Lanthanide and lanthanide-like transition metal complexes

Abstract

The disclosed and claimed invention provides precursors having at least one tethered cyclopentadienyl ligand (“Cp ligand”), at least one amidinate ligand (“Ad ligand”), and a lanthanide and / or lanthanide-like transition metal (“M”) of the general formula (i) (Cp ligand)2-M-(Ad ligand) or (ii) (Cp ligand)-M-(Ad ligand)2.

Description

Technical Field

[0001] The disclosed and claimed invention relates to organometallic compounds containing lanthanides and / or lanthanide-like transition metals, compositions containing said compounds, and methods of using said compounds as precursors for the deposition of metal-containing films.

Background Art

[0002] Transition metal-containing films are used in semiconductor and electronics applications. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) have been used as the main deposition techniques for forming thin films for semiconductor devices. These methods enable the achievement of conformal films (metals, metal oxides, metal nitrides, metal silicides, and the like) through chemical reactions of metal-containing compounds (precursors). The said chemical reactions occur on a surface that may include a metal, metal oxide, metal nitride, metal silicide, or other surface. In CVD and ALD, precursor molecules play an important role in achieving high-quality films with high conformality and low impurities. The substrate temperature in CVD and ALD processes is an important matter when selecting precursor molecules. A relatively high substrate temperature in the range of 150 to 500 °C promotes a faster film growth rate. Preferred precursor molecules need to be stable in this temperature range. Preferred precursors can be supplied to the reaction vessel in the liquid phase. The liquid-phase supply of precursors generally provides a more uniform supply of precursors to the reaction vessel compared to solid-phase precursors.

[0003] U.S. Patent No. 8,283,201 (Patent Document 1) discloses a precursor compound having a cyclopentadienyl ligand having at least one aliphatic group as a substituent and an amidine ligand. In particular, the disclosed structure has the formula Ln(R 1 Cp) m (R 2 -N-C(R 4 )=N-R 2 ) ncomprising a lanthanide-containing precursor, wherein (i) Ln is a lanthanide metal having an ionic radius of approximately 0.75 Å to approximately 0.94 Å, a 3+ charge, and a coordination number of 6, and (ii) R 1 is selected from the group consisting of H and C 1 ~C 5 alkyl chains, and (iii) R 2 is selected from the group consisting of H and C 1 ~C 5 alkyl chains, and (iv) R 4 is selected from the group consisting of H and Me, and (vi) the precursor has a melting point of less than approximately 105 °C. Among others, the disclosed precursor does not contain a heteroatom substituent on the Cp ring (i.e., as any of the R 1 groups).

[0004] U.S. Patent Application Publication No. 2019 / 0152996 (U.S. Patent Application No. 16 / 251,236) (Patent Document 2) discloses a lanthanum-containing compound of the following formula.

[0005]

Chemical formula

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0007]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0009] The disclosed and claimed invention is of the general formula (i) (Cp ligand) 2 -M-(Ad ligand) or (ii) (Cp ligand)-M-(Ad ligand) 2Provided is a precursor 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”). The disclosed and claimed invention further includes a composition comprising the compound, a method of using the compound as a precursor for the deposition of a metal-containing film, and a film derived from the precursor.

[0010] In some embodiments, the precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand has the following formula I:

[0011] [Chemical Formula] 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 H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, and a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, and -Si(CH 3 ) 3 selected from, (iii) R is a linear or branched C 1 -C 6 alkylene, (iv) R c is H, D, an unsubstituted linear C1 -C 3 linear alkyl group or unsubstituted branched C 3 -C 6 alkyl group, and (v) n is 1 or 2. The precursor of formula I is a compound of 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 another aspect, said precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand has the following formula II:

[0013]

Chemical formula

[0014] Each of general formula (i) (Cp ligand) 2 -M-(Ad ligand) and (ii) (Cp ligand)-M-(Ad ligand) 2 More specific aspects and embodiments of the precursors of formula I and formula II are detailed below.

[0015] The disclosed and claimed invention further includes (i) compositions and formulations containing 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.

[0016] The accompanying drawings provide a further understanding of the disclosed invention and are incorporated herein and constitute a part thereof, but these illustrate aspects of the disclosed invention and, together with the detailed description of the invention, serve to explain the principles of the disclosed invention.

Brief Description of the Drawings

[0017]

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[0018] All publications, patent applications, and patents, including U.S. Patent No. 8,283,201 (Patent Document 1) and U.S. Patent Application Publication No. 2019 / 0152996 (Patent Document 2), cited herein are hereby incorporated by reference as if each individual publication, patent application, or patent were specifically and individually indicated to be incorporated by reference and were set forth in its entirety.

[0019] In relation to the disclosure and the description of the claimed invention, particularly in relation to the claims described hereinafter, the use of the singular form is to be understood to include both the singular and the plural forms, unless otherwise indicated herein or clearly contradicted by the context. The expressions “comprising,” “having,” “including,” and “containing” are to be construed as non-limiting expressions (i.e., “including but not limited to”) when there is no other annotation. The description of a numerical range is intended, unless otherwise indicated herein, merely as a convenient way to refer to each individual value falling within that range, and each individual value is to be considered as if it were specifically recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by the context. The use of any and all examples, or exemplary language (e.g., “such as”) herein is merely intended to better illustrate the invention being disclosed and claimed and does not limit the scope of the invention being disclosed and claimed, unless otherwise claimed. No language in this specification should be construed as indicating any non-claimed element as essential to the practice of the invention being disclosed and claimed. The use of the expressions “comprising” or “including” in this specification and the claims encompasses the more restrictive expressions “consisting essentially of” and “consisting of.”

[0020] The aspects of the disclosure and claimed invention are described herein, including the best mode known to the inventors for practicing the disclosure and claimed invention. Variations of these aspects will be apparent to those skilled in the art upon reading the following description. The inventors expect those skilled in the art to use such variations as appropriate, and the inventors contemplate the disclosure and claimed invention being practiced otherwise than as specifically described herein. Accordingly, the disclosure and claimed invention includes all modifications and equivalents of the invention as set forth in the claims appended hereto, to the extent permitted by applicable law. Further, any combination of the above-described matters in all possible variations thereof is included in the disclosure and claimed invention unless otherwise indicated or clearly inconsistent from the context.

[0021] The term "alkylene" refers to an alkylene linkage between (i) one carbon atom in a cyclopentadienyl ("Cp") group and (ii) an O or N atom, preferably a C 1-4 alkylene linkage such as an ethylene bridge. Specific examples of alkylene linkages include methylene (-CH 2 -), ethylene (-CH 2 CH 2 -), substituted ethylene (e.g., -CH(CH 3 )CH 2 -; -CH(CH 3 )CH(CH 3 )-; -C(CH 3 ) 2 CH 2 -), propylene (-CH 2 CH 2 CH 2 -), and substituted propylene, and the like.

[0022] The term "silicon" is understood to include polysilicon when deposited as a material on a microelectronic device.

[0023] For ease of reference, "microelectronic device" or "semiconductor device" corresponds to semiconductor wafers having integrated circuits and memory, semiconductor wafers on which other electronic structures are fabricated on top, which are manufactured for use in microelectronics, integrated circuits or computer chip applications, and other products including flat panel displays, phase change memory devices, solar panels, and solar substrates, solar power generation devices, and microelectromechanical systems (MEMS). Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. The solar substrate may or may not be doped. The terms "microelectronic device" or "semiconductor device" are not meant to be limiting in any way and include any substrate that ultimately becomes a microelectronic device or microelectronic assembly.

[0024] As defined herein, the term "barrier material" corresponds to any material used in the art to seal metal lines, such as copper interconnects, to minimize the diffusion of the metal, such as copper, into the dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals, and their nitrides and silicides, among others.

[0025] "Substantially free of" is defined as less than 0.001 weight %. "Substantially free of" also includes 0.000 weight %. The expression "free of" means 0.000 weight %. As used herein, "about" or "approximately" is intended to correspond to within ±5% of the stated value.

[0026] In all such compositions where the specific components of the composition are described with reference to a weight percentage (or "wt%") range including a lower limit of zero, such components may or may not be present in various specific embodiments of the composition, and when such components are present, they may be present at concentrations as low as 0.001 wt% based on the total weight of the composition in which such components are used. It should be noted that all percentages of these components are weight percentages and are based on the total weight of the composition, i.e., 100%. When referring to "one or more" or "one kind or more" or "at least one" or "at least one kind", this includes, in any case, "two or more" or "two kinds or more" or "three or more" or "three kinds or more", etc.

[0027] When applicable, unless otherwise indicated, all weight percentages are "neat", meaning that when added to the composition, they do not include the aqueous solutions in which they are present. For example, "neat" refers to the amount of the weight percentage of undiluted acid or other material (i.e., a 100 g inclusion of 85% phosphoric acid consists of 85 g of acid and 15 g of diluent).

[0028] Furthermore, when referring to the compositions described herein in terms of weight percentages, it should be understood that in all cases, the weight percentages of all components including non-essential components such as impurities do not total more than 100% by weight. In a composition that "consists essentially of" the recited components, such components can total 100% by weight of the composition or can total less than 100% by weight. When the total of the components is less than 100% by weight, such a composition can contain some minor non-essential contaminants or impurities. For example, in one such embodiment, the formulation can contain up to 2% by weight of impurities. In one of another embodiment, the formulation can contain up to 1% by weight of impurities. In one of yet another embodiment, the formulation can contain up to 0.05% by weight of impurities. In other such embodiments, the constituents can form 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, and most preferably at least 99.9% by weight, and can contain other components that do not significantly affect the performance of the wet etching solution. In other cases, when no significant non-essential impurity components are present, it should be understood that the composition of all essential constituents totals essentially 100% by weight.

[0029] The headings used herein are not intended to be limiting, but rather are included only for purposes of document organization.

[0030] Exemplary embodiments One aspect of the disclosed and claimed invention relates to a precursor having at least one tethered cyclopentadienyl ligand ("Cp ligand"), at least one amidinate ligand ("Ad ligand"), and a lanthanide and / or lanthanide-like transition metal ("M") of general formula (i) (Cp ligand) 2 -M-(Ad ligand) or (ii) (Cp ligand)-M-(Ad ligand) 2

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

[0032] One aspect of the disclosed and claimed invention is a precursor of the general formula (Cp ligand)-M-(Ad ligand) 2 (where M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), 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”). In one aspect of this embodiment, M is La.

[0033] In some embodiments, the tethered Cp ligand has the structure shown in Table 1 below (where the Cp ligand has an oxygen-containing side chain) or Table 2 (where the Cp ligand has a nitrogen-containing side chain) and / or the Ad ligand shown in Table 3.

[0034] [Table 1]

[0035] [Table 2]

[0036] [Table 3] Preferred embodiments of the general formulas (i) (Cp ligand) 2 -M-(Ad ligand) and (ii) (Cp ligand)-M-(Ad ligand) 2 are described in Tables 4 - 6:

[0037]

Table 4

[0038]

Table 5

[0039]

Table 6

[0040] The disclosed and claimed precursors are not limited to those exemplified in Tables 4-6. Additionally, the Cp ligands and Ad ligands are not limited to those exemplified in Tables 1-3. Additional aspects of the disclosed and claimed precursors are described below with reference to Formulas I and II.

[0041] Aspects of Formula 1 Aspects and perspectives of precursors having Formula I having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand are exemplified below. As described above, the precursors of Formula I are 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.

[0042] In one aspect, a precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand has Formula I:

[0043] [Chemical formula] In the formula, (i) M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; (ii) R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently H, D, an unsubstituted linear C 1 -C 6 alkyl group, a linear C 1 -C 6 alkyl group substituted with a halogen, a linear C 1 -C 6 alkyl group substituted with an amino group, an unsubstituted branched C 3 -C 6 alkyl group, a branched C 3 -C 6 alkyl group substituted with a halogen, a branched C 3 -C 6 alkyl group substituted with an amino group, and -Si(CH 3 ) 3 selected from; (iii) R is a linear or branched C 1 -C 6 alkylene; (iv) R c is H, D, or an unsubstituted linear C 1 -C 3 linear alkyl group; (v) is 1 or 2.

[0044] 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.

[0045] 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.

[0046] 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 .

[0047] In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6and R 7 are each independently H, D, unsubstituted linear C 1 -C 4 linear alkyl group, unsubstituted branched C 3 -C 6 alkyl group and -Si(Me) 3 selected from. 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 linear C 1 -C 4 alkyl group, unsubstituted branched C 3 -C 6 alkyl group and -Si(Me) 3 selected from. In one aspect of this embodiment, R 6 is H or D, and R 5 , R 7 are independently unsubstituted linear C 1 -C 4 alkyl group, unsubstituted branched C 3 -C 6 alkyl group and -Si(Me) 3 .

[0048] In one aspect of this embodiment, one or more of R 5 , R 6 and R 7 is an isopropyl group. In one other aspect of this embodiment, two or more of R 5 , R 6 and R 7 are isopropyl groups. In one other aspect of this embodiment, R 5 , R 6 and R 7 are each isopropyl groups.

[0049] In one aspect of this embodiment, n is 1. In one other aspect of this embodiment, n is 2.

[0050] In one aspect of this embodiment, R is -(CH 2 )-.

[0051] In one aspect of this embodiment, R is -(CH 2 ) 2 -.

[0052] In one aspect of this embodiment, R is -(CH 2 ) 3 -.

[0053] In one aspect of this embodiment, R is -(CH 2 ) 4 -.

[0054] In one aspect of this embodiment, R is -C(CH 3 ) 2 -.

[0055] In one aspect of this embodiment, R is -CH(CH 3 )-.

[0056] In one aspect of this embodiment, R is -C(CH 3 ) 2 CH 2 -.

[0057] In one aspect of this embodiment, R is -CH(CH 3 )CH 2 -.

[0058] In one aspect of this embodiment, R is -C(CH 3 ) 2 (CH 2 ) 2 -.

[0059] In one aspect of this embodiment, R is -CH(CH 3 )(CH 2 ) 2 -.

[0060] In one aspect of this embodiment, R cis - D. In one aspect of this embodiment, R c is - H.

[0061] In one aspect of this embodiment, R c is - CH 3 .

[0062] In one aspect of this embodiment, R c is - CH 2 CH 3 .

[0063] In one aspect of this embodiment, R c is - CH 2 CH 2 CH 3 .

[0064] In one aspect of this embodiment, (i) R 5 , and R 7 are each an isopropyl group, and (ii) R 6 is H.

[0065] In one aspect of this embodiment, (i) n is 1, (ii) R 5 , and R 7 are each an isopropyl group, and (iii) R 6 is H.

[0066] In one aspect of this embodiment, (i) n is 2, (ii) R 5 , and R 7 are each an isopropyl group, and (iii) R 6 is H.

[0067] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 5 , and R 7 are each an isopropyl group, and (iv) R 6 is H.

[0068] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R5 and R 7 are each an isopropyl group, and (iv) R 6 is H.

[0069] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is H.

[0070] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 ]-, (v) R c is -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is H.

[0071] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is H.

[0072] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each isopropyl groups, and (vii) R 6 is H.

[0073] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is H.

[0074] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is H.

[0075] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is H.

[0076] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is H.

[0077] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 3 , and (vii) R 6 is H.

[0078] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 3 , and (vii) R 6 is H.

[0079] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 3 , and (vii) R 6 is H.

[0080] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 3 , and (vii) R 6 is H.

[0081] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2, R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each -C(CH 3 ) 3 , and (vii) R 6 is H.

[0082] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -C(CH 3 ) 3 , and (vii) R 6 is H.

[0083] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -C(CH 3 ) 3 , and (vii) R 6 is H.

[0084] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R3 and R 4 are each H, (iv) R is -CH 2 -, (v) R c is -CH 3 -, (vi) R 5 and R 7 are each -C(CH 3 ) 3 -, and (vii) R 6 is H.

[0085] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c is -CH 3 (-), (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is -CH 3 (-).

[0086] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 -, (v) R c is -CH 3 (-), (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is -CH 3 (-).

[0087] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4are each H, and (iv) R is -(CH 2 ) 2 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each isopropyl groups, and (vii) R 6 is -CH 3 .

[0088] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 (v) R c is -CH 3 , (vi) R 5 and R 7 are each isopropyl groups, and (vii) R 6 is -CH 3 .

[0089] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is -CH 3 .

[0090] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH2 ) 3 - and (v) R c is -CH 3 and (vi) R 5 and R 7 are each -CH 2 CH 3 and (vii) R 6 is -CH 3 .

[0091] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c is -CH 3 and (vi) R 5 and R 7 are each -CH 2 CH 3 and (vii) R 6 is -CH 3 .

[0092] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 -, (v) R c is -CH 3 and (vi) R 5 and R 7 are each -CH 2 CH 3 and (vii) R 6 is -CH 3 .

[0093] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4is H respectively, (iv) R is -(CH 2 ) 4 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are -CH 3 respectively, and (vii) R 6 is -CH 3 .

[0094] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are H respectively, (iv) R is -(CH 2 ) 3 (v) R c is -CH 3 , (vi) R 5 and R 7 are -CH 3 respectively, and (vii) R 6 is -CH 3 .

[0095] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are H respectively, (iv) R is -(CH 2 ) 2 , (v) R c is -CH 3 , (vi) R 5 and R 7 are -CH 3 respectively, and (vii) R 6 is -CH 3 .

[0096] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4is H respectively, (iv) R is -CH 2 -, (v) R c is -CH 3 (vi) R 5 and R 7 are -CH 3 respectively, and (vii) R 6 is -CH 3 .

[0097] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are H respectively, (iv) R is -(CH 2 ) 4 (v) R c is -CH 3 (vi) R 5 and R 7 are -C(CH 3 ) 3 respectively, and (vii) R 6 is -CH 3 .

[0098] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are H respectively, (iv) R is -(CH 2 ) 3 (v) R c is -CH 3 (vi) R 5 and R 7 are -C(CH 3 ) 3 respectively, and (vii) R 6 is -CH 3 .

[0099] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each -C(CH 3 ) 3 , and (vii) R 6 is -CH 3 .

[0100] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 (-), (v) R c is -CH 3 , (vi) R 5 and R 7 are each -C(CH 3 ) 3 , and (vii) R 6 is -CH 3 .

[0101] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 (-), (v) R c is -CH 3 , (vi) R 5 and R 7 are each isopropyl groups, and (vii) R 6 is H.

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

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

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

[0105] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 (v) R c is -CH 3 and (vi) R5 and R 7 are each -CH 2 CH 3 respectively, and (vii) R 6 is H.

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

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

[0108] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 (-), (v) R c is -CH 3 , (vi) R 5 and R7 is each -CH 2 CH 3 respectively, and (vii) R 6 is H.

[0109] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each -CH 3 respectively, and (vii) R 6 is H.

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

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

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

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

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

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

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

[0117] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c is -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is -CH 3 .

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

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

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

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

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

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

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

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

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

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

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

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

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

[0131] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 (v) R c is -CH 3 , (vi) R 5 and R 7 are each -C(CH 3 ) 3 and (vii) R 6 is -CH 3 .

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

[0133] Embodiments of Formula II Embodiments and aspects of a precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand of Formula II are illustrated below. As described above, the precursor of Formula II is 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.

[0134] In one of the other embodiments, a precursor having at least one tethered cyclopentadienyl ligand and at least one amidinate ligand has Formula II:

[0135]

Chemical formula

[0136] 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.

[0137] 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.

[0138] 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 R 1 , R 2 , R 3 、R4 , R 5 , R 6 and R 7 It is different from the others.

[0139] In one aspect of this embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently H, D, or unsubstituted linear C 1 -C 4 Linear alkyl groups, unsubstituted branched C 3 -C 6 Alkyl groups 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 H, D, or unsubstituted linear C 1 -C 4 Alkyl groups, unsubstituted branched C 3 -C 6 Alkyl groups and -Si(Me) 3 In one aspect of this embodiment, R 6 is H or D, and R 5 , R 7 are independently unsubstituted linear C 1 -C 4 Alkyl groups, unsubstituted branched C 3 -C 6 Alkyl groups and -Si(Me) 3 It is.

[0140] In one aspect of this embodiment, R 5 , R 6 and R 7 In another aspect of this embodiment, one or more of R 5 , R 6 and R7 Two or more of them are isopropyl groups. In one aspect of this embodiment, R 5 , R 6 and R 7 are each an isopropyl group.

[0141] In one aspect of this embodiment, n is 1. In another aspect of this embodiment, n is 2.

[0142] In one aspect of this embodiment, R is -(CH 2 )-.

[0143] In one aspect of this embodiment, R is -(CH 2 ) 2 -.

[0144] In one aspect of this embodiment, R is -(CH 2 ) 3 -.

[0145] In one aspect of this embodiment, R is -(CH 2 ) 4 -.

[0146] In one aspect of this embodiment, R is -C(CH 3 ) 2 -.

[0147] In one aspect of this embodiment, R is -CH(CH 3 )-.

[0148] In one aspect of this embodiment, R is -C(CH 3 ) 2 CH 2 -.

[0149] In one aspect of this embodiment, R is -CH(CH 3 )CH 2 -.

[0150] In one aspect of this embodiment, R is -C(CH 3 ) 2 (CH2 ) 2 - is.

[0151] In one aspect of this embodiment, R is -CH(CH 3 )(CH 2 ) 2 - is.

[0152] In one aspect of this embodiment, at least one of R c and R d is -H. In another aspect of this embodiment, each of R c and R d is -H.

[0153] In one aspect of this embodiment, at least one of R c and R d is -D. In another aspect of this embodiment, each of R c and R d is -D.

[0154] In one aspect of this embodiment, at least one of R c and R d is -CH 3 . In another aspect of this embodiment, each of R c and R d is -CH 3 .

[0155] In one aspect of this embodiment, at least one of R c and R d is -CH 2 CH 3 . In another aspect of this embodiment, each of R c and R d is -CH 2 CH 3 .

[0156] In one aspect of this embodiment, at least one of R c and R d is -CH 2 CH 2 CH 3 is. In another aspect of this embodiment, Rc and R d are each -CH 2 CH 2 CH 3 respectively.

[0157] In one aspect of this embodiment, (i) R 5 , and R 7 are each isopropyl groups, and (ii) R 6 is H.

[0158] In one aspect of this embodiment, (i) n is 1, (ii) R 5 , and R 7 are each isopropyl groups, and (iii) R 6 is H.

[0159] In one aspect of this embodiment, (i) n is 2, (ii) R 5 , and R 7 are each isopropyl groups, and (iii) R 6 is H.

[0160] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 5 , and R 7 are each isopropyl groups, and (iv) R 6 is H.

[0161] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 5 , and R 7 are each isopropyl groups, and (iv) R 6 is H.

[0162] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) Rc and R d is each -CH 3 respectively, and (vi) R 5 and R 7 are each isopropyl groups, and (vii) R 6 is H.

[0163] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 -, (v) R c and R d are each -CH 3 respectively, and (vi) R 5 and R 7 are each isopropyl groups, and (vii) R 6 is H.

[0164] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c and R d are each -CH 3 respectively, and (vi) R 5 and R 7 are each isopropyl groups, and (vii) R 6 is H.

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

[0166] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is H.

[0167] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is H.

[0168] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 (v) R cand R d is each -CH 3 and (vi) R 5 and R 7 is each -CH 2 CH 3 and (vii) R 6 is H.

[0169] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 -, (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -CH 2 CH 3 and (vii) R 6 is H.

[0170] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -CH 3 and (vii) R 6 is H.

[0171] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3- and (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -CH 3 and (vii) R 6 is H.

[0172] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, and (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -CH 3 and (vii) R 6 is H.

[0173] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 -, and (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -CH 3 and (vii) R 6 is H.

[0174] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4- and (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -C(CH 3 ) 3 and (vii) R 6 is H.

[0175] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 -, (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -C(CH 3 ) 3 and (vii) R 6 is H.

[0176] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -C(CH 3 ) 3 and (vii) R 6 is H.

[0177] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R4 are each H, and (iv) R is -CH 2 -, and (v) R c and R d are each -CH 3 , and (vi) R 5 and R 7 are each -C(CH 3 ) 3 , and (vii) R 6 is H.

[0178] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each isopropyl groups, and (vii) R 6 is -CH 3 .

[0179] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each isopropyl groups, and (vii) R 6 is -CH 3 .

[0180] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2, R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is -CH 3 .

[0181] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 (-), (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is -CH 3 .

[0182] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 (-), (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is -CH 3 .

[0183] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is -CH 3 .

[0184] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is -CH 3 .

[0185] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3and (vii) R 6 is -CH 3 .

[0186] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 3 , and (vii) R 6 is -CH 3 .

[0187] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 3 , and (vii) R 6 is -CH 3 .

[0188] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 (v) R c and R d are each -CH 3and (vi) R 5 and R 7 are each -CH 3 and (vii) R 6 is -CH 3 .

[0189] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 -, (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -CH 3 and (vii) R 6 is -CH 3 .

[0190] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -C(CH 3 ) 3 and (vii) R 6 is -CH 3 .

[0191] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3- and (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -C(CH 3 ) 3 and (vii) R 6 is -CH 3 .

[0192] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -C(CH 3 ) 3 and (vii) R 6 is -CH 3 .

[0193] In one aspect of this embodiment, (i) M is La, (ii) n is 1, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -CH 2 -, (v) R c and R d are each -CH 3 and (vi) R 5 and R 7 are each -C(CH 3 ) 3 and (vii) R 6 is -CH 3 .

[0194] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is H.

[0195] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is H.

[0196] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is H.

[0197] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R3 and R 4 are each H, and (iv) R is -CH 2 -, and (v) R c and R d are each -CH 3 -, and (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is H.

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

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

[0200] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 2 CH 3 , and (vii) R 6 is H.

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

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

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

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

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

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

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

[0208] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -C(CH 3 ) 3 and (vii) R6 is H.

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

[0210] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each an isopropyl group, and (vii) R 6 is -CH 3 .

[0211] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 3 , (v) R c and R d are each -CH 3 , (vi) R 5 and R 7are each an isopropyl group, and (vii) R 6 is -CH 3 .

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

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

[0214] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 4 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R7 is each -CH 2 CH 3 and (vii) R 6 is -CH 3 .

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

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

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

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

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

[0220] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R3 and R 4 are each H, (iv) R is -(CH 2 ) 2 -, (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -CH 3 , and (vii) R 6 is -CH 3 .

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

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

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

[0224] In one aspect of this embodiment, (i) M is La, (ii) n is 2, (iii) R 1 , R 2 , R 3 and R 4 are each H, (iv) R is -(CH 2 ) 2 (v) R c and R d are each -CH 3 , (vi) R 5 and R 7 are each -C(CH 3 ) 3 , and (vii) R 6 is -CH 3 .

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

[0226] Usage The disclosed precursors can be deposited using any chemical vapor deposition process known to those skilled in the art to form a lanthanide-containing film. 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) continuous surface chemical reaction for depositing a film of material on a substrate of various compositions. Although the precursors, reagents, and sources used herein are sometimes described as "gaseous," it is understood that the precursors can be liquid or solid and are transported into the reactor via direct evaporation, bubbling, or sublimation, with or without an inert gas. In some cases, the evaporated precursor can pass through a plasma generator. As used herein, the term "reactor" includes, but is not limited to, reaction chambers, reaction vessels, or deposition chambers.

[0227] Chemical vapor deposition processes in which the disclosed and claimed precursors can be utilized include, but are not limited to, processes used in the manufacture of semiconductor type microelectronic devices such as ALD, CVD, pulsed CVD, plasma ALD (PEALD) and / or plasma CVD (PECVD). Examples of suitable deposition processes for the methods described herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (metalorganic CVD), thermal chemical vapor deposition, plasma chemical vapor deposition (“PECVD”), high density PECVD, photon-assisted CVD, plasma-photon assisted (“PPECVD”), very low temperature chemical vapor deposition, chemical assisted deposition, hot filament chemical vapor deposition, CVD of liquid polymer precursors, deposition from supercritical fluids, and low energy CVD (LECVD). In one aspect, the metal-containing film is deposited by an atomic layer deposition (ALD), plasma ALD (PEALD) or plasma cyclic CVD (PECCVD) process.

[0228] In one aspect, for example, the metal-containing film is deposited using an ALD process. In one of other aspects, the metal-containing film is deposited using a CCVD process. In yet another aspect, the metal-containing film is deposited using a thermal CVD process.

[0229] 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 may be selected from oxides such as HfO 2 -based materials, TiO 2 -based materials, ZrO 2 -based materials, rare earth oxide-based materials, ternary oxide-based materials, or from nitride-based films. Other substrates include metal substrates (e.g., Au, Pd, Rh, Ru, W, Al, Ni, Ti, Co, Pt) and metal silicides (e.g., TiSi 2 , CoSi 2 , and NiSi 2); A metal nitride-containing substrate (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); a semiconductor material (e.g., Si, SiGe, GaAs, InP, diamond, GaN, and SiC); an insulator (e.g., SiO 2 、Si 3 N 4 、SiON, HfO 2 、Ta 2 O 5 、ZrO 2 、TiO 2 、Al 2 O 3 、and strontium barium titanate); Solid substrates such as combinations thereof may also be included. Preferred substrates include TiN, Ru, and Si type substrates.

[0230] In such deposition methods and processes, an oxidizing agent can be utilized. This oxidizing agent is typically introduced in the form of a gas. Examples of suitable oxidizing agents include, but are not limited to, oxygen gas, water vapor, ozone, oxygen plasma, or mixtures thereof.

[0231] The deposition method and process may also require one or more purge gases. The purge gas used to purge and remove unconsumed reactants and / or reaction by-products is an inert gas that does not react with the precursor. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N 2 ), helium (He), neon, and mixtures thereof. For example, a purge gas such as Ar is supplied into the reactor at a flow rate in the range of about 10 to about 2000 sccm for a period of about 0.1 to 10000 seconds, thus purging unreacted materials and any by-products that may remain in the reactor.

[0232] The deposition method and process require applying energy to at least one of a precursor, an oxidizing agent, other precursors, or combinations thereof to induce a reaction and form a metal-containing film or coating on a substrate. Such energy can be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-rays, electron beam, photons, remote plasma processes, and combinations thereof. In some processes, a secondary RF frequency source can be used to modify plasma characteristics at the substrate surface. When using plasma, plasma generation processes include direct plasma generation processes where plasma is generated directly in the reactor, or alternatively remote plasma generation processes where plasma is generated outside the reactor and supplied into the reactor.

[0233] When used in such deposition methods and processes, suitable precursors such as those disclosed and patented by this application can be supplied to a reaction chamber such as a CVD or ALD reactor in various ways. In some cases, a liquid supply mechanism can be utilized. In other cases, a combined unit of liquid supply and flash evaporation process, for example, a turbo vaporizer manufactured by MSP Corporation of Shoreview, Minnesota, can be used to enable metered supply of low volatility materials, which results in reproducible transport and deposition without thermal decomposition of the precursor. The precursor compositions described herein can be effectively used as raw materials by direct liquid injection (DLI) to provide a vapor stream of the metal precursor into an ALD or CVD reactor.

[0234] When used in these deposition methods and processes, the disclosed and claimed precursors include hydrocarbon solvents and the like, which are particularly desirable in that they can be dried to a water content of less than ppm. Exemplary hydrocarbon solvents that can be used in the precursors include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cumene (4-isopropyltoluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decane). The disclosed and claimed precursors can also be stored and used in stainless steel containers. In certain embodiments, the hydrocarbon solvent is a high-boiling solvent or has a boiling point of 100 °C or higher. The disclosed and claimed precursors can also be mixed with other suitable metal precursors, and this mixture can be used to simultaneously supply both metals for the growth of a binary metal-containing film.

[0235] A flow of argon and / or other gases may be used as a carrier gas to assist in supplying a vapor containing at least one of the disclosed and claimed precursors to the reaction chamber during the precursor pulse. When supplying the precursor, the reaction chamber process pressure is between 1 torr and 50 torr, preferably between 5 torr and 20 torr.

[0236] The substrate temperature can be one of the important process variables in the deposition of high-quality metal-containing films. A typical substrate temperature ranges from about 150 °C to about 550 °C. The higher the temperature, the more it can promote a faster film growth rate.

[0237] From the above, those skilled in the art will recognize that the disclosed and claimed invention further includes the use of the disclosed and claimed precursors in a chemical vapor deposition process as follows.

[0238] In one aspect, the disclosed and claimed invention is a method of forming a transition metal-containing film on at least one surface of a substrate, the following steps: a. Preparing the at least one surface of the substrate in a reaction vessel; b. Using one or more of the disclosed and claimed precursors as metal source compounds for a deposition process to form a transition metal-containing film on the at least one surface by a deposition process selected from a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process; A method comprising the steps is included.

[0239] In yet another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel. In yet another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, and the at least one reactant is selected from the group consisting of water, diatomic oxygen, oxygen plasma, ozone, NO, N 2 O, NO 2 , carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel, and 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, and 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.

[0240] In one embodiment, the disclosed and claimed invention is a method for forming a transition metal-containing film via an atomic layer deposition (ALD) process or an ALD-like process, the steps being a. Preparing a substrate in a reaction vessel; b. Introducing one or more of the disclosed and claimed precursors into the reaction vessel; c. Purging the reaction vessel with a first purge gas; d. A step of introducing a raw material gas into a reaction vessel; e. A step of purging the reaction vessel with a second purge gas; f. A step of continuously repeating steps b to e until a transition metal-containing film of a desired thickness is obtained, is included, including a method.

[0241] In another aspect of this embodiment, the raw material gas is one or more oxygen-containing raw material gases selected from water, diatomic oxygen, oxygen plasma, ozone, NO, N 2 O, NO 2 , carbon monoxide, carbon dioxide, and combinations thereof. In another aspect of this embodiment, the raw material gas is one or more nitrogen-containing raw material gases selected from ammonia, hydrazine, monoalkyl hydrazine, dialkyl hydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof. In yet another aspect of this embodiment, the first and second purge gases are each independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof. In yet another aspect of this embodiment, the method further includes applying energy to at least one of the precursor, the raw material gas, the substrate, and combinations thereof, where this energy is one or more of heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-rays, electron beam, photons, remote plasma method, and combinations thereof. In yet another aspect of this embodiment, step b of the method further includes introducing the precursor into the reaction vessel using a flow of carrier gas to supply vapor of the precursor to the reaction vessel. In yet another aspect of this embodiment, step b of the method includes the use of a solvent including one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyltoluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene, and combinations thereof.

[0242] In one of the other aspects, the 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 aspects, the metal-containing films are deposited using an ALD, ALD-like or CVD process such as the processes described herein, using a metal alkoxide, metal amide, or volatile organometallic precursor. Examples of suitable metal alkoxide precursors that can be used with the methods described herein include, but are not limited to, Group 3 to Group 13 metal alkoxides, Group 3 to Group 13 metal complexes having both alkoxy and alkyl-substituted cyclopentadienyl ligands, Group 3 to Group 6 metal complexes having both alkoxy and alkyl-substituted pyrrolyl ligands, Group 3 to Group 13 metal complexes having both alkoxy and diketonate ligands; Group 3 to Group 13 metal complexes having alkyl ligands, etc. Exemplary Group 3 to Group 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, etc.

[0243] Examples of suitable metal amide precursors that can be used with the methods described 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-amylimino tris(dimethylamino)tantalum (TAIMAT), tert-amylimino tris(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino 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 with the methods disclosed herein include, but are not limited to, Group 3 metal cyclopentadienyl or alkylcyclopentadienyl, etc.

[0244] Examples of suitable metal complexes having 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 alanate (DMEAA), trimethylamine alanate (TEAA), N-methylpyrrolidine-alanate (MPA), tri-isobutylaluminum (TIBA), and the like.

[0245] In one aspect, the disclosed and claimed invention is a method of forming a transition metal-containing film on at least one surface of a substrate, comprising: a. providing the at least one surface of the substrate in a reaction vessel; b. forming a transition metal-containing film on the at least one surface using a precursor as a metal source compound for this deposition process by a deposition process selected from a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process; and c. using one or more of the disclosed and claimed precursors as a dopant material. The method includes the steps described above.

[0246] In one aspect, the disclosed and claimed invention includes a precursor supply package comprising a container and one or more of the disclosed and claimed precursors, wherein the container is adapted to contain and dispense the precursor.

[0247] In one aspect, the disclosed and claimed invention includes a compound of the formula La[Cp(CH 2 ) 3 OCH 3 3 and a method for synthesizing a compound of formula I that includes using a compound of the formula La[Cp(CH 2 ) 3 OCH 3 3 In one of other aspects, the disclosed and claimed invention is a compound of the formula La[CpCH​​2 N(CH 3 ) 2 3 compounds, and in the synthesis of the compounds of formula II, the use of compounds of formula La[CpCH 2 N(CH 3 ) 2 3 is included. A method for synthesizing a compound of formula II is included, which comprises using a compound of formula La[CpCH

[0248] In one aspect, the disclosed and claimed invention includes the use of one or more of the disclosed and claimed precursors in a method for forming a transition metal-containing film on at least one surface of a substrate.

Examples

[0249] Hereinafter, more specific aspects of the present disclosure and experimental results supporting such aspects will be described. These examples are described below to more fully explain the disclosed invention and should not be construed as limiting the disclosed invention in any way.

[0250] It will be apparent to those skilled in the art that various modifications and changes can be made to the disclosed invention and the specific examples provided herein without departing from the spirit or scope of the disclosed invention. Therefore, the disclosed invention, including the description provided by the following examples, is intended to include modifications and changes to the disclosed invention that fall within the scope of any claims and their equivalents.

[0251] Materials and Methods: All solvents and raw materials were purchased from Sigma-Aldrich unless otherwise stated. La(FAMD) 3 was purchased from Strem Chemicals. La(iPr-AMD) 3 was synthesized according to the method reported by Gordon et al., Inorg. Chem., 42, 7951-7958 (2003) (Non-Patent Document 1). KCpCH 2 CH 2 CH 2 OCH 3 ​​and KCpCH 2 N(CH 3 ) 2 was prepared from KN(TMS) 2 and the corresponding Cp in toluene according to the method reported by Evans et al., Inorg. Chem., 44, 3993 - 4000 (2005) (Non-Patent Document 2).

[0252] Ligand Synthesis A. Cp Ligand 1A (Table 1)

[0253]

Chemical Formula

[0254] Sodium cyclopentadienide (2 M in THF) and 1-chloro-4-methoxybutane were purchased from Sigma-Aldrich and used as received.

[0255] B. Cp Ligand 1B (Table 1)

[0256]

Chemical Formula

[0257] Sodium cyclopentadienide (2 M in THF) and 1-chloro-3-methoxypropane were purchased from Sigma-Aldrich and used as received.

[0258] C.Cp ligand 1D (Table 1)

[0259]

Chemical Structure

[0260] Sodium cyclopentadienide and chloromethyl methyl ether were purchased from Sigma-Aldrich and used as received.

[0261] D.Cp ligand 2D (Table 2)

[0262]

Chemical formula

[0263] Dimethylaminofulvene was purchased from Sigma-Aldrich and used as received.

[0264] Synthesis of intermediate precursors A1.La[Cp(CH 2 ) 3 OCH 3 3 Synthesis N 2 Inside a nitrogen-filled glove box, THF (100 mL) was added to a 250 mL Schlenk round-bottom flask containing a solid mixture of LaBr 3 (4.29 g, 11.3 mmol) and K[Cp(CH 2 ) 3 OCH 3 (6.0 g, 34.0 mmol) and a stir bar. The resulting slurry was stirred at room temperature for 16 h under N 2 . Volatiles were then removed under vacuum to give a sticky orange solid. Further, this crude material was purified by toluene extraction and filtration through a medium frit. Toluene was removed under vacuum to give the final product as an orange oil. (3.1 g, 49% yield).​ 1H-NMR (C 6 D 6 , 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).

[0265] A2. Synthesis of La[Cp(CH 2 ) 3 OCH 3 ) 3 Inside a nitrogen-filled glove box, THF (100 mL) was added to a flask containing a solid mixture of LaBr N 2 (2.39 g, 6.3 mmol) and K[Cp(CH 3 ) 2 OCH 3 ) 3 (3.10 g, 19.1 mmol) and a stir bar. The resulting slurry was stirred at room temperature for 18 h under N 2 . Then the volatiles were removed under vacuum. Further, the crude material was purified by toluene extraction and removal of toluene under vacuum to afford the final product as an oil. (1.9 g, 59% yield). 1H-NMR (C 6 D 6 , 400 MHz): δ = 2.66 (t, J = 6.5 Hz; 6H, -CH 2 -); 3.09 (s, 9H, -OCH 3 ); 3.36 (t, J = 6.5 Hz, 6H, -CH 2 -Cp); 5.89 (s, 12H, CpH 4 ).

[0266] B. Synthesis of La[CpCH 2 N(CH 3 ) 2 ) 3 Inside a nitrogen-filled glove box, THF (100 mL) was added to a flask containing LaBr N 2 (1.95 g, 5.2 mmol) and K[CpCH 3 N(CH 2 ) 3 ) 2(2.50 g, 15.5 mmol) and a stir bar were added to a 250 mL Schlenk round-bottom flask containing a solid mixture. The resulting slurry was stirred at room temperature for 16 h under N 2 . Volatiles were then removed under vacuum to afford a yellow solid. Further, this crude material was purified by Et 2 O extraction and filtration through a medium frit. Et 2 O was removed under vacuum to afford the final product as a yellow solid. (1.33 g, 51% yield). 1H-NMR (C 6 D 6 , 400 MHz): δ = 5.99 (m, 6H), 5.93 (m, 6H), 3.32 (s, 6H), 2.16 (s, 18H).

[0267] Final Precursor Synthesis Example 1: La[Cp(CH 2 ) 3 OCH 3 [(C 3 H 7 )NC(H)N(C 3 H 7 )] 2 “(1B)-La-(3C) 2 ”

[0268] [Chemical formula] N 2 Inside a nitrogen-filled glove box, a toluene solution of La[Cp(CH 2 ) 3 OCH 3 3 (0.40 g, 0.72 mmol) was added to a thick-walled pressure vessel charged with La(FAMD) 3 (0.748 g, 1.44 mmol). The solution was heated to 100 °C for 4 h under N 2 . Volatiles were removed under vacuum to afford a yellow solid. Further, this crude material was purified by sublimation at 120 °C and 130 mTorr to afford the final product as a white solid (0.45 g, 37% yield).

[0269] ​ Precursor (1B)-La-(3C) 2 Characterization: 1H-NMR (C 6 D 6 , 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. The TGA shows a clean evaporation with little non-volatile residue. The TGA / DSC analysis of this precursor is shown in Figure 2 (scan rate 10 K / min).

[0270] Example 2: La[Cp(CH 2 ) 3 OCH 3 [(C 3 H 7 )NC(CH 3 )N(C 3 H 7 )] 2 ("(1B)-La-(3G) 2 ")

[0271]

Chemical formula

[0272] Precursor (1B)-La-(3G) 2 ​Characterization: 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. The TGA shows a clean evaporation with little non-volatile residue.

[0273] Example 3: La[CpCH 2 N(CH 3 ) 2 [(C 3 H 7 )NC(H)N(C 3 H 7 )] 2 (“(2D)-La-(3C) 2 ”)

[0274]

Chemical formula

[0275] Precursor (2D)-La-(3C) 2 Characterization: 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. The TGA shows a clean evaporation with little non-volatile residue. ​

[0276] Example 4: La[CpCH 2 N(CH 3 ) 2 [(C 3 H 7 )NC(CH 3 )N(C 3 H 7 )] 2 ("(2D)-La-(3G) 2 ")

[0277]

Chem.

[0278] 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. The TGA shows a clean evaporation with little non-volatile residue.

[0279] Example 5: La[Cp(CH 2 ) 2 OCH 3 [(C 3 H 7 )NC(H)N(C 3 H 7 )] 2“(1C)-La-(3C) 2 ”

[0280]

Chem.

[0281] Characterization of the precursor (1C)-La-(3C) 2 : 1H-NMR (C 6 D 6 , 400 MHz): δ = 1.18 (d, J = 6.6 Hz, 24H, 8-CH 3 ); 2.58 (t, J = 5.8 Hz, 2H-CH 2 -); 3.10 (qq, J = 6.5 Hz, 4H, -CHMe 2 ); 3.11 (s; 3H, -OMe); 3.47 (t, J = 5.8 Hz, 2H; -CH 2 -Cp); 6.36 (t, J = 2.6 Hz, 2H, CpH 2 ); 6.47 (t, J = 2.6 Hz, 2H, CpH 2 ). The TGA / DSC analysis of this precursor is shown in Fig. 6 (scan rate 10 K / min).

[0282] La[Cp(CH 2 ) 3 OCH 3 [(C 3 H 7 )NC(H)N(C 3 H 7 )] 2 “(1B)-La-(3C)​2 Atomic Layer Deposition of Lanthanum Oxide Film Using “ An Atomic Premex CN-1 200 mm reactor was used to perform atomic layer deposition of lanthanum oxide film using the precursor of the present invention. (1B)-La-(3C) as the precursor 2 was supplied from an SS316 ampoule (container) maintained at 160 °C (ampoule wall temperature). A 50 sccm argon carrier gas flow was used to supply the precursor vapor to the reactor chamber. The reactor chamber pressure was 1 torr. Si and SiO 2 substrates were used to deposit the lanthanum oxide film. The lanthanum oxide film thickness was calibrated using cross-sectional SEM images of the deposited lanthanum oxide film and measured by ellipsometry and X-ray fluorescence analysis (XRF).

[0283] Example 6: Precursor Thermal Decomposition Test on Si Wafer In this experiment, the precursor vapor was supplied to the deposition chamber in pulse mode separated by argon purges. The pulse sequence was as follows: a 5-second precursor pulse and a 20-second argon purge. The total number of precursor / Ar purge cycles was 100. No oxidant pulse was used in this experiment to demonstrate the good thermal stability of the precursor in the absence of an oxidant. Good thermal stability (absence of deposition in the absence of an oxidant) is an important precursor property for the atomic layer deposition process. The wafer temperature was varied from 200 °C to 450 °C. After this experiment, the lanthanum layer density on the surface was measured by X-ray fluorescence analysis. It is shown in FIG. 7. No lanthanum film was deposited in the absence of an oxidant up to at least 350 °C. This suggests that this precursor can be used for atomic layer deposition up to at least this wafer temperature.

[0284] Example 7: Precursor Saturation Behavior During Deposition Process In this experiment, a lanthanum oxide film was deposited by an atomic layer deposition method including the following steps. a. Step of preparing a Si or SiO 2 substrate in a reaction vessel; b. (1B)-La-(3C) 2The step of introducing a precursor into a reaction vessel; c. The step of purging the reaction vessel with argon; d. The step of introducing ozone into the reaction vessel; e. The step of purging the reaction vessel with argon; f. The step of continuously repeating steps b to e until a transition metal-containing film of a desired thickness is obtained.

[0285] To demonstrate the saturation behavior when the pulse time was lengthened, the lanthanum precursor pulse was varied from 1 second to 3 seconds. 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 shows very good saturation behavior at 200 and 250 °C, and soft saturation at a wafer temperature of 275 °C. Saturation behavior is one of the key characteristics of the atomic layer deposition process.

[0286] Example 8: Film thickness vs. number of ALD cycles In this experiment, a lanthanum oxide film was deposited by an atomic layer deposition method including the following steps. a. Preparing a substrate in a reaction vessel with Si or SiO 2 The step of preparing a substrate; b. (1B)-La-(3C) 2 The step of introducing a precursor into a reaction vessel; c. The step of purging the reaction vessel with argon; d. The step of introducing ozone into the reaction vessel; e. The step of purging the reaction vessel with argon; f. The step of continuously repeating steps b to e until a transition metal-containing film of a desired thickness is obtained.

[0287] 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 demonstrate the linear growth length of the lanthanum oxide film with respect to the number of cycles. The wafer temperatures were 200 °C, 250 °C, 275 °C, 300 °C, and 325 °C. Figure 9 shows the linear growth length of the lanthanum oxide film with respect to the number of cycles. The linear growth length when the number of cycles increased is one of the other characteristics 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, suggesting a relatively wide ALD thermal window for the precursors of the present invention.

[0288]

Table 7

[0289] Example 9: Deposition of Lanthanum Oxide Film In this experiment, a lanthanum oxide film was deposited by an atomic layer deposition method including the following steps. a. Preparing a substrate of Si or SiO in a reaction vessel; 2 Step of preparing a substrate; b. Introducing a precursor of (1B)-La-(3C) into the reaction vessel; 2 Step of introducing a precursor into the reaction vessel; c. Purging the reaction vessel with argon; d. Introducing ozone into the reaction vessel; e. Purging the reaction vessel with argon; f. Repeating steps b to e continuously until a transition metal-containing film of a desired thickness is obtained.

[0290] The lanthanum precursor pulse was 2 seconds. The Ar purge after the precursor pulse was 20 seconds, the ozone pulse was 5 seconds, and the Ar purge after the precursor pulse was 20 seconds. The number of ALD cycles was 100. The wafer temperature was 200 °C. Figure 10 shows SiO 2The cross-sectional SEM image of the lanthanum oxide film deposited on the substrate is shown. Figure 12 shows the top-down SEM image of the lanthanum oxide film deposited on the Si substrate.

[0291] Example 10: Deposition of Lanthanum Oxide Film In this experiment, a lanthanum oxide film was deposited by atomic layer deposition including the following steps. a. Prepare a substrate of Si or SiO 2 in the reaction vessel; b. Introduce the (1B)-La-(3C) 2 precursor into the reaction vessel; c. Purge the reaction vessel with argon; d. Introduce ozone into the reaction vessel; e. Purge the reaction vessel with argon; f. Continuously repeat steps b to e until a transition metal-containing film of the desired thickness is obtained.

[0292] The lanthanum precursor pulse was 2 seconds. 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 300. The wafer temperature was 200 °C. Figure 11 shows the cross-sectional SEM image of the lanthanum oxide film deposited on the SiO 2 substrate. Figure 13 shows the top-down SEM image of the lanthanum oxide film deposited on the Si substrate.

[0293] The above description is mainly intended for purposes of illustration. Although the disclosed and claimed invention has been described and illustrated with respect to exemplary embodiments thereof, various other changes, omissions, and additions in form and detail will be understood by those skilled in the art without departing from the spirit and scope of the disclosed and claimed invention. This application relates to the invention described in the claims, but the disclosure of this application also includes the following: 1. A precursor represented by the formula (cyclopentadienyl ligand)-M-(amidinato ligand), where M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. 2 2. A precursor represented by the formula (cyclopentadienyl ligand)-M-(amidinato ligand), where M is one of La, Sc, Y, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. 3. The precursor according to item 1 or 2 above, where M is La. 2 4. The precursor according to any one of items 1 to 3 above, where each cyclopentadienyl ligand is independently selected from the cyclopentadienyl ligands shown in Table 1 or Table 2. 5. The precursor according to any one of items 1 to 3 above, where the amidinato ligand is selected from the amidinato ligands shown in Table 3. 6. A precursor having the following formula I.

Table 8

Table 9

Table 10

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Claims

1. A precursor having the following Formula I or Formula II. 【Chemical 1】 【Chemical 2】 In the formulae, 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 H, unsubstituted linear C １ -C ６ alkyl group, linear C substituted with halogen １ -C ６ alkyl group, linear C substituted with amino group １ -C ６ alkyl group, unsubstituted branched C ３ -C ６ alkyl group, branched C substituted with halogen ３ -C ６ alkyl group, branched C substituted with amino group ３ -C ６ alkyl group and -Si(CH ３ ) ３ selected from; iii. R is linear or branched C １ -C ６ alkylene; iv. R ｃ and Rd are each independently selected from H and unsubstituted linear C １ -C ３ alkyl groups; and v. n is 1 or 2.

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

3. R １ 、R ２ 、R ３ 、R ４ are each H, and R ５ 、R ６ and R ７ are each independently H, unsubstituted linear C １ -C ４ alkyl group, unsubstituted branched C ３ -C ６ alkyl group and -Si(Me) ３ selected from, the precursor according to claim 1 or 2.

4. R １ 、R ２ 、R ３ 、R ４ 、R ５ 、R ６ and R ７ are each independently H, an unsubstituted linear C １ -C4 alkyl group, an unsubstituted branched C ３ -C ６ alkyl group and -Si(Me) ３ selected from, the precursor according to claim 1 or 2.

5. R ５ , R ６ and R ７ The precursor according to any one of claims 1 to 4, wherein one or more of them are isopropyl groups.

6. R ５ , R ６ and R ７ The precursor according to any one of claims 1 to 4, wherein two or more of R

7. R ６ is H, and R ５ , R ７ is, independently, an unsubstituted linear C １ -C ４ alkyl group, an unsubstituted branched C ３ -C ６ alkyl group and -Si(Me) ３ and is the precursor according to any one of claims 1 to 4.

8. The precursor according to any one of Claims 1 to 7, wherein n is 1.

9. The precursor according to any one of Claims 1 to 7, wherein n is 2.

10. R is -(CH ２ )-, -(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-, and the precursor according to any one of claims 1 to 9, which is selected from the group consisting of

11. R ｃ is -CH ３ The precursor according to any one of claims 1 to 10, wherein

12. R ｃ is -CH ２ CH ３ and is the precursor according to any one of claims 1 to 10.

13. R ｃ is -CH ２ CH ２ CH ３ The precursor according to any one of claims 1 to 10, wherein it is

14. R ｃ and R ｄ at least one of which is -CH ３ The precursor according to any one of claims 1 to 10, wherein is

15. R ｃ and R ｄ at least one of which is -CH ２ CH ３ The precursor according to any one of claims 1 to 10, wherein the precursor is

16. R ｃ and R ｄ are each —CH ３ The precursor according to any one of claims 1 to 10, wherein is

17. R ｃ and R ｄ are each -CH ２ CH ３ The precursor according to any one of claims 1 to 10, wherein is

18. The precursor according to any one of Claims 1 to 13, including the structure of Formula I.

19. The precursor according to any one of Claims 1 to 17, including the structure of Formula II.

20. The precursor according to Claim 1, having the following structure. [Chemical Formula 3]

21. The precursor according to Claim 1, having the following structure. 【Chemical Formula 4】

22. The precursor according to Claim 1, having the following structure. 【Chemical Formula 5】

23. The precursor according to Claim 1, having the following structure. 【Chemical Formula 6】

24. The precursor according to Claim 1, having the following structure. [Chemical Formula 7]

25. A method for forming a transition metal-containing film on at least one surface of a substrate, comprising: a. preparing the at least one surface of the substrate in a reaction vessel; b. forming a transition metal-containing film on the at least one surface by a deposition process selected from a chemical vapor deposition (CVD) process and an atomic layer deposition (ALD) process, using as a metal source compound for this deposition process the precursor according to any one of Claims 1 to 24; The method comprising the above steps.

26. Use of the precursor according to any one of Claims 1 to 24 in a method for forming a transition metal-containing film on at least one surface of a substrate.

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