Polysubstituted cyclopentadienyl rare earth complexes as precursors for vapor-phase thin film deposition processes

Abstract

The disclosed and claimed subject matter provides precursors having at least one tethered cyclopentadienyl ligand (“Cp ligand”), at least one amidinate ligand (“Ad ligand”), and a lanthanide and / or lanthanide-like transition metal (“M”) of the general formula (i) (Cp ligand)-M-(Ad ligand) or (ii) (Cp ligand)-M-(Ad ligand)

Description

[Technical Field]

[0001] FIELD OF THE INVENTION

[0002] The disclosed and claimed subject matter relates to organometallic compounds containing lanthanide and / or lanthanide-like transition metals, compositions containing such compounds, and methods of using such compounds as precursors for the deposition of metal-containing films. [Background technology]

[0003] Related technologies

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

[0005] In ALD, 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, ALD is capable of coating three-dimensional (3D) surfaces with atomic precision, making it essential to the semiconductor industry.

[0006] U.S. Pat. No. 8,283,201 discloses precursor compounds having cyclopentadienyl and amidine ligands with at least one aliphatic group as a substituent. In particular, the disclosed structures have the formula Ln(R 1 Cp) m (R 2 -NC(R 4 )=NR 2 ) n wherein (i) Ln is a lanthanide metal having an ionic radius of about 0.75 Å to about 0.94 Å, a 3+ charge, and a coordination number of 6; and (ii) R 1 is selected from the group consisting of H and C1-C5 alkyl chains; and (iii) R 2 is selected from the group consisting of H and C1-C5 alkyl chains; and (iv) R 4 is selected from the group consisting of H and Me; (v) n and m are in the range of 1 to 2; and (vi) the precursor has a melting point of less than about 105°C.

[0007] U.S. Patent Application Publication No. 2019 / 0152996 (U.S. Patent Application No. 16 / 251,236) discloses a compound of the formula [ka] [In the formula, R 1 is a hydrogen atom or a C1-C4 linear or branched alkyl group, and R 2 and R 3 are each independently a hydrogen atom or a C1-C5 linear or branched alkyl group, and R 2 and R 3 At least one of R is a C3 to C5 branched alkyl group, 4 is a hydrogen atom or a C1-C4 linear or branched alkyl group. In this regard, during the prosecution of this application, the USPTO found that U.S. Pat. No. 8,283,201 discloses lanthanum-containing compounds of the formula: 2 and R 3 does not teach or suggest unsymmetrical amidinates that are different from each other.

[0008] There is a need in the art for thermally stable lanthanide and / or lanthanide-like organometallic compounds suitable as CVD and ALD precursors that can be delivered preferably in the liquid phase and produce high quality films with low impurities and high conformality.

[0009] In this regard, common rare earth (RE) precursors for ALD often include THD (2,2,6,6-tetramethyl-3,5-heptanedionate), different cyclopentadienyl ligands ("Cp ligand" or "Cp"), and amidinate ligands ("Ad ligand" or "AMD"). In the case of La, for example, the precursors La(iPr-Cp)3 (tris-isopropylcyclopentadienyllanthanum(III)), La(iPr2-FAMD)3 (tris-diisopropylformamidinatelanthanum(III)), and heteroleptic La(iPr-Cp)2 (iPr2-MeAMD) (bis(isopropylcyclopentadienyl)(diisopropylacetamidinate)lanthanum(III)) can be considered benchmark precursors. La(iPr-Cp)3 is a volatile, thermally stable, low-melting solid with low reactivity. Good reactivity combined with the high volatility of the La precursor can be found in La(iPr2-FAMD). However, it has no melting point and is less stable than La(iPr-Cp)3, which presents drawbacks in terms of evaporation behavior and application in ALD. Therefore, using the combination of a stable iPr-Cp ligand with a reactive amidinate, we obtained the heteroleptic precursor La(iPr-Cp)2 (iPr2-MeAMD), which is liquid at room temperature but less volatile than La(iPr2-FAMD). An approach to increasing the volatility of such compounds was achieved by modifying the amidinate using an asymmetric alkyl substitution pattern on the ligand.

[0010] Notably, no attempt has been made to use asymmetric substitution on the Cp ring, even though this asymmetry may have a greater impact on volatility, melting point, and thermal stability. The disclosed and claimed subject matter provides such materials. Summary of the Invention

[0011] The disclosed and claimed subject matter provides precursors having at least one tethered cyclopentadienyl ligand (“Cp ligand”), at least one amidinate ligand (“Ad ligand”), and a lanthanide and / or lanthanide-like transition metal (“M”) of the general formula (i) (Cp ligand)-M-(Ad ligand) or (ii) (Cp ligand)-M-(Ad ligand) . The disclosed and claimed subject matter further includes compositions containing the compounds, methods of using the compounds as precursors for the deposition of metal-containing films, and films derived from the precursors.

[0012] In one embodiment, the precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand has Formula I [ka] Formula I [In the formula, (i) M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; (ii)R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from H, an unsubstituted linear C1-C6 alkyl group, a linear C1-C6 alkyl group substituted with a halogen, a linear C1-C6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, a branched C3-C6 alkyl group substituted with an amino group, and —Si(CH3)3; (a)R 1 , R 2 , R 3 , R 4 and R 5 contains at least three different substituents; and (b) R 1 , R 2 , R 3 , R4 and R 5 at least two of are H; (iii)R 6 , R 7 and R 8 are each independently selected from H, an unsubstituted linear C1-C6 alkyl group, a linear C1-C6 alkyl group substituted with a halogen, a linear C1-C6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, a branched C3-C6 alkyl group substituted with an amino group, and —Si(CH3)3; (iv) n=1 or 2; (v) the precursor is liquid below about 80°C; Thus, precursors of Formula I include compounds of formula (i) (Cp ligand)-M-(Ad ligand) when n = 2, and (ii) (Cp ligand)-M-(Ad ligand) when n = 1. More specific aspects and embodiments of precursors of Formula I (Cp ligand)-M-(Ad ligand) and (Cp ligand)-M-(Ad ligand) are detailed below.

[0013] Without wishing to be bound by theory, it is believed that the asymmetric substitution of the Cp ring with at least two different alkyl chains results in a highly asymmetric complex, which has a lower melting point and increased volatility.

[0014] The disclosed and claimed subject matter further includes (i) compositions and formulations including the disclosed and claimed precursors, (ii) methods of using the disclosed and claimed precursors in deposition processes, and (iii) metal-containing films derived from the disclosed and claimed precursors produced in the deposition processes. [Brief explanation of the drawings]

[0015] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter, and which are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and, together with the detailed description, serve to explain the principles of the disclosed subject matter.

[0016] [Figure 1] Comparative Example 1: Thermogravimetric analysis (TGA) of La(iPr-Me-Cp)3. [Figure 2] Synthesis Example 1: 1H NMR of La(iPr-Me-Cp)2 (iPr2-FAMD) [Figure 3] 1 shows TGA of Synthesis Example 1, La(iPr-Me-Cp)2 (iPr2-FAMD). [Figure 4] 1 shows the differential scanning calorimetry (DSC) of Synthesis Example 1, La(iPr-Me-Cp)2 (iPr2-FAMD). [Figure 5] Figure 1 shows the thermal decomposition of the La(iPr-Me-Cp)2 (iPr2-FAMD) precursor on a Si wafer. [Figure 6] Figure 1 shows the dependence of lanthanum oxide film thickness on Si and SiO wafers on the pulse time of the La(iPr-Me-Cp)2 (iPr2-FAMD) precursor in an atomic layer deposition process. [Figure 7] 1 shows cross-sectional TEM of structured wafers with lanthanum oxide films deposited using the La(iPr-Me-Cp)2 (iPr2-FAMD) precursor at 175°C and 275°C. DETAILED DESCRIPTION OF THE INVENTION

[0017] All references cited in this specification, including publications, patent applications, and patents, are herein incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.

[0018] In the context of describing the disclosed and claimed subject matter (particularly in the context of the claims below), the use of the terms "a," "an," and "the," and similar references, should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better elucidate the disclosed and claimed subject matter and does not impose limitations on the scope of the disclosed and claimed subject matter unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed and claimed subject matter. The use of the terms "comprising" or "including" in the specification and claims includes the narrower language of "consisting essentially of" and "consisting of."

[0019] Embodiments of the disclosed and claimed subject matter are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed subject matter. Variations of these embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors anticipate that skilled artisans will employ such variations as appropriate, and the inventors intend for the disclosed and claimed subject matter to be practiced otherwise than as specifically described herein. Accordingly, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Furthermore, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosed and claimed subject matter unless otherwise indicated herein or clearly contradicted by context.

[0020] It will be understood that the term "silicon" deposited as a material on a microelectronic device includes polysilicon.

[0021] For ease of reference, "microelectronic device" or "semiconductor device" corresponds to semiconductor wafers having integrated circuits, memory, and other electronic structures fabricated for use in microelectronic, integrated circuit, or computer chip applications, as well as other products including flat panel displays, phase change memory devices, solar panels and solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS). Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. It should be understood that the terms "microelectronic device" or "semiconductor device" are not intended to be limiting in any way and include any substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0022] As defined herein, the term "barrier material" corresponds to any material used in the art to encapsulate metal lines, e.g., copper interconnects, to minimize the diffusion of the metal, e.g., copper, into dielectric materials. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals, as well as their nitrides and silicides.

[0023] "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 correspond to ±5% of the stated value.

[0024] In all such compositions where a particular component of a composition is discussed with reference to a weight percent (or wt. %) range including a lower limit of zero, it will be understood that such component may or may not be present in various specific embodiments of the composition, and that when present, such component may be present in concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such component is used. Note that all percentages of components are weight percents and are based on the total weight of the composition, i.e., 100%. References to "one or more" or "at least one" include "two or more" and "three or more," etc.

[0025] Where applicable, all weight percentages are "neat" unless otherwise indicated, meaning that they do not include the aqueous solution present when added to the composition. For example, "neat" refers to the weight percent amount of undiluted acid or other material (i.e., a 100g inclusion of 85% phosphoric acid would be composed of 85g of acid and 15g of diluent).

[0026] Furthermore, when referring to compositions described herein in terms of weight percent, it is understood that the weight percent of all components, including non-essential components such as impurities, never exceeds 100 weight percent. In a composition "consisting essentially of" listed components, such components may add up to 100 weight percent of the composition, or may add up to less than 100 weight percent. Where components add up to less than 100 weight percent, such compositions may contain small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2 weight percent or less of impurities. In another embodiment, the formulation may contain less than 1 weight percent of impurities. In a further embodiment, the formulation may contain less than 0.05 weight percent of impurities. In other such embodiments, the components may form at least 90 weight percent, more preferably at least 95 weight percent, more preferably at least 99 weight percent, more preferably at least 99.5 weight percent, and most preferably at least 99.9 weight percent, and may include other components that do not significantly affect the performance of the wet etchant. Otherwise, it is understood that in the absence of significant non-essential impurity ingredients, the composition of all essential components essentially totals 100% by weight.

[0027] The headings used herein are not intended to be limiting; rather, they are included for organizational purposes only.

[0028] Illustrative Embodiments

[0029] One aspect of the disclosed and claimed subject matter relates to precursors having at least one tethered cyclopentadienyl ligand (“Cp ligand”), at least one amidinate ligand (“Ad ligand”), and a lanthanide and / or lanthanide-like transition metal (“M”) of the general formula (i) (Cp ligand)-M-(Ad ligand) or (ii) (Cp ligand)-M-(Ad ligand)

[0030] One aspect of the disclosed and claimed subject matter relates to precursors having at least two tethered cyclopentadienyl ligands ("Cp ligands") and at least one amidinate ligand ("Ad ligand") of the general formula (Cp ligand)2-M-(Ad ligand), where M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. In one aspect of this embodiment, M is one of Sc, Y, La, and Ce. In one aspect of this embodiment, M is Sc. In one aspect of this embodiment, M is Y. In one aspect of this embodiment, M is La. In one aspect of this embodiment, M is Ce.

[0031] One aspect of the disclosed and claimed subject matter relates to precursors having at least one tethered cyclopentadienyl ligand ("Cp ligand") and at least two amidinate ligands ("Ad ligand") of the general formula (Cp ligand)-M-(Ad ligand)2, where M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. In one aspect of this embodiment, M is one of Sc, Y, La, and Ce. In one aspect of this embodiment, M is Sc. In one aspect of this embodiment, M is Y. In one aspect of this embodiment, M is La. In one aspect of this embodiment, M is Ce.

[0032] In some embodiments, the tethered Cp ligand is derived from the structure shown in Table 1 below, and the tethered Ad ligand has the structure shown in Table 2 below. [Table 1] [Table 2]

[0033] Preferred embodiments of the general formulae (i) (Cp ligand)2-M-(Ad ligand) and (ii) (Cp ligand)-M-(Ad ligand)2, including the ligands shown in Tables 1 and 2, are set forth in Tables 3 and 4. [Table 3-1] [Table 3-2] [Table 4-1] [Table 4-2]

[0034] The disclosed and claimed precursors are not limited to those exemplified in Tables 3 and 4. Additionally, the Cp and Ad ligands are not limited to those exemplified in Tables 1 and 2. Further embodiments of the disclosed and claimed precursors are described below with reference to Formula I.

[0035] Formula I Embodiments

[0036] Embodiments and aspects of precursors having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand having formula I are exemplified as follows: As noted above, precursors of formula I include compounds of the general formula (i)(Cp ligand)2 and (ii)(Cp ligand)-M-(Ad ligand)2, where Cp has at least three different substituents.

[0037] In one embodiment, the precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand has Formula I [ka] Formula I [In the formula, (i) M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; (ii)R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from H, an unsubstituted linear C1-C6 alkyl group, a linear C1-C6 alkyl group substituted with a halogen, a linear C1-C6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, a branched C3-C6 alkyl group substituted with an amino group, and —Si(CH3)3; (a)R 1 , R 2 , R 3 , R 4 and R 5 contains at least three different substituents; and (b) R 1 , R 2 , R 3 , R 4 and R 5 at least two of are H; (iii)R 6 , R 7 and R 8 are each independently selected from H, an unsubstituted linear C1-C6 alkyl group, a linear C1-C6 alkyl group substituted with a halogen, a linear C1-C6 alkyl group substituted with an amino group, an unsubstituted branched C3-C6 alkyl group, a branched C3-C6 alkyl group substituted with a halogen, a branched C3-C6 alkyl group substituted with an amino group, and —Si(CH3)3; (iv) n=1 or 2; (v) the precursor is liquid below about 80°C;

[0038] In one aspect of this embodiment, M is one of Sc, Y, La, and Ce. In one aspect of this embodiment, M is La. In another aspect of this embodiment, M is Sc. In another aspect of this embodiment, M is Y. In another aspect of this embodiment, M is Ce. In another aspect of this embodiment, M is Pr. In another aspect of this embodiment, M is Nd. In another aspect of this embodiment, M is Pm. In another aspect of this embodiment, M is Sm. In another aspect of this embodiment, M is Eu. In another aspect of this embodiment, M is Gd. In another aspect of this embodiment, M is Tb. In another aspect of this embodiment, M is Dy. In another aspect of this embodiment, M is Ho. In another aspect of this embodiment, M is Er. In another aspect of this embodiment, M is Tm. In another aspect of this embodiment, M is Yb. In another aspect of this embodiment, M is Lu. Preferably, M is La.

[0039] In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from H, an unsubstituted linear C1-C5 linear alkyl group, and an unsubstituted branched C3-C6 alkyl group.

[0040] In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 and R 5 Three of R are H. In one aspect of this embodiment, 1 , R 2 , R 3 , R 4 and R 5 Two of them are H.

[0041] In one aspect of this embodiment, R 5 , R 6 and R 8In another aspect of this embodiment, one or more of R 5 , R 6 and R 8 In another aspect of this embodiment, two or more of R 5 , R 6 and R 8 Each of is an isopropyl group.

[0042] In one aspect of this embodiment, n = 1. In another aspect of this embodiment, n = 2.

[0043] In one embodiment, R 1 , R 6 and R 8 are each an isopropyl group, and R 3 is a methyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen. In one aspect of this embodiment, M=La. In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In a preferred aspect of this embodiment, M=La, R 1 , R 6 and R 8 are each an isopropyl group, and R 3 is a methyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen and n=2. [ka]

[0044] In one embodiment, R 1 is a tert-butyl group, and R 3 is a methyl group, and R 2 , R 4 , R 5 are each hydrogen, and R 6 and R 8 are each an isopropyl group, and R 7is hydrogen. In one aspect of this embodiment, M=La. In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In a preferred aspect of this embodiment, M=La and R 1 is a tert-butyl group, and R 3 is a methyl group, and R 2 , R 4 , R 5 are each hydrogen, and R 6 and R 8 are each an isopropyl group, and R 7 is hydrogen and n=2. [ka]

[0045] In one embodiment, R 1 , R 6 and R 8 are each an isopropyl group, and R 3 and R 7 are each a methyl group, and R 2 , R 4 and R 5 are each hydrogen. In one aspect of this embodiment, M=La. In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In a preferred aspect of this embodiment, M=La and R 1 , R 6 and R 8 are each an isopropyl group, and R 3 and R 7 are each a methyl group, and R 2 , R 4 and R 5 are each hydrogen and n=2. [ka]

[0046] In one embodiment, R 1 is a sec-butyl group, and R 3 is a methyl group, and R 6 and R 8are each an isopropyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen. In one aspect of this embodiment, M=La. In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In a preferred aspect of this embodiment, M=La and R 1 is a sec-butyl group, and R 3 is a methyl group, and R 6 and R 8 are each an isopropyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen and n=2. [ka]

[0047] In one embodiment, R 1 is an isopropyl group, and R 3 is a methyl group, and R 6 is an ethyl group, and R 8 is a tert-butyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen. In one aspect of this embodiment, M=La. In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In a preferred aspect of this embodiment, M=La and R 1 is an isopropyl group, and R 3 is a methyl group, and R 6 is an ethyl group, and R 8 is a tert-butyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen and n=2. [ka]

[0048] In one embodiment, R 1 is an ethyl group, and R 3 is a methyl group, and R 6 and R 8 are each an isopropyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen. In one aspect of this embodiment, M=La. In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In a preferred aspect of this embodiment, M=La and R 1 is an ethyl group, and R 3 is a methyl group, and R 6 and R 8 are each an isopropyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen and n=2. [ka]

[0049] In one embodiment, R 1 and R 6 are each an ethyl group, and R 3 is a methyl group, and R 8 is a tert-butyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen. In one aspect of this embodiment, M=La. In one aspect of this embodiment, n=1. In another aspect of this embodiment, n=2. In a preferred aspect of this embodiment, M=La and R 1 and R 6 are each an ethyl group, and R 3 is a methyl group, and R 8 is a tert-butyl group, and R 2 , R 4 , R 5 and R 7 are each hydrogen and n=2. [ka]

[0050] How to use

[0051] The disclosed precursors can be deposited to form lanthanide-containing films using any chemical vapor deposition process 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 the 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) sequential surface chemistry that deposits films of material on substrates of various compositions. While the precursors, reagents, and sources used herein may be described as "gaseous," it is understood that the precursors can be either liquids or solids that are transported into the reactor by direct vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, the vaporized precursor can be passed through a plasma generator. As used herein, the term "reactor" includes, but is not limited to, a reaction chamber, reaction vessel, or deposition chamber.

[0052] Chemical vapor deposition processes that can utilize the disclosed and claimed precursors include, but are not limited to, those 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 temperature chemical vapor deposition, chemically-assisted vapor deposition, hot-filament chemical vapor deposition, CVD of liquid polymer precursors, deposition from supercritical fluids, and low-energy CVD (LECVD). In certain embodiments, metal-containing films are deposited by atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), or plasma-enhanced cyclic CVD (PECCVD) processes.

[0053] In one embodiment, for example, the metal-containing film is deposited using an ALD process. In another embodiment, the metal-containing film is deposited using a CCVD process. In a further embodiment, the metal-containing film is deposited using a CVD process.

[0054] Suitable substrates onto which the disclosed and claimed precursors can be deposited are not particularly limited and vary depending on the intended end use. For example, the substrate may be selected from oxides such as HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, or nitride-based films. Other substrates include metal substrates (e.g., 、Solid substrates such as Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt, and metal silicides (e.g., TiSi2, CoSi2, and NiSi2), metal nitride-containing substrates (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN), semiconductor materials (e.g., Si, SiGe, GaAs, InP, diamond, GaN, and SiC), insulators (e.g., SiO2, Si3N4, SiON, HfO2, Ta2O5, ZrO2, TiO2, Al2O3, and barium strontium titanate), and combinations thereof may be included. Preferred substrates include TiN, Ru, and Si type substrates.

[0055] Such deposition methods and processes may utilize an oxidizing agent, which is typically introduced in gaseous form. Examples of suitable oxidizing agents include, but are not limited to, oxygen gas, water vapor, ozone, oxygen plasma, or mixtures thereof.

[0056] Deposition methods and processes may also involve the use of one or more purge gases. Purge gases, used to purge away unconsumed reactants and / or reaction by-products, are inert gases that do not react with the precursors. Exemplary purge gases include argon (Ar), nitrogen (N), helium (He), neon, and mixtures thereof. For example, a purge gas, such as Ar, is supplied into the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 10,000 seconds, thereby purging unreacted materials and any by-products that may remain in the reactor.

[0057] Deposition methods and processes require the addition of energy to at least one of a precursor, an oxidizer, another precursor, or a combination 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, and combinations thereof. In some processes, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. When utilizing plasma, the plasma generation process can include a direct plasma generation process in which the plasma is generated directly within the reactor, or a remote plasma generation process in which the plasma is generated outside the reactor and fed into the reactor.

[0058] When utilized in such deposition methods and processes, suitable precursors—such as those presently disclosed and claimed—can be delivered to a reaction chamber, such as a CVD or ALD reactor, in a variety of ways. In some instances, a liquid delivery system can be utilized. In other instances, a combined liquid delivery and flash evaporation process unit, such as a turbo-vaporizer manufactured by MSP Corporation (Shoreview, MN), may be used to enable volumetric delivery of low-volatility materials, resulting in reproducible transport and deposition without thermal decomposition of the precursor. The precursor compositions described herein can be effectively used as source reagents by direct liquid injection (DLI) to provide a vapor flow of these metal precursors to an ALD or CVD reactor.

[0059] When used in these deposition methods and processes, the disclosed and claimed precursors can contain hydrocarbon solvents, which are particularly desirable because they can be dried to sub-ppm levels of water. Exemplary hydrocarbon solvents that can be used with the precursors include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decalin). The disclosed and claimed precursors can also be stored and used in stainless steel containers. In certain embodiments, the hydrocarbon solvent is a high-boiling solvent or has a boiling point of 100°C or higher. The disclosed and claimed precursors can also be mixed with other suitable metal precursors, and the mixture used to simultaneously deliver both metals for the growth of bimetallic films.

[0060] A flow of argon and / or other gases can be used as a carrier gas to help deliver a vapor containing at least one of the disclosed and claimed precursors to the reaction chamber during precursor pulsing. When delivering the precursor, the reaction chamber process pressure is between 1 and 50 Torr, preferably between 5 and 20 Torr.

[0061] Substrate temperature can be an important process variable in the deposition of high-quality metal-containing films. Typical substrate temperatures range from about 150°C to about 550°C. Higher temperatures can promote higher film growth rates.

[0062] In view of the above, one skilled in the art will recognize that the disclosed and claimed subject matter further includes the use of the disclosed and claimed precursors in chemical vapor deposition processes such as:

[0063] In one embodiment, the disclosed and claimed subject matter comprises a method for forming a transition metal-containing film on at least one surface of a substrate, the method comprising: a. providing the at least one surface of the substrate in a reaction vessel; b. forming a transition metal-containing film on at least one surface by a deposition process selected from a chemical vapor deposition (CVD) and an atomic layer deposition (ALD) process using one of the disclosed and claimed precursors as a metal source compound for the deposition process. In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel. In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from the group consisting of water, diatomic oxygen, oxygen plasma, ozone, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, wherein the at least one reactant is selected from the group consisting of hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen / helium plasma, hydrogen / argon plasma, a boron-containing compound, a silicon-containing compound, and combinations thereof.

[0064] In one embodiment, the disclosed and claimed subject matter is a method of forming a transition metal-containing film by an atomic layer deposition (ALD) process or an ALD-like process, comprising: a. providing a substrate to a reaction vessel; b. introducing one or more of the disclosed and claimed precursors into a 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. sequentially repeating steps b to e until a transition metal-containing film of a desired thickness is obtained. In a further aspect of this embodiment, the source gas is one or more oxygen-containing source gases selected from water, diatomic oxygen, oxygen plasma, ozone, NO, NO, NO, carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the source gas is one or more nitrogen-containing source gases selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof. In a further aspect of this embodiment, the first and second purge gases 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 at least one of the precursor, the source gas, the 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. In a further aspect of this embodiment, step b of the method further comprises introducing the precursor into the reaction vessel using a carrier gas flow to deliver vapor of the precursor to the reaction vessel. In a further aspect of this embodiment, step b of the method further comprises using a solvent medium comprising one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyltoluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene, and combinations thereof.

[0065] In another embodiment, precursors having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand having Formula I can be used as dopants for metal-containing films, such as, but not limited to, metal oxide films or metal nitride films. In these embodiments, the metal-containing films are deposited using ALD, ALD-like, or CVD processes, such as those described herein using metal alkoxides, metal amides, or volatile organometallic precursors. Examples of suitable metal alkoxide precursors that can be used in the methods disclosed herein include, but are not limited to, Group 3-13 metal alkoxides, Group 3-13 metal complexes with both alkoxy- and alkyl-substituted cyclopentadienyl ligands, Group 3-6 metal complexes with both alkoxy- and alkyl-substituted pyrrolyl ligands, Group 3-13 metal complexes with both alkoxy- and diketonate ligands, and Group 3-13 metal complexes with alkyl ligands. Exemplary Group 3-13 metals herein include, but are not limited to, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, W, Co, Ru, and Al.

[0066] Examples of suitable metal amide precursors that can be used in the methods disclosed herein include tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tris(dimethylamino)(cyclopentadienyl)zirconium, tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tris(dimethylamino)(cyclopentadienyl)hafnium, tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri( tert-butyliminotri(dimethylamino)tantalum (TBTDMT), tert-butyliminotri(ethylmethylamino)tantalum (TBTEMT), ethyliminotri(diethylamino)tantalum (EITDET), ethyliminotri(dimethylamino)tantalum (EITDMT), ethyliminotri(ethylmethylamino)tantalum (EITEMT), tert-amyliminotri(dimethylamino)tantalum (TAIMAT), tert-amyliminotri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amyliminotri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, and combinations thereof. Examples of suitable organometallic precursors that can be used in the methods disclosed herein include, but are not limited to, Group 3 metal cyclopentadienyls or alkylcyclopentadienyls.

[0067] Examples of suitable metal complexes having alkyl ligands that can be used in the methods disclosed herein include, but are not limited to, tri-tertbutylaluminum (TTBA), trimethylaluminum (TMA), triethylaluminum (TEA), dimethylaluminum hydride (DMAH), dimethylethylamine alane (DMEAA), trimethylamine alane (TEAA), N-methylpyrrolidine alane (MPA), triisobutylaluminum (TIBA). [Example]

[0068] Reference will now be made to more specific embodiments of the present disclosure, as well as experimental results supporting such embodiments. The examples are provided below to more fully explain the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0069] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and the specific examples provided herein without departing from the spirit and scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the description provided by way of example below, is intended to cover modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.

[0070] Materials and Methods:

[0071] All solvents and starting materials were purchased from Sigma-Aldrich unless otherwise indicated. Tris-(1-isopropyl-3-methylcyclopentadienyl)lanthanum(III) [La(iPr-Me-Cp)] was prepared in-house. La(iPr-FAMD) was purchased from STREM and used as received.

[0072] Comparative Example 1: Synthesis of La(iPr-Me-Cp)

[0073] Tris-trimethylsilylamide lanthanum(III) (La(HMDS)3) (8.2 g, 13 mmol) was suspended in 30 mL of toluene. Excess 1-isopropyl-3-methylcyclopentadiene (iPr-Me-CpH) (11.1 g, 91 mmol) was added to the suspension. The mixture was stirred at 80 °C for 5 days. The solvent and volatile by-products were removed from the mixture under reduced pressure, and the crude product was distilled in vacuo (260 °C, 2 × 10 -2 mbar). Yield 54%

[0074] Characterization: 1 H NMR(500MHz,C6D6)δ6.00-5.78(m,9H),2.85-2.67(m,3H),2.13-2.05(m,9H),1.20-1.09(m,19H);TGA: Melting point 55℃;Initial mass: 4.478mg;T 50% =280.1℃, see Figure 1.

[0075] Synthesis Example 1: Synthesis of La(iPr-Me-Cp)2 (iPr2-FAMD)

[0076] Tris-(1-isopropyl-3-methylcyclopentadienyl)lanthanum(III) [La(iPr-Me-Cp)] (1.35 g, 2.69 mmol) was dissolved in 15 mL of toluene. Tris-(diisopropylformamidinato)lanthanum(III) [La(iPr-FAMD)] (0.699 g, 1.34 mmol) was dissolved in another 15 mL of toluene, and the two solutions were combined and stirred at 100 °C for 72 h. The solvent was removed from the mixture, and the crude product was distilled (90 °C, 2 × 10 -2 mbar), 1.38 g of a yellow liquid product was produced. Yield: 67.5%.

[0077] Characterization: 1H NMR(500MHz,C6D6)δ6.04(dt,J=9.6,2.8Hz,2H),6.00(q,J=2.8Hz,2H),5.92(dt,J=15.9,2.8Hz,2H),3.06(hept,J=6.5Hz,2H),2 .91(heptd,J=6.9,3.2Hz,2H),2.18(d,J=2.9Hz,6H),1.26(dd,J=7.0,4.3Hz,12H),1.08(d,J=6.4Hz,12H);TGA:Initial mass:8.720mg,T 50% = 254.9°C; DSC: Endothermic effect onset: 365°C.

[0078] Notably, the product remained liquid after distillation. NMR shows a clean product, as shown in Figure 2. TGA shows a clean evaporation indicating good volatility, and DSC shows good thermal stability up to 365°C (no melting point was detectable between -100°C and 365°C). See Figures 3 and 4, respectively.

[0079] The foregoing description has been primarily for purposes of illustration. While the disclosed and claimed subject matter has been shown and described with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in form and detail thereof may be made without departing from the spirit and scope of the disclosed and claimed subject matter.

[0080] Synthesis Example 2: Synthesis of La(tBu-Me-Cp)2(iPr2-FAMD)

[0081] Tris-(1-tert-butyl-3-methylcyclopentadienyl)lanthanum(III) [La(tBu-Me-Cp)] (588.5 mg, 1.08 mmol) was dissolved in 15 mL of toluene. Tris-(diisopropylformamidinato)lanthanum(III) [La(iPr-FAMD)] (281.2 mg, 0.54 mmol) was dissolved in another 15 mL of toluene, and the two solutions were combined and stirred at 100 °C for 72 h. The solvent was removed from the mixture, and the crude product was distilled (90 °C, 2 × 10 -2mbar), 240 mg of a yellow liquid product was produced. Yield: 27.6%.

[0082] Characterization: 1 H NMR(500MHz,C6D6)δ8.00(d,J=3.3Hz,1H),6.15(dt,J=12.8,2.8Hz,2H),6.10(dt,J=9.8,2.6Hz,2H),5.89(dt,J=29. 6,2.9Hz,2H),3.10(hept,J=6.4Hz,2H),2.21(d,J=8.5Hz,6H),1.32(d,J=9.2Hz,18H),1.12(dd,J=6.5,3.7Hz,12H). TGA: Initial mass: 9.6460mg, T 50% = 273.7°C; DSC: Endothermic effect onset: 390°C.

[0083] Notably, the product remained liquid after distillation. NMR shows a clean product. TGA shows clean evaporation indicating good volatility, and DSC shows good thermal stability up to 390°C (no melting point was detectable between -50°C and 365°C).

[0084] ALD of lanthanum oxide films with La(iPr-Me-Cp)2 (iPr2-FAMD)

[0085] Atomic layer deposition of lanthanum oxide films using the precursor of the present invention was demonstrated using an Atomic Premium CN-1 200 mm reactor. The precursor, La(iPr-Me-Cp)2 (iPr2-FAMD), was delivered from an SS316 ampoule maintained at 130 °C (ampoule wall temperature). A 50 sccm argon carrier gas flow was used to deliver the precursor vapor to the reactor chamber. The reactor chamber pressure was 1 Torr. Si and SiO2 substrates were used to deposit lanthanum oxide films. The thickness of the lanthanum oxide films was measured by ellipsometry, and X-ray fluorescence (XRF) was calibrated using cross-sectional SEM images of the deposited lanthanum oxide films.

[0086] Example 3: Precursor pyrolysis test on Si wafer

[0087] In this experiment, the precursor vapor was delivered to the deposition chamber in a pulsed mode separated by an argon purge. The pulse sequence was a 5-second precursor pulse followed by a 20-second argon purge. The total number of precursor / Ar purge cycles was 100. To demonstrate the precursor's good thermal stability in the absence of an oxidizer, no oxidizer pulses were used in this experiment. Good thermal stability (no deposition in the absence of an oxidizer) is an important precursor property for atomic layer deposition processes. The wafer temperature was varied from 200 °C to 450 °C. After the experiment, the lanthanum layer density on the surface was measured by X-ray fluorescence analysis and is shown in Figure 5. No increase in lanthanum concentration on the silicon wafer was observed up to at least 450 °C, suggesting the very good thermal stability of this precursor in the gas phase and its usefulness for gas-phase deposition applications.

[0088] Example 4: Precursor saturation behavior during the deposition process

[0089] In this experiment, the following steps were performed: a. providing a SiO2 substrate in a reaction vessel; b. Introducing La(iPr-Me-Cp-Cp)2 (iPr2-FAMD) precursor into the reaction vessel; c. purging the reaction vessel with argon; d. introducing ozone into the reaction vessel; e. purging the reaction vessel with argon; f. sequentially repeating steps b to e until a transition metal-containing film of a desired thickness is obtained. The lanthanum precursor pulse was varied from 0.5 to 3 seconds, demonstrating saturation behavior with increasing pulse time. The Ar purge after the precursor pulse was 10 seconds, the ozone pulse was 1 second, and the Ar purge after the precursor pulse was 30 seconds. The number of ALD cycles was 100. Figure 6 shows very good saturation behavior at temperatures of 200 °C and 250 °C. Saturation behavior is one of the key characteristics of the atomic layer deposition process.

[0090] Example 5: Deposition of lanthanum oxide films

[0091] In this experiment, the following steps were performed: a. providing a SiO2 substrate in a reaction vessel; b. Introducing La(iPr-Me-Cp-Cp)2 (iPr2-FAMD) precursor into the reaction vessel; c. purging the reaction vessel with argon; d. introducing ozone into the reaction vessel; e. purging the reaction vessel with argon; f. sequentially repeating steps b to e until a transition metal-containing film of a desired thickness is obtained. The lanthanum precursor pulse was 3 seconds. The Ar purge after the precursor pulse was 30 seconds. The ozone pulse was 1 second, followed by a 30-second Ar purge after the precursor pulse. The number of ALD cycles was 100. The wafer temperatures were 175°C and 275°C. Figure 7 shows cross-sectional TEM images of lanthanum oxide films deposited on structured wafers at 175°C and 275°C. Table 5 shows the film thicknesses at the top, middle, and bottom of the trenches on the patterned wafers. TEM images show the deposition of smooth, dense films. Experiments also showed only a slight change in step coverage between 175°C and 275°C, suggesting good ALD behavior. Without being bound by theory, it is believed that step coverage can be further improved by process optimization, such as longer precursor pulse times. [Table 5]

[0092] The foregoing description has been primarily for purposes of illustration. While the disclosed and claimed subject matter has been shown and described with respect to exemplary embodiments thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in form and detail thereof may be made without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. Formula (cyclopentadienyl ligand) ２ -M-(amidinate ligand) precursors, where M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

2. Formula (cyclopentadienyl ligand)-M-(amidinate ligand) ２ wherein M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

3. 3. The precursor of claim 1 or 2, wherein M is one of La, Ce, Y and Sm.

4. 3. The precursor of claim 1, wherein M is La.

5. 3. The precursor of claim 1, wherein M is Ce.

6. 3. The precursor of claim 1 or 2, wherein M is Y.

7. 3. The precursor of claim 1, wherein M is Sm.

8. 3. The precursor of claim 1 or 2, wherein each cyclopentadienyl ligand is independently derived from a cyclopentadiene shown in Table 1. 【Table 1】

9. 3. The precursor of claim 1 or 2, wherein the amidinate ligand is selected from the amidinate ligands shown in Table 2. 【Table 2】

10. 10. The precursor of claim 1 having the structure shown in Table 3. 【Table 3-1】 【Table 3-2】

11. 3. The precursor of claim 2 having the structure shown in Table 4. 【Table 4-1】 【Table 4-2】

12. Formula I 【Chemical 1】 Formula I [During the ceremony (i) M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; (ii) R １ , R ２ , R ３ , R ４ and R ５ are each H, unsubstituted linear C １ ~C ６ Alkyl group, halogen-substituted linear C １ ~C ６ Linear C substituted with alkyl or amino groups １ ~C ６ Alkyl group, unsubstituted branched C ３ ~C ６ Branched C substituted with alkyl groups and halogens ３ ~C ６ Branched C substituted with alkyl and amino groups ３ ~C ６ Alkyl groups, and -Si(CH ３ ) ３ are substituents independently selected from (a) R １ , R ２ , R ３ , R ４ and R ５ (b) R １ , R ２ , R ３ , R ４ and R ５ at least two of are H; (iii) R ６ , R ７ and R ８ are each H, unsubstituted linear C １ ~C ６ Alkyl group, halogen-substituted linear C １ ~C ６ Linear C substituted with alkyl or amino groups １ ~C ６ Alkyl group, unsubstituted branched C ３ ~C ６ Branched C substituted with alkyl groups and halogens ３ ~C ６ Branched C substituted with alkyl and amino groups ３ ~C ６ Alkyl groups, and -Si(CH ３ ) ３ are substituents independently selected from (iv) n=1 or 2; (v) A precursor that is liquid below about 80°C.

13. 13. The precursor of claim 12, wherein M is Sc.

14. 13. The precursor of claim 12, wherein M is Y.

15. 13. The precursor of claim 12, wherein M is La.

16. 13. The precursor of claim 12, wherein M is Ce.

17. R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ and R ８ each independently represents H, unsubstituted linear C １ ~C ５ Linear alkyl groups and unsubstituted branched C ３ ~C ６ 13. The precursor of claim 12, wherein the alkyl group is selected from the group consisting of:

18. R １ , R ２ , R ３ , R ４ and R ５ 13. The precursor of claim 12, wherein three of

19. R １ , R ２ , R ３ , R ４ and R ５ 13. The precursor of claim 12, wherein two of

20. R ５ , R ６ and R ８ 13. The precursor of claim 12, wherein one or more of: is an isopropyl group.

21. R ５ , R ６ and R ８ 13. The precursor of claim 12, wherein two or more of:

22. R ５ , R ６ and R ８ 13. The precursor of claim 12, wherein each of is an isopropyl group.

23. 13. The precursor of claim 12, wherein n=1.

24. 13. The precursor of claim 12, wherein n=2.

25. (ii) R １ , R ６ and R ８ are each an isopropyl group, and R ３ is a methyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen, and (iv) n=2. (See claim 31).

26. (i) M=La, and (ii) R １ , R ６ and R ８ are each an isopropyl group, and R ３ is a methyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen, and (iv) n=2.

27. (ii) R １ , R ６ and R ８ are each an isopropyl group, and R ３ and R ７ are each a methyl group, and R ２ , R ４ and R ５ 13. The precursor of claim 12, wherein each is hydrogen.

28. (i) M=La, and (ii) R １ , R ６ and R ８ are each an isopropyl group, and R ３ and R ７ are each a methyl group, and R ２ , R ４ and R ５ 13. The precursor of claim 12, wherein each is hydrogen, and (iv) n=2.

29. (ii) R １ is a sec-butyl group, and R ３ is a methyl group, and R ６ and R ８ are each an isopropyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen.

30. (i) M=La, and (ii) R １ is a sec-butyl group, and R ３ is a methyl group, and R ６ and R ８ are each an isopropyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen, and (iv) n=2.

31. (ii) R １ , R ６ and R ８ are each an isopropyl group, and R ３ is a methyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen, and (iv) n=1.

32. (i) M=La, and (ii) R １ is an isopropyl group, and R ３ is a methyl group, and R ６ is an ethyl group, and R ８ is a tert-butyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen, and (iv) n=2.

33. (ii) R １ is an ethyl group, and R ３ is a methyl group, and R ６ and R ８ are each an isopropyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen.

34. (i) M=La, and (ii) R １ is an ethyl group, and R ３ is a methyl group, and R ６ and R ８ are each an isopropyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen, and (iv) n=2.

35. (ii) R １ and R ６ are each an ethyl group, and R ３ is a methyl group, and R ８ is a tert-butyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen.

36. (i) M=La, and (ii) R １ and R ６ are each an ethyl group, and R ３ is a methyl group, and R ８ is a tert-butyl group, and R ２ , R ４ , R ５ and R ７ 13. The precursor of claim 12, wherein each is hydrogen, and (iv) n=2.

37. 13. The precursor of claim 12, comprising at least one cyclopentadienyl ligand as shown in Table 1.

38. 13. The precursor of claim 12, comprising at least one amidinate ligand as shown in Table 2.

39. 13. The precursor of claim 12 having the structure shown in Table 3.

40. 13. The precursor of claim 12 having the structure shown in Table 4.

41. A precursor having the following structure: 【Chemistry 2】

42. A precursor having the following structure: 【Chemistry 3】

43. A precursor having the following structure: 【Chemistry 4】

44. A precursor having the following structure: 【Chemistry 5】

45. A precursor having the following structure: 【Chemistry 6】

46. A precursor having the following structure: 【Chemistry 7】

47. A precursor having the following structure: 【Chemistry 8】

48. 1. A method for forming a transition metal-containing film on at least one surface of a substrate, comprising: a. providing the at least one surface of the substrate in a reaction vessel; b) forming a transition metal-containing film on said at least one surface by a deposition process selected from a chemical vapor deposition (CVD) and an atomic layer deposition (ALD) process using the precursor of any one of claims 1 to 47 as a metal source compound for said deposition process.

49. 49. The method of claim 48, further comprising introducing at least one reactant into the reaction vessel.

50. Water, diatomic oxygen, oxygen plasma, ozone, NO, N ２ O, NO ２ 49. The method of claim 48, further comprising introducing at least one reactant into the reaction vessel selected from the group consisting of carbon monoxide, carbon dioxide, and combinations thereof.

51. 49. The method of claim 48, further comprising introducing at least one reactant into the reaction vessel selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and combinations thereof.

52. 49. The method of claim 48, further comprising introducing at least one reactant into the reaction vessel 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.

53. 1. A method for forming a transition metal-containing film by an atomic layer deposition (ALD) or ALD-like process, comprising: a. providing a substrate to a reaction vessel; b. introducing the precursor of any one of claims 1 to 47 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. sequentially repeating steps b through e until a desired thickness of the transition metal-containing film is obtained.

54. The source gas may be water, diatomic oxygen, oxygen plasma, ozone, NO, N ２ O, NO ２ 54. The method of claim 53, wherein the oxygen-containing source gas is one or more selected from the group consisting of carbon monoxide, carbon dioxide, and combinations thereof.

55. 54. The method of claim 53, 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.

56. 54. The method of claim 53, wherein the first and second purge gases are each independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof.

57. 54. The method of claim 53, further comprising applying energy to at least one of the precursor, the source gas, the 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.

58. 54. The method of claim 53, wherein step b further comprises introducing the precursor into the reaction vessel using a carrier gas flow to deliver vapor of the precursor into the reaction vessel.

59. 54. The method of claim 53, 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 decahydronaphthalene, and combinations thereof.

60. 1. A method for forming a transition metal-containing film on at least one surface of a substrate, comprising: a. providing the at least one surface of the substrate in a reaction vessel; b. forming a transition metal-containing film on the at least one surface by a deposition process selected from a chemical vapor deposition (CVD) and an atomic layer deposition (ALD) process using a precursor as a metal source compound for the deposition process; c) using the precursor of any one of claims 1 to 47 as a dopant material.

61. A precursor supply package comprising a container and a precursor according to any one of claims 1 to 47, said container adapted to contain and dispense said precursor.

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