Metal Carbonyl Complexes with Phosphorus-Based Ligands for Use in CVD and ALD

Abstract

The disclosed and claimed invention relates to metal (e.g., Cr, Mo, and W) carbonyl complexes with phosphorus-based ligands that have improved (i.e., higher) thermal stability and low melting points, compositions containing the compounds, and methods of using the compounds as precursors for the deposition of metal-containing films.

Description

[Technical field]

[0001] The disclosed and claimed invention relates to molybdenum carbonyl complexes having phosphorus-based ligands with improved (i.e., higher) thermal stability and low melting points, compositions containing the compounds, and methods of using the compounds as precursors for the deposition of metal-containing films. [Background technology]

[0002] Transition metal-containing films are used in semiconductor and electronics applications. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been used as the primary deposition techniques to produce thin films for semiconductor devices. These methods allow the achievement of conformal films (metal, metal oxide, metal nitride, metal silicide, etc.) through chemical reactions of metal-containing compounds (precursors). These chemical reactions occur on surfaces that may include metal, metal oxide, metal nitride, metal silicide, and other surfaces. In CVD and ALD, the precursor molecules play a key role in achieving high quality films with high conformality and low impurities. The temperature of the substrate in CVD and ALD processes is one of the important points to consider when selecting the precursor molecules. Higher substrate temperatures, ranging from 150° C. to 500° C., result in faster film growth rates. The preferred precursor molecules should be stable in this temperature range. The preferred precursors can be delivered to the reaction vessel in liquid phase. Liquid phase delivery of precursors generally results in more uniform delivery of precursors to the reaction vessel than solid phase precursors.

[0003] CVD and ALD processes are increasingly used because they have the advantages of enhanced composition control, high film uniformity, and effective control of doping. In addition, CVD and ALD processes provide excellent conformal step coverage on the highly non-planar topography associated with modern microelectronic devices. CVD and ALD are particularly attractive for producing conformal metal-containing films using these metal-containing precursors on substrates such as silicon, silicon oxide, metal nitride, metal oxide, and other metal-containing layers. In these techniques, the vapor of a volatile metal complex is introduced into a process chamber where it contacts the surface of a silicon wafer, and then a chemical reaction occurs to deposit a thin film of a pure metal or metal compound.

[0004] CVD is a chemical process in which precursors are used to form thin films on a substrate surface. In a typical CVD process, precursors are flowed onto the surface of a substrate (e.g., a wafer) in a low-pressure or ambient pressure reaction chamber. The precursors react and / or decompose on the substrate surface to form a thin film of deposited material. Plasma can be used to assist the reaction of the precursors or to improve the properties of the material. Non-volatile by-products are removed by flowing gas through the reaction chamber. The deposited film thickness can be difficult to control, as it depends on the coordination of many parameters such as temperature, pressure, gas volume flow and uniformity, chemical depletion effects, and time. Thus, CVD occurs when precursors react on the wafer surface, either thermally or with reagents added simultaneously in the process chamber, and film growth occurs in steady-state deposition. CVD can be applied in a continuous or pulsed mode to achieve the desired film thickness.

[0005] ALD is one of the chemical methods for the deposition of thin films. It is a self-limiting, continuous, and unique film growth technique based on surface reactions that can provide precise thickness control and can deposit conformal thin films of materials provided by precursors on surface substrates of various compositions. In ALD, each precursor is separated during the reaction. A first precursor is flowed onto the substrate surface to produce a monolayer on the substrate surface. Excess unreacted precursor is evacuated from the reaction chamber. A second precursor or co-reactant is then flowed onto the substrate surface and reacts with the first precursor to form a second monolayer of film on the first formed monolayer of film on the substrate surface. Plasma can be used to assist the reaction of precursors or co-reactants or to improve material quality. This cycle is repeated until a film of the desired thickness is formed. ALD provides the deposition of ultra-thin, yet continuous, metal-containing films with precise control of film thickness, excellent film thickness uniformity, and exceptionally conformal film growth for flat coating of deeply etched and highly intricate structures such as interconnect vias and trenches. Therefore, ALD is typically preferred for depositing thin films on features with high aspect ratios.

[0006] Thin films, particularly metal-containing thin films, have a variety of important applications in nanotechnology and in the manufacture of semiconductor devices. Examples of such applications include capacitor electrodes, gate electrodes, adhesive diffusion barriers, and integrated circuits. However, the size of microelectronic components, such as semiconductor devices, is constantly shrinking, presenting several technical challenges and increasing the demand for improved thin film technologies. In particular, microelectronic components may include features on or in a substrate that require filling, for example, to form conductive paths or to form interconnects. Filling such features, especially in smaller and smaller microelectronic components, can be difficult as these features can become increasingly thin or narrow. As a result, complete filling of the feature, for example by ALD, would require infinitely long cycle times as the feature thickness approaches zero. Furthermore, when the feature thickness becomes thinner than the molecular size of the precursor, the feature cannot be completely filled. As a result, ALD may leave a hollow seam in the center of the feature. The presence of such a hollow seam in the feature is undesirable as it may lead to device failure. Therefore, there is great interest in developing thin film deposition methods, particularly ALD methods, that can selectively grow films on more than one substrate and achieve improved filling of features on or in a substrate, such as depositing metal-containing films such that the features are substantially filled without the introduction of voids.

[0007] As can be seen from the above, in conventional semiconductor device manufacturing, patterning is a "top-down" process based mainly on photolithography and etching, which is the main bottleneck for device size reduction. In contrast, area-selective deposition (e.g., CVD and ALD) provides an alternative "bottom-up" method of patterning for advanced semiconductor manufacturing, in which a metal layer (e.g., Ru) does not grow on the dielectric (e.g., SiO2) sidewalls, but grows on the bottom metal surface (e.g., Ru and TiN) adjacent to the passivated dielectric substrate. See, e.g., FIG. 1. It is also desirable that these processes be oxygen-free and / or have relatively low resistance.

[0008] In other applications, it is desirable to deposit dielectric films only on other dielectric films and not on metal surfaces. See, for example, FIG. 2. One potential application of such a process is self-aligned fabrication. The most common strategy to achieve selective growth is based on selective passivation of the non-growth surface. Small volatile molecules are highly desirable for passivation because they can be delivered via the gas phase. The selective passivation of non-metallic surfaces that contain a high concentration of hydroxyl groups is becoming widely used, which can be achieved by using a variety of silylating agents, e.g., R x SiCl y , R x Si(NR2) y On the other hand, selective passivation of metal surfaces is much more difficult, and the selectivity of this approach can easily be lost due to desorption of the passivating agent and incomplete passivation due to residual impurities on the surface of the metal film, etc. Typically, single-component reagents are used to passivate non-growth surfaces. However, single-component reagents may not provide complete surface coverage of the metal surface due to the presence of various sites on the metal surface, such as "bare" metal, metal terminated with hydrogen atoms, metal terminated with oxygen atoms or hydroxyl groups, etc.

[0009] As shown above, in the ALD process, thin films can be deposited by the reaction of organometallic precursors and co-reactants separated by an inert gas purge. Due to its unique mechanism, only ALD is capable of coating three-dimensional (3D) surfaces with atomic precision, making this method essential for the semiconductor industry.

[0010] One of the benchmark precursors for the deposition of Mo-containing materials is molybdenum hexacarbonyl (i.e., Mo(CO)6). Despite its excellent volatility for vapor deposition methods, the main problems of Mo(CO)6 are its physical solid-state state and narrow ALD window (temperature area where the precursor undergoes ALD-like surface-limited processes). The lowest possible deposition temperature is limited by its weak reactivity, while its lack of thermal stability limits the temperature window at relatively high temperatures. The unfavorable thermal properties of Mo(CO)6 can be attributed to the binding motif of the neutral CO ligand to the Mo(0) center. First, Mo(CO)6 is an 18-electron complex with strong σ-bonds and π-backbonds, and therefore is stable with low reactivity at room temperature. Second, CO is a stable molecule in itself and is therefore a good leaving group, which results in low thermal stability at elevated temperatures. As a result, Mo(CO)6 exhibits very narrow process conditions, which makes it unsuitable for many practical applications. Furthermore, deposition temperatures close to the decomposition temperature of Mo(CO)6 are required, which may result in increased amounts of impurities in the film.

[0011] In view of the above, the art has recognized a need to provide alternative precursors for deposition processes such as CVD and ALD to address the shortcomings of Mo(CO)6. For example, Mo(PCl2Me)(CO)5 has been described as an attractive alternative due to its enhanced thermal stability. The thermal stability of Mo(PCl2Me)(CO)5 is due to the presence of chlorine-phosphorus, which is an electron donor and accordingly (i) enhances the electron density at the Mo center and (ii) consequently enhances π back-donation to the CO ligand. However, a problem with Mo(PCl2Me)(CO)5 and similar materials is that they contain chloride, which should generally be avoided in deposition processes to avoid chlorine contamination of the as-deposited film.

[0012] Therefore, there is a need for a precursor that eliminates the drawbacks of Mo(CO)6 while avoiding the contamination issues associated with Mo(PCl2Me)(CO)5 and similar materials, yet is still suitable as a CVD and ALC precursor. Preferably, such an alternative precursor would be capable of being delivered in the liquid phase, and would produce high quality films with low impurity levels and high conformality. [Prior art documents] [Non-patent literature]

[0013] [Non-Patent Document 1] Smith, Donald, Thin-Film Deposition: Principles and Practice, McGraw-Hill (1995) [Non-Patent Document 2] George et al.J.Phys.Chem.100:13121-31(1996) [Non-Patent Document 3] Potter et al.,Chem.Vap.Deposition11(3):159-69(2005) [Non-Patent Document 4] Brown and Darensbourg,Inorg.Chem.,Vol.7,No.5(1968) Summary of the Invention

[0014] The disclosed and claimed invention relates to halogen-free molybdenum carbonyl compounds having phosphorus-based ligands with improved (i.e., higher) thermal stability and low melting points, compositions containing the compounds, and methods of using the compounds as precursors for the deposition of metal-containing films.

[0015] In one aspect, the disclosed and claimed invention relates to compounds of formula IA, formula IB, and IC (and mixtures thereof) (collectively, "compounds of formula I").

[0016] [ka] In the formula, (i) M is one of Mo, W, and Cr; and (ii) R 1 , R 2 and R 3 are each independently one of an unsubstituted linear C1-C8 alkyl, an unsubstituted branched C3-C8 alkyl group, a linear or branched C2-C6 alkylene, a C3-C8 saturated cyclic alkyl, and a C5-C8 arene, and (iii) X is 1, 2, 3, 4, or 5. Importantly, the disclosed and claimed compounds are substantially free or free of halogens (i.e., R 1 , R 2 and R 3 (none of which contain halogens) and are substantially free or free of other materials that would interfere with the use of the precursors in CVD and ALD applications. More specific aspects and embodiments of the compounds of formula I are described in detail below.

[0017] The disclosed and claimed invention further includes (i) compositions and formulations comprising the compounds of formula I, (ii) methods of using the disclosed and claimed compounds of formula I in deposition processes, and (iii) metal-containing films derived from the disclosed and claimed compounds of formula I produced in deposition processes.

[0018] The accompanying drawings are intended to provide a further understanding of the disclosed invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed invention, and together with the detailed description of the invention, serve to explain the principles of the disclosed invention. [Brief description of the drawings]

[0019] [Figure 1] FIG. 1 shows an exemplary target for a selective deposition process in which a metal film is selectively deposited onto a conductive film, while a dielectric film is passivated. [Diagram 2] FIG. 2 shows an exemplary target for a selective deposition process in which a dielectric film is selectively deposited on a dielectric film while the metal surface is passivated. [Diagram 3] FIG. 3 shows a thermogravimetric analysis (TGA) of an exemplary precursor (trimethylphosphite pentacarbonylmolybdenum) of the disclosure and claimed invention from Example 1. [Figure 4] FIG. 4 shows the differential scanning calorimetry (DSC) of an exemplary precursor (trimethylphosphite pentacarbonylmolybdenum) of the disclosure and claimed invention from Example 1. [Diagram 5] FIG. 5 shows the 1H NMR spectrum of an exemplary precursor (trimethylphosphite pentacarbonylmolybdenum) of the disclosure and claimed invention from Example 1. [Figure 6] FIG. 6 shows the 13C NMR spectrum of an exemplary precursor (trimethylphosphite pentacarbonylmolybdenum) of the disclosure and claimed invention from Example 1. [Figure 7] FIG. 7 shows the 31P NMR spectrum of an exemplary precursor (trimethylphosphite pentacarbonylmolybdenum) of the disclosure and claimed invention from Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The use of the singular and similar referents in the context of the description of the disclosed and claimed invention (especially in the context of the subclaims) should be construed to include both the singular and the plural, unless otherwise indicated or clearly contradicted by the context. The terms "comprises," "having," "including," and "containing" should be construed as non-exclusive (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of numerical ranges, unless otherwise indicated herein, is merely intended to serve as a shorthand method of referring to each and every separate value falling within the range, and each separate value shall be set forth in the specification as if each were set forth herein individually. All methods described herein may be performed in any suitable order, unless otherwise indicated or otherwise clearly contradicted by the context. The use of any and all examples or exemplary language (e.g., "etc.") described herein, unless otherwise indicated, is merely intended to facilitate easier understanding of the disclosed and claimed invention, and does not limit the scope of the disclosed and claimed invention. Nothing in the specification should be construed as representing any non-claimed subject matter as essential to the practice of the disclosed and claimed invention. Use of terms such as "comprising" in the specification and claims encompasses the narrower terms "consisting essentially of" and "consisting of."

[0021] Aspects of the disclosed and claimed invention are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed invention. Variations of these aspects will become apparent to those of skill in the art upon reading the foregoing description. The inventors anticipate that such variations may be employed by those of skill in the art, and the inventors intend that the disclosed and claimed invention may be practiced otherwise than as specifically described herein. Accordingly, the disclosed and claimed invention is intended to include all modifications and equivalents / methods of the claimed invention to the extent permitted by applicable law. Moreover, any combination of the above-described features in all possible variations is included in the disclosed and claimed invention unless otherwise indicated or clearly contradicted by context.

[0022] The term “alkylene” refers to an alkylene linkage between (i) one carbon atom in a cyclopentadienyl (“Cp”) group and (ii) an O or N atom, preferably a C bridge, such as an ethylene bridge. 1-4 It refers to an alkylene linkage. Specific examples of alkylene linkages include methylene (-CH-), ethylene (-CHCH-), substituted ethylene (e.g., -CH(CH)CH-; -CH(CH)CH(CH)-; -C(CH)CH-), propylene (-CHCHCH-), substituted propylene, and the like.

[0023] The term "arene" refers to aromatic organic compounds containing only carbon and hydrogen atoms.

[0024] The term "silicon" (silicon) as the material deposited on a microelectronic device is understood to include polysilicon.

[0025] For ease of reference, "microelectronic devices" or "semiconductor devices" are It corresponds to semiconductor wafers with integrated circuits, memories and other electronic structures formed thereon, and microelectromechanical systems (MEMS) manufactured for use in flat panel displays, phase change memory devices, solar panels, and other products including substrates for solar cells, photovoltaic power generation devices, and microelectronic, integrated circuit, or computer chip applications. Substrates for solar cells include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Substrates for solar cells may be doped or undoped. The terms "microelectronic device" or "semiconductor device" are not meant to be limiting in any way and include any substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0026] As defined herein, the term "barrier material" corresponds to any material used in the art to encapsulate metal lines, e.g., copper interconnects, to minimize the diffusion of said 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.

[0027] "Substantially free" is defined herein as less than 0.001% by weight. "Substantially free" also includes 0.000% by weight. The term "free" means 0.000% by weight. As used herein, "about" or "approximately" is intended to mean within ±5% of the stated value.

[0028] In all such compositions where specific components of the composition are described by reference to weight percentage (or "wt %") ranges, including a zero lower limit, it is understood that such components may be present or absent in various specific embodiments of the composition, and that in instances 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 component is used. All of these percentages of components are weight percents and are based on the total weight of the composition, i.e., 100%. References to "one or more" or "at least one" include "two or more," "three or more," etc.

[0029] If applicable, and unless otherwise indicated, all weight percentages are "net," meaning that they do not include the aqueous solution they are in when added to the composition. For example, "net" refers to the weight percent amount of undiluted acid or other material (i.e., if you have 100 g of 85% phosphoric acid, it is made up of 85 g of that acid and 15 g of diluent).

[0030] Further, when compositions described herein are referred to in terms of weight percent, it is understood that in any case the weight percents of all components, including non-essential components such as impurities, do not add up to more than 100 weight percent. In a composition "consisting essentially" of the described components, such components may add up to 100 weight percent of the composition or may add up to less than 100 weight percent. When the components add up to less than 100 weight percent, such compositions may contain some small amount of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 weight percent or less of impurities. In another embodiment, the formulation may contain 1 weight percent or less of impurities. In yet another embodiment, the formulation may contain 0.05 weight percent or less of impurities. In other such embodiments, the components may comprise at least 90 weight percent, more preferably at least 95 weight percent, more preferably at least 99 weight percent, more preferably at least 99.5 weight percent, and most preferably at least 99.9 weight percent, and may include other components that do not substantially affect the performance of the wet etchant. Otherwise, in the absence of significant non-essential impurity components, the composition of all essential constituents will be understood to add up to essentially 100% by weight.

[0031] The headings used herein are not intended to be limiting; they are included solely for organizational purposes.

[0032] Exemplary embodiments In one aspect, the disclosed and claimed invention relates to compounds of formula IA, formula IB, and IC (and mixtures thereof) (collectively, "compounds of formula I").

[0033] [ka] In the formula, (i) M is one of Mo, W, and Cr; and (ii) R 1 , R 2 and R 3are each independently one of an unsubstituted linear C1-C8 alkyl group, an unsubstituted branched C3-C8 alkyl group, a linear or branched C2-C6 alkylene, a C3-C8 saturated cyclic alkyl, and a C5-C8 arene; and (iii) X is 1, 2, 3, 4, or 5.

[0034] In one aspect of this embodiment, M is molybdenum (Mo). In another aspect of this embodiment, M is tungsten (W). In another aspect of this embodiment, M is chromium (Cr).

[0035] In one aspect of this embodiment, the compound comprises, consists essentially of, or consists of one or more compounds of formula IA. In one aspect of this embodiment, the compound comprises, consists essentially of, or consists of one or more compounds of formula IB. In one aspect of this embodiment, the compound comprises, consists essentially of, or consists of one or more compounds of formula IC. In one aspect of this embodiment, the compound comprises, consists essentially of, or consists of a mixture of two or more of compounds of formula IA, compounds of formula IB, and compounds of formula IC. In one aspect of this embodiment, the compound comprises, consists essentially of, or consists of a mixture of one or more compounds of each of compounds of formula IA, compounds of formula IB, and compounds of formula IC.

[0036] In one aspect of this embodiment, R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 One or more of are each independently an octyl group.

[0037] In another aspect of this embodiment, R 1 , R 2 and R 3 and R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 One or more of R are each independently a tert-butyl group. 1, R 2 and R 3 One or more of are each independently a tert-pentyl group.

[0038] In one aspect of this embodiment, R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 One or more of are each independently a 2-propylene group.

[0039] In one aspect of this embodiment, R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 One or more of are each independently a C8 saturated cyclic alkyl.

[0040] In another aspect of this embodiment, R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 , R 2 and R 3 In another aspect of this embodiment, one or more of R 1 is a C7 arene. In another aspect of this embodiment, R 1 , R 2 and R 3 One or more of are independently a C arene.

[0041] In one aspect of this embodiment, R 2 is R 1 In another aspect of this embodiment, R 2 is R 1 is different from.

[0042] In one aspect of this embodiment, R 3 is R1 In another aspect of this embodiment, R 3 is R 1 is different from.

[0043] In one aspect of this embodiment, R 2 is R 3 In another aspect of this embodiment, R 2 is R 3 is different from.

[0044] In one aspect of this embodiment, R 1 and R 2 and R 3 In another aspect of this embodiment, R 1 , R 2 and R 3 In another aspect of this embodiment, R 1 , R 2 and R 3 are different from each other.

[0045] In one aspect of this embodiment, x is 1. In one aspect of this embodiment, x is 2. In one aspect of this embodiment, x is 3. In one aspect of this embodiment, x is 4. In one aspect of this embodiment, x is 5.

[0046] In one aspect of this embodiment, the compound comprises a compound of formula IA, where M is molybdenum (Mo) and R 1 , R 2 and R 3 are each a methyl group. In one aspect of this embodiment, the compound comprises a compound of formula IB, where M is molybdenum (Mo) and R 1 , R 2 and R 3 are each a methyl group. In one aspect of this embodiment, the compound comprises a compound of formula IC, where M is molybdenum (Mo) and R 1 , R 2 and R 3 and each is a methyl group. In each of the foregoing, x is 5.

[0047] In one aspect of this embodiment, the compound comprises a compound of formula IA, where M is tungsten (M) and R 1 , R 2 and R 3 are each a methyl group. In one aspect of this embodiment, the compound comprises a compound of formula IB, where M is tungsten (M) and R 1 , R 2 and R 3 are each a methyl group. In one aspect of this embodiment, the compound comprises a compound of formula IC, where M is tungsten (M) and R 1 , R 2 and R 3 and each is a methyl group. In each of the foregoing, x is 5.

[0048] In one aspect of this embodiment, the compound comprises a compound of formula IA, where M is chromium (Cr) and R 1 , R 2 and R 3 are each a methyl group. In one aspect of this embodiment, the compound comprises a compound of formula IB, where M is chromium (Cr) and R 1 , R 2 and R 3 are each a methyl group. In one aspect of this embodiment, the compound comprises a compound of formula IC, where M is chromium (Cr) and R 1 , R 2 and R 3 and each is a methyl group. In each of the foregoing, x is 5.

[0049] In one aspect of this embodiment, the compound comprises a compound of formula IA, where M is molybdenum (Mo) and R 1 , R 2 and R 3 are each an ethyl group. In one aspect of this embodiment, the compound comprises a compound of formula IB, where M is molybdenum (Mo) and R 1 , R 2and R 3 are each an ethyl group. In one aspect of this embodiment, the compound comprises a compound of formula IC, where M is molybdenum (Mo) and R 1 , R 2 and R 3 and each is an ethyl group. In each of the foregoing, x is 5.

[0050] In one aspect of this embodiment, the compound comprises a compound of formula IA, where M is tungsten (W) and R 1 , R 2 and R 3 are each an ethyl group. In one aspect of this embodiment, the compound comprises a compound of formula IB, where M is tungsten (W) and R 1 , R 2 and R 3 are each an ethyl group. In one aspect of this embodiment, the compound comprises a compound of formula IC, where M is tungsten (W) and R 1 , R 2 and R 3 and each is an ethyl group. In each of the foregoing, x is 5.

[0051] In one aspect of this embodiment, the compound comprises a compound of formula IA, where M is chromium (Cr) and R 1 , R 2 and R 3 are each an ethyl group. In one aspect of this embodiment, the compound comprises a compound of formula IB, where M is chromium (Cr) and R 1 , R 2 and R 3 are each an ethyl group. In one aspect of this embodiment, the compound comprises a compound of formula IC, where M is chromium (Cr) and R 1 , R 2 and R 3 and each is an ethyl group. In each of the foregoing, x is 5.

[0052] In one aspect of this embodiment, the compound comprises a compound of formula IA, where M is molybdenum (Mo) and R 1 , R 2 and R 3 are each a propyl group. In one aspect of this embodiment, the compound comprises a compound of formula IB, where M is molybdenum (Mo) and R 1 , R 2 and R 3 are each a propyl group. In one aspect of this embodiment, the compound comprises a compound of formula IC, where M is molybdenum (Mo) and R 1 , R 2 and R 3 and each is a propyl group. In each of the foregoing, x is 5.

[0053] In one aspect of this embodiment, the compound comprises a compound of formula IA, where M is tungsten (W) and R 1 , R 2 and R 3 are each a propyl group. In one aspect of this embodiment, the compound comprises a compound of formula IB, where M is tungsten (W) and R 1 , R 2 and R 3 are each a propyl group. In one aspect of this embodiment, the compound comprises a compound of formula IC, where M is tungsten (W) and R 1 , R 2 and R 3 and each is a propyl group. In each of the foregoing, x is 5.

[0054] In one aspect of this embodiment, the compound comprises a compound of formula IA, where M is chromium (Cr) and R 1 , R 2 and R 3 are each a propyl group. In one aspect of this embodiment, the compound comprises a compound of formula IB, where M is chromium (Cr) and R 1 , R 2 and R 3are each a propyl group. In one aspect of this embodiment, the compound comprises a compound of formula IC, where M is chromium (Cr) and R 1 , R 2 and R 3 are each a propyl group.

[0055] Preferred compounds of formula I (i.e., compounds of formula IA, formula IB, and formula IC) are illustrated in Tables 1-3. However, it should be understood that the compounds of formula I encompassed by the disclosed and claimed invention are not limited to the compounds of formula I illustrated in Tables 1-3.

[0056] [Table 1]

[0057] [Table 2]

[0058] [Table 3]

[0059] How to use The disclosed precursors may be deposited to form metal-containing films, particularly molybdenum-containing films, using chemical vapor deposition processes known to those skilled in the art. 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 a desired deposition. As used herein, the term "atomic layer deposition process" refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant), continuous surface chemistry that deposits a film of material onto a substrate of varying composition. Although the precursors, reagents, and sources used herein are sometimes described as "gaseous," it is understood that the precursors can be liquid or solid that are transported into the reactor via direct vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, the vaporized precursors can be passed through a plasma generator. As used herein, the term "reactor" includes, but is not limited to, a reaction chamber, a reaction vessel, or a deposition chamber.

[0060] The disclosed and claimed chemical vapor deposition process comprises vaporizing at least one organometallic complex whose structure corresponds to Formula I as disclosed herein. For example, this may comprise vaporizing the at least one complex and delivering the at least one complex to a substrate surface or flowing the at least one complex over the substrate and / or decomposing the at least one complex on the substrate surface.

[0061] In one embodiment, the organometallic complex may be dissolved in a suitable hydrocarbon or amine solvent. Suitable hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as hexane, heptane, and nonane; aromatic hydrocarbons such as toluene and xylene; aliphatic and cyclic ethers such as diglyme, triglyme, and tetraglyme. Examples of suitable amine solvents include, but are not limited to, octylamine and N,N-dimethyldodecylamine. For example, the organometallic complex may be dissolved in toluene to provide a solution having a concentration of about 50 mM to about 1 M.

[0062] The compound of formula I, when utilized in these methods, may be liquid, solid, or gas. Typically, the compound is a liquid or low melting point solid with sufficient vapor pressure at ambient temperature to allow constant vapor transport to the process chamber. In another embodiment, at least one complex having a structure corresponding to the formula may be delivered to the substrate "neat" (undiluted by a carrier gas). In one embodiment, the compound of formula I is a solid with a melting point of about 50°C or less, about 45°C or less, about 40°C or less, about 35°C or less, or about 30°C or less.

[0063] The disclosed and claimed ALD and CVD methods encompass various types of ALD and CVD processes, including, but not limited to, continuous or pulsed injection processes, liquid injection processes, photoassisted processes, and plasma-assisted processes. Thus, chemical vapor deposition processes that can utilize the disclosed and claimed compounds include, but are not limited to, processes used in the manufacture of semiconductor-type microelectronic devices, such as ALD, CVD, pulsed CVD, plasma-enhanced ALD (PEALD) and / or plasma-enhanced CVD (PECVD). Examples of deposition processes suitable for the methods disclosed herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (metal organic CVD), thermal chemical vapor deposition, plasma-enhanced chemical vapor deposition ("PECVD"), high density PECVD, photon-assisted CVD, plasma-photon assisted ("PPECVD"), cryogenic chemical vapor deposition, chemically assisted deposition, hot-filament chemical vapor deposition, CVD of liquid polymer precursors, deposition from supercritical fluids, and low energy CVD (LECVD). In certain embodiments, the metal-containing film is deposited via atomic layer deposition (ALD), plasma-enhanced ALD (PEALD) or plasma-enhanced cyclic CVD (PECCVD) processes. For clarity, the method of the present invention specifically includes direct liquid injection processes. For example, in direct liquid injection CVD ("DLI-CVD"), a solid or liquid complex can be dissolved in a suitable solvent and the solution formed therefrom can be injected into a vaporization chamber as a means for vaporizing the complex. The vaporized complex is then transported / delivered to the substrate. In general, DLI-CVD can be particularly useful when the complex exhibits relatively low volatility or is otherwise difficult to vaporize.

[0064] Suitable substrates onto which the disclosed and claimed compounds can be deposited are not particularly limited and vary depending on the intended end use. By way of example, the substrate can be selected from oxides, such as HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth metal oxide-based materials, ternary oxide-based materials, etc., or from nitride-based films. Other substrates may include solid substrates, such as metal substrates (e.g., Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt) and metal silicides (e.g., TiSi2, CoSi2, and NiSi2); metal nitride-containing substrates (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); semiconductor materials (e.g., Si, SiGe, GaAs, InP, diamond, GaN, and SiC); insulators (e.g., SiO2, Si3N4, SiON, HfO2, Ta2O5, ZrO2, TiO2, Al2O3, and strontium barium titanate); combinations thereof, and the like. Preferred substrates include TiN, Ru, and Si type substrates, and the like.

[0065] Such deposition methods and processes may utilize an oxidizing agent, which is typically introduced in the form of a gas. Examples of suitable oxidizing agents include, but are not limited to, oxygen gas, water vapor, ozone, oxygen plasma, or mixtures thereof.

[0066] The deposition methods and processes may also use one or more purge gases. The purge gases used to purge unconsumed reactants and / or reaction by-products are inert gases that do not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, and mixtures thereof. For example, a purge gas such as Ar is fed into 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 by-products that may remain in the reactor.

[0067] The deposition methods and processes require the addition of energy to at least one of the precursors, oxidizers, other precursors, or combinations thereof to induce a reaction and form a metal-containing film or coating on the substrate. Such energy can be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma methods, and combinations thereof. In some processes, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. When utilizing plasma, the plasma generation process can include a direct plasma generation process in which the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process in which the plasma is generated outside the reactor and fed into the reactor.

[0068] When utilized in such deposition methods and processes, suitable compounds, such as those disclosed and claimed herein, may be delivered to a reaction chamber, such as a CVD or ALD reactor, in a variety of ways. In some cases, liquid delivery systems may be utilized. In other cases, combined liquid delivery and flash vaporization process units, such as the Turbo Vaporizer manufactured by MSP Corporation of Showaview, Minnesota, may be used to enable volumetric delivery of low volatility materials, thereby allowing reproducible transport and deposition without thermal decomposition of the precursor. The precursor compositions described herein may be effectively used as source reagents via direct liquid injection (DLI) to provide a vapor stream of these metal precursors into an ALD or CVD reactor.

[0069] For use in these deposition methods and processes, the disclosed and claimed compounds include hydrocarbon solvents, which are particularly desirable because they can be dried to sub-ppm water content. Exemplary hydrocarbon solvents that can be used with the precursors include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decalin). The disclosed and claimed compounds can also be stored and used in stainless steel containers. In some embodiments, the hydrocarbon solvent is a high boiling solvent or has a boiling point of 100° C. or higher. The disclosed and claimed compounds can be mixed with other suitable metal precursors, and the mixture can be used to simultaneously deliver both metals for the growth of bimetallic-containing films.

[0070] A flow of argon and / or other gases may be used as a carrier gas to help deliver vapor containing at least one of the disclosed and claimed compounds into the reaction chamber during precursor pulse delivery. When delivering the precursor, the reaction chamber process pressure is between 1 and 50 torr, preferably between 5 and 20 torr.

[0071] Substrate temperature can be one of the important process variables in the deposition of high quality metal-containing films. Typical substrate temperatures range from about 150° C. to about 550° C. Higher temperatures can promote faster film growth rates.

[0072] In one embodiment, for example, Mo, molybdenum nitride (e.g., MoN, Mo2N, or MoN / Mo2N), and / or molybdenum oxide (e.g., MoO2, MoO3, or MoO2 / MoO3) films can be formed by delivering at least one compound according to formula I, where M is molybdenum, for deposition, either independently or in combination with one or more co-reactants. The one or more co-reactants may be deposited or delivered or flowed onto a substrate, either independently or in combination with the at least one complex. Examples of such co-reactants include, but are not limited to, hydrogen, hydrogen plasma, oxygen, air, water, H2O2, ammonia, hydrazines, boranes, silanes, such as trisilanes, ozone, or any combination thereof. Examples of suitable boranes include, but are not limited to, hydrogenating (i.e., reducing) boranes, such as borane, diborane, triborane, and the like. Examples of suitable silanes include, but are not limited to, hydrogenatable silanes, such as silane, disilane, trisilane, and the like. Examples of suitable hydrazines include, but are not limited to, hydrazine (NH) and / or hydrazines optionally substituted with one or more alkyl groups (i.e., alkyl-substituted hydrazines), such as methylhydrazine, tert-butylhydrazine, N,N- or N,N'-dimethylhydrazine, and the like. Those skilled in the art will appreciate that the above detailed description of the method in which molybdenum is used can be adjusted as necessary when other metals, such as when M is chromium or tungsten, are used.

[0073] In one particular embodiment, one or more co-reactants are used to form MoO2, MoO3, or MoO2 / MoO3 films by delivering one or more compounds according to formula I, where M is molybdenum, either independently or in combination with the one or more co-reactants, such as, but not limited to, air, H2O, O2, and / or ozone, to a reaction chamber for deposition. Multiple such co-reactants may be used. Those skilled in the art will appreciate that the above detailed description of the method using molybdenum can be adjusted as necessary when other metals, such as M is chromium or tungsten, are used.

[0074] In another particular embodiment, one or more co-reactants are used to form MoN, Mo2N, or MoN / Mo2N films by delivering one or more compounds according to formula I, where M is molybdenum, either independently or in combination with the one or more co-reactants, such as, but not limited to, ammonia, hydrazines, or other nitrogen-containing compounds, such as, but not limited to, amines, to a reaction chamber for deposition. Multiple such co-reactants may be used. Those skilled in the art will appreciate that the above detailed description of the method in which molybdenum is used can be adjusted as necessary when other metals, such as, for example, M is chromium or tungsten.

[0075] In another particular embodiment, a co-reactant is used to form a molybdenum-containing metal film by delivering at least one complex according to formula I, where M is molybdenum, either alone or in combination with a co-reactant, such as, but not limited to, H2, hydrazines, silanes, such as trisilane, and / or ammonia, to a reaction chamber for deposition. Those skilled in the art will appreciate that the above detailed description of the method in which molybdenum is used can be adjusted as necessary when other metals, such as M is chromium or tungsten.

[0076] Specific aspects Based on the foregoing, one of ordinary skill in the art will recognize that the disclosed and claimed invention also includes the use of the disclosed and claimed compounds in chemical vapor deposition processes, as follows:

[0077] In one aspect, the disclosed and claimed invention includes a method of forming a transition metal-containing film on at least one surface of a substrate, the method comprising the steps of: (i) providing at least one surface of a substrate in a reaction vessel; (ii) forming a transition metal-containing film on the at least one surface by a deposition process selected from a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process using one or more of the compounds disclosed and claimed as metal source compounds for the deposition process.

[0078] In yet another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel. In yet another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, the at least one reactant being selected from the group of water, dioxygen, oxygen plasma, ozone, NO, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, the at least one reactant being selected from the group of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, the at least one reactant being selected from the group of hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, a boron-containing compound, a silicon-containing compound, and combinations thereof.

[0079] CVD In one embodiment, conventional or pulsed injection CVD is used to form metal-containing thin films by vaporizing and / or flowing at least one complex according to Formula I described herein onto a substrate. For conventional and pulsed CVD processes, see, for example, Smith, Donald, Thin-Film Deposition: Principles and Practice, McGraw-Hill (1995).

[0080] Based on the above description, one skilled in the art will recognize that the disclosed and claimed invention further includes the use of the disclosed and claimed formulations in a method for forming a transition metal-containing film on a substrate via a CVD process, the method comprising the steps of: (i) forming a metal-containing film on at least one surface of said substrate by contacting one or more compounds of formula I, alone or optionally in combination with one or more co-reactants, with said at least one surface; and (ii) optionally purging with an inert gas.

[0081] In yet another aspect of this embodiment, the method optionally includes passivating the at least one surface prior to step (i). In yet another aspect of this embodiment, the method includes one or more co-reactants are utilized and are one or more of water, dioxygen, oxygen plasma, ozone, NO, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In yet another aspect of this embodiment, the method includes one or more co-reactants are utilized and are one or more of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof. In yet another aspect of this embodiment, the method includes one or more co-reactants are utilized and are one or more of hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, a boron-containing compound, a silicon-containing compound, and combinations thereof. In yet another aspect, the compound of formula I is introduced as a component of a vapor that includes one or more carrier gases.

[0082] In one aspect, the above CVD process utilizes one or more of the following growth conditions, including but not limited to: (1) Substrate temperature: 50 to 600°C (for example, 250 to 450°C, or 300 to 350°C); (2) Evaporator temperature: 0~200℃; (3) Reactor pressure: 0-100 Torr (for example, 0.5-10 Torr, or 0.7-2 Torr); (4) Purge gas flow rate: 0~500sccm; (5) O gas flow rate: 0~500sccm; (6) H gas flow rate: 0~500sccm; (7) Run time: depending on the desired film thickness; and / or (8) H gas:Mo precursor: ratio = about 2:1 to 10000:1 (e.g., 500:1 to 1000:1, or 5000:1 to 10000:1).

[0083] In another embodiment, photo-assisted CVD is used to form a molybdenum-containing thin film by vaporizing and / or flowing at least one molybdenum complex of formula I disclosed herein onto a substrate.

[0084] ALD In one embodiment, ALD is used to form a metal-containing thin film by vaporizing and / or flowing at least one complex according to Formula I disclosed herein onto a substrate. In one aspect, conventional (i.e., pulsed injection) ALD is used to form a metal-containing thin film by vaporizing and / or flowing at least one complex according to Formula I disclosed herein onto a substrate. For a conventional ALD process, see, for example, George et al. J. Phys. Chem. 100:13121-31 (1996). In another aspect, liquid injection ALD is used to form a metal-containing thin film, e.g., a molybdenum film, by vaporizing and / or flowing at least one complex according to Formula I disclosed herein onto a substrate, where at least one liquid complex is delivered into a reaction chamber by direct liquid injection as opposed to vapor draw by a bubbler. For liquid injection ALD processes, see, for example, Potter et al., Chem. Vap. Deposition 11(3):159-69 (2005).

[0085] In one embodiment, the disclosed and claimed invention includes a method of forming a transition metal-containing film on a substrate via an ALD process or an ALD-like process, the method comprising the steps of: (i) contacting a substrate with one or more compounds of the disclosed and claimed formula I; (ii) purging unreacted compound of formula I with an inert gas; (iii) contacting the substrate with at least one co-reactant (e.g., a nitrogen source to form a metal nitride, or an oxygen source to form a metal oxide) in a deposition reactor; and (iv) Optionally, purging the reactants, including any unreacted co-reactant, with an inert gas.

[0086] In yet another aspect of this embodiment, the method consists essentially of steps (i), (ii), (iii), and (iv). In yet another aspect of this embodiment, the method consists of steps (i), (ii), (iii), and (iv). The process can optionally further include a step (v) of treating the substrate with a plasma (e.g., nitrogen plasma, hydrogen plasma) to remove residual impurities. Thus, in yet another aspect of this embodiment, the method consists essentially of steps (i), (ii), (iii), (iv), and (v). In yet another aspect of this embodiment, the method consists of steps (i), (ii), (iii), (iv), and (v). As will be appreciated by those skilled in the art, the above steps can be repeated until a metal-containing film of a desired thickness is obtained. In yet another aspect of this embodiment, the co-reactant source gas is one or more of an oxygen-containing source gas selected from water, diatomic oxygen, oxygen plasma, ozone, NO, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the co-reactant 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 yet another aspect of this embodiment, the first and second purge gases are each independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof. In yet another aspect of this embodiment, the method further comprises applying energy to at least one of the precursor, source gas, substrate, and combinations thereof, where the energy is one or more of thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma, and combinations thereof. In yet another aspect of this embodiment, step b of the method further comprises introducing the precursor into the reaction vessel using a flow of carrier gas to deliver vapor of the precursor into the reaction vessel.In yet another aspect of this embodiment, step b of the process includes using a solvent that includes one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyltoluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene, and combinations thereof.

[0087] In one aspect, the ALD process described above utilizes one or more of the following growth conditions, including but not limited to: (1) Base material temperature: 0~400℃; (2) Evaporator (metal source) temperature: 0~200℃; (3) Reactor pressure: 0~100 Torr; (4) Purge gas flow rate: 0~500sccm; (5) Reactive gas flow rate: 0-500sccm; (6) Pulse sequence (seconds): The time for each step of the complex / purge / reactive gas / purge cycle varies depending on the chamber size; and / or (7) Number of cycles: Varies depending on desired film thickness.

[0088] Delivery of the compound(s) of formula I As previously described, step (i) of the disclosed and claimed method involves contacting the substrate with one or more compounds of formula I as disclosed and claimed.

[0089] In another embodiment, the one or more compounds of the disclosed and claimed formula I are delivered in vapor form for a period of time (i.e., pulse time). In another embodiment, the pulse time of the one or more compounds of the disclosed and claimed formula I is from about 0.1 seconds to about 3 seconds. In another embodiment, the vapor pulse time of the one or more compounds of the disclosed and claimed formula I is from about 0.3 seconds to about 3 seconds. In another embodiment, the vapor pulse time of the one or more compounds of the disclosed and claimed formula I is about 0.1 seconds. In another embodiment, the vapor pulse time of the one or more compounds of the disclosed and claimed formula I is about 0.25 seconds. In another embodiment, the vapor pulse time of the one or more compounds of the disclosed and claimed formula I is about 0.5 seconds. In another embodiment, the vapor pulse time of the one or more compounds of the disclosed and claimed formula I is about 1 second. In another embodiment, the vapor pulse time of the one or more compounds of the disclosed and claimed formula I is about 1.5 seconds. In another embodiment, the vapor pulse time of the one or more compounds of the disclosed and claimed formula I is about 2 seconds.

[0090] In one embodiment, the vapor of one or more compounds of the disclosed and claimed formula I is separated from other precursor materials before and / or during its introduction into the reactor, this process avoiding pre-reaction of the metal precursor with other materials.

[0091] In another embodiment, vapor of one or more compounds of the disclosed and claimed formula I are alternatively exposed to the substrate along with other reactants (e.g., ammonia vapor, and / or other precursors or co-reactants). This process allows film growth to proceed through self-limiting control of the surface reaction, pulse length of each precursor or reagent, and deposition temperature. However, it should be noted that once the surface of the substrate is saturated with vapor of one or more compounds of the disclosed and claimed formula I vanadium oxide trichloride, film growth ceases.

[0092] In another embodiment, a flow of argon and / or other gas is used as a carrier gas to help deliver vapor of one or more compounds of the disclosed and claimed formula I to the reaction reactor during precursor pulse delivery.

[0093] Purge Step As previously described, step (ii) of the disclosed and claimed methods involves purging the unreacted compound of formula I with an inert gas. Purging with an inert gas removes unabsorbed excess complex from the process reactor.

[0094] In one embodiment, for example, the purge time is between about 1 second and about 90 seconds. In one embodiment, for example, the purge time is between about 15 seconds and about 90 seconds. In one embodiment, for example, the purge time is between about 15 seconds and about 60 seconds. In another embodiment, the purge time is about 30 seconds. In another embodiment, the purge time is about 60 seconds. In another embodiment, the purge time is about 90 seconds.

[0095] In one embodiment, the purge gas comprises argon, hi another embodiment, the purge gas comprises nitrogen.

[0096] Coreactant Treatment As previously described, step (iii) of the disclosed and claimed methods involves contacting the substrate with at least one co-reactant (e.g., a nitrogen source to form a metal nitride, or an oxygen source to form a metal oxide) in a deposition reactor.

[0097] In one embodiment, the co-reactant comprises a nitrogen source, which may include one or more nitrogen-containing source gases selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, and nitrogen / hydrogen plasma. In another embodiment, the nitrogen source comprises ammonia gas. In one embodiment, for example, the pulse time of the nitrogen source is between about 0.5 seconds and about 5 seconds. In one embodiment, for example, the pulse time of the nitrogen source is about 2.5 seconds. In one embodiment, for example, the pulse time of the nitrogen source is about 5 seconds.

[0098] In one embodiment, the co-reactant comprises an oxygen source, which may include one or more of water, dioxygen, oxygen plasma, ozone, NO, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In one embodiment, for example, the pulse time of the oxygen source is between about 0.5 seconds and about 5 seconds. In one embodiment, for example, the pulse time of the oxygen source is about 2.5 seconds. In one embodiment, for example, the pulse time of the oxygen source is about 5 seconds.

[0099] Optional Co-Reactant Purge Step As previously described, step (iv) of the disclosed and claimed methods optionally includes purging unreacted co-reactants with an inert gas. Purging with an inert gas removes remaining co-reactants from the process reactor. In one embodiment, the purge gas includes argon. In another embodiment, the purge gas includes nitrogen. As one skilled in the art will recognize, in many, if not most cases, the disclosed and claimed processes include a step of purging unreacted co-reactants. One exception may be when a nitrogen-based co-reactant is used, which is not purged but instead is utilized as a nitrogen source for the subsequent plasma treatment (described below).

[0100] In one embodiment, for example, the optional co-reactant purge time is between about 15 seconds and about 90 seconds. In one embodiment, for example, the optional co-reactant purge time is between about 15 seconds and about 60 seconds. In another embodiment, the optional co-reactant purge time is about 30 seconds. In another embodiment, the optional co-reactant purge time is about 60 seconds. In another embodiment, the optional co-reactant purge time is about 90 seconds.

[0101] Optional plasma treatment As previously described, step (v) of the disclosed and claimed method involves treatment of the substrate with a nitrogen or hydrogen plasma to remove residual impurities generated during the preceding steps.

[0102] In one embodiment, the use of plasma constitutes a direct plasma generation process, where the plasma is generated directly in the reactor. In another embodiment, the use of plasma constitutes a remote plasma generation process, where the plasma is generated outside the reactor and fed into the reactor. In this regard, and as described above, when utilizing as the plasma source a material that is also used as a co-reactant (e.g., ammonia as a nitrogen source), the optional co-reactant purge step (iv) can be omitted. When utilizing nitrogen plasma, the nitrogen source can include nitrogen (N2), ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine.

[0103] Working conditions As previously described, the disclosed and claimed vanadium deposition process can be effectively carried out under highly favorable ALD conditions to provide highly conformal films of vanadium nitride.

[0104] In one embodiment, a substrate (e.g., silicon oxides, aluminum oxide (Al2O3), titanium nitride (TiN), silicon oxide (SiO2), and zirconium oxide (ZrO2)) is heated on a heater stage in a reaction reactor and first exposed to a vanadium oxide trichloride precursor to chemically adsorb the complex onto the substrate surface. In one embodiment, the substrate temperature is from about 300°C to about 600°C. In yet another aspect of this embodiment, the substrate temperature is from about 350°C to about 550°C. In yet another aspect of this embodiment, the substrate temperature is from about 400°C to about 500°C.

[0105] In another embodiment, the reactor pressure for deposition according to the disclosed and claimed processes is about 50 torr or less. In another embodiment, the reactor pressure for deposition according to the disclosed and claimed processes is about 40 torr or less. In another embodiment, the reactor pressure for deposition according to the disclosed and claimed processes is about 30 torr or less. In yet another aspect of this embodiment, the reactor pressure is about 20 torr or less. In yet another aspect of this embodiment, the reactor pressure is about 10 torr or less. In yet another aspect of this embodiment, the reactor pressure is about 5 torr or less.

[0106] Cycle and step order In the embodiment described above, as well as other embodiments described herein, the described steps (e.g., (i) through (iv), or (i) through (v)) define one cycle of the method. It is understood that the cycle can be repeated until the desired thickness of the film is obtained.

[0107] In the embodiments described herein, each step of the method can be performed in various orders, sequentially or simultaneously (e.g., between at least some of the other steps), and combinations thereof. In addition, each step of providing one or more compounds of the disclosed and claimed formula I and a co-reactant source may be performed by varying the duration for their provision in order to vary the film composition.

[0108] In one embodiment, the disclosed and claimed invention includes a film deposited by the method and using the compound of formula I as disclosed and claimed. In one aspect of this embodiment, the film deposited by the method and using the compound of formula I as disclosed and claimed has a resistivity of less than approximately 500 μOhm cm. In another aspect of this embodiment, the film deposited by the method and using the compound of formula I as disclosed and claimed has a resistivity of less than approximately 400 μOhm cm. In another aspect of this embodiment, the film deposited by the method and using the compound of formula I as disclosed and claimed has a resistivity of less than approximately 300 μOhm cm. In another aspect of this embodiment, the film deposited by the method and using the compound of formula I as disclosed and claimed has a resistivity of less than approximately 200 μOhm cm. In another aspect of this embodiment, the film deposited by the method and using the compound of formula I as disclosed and claimed has a resistivity of less than approximately 100 μOhm cm. EXAMPLES

[0109] More specific embodiments of the present disclosure and experimental results supporting such embodiments are described below. These examples are provided below to more fully explain the disclosed invention, and should not be construed as limiting the disclosed invention in any way.

[0110] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed invention and the specific examples provided herein without departing from the spirit or scope of the disclosed invention. Thus, the disclosed invention, including the description provided by the following examples, is intended to cover modifications and variations of the disclosed invention that come within the scope of any claims and their equivalents.

[0111] Materials and Methods: All manipulations were carried out under an inert atmosphere of dry argon using standard Schlenk and drybox techniques. Anhydrous and oxygen-free solvents were purchased from Arcos, degassed before use, and stored over molecular sieves (3 and 4 Å). All glassware was oven-dried at 120°C before use. Reagents and handling: [Mo(CO)6] and trimethylphosphite were purchased from Sigma-Aldrich and used as delivered.

[0112] Example 1 Trimethylphosphite pentacarbonylmolybdenum can be synthesized by well-known methods, for example, the method described in Brown and Darensbourg, Inorg. Chem., Vol. 7, No. 5 (1968) (Non-Patent Document 4).

[0113] The trimethyl phosphite (1.41 g, 11.36 mmol) and [Mo(CO)6] (3.0 g, 11.36 mmol) were refluxed in toluene (50 mL) for 24 h. During this time, the reaction mixture turned into a brown slurry. After 24 h, the reaction mixture solvent was evaporated in vacuo. The desired complex was obtained by distillation (110 °C, 1.0 × 10 -2 It was obtained as a colorless liquid after 300 MPa (1000 MPa) at 1000 MPa (mbar). Yield: 72%. Purity: >99% (shown in Figure 5).

[0114] Characterization: 1 H NMR (500MHz, C6D6) δ = 3.13 (d, 3 J HP =11.7Hz,9H)ppm,Figure 5; 13 C NMR (125 Hz, C6D6) δ = 208.7 (d, 2 J CP =40.2Hz, trans-CO), 205.1(d, 2 J CP =14.2Hz, cis-CO), 51.2(d, 2 J CP = 3.1Hz, CH3) ppm, Figure 6; 31 P NMR (202MHz, C6D6) δ=162.1ppm, Figure 7; Boiling point: 57℃ (1.0×10 -2mbar); TGA: see Figure 1. Melting point: 17°C (i.e. lower boiling point than Mo(CO)6 or liquid complex at room temperature).

[0115] Example 2 Differential scanning calorimetry (DSC) measurements were performed to demonstrate the higher thermal stability of Mo(CO)5P(OMe)3 from Example 1 compared to Mo(CO)6. As shown in Figure 4, the DSC measurements indicate that decomposition begins at 300°C for Mo(CO)5P(OMe)3. In comparison, Mo(CO)6 decomposes at 150°C. Therefore, compounds with phosphorus-based ligands have higher thermal stability than Mo(CO)6.

[0116] The foregoing description is intended primarily for purposes of illustration. Although the disclosed and claimed invention has been illustrated and described with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that various other changes, omissions and additions thereto in form and detail may be made without departing from the spirit and scope of the disclosed and claimed invention.

Claims

1. A compound comprising one or more of formula IA, formula IB and formula IC. 【Chemistry 1】 During the ceremony, (i) M is one of Mo, W, and Cr; (ii) R ２ and R ３ each independently represents an unsubstituted linear C １ -C ８ Alkyl group, unsubstituted branched C ３ -C ８ Alkyl group, linear or branched C ２ -C ６ Alkylene, C ３ -C ８ Saturated cyclic alkyl and C ５ -C ８ It is one of the arenes, (iii) x is 1, 2, 3, 4 or 5.

2. The compound of claim 1, comprising one or more compounds of formula IA.

3. The compound of claim 1 consisting essentially of one or more compounds of formula IA.

4. The compound of claim 1, consisting of one or more compounds of formula IA.

5. The compound of claim 1, comprising one or more compounds of formula I-B.

6. The compound of claim 1 consisting essentially of one or more compounds of formula IB.

7. The compound of claim 1, consisting of one or more compounds of formula I-B.

8. The compound of claim 1, comprising one or more compounds of formula IC.

9. The compound of claim 1 consisting essentially of one or more compounds of formula IC.

10. The compound of claim 1, consisting of one or more compounds of formula IC.

11. The compound of claim 1 comprising two or more compounds of formula IA.

12. The compound of claim 1 comprising two or more compounds of formula IB.

13. The compound of claim 1, comprising two or more compounds of formula IC.

14. The compound of claim 1, comprising a mixture of two or more of the compounds of formula IA, IB and IC.

15. The compound of claim 1, comprising a mixture of one or more compounds of each of formulas IA, IB, and IC.

16. The compound of claim 1 , wherein M is Mo.

17. The compound of claim 1 , wherein M is W.

18. The compound of claim 1 , wherein M is Cr.

19. R １ , R ２ and R ３ one or more of each independently represents an unsubstituted linear C １ -C ８ The compound of claim 1 which is an alkyl group.

20. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently a methyl group.

21. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently an ethyl group.

22. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently a propyl group.

23. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently a butyl group.

24. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently a pentyl group.

25. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently a hexyl group.

26. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently a heptyl group.

27. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently an octyl group.

28. R １ , R ２ and R ３ One or more of each independently represents an unsubstituted branched C ３ -C ８ The compound of claim 1 which is an alkyl group.

29. R １ , R ２ and R ３ and n is an integer from 1 to 3. The compound of claim 1 , wherein one or more of

30. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of:

31. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently an isobutyl group.

32. R １ , R ２ and R ３ The compound according to claim 1 , wherein one or more of:

33. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of:

34. R １ , R ２ and R ３ One or more of the following are each independently a linear or branched C ２ -C ６ The compound of claim 1 which is an alkylene.

35. R １ , R ２ and R ３ and n is an integer from 1 to 10. The compound of claim 1 , wherein one or more of are each independently an ethylene group.

36. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of are each independently a 1-propylene group.

37. R １ , R ２ and R ３ The compound of claim 1 , wherein one or more of:

38. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ３ -C ８ The compound of claim 1 which is a saturated cyclic alkyl.

39. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ３ The compound of claim 1 which is a saturated cyclic alkyl.

40. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ４ The compound of claim 1 which is a saturated cyclic alkyl.

41. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ５ The compound of claim 1 which is a saturated cyclic alkyl.

42. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ６ The compound of claim 1 which is a saturated cyclic alkyl.

43. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ７ The compound of claim 1 which is a saturated cyclic alkyl.

44. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ８ The compound of claim 1 which is a saturated cyclic alkyl.

45. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ５ -C ８ The compound of claim 1 which is an arene.

46. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ３ The compound of claim 1 which is an arene.

47. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ４ The compound of claim 1 which is an arene.

48. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ５ The compound of claim 1 which is an arene.

49. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ６ The compound of claim 1 which is an arene.

50. R １ C ７ The compound of claim 1 which is an arene.

51. R １ , R ２ and R ３ One or more of the following are each independently selected from the group consisting of C ８ The compound of claim 1 which is an arene.

52. R ２ R １ The compound of claim 1, wherein

53. R ２ R １ The compound of claim 1 , which is different from

54. R ３ R １ The compound of claim 1, wherein

55. R ３ R １ The compound of claim 1 , which is different from

56. R ２ R ３ The compound of claim 1, wherein

57. R ２ R ３ The compound of claim 1 , which is different from

58. R １ , R ２ and R ３ The compound of claim 1 , wherein two of

59. R １ , R ２ , R ３ The compound of claim 1 , wherein all are the same.

60. R １ , R ２ and R ３ The compound according to claim 1 , wherein each of

61. The compound of claim 1 , wherein x is 1.

62. The compound of claim 1 , wherein x is 2.

63. The compound of claim 1 , wherein x is 3.

64. The compound of claim 1 , wherein x is 4.

65. The compound of claim 1 , wherein x is 5.

66. M is molybdenum (Mo), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IA, wherein each is a methyl group.

67. M is molybdenum (Mo), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IB, wherein each is a methyl group.

68. M is molybdenum (Mo), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IC, wherein each is a methyl group.

69. M is tungsten (W), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IA, wherein each is a methyl group.

70. M is tungsten (W), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IB, wherein each is a methyl group.

71. M is tungsten (W), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IC, wherein each is a methyl group.

72. M is chromium (Cr), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IA, wherein each is a methyl group.

73. M is chromium (Cr), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IB, wherein each is a methyl group.

74. M is chromium (Cr), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IC, wherein each is a methyl group.

75. M is molybdenum (Mo), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IA, wherein each is an ethyl group.

76. M is molybdenum (Mo), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IB, wherein each is an ethyl group.

77. M is molybdenum (Mo), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IC, wherein each is an ethyl group.

78. M is tungsten (W), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IA, wherein each is an ethyl group.

79. M is tungsten (W), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IB, wherein each is an ethyl group.

80. M is tungsten (W), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IC, wherein each is an ethyl group.

81. M is chromium (Cr), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IA, wherein each is an ethyl group.

82. M is chromium (Cr), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IB, wherein each is an ethyl group.

83. M is chromium (Cr), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IC, wherein each is an ethyl group.

84. M is molybdenum (Mo), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IA, wherein each is a propyl group.

85. M is molybdenum (Mo), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IB, wherein each is a propyl group.

86. M is molybdenum (Mo), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IC, wherein each is a propyl group.

87. M is tungsten (W), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IA, wherein each is a propyl group.

88. M is tungsten (W), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IB, wherein each is a propyl group.

89. M is tungsten (W), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IC, wherein each is a propyl group.

90. M is chromium (Cr), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising a compound of formula IA, wherein each is a propyl group.

91. M is chromium (Cr), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IB, wherein each is a propyl group.

92. M is chromium (Cr), x is 5, and R １ , R ２ and R ３ The compound of claim 1, comprising the compound of formula IC, wherein each is a propyl group.

93. 2. The compound of claim 1, comprising one or more of the following compounds: 【Table 1】

94. 2. The compound of claim 1, comprising one or more of the following compounds: 【Table 2】

95. 2. The compound of claim 1, comprising one or more of the following compounds: 【Table 3】

96. A composition comprising one or more compounds according to any one of claims 1-95.

97. 1. 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. forming a transition metal-containing film on said at least one surface by a deposition process selected from a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process using a compound according to any one of claims 1 to 95 as a metal source compound for said deposition process; A method comprising:

98. 98. The method of claim 97, further comprising introducing at least one reactant into the reaction vessel.

99. Water, diatomic oxygen, oxygen plasma, ozone, NO, N ２ O, NO ２ 98. The method of claim 97, further comprising introducing at least one reactant selected from the group consisting of carbon monoxide, carbon dioxide, and combinations thereof into the reaction vessel.

100. 98. The method of claim 97, further comprising introducing at least one reactant selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof into the reaction vessel.

101. 98. The method of claim 97, further comprising introducing into the reaction vessel at least one reactant selected from the group consisting of hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, a boron-containing compound, a silicon-containing compound, and combinations thereof.

102. 1. A method for forming a transition metal-containing film via an atomic layer deposition (ALD) or ALD-like process, comprising the steps of: a. providing a substrate in a reaction vessel; b. introducing a compound according to any one of claims 1 to 95 into the reaction vessel; 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. Successively repeating steps b through e until a transition metal-containing film of desired thickness is obtained; A method comprising:

103. The source gas is water, diatomic oxygen, oxygen plasma, ozone, NO, N ２ O, NO ２ 103. The method of claim 102, wherein the oxygen-containing source gas is one or more selected from the group consisting of carbon monoxide, carbon dioxide, and combinations thereof.

104. 103. The method of claim 102, 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.

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

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

107. 103. The method of claim 102, wherein step b further comprises introducing the compound into the reaction vessel using a flow of carrier gas to deliver vapor of the compound into the reaction vessel.

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

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