Complexes of lanthanides and lanthanide-like transition metals

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”) having the general formula (i) (Cp ligand)2-M-(Ad ligand) or (ii) (Cp ligand)-M-(Ad ligand)2.

Description

TECHNICAL FIELD

[0001] The disclosed and claimed subject matter relates to organometallic compounds (including lanthanide and / or lanthanide-like transition metals), compositions containing such compounds, and methods of using such compounds as precursors for depositing metal-containing films. BACKGROUND OF THE INVENTION

[0002] Transition metal-containing films are used in semiconductor and electronic device applications. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been used as the primary deposition techniques for producing thin films for semiconductor devices. These methods enable conformal films (metals, metal oxides, metal nitrides, metal silicides, etc.) to be achieved through chemical reactions of metal-containing compounds (precursors). The chemical reactions occur on surfaces that can include metals, metal oxides, metal nitrides, metal silicides, 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 the CVD and ALD processes is an important consideration in the selection of precursor molecules. Higher substrate temperatures in the range of 150 to 500 degrees Celsius (°C) promote higher film growth rates. The preferred precursor molecules must be stable within this temperature range. The preferred precursors can be delivered to the reaction vessel in the liquid phase. Compared to solid-phase precursors, the liquid-phase delivery of precursors generally enables more uniform delivery of the precursors to the reaction vessel.

[0003] U.S. Patent No. 8,283,201 discloses precursor compounds having a cyclopentadienyl ligand and an amidine ligand containing at least one aliphatic group as a substituent. In particular, the disclosed structure includes a lanthanide-containing precursor of the formula Ln(R 1 Cp) m (R 2 —N—C(R 4 )=N—R 2 ) n where (i) Ln is a lanthanide metal having an ionic radius of about to about , a 3+ charge, and a coordination number of 6, (ii) R 1 is selected from the group consisting of H and C1-C5 alkyl chains, (iii) R 2 is selected from the group consisting of H and C1-C5 alkyl chains, (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 below about 105 °C. The disclosed precursors do not particularly contain any heteroatom substituents on the Cp ring (i.e., as any R 1 group).

[0004] U.S. Patent Application Publication No. 2019 / 0152996 (U.S. Patent Application No. 16 / 251,236) discloses a lanthanide-containing compound of the following formula

[0005]

[0006] wherein R 1 is a hydrogen atom or a C1-C4 straight-chain or branched alkyl group, R 2 and R 3 are each independently a hydrogen atom or a C1-C5 straight-chain or branched alkyl group, at least one of R 2 and R 3 is a C3-C5 branched alkyl group, and R 4 is a hydrogen atom or a C1-C4 straight-chain or branched alkyl group. The same is true for the compounds disclosed in USP8,283,201. The disclosed compounds do not contain any heteroatom substituents (i.e., as any R 1 group), and can provide further coordination with metals. In this regard, during the examination history of this application, the USPTO admitted that USP8,283,201 failed to teach or suggest an asymmetric amidinate in which R 2 and R 3 are different from each other.

[0007] There is a need in the art for thermally stable lanthanide and / or lanthanide-like organometallic compounds suitable as CVD and ALD precursors, which can preferably be delivered in a liquid phase, have low impurities and can produce high-quality films with high conformality. SUMMARY OF THE INVENTION

[0008] 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"), having the general formula (i) (Cp ligand)2-M-(Ad ligand) or (ii) (Cp ligand)-M-(Ad ligand)2. The disclosed and claimed subject matter further includes compositions containing the compound, methods of using the compound as a precursor for depositing a metal-containing film, and films derived from the precursor.

[0009] In some embodiments, the precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand has the formula I:

[0010]

[0011] wherein (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 、R2 , R 3 , R 4 , R 5 , R 6 and R 7 Each independently selected from H, D, unsubstituted straight-chain C1-C6 alkyl, halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, unsubstituted branched C3-C6 alkyl, halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, and -Si(CH3)3, (iii) R is a straight-chain or branched C1-C6 alkylene, (iv) R c is H, D, unsubstituted straight-chain C1-C3 straight-chain alkyl or unsubstituted branched C3-C6 alkyl, (v) n = 1 or 2. The precursor of Formula I includes compounds of the general formula (i) (Cp ligand)2-M-(Ad ligand) and (ii) (Cp ligand)-M-(Ad ligand)2, wherein the Cp ligand contains an oxygen-containing side chain.

[0012] In other embodiments, a precursor having at least one tethered cyclopentadienyl ligand and at least one amidide ligand has Formula II:

[0013]

[0014] wherein (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 , R 5 , R 6 and R 7 Each independently selected from H, D, unsubstituted straight-chain C1-C6 alkyl, halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, unsubstituted branched C3-C6 alkyl, halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6 alkyl, and -Si(CH3)3, (iii) R is a straight-chain or branched C1-C6 alkylene, (iv) R c and R d Each independently selected from H, D, unsubstituted straight-chain C1-C3 straight-chain alkyl or unsubstituted branched C3-C6 alkyl, (v) n = 1 or 2. The precursor of Formula II includes compounds of the general formula (i) (Cp ligand)2-M-(Ad ligand) and (ii) (Cp ligand)-M-(Ad ligand)2, wherein the Cp ligand contains a nitrogen-containing side chain.

[0015] More specific aspects and embodiments of precursors of general formula (i) (Cp ligand)2-M-(Ad ligand) and (ii) (Cp ligand)-M-(Ad ligand)2 (Formula I and Formula II) are detailed below, respectively.

[0016] The disclosed and claimed subject matter further includes (i) compositions and formulations comprising 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 deposition processes. Description of the Drawings

[0017] The embodiments of the disclosed subject matter included to further understand the disclosed subject matter and incorporated into and forming a part of this specification are illustrated in the description of the drawings used together with the description to explain the principles of the disclosed subject matter. In the drawings:

[0018] Figure 1 Illustrating the thermogravimetric analysis (TGA) of Example 1, La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”);

[0019] Figure 2 Illustrating the thermogravimetric analysis / differential scanning calorimetry (DSC) of Example 1, La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”);

[0020] Figure 3 Illustrating the thermogravimetric analysis (TGA) of Example 2, La[Cp(CH2)3OCH3][(C3H7)NC(CH3)N(C3H7)]2 (“(1B)-La-(3G)2”);

[0021] Figure 4 Illustrating the thermogravimetric analysis (TGA) of Example 3, La[CpCH2N(CH3)2][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3G)2”);

[0022] Figure 5 Illustrating the thermogravimetric analysis (TGA) of Example 4, La[CpCH2N(CH3)2][(C3H7)NC(CH3)N(C3H7)]2 (“(2D)-La-(3G)2”);

[0023] Figure 6 Illustrating the thermogravimetric analysis / differential scanning calorimetry (DSC) of Example 5, La[Cp(CH2)2OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1C)-La-(3C)2”);

[0024] Figure 7 Describe the thermal decomposition of the precursor La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”) on Si and SiO2 wafers.

[0025] Figure 8 Describe the dependence of the thickness of the lanthanum oxide film on the SiO2 wafer on the pulse time of the La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”) precursor in an atomic layer deposition process;

[0026] Figure 9 Describe the dependence of the thickness of the lanthanum oxide film on the SiO2 wafer on the number of ALD cycles in an atomic layer deposition process using the La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”) precursor;

[0027] Figure 10 Describe the cross-sectional SEM image of the lanthanum oxide film deposited on a SiO2 substrate using the La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”) precursor and the following process conditions: precursor pulse 2 s; Ar pulse 20 s; ozone pulse 5 s; Ar pulse 20 s; 100 pulses; wafer temperature 200 °C;

[0028] Figure 11 Describe the cross-sectional SEM image of the lanthanum oxide film deposited on a SiO2 substrate using the La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”) precursor and the following process conditions: precursor pulse 2 s; Ar pulse 10 s; ozone pulse 1 s; Ar pulse 30 s; 300 pulses; wafer temperature 200 °C;

[0029] Figure 12 Describe the top-down SEM image of the lanthanum oxide film deposited on a Si substrate using the La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”) precursor and the following process conditions: precursor pulse 2 s; Ar pulse 20 s; ozone pulse 5 s; Ar pulse 20 s; 100 pulses; wafer temperature 200 °C; and

[0030] Figure 13Top-down SEM image of a lanthanum oxide film deposited on a Si substrate using the precursor La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”) and the following process conditions: precursor pulse of 2 seconds; Ar pulse of 10 seconds; ozone pulse of 1 second; Ar pulse of 30 seconds; 300 pulses; wafer temperature of 200 °C. Detailed Description

[0031] All references cited herein (including publications, patent applications, and patents) are hereby incorporated by reference as if each reference were specifically and individually indicated to be incorporated by reference and were set forth in its entirety herein, including USP 8,283,201 and U.S. Patent Application Publication No. 2019 / 0152996.

[0032] Unless otherwise specified herein or clearly contradicted by the context, the terms “a,” “an,” “the,” and similar referents used in the context of describing the presently disclosed and claimed subject matter (especially in the context of the following claims) shall be construed to cover both the singular and the plural. The terms “comprising,” “having,” “including,” and “containing” shall be construed as open-ended terms (i.e., meaning “including, but not limited to”) unless otherwise noted. 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, and each separate value is incorporated into the specification as if it were individually recited herein. Unless otherwise specified herein or otherwise clearly contradicted by the context, all methods described herein can be performed in any suitable order. Unless otherwise required, the use of any and all examples, or exemplary language (e.g., “such as”) provided herein is merely intended to better illustrate the presently disclosed and claimed subject matter and does not pose a limitation on the scope of the presently disclosed and claimed subject matter. Any language in the specification should not be construed as indicating any non-claimed element as essential to the practice of the presently disclosed and claimed subject matter. The use of the term “comprising” or “including” in the specification and claims includes the narrower language “consisting essentially of” and “consisting of.”

[0033] This description sets forth embodiments of the presently disclosed and claimed subject matter, including the best mode known to the inventors for practicing the presently disclosed and claimed subject matter. Variations of those embodiments will be apparent to those skilled in the art upon reading the foregoing description. The inventors expect those skilled in the art to appropriately employ such variations, and the inventors expect the presently disclosed and claimed subject matter to be practiced otherwise than as specifically described herein. Accordingly, the presently 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. In addition, unless otherwise indicated herein or otherwise clearly contradicted by context, the presently disclosed and claimed subject matter covers any combination of the above elements in all possible variations thereof.

[0034] The term “alkylene” refers to an alkylene linkage between (i) a carbon atom in a cyclopentadienyl (“Cp”) group and (ii) an O or N atom, preferably a C1-4 alkylene linkage such as an ethylene bridge. Specific examples of alkylene linkages include methylene (—CH2—), ethylene (—CH2CH2—), substituted ethylene (e.g., —CH(CH3)CH2—; —CH(CH3)CH(CH3)—; —C(CH3)2CH2—), propylene (—CH2CH2CH2—), and substituted propylene.

[0035] It should be understood that the term “silicon” will include polysilicon when deposited as a material on a microelectronic device.

[0036] For reference purposes, a “microelectronic device” or “semiconductor device” corresponds to a semiconductor wafer having integrated circuits, memory, and other electronic structures fabricated thereon, and flat panel displays, phase change memory devices, solar panels, and other products fabricated for microelectronic, integrated circuit, or computer chip applications (including solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS)). Solar substrates include, but are not limited to, silicon, amorphous silicon, polysilicon, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide phosphide. Solar substrates may be doped or undoped. It should be understood that 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.

[0037] As defined herein, the term “barrier material” corresponds to any material used in the art to seal metal lines (e.g., copper interconnects) to minimize diffusion of the metal (e.g., copper) into a dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.

[0038] "Substantially free of" is defined herein as less than 0.001% by weight. "Substantially free of" also includes 0.000% by weight. The term "free of" means 0.000% by weight. As used herein, "about / approximately" is intended to correspond to within ±5% of a specified value.

[0039] In all such compositions, where a particular component of the composition is discussed in terms of a range of weight percentages (or "wt%") including a zero lower limit, it is understood that such a component may be present or absent in various specific embodiments of the composition, and where such a component is present, it may be present at a concentration as low as 0.001 weight percentage based on the total weight of the composition in which such a component is employed. Note that all percentages of components are weight percentages and are based on the total weight of the composition (i.e., 100%). Any reference to "one or more" or "at least one" includes "two or more" and "three or more" and so on.

[0040] Where applicable, unless otherwise specified, all weight percentages are "net", meaning that they do not include the aqueous solution that is present when added to the composition. For example, "net" refers to the wt% amount of an undiluted acid or other material (i.e., 100 g of 85% phosphoric acid contains 85 g of acid and 15 g of diluent).

[0041] In addition, when referring to the compositions described herein in terms of wt%, it is understood that in any case, the weight percentages of all components (including non-essential components such as impurities) shall not add up to more than 100% by weight. In a composition "consisting essentially of the recited components", such components may total 100% by weight of the composition or may total less than 100% by weight. In cases where the components total less than 100% by weight, such compositions may include certain minor non-essential contaminants or impurities. For example, in one such embodiment, the formulation may contain 2% by weight or less of impurities. In another embodiment, the formulation may contain 1% by weight or less than 1% by weight of impurities. In another embodiment, the formulation may contain 0.05% by weight or less than 0.05% by weight of impurities. In other such embodiments, the ingredients may account for at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight, more preferably at least 99.5% by weight, most preferably at least 99.9% by weight, and may include other ingredients that do not substantially affect the performance of the wet etchant. Otherwise, if there are no significant non-essential impurity components, it is understood that the composition of all essential components will total substantially 100% by weight.

[0042] The headings used herein are not intended to be limiting; rather, they are included for organizational purposes only.

[0043] Exemplary embodiments

[0044] 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”), having the general formula (i) (Cp ligand)2-M-(Ad ligand) or (ii) (Cp ligand)-M-(Ad ligand)2.

[0045] 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”), having the general formula (Cp ligand)2-M-(Ad ligand), wherein 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 La.

[0046] 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”), having the general formula (Cp ligand)-M-(Ad 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. In one aspect of this embodiment, M is La.

[0047] In some embodiments, the tethered Cp ligand has a structure illustrated in Table 1 (Cp ligands include oxygen-containing side chains) or Table 2 (Cp ligands contain nitrogen-containing side chains) and the Ad ligands shown in Table 3 below.

[0048]

[0049] Table 1

[0050]

[0051]

[0052] Table 2

[0053]

[0054]

[0055] Table 3

[0056] Preferred embodiments of the general formulas (i) (Cp ligand)2-M-(Ad ligand) and (ii) (Cp ligand)-M-(Ad ligand)2 including the ligands stated in Tables 1 to 3 are described in Tables 4 to 6:

[0057]

[0058]

[0059]

[0060]

[0061] Table 4

[0062]

[0063]

[0064]

[0065] Table 5

[0066]

[0067]

[0068]

[0069]

[0070] Table 6

[0071] The disclosed and claimed precursors are not limited to those listed in Tables 4 to 6. Additionally, the Cp ligands and Ad ligands are not limited to those listed in Tables 1 to 3. Additional embodiments of the disclosed and claimed precursors are described below with reference to Formulas I and II.

[0072] Embodiments of Formula I

[0073] Embodiments and aspects of precursors of Formula I having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand are listed below. As noted above, the Formula I precursors include compounds of the general formulas (i) (Cp ligand)2-M-(Ad ligand) and (ii) (Cp ligand)-M-(Ad ligand)2, where the Cp ligand contains an oxygen-containing side chain.

[0074] In one embodiment, a precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand has Formula I:

[0075]

[0076] where (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 , R 5 , R 6 , and R 7 are each independently selected from H, D, unsubstituted straight-chain C1-C6 alkyl, halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, unsubstituted branched-chain C3-C6 alkyl, halogen-substituted branched-chain C3-C6 alkyl, amino-substituted branched-chain C3-C6 alkyl, and -Si(CH3)3; (iii) R is a straight-chain or branched-chain C1-C6 alkylene; (iv) R c is H, D, or unsubstituted straight-chain C1-C3 alkyl; and (v) n = 1 or 2.

[0077] 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.

[0078] In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are all the same.

[0079] In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R7 At least one of them is different from R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 and the others in

[0080] In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from H, D, unsubstituted straight-chain C1-C4 alkyl, unsubstituted branched-chain C3-C6 alkyl, and -Si(Me)3. In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 are each independently selected from H, D, and R 5 , R 6 and R 7 are each independently selected from H, D, unsubstituted straight-chain C1-C4 alkyl, unsubstituted branched-chain C3-C6 alkyl, and -Si(Me)3. In one aspect of this embodiment, R 6 is H or D and R 5 , R 7 are independently unsubstituted straight-chain C1-C4 alkyl, unsubstituted branched-chain C3-C6 alkyl, and -Si(Me)3.

[0081] In one aspect of this embodiment, R 5 , R 6 and R 7 One or more of them are isopropyl. In another aspect of this embodiment, R 5 , R 6 and R 7 Two or more of them are isopropyl. In another aspect of this embodiment, R 5 , R 6 and R 7 Each of them is isopropyl.

[0082] In one aspect of this embodiment, n = 1. In another aspect of this embodiment, n = 2.

[0083] In one aspect of this embodiment, R is –(CH2)–.

[0084] In one aspect of this embodiment, R is –(CH2)2–.

[0085] In one aspect of this embodiment, R is –(CH2)3–.

[0086] In one aspect of this embodiment, R is –(CH2)4–.

[0087] In one aspect of this embodiment, R is –C(CH3)2–.

[0088] In one aspect of this embodiment, R is –CH(CH3)–.

[0089] In one aspect of this embodiment, R is –C(CH3)2CH2–.

[0090] In one aspect of this embodiment, R is –CH(CH3)CH2–.

[0091] In one aspect of this embodiment, R is –C(CH3)2(CH2)2–.

[0092] In one aspect of this embodiment, R is –CH(CH3)(CH2)2–.

[0093] In one aspect of this embodiment, R c is -D. In one aspect of this embodiment, R c is -H.

[0094] In one aspect of this embodiment, R c is -CH3.

[0095] In one aspect of this embodiment, R c is -CH2CH3.

[0096] In one aspect of this embodiment, R c is -CH2CH2CH3.

[0097] In one aspect of this embodiment, (i) R 5 and R 7 are each isopropyl and (ii) R 6 is H.

[0098] In one aspect of this embodiment, (i) n = 1, (ii) R 5 and R 7 are each isopropyl and (iii) R 6 is H.

[0099] In one aspect of this embodiment, (i) n = 2, (ii) R 5 and R 7 are each isopropyl and (iii) R6 is H.

[0100] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 5 and R 7 are each isopropyl and (iv) R 6 is H.

[0101] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 5 and R 7 are each isopropyl and (iv) R 6 is H.

[0102] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 are each isopropyl and (vii) R 6 is H.

[0103] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 are each isopropyl and (vii) R 6 is H.

[0104] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 are each isopropyl and (vii) R 6 is H.

[0105] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is H.

[0106] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0107] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0108] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0109] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R5 and R 7 are each -CH2CH3 and (vii) R 6 is H.

[0110] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is H.

[0111] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is H.

[0112] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is H.

[0113] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is H.

[0114] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 and R 2 and R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0115] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 and R 2 and R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0116] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 and R 2 and R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0117] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 and R 2 and R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0118] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 and R 2 and R 3 and R4 each of them is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is -CH3.

[0119] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each of them is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is -CH3.

[0120] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each of them is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 -CH3.

[0121] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each of them is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is -CH3.

[0122] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each of them is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7Each is -CH2CH3 and (vii) R 6 is -CH3.

[0123] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0124] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0125] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0126] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is -CH3.

[0127] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is -CH3.

[0128] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is -CH3.

[0129] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is -CH3.

[0130] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0131] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R4 each of which is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0132] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each of which is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0133] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each of which is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0134] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of which is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is H.

[0135] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of which is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R7 Each is isopropyl and (vii) R 6 is H.

[0136] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is H.

[0137] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is H.

[0138] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0139] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0140] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0141] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0142] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0143] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0144] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4each of them is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0145] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of them is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0146] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of them is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0147] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of them is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0148] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of them is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7are each -C(CH3)3 and (vii) R 6 is H.

[0149] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 are each -C(CH3)3 and (vii) R 6 is H.

[0150] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 are each isopropyl and (vii) R 6 is -CH3.

[0151] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 are each isopropyl and (vii) R 6 is -CH3.

[0152] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 are each isopropyl and (vii) R 6 is -CH3.

[0153] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 where each is H, (iv) R is –CH2–, (v) R c is -CH3, (vi)R 5 and R 7 each is isopropyl and (vii) R 6 It is -CH3.

[0154] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 where each is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi)R 5 and R 7 Each is -CH2CH3 and (vii) R 6 It is -CH3.

[0155] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 where each is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi)R 5 and R 7 Each is -CH2CH3 and (vii) R 6 It is -CH3.

[0156] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 where each is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi)R 5 and R 7 Each is -CH2CH3 and (vii) R 6 It is -CH3.

[0157] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R4 each of which is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 are each -CH2CH3 and (vii) R 6 is -CH3.

[0158] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of which is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is -CH3.

[0159] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of which is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is -CH3.

[0160] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of which is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is -CH3.

[0161] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each of which is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7Each is -CH3 and (vii) R 6 is -CH3.

[0162] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0163] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0164] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0165] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0166] Embodiment of Formula II

[0167] Embodiments and aspects of a precursor of Formula II having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand are listed below. As described above, the Formula II precursor includes compounds of the general formula (i) (Cp ligand)2-M-(Ad ligand) and (ii) (Cp ligand)-M-(Ad ligand)2, wherein the Cp ligand contains a nitrogen-containing side chain.

[0168] In another embodiment, a precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand has Formula II:

[0169]

[0170] wherein (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 、R 5 、R 6 and R 7 are each independently selected from H, D, unsubstituted straight-chain C1-C6 alkyl, halogen-substituted straight-chain C1-C6 alkyl, amino-substituted straight-chain C1-C6 alkyl, unsubstituted branched C3-C6 alkyl, halogen-substituted branched C3-C6 alkyl, amino-substituted branched C3-C6, and -Si(CH3)3, (iii) R is a straight-chain or branched C1-C6 alkylene, (iv) R c and R d are each independently selected from H, D, and unsubstituted straight-chain C1-C3 alkyl, and (v) n = 1 or 2.

[0171] 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.

[0172] In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are all the same.

[0173] In one aspect of this embodiment, at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is different from the others of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 .

[0174] In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from H, D, unsubstituted straight-chain C1-C4 alkyl, unsubstituted branched-chain C3-C6 alkyl, and -Si(Me)3. In one aspect of this embodiment, R 1 , R 2 , R 3 , R4 Each is independently selected from H, D, and R 5 , R 6 and R 7 Each is independently selected from H, D, unsubstituted straight-chain C1-C4 alkyl, unsubstituted branched-chain C3-C6 alkyl, and -Si(Me)3. In one aspect of this embodiment, R 6 is H or D and R 5 , R 7 are independently unsubstituted straight-chain C1-C4 alkyl, unsubstituted branched-chain C3-C6 alkyl, and -Si(Me)3.

[0175] In one aspect of this embodiment, R 5 , R 6 and R 7 One or more of them is isopropyl. In another aspect of this embodiment, R 5 , R 6 and R 7 Two or more of them are isopropyl. In another aspect of this embodiment, R 5 , R 6 and R 7 Each of them is isopropyl.

[0176] In one aspect of this embodiment, n = 1. In another aspect of this embodiment, n = 2.

[0177] In one aspect of this embodiment, R is –(CH2)–.

[0178] In one aspect of this embodiment, R is –(CH2)2–.

[0179] In one aspect of this embodiment, R is –(CH2)3–.

[0180] In one aspect of this embodiment, R is –(CH2)4–.

[0181] In one aspect of this embodiment, R is –C(CH3)2–.

[0182] In one aspect of this embodiment, R is –CH(CH3)–.

[0183] In one aspect of this embodiment, R is –C(CH3)2CH2–.

[0184] In one aspect of this embodiment, R is –CH(CH3)CH2–.

[0185] In one aspect of this embodiment, R is –C(CH3)2(CH2)2–.

[0186] In one aspect of this embodiment, R is –CH(CH3)(CH2)2–.

[0187] In one aspect of this embodiment, R c and R d at least one of which is -H. In another aspect of this embodiment, R c and R d each is -H.

[0188] In one aspect of this embodiment, R c and R d at least one of which is -D. In another aspect of this embodiment, R c and R d each is -D.

[0189] In one aspect of this embodiment, R c and R d at least one of which is -CH3. In another aspect of this embodiment, R c and R d each is -CH3.

[0190] In one aspect of this embodiment, R c and R d at least one of which is -CH2CH3. In another aspect of this embodiment, R c and R d each is -CH2CH3.

[0191] In one aspect of this embodiment, R c and R d at least one of which is -CH2CH2CH3. In another aspect of this embodiment, R c and R d each is -CH2CH2CH3.

[0192] In one aspect of this embodiment, (i) R 5 and R 7 are each isopropyl and (ii) R 6 is H.

[0193] In one aspect of this embodiment, (i) n = 1, (ii) R 5 and R 7 are each isopropyl and (iii) R 6 is H.

[0194] In one aspect of this embodiment, (i) n = 2, (ii) R 5 and R 7Each is isopropyl and (iii) R 6 is H.

[0195] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 5 and R 7 Each is isopropyl and (iv) R 6 is H.

[0196] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 5 and R 7 Each is isopropyl and (iv) R 6 is H.

[0197] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 Each of is H, (iv) R is –(CH2)4–, (v) R c and R d Each is -CH3, (vi) R 5 and R 7 Each is isopropyl and (vii) R 6 is H.

[0198] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 Each of is H, (iv) R is –(CH2)3–, (v) R c and R d Each is -CH3, (vi) R 5 and R 7 Each is isopropyl and (vii) R 6 is H.

[0199] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 Each of is H, (iv) R is –(CH2)2–, (v) R c and R d Each is -CH3, (vi) R 5 and R 7 Each is isopropyl and (vii) R 6 is H.

[0200] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) each of R 1 , R 2 , R 3 and R 4 is H, (iv) R is –CH2–, (v) each of R c and R d is -CH3, (vi) each of R 5 and R 7 is isopropyl and (vii) R 6 is H.

[0201] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) each of R 1 , R 2 , R 3 and R 4 is H, (iv) R is –(CH2)4–, (v) each of R c and R d is -CH3, (vi) each of R 5 and R 7 is -CH2CH3 and (vii) R 6 is H.

[0202] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) each of R 1 , R 2 , R 3 and R 4 is H, (iv) R is –(CH2)3–, (v) each of R c and R d is -CH3, (vi) each of R 5 and R 7 is -CH2CH3 and (vii) R 6 is H.

[0203] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) each of R 1 , R 2 , R 3 and R 4 is H, (iv) R is –(CH2)2–, (v) each of R c and R d is -CH3, (vi) each of R 5 and R 7 is -CH2CH3 and (vii) R 6 is H.

[0204] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0205] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0206] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0207] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0208] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0209] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0210] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0211] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0212] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –CH2–, (v) R c and R d are each -CH3, (vi) R 5 and R 7 are each -C(CH3)3 and (vii) R 6 is H.

[0213] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)4–, (v) R c and R d are each -CH3, (vi) R 5 and R 7 are each isopropyl and (vii) R 6 is -CH3.

[0214] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)3–, (v) R c and R d are each -CH3, (vi) R 5 and R 7 are each isopropyl and (vii) R 6 is -CH3.

[0215] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)2–, (v) R c and R d are each -CH3, (vi) R 5 and R 7 are each isopropyl and (vii) R 6 is -CH3.

[0216] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is -CH3.

[0217] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0218] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0219] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0220] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –CH2–, (v) R c and R d are each -CH3, (vi) R 5 and R 7 are each -CH2CH3 and (vii) R 6 is -CH3.

[0221] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)4–, (v) R c and R d are each -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is -CH3.

[0222] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)3–, (v) R c and R d are each -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is -CH3.

[0223] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is –(CH2)2–, (v) R c and R d are each -CH3, (vi) R 5 and R 7 are each -CH3 and (vii) R 6 is -CH3.

[0224] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 where each is H, (iv) R is –CH2–, (v) R c and R d Each is -CH3, (vi) R 5 and R 7 Each is -CH3 and (vii) R 6 It is -CH3.

[0225] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 where each is H, (iv) R is –(CH2)4–, (v) R c and R d Each is -CH3, (vi) R 5 and R 7 Each is -C(CH3)3 and (vii)R 6 It is -CH3.

[0226] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 where each is H, (iv) R is –(CH2)3–, (v) R c and R d Each is -CH3, (vi) R 5 and R 7 Each is -C(CH3)3 and (vii)R 6 It is -CH3.

[0227] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 where each is H, (iv) R is –(CH2)2–, (v) R c and R d Each is -CH3, (vi) R 5 and R 7 Each is -C(CH3)3 and (vii)R 6 It is -CH3.

[0228] In one aspect of this embodiment, (i) M = La, (ii) n = 1, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0229] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is H.

[0230] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is H.

[0231] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is H.

[0232] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is H.

[0233] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0234] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0235] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0236] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is H.

[0237] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0238] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0239] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0240] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is H.

[0241] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0242] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0243] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0244] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is H.

[0245] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is -CH3.

[0246] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is -CH3.

[0247] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is -CH3.

[0248] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is isopropyl and (vii) R 6 is -CH3.

[0249] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0250] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0251] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0252] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH2CH3 and (vii) R 6 is -CH3.

[0253] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is -CH3.

[0254] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is -CH3.

[0255] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is -CH3.

[0256] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -CH3 and (vii) R 6 is -CH3.

[0257] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)4–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0258] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)3–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0259] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –(CH2)2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0260] In one aspect of this embodiment, (i) M = La, (ii) n = 2, (iii) R 1 , R 2 , R 3 and R 4 each is H, (iv) R is –CH2–, (v) R c and R d each is -CH3, (vi) R 5 and R 7 each is -C(CH3)3 and (vii) R 6 is -CH3.

[0261] Method of Use

[0262] The disclosed precursors can be deposited using any chemical vapor deposition process known to those skilled in the art to form a lanthanum-containing membrane. 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 surface of the substrate 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 for depositing a film of a material onto substrates of various compositions. Although the precursors, reagents, and sources used herein may sometimes be described as "gaseous," it should be understood that the precursors can be liquids or solids that are transported to the reactor via direct evaporation, bubbling, or sublimation, with or without an inert gas. In some cases, the vaporized precursor can pass through a plasma generator. The term "reactor" as used herein includes, but is not limited to, a reaction chamber, a reaction vessel, or a deposition chamber.

[0263] Chemical vapor deposition processes in which the disclosed and claimed precursors can be utilized include, but are not limited to, processes for manufacturing 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 (metalorganic CVD), thermal chemical vapor deposition, plasma-enhanced chemical vapor deposition ("PECVD"), high-density PECVD, photon-assisted CVD, plasma-photon-assisted ("PPECVD"), low-temperature chemical vapor deposition, chemical-assisted vapor deposition, hot-wire 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 an atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), or plasma-enhanced cyclic CVD (PECCVD) process.

[0264] In one embodiment, for example, a metal-containing film is deposited using an ALD process. In another embodiment, a metal-containing film is deposited using a CCVD process. In another embodiment, a metal-containing film is deposited using a thermal CVD process.

[0265] Suitable substrates on 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 can be selected from oxides such as HfO2-based materials, TiO2-based materials, ZrO2-based materials, rare earth oxide-based materials, ternary oxide-based materials, etc., or from nitride-based films. Other substrates can 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)); substrates containing metal nitrides (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN and TiSiN); semiconductor materials (e.g., Si, SiGe, GaAs, InP, diamond, GaN and SiC); insulators (e.g., SiO2, Si3N4, SiON, HfO2, Ta2O5, ZrO2, TiO2, Al2O3 and strontium barium titanate); combinations thereof. Preferred substrates include TiN, Ru and Si-type substrates.

[0266] In such deposition methods and processes, an oxidizing agent can be utilized. The oxidizing agent is typically introduced in gaseous form. Examples of suitable oxidizing agents include, but are not limited to, oxygen, water vapor, ozone, oxygen plasma, or mixtures thereof.

[0267] The deposition methods and processes can also involve 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 supplied to the reactor at a flow rate in the range of about 10 to about 2000 sccm for about 0.1 to 10000 seconds to purge unreacted materials and any by-products that may remain in the reactor.

[0268] A deposition method and process requirements involve applying energy to at least one of a precursor, an oxidant, other precursors, or a combination thereof to cause a reaction and form a metal-containing film or coating on a substrate. This energy can be provided by, but not limited to, heat, plasma, pulsed plasma, helicon plasma, high-density plasma (helicon plasma), inductively coupled plasma, X-rays, electron beam (e-beam), photons, 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 using plasma, the plasma generation process can include a direct plasma generation process where plasma is directly generated in the reactor, or alternatively, a remote plasma generation process where plasma is generated outside the reactor and supplied to the reactor.

[0269] When used in such deposition methods and processes, suitable precursors (such as the precursors disclosed and claimed in the present invention) can be delivered to a reaction chamber such as a CVD or ALD reactor in various ways. In some cases, a liquid delivery system can be utilized. In other cases, a combined liquid delivery and flash vaporization process unit, such as, for example, a turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, can be employed to enable volume delivery of low volatility materials, which results in repeated delivery and deposition without thermal decomposition of the precursor. The precursor compositions described herein can 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.

[0270] When used in these deposition methods and processes, the disclosed and claimed precursors include a hydrocarbon solvent, which is particularly desirable because it can be dried to sub-ppm levels of water. Exemplary hydrocarbon solvents that can be used in the precursor include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), cymene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decalin (decahydronaphthalene). The disclosed and claimed precursors can also be stored and used in stainless steel containers. In certain embodiments, the hydrocarbon solvent is a high boiling point solvent or has a boiling point of 100 degrees Celsius or higher. The disclosed and claimed precursors can also be mixed with other suitable metal precursors, and the mixture can be used for simultaneous delivery of two metals for the growth of a binary metal-containing film.

[0271] Argon gas and / or other gas flows can be used as carrier gases to assist in delivering the vapor containing at least one of the disclosed and claimed precursors to the reaction chamber during precursor pulses. When delivering the precursor, the process pressure in the reaction chamber is between 1 and 50 Torr, preferably between 5 and 20 Torr.

[0272] Substrate temperature can be an important process variable in the deposition of high-quality metal-containing films. A typical substrate temperature range is from about 150 °C to about 550 °C. Higher temperatures can promote higher film growth rates.

[0273] In view of the foregoing, those skilled in the art will recognize that the disclosed and claimed subject matter further includes the use of the disclosed and claimed precursors in a chemical vapor deposition process as follows.

[0274] In one embodiment, the disclosed and claimed subject matter includes a method for forming a transition metal-containing film on at least one surface of a substrate, the method comprising the steps of:

[0275] a. Providing at least one surface of the substrate in a reaction vessel;

[0276] b. Forming a transition metal-containing film on the at least one surface by a deposition process selected from the group consisting of chemical vapor deposition (CVD) processes and atomic layer deposition (ALD) processes, using one or more of the disclosed and claimed precursors as metal source compounds for the deposition process.

[0277] In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel. 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 water, diatomic oxygen, oxygen plasma, ozone, NO, N2O, NO2, 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, boron-containing compounds, silicon-containing compounds, and combinations thereof.

[0278] In one embodiment, the disclosed and claimed subject matter includes a method for forming a transition metal-containing film via an atomic layer deposition (ALD) process or an ALD-like process, the method comprising the steps of:

[0279] a. Providing a substrate in a reaction vessel;

[0280] b. Introducing one or more of the disclosed and claimed precursors into the reaction vessel;

[0281] c. Purifying the reaction vessel with a first purge gas;

[0282] d. Introduce the source gas into the reaction vessel;

[0283] e. Purify the reaction vessel with a second purge gas;

[0284] f. Repeat steps b to e sequentially until the desired thickness of the transition metal film is obtained.

[0285] In another aspect of this embodiment, the source gas is one or more oxygen-containing source gases selected from water, diatomic oxygen, oxygen plasma, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide, and combinations thereof. 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 another aspect of this embodiment, each of the first and second purge gases is independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof. In another aspect of this embodiment, the method further comprises 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 heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma method, and combinations thereof. In another aspect of this embodiment, step b of the method further comprises introducing the precursor into the reaction vessel using a carrier gas to transport the vapor of the precursor into the reaction vessel. In another aspect of this embodiment, step b of the method further comprises using a solvent medium comprising one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyltoluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decalin, and combinations thereof.

[0286] In another embodiment, precursors of Formulas I and II having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand 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 an ALD, ALD-like, or CVD process 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 to 13 metal alkoxides, Group 3 to 13 metal complexes having cyclopentadienyl ligands substituted with both alkoxy and alkyl groups, Group 3 to 6 metal complexes having pyrrolyl ligands substituted with both alkoxy and alkyl groups, Group 3 to 13 metal complexes having both alkoxy and diketonate ligands; Group 3 to 13 metal complexes having alkyl ligands. Exemplary Group 3 to 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, Al.

[0287] Examples of suitable metal amide precursors that can be used in the methods disclosed herein include, but are not limited to, 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-butylimino tris(diethylamino)tantalum (TBTDET), tert-butylimino tris(dimethylamino)tantalum (TBTDMT), tert-butylimino tris(ethylmethylamino)tantalum (TBTEMT), ethylimino tris(diethylamino)tantalum (EITDET), ethylimino tris(dimethylamino)tantalum (EITDMT), ethylimino tris(ethylmethylamino)tantalum (EITEMT), tert-pentylimino tris(dimethylamino)tantalum (TAIMAT), tert-pentylimino tris(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-pentylimino tris(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.

[0288] Examples of suitable metal complexes with alkyl ligands that can be used in the methods disclosed herein include, but are not limited to, tri-tert-butylaluminum (TTBA), trimethylaluminum (TMA), triethylaluminum (TEA), dimethylaluminum hydride (DMAH), dimethylethylamine alane (DMEAA), triethylamine alane (TEAA), N-methylpyrrolidine-alane (MPA), tri-isobutylaluminum (TIBA).

[0289] In one embodiment, the disclosed and claimed subject matter includes a method of forming a transition metal-containing film on at least one surface of a substrate, the method comprising:

[0290] a. providing at least one surface of the substrate in a reaction vessel;

[0291] b. forming a transition metal-containing film on the at least one surface by a deposition process selected from chemical vapor deposition (CVD) processes and atomic layer deposition (ALD) processes, using a precursor as a metal source compound for the deposition process; and

[0292] c. using one or more of the disclosed and claimed precursors as a dopant material.

[0293] In one embodiment, the disclosed and claimed subject matter includes a precursor supply package that includes a container and one or more of the disclosed and claimed precursors, wherein the container is adapted to contain and dispense the precursor.

[0294] In one embodiment, the disclosed and claimed subject matter includes a compound of formula La[Cp(CH2)3OCH3]3 and a method of synthesizing a compound of formula I, including using La[Cp(CH2)3OCH3]3 in the synthesis of the compound of formula I. In another embodiment, the disclosed and claimed subject matter includes a compound of formula La[CpCH2N(CH3)2]3 and a method of synthesizing a compound of formula II, the method including using the compound of formula La[CpCH2N(CH3)2]3 in the synthesis of the compound of formula II.

[0295] In one embodiment, the disclosed and claimed subject matter includes the use of one or more of the disclosed and claimed precursors in a process for forming a transition metal-containing film on at least one surface of a substrate.

[0296] Examples

[0297] Reference will now be made to more specific embodiments of the disclosure and to experimental results that support such embodiments. The following examples are given to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0298] Those skilled in the art will recognize that various modifications and variations can be made to the disclosed subject matter and the specific embodiments provided herein without departing from the spirit or scope of the disclosed subject matter. Accordingly, it is intended that the disclosed subject matter, including the description provided by the following examples, cover modifications and variations of the disclosed subject matter that fall within the scope of any claim and its equivalents.

[0299] Materials and Methods:

[0300] Unless otherwise specified, all solvents and starting materials were purchased from Sigma-Aldrich. La(FAMD)3 was purchased from Strem Chemicals. La(iPr-AMD)3 was synthesized following the procedure reported by Gordon et al., Inorg. Chem., 42, 7951 - 7958 (2003). KCpCH2CH2CH2OCH3 and KCpCH2N(CH3)2 were prepared from KN(TMS)2 and the corresponding Cps in toluene following the procedure reported by Evans et al., Inorg. Chem., 44, 3993 - 4000 (2005).

[0301] Ligand Synthesis

[0302] A. Cp Ligand 1A (Table 1)

[0303]

[0304] Sodium cyclopentadienide (290 mL, 0.70 mol, 2 M in THF) was added dropwise to a solution of 1-chloro-4-methoxybutane (85.32 g, 0.70 mol) in THF (310 mL) at -65 °C. The resulting mixture was warmed to room temperature overnight. The resulting solid was filtered off and the solvent was carefully removed under reduced pressure at 20 °C. Final purification by distillation (45 °C, 0.03 mbar) gave a 20% yield of a mixture of 1-(4-methoxybutyl)cyclopent-1,3-diene and 2-(4-methoxybutyl)cyclopent-1,3-diene (21.2 g, 0.14 mol) as a colorless liquid.

[0305] 1 1H-NMR (CDCl3, 500 MHz): δ = 6.45 – 5.98 (m, 3H), 3.41 – 3.36 (m, 2H), 3.32 (s, 3H), 2.95 – 2.80 (m, 2H), 2.47 – 2.36 (m, 2H), 1.64 – 1.45 (m, 4H).

[0306] EI-MS: m / z: 152.1.

[0307] Sodium cyclopentadienide (2 M in THF) and 1-chloro-4-methoxybutane were purchased from Sigma-Aldrich and used as received.

[0308] B. Cp ligand 1B (Table 1)

[0309]

[0310] At -65 °C, sodium cyclopentadienide (200 mL, 0.48 mol, 2 M in THF) was added dropwise to a solution of 1-chloro-3-methoxypropane (51.11 g, 0.48 mol) in THF (200 mL). The resulting mixture was warmed to room temperature overnight. The resulting solid was filtered off and the solvent was carefully removed at 20 °C under reduced pressure. Final purification by distillation (40 °C, 0.11 mbar) gave a mixture of 1-(3-methoxypropyl)cyclopent-1,3-diene and 2-(3-methoxypropyl)cyclopent-1,3-diene (25.2 g, 0.18 mol) as a colorless liquid in 37% yield.

[0311] 1 1H-NMR (CDCl3, 500 MHz): δ = 6.45–6.00 (m, 3H), 3.41–3.37 (m, 2H), 3.33 (s, 3H), 2.95–2.80 (m, 2H), 2.49–2.40 (m, 2H), 1.86–1.79 (m, 2H).

[0312] EI-MS: m / z: 138.

[0313] Sodium cyclopentadienide (2 M in THF) and 1-chloro-3-methoxypropane were purchased from Sigma-Aldrich and used as received.

[0314] C. Cp ligand 1D (Table 1)

[0315]

[0316] At -65 °C, a solution of chloromethyl methyl ether (16.82 mL, 0.22 mol) in n-pentane (150 mL) was added dropwise to a stirred mixture of sodium cyclopentadienide (19.50 g, 0.22 mol) in n-pentane (350 mL). The resulting mixture was warmed to room temperature overnight. The resulting solid was filtered off and the solvent was carefully removed at 20 °C under reduced pressure. Final purification by column chromatography (silica gel; n-pentane / methyl tert-butyl ether 9:1) gave a mixture of 1-(methoxymethyl)cyclopent-1,3-diene and 2-(methoxymethyl)cyclopent-1,3-diene (12.10 g, 0.09 mol; GC: 85%) as a colorless liquid in 41% yield.

[0317] 1 H-NMR (CDCl3, 500 MHz): δ = 6.51–6.21 (m, 3H), 4.19–4.17 (m, 2H), 3.25–3.22 (m, 3H), 2.99–2.94 (m, 2H).

[0318] EI-MS: m / z: 110.

[0319] Sodium cyclopentadienide and chloromethyl methyl ether were purchased from Sigma-Aldrich and used as received.

[0320] D.Cp ligand 2D (Table 2)

[0321]

[0322] A suspension of dimethylamino fulvene (20.00 g, 0.17 mol) in diethyl ether (700 mL) was added dropwise to a suspension of LiAlH4 (7.52 g, 0.20 mol) in diethyl ether (100 mL) at -15 °C and the reaction mixture was stirred for an additional 150 minutes at this temperature. Water (30 mL) and aqueous NaOH solution (10 mL, 10 wt%) were carefully added to the mixture at -35 °C. Magnesium sulfate was added and the reaction mixture was allowed to warm to room temperature. The mixture was filtered and the solvent was removed. Final purification by distillation gave [cyclopent-2,4-dien-1-yl)methyl]dimethylamine and [cyclopent-1,3-dien-1-yl)methyl]dimethylamine (7.10 g, 0.06 mol) as a colorless liquid in 35% yield.

[0323] 1 H-NMR (CDCl3, 500 MHz): δ = 6.54–6.11 (m, 3H), 3.25–3.22 (m, 2H), 3.01–3.00 (m, 2H), 2.25–2.23 (m, 6H).

[0324] EI-MS: m / z: 123.1.

[0325] Dimethylamino fulvene was purchased from Sigma-Aldrich and used as received.

[0326] Synthesis of intermediate precursors

[0327] Synthesis of A1.La[Cp(CH2)3OCH3]3

[0328] Inside a glove box filled with N2, THF (100 mL) was added to a 250 mL Schlenk round-bottom flask containing a solid mixture of LaBr3 (4.29 g, 11.3 mmol) and K[Cp(CH2)3OCH3] (6.0 g, 34.0 mmol) and a stir bar. The resulting slurry was stirred at RT under N2 for 16 h. The volatiles were then removed under vacuum to give a viscous orange solid. The crude material was further purified by extraction with toluene and filtration through a medium frit, and toluene was removed under vacuum to give the final product as an orange oil. (3.1 g, 49% yield).

[0329] 1H-NMR (C6D6, 400 MHz): δ = 6.04 (m, 6H), 5.90 (m, 6H), 3.17 (m, 6H), 3.07 (s, 9H), 2.59 (t, 6H), 1.75 (m, 6H).

[0330] A2. Synthesis of La[Cp(CH2)3OCH3]3

[0331] Inside a glove box filled with N2, THF (100 mL) was added to a flask containing a solid mixture of LaBr3 (2.39 g, 6.3 mmol) and K[Cp(CH2)3OCH3] (3.10 g, 19.1 mmol) and a stir bar. The resulting slurry was stirred at RT under N2 for 18 h. The volatiles were then removed under vacuum. The crude material was further purified by extraction with toluene and toluene was removed under vacuum to give the final product as an oil. (1.9 g, 59% yield).

[0332] 1H-NMR (C6D6, 400 MHz): δ = 2.66 (t, J = 6.5 Hz; 6H, -CH2-); 3.09 (s, 9H, -OCH3); 3.36 (t, J = 6.5 Hz, 6H, -CH2-Cp); 5.89 (s, 12H, CpH4).

[0333] B. Synthesis of La[CpCH2N(CH3)2]3

[0334] Inside a glove box filled with N2, THF (100 mL) was added to a 250 mL Schlenk round-bottom flask containing a mixture of LaBr3 (1.95 g, 5.2 mmol) and K[CpCH2N(CH3)2] (2.50 g, 15.5 mmol) and a stir bar. The resulting slurry was stirred at RT under N2 for 16 h. The volatiles were then removed under vacuum to give a yellow solid. The crude material was further purified by extraction with Et2O and filtration through a medium frit, and Et2O was removed under vacuum to give the final product as a yellow solid. (1.33 g, 51% yield).

[0335] 1H-NMR (C6D6, 400 MHz): δ = 5.99 (m, 6H), 5.93 (m, 6H), 3.32 (s, 6H), 2.16 (s, 18H).

[0336] Synthesis of the final precursor

[0337] Example 1: La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”)

[0338]

[0339] Inside a glove box filled with N2, a toluene solution of La[Cp(CH2)3OCH3]3 (0.40 g, 0.72 mmol) was added to a heavy-walled pressure vessel filled with La(FAMD)3 (0.748 g, 1.44 mmol). The solution was heated at 100 °C for 4 hours under N2. Volatiles were removed under vacuum to obtain a yellow solid. The crude material was further purified by sublimation at 120 °C and 130 mTorr to obtain the final product as a white solid (0.45 g, 37% yield).

[0340] Characterization of the precursor (1B)-La-(3C)2: 1H-NMR (C6D6, 400 MHz): δ = 8.20 (s, 2H), 6.56 (m, 2H), 6.31 (m, 2H), 3.18–3.08 (m, 6H), 3.07 (s, 3H), 2.65 (m, 2H), 1.66 (m, 2H), 1.21 (d, 24H). The TGA of this precursor is shown in Figure 1 below. The TGA shows clean evaporation and low non-volatile residues. The TGA / DSC analysis of this precursor is shown in Figure 2 below (scan rate 10 °C / min).

[0341] Example 2: La[Cp(CH2)3OCH3][(C3H7)NC(CH3)N(C3H7)]2 (“(1B)-La-(3G)2”)

[0342]

[0343] Inside a glove box filled with N2, a toluene solution of La[Cp(CH2)3OCH3]3 (0.25 g, 0.45 mmol) was added to a thick-walled pressure vessel filled with La(iPr-AMD)3 (0.50 g, 0.89 mmol). The solution was heated at 100 °C for 4 hours under N2. Volatiles were removed under vacuum to obtain a yellow solid. The crude material was further purified by sublimation at 130 °C and 130 mTorr to obtain the final product as a white solid (0.38 g, 51% yield).

[0344] Characterization of the precursor (1B)-La-(3G)2: 1H-NMR (C6D6, 400 MHz): δ = 6.56 (m, 2H), 6.39 (m, 2H), 3.49 (m, 4H), 3.14 - 3.18 (m, 5H), 2.69 (m, 2H), 1.70 (s, 6H), 1.68 (m, 2H), 1.20 (d, 24H). The TGA of this precursor is shown in Figure 3 It shows clean evaporation and low non-volatile residues.

[0345] Example 3: La[CpCH2N(CH3)2][(C3H7)NC(H)N(C3H7)]2 (“(2D)-La-(3C)2”)

[0346]

[0347] Inside a glove box filled with N2, a toluene solution of La[CpCH2N(CH3)2]3 (0.50 g, 1.0 mmol) was added to a thick-walled pressure vessel filled with La(FAMD)3 (1.03 g, 2.00 mmol). The solution was heated at 100 °C for 4 hours under N2. Volatiles were removed under vacuum to obtain an off-white solid. The crude material was further purified by sublimation at 130 °C and 130 mTorr to obtain the final product as a white solid (0.85 g, 55% yield).

[0348] Characterization of the precursor (2D)-La-(3C)2: 1H-NMR (C6D6, 400 MHz): δ = 8.18 (s, 2H), 6.51 (m, 2H), 6.43 (m, 2H), 3.42 (s, 2H), 3.05 (m, 4H), 2.06 (s, 6H), 1.17 (d, 24H). The TGA of this precursor is shown in Figure 4 It shows clean evaporation and low non-volatile residues.

[0349] Example 4: La[CpCH2N(CH3)2][(C3H7)NC(CH3)N(C3H7)]2 (“(2D)-La-(3G)2”)

[0350]

[0351] Inside a glove box filled with N2, a toluene solution of La[CpCH2N(CH3)2]3 (0.27 g, 0.53 mmol) was added to a thick-walled pressure vessel filled with La(iPr-AMD)3 (0.60 g, 1.1 mmol). The solution was heated at 100 °C for 4 hours under N2. Volatiles were removed under vacuum to obtain a yellow solid. The crude material was further purified by sublimation at 150 °C and 130 mTorr to give the final product as a white solid (0.49 g, 56% yield).

[0352] Characterization of the precursor (2D)-La-(3G)2: 1H-NMR (C6D6, 400 MHz): δ = 6.51 (m, 2H), 6.47 (m, 2H), 3.45 (m, 4H), 3.41 (s, 2H), 2.10 (s, 6H), 1.67 (s, 6H), 1.18 (d, 24H). The TGA of this precursor is shown in Figure 5 It shows clean evaporation and low non-volatile residues.

[0353] Example 5: La[Cp(CH2)2OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1C)-La-(3C)2”)

[0354]

[0355] Inside a glove box filled with N2, a toluene solution of La[Cp(CH2)2OCH3]3 (0.36 g, 0.72 mmol) was added to La(FAMD)3 (0.748 g, 1.44 mmol). The solution was heated at 100 °C for 4 hours under N2. Volatiles were removed under vacuum to obtain a brown solid. The crude material was further purified by sublimation at 170 °C and 28 mTorr to give the final product as a white solid (0.50 g, 45% yield).

[0356] Characterization of the precursor (1C)-La-(3C)2: 1H-NMR (C6D6, 400 MHz): δ = 1.18 (d, J = 6.6 Hz, 24H, 8-CH3); 2.58 (t, J = 5.8 Hz, 2H-CH2-); 3.10 (qq, J = 6.5 Hz, 4H, -CHMe2); 3.11 (s; 3H, -OMe); 3.47 (t, J = 5.8 Hz, 2H; -CH2-Cp); 6.36 (t, J = 2.6 Hz, 2H, CpH2); 6.47 (t, J = 2.6 Hz, 2H, CpH2). The TGA / DSC analysis of this precursor is shown in Figure 6China (scanning rate 10 k / min).

[0357] Deposit a lanthanum oxide film using La[Cp(CH2)3OCH3][(C3H7)NC(H)N(C3H7)]2 (“(1B)-La-(3C)2”) atomic layer deposition

[0358] Use an AtomicPremium CN-1200 mm reactor to demonstrate the deposition of a lanthanum oxide film using the precursor of the present invention. Deliver the precursor (1B)-La-(3C)2 from an SS316 ampoule (container) maintained at 160 °C (ampoule wall temperature). Use a 50 sccm argon carrier gas flow to deliver the precursor vapor to the reactor chamber. The reactor chamber pressure is 1 Torr. Use Si and SiO2 substrates to deposit the lanthanum oxide film. Determine the lanthanum oxide film thickness by ellipsometry and X-ray fluorescence (XRF) and calibrate using the cross-sectional SEM image of the deposited lanthanum oxide film.

[0359] Example 6: Precursor Thermal Decomposition Test on Si Wafer

[0360] In this experiment, deliver the precursor vapor to the deposition chamber in a pulsed mode separated by argon purging. The pulse sequence is: 5-second precursor pulse and 20-second argon purge. The total number of precursor / Ar purge cycles is 100. No oxidant pulse is used in this experiment to confirm the good thermal stability of the precursor in the absence of an oxidant. Good thermal stability (no deposition in the absence of an oxidant) is an important precursor characteristic for the atomic layer deposition process. Change the wafer temperature from 200 °C to 450 °C. After the experiment, determine the lanthanum layer density on the surface by X-ray fluorescence analysis and show it in Figure 7 . No lanthanum oxide film is deposited in the absence of an oxidant at up to at least 350 °C, indicating that this precursor can be used for atomic layer deposition at up to at least this wafer temperature.

[0361] Example 7: Precursor Saturation Behavior During the Deposition Process

[0362] In this experiment, deposit a lanthanum oxide film by an atomic layer deposition method, which includes the following steps:

[0363] a. Provide a Si or SiO2 substrate in a reaction vessel

[0364] b. Introduce the (1B)-La-(3C)2 precursor into the reaction vessel

[0365] c. Purge the reaction vessel with argon

[0366] d. Introduce ozone into the reaction vessel

[0367] e. Purge the reaction vessel with argon

[0368] f. Repeat steps b to e sequentially until the desired thickness of the transition metal film is obtained.

[0369] The lanthanum precursor pulse was changed from 1 to 3 seconds to confirm the 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 8 Excellent saturation behavior at 200 and 250 °C and soft saturation at 275 °C wafer temperature were shown. The saturation behavior is one of the main characteristics of the atomic layer deposition process.

[0370] Example 8: Film thickness versus number of ALD cycles

[0371] In this experiment, the lanthanum oxide film was deposited by an atomic layer deposition method, which included the following steps:

[0372] a. Provide a Si or SiO2 substrate in the reaction vessel

[0373] b. Introduce the (1B)-La-(3C)2 precursor into the reaction vessel

[0374] c. Purge the reaction vessel with argon

[0375] d. Introduce ozone into the reaction vessel

[0376] e. Purge the reaction vessel with argon

[0377] f. Repeat steps b to e sequentially until the desired thickness of the transition metal film is obtained.

[0378] The lanthanum precursor pulse was 1 second. The Ar purge after the precursor pulse was 10 seconds, the ozone pulse time was 1 second, and the Ar purge after the precursor pulse was 30 seconds. The number of ALD cycles was 100 and 300 to confirm the linear growth of the lanthanum oxide film relative to the number of cycles. The wafer temperatures were 200 °C, 250 °C, 275 °C, 300 °C, and 325 °C. Figure 9 The linear growth of the lanthanum oxide film with the number of cycles was shown. The linear growth with increasing number of cycles is another characteristic of the atomic layer deposition process. The following table shows that there is no significant change in the ALD deposition rate between 250 °C and 325 °C, indicating the relatively broad ALD thermal window of the precursor of the present invention.

[0379]

[0380] Example 9: Deposition of lanthanum oxide film

[0381] In this experiment, the lanthanum oxide film was deposited by an atomic layer deposition method, which included the following steps:

[0382] a. Provide a Si or SiO2 substrate in the reaction vessel

[0383] b. Introduce the (1B)-La-(3C)2 precursor into the reaction vessel.

[0384] c. Purge the reaction vessel with argon.

[0385] d. Introduce ozone into the reaction vessel.

[0386] e. Purge the reaction vessel with argon.

[0387] f. Repeat steps b to e sequentially until the desired thickness of the transition metal film is obtained.

[0388] The lanthanum precursor pulse is 2 seconds. The Ar purge after the precursor pulse is 20 seconds, the ozone pulse is 5 seconds, and the Ar purge after the precursor pulse is 20 seconds. The number of ALD cycles is 100. The wafer temperature is 200 °C. Figure 10 Show a cross-sectional SEM image of the lanthanum oxide film deposited on the SiO2 substrate. Figure 12 Show a top-down SEM image of the lanthanum oxide film deposited on the Si substrate.

[0389] Example 10: Deposition of Lanthanum Oxide Film

[0390] In this experiment, the lanthanum oxide film was deposited by atomic layer deposition, which included the following steps:

[0391] a. Provide a Si or SiO2 substrate in the reaction vessel

[0392] b. Introduce the (1B)-La-(3C)2 precursor into the reaction vessel

[0393] c. Purge the reaction vessel with argon

[0394] d. Introduce ozone into the reaction vessel

[0395] e. Purge the reaction vessel with argon

[0396] f. Repeat steps b to e sequentially until the desired thickness of the transition metal film is obtained.

[0397] The lanthanum precursor pulse is 2 seconds. The Ar purge after the precursor pulse is 10 seconds, the ozone pulse is 1 second, and the Ar purge after the precursor pulse is 30 seconds. The number of ALD cycles is 300. The wafer temperature is 200 °C. Figure 11 Show a cross-sectional SEM image of the lanthanum oxide film deposited on the SiO2 substrate. Figure 13 Show a top-down SEM image of the lanthanum oxide film deposited on the Si substrate.

[0398] The foregoing description is primarily intended for illustrative purposes. Although the disclosed and claimed subject matter has been shown and described in connection with its exemplary embodiments, those skilled in the art will understand that various other changes, omissions, and additions may be made thereto in its form and details without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A precursor having formula I or formula II: Formula I Formula II wherein 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 、R 5 、R 6 and R 7 each independently selected from H, unsubstituted straight-chain C1-C6 alkyl, and unsubstituted branched-chain C3-C6 alkyl; iii. R is a straight-chain or branched C1-C6 alkylene group; iv.R c and R d each independently selected from H and unsubstituted straight-chain C1-C3 alkyl; and v. n = 1 or 2.

2. The precursor according to claim 1, wherein M is La.

3. The precursor according to claim 1, wherein R 1 , R 2 , R 3 , R 4 are each H and R 5 , R 6 and R 7 are each independently selected from H, unsubstituted straight-chain C1-C4 alkyl, and unsubstituted branched-chain C3-C6 alkyl.

4. The precursor according to claim 1, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from H, unsubstituted straight-chain C1-C4 alkyl, and unsubstituted branched-chain C3-C6 alkyl.

5. The precursor according to claim 1, wherein one or more of R 5 , R 6 , and R 7 is isopropyl.

6. The precursor according to claim 1, wherein two or more of R 5 , R 6 and R 7 are isopropyl groups.

7. The precursor according to claim 1, wherein R 6 is H, and R 5 , R 7 are independently unsubstituted straight-chain C1-C4 alkyl and unsubstituted branched-chain C3-C6 alkyl.

8. The precursor according to claim 1, wherein n = 1.

9. The precursor according to claim 1, wherein n = 2.

10. The precursor according to claim 1, wherein R is selected from –(CH2)–, –(CH2)2–, –(CH2)3–, –(CH2)4–, –C(CH3)2–, –CH(CH3)–, –C(CH3)2CH2–, –CH(CH3)CH2–, –C(CH3)2(CH2)2– and –CH(CH3)(CH2)2–.

11. The precursor according to claim 1, wherein R c is -CH3.

12. The precursor according to claim 1, wherein R c is -CH2CH3.

13. The precursor according to claim 1, wherein R c is -CH2CH2CH3.

14. The precursor according to claim 1, wherein at least one of R c and R d is -CH3.

15. The precursor according to claim 1, wherein at least one of R c and R d is -CH2CH3.

16. The precursor according to claim 1, wherein each of R c and R d is -CH3.

17. The precursor according to claim 1, wherein each of R c and R d is -CH2CH3.

18. The precursor according to claim 1, wherein the precursor has the structure of formula I.

19. The precursor according to claim 1, wherein the precursor has the structure of formula II.

20. The precursor according to claim 1, which has the following structure: .

21. The precursor according to claim 1, which has the following structure: .

22. The precursor according to claim 1, having the following structure: 。 23. The precursor according to claim 1 has the following structure: .

24. The precursor according to claim 1, having the following structure: .

25. A method for forming a transition metal-containing film on at least one surface of a substrate, the method comprising: a. providing at least one surface of the substrate in a reaction vessel; b. forming a transition metal-containing film on the at least one surface using a precursor according to any one of claims 1 to 23 as a metal source compound for the deposition process by a deposition process selected from chemical vapor deposition (CVD) process and atomic layer deposition (ALD) process.

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