assist the reaction of the precursor or co-reactant or to improve the material quality. The cycle is repeated to produce a film of the desired thickness.

[0008] Thin films, especially metal-containing films, have a variety of important applications, such as in nanotechnology and the fabrication of semiconductor devices. Examples of such applications include capacitor electrodes, gate electrodes, adhesive diffusion barriers, and integrated circuits.

[0009] Molybdenum-containing films have attracted attention due to their lower resistivity and thermal stability compared to other metals such as tungsten and cobalt. Therefore, molybdenum (Mo) has become an increasingly preferred material in the electronics industry for forming Mo-containing films using CVD or ALD techniques in next-generation devices. There has always been a need for halogen-free molybdenum precursors that are liquid at room temperature or low temperatures, have relatively high vapor pressures, high thermal stability, and reactivity. Most known molybdenum precursors contain molybdenum in high oxidation states (4-6), which generally produces high-resistivity molybdenum-containing films. Low-oxidation state molybdenum complexes (0-4) are ideal for the deposition of low-resistivity molybdenum-containing films.

[0010] Molybdenum bis(arene) precursors are a series of formula Mo(arene) 2 Organometallic compounds wherein the aromatic hydrocarbon is the same or different unsubstituted or substituted benzenes such as benzene, toluene, mesitylene, ethylbenzene, diethylbenzene and xylenes. Such precursors generally have relatively high vapor pressures, which makes them good candidates for use in CVD or ALD to produce Mo films with low resistivity and low amounts of carbon and nitrogen contaminants. Including Mo(EtBz) 2 Commercially available mixtures of have been used to deposit Mo-containing films such as MoO, MoC seed layers, and Mo metal films.

[0011] For example, U.S. Patent Application Publication No. 2022 / 0139713A1 describes a method for depositing an elemental molybdenum film on a substrate using a liquid precursor including molybdenum bis(ethylbenzene). In this method, a molybdenum film containing carbon as a contaminant is deposited on a substrate by a cyclic deposition process, then oxidized to remove the carbon, and the method includes providing a substrate in a deposition chamber, providing a gaseous molybdenum precursor to the deposition chamber, and providing a gaseous reactant to a reaction chamber to form a molybdenum film on the substrate. The molybdenum precursor is provided in the form of a mixture, and the reactant is a halogen (I 2 ) or halogenated hydrocarbons (ICH 2 CH 2 I), wherein at least two halogen atoms are attached to different carbon atoms of the hydrocarbon.

[0012] U.S. Patent Application Publication No. 2021 / 0047726A1 describes the use of a zero-valent halogen-free organometallic molybdenum precursor [Mo(EtBz) 2 、CpMo(CO) 2 (NO) and MeCpMo(CO) 2 (NO)] A method for forming a molybdenum thin film by oxidation and reduction. The first step is to form a molybdenum oxide film by CVD or ALD, but the film contains a small amount of carbon as a contaminant. Therefore, the molybdenum oxide film requires additional treatment (i.e., oxidation) to remove carbon, and then reduction to remove oxygen, and finally form a high-purity molybdenum film. The molybdenum film has low resistance and properties similar to bulk molybdenum.

[0013] U.S. Patent Application Publication No. 2020 / 0115798 describes a vapor deposition method for depositing a molybdenum or tungsten metal film or layer onto a substrate, the method involving an organometallic molybdenum or tungsten precursor, such as Mo(EtBz), that includes only metal, carbon, and hydrogen. 2 or W(EtBz) 2 The deposited metal layer contains carbon as a contaminant derived from the precursor. Therefore, additional treatment is required to remove the carbon; that is, after hydrogen gas is flowed into the deposition chamber to expose the deposited metal to hydrogen, an oxidant is introduced to react with and remove the carbon contaminants from the deposited metal layer, thereby obtaining a high-quality metal film or layer.

[0014] U.S. Patent Application Publication No. 2019 / 226086 describes the use of a catalyst comprising Mo(EtBz) 2 The bis(alkyl-aromatic) molybdenum composition of the present invention is used as a precursor to deposit a molybdenum film on a titanium nitride surface (3D NAND device with vertical walls) at a pressure of 10-50 Torr at less than 300° C. to form a MoC seed layer (Mo:C=40:60 to 99:1, thickness: ) or chemical vapor deposition method of metal film containing Mo.

[0015] Although using Mo(EtBz) 2 Liquid Mo (aromatic hydrocarbons) 2 The composition demonstrates deposition of molybdenum-containing films, but this commercially available composition contains a mixture of molybdenum aromatic complexes with different ligands; in particular, the mixture contains <60 mol% ethylbenzene ligands, >10 mol% benzene ligands, >30 mol% diethylbenzene ligands, and >1 mol% triethylbenzene. Without being bound by theory, it is believed that the composition contains various molybdenum aromatic complexes, such as Mo(Bz) 2 、Mo(EtBz)(Bz)、Mo(EtBz) 2 、Mo(EtBz)(Et 2 Bz), Mo(Et 2 Bz) 2 、Mo(Et 3 Bz) 2 etc. These complexes have sufficiently different molecular weights, sufficiently different thermal stabilities and vapor pressures, which lead to inconsistent chemical delivery to the device and irreproducible deposition of molybdenum-containing films. It is highly desirable to obtain liquid compositions in which the aromatic ligands contain a relatively high concentration of ethylbenzene to reduce the boiling point differences of the different mixture components.

[0016] U.S. Patent Application Publication No. US2022 / 0372053A1 describes a method for forming a metal-containing film on a substrate, comprising the following steps: exposing the substrate to a vapor of a film-forming composition comprising a metal-containing precursor; and depositing at least a portion of the metal-containing precursor onto the substrate by a vapor deposition process to form a metal-containing film on the substrate, wherein relative to pure Mo(EtBz) 2 and the commercially available metal aromatic composition "Mo(EtBz) 2 " mixture, the metal-containing precursor is said to be pure Mo (aromatic) 2 , such as Mo (toluene) 2 、Mo(m-xylene) 2 、Mo (mesitylene) 2 However, no determination of Mo(aromatic) is provided. 2 Purity data. Moreover, the purportedly pure material is prepared by previously reported methods (discussed below) without any additional purification steps known to affect impurities. Thus, while the reference describes that it is desirable to use a "pure" material in the disclosed methods, it does not describe how such a pure material is obtained. Thus, it describes a continuing need for high purity molybdenum aromatic complexes that are substantially free of impurities that affect the quality of deposited molybdenum-containing films.

[0017] Compositionally pure Mo(EtBz) cannot be prepared directly by the Fischer-Hafner method. 2The Fischer-Hafner process has the problem of isomerization of alkylbenzenes with alkyl groups larger than the methyl group. Therefore, this molybdenum aromatic complex contains a mixture of various aromatics with different molecular weights. For example, when ethylbenzene is used for Mo (aromatics) 2 When synthesizing the complex, the aromatic ligand comprises a mixture of benzene, ethylbenzene, diethylbenzene and triethylbenzene, wherein the amount of ethylbenzene is <60 mol%. On the other hand, relatively pure Mo (aromatic) can be prepared using benzene, methylbenzene (toluene), dimethylbenzene (xylene) and trimethylbenzene (mesitylene). 2 However, all of these compounds are solids with melting points above 80°C: Mo(benzene) 2 (mp=115℃)、Mo(toluene) 2 (mp=82℃), Mo(m-xylene) 2 (mp=104℃)、Mo(mesitylene) 2 (mp=110℃).

[0018] MT Ashby et al. in Organometallics, 20, 1687–1688 (2001) used aromatic hydrocarbons and Mo (benzene) 2 Metathesis to generate Mo(RC 6 H 5 ) 2 (R=Et, i Pr, t Bu). However, due to Mo (benzene) 2 Due to thermal instability, all the composites were produced as solids in low yields. In addition, these compositions still had residual Mo(benzene) 2 , which has different vapor pressure and low thermal stability. Therefore, it is still necessary to substantially not contain Mo (benzene) 2 The molybdenum aromatic composition.

[0019] It is highly desirable to obtain molybdenum(arene) that is liquid at room temperature 2 mixture of compounds. This is because it is much easier to transfer the liquid from a bulk container to an onboard container on a semiconductor device. Generally, compositions with a melting point < 35°C are preferred.

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

[0021] The disclosed and claimed subject matter is achieved by providing Mo(Ar1 )(Ar 2 ) compounds overcome the above-mentioned disadvantages and the mixture is particularly suitable for CVD and ALD applications. SUMMARY OF THE INVENTION

[0023] The disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds wherein the amount of ethylbenzene ligand ("EtBz") in the composition is increased from about 54% (commercial grade) to about 60 mol % to about 95 mol %, while the undesirable ligands, i.e., benzene ligand ("Bz"), diethylbenzene ligand ("Et 2 Bz") and triethylbenzene ligand ("Et 3 Importantly, this composition change still provides a room temperature liquid composition with a more highly consistent vapor pressure during evaporation.

[0024] For example, in one embodiment, Mo(Ar 1 )(Ar 2 ) compounds comprises (i) about 60 mol % to about 95 mol % EtBz and (ii) reduced amounts of other undesirable ligands. In a further aspect of this embodiment, Mo(Ar 1 )(Ar 2 ) compounds comprises (i) about 60 mol % to about 95 mol % of EtBz, (iia) about 0.25 mol % to about 13 mol % of Bz, (iib) about 6.75 mol % to about 44.5 mol % of Et 2 Bz and (iic) from about 0.75 mol % to about 7 mol % Et 3 It is highly unexpected that these compositions are liquid at room temperature, for example, considering that the compositions contain greater than about 97% EtBz, about 0.48% Bz, and about 2.35% Et 2 Bz’s Mo(Ar 1 )(Ar 2 ) compounds are solid below 37° C. (melting point). Thus, the disclosed and claimed compositions include significantly increased amounts of a desired ligand (e.g., ethylbenzene ligand) while surprisingly being able to remain liquid at room temperature.

[0025] In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds contain >60 mol % EtBz and < about 1 mol % each of Bz and Et 3 Bz.

[0026] In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds contain < about 1 mol % each of Bz and / or Et3Bz. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds contain < about 0.5 mol % each of Bz and / or Et3Bz. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds contain < about 0.1 mol % of each of Bz and / or Et 3 In one embodiment, Mo(Ar 1 )(Ar 2 ) The liquid mixture of the compound does not contain Bz and / or Et 3 Every kind of Bz.

[0027] In another embodiment, the disclosed and claimed subject matter comprises Mo(Ar 1 )(Ar 2 ) compounds, comprising (i) from about 60 mol % to about 95 mol % of EtBz, and (ii) at least 5 mol % of a xylene ligand ("Me 2 Bz”). Contains EtBz and Me 2 Bz liquid Mo (Ar 1 )(Ar 2 ) compounds are more attractive because Mo(EtBz) 2 and Mo(Me 2 Bz) 2 and Mo(EtBz)(Me 2 Bz) have the same MW and are expected to have the same boiling point or vapor pressure.

[0028] In one embodiment, the specified mixture comprises Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Each is a different aromatic hydrocarbon, (ii) Ar 1 and Ar 2 Each has the same amount of carbon, and (iii) the composition is liquid at a temperature ranging from about 20°C to about 35°C.

[0029] In another embodiment, the specified mixture comprises Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2Each is a different aromatic structure, (ii) Ar 1 and Ar 2 Each has substantially the same or the same molecular weight, and (iii) the composition is liquid in the temperature range of about 20°C to about 35°C. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:

[0032] Figure 1 Shows >97% compositionally pure Mo(EtBz) from Example 6 2 of 1 H NMR;

[0033] Figure 2 Shows >97% compositionally pure Mo(EtBz) from Example 6 2 DSC;

[0034] Figure 3 Shows >97% compositionally pure Mo(EtBz) from Example 6 2 the TGA; and

[0035] Figure 4 The composition from Example 10 is shown 1 H NMR, the composition contains 60% Mo(EtBz) 2 , 30% Mo(EtBz)(m-xylene) and 10% Mo(m-xylene) 2 mixture. DETAILED DESCRIPTION OF THE INVENTION

[0037] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0038] In the context of describing the disclosed and claimed subject matter (especially in the context of the appended claims), the use of the terms "one" and "an" and "the" and similar indicators should be interpreted as covering the singular and plural, unless otherwise stated herein or clearly contradicted by the context. Unless otherwise stated, the terms "comprising", "having", "including" and "containing" should be understood as open terms (i.e., meaning "including but not limited to"). Unless otherwise stated herein, the description of the numerical range herein is intended only to be used as a shorthand method for individually referring to each individual value falling within the range, and each individual value is incorporated into the specification as if it is individually stated herein. All methods described herein can be performed in any suitable order, unless otherwise stated herein or clearly contradicted by the context. Unless otherwise stated, the use of any and all embodiments or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the disclosed and claimed subject matter, without limiting the scope of the disclosed and claimed subject matter. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential for implementing the disclosed and claimed subject matter. Use of the terms "comprising" or "including" in the specification and claims includes the narrower language of "consisting essentially of" and "consisting of.

[0039] Embodiments of the disclosed and claimed subject matter are described herein, including the best modes known to the inventors for implementing the disclosed and claimed subject matter. Variations of these embodiments will become apparent to those of ordinary skill in the art after reading the foregoing description. The inventors expect that a skilled technician will appropriately adopt such variations, and the inventors envision implementing the disclosed and claimed subject matter in a manner different from that specifically described herein. Therefore, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter described in the appended claims as permitted by applicable law. In addition, any combination of the above elements in all possible variations thereof is included in the disclosed and claimed subject matter, unless otherwise stated herein or the context is clearly contradictory.

[0040] It should be understood that the term "silicon" as a material deposited on a microelectronic device includes polysilicon.

[0041] For ease of reference, "microelectronic devices" or "semiconductor devices" correspond to semiconductor wafers on which integrated circuits, memories, and other electronic structures are fabricated, as well as flat panel displays, phase change memory devices, solar panels, and other products, including solar substrates, photovoltaic devices, and micro-electromechanical systems (MEMS), which are manufactured for microelectronic, integrated circuit, or computer chip applications. 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 devices" or "semiconductor devices" are not meant to be limiting in any way, but include any substrate that will eventually become a microelectronic device or microelectronic assembly.

[0042] As defined herein, the term "barrier material" corresponds to any material used in the art to seal metal lines (e.g., copper interconnects) to minimize diffusion of the metal (e.g., copper) into dielectric materials. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium and other refractory metals and their nitrides and silicides.

[0043] As used herein, the term "aromatic hydrocarbon" refers to a cyclic hydrocarbon (i.e., an aromatic ring) having alternating double bonds and single bonds between carbon atoms, and also includes heteroaromatic hydrocarbons in which one or more carbon atoms forming such an aromatic ring are replaced by heteroatoms (e.g., oxygen, sulfur, nitrogen, silicon, germanium, phosphorus). Examples of aromatic hydrocarbons include, for example, benzene, substituted benzenes, naphthalene, anthracene, etc. Examples of heteroaromatic hydrocarbons include, for example, pyridine, furan, indole, benzimidazole, thiophene, benzothiazole, etc.

[0044] "Substantially free" is defined herein as less than 0.001 wt%. The term "free" refers to 0.000 wt%. As used herein, "approximately" or "approximately" is intended to correspond to within ±5% of the stated value. The terms "substantially free" and "free" may also be associated with halide ions (or halides), such as, for example, chlorides, fluorides, bromides, and iodides. The level of halide impurities measured by ion chromatography (IC) is less than 100 ppm (by weight), preferably less than 25 ppm measured by IC, more preferably less than 5 ppm measured by IC, and most preferably 0 ppm measured by IC. In addition, the terms "substantially free" or "free" may also refer to the molybdenum aromatic compound being substantially free of metal ions such as Li as impurities. + 、Na + , K + Mg 2+ , Ca 2+ 、Al 3 + , Fe 2+ , Fe 3+ 、Ni 2+ and Cr 3+As used herein, the term "substantially free" when referring to Li, Na, K, Mg, Ca, Al, Fe, Ni and Cr, each of these metals is less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, most preferably 0.1 ppm, as measured by ICP-MS or other analytical methods for measuring metals.

[0045] In all such compositions, where specific components of the composition are discussed with reference to weight percentage (or "wt %) ranges including a zero lower limit, it is understood that such components may or may not be present in various embodiments of the composition, and where such components are present, they may be present in concentrations as low as 0.001 wt % based on the total weight of the composition in which such components are used. It should be noted that the percentages of all components are weight percentages and are based on the total weight of the composition, i.e., 100%. Any reference to "one or more" or "at least one" includes "two or more" and "three or more", etc.

[0046] Where applicable, unless otherwise noted, all weight percentages are "neat", meaning they do not include the aqueous solution in which they are present when added to the composition. For example, "neat" refers to the weight % amount of the undiluted acid or other material (i.e., 100 grams of 85% phosphoric acid comprises 85 grams of acid and 15 grams of diluent).

[0047] In addition, when referring to the compositions described herein in % by weight, it should be understood that the % by weight of all components (including non-essential components such as impurities) does not add up to more than 100 % by weight in any case. In the composition "essentially composed of said components", these components may add up to 100 % by weight of the composition or may add up to less than 100 % by weight. When the components add up to less than 100 % by weight, such a composition may contain some small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 % by weight or less impurities. In another embodiment, the formulation may contain 1 % by weight or less impurities. In a further embodiment, the formulation may contain 0.05 % by weight or less impurities. In other such embodiments, the ingredients may account for at least 90 % by weight, more preferably at least 95 % by weight, more preferably at least 99 % by weight, more preferably at least 99.5 % by weight, most preferably at least 99.9 % by weight, and may include other ingredients that do not substantially affect the performance of the wet etchant. Otherwise, if there is no significant non-essential impurity component, it should be understood that the composition of all the necessary components essentially adds up to 100 % by weight.

[0048] As will be appreciated by those skilled in the art, in the disclosed and claimed subject matter, the Mo-compositions comprise arene (Ar) ligands or simply "arenes". The following abbreviations are used herein for those arene ligands:

[0049]

[0050]

[0051] It should be understood that unless a particular isomer of a given aromatic hydrocarbon is specified, a recitation of an aromatic hydrocarbon that may include more than one isomer may include any single isomer or mixture of such isomers. Thus, for example, when the abbreviation "Me 2 Bz" should be understood to include o-Me 2 Bz, m-Me 2 Bz and p-Me 2 Any of Bz, o-Me 2 Bz, m-Me 2 Bz and p-Me 2 A mixture of two or more of Bz, or o-Me 2 Bz, m-Me 2 Bz and p-Me 2 All three types of Bz.

[0052] The headings used herein are not intended to be limiting; rather, they are used for organizational purposes only.

[0053] The disclosed and claimed Mo(Ar 1 )(Ar 2 ) Composition

[0054] I. Improved Mo(Ar 1 )(Ar 2 ) Composition

[0055] As noted above, in one aspect, the disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds, comprising (i) from about 60 mol % to about 95 mol % of ethylbenzene ligand ("EtBz") and (ii) reduced amounts of other undesirable ligands, wherein the mixture of compounds is liquid at less than 35°C. In a further aspect, the liquid Mo(Ar 1 )(Ar 2 ) the composition further comprises (iii) at least 5 mol % of a xylene ligand ("Me 2 Bz”).

[0056] In one embodiment, Mo(Ar 1 )(Ar 2) compounds comprises (i) about 60 mol % to about 95 mol % of EtBz, (iia) about 0.25 mol % to about 13 mol % of Bz, (iib) about 6.75 mol % to about 44.5 mol % of Et 2 Bz, and (iic) from about 0.75 mol % to about 7 mol % Et 3 In a further aspect of this embodiment, Mo(Ar 1 )(Ar 2 ) the liquid mixture of compounds further comprising (iii) at least 5 mol % of Me 2 Bz.

[0057] In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds is liquid in the temperature range of about 20°C to about 35°C. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds is liquid at or below about 35°C. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds is liquid at or below about 30°C. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds is liquid at or below about 25°C. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds are liquid at a temperature at or below about 20°C.

[0058] In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds has a viscosity of less than or equal to about 500 cP. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds has a viscosity of less than or equal to about 250 cP. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds has a viscosity of less than or equal to about 100 cP. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds has a viscosity of less than or equal to about 50 cP. In one embodiment, Mo(Ar 1 )(Ar 2) compounds has a viscosity of less than or equal to about 25 cP. In one embodiment, Mo(Ar 1 )(Ar 2 )The liquid mixture of the compound has a viscosity less than or equal to about 15 cP.

[0059] Ligand content

[0060] (i) Ethylbenzene ("EtBz") ligand

[0061] As described above, in one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 60 mol % to about 95 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain 60 mol % to about 90 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain 65 mol % to about 85 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain 70 mol % to about 80 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain 60 mol % to about 65 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain 65 mol % to about 70 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain 70 mol % to about 75 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain 75 mol % to about 80 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain 80 mol % to about 85 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2) compounds contain 85 mol % to about 90 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain 85 mol % to about 95 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises 90 mol % to about 95 mol % EtBz.

[0062] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 60 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 65 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 70 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 75 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 80 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 85 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 90 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 91 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 92 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2) compounds contain about 93 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 94 mol % EtBz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contained about 95 mol % EtBz.

[0063] (ii) Unwanted ligand content

[0064] As described above, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain reduced amounts of undesirable ligands, namely (1) benzene ligand (Bz), (2) diethylbenzene ligand (Et 2 Bz, three isomers) and (3) triethylbenzene ligand (Et 3 Bz, three isomers). As will be appreciated by those skilled in the art, in Mo(Ar 1 )(Ar 2 ) compounds, the total amount of EtBz and any one or more undesirable ligands does not exceed 100 mole %.

[0065] (iia) Benzene ligand ("Bz")

[0066] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 0.25 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 0.5 mol % to about 10 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compound comprises about 1 mol % to about 10 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 0.25 mol % to about 5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 0.75 mol % to about 5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar1 )(Ar 2 ) compounds contain about 1 mol % to about 5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 2.5 mol % to about 5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 5 mol % to about 10 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 5 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 6 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo Mo (Ar 1 )(Ar 2 ) compounds contain about 7 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 7.5 mol % to about 13 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises from about 10 mol % to about 13 mol % Bz.

[0067] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 0.25 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 0.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 0.75 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 1 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar2 ) compounds contain about 1.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 2.0 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 2.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 3 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 3.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 4 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 4.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compound comprises about 5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 5.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 6 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 6.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 7 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 7.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2) compounds contain about 8 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 8.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 9 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 9.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 10 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 10.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 11 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 11.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 12 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 12.5 mol % Bz. In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contained about 13 mol % Bz.

[0068] (iib) diethylbenzene ligand (“Et 2 Bz”)

[0069] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises from about 6.75 mol % to about 44.5 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1)(Ar 2 ) compounds comprises about 6.75 mol % to about 10 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 10 mol % to about 15 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 15 mol % to about 20 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 20 mol % to about 25 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 25 mol % to about 30 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 30 mol % to about 35 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 35 mol % to about 40 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 40 mol % to about 44.5 mol % of Et 2 Bz.

[0070] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contained about 6.75 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 7 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar2 ) compounds contain about 8 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contained about 9 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 10 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 15 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 20 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 25 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 30 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 35 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 40 mol % of Et 2 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contained about 44.5 mol % of Et 2 Bz.

[0071] (iic) triethylbenzene ligand (“Et 3 Bz”)

[0072] In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2) The composition comprises from about 0.75 mol % to about 7 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises from about 1 mol % to about 7 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises from about 1.5 mol % to about 6.5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 2 mol % to about 6 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 3 mol % to about 5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 1 mol % to about 3 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 1 mol % to about 5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 1 mol % to about 4 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 1 mol % to about 3 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds comprises about 1 mol % to about 2 mol % of Et 3 Bz.

[0073] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contains about 0.75 mol % of Et3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 1 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 1.5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 2 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 2.5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 3 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contained about 3.5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 4 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contained about 4.5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contained about 5.5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 6 mol % of Et 3In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contained about 6.5 mol % of Et 3 In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds contain about 7 mol % of Et 3 Bz.

[0074] combination

[0075] In one embodiment, the disclosed and claimed Mo(Ar 1 )(Ar 2 The liquid mixture of the compound comprises EtBz and (1) a benzene ligand (Bz), (2) a diethylbenzene ligand (Et 2 Bz) and (3) triethylbenzene ligand (Et 3 Bz) wherein the total amount of Ar ligands does not exceed 100 mol%. In this regard, the disclosed and claimed Mo(Ar 1 )(Ar 2 ) compounds include any combination and amount of EtBz ligand and one or more of the above ligands. For example, in one embodiment, Mo(Ar 1 )(Ar 2 ) compounds contain (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) from about 0.75 mol % to about 7 mol % of Et 3 Bz, wherein the total amount of ligands does not exceed 100 mol%.

[0076] II. Designated Mo(Ar 1 )(Ar 2 ) Composition

[0077] In another aspect, the disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 different, and (ii)Ar 1 and Ar 2 The ligands comprise greater than 95 mole % of the aromatic ligands present. In another aspect, the disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar1 and Ar 2 Different, (ii)Ar 1 and Ar 2 The ligands comprise greater than about 97 mole percent of the aromatic ligands present. In another aspect, the disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Different, (ii)Ar 1 and Ar 2 The ligands comprise about 97 mole percent or more of the aromatic ligands present. In another aspect, the disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Different, (ii)Ar 1 and Ar 2 The ligands comprise about 99 mole percent or more of the arene ligands present.

[0078] In another aspect, the disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Different, (ii)Ar 1 and Ar 2 The ligands comprise greater than 95 mole % of the aromatic ligands present. In another aspect, the disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Different, (ii)Ar 1 and Ar 2 The ligands comprise greater than about 97 mole percent of the aromatic ligands present, and (iii) the compound is a liquid. In another aspect, the disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Different, (ii)Ar 1 and Ar 2 The ligands comprise about 97 mole percent or more of the aromatic ligands present. In another aspect, the disclosed and claimed subject matter relates to Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar1 and Ar 2 Different, (ii)Ar 1 and Ar 2 The ligands comprise about 99 mole percent or more of the arene ligands present.

[0079] In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds have a viscosity of less than or equal to about 500 cP. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds have a viscosity of less than or equal to about 250 cP. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds have a viscosity of less than or equal to about 100 cP. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds have a viscosity of less than or equal to about 50 cP. In one embodiment, Mo(Ar 1 )(Ar 2 ) compounds have a viscosity of less than or equal to about 25 cP. In one embodiment, Mo(Ar 1 )(Ar 2 )The specified mixture of compounds has a viscosity of less than or equal to about 15 cP.

[0080] A. Specified Implementation Method 1

[0081] In one embodiment, the specified mixture comprises Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Each is a different aromatic hydrocarbon, (ii) Ar 1 and Ar 2 Each has the same amount of carbon. In one embodiment, a given mixture comprises Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Each is a different aromatic hydrocarbon, (ii) Ar 1 and Ar 2 Each has the same number of carbons, and (iii) the compound is liquid within a temperature range of about 20°C to about 35°C.

[0082] In one aspect of this embodiment, Ar 1 and Ar 2At least one of the following comprises one or more unsubstituted linear C 1 -C 6 Alkyl, halogen-substituted straight-chain C 1 -C 6 Alkyl, amino-substituted straight-chain C 1 -C 6 Alkyl, unsubstituted branched C 3 -C 6 Alkyl, branched C substituted by halogen 3 -C 6 Alkyl or amino substituted branched C 3 -C 6 alkyl, an unsubstituted amine or a substituted amine substituent. 1 and Ar 2 At least one of them contains one or more C 1 -C 6 In one aspect, Ar 1 and Ar 2 At least one of the following comprises one or more linear C 1 -C 6 In one aspect, Ar 1 and Ar 2 At least one of the following comprises one or more linear C 1 -C 6 In one aspect, Ar 1 and Ar 2 At least one of which contains one or more unsubstituted branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 At least one of the following comprises one or more branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 At least one of the following comprises one or more branched C residues substituted by amino groups: 3 -C 6 In one aspect, Ar 1 and Ar 2 At least one of Ar comprises one or more substituents which are unsubstituted amines. 1 and Ar 2 At least one of Ar comprises one or more substituents which are substituted amines. 1 and Ar 2At least one of them contains one or more C 1 -C 3 In a preferred aspect, Ar 1 and Ar 2 In a preferred aspect, at least one of Ar comprises one or more methyl substituents. 1 and Ar 2 In one preferred aspect, at least one of Ar comprises one or more ethyl substituents. 1 and Ar 2 In a preferred aspect, at least one of Ar comprises one or more substituents which are propyl groups. 1 and Ar 2 In a preferred aspect, at least one of Ar 1 and Ar 2 At least one of contains two substituents.

[0083] In one aspect of this embodiment, Ar 1 and Ar 2 Each contains one or more different substituents selected from unsubstituted straight chain C 1 -C 6 Alkyl, halogen-substituted straight-chain C 1 -C 6 Alkyl, amino-substituted straight-chain C 1 -C 6 Alkyl, unsubstituted branched C 3 -C 6 Alkyl, branched C substituted by halogen 3 -C 6 Alkyl or amino substituted branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 Each contains one or more C 1 -C 6 In one aspect, Ar 1 and Ar 2 Each contains one or more linear C 1 -C 6 In one aspect, Ar 1 and Ar 2 Each of them contains one or more linear C 1 -C 6 In one aspect, Ar 1 and Ar 2 Each contains one or more unsubstituted branched C3 -C 6 In one aspect, Ar 1 and Ar 2 Each contains one or more branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 Each of them contains one or more branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 Each contains one or more substituents which are unsubstituted amines. In one aspect, Ar 1 and Ar 2 Each contains one or more substituents which are substituted amines. In a preferred aspect, Ar 1 and Ar 2 Each contains one or more C 1 -C 3 In a preferred aspect, Ar 1 and Ar 2 Each contains one or more methyl substituents. In a preferred aspect, Ar 1 and Ar 2 Each contains one or more substituents which are ethyl. In a preferred aspect, Ar 1 and Ar 2 Each contains one or more substituents which are propyl. In a preferred aspect, Ar 1 and Ar 2 Each contains a substituent. In a preferred aspect, Ar 1 and Ar 2 Each contains two substituents.

[0084] In one aspect, Ar 1 and Ar 2 At least one of is a 5-membered aromatic hydrocarbon. 1 and Ar 2 At least one of is a 6-membered aromatic hydrocarbon. 1 and Ar 2 At least one of Ar is a 5-membered heterocyclic aromatic hydrocarbon. 1 and Ar 2 At least one of Ar is a 6-membered heteroaromatic hydrocarbon. 1 and Ar 2 Each is a 5-membered aromatic hydrocarbon. 1 and Ar 2Each is a 6-membered aromatic hydrocarbon. 1 and Ar 2 Each is a 5-membered heterocyclic aromatic hydrocarbon. 1 and Ar 2 Each is a 6-membered heterocyclic aromatic hydrocarbon. 1 and Ar 2 At least one of Ar is substituted benzene, pyridine, pyrrole, furan and thiophene. 1 and Ar 2 Each is a substituted benzene, pyridine, pyrrole, furan and thiophene.

[0085] B. Designation of implementation method 2

[0086] In another embodiment, the specified mixture comprises Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Each is a different aromatic structure, (ii) Ar 1 and Ar 2 Each has substantially the same or identical molecular weight. In another embodiment, a given mixture comprises Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 Each is a different aromatic structure, (ii) Ar 1 and Ar 2 Each has substantially the same or the same molecular weight, and (iii) the compound is liquid in the temperature range of about 20°C to about 35°C. As will be appreciated by those skilled in the art, in these embodiments, Ar 1 and Ar 2 Neither can be Bz, because Bz has no isomers.

[0087] In one aspect of this embodiment, Ar 1 and Ar 2 At least one of the following comprises one or more unsubstituted linear C 1 -C 6 Alkyl, halogen-substituted straight-chain C 1 -C 6 Alkyl, amino-substituted straight-chain C 1 -C 6 Alkyl, unsubstituted branched C 3 -C 6 Alkyl, branched C substituted by halogen 3 -C 6 Alkyl or amino substituted branched C 3 -C6 alkyl, an unsubstituted amine or a substituted amine substituent. 1 and Ar 2 At least one of them contains one or more C 1 -C 6 In one aspect, Ar 1 and Ar 2 At least one of the following comprises one or more linear C 1 -C 6 In one aspect, Ar 1 and Ar 2 At least one of the following comprises one or more linear C 1 -C 6 In one aspect, Ar 1 and Ar 2 At least one of which contains one or more unsubstituted branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 At least one of the following comprises one or more branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 At least one of the following comprises one or more branched C residues substituted by amino groups: 3 -C 6 In one aspect, Ar 1 and Ar 2 At least one of Ar comprises one or more substituents which are unsubstituted amines. 1 and Ar 2 At least one of Ar comprises one or more substituents which are substituted amines. 1 and Ar 2 At least one of them contains one or more C 1 -C 3 In a preferred aspect, Ar 1 and Ar 2 In a preferred aspect, at least one of Ar comprises one or more methyl substituents. 1 and Ar 2 In one preferred aspect, at least one of Ar comprises one or more ethyl substituents. 1 and Ar 2 In a preferred aspect, at least one of Ar comprises one or more substituents which are propyl groups.1 and Ar 2 In a preferred aspect, at least one of Ar 1 and Ar 2 At least one of contains two substituents.

[0088] In one aspect of this embodiment, Ar 1 and Ar 2 Each contains one or more different substituents selected from unsubstituted straight chain C 1 -C 6 Alkyl, halogen-substituted straight-chain C 1 -C 6 Alkyl, amino-substituted straight-chain C 1 -C 6 Alkyl, unsubstituted branched C 3 -C 6 Alkyl, branched C substituted by halogen 3 -C 6 Alkyl or amino substituted branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 Each contains one or more C 1 -C 6 In one aspect, Ar 1 and Ar 2 Each contains one or more linear C 1 -C 6 In one aspect, Ar 1 and Ar 2 Each of them contains one or more linear C 1 -C 6 In one aspect, Ar 1 and Ar 2 Each contains one or more unsubstituted branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 Each of them contains one or more branched C 3 -C 6 In one aspect, Ar 1 and Ar 2 Each of them contains one or more branched C 3 -C 6 In one aspect, Ar 1 and Ar2 Each contains one or more substituents which are unsubstituted amines. In one aspect, Ar 1 and Ar 2 Each contains one or more substituents which are substituted amines. In a preferred aspect, Ar 1 and Ar 2 Each contains one or more C 1 -C 3 In a preferred aspect, Ar 1 and Ar 2 Each contains one or more methyl substituents. In a preferred aspect, Ar 1 and Ar 2 Each contains one or more substituents which are ethyl. In a preferred aspect, Ar 1 and Ar 2 Each contains one or more substituents which are propyl. In a preferred aspect, Ar 1 and Ar 2 Each contains a substituent. In a preferred aspect, Ar 1 and Ar 2 Each contains two substituents.

[0089] In one aspect, Ar 1 and Ar 2 At least one of is a 5-membered aromatic hydrocarbon. 1 and Ar 2 At least one of is a 6-membered aromatic hydrocarbon. 1 and Ar 2 At least one of Ar is a 5-membered heterocyclic aromatic hydrocarbon. 1 and Ar 2 At least one of Ar is a 6-membered heteroaromatic hydrocarbon. 1 and Ar 2 Each is a 5-membered aromatic hydrocarbon. 1 and Ar 2 Each is a 6-membered aromatic hydrocarbon. 1 and Ar 2 Each is a 5-membered heterocyclic aromatic hydrocarbon. 1 and Ar 2 Each is a 6-membered heterocyclic aromatic hydrocarbon. 1 and Ar 2 At least one of Ar is substituted benzene, pyridine, pyrrole, furan and thiophene. 1 and Ar 2 Each is a substituted benzene, pyridine, pyrrole, furan and thiophene.

[0090] Representative Designated Implementation Methods

[0091] In the above embodiment, preferred aromatic ligands include:

[0092] Aromatic ligands abbreviation Xylene <![CDATA[Me 2 Bz]]> o-Xylene <![CDATA[o-Me 2 Bz]]> Meta-Xylene <![CDATA[m-Me 2 Bz]]> p-Xylene <![CDATA[p-Me 2 Bz]]> Ethylbenzene E Diethylbenzene <![CDATA[Et 2 Bz]]> o-Diethylbenzene <![CDATA[o-Et 2 Bz]]> m-Diethylbenzene <![CDATA[m-Et 2 Bz]]> p-Diethylbenzene <![CDATA[p-Et 2 Bz]]> Triethylbenzene <![CDATA[Et 3 Bz]]> Pyridine Py Ethylpyridine EtPy 2,6-Dimethylpyridine Lt

[0093] As will be appreciated by those skilled in the art, in some embodiments, some aromatic hydrocarbons may include a mixture of isomers. It should be understood that unless a particular isomer of a given aromatic hydrocarbon is specified, a description of an aromatic hydrocarbon that may include more than one isomer may include any single isomer or mixture of such isomers. Thus, for example, when the abbreviation "Me 2 Bz" should be understood to include o-Me 2 Bz, m-Me 2 Bz and p-Me 2 Any of Bz, o-Me 2 Bz, m-Me 2 Bz and p-Me 2 A mixture of two or more of Bz, or o-Me 2 Bz, m-Me 2 Bz and p-Me 2 All three types of Bz.

[0094] In the above embodiment, preferred Mo(Ar1)(Ar2) compounds include:

[0095] <![CDATA[Mo(EtBz)(m-Me 2 Bz)]]> <![CDATA[Mo(EtBz)(o-Me 2 Bz)]]> <![CDATA[Mo(EtBz)(p-Me 2 Bz) <!-- 14 -->]]> <![CDATA[Mo(m-Me 2 Bz)(o-Me 2 Bz)]]> <![CDATA[Mo(m-Me 2 Bz)(p-Me 2 Bz)]]> <![CDATA[Mo(o-Me 2 Bz)(p-Me 2 Bz)]]> <![CDATA[Mo(m-Et 2 Bz)(o-Et 2 Bz)]]> <![CDATA[Mo(m-Et 2 Bz)(p-Et 2 Bz)]]>

[0096] Mo(Ar 1 )(Ar 2 ): ethylbenzene (EtBz) and xylene (“Me 2 Bz”) ligand

[0097] Preferred embodiments of the specified mixture include Mo(Ar 1 )(Ar 2 ) compounds, wherein (i) Ar 1 and Ar 2 One of them is ethylbenzene ("EtBz"), and Ar 1 and Ar 2 Another one is xylene (“Me 2 Bz”). As mentioned above, in these Mo (Ar 1 )(Ar 2 ) compounds, Ar 1 and Ar 2 The ligands comprise 100 mol% of the aromatic ligands present. Thus, in this embodiment, Mo(Ar 1 )(Ar 2) There is no EtBz and Me in the compound 2 Aromatic ligands other than Bz (i.e., the mole % of EtBz plus Me 2 The mole % of Bz is equal to 100 mole % of the arene ligand present).

[0098] In one embodiment, the disclosed and claimed liquid Mo(Ar 1 )(Ar 2 ) compounds contain up to about 95 mol % EtBz and at least about 5 mol % Me 2 In one embodiment, the disclosed and claimed liquid Mo (Ar 1 )(Ar 2 ) compound comprises about 95 mol % to about 60 mol % of EtBz and about 5 mol % to about 40 mol % of Me 2 In one embodiment, the disclosed and claimed liquid Mo (Ar 1 )(Ar 2 ) compound comprises about 95 mol % to about 90 mol % of EtBz and about 5 mol % to about 10 mol % of Me 2 In one embodiment, the disclosed and claimed liquid Mo (Ar 1 )(Ar 2 ) compounds contain about 90 mol % to about 85 mol % of EtBz and about 10 mol % to about 15 mol % of Me 2 In one embodiment, the disclosed and claimed liquid Mo (Ar 1 )(Ar 2 ) compound comprises about 85 mol % to about 80 mol % of EtBz and about 15 mol % to about 20 mol % of Me 2 In one embodiment, the disclosed and claimed liquid Mo (Ar 1 )(Ar 2 ) compound comprises about 80 mol % to about 75 mol % of EtBz and about 20 mol % to about 25 mol % of Me 2 In one embodiment, the disclosed and claimed liquid Mo (Ar 1 )(Ar 2 ) compound comprises about 75 mol % to about 70 mol % of EtBz and about 25 mol % to about 30 mol % of Me 2 In one embodiment, the disclosed and claimed liquid Mo (Ar 1 )(Ar 2 ) compounds contain about 70 mol % to about 65 mol % of EtBz and about 30 mol % to about 35 mol % of Me 2In one embodiment, the disclosed and claimed liquid Mo (Ar 1 )(Ar 2 ) compound comprises about 65 mol % to about 60 mol % of EtBz and about 35 mol % to about 40 mol % of Me 2 Bz.

[0099] How to use

[0100] The disclosed and claimed subject matter also includes the use of Mo(Ar 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.

[0101] In one embodiment, the method includes using an atomic layer deposition process (ALD) using one or more Mo (Ar 1 )(Ar 2 ) compounds to deposit a molybdenum-containing film. 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 for depositing a film of material onto a substrate of varying composition. Although the precursors, reagents, and sources used herein may sometimes be described as "gaseous," it should be understood that the precursor may be a liquid or solid that is delivered to 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. The term "reactor" as used herein includes, but is not limited to, a reaction chamber, a reaction vessel, or a deposition chamber.

[0102] Among them, the above Mo(Ar 1 )(Ar 2 ) compounds include, but are not limited to, those used to manufacture semiconductor-type microelectronic devices such as ALD and plasma-enhanced ALD (PEALD). Thus, in one embodiment, for example, the metal-containing film is deposited using an ALD process. In another embodiment, for example, the metal-containing film is deposited using a plasma-enhanced ALD (PEALD) process.

[0103] Mo(Ar 1 )(Ar 2 There is no particular limitation on the suitable substrate for the mixture of HfO compounds and the like, and the substrate may vary depending on the intended end use. For example, the substrate may be selected from oxides such as HfO 2 Base material, TiO2 Base material, ZrO 2 The substrate may be a nitride-based film, a rare earth oxide-based material, a ternary oxide-based material, or a nitride-based film. 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., TiSi 2 、CoSi 2 and NiSi 2 ); substrates containing metal nitrides (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., SiO 2 、Si 3 N 4 、SiON、HfO 2 、 2 O 5 、ZrO 2 、TiO 2 、Al 2 O 3 and barium strontium titanate); combinations thereof.

[0104] In such deposition methods and processes, an oxidant may be used. The oxidant is usually introduced in gaseous form. Examples of suitable oxidants include, but are not limited to, oxygen, water vapor, ozone, oxygen plasma, or mixtures thereof.

[0105] The deposition method and process may also include one or more purge gases. The purge gas used to purge away unconsumed reactants and / or reaction byproducts is an inert gas that does not react with the precursor. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N 2 ), helium (He), neon and mixtures thereof. For example, a purge gas such as Ar is supplied to the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 10000 seconds to purge unreacted materials and any byproducts that may remain in the reactor.

[0106] The deposition methods and processes require the application of energy to the above-mentioned molybdenum aromatic precursor to initiate the reaction and form a metal-containing film or coating on the substrate. This energy can be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods, and combinations thereof. In some processes, a secondary RF frequency source can be used to change the plasma characteristics at the substrate surface. When plasma is utilized, the plasma generation process can include a direct plasma generation process, in which the plasma is generated directly in the reactor, or alternatively includes a remote plasma generation process, in which the plasma is generated outside the reactor and supplied to the reactor.

[0107] When used in these deposition methods and processes, the above Mo(Ar 1 )(Ar 2 ) compounds can be delivered to a reaction chamber such as an ALD reactor in a variety of ways. In some cases, a liquid delivery system can be used. In other cases, a combined liquid delivery and flash processing unit can be used, such as, for example, a turbo evaporator manufactured by MSP Corporation of Shoreview, MN, to enable quantitative delivery of low volatility materials, which results in reproducible delivery and deposition without thermal decomposition of the precursor.

[0108] When used in these deposition methods and processes, Mo(Ar 1 )(Ar 2 ) compounds can be mixed with hydrocarbon solvents, and can include hydrocarbon solvents, which are particularly desirable because they can be dried to sub-ppm water content. Exemplary hydrocarbon solvents that can be used for 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 decalin (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 point solvent or has a boiling point of 100 degrees Celsius or higher. The disclosed and claimed precursors can also be mixed with other suitable metal precursors, and the mixture is used to simultaneously deliver two metals for growing binary metal-containing films.

[0109] A flow of argon and / or other gases may be used as a carrier gas to aid in the transport of the Mo (Ar)-containing precursor during the precursor pulse. 1 )(Ar 2 ) compounds are transported to the reaction chamber. 1 )(Ar 2) compounds, the process pressure of the reaction chamber is between 1 and 50 Torr, preferably between 5 and 20 Torr.

[0110] Substrate temperature can be an important process variable in depositing 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.

[0111] In view of the foregoing, those skilled in the art will recognize that the disclosed and claimed subject matter also includes the following methods of using Mo(Ar) in a chemical vapor deposition process: 1 )(Ar 2 ) mixture of compounds.

[0112] 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 the steps of:

[0113] a. providing the at least one surface of the substrate in a reaction vessel;

[0114] b. Use Mo(Ar 1 )(Ar 2 ) compounds as metal source compounds for a deposition process, and forming a transition metal-containing film on at least one surface by a thermal chemical vapor deposition (CVD) or atomic layer deposition (ALD) process.

[0115] 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 water, diatomic oxygen, oxygen plasma, ozone, NO, N 2 O、NO 2 , 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 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 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.

[0116] In one embodiment, the disclosed and claimed subject matter includes a method of forming a Mo-containing film by a cyclic chemical vapor deposition (CCVD) process at a temperature above 300° C., the method comprising the steps of:

[0117] a. providing a substrate in a reaction vessel;

[0118] b. Introduce Mo(Ar) into the reaction vessel 1 )(Ar 2 ) one of the combined mixtures and a source gas;

[0119] c. purging the reaction vessel with a second purge gas;

[0120] d. Repeat steps b to c sequentially until a transition metal-containing film of desired thickness is obtained.

[0121] In a further aspect of this embodiment, the source gas is selected from water, diatomic oxygen, oxygen plasma, ozone, NO, N 2 O、NO 2 , carbon monoxide, carbon dioxide and one or more oxygen-containing source gases of 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 first and second purge gases of the method are each independently selected from one or more of argon, nitrogen, helium, neon and combinations thereof. In a further aspect of this embodiment, the method further includes applying energy to one or more precursors, source gases, substrates and combinations thereof, wherein the energy is one or more of heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma method and combinations thereof. In a further aspect of this embodiment, step b of the method further includes introducing the precursor into the reaction vessel by transporting the vapor of the precursor into the reaction vessel using a carrier gas flow. 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 decalin, and combinations thereof.

[0122] In one embodiment, the disclosed and claimed subject matter includes a method of forming a Mo-containing film by a thermal atomic layer deposition (ALD) process or a thermal ALD-like process, the method comprising the steps of:

[0123] a. providing a substrate in a reaction vessel;

[0124] b. Introduce Mo(Ar) into the reaction vessel 1 )(Ar 2 ) is one of a mixture of compounds;

[0125] c. purging the reaction vessel with a first purge gas;

[0126] d. introducing source gas into the reaction vessel;

[0127] e. purging the reaction vessel with a second purge gas;

[0128] f. Repeat steps b to e sequentially until a transition metal-containing film of a desired thickness is obtained.

[0129] In a further aspect of this embodiment, the source gas is selected from water, diatomic oxygen, ozone, NO, N 2 O、NO 2 , 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 first and second purge gases in the method are each independently selected from one or more of argon, nitrogen, helium, neon and combinations thereof. In a further aspect of this embodiment, the method further includes applying energy to one or more precursors, source gases, substrates and combinations thereof, wherein the energy is one or more of heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma method and combinations thereof. In a further aspect of this embodiment, step b of the method further includes introducing the precursor into the reaction vessel by transporting the vapor of the precursor into the reaction vessel using a carrier gas flow. 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 decalin, and combinations thereof. Example

[0130] Reference will now be made to more specific embodiments of the present disclosure and to experimental results supporting these embodiments.The examples given below more fully illustrate the disclosed and claimed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0131] It will be apparent to those skilled in the art that various modifications and variations may be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, it is intended that the disclosed subject matter (including the description provided by the following embodiments) encompass modifications and variations of the disclosed subject matter within the scope of any claims and their equivalents.

[0132] Materials and methods:

[0133] All reactions and manipulations described in the examples were performed under nitrogen atmosphere using an inert atmosphere glove box or standard Schlenk techniques. All chemicals were from Millipore-Sigma and Strem.

[0134] Comparative Example 1: Mo(EtBz) 2 Synthesis of compounds

[0135] With stirring, 5.4 g of MoCl 5 Slowly add 0.3 g AlCl 3 and 2.1 g of Al in a suspension in 30 ml of anhydrous deoxygenated ethylbenzene. The mixture was heated to 135 °C and maintained for 24 hours and then cooled to room temperature. Thereafter, 20 ml of deoxygenated THF was slowly added to the reaction. The mixture was heated to 100 °C for 8 hours. After cooling to room temperature, the volatiles were removed under vacuum. Then 60 ml of pentane was added and the mixture was stirred for 1 hour. In a 250 ml flask below 0 °C, the dark green solution was slowly decanted into 25 ml of deoxygenated KOH solution. After separation from the mixture, the organic green solution was washed with 25 ml of water. 10 g of MgSO 4 The green solution was dried. The solvent was removed to give 3.7 g of dark green liquid. Distillation at 130-170°C / 0.075-0.1 mmHg gave 1.65 g of pure product with a yield of 30%.

[0136] Comparative Example 2: Mo(EtBz) 2 Synthesis of compounds

[0137] With stirring, 5.4 g of MoCl 5 Slowly add 0.3 g AlCl 3 and 2.1 g of Al in a suspension in 30 ml of anhydrous deoxygenated ethylbenzene. The mixture was heated to 135 °C and maintained for 24 hours and then cooled to room temperature. Thereafter, 20 ml of deoxygenated THF was slowly added to the reaction. The mixture was heated to 100 °C for 8 hours. After cooling to room temperature, the volatiles were removed under vacuum. 60 ml of pentane was then added and the mixture was stirred for 1 hour to form a suspension. At below 0 °C, the suspension was slowly added to 25 ml of deoxygenated KOH solution. After separation from the mixture, the organic green solution was washed with 25 ml of water. 10 g of anhydrous MgSO 4 The green solution was dried. The solvent was removed to give 4.0 g of dark green liquid. Distillation at 130-170°C / 0.075-0.1 mmHg gave 2.2 g of pure product with a yield of 40%.

[0138] Example 3: Comparison of Mo(EtBz) 2 Composition analysis of compounds

[0139] The following analytical method was developed to analyze Mo(EtBz) 2 Compound. 50 mg of the sample was dissolved in 4 ml of toluene to form a green solution which was oxidized by oxygen to give a colorless solution containing the aromatic ligands and a brown solid (MoO species) after filtration. The colorless solution was directly used for GC-FID analysis. The results of the commercial product available from Strem and the materials prepared as in Comparative Examples 1 and 2 are summarized in Table 1. GC analysis showed that the sample from Comparative Example 1 had a similar composition to the commercial product from Strem. However, the sample from Comparative Example 2 showed that the compound contained more than 40% Et when prepared by a different synthetic route. 2 Bz and 6% Et 3 Bz. Therefore, all these samples have Mo(aromatic) 2 The aromatic mixture used in the composite contained <60 mol % EtBz.

[0140]

[0141]

[0142] Table 1

[0143] Comparative Example 4: Commercial Mo(EtBz) 2 Vacuum evaporation

[0144] A 10.2 gram sample from Strem was vacuum distilled 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 GC results are summarized in Table 2. GC analysis showed that the three fractions contained different components, which may have led to inconsistent delivery during vacuum evaporation.

[0145] Fraction temperature Quantity (yield) benzene Ethylbenzene Diethylbenzene Triethylbenzene 1 <135℃ 0.66 g (6.5%) 16.76％ 54.39％ 27.18％ 1.67％ 2 135-143℃ 7.0 g (68.6%) 10.77％ 51.79％ 34.95％ 2.48％ 3 143-153℃ 1.9 g (18.6%) 6.39％ 46.56％ 43.12％ 3.93％

[0146] Table 2

[0147] Example 5: Liquid Mo (Ar 1 )(Ar 2 ) Compound (>60 mol% EtBz)

[0148] The slurry contains about 7.06% Bz, 41.52% EtBz, 44.48% Et 2 Bz and 6.93% Et 3 Bz's Mo (EtBz) 2The mixture of compound (4.5 grams) is dissolved in ethylbenzene (22.5 grams) to form a green solution. Under nitrogen, the green solution was heated at 120 ℃, 125 ℃ and 135 ℃ for 18 hours. After the solution was cooled to room temperature, black solid was filtered out, and remaining green filtrate was collected. All volatiles were removed under vacuum from the green filtrate to obtain green residue (4.0 grams) at less than 90 ℃. Distillation obtained 3.2 grams of products (80% productive rate) at 130-170 ℃ and 0.1mmHg. The GC-FID method analysis product described in the embodiment 3, the results are summarized in Table 3.

[0149] Example temperature benzene Ethylbenzene Diethylbenzene Triethylbenzene 5a 120℃ 4.34％ 64.4％ 27.29％ 3.97％ 5b 125℃ 3.39％ 75.18％ 19.59％ 1.84％ 5c 135℃ 0.37％ 91.97％ 6.76％ 0.89％

[0150] Table 3

[0151] GC analysis showed that aromatic substitution significantly changed the Mo(EtBz) 2 Composition of the mixture. According to the data in Table 3, the EtBz in the mixture increases from 41.5 mol% to more than 64% at 120°C, increases to 75 mol% at 125°C, and increases to 92 mol% at 135°C. The product is still liquid, while the other ligands decrease to less than 0.5 mol% for Bz and less than 0.5 mol% for Et at 135°C. 3 Bz is reduced to less than 1 mol%, and for Et 2 Bz was reduced to less than 8 mol%.

[0152] Example 6: Mo(Ar) with melting point <50°C and >97 mol% EtBz 1 )(Ar 2 Preparation of a mixture of compounds

[0153] The liquid product from Example 5c was purified by recrystallization to give a green solid. 3.5 g of it 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 green solid was isolated (yield 55.7%). Mo(EtBz) 2 of 1 H NMR Figure 1 As shown: 1 H NMR (C 6 D 6 ,500MHz,20℃)δ4.64(d,4H,C 6 H 5 CH 2 CH 3 ),4.59(t,10H,C 6 H 5 CH 2 CH 3 ),4.54(t,2H,C6 H 5 CH 2 CH 3 ),2.10(q,4H,C 6 H 5 CH 2 CH 3 ),1.07(t,6H,C 6 H 5 CH 2 CH 3 ); The green solid was also analyzed by DSC and GC-FID as described in Example 3. DSC showed that the green solid melted at 36.9°C ( Figure 2 ). TGA showed the residue was 0.23% ( Figure 3 ), GC analysis as described in Example 3 showed that the sample composition contained 97.17 mol % EtBz, 2.35 mol % Et 2 Bz, 0.48 mol% Bz, <0.01 mol% Et 3 Bz.

[0154] Example 7: Preparation of Mo aromatics composition substantially free of chlorine

[0155] Commercially available platinum aromatics or platinum aromatics prepared by literature methods contain at least 27 ppm of chlorine, as determined by ion chromatography. Residual chlorine may cause corrosion of stainless steel containers containing the platinum aromatics and / or may cause the molybdenum-containing films deposited by the platinum aromatics to be contaminated by undesirable chlorides. The following procedure effectively reduces chlorine to <5 ppm. A sample (5 g) of commercially available platinum aromatics is dissolved in hexane (100 ml) or MTBE (methyl tert-butyl ether) (100 ml) to form a green solution. 50 ml of 10% KOH / H 2 The solution was washed twice with 0 solution. After separation, the organic solution was dried over anhydrous sodium sulfate. After filtration, the solution was passed through an adsorbent to obtain a dark green solution. Volatiles were removed under vacuum to obtain 4.8 grams of green liquid. The liquid was analyzed by ion chromatography. The results showed that chlorine was reduced from 27 ppm to less than 1 ppm.

[0156] Example 8: Viscosity of Mo Aromatic Compositions

[0157] The viscosity of a commercial molybdenum aromatic composition (13.1% benzene, 54.0% ethylbenzene, 31.1% diethylbenzene and 1.9% triethylbenzene) containing a mixture of various aromatic ligands and described in Example 3 was measured using a capillary viscometer tube and a set of ISO 17025 standards available from Paragon Scientific Ltd. The viscosity at 20°C was 15 cP. The viscosity of the molybdenum aromatic composition from Example 2 with a larger amount of diethylbenzene and triethylbenzene ligands was 20.5 cP. We have found that the improved composition of the present invention (sample 5c in Table 3 of Example 5) has a significantly lower viscosity of 11 cP at 20°C. This example shows that reducing the amount of diethylbenzene and triethylbenzene ligands is effective in reducing the viscosity of the Mo(EtBz) based molybdenum aromatic composition. 2 The viscosity of the molybdenum arene composition is critical. A viscosity < 15 cP is important for efficient delivery of the precursor to the deposition equipment by direct liquid injection.

[0158] Example 9: Mo(m-Me 2 Bz) 2 Preparation of compounds

[0159] Under nitrogen, 5.4 g MoCl 5 Slowly add 2.6 g AlCl 3 and a suspension of 1.0 g of Al in 30 ml of anhydrous deoxygenated meta-xylene. The mixture was heated to 135°C for 20 hours and then cooled to room temperature. Thereafter, 60 ml of MTBE were slowly added to the reaction mixture at room temperature. Next, 100 ml of cold 30% KOH solution was slowly (first dropwise) added to a flask below 0°C. After the addition of KOH, the flask was stirred for 4 hours. The green organic portion was then separated from the aqueous portion and washed with water (100 ml). All volatiles were evaporated and the residue was extracted with hexane / MTBE (100 / 100 ml) to obtain a dark green solution, which was treated in a glove box with 10 g of Na 2 SO 4 Dry. After filtering in a glove box, all volatiles were removed under vacuum to obtain a green solid. The green solid was washed with 10 ml of hexane to obtain 1.95 g of product (32% yield). The solid was analyzed by TGA and DSC. The melting point of this complex is 104°C.

[0160] Example 10: Mo(Ar 1 )(Ar 2 Preparation of a liquid mixture of compounds (wherein Ar 1 and Ar 2 are each independently selected aromatic hydrocarbon, and Mo(EtBz) 2 About 60%

[0161] Mo (m-xylene) from Example 9 2 The sample (10 g) 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 out through silica gel and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum at less than 90°C to obtain a green liquid residue. After distillation at 130-150°C and 0.1 mmHg, 8.5 g of product was obtained with a yield of 85%. The product was obtained by 1 H NMR spectroscopy was used to characterize ( Figure 4 Based on NMR analysis, the product contains 60% Mo(EtBz) 2 , 30% Mo(EtBz)(m-xylene) and 10% Mo(m-xylene) 2 Liquid. TGA residue was 0.3%, DSC showed an exothermic event at 272°C. Mo(EtBz) 2 : 1 H NMR (C 6 D 6 ,500MHz,20℃)δ4.60(d,4H,C 6 H 5 CH 2 CH 3 ),4.54(t,10H,C 6 H 5 CH 2 CH 3 ),4.50(m,2H,C 6 H 5 CH 2 CH 3 ),2.09(q,4H,C 6 H 5 CH 2 CH 3 ),1.07(t,6H,C 6 H 5 CH 2 CH 3 ); Mo(EtBz)(m-xylene): 1 H NMR (C 6 D 6 ,500MHz,20℃)δ4.72(s,1H,C 6 H 5 (CH 3 ) 2 ),4.54(m,1H,C 6 H 5 (CH 3 ) 2),4.42(m,2H,C 6 H 5 (CH 3 ) 2 ),2.01(q,2H,C 6 H 5 CH 2 CH 3 ),1.93(s,6H,C 6 H 5 (CH 2 ) 2 ),1.09(t,3H,C 6 H 5 CH 2 CH 3 ); Mo (m-xylene) 2 : 1 H NMR (C 6 D 6 ,500MHz,20℃)δ4.54(s,2H,C 6 H 5 (CH 3 ) 2 ),4.50(m,6H,C 6 H 5 (CH 3 ) 2 ),1.84(s,12H,C 6 H 5 (CH 2 ) 2 ).

[0162] Example 11: Mo(Ar 1 )(Ar 2 Preparation of a liquid mixture of compounds (wherein Ar 1 and Ar 2 are each independently selected aromatic hydrocarbon, and Mo(EtBz) 2 About 80%

[0163] Mo (m-xylene) from Example 9 2 The sample (27 g) 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 the solution was cooled to room temperature, the black solid was filtered out through silica gel and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum to obtain a green liquid residue. After distillation at 130-142°C and 0.1 mmHg, 25 g of product was obtained with a yield of 92%. The product was characterized by NMR spectroscopy and its composition was analyzed based on the peak integration described in Example 10. Based on NMR analysis, the product contained 80.5% Mo(EtBz)2 , 18% Mo(EtBz)(m-xylene) and 1.5% Mo(m-xylene) 2 The TGA residual was 0.013% and the DSC showed an exothermic event at 278°C.

[0164] Example 12: Mo(Ar 1 )(Ar 2 Preparation of a liquid mixture of compounds (wherein Ar 1 and Ar 2 are each independently selected aromatic hydrocarbon, and Mo(EtBz) 2 About 80%

[0165] Mo (m-xylene) from Example 9 2 The sample (69 g) 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 the solution was cooled to room temperature, the black solid was filtered out through silica gel and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum to obtain a green liquid residue. After distillation at 130-140°C and 0.15-0.2 mmHg, 61.5 g of product was obtained with a yield of 89%. The product was characterized by NMR spectroscopy and its composition was analyzed based on the peak integration described in Example 10. Based on NMR analysis, the product contained 80% Mo(EtBz) 2 , 18% Mo(EtBz)(m-xylene) and 2% Mo(m-xylene) 2 The TGA residue was 0.05%, and DSC showed an exotherm at 280°C.

[0166] Example 13: Mo(Ar 1 )(Ar 2 Preparation of a liquid mixture of compounds (wherein Ar 1 and Ar 2 are independently selected aromatic hydrocarbons, and Mo (m-xylene) 2 Greater than 15%)

[0167] Mo (m-xylene) from Example 9 2The sample (52 g) 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 the solution was cooled to room temperature, the black solid was filtered out through silica gel and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum to obtain a green liquid residue. After distillation at 130-140°C and 0.15-0.2 mmHg, 47 g of product was obtained with a yield of 90%. 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) 2 After overnight, a solid formed in the flask. TGA residual was 1%, and DSC showed an exothermic event at 272°C. Experiments have shown that in order to avoid the formation of solids in the desired liquid formulation, residual Mo (m-xylene) 2 The amount should be <15 mol%.

[0168] Example 14: Mo(Ar 1 )(Ar 2 ) The viscosity of the liquid mixture of the compound (where Ar 1 and Ar 2 are each independently selected aromatic hydrocarbon, and Mo(EtBz) 2 About 80%

[0169] Mo (m-xylene) from Example 9 2 The sample (55 g) was dissolved in anhydrous ethylbenzene (250 g) to form a green suspension. The green suspension was heated to 139.7°C for 24 hours under nitrogen. After the solution was cooled to room temperature, the black solid was filtered out through silica gel, and the remaining green filtrate was collected. After filtering through silica gel, mirror-like Mo metal was found on the top of the silica gel. All volatiles were removed from the green filtrate under vacuum to obtain a green liquid residue. 50 g of product was obtained with a yield of 90%. 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 contains 81% Mo(EtBz) 2 , 17.4% Mo(EtBz)(m-xylene) and 1.6% Mo(m-xylene) 2 The viscosity of this sample is 10 mPa-s, which is significantly lower than the commercially available Mo(EtBz) 2 The composition of the present invention is 100% pure. Trace metal analysis by ICP-MS showed that the composition contained only less than 3 ppm of aluminum. Ion chromatography showed that the amount of residual chlorine was also reduced to <1 ppm.

[0170] The compositions of the molybdenum aromatic mixtures of Examples 10-14 are summarized in Table 4:

[0171] Example <![CDATA[Mo(EtBz) 2 ]]> Mo(EtBz)(m-Xylene) <![CDATA[Mo(m - xylene) 2 > EtBz: Meta-xylene 10 60 30 10 75:25 11 80.5 18 1.5 89.5:10.5 12 80 18 2 89:11 13 65 19 16 74.5:25.5 14 81 17.4 1.6 89.7:10.3

[0172] Table 4

[0173] Example 15: Mo(Ar 1 )(Ar 2 Preparation of a liquid mixture of compounds (wherein Ar 1 and Ar 2 are each independently selected aromatic hydrocarbon, and Mo(EtBz) 2 More than 90%)

[0174] 110 grams of the composition from Example 12 was dissolved in anhydrous ethylbenzene (120 grams) 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 out through silica gel and the remaining green filtrate was collected. All volatiles were removed from the green filtrate under vacuum to obtain a green liquid residue. The product was characterized by NMR spectroscopy and its composition was analyzed based on the peak integration described in Example 10. Based on NMR analysis, the product contained 90% Mo(EtBz) 2 , 9.5% Mo(EtBz)(m-xylene) and 0.5% Mo(m-xylene) 2 .

[0175] Example 16: Using hot hydrogen and Mo(Ar 1 )(Ar 2 ) liquid mixture of compounds (where Ar 1 and Ar 2 are each independently selected aromatic hydrocarbon, and Mo(EtBz) 2 Mo-containing film is deposited at about 70%

[0176] During the deposition process, 50 sccm of argon gas was passed through a molten-liquid phase filled with 70.6% Mo(EtBz) 2 , 22.0% Mo(EtBz)(m-xylene) and 7.4% Mo(m-xylene) 2 The compound was delivered to the deposition reactor chamber by a stainless steel container heated to 110°C. The chamber pressure was 20 Torr. The substrates were TiN, Cu, Pt and SiO 2 The Mo-containing film was deposited at 400°C by a cyclic chemical vapor deposition (CCVD) process, which included the following steps:

[0177] a. providing a substrate in a deposition reaction chamber;

[0178] b. Introducing molybdenum aromatic vapor into the deposition reaction chamber for 10 seconds;

[0179] c. Purge the deposition reaction chamber with argon purge gas for 30 seconds;

[0180] d. Introducing hydrogen gas into the deposition reactor chamber at 1000 sccm for 10 seconds;

[0181] e. purging the deposition chamber with argon for 10 seconds; and

[0182] f. Repeat steps b to e sequentially 100 times.

[0183] The film thicknesses of the Mo-containing films on different substrates are summarized in Table 5.

[0184]

[0185] This example shows the selective deposition of a molybdenum-containing film on a copper substrate.

[0186] Example 17: Using diiodobutane and Mo(Ar 1 )(Ar 2 ) liquid mixture of compounds (where Ar 1 and Ar 2 are each independently selected aromatic hydrocarbon, and Mo(EtBz) 2 Mo-containing film is deposited at about 70%

[0187] During the deposition process, 50 sccm of argon gas was passed through a 70.6% Mo(EtBz) filled 2 , 22.0% Mo(EtBz)(m-xylene) and 7.4% Mo(m-xylene) 2 A stainless steel container containing molybdenum aromatic compounds and heated to 110°C was used to deliver the compounds to the deposition reactor chamber. The chamber pressure was 10 Torr. The substrates were TiN, Cu, Pt, and SiO 2 A separate pulse of diiodobutane was also delivered to the deposition reactor chamber by passing 50 seem of argon through a stainless steel vessel filled with diiodobutane and heated to 50°C. The Mo-containing film was deposited at 400°C by a cyclic chemical vapor deposition (CCVD) process comprising the following steps:

[0188] a. providing a substrate in a deposition reaction chamber;

[0189] b. introducing molybdenum aromatic vapor into the deposition reaction chamber for 20 seconds;

[0190] c. Purge the deposition reaction chamber with argon purge gas for 30 seconds;

[0191] d. introducing diiodobutane vapor into the deposition chamber for 20 seconds;

[0192] e. purging the deposition chamber with argon for 42 seconds; and

[0193] f. Repeat steps b to e sequentially 100 times.

[0194] The film thickness of Mo-containing films on different substrates is summarized in Table 6

[0195]

[0196] The resistivity of the Mo-containing film deposited on silicon oxide was measured by a four-point probe method and was 260 μOhm·cm.

[0197] Example 18: Using diiodobutane and Mo(Ar 1 )(Ar 2 ) liquid mixture of compounds (where Ar 1 and Ar 2 are each independently selected aromatic hydrocarbon, and Mo(EtBz) 2 Mo-containing film is deposited at about 70%

[0198] During the deposition process, 50 sccm of argon gas was passed through a 70.6% Mo(EtBz) filled 2 , 22.0% Mo(EtBz)(m-xylene) and 7.4% Mo(m-xylene) 2 A stainless steel container containing molybdenum aromatic compounds and heated to 110°C was used to deliver the compounds to the deposition reactor chamber. The chamber pressure was 10 Torr. The substrates were TiN, Cu, Pt, and SiO 2 A separate pulse of diiodobutane was also delivered to the deposition reactor chamber by passing 50 seem of argon through a stainless steel vessel filled with diiodobutane and heated to 50°C. The Mo-containing film was deposited at 300°C by a cyclic chemical vapor deposition (CCVD) process comprising the following steps:

[0199] a. providing a substrate in a deposition reaction chamber;

[0200] b. introducing molybdenum aromatic vapor into the deposition reaction chamber for 20 seconds;

[0201] c. Purge the deposition reaction chamber with argon purge gas for 30 seconds;

[0202] d. introducing diiodobutane vapor into the deposition reactor chamber for 2 seconds;

[0203] e. Purge the deposition reaction chamber with argon for 42 seconds;

[0204] f. Repeat steps b to e sequentially 100 times.

[0205] The film thicknesses of the Mo-containing films on different substrates are summarized in Table 7.

[0206]

[0207] The resistivity of the Mo-containing film deposited on silicon oxide was measured by a four-point probe method and was 131 μOhm·cm. This example shows the deposition of a Mo-containing film with a resistivity below 150 μOhm·cm. It is expected that with further process optimization, the film resistivity can be reduced to below 50 μOhm.

[0208] It is expected that the method of the present invention can be used in conjunction with deposition equipment commonly found in semiconductor manufacturing locations to produce molybdenum-containing layers for logic applications and other potential functions.

[0209] The foregoing description is intended primarily for illustrative purposes. Although the disclosed and claimed subject matter has been shown and described with respect to exemplary embodiments thereof, it will be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions may be made to its form and details without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A Mo(Ar 1 )(Ar 2 ) compounds, comprising from about 60 mol % to about 95 mol % of an EtBz ligand, wherein Ar 1 and Ar 2 is an aromatic ligand, and the mole % is based on Ar 1 and Ar 2 The total number of moles of a compound wherein the compound is a liquid.

2. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture comprises from about 60 mol % to about 90 mol % of the EtBz ligand.

3. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture comprises from about 65 mol % to about 85 mol % of the EtBz ligand.

4. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture comprises from about 70 mol % to about 80 mol % of the EtBz ligand.

5. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture comprises from about 60 mol % to about 65 mol % of the EtBz ligand.

6. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture comprises from about 65 mol % to about 70 mol % of the EtBz ligand.

7. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture comprises from about 70 mol % to about 75 mol % of the EtBz ligand.

8. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture comprises from about 75 mol % to about 80 mol % of the EtBz ligand.

9. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture comprises from about 80 mol % to about 85 mol % of the EtBz ligand.

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

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

12. Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises from about 0.25 mol % to about 13 mol % of a Bz ligand, and wherein the total amount of the ligand does not exceed 100 mol %.

13. Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises from about 5 mol % to about 13 mol % of a Bz ligand, and wherein the total amount of the ligand does not exceed 100 mol %.

14. Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises from about 5 mol % to about 10 mol % of a Bz ligand, and wherein the total amount of the ligand does not exceed 100 mol %.

15. The Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises from about 10 mol % to about 13 mol % of a Bz ligand, and wherein the total amount of the ligand does not exceed 100 mol %.

16. Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises from about 6.75 mol % to about 44.5 mol % of Et2Bz ligands, and wherein the total amount of the ligands does not exceed 100 mol %.

17. The Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises from about 6.75 mol % to about 10 mol % of Et2Bz ligands, and wherein the total amount of the ligands does not exceed 100 mol %.

18. Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises from about 10 mol % to about 15 mol % of Et2Bz ligands, and wherein the total amount of the ligands does not exceed 100 mol %.

19. The Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises from about 15 mol % to about 20 mol % of Et2Bz ligands, and wherein the total amount of the ligands does not exceed 100 mol %.

20. The Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises from about 0.75 mol % to about 7 mol % of Et3Bz ligands, and wherein the total amount of the ligands does not exceed 100 mol %.

21. Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises about 1 mol % to about 3 mol % of Et3Bz ligands, and wherein the total amount of the ligands does not exceed 100 mol %.

22. The Mo(Ar) according to claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises about 3 mol % to about 7 mol % of Et3Bz ligands, and wherein the total amount of the ligands does not exceed 100 mol %.

23. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises about 1 mol % to about 2 mol % of Et3Bz ligands, and wherein the total amount of the ligands does not exceed 100 mol %.

24. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture further comprises (i) from about 0.25 mol % to about 13 mol % of a Bz ligand, (ii) from about 6.75 mol % to about 44.5 mol % of an Et2Bz ligand, and (iii) from about 0.75 mol % to about 7 mol % of Et3Bz, and wherein the total amount of the ligands does not exceed 100 mol %.

25. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 500 cP.

26. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 250 cP.

27. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 100 cP.

28. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 50 cP.

29. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 25 cP.

30. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 10 cP.

31. A method comprising Mo(Ar 1 )(Ar 2 ) a mixture of compounds, wherein (i)Ar 1 and Ar 2 each comprising a different aromatic structure; and (ii)Ar 1 and Ar 2 Each has the same amount of carbon.

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

33. The mixture of claim 31, wherein Ar 1 and Ar 2 At least one of the above comprises one or more substituents selected from unsubstituted straight-chain C1-C6 alkyl, straight-chain C1-C6 alkyl substituted by halogen, straight-chain C1-C6 alkyl substituted by amino, unsubstituted branched C3-C6 alkyl, branched C3-C6 alkyl substituted by halogen or branched C3-C6 alkyl substituted by amino, unsubstituted amine or substituted amine.

34. The mixture of claim 31, wherein Ar 1 and Ar 2 Each contains one or more different substituents selected from unsubstituted straight-chain C1-C6 alkyl groups, straight-chain C1-C6 alkyl groups substituted by halogen, straight-chain C1-C6 alkyl groups substituted by amino groups, unsubstituted branched-chain C3-C6 alkyl groups, branched-chain C3-C6 alkyl groups substituted by halogen or branched-chain C3-C6 alkyl groups substituted by amino groups, unsubstituted amines or substituted amines.

35. The mixture of claim 31, wherein Ar 1 and Ar 2 At least one of the above comprises one or more substituents which are unsubstituted linear C1-C3 alkyl groups.

36. The mixture of claim 31, wherein Ar 1 and Ar 2 Each contains one or more substituents which are unsubstituted straight-chain C1-C3 alkyl groups.

37. The mixture of claim 31, wherein Ar 1 and Ar 2 Each contains one or more substituents which are C1-C3 alkyl groups.

38. The mixture of claim 31, wherein Ar 1 and Ar 2 Each contains one or more substituents which are methyl groups.

39. The mixture of claim 31, wherein Ar 1 and Ar 2 Each contains one or more substituents which are ethyl groups.

40. The mixture of claim 31, wherein Ar 1 and Ar 2 Each contains one or more substituents which are propyl groups.

41. The mixture of claim 31, wherein Ar 1 and Ar 2 Each contains one substituent or two substituents.

42. The mixture of claim 31, wherein Ar 1 and Ar 2 At least one of them is a 5-membered aromatic hydrocarbon.

43. The mixture of claim 31, wherein Ar 1 and Ar 2 At least one of them is a 6-membered aromatic hydrocarbon.

44. The mixture of claim 31, wherein Ar 1 and Ar 2 At least one of the is a 5-membered heteroaromatic hydrocarbon.

45. The mixture of claim 31, wherein Ar 1 and Ar 2 At least one of the is a 6-membered heteroaromatic hydrocarbon.

46. ​​The mixture of claim 31, wherein Ar 1 and Ar 2 Each is a 5-membered ring aromatic hydrocarbon.

47. The mixture of claim 31, wherein Ar 1 and Ar 2 Each is a 6-membered aromatic hydrocarbon.

48. The mixture of claim 31, wherein Ar 1 and Ar 2 Each is a 5-membered heterocyclic aromatic hydrocarbon.

49. The mixture of claim 31, wherein Ar 1 and Ar 2 Each is a 6-membered heterocyclic aromatic hydrocarbon.

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

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

52. The mixture of claim 31, wherein Ar 1 and Ar 2 One of them is EtBz, and Ar 1 and Ar 2 Another one in the list is Me2Bz.

53. The mixture of claim 31, wherein Ar 1 and Ar 2 One of them is EtBz, and Ar 1 and Ar 2 Another one of them is m-Me2Bz.

54. The mixture of claim 31, wherein the Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 500 cP.

55. The mixture of claim 31, wherein the mixture comprises Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 250 cP.

56. The mixture of claim 31, wherein the mixture comprises Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 100 cP.

57. The mixture of claim 31, wherein the mixture comprises Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 50 cP.

58. The mixture of claim 31, wherein the mixture comprises Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 25 cP.

59. The mixture of claim 31, wherein the mixture comprises Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 10 cP.

60. A method comprising Mo(Ar 1 )(Ar 2 ) a mixture of compounds, wherein (i)Ar 1 and Ar 2 each comprising a different aromatic structure; and (ii)Ar 1 and Ar 2 Each has substantially the same molecular weight.

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

62. The mixture of claim 60, wherein Ar 1 and Ar 2 have the same molecular weight.

63. The mixture of claim 60, wherein Ar 1 and Ar 2 At least one of the above comprises one or more substituents selected from unsubstituted straight-chain C1-C6 alkyl, straight-chain C1-C6 alkyl substituted by halogen, straight-chain C1-C6 alkyl substituted by amino, unsubstituted branched C3-C6 alkyl, branched C3-C6 alkyl substituted by halogen or branched C3-C6 alkyl substituted by amino, unsubstituted amine or substituted amine.

64. The mixture of claim 60, wherein Ar 1 and Ar 2 Each contains one or more different substituents selected from unsubstituted straight-chain C1-C6 alkyl groups, straight-chain C1-C6 alkyl groups substituted by halogen, straight-chain C1-C6 alkyl groups substituted by amino groups, unsubstituted branched-chain C3-C6 alkyl groups, branched-chain C3-C6 alkyl groups substituted by halogen or branched-chain C3-C6 alkyl groups substituted by amino groups, unsubstituted amines or substituted amines.

65. The mixture of claim 60, wherein Ar 1 and Ar 2 At least one of the above comprises one or more substituents which are unsubstituted linear C1-C3 alkyl groups.

66. The mixture of claim 60, wherein Ar 1 and Ar 2 Each contains one or more substituents which are unsubstituted straight-chain C1-C3 alkyl groups.

67. The mixture of claim 60, wherein Ar 1 and Ar 2 Each contains one or more substituents which are C1-C3 alkyl groups.

68. The mixture of claim 60, wherein Ar 1 and Ar 2 Each contains one or more substituents which are methyl groups.

69. The mixture of claim 60, wherein Ar 1 and Ar 2 Each contains one or more substituents which are ethyl groups.

70. The mixture of claim 60, wherein Ar 1 and Ar 2 Each contains one or more substituents which are propyl groups.

71. The mixture of claim 60, wherein Ar 1 and Ar 2 Each contains one substituent or two substituents.

72. The mixture of claim 60, wherein Ar 1 and Ar 2 At least one of them is a 5-membered aromatic hydrocarbon.

73. The mixture of claim 60, wherein Ar 1 and Ar 2 At least one of them is a 6-membered aromatic hydrocarbon.

74. The mixture of claim 60, wherein Ar 1 and Ar 2 At least one of the is a 5-membered heteroaromatic hydrocarbon.

75. The mixture of claim 60, wherein Ar 1 and Ar 2 At least one of the is a 6-membered heteroaromatic hydrocarbon.

76. The mixture of claim 60, wherein Ar 1 and Ar 2 Each is a 5-membered ring aromatic hydrocarbon.

77. The mixture of claim 60, wherein Ar 1 and Ar 2 Each is a 6-membered aromatic hydrocarbon.

78. The mixture of claim 60, wherein Ar 1 and Ar 2 Each is a 5-membered heterocyclic aromatic hydrocarbon.

79. The mixture of claim 60, wherein Ar 1 and Ar 2 Each is a 6-membered heterocyclic aromatic hydrocarbon.

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

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

82. The mixture of claim 60, wherein Ar 1 and Ar 2 One of them is EtBz, and Ar 1 and Ar 2 Another one in the list is Me2Bz.

83. The mixture of claim 60, wherein Ar 1 and Ar 2 One of them is EtBz, and Ar 1 and Ar 2 Another one of them is m-Me2Bz.

84. The mixture of claim 60, wherein the 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 500 cP.

85. The mixture of claim 60, wherein the 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 250 cP.

86. The mixture of claim 60, wherein the 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 100 cP.

87. The mixture of claim 60, wherein the 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 50 cP.

88. The mixture of claim 60, wherein the 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 25 cP.

89. The mixture of claim 60, wherein the mixture comprises Mo(Ar 1 )(Ar 2 )The mixture of compounds has a viscosity less than or equal to about 15 cP.

90. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture is substantially free of halide ions.

91. Mo(Ar) as claimed in claim 1 1 )(Ar 2 ) compounds, wherein the mixture is substantially free of chloride ions.

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

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

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

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

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

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

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

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

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

101. A method for forming a transition metal-containing film on at least one surface of a substrate, comprising: a. providing a substrate in a reaction vessel; b. introducing into the reaction vessel one or more precursors comprising one or more mixtures as described in 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. Repeat steps b to e sequentially until a Mo-containing film of desired thickness is obtained.

102. The method of claim 101, wherein the source gas is one or more oxygen-containing source gases selected from water, diatomic oxygen, oxygen plasma, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide, and combinations thereof.

103. 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. 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. The method of claim 101 further comprises applying energy to the one or more precursors, the source gas, the substrate or a combination thereof, wherein the energy is one or more of heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods and combinations thereof.

106. 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 transport the vapor of the one or more precursors into the reaction vessel.

107. 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 and decalin and combinations thereof.

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

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