Metal complexes containing cyclopentadienyl ligands

Abstract

This invention provides metal complexes containing cyclopentadienyl ligands and methods for preparing metal-containing films using the metal complexes.

Description

Technical Field

[0001] This invention relates to metal complexes containing cyclopentadienyl ligands, methods for preparing such complexes, and methods for preparing metal-containing thin films using such complexes. Background Technology

[0002] Various precursors are used to form thin films, employing a variety of deposition techniques. These techniques include reactive sputtering, ion-assisted deposition, sol-gel deposition, chemical vapor deposition (CVD) (also known as metal-organic CVD or MOCVD), and atomic layer deposition (ALD) (also known as atomic layer epitaxy). CVD and ALD processes are increasingly used due to their advantages such as strong compositional control, good film uniformity, and excellent doping control. Furthermore, CVD and ALD processes provide excellent conformal step coverage properties on the highly non-planar geometries associated with modern microelectronic devices.

[0003] CVD is a chemical process in which precursors are used to form thin films on the surface of a substrate. In a typical CVD process, the precursor passes through a low-pressure or ambient-pressure reaction chamber onto the surface of a substrate (such as a wafer). The precursor reacts and / or decomposes on the substrate surface to form a thin film of deposited material. Volatile byproducts are removed by gas streams flowing through the reaction chamber. The thickness of the deposited film is difficult to control because it depends on the coordination of many parameters such as temperature, pressure, gas flow rate and uniformity, chemical depletion effect, and time.

[0004] ALD (Alternating Layer Deposition) is also a thin film deposition method. It is a self-limiting, ordered, and unique thin film growth technique based on surface reactions, capable of providing precise thickness control and depositing conformal films of precursor-provided materials onto substrate surfaces with different compositions. In ALD, the precursors are separated during the reaction process. A first precursor passes through the substrate surface, forming a monolayer on the substrate surface. Any excess unreacted precursor is removed from the reaction chamber. Then, a second precursor passes through the substrate surface and reacts with the first precursor, forming a second monolayer on top of the first monolayer formed on the substrate surface. This cycle is repeated to generate a film of the desired thickness.

[0005] Thin films, especially metal-containing thin films, have many important applications, such as in nanotechnology and semiconductor device manufacturing. Examples of these applications include high-refractive-index optical coatings, anti-corrosion coatings, photocatalytic self-cleaning glass coatings, biocompatible coatings, dielectric capacitor layers, and gate dielectric insulating films, capacitor electrodes, gates, binder diffusion barrier layers, and integrated circuits in field-effect transistors (FETs). Dielectric thin films are also used in microelectronic applications, such as high-dielectric-coefficient dielectric oxides for dynamic random-access memory (DRAM) applications and ferroelectric perovskites for infrared detectors and non-volatile ferroelectric random-access memory (NV-FeRAM). The continuous reduction in the size of microelectronic components increases the demand for improved thin-film technologies.

[0006] Techniques related to the preparation of scandium- and yttrium-containing thin films (such as scandium oxide and yttrium oxide) are of particular interest. For example, scandium-containing films have already found numerous practical applications in catalysts, batteries, storage devices, displays, sensors, nano- and microelectronic devices, and semiconductor devices. In electronic applications, there is a need for commercially viable deposition methods using scandium- and yttrium-containing precursors with suitable properties, including volatility, low melting point, reactivity, and stability. However, the number of scandium- and yttrium-containing compounds with these suitable properties is limited. Therefore, there is a strong interest in developing scandium- and yttrium-containing complexes with performance characteristics that make them suitable as precursor materials in vapor deposition processes for the preparation of scandium- and yttrium-containing films. For example, there is a need for scandium- and yttrium-containing precursors with improved performance characteristics (e.g., thermal stability, vapor pressure, and deposition rate), as well as methods for depositing thin films from these precursors. Summary of the Invention

[0007] According to one aspect, the present invention provides a metal complex of formula I: [(R 1 ) n Cp]2M 1 L 1 (I), where M 1 It is a Group 3 metal or a lanthanide element (e.g., scandium, yttrium, and lanthanum); each R 1 Independently hydrogen, C1-C5 alkyl or silyl; n is 1, 2, 3, 4 or 5; Cp is a cyclopentadienyl ring; L 1 Choose Free NR 2 R 3 , N(SiR 4 R 5 R 6 )2, 3, 5-R 7 R 8 -C3HN2、1-(R 32 C3H4, 1-R 33 -3-R 34-C3H3 and R 35 ,R 36 The group consists of -C3HO2; among which, R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each is independently hydrogen or a C1-C5 alkyl group; and R 32 R 33 R 34 R 35 and R 36 Each is independently an alkyl or silyl group; wherein when M 1 It is yttrium and L 1 It is 3,5-R 7 R 8 When -C3HN2, R 1 It is a C1-C5 alkyl or silyl group; wherein when M 1 It is yttrium and L 1 It is N(SiR) 4 R 5 R 6 When n = 2, n is 1, 2, 3 or 4.

[0008] In other respects, the present invention provides a metal complex of formula II: [((R 9 ) n Cp)2M 2 L 2 ]2(II), where M 2 It is a Group 3 metal or a lanthanide element (e.g., scandium, yttrium, and lanthanum); each R 9 Independently hydrogen or a C1-C5 alkyl group; n is 1, 2, 3, 4 or 5; Cp is a cyclopentadienyl ring; L 2 Choose freely from Cl, F, Br, I, and 3,5-R 10 R 11 The group consisting of -C3HN2; where R 10 and R 11 Each is independently hydrogen or a C1-C5 alkyl group; wherein when M 2 It is scandium and L 2 When it is Cl, R 9 It is a C1-C5 alkyl group.

[0009] In other respects, the present invention provides a method for forming a metal-containing film by vapor deposition, such as CVD and ALD. The method includes vaporizing at least one metal complex structurally corresponding to Formula I, where Formula I is (R... 1 Cp)2M 1 L 1 (I), where M1 It is a Group 3 metal or a lanthanide element (e.g., scandium, yttrium, and lanthanum); each R 1 It is an independent hydrogen atom, a C1-C5 alkyl group, or a silyl group; Cp is a cyclopentadienyl ring; L 1 Choose Free NR 2 R 3 , N(SiR 4 R 5 R 6 )2, 3, 5-R 7 R 8 -C3HN2、1-(R 32 C3H4, 1-R 33 -3-R 34 -C3H3 and R 35 ,R 36 The group consists of -C3HO2; among which, R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each is independently hydrogen or a C1-C5 alkyl group; and R 32 R 33 R 34 R 35 and R 36 Each is independently an alkyl or silyl group.

[0010] Other embodiments incorporating some specific aspects of the embodiments outlined above will become apparent from the following detailed description. Attached Figure Description

[0011] Figure 1 XPS (X-ray photoelectron spectroscopy) analysis of Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolite).

[0012] Figure 2 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0013] Figure 3 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0014] Figure 4 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0015] Figure 5XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0016] Figure 6 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0017] Figure 7 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0018] Figure 8 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0019] Figure 9 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0020] Figure 10 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0021] Figure 11 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0022] Figure 12 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0023] Figure 13 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0024] Figure 14 XPS analysis of Sc2O3 membrane using Sc(MeCp)2(3,5-dimethylpyrazolite).

[0025] Figure 15 This is a graph showing the ALD Y2O3 growth rate per cycle depending on the deposition temperature during the deposition of [Y(MeCp)2(3,5-MePn-C3HN2)]2.

[0026] Figure 16 The graph shows the ALD Y2O3 growth rate per cycle as a function of water purification time when [Y(MeCp)2(3,5-MePn-C3HN2)]2 is deposited at 125℃, 150℃ and 200℃.

[0027] Figure 17 This is a graph showing the ALD Y2O3 growth rate for each cycle at three different locations in a cross-flow reactor along the precursor / carrier gas flow direction: the precursor inlet, the reactor center, and the precursor outlet. Detailed Implementation

[0028] Before describing several exemplary embodiments of the present invention, it should be understood that the technology is not limited to the details of the structures or process steps illustrated in the following description. The present invention may have other embodiments and can be practiced or implemented in different ways. It should also be understood that metal complexes and other compounds herein can be described using structural formulas having specific stereochemistry. These descriptions are merely illustrative and should not be construed as limiting the disclosed structures to any particular stereochemistry. Rather, the illustrated structures are intended to encompass all such metal complexes and compounds having the specified chemical formulas.

[0029] In various aspects, metal complexes, methods for preparing these metal complexes, and methods for forming metal-containing thin films using these metal complexes via vapor deposition processes are provided.

[0030] As used herein, the terms "metal complex" (or more simply, "complex") and "precursor" are used interchangeably and refer to a metal-containing molecule or compound that can be used to prepare a metal-containing film by a vapor deposition process such as ALD or CVD. Metal complexes can be deposited, adsorbed, decomposed, transported, and / or passed through a substrate or its surface to form a metal-containing film. In one or more embodiments, the metal complexes disclosed herein are nickel complexes.

[0031] As used herein, the term "metal-containing film" includes not only the basic metal film as more fully defined below, but also films containing a metal with one or more elements, such as metal oxide films, metal nitride films, metal silicide films, etc. As used herein, the terms "basic metal film" and "pure metal film" are used interchangeably and refer to a film composed of or essentially composed of pure metal. For example, a basic metal film may contain 100% pure metal, or a basic metal film may contain at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, at least about 99.9%, at least about 99.99% pure metal, and one or more impurities. Unless the context otherwise requires, the term "metal film" should be construed as referring to a basic metal film. In some embodiments, the metal-containing film is a basic scandium film or a basic yttrium film. In other embodiments, the metal-containing film is a scandium oxide film, a yttrium oxide film, a scandium nitride film, a yttrium nitride film, a scandium silicide film, or a yttrium silicide film. Such scandium-containing and yttrium-containing films can be prepared from various scandium complexes and yttrium complexes described herein.

[0032] As used herein, the term "vapor deposition process" is used to refer to any type of vapor deposition technique, including but not limited to CVD and ALD. In various embodiments, CVD may take the form of conventional (i.e., continuous flow) CVD, liquid injection CVD, or light-assisted CVD. CVD may also take the form of pulsed techniques, such as pulsed CVD. In other embodiments, ALD may take the form of conventional (e.g., pulsed injection) ALD, liquid injection ALD, light-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. The term "vapor deposition process" also includes the various vapor deposition techniques described in Chemical Vapor Deposition: Precursors, Processes, and Applications; Jones, AC; Hitchman, ML, Eds. The Royal Society of Chemistry: Cambridge, 2009; Chapter 1, pp 1–36.

[0033] The term "alkyl" (alone or in combination with another term(s)) refers to a saturated hydrocarbon chain having 1 to 12 carbon atoms in length, such as, but not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc. Alkyl groups can be straight-chain or branched. "Alkyl" is intended to encompass all isomeric forms of alkyl groups. For example, as used herein, propyl includes n-propyl and isopropyl; butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl; and pentyl includes n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, and 3-pentyl. Furthermore, as used herein, "Me" refers to methyl, "Et" to ethyl, "Pr" to propyl, "i-Pr" to isopropyl, "Bu" to butyl, "t-Bu" to tert-butyl, "iBu" to isobutyl, and "Pn" and "NPn" to neopentyl. In some embodiments, the alkyl group is a C1-C5 alkyl group or a C1-C4 alkyl group.

[0034] The term "allyl" refers to an allyl (C3H5) ligand bonded to a metal center. As used herein, the allyl ligand has a resonant double bond and all three carbon atoms of the allyl ligand are bonded by π-bonds with an η bond. 3 - Coordinated to the metal center. Therefore, the complexes of this invention are π-complexes. Both of these characteristics are indicated by dashed bonds. When the allyl moiety is replaced by an X group, X... 1 The group replaces the hydrogen in the allyl group to become [X]. 1 C3H4]; when using X 1 and X 2 When two X groups are substituted, it becomes [X] 1 X 2 [C3H3], where X1 and X 2 But the same or different, etc.

[0035] The term "silyl group" refers to a-SiZ 1 Z 2 Z 3 atomic groups, of which Z 1 Z 2 and Z 3 Each is independently selected from the group consisting of hydrogen and optionally substituted alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, amino, and combinations thereof.

[0036] The term "trialkylsilyl" refers to a-SiZ 4 Z 5 Z 6 atomic groups, of which Z 5 Z 6 and Z 7 It is an alkyl group, and Z is therein. 5 Z 6 and Z 7 However, the same or different alkyl groups are acceptable. Non-limiting examples of trialkylsilanes include trimethylsilane (TMS), triethylsilane (TES), triisopropylsilane (TIPS), and tert-butyldimethylsilane (TBDMS).

[0037] The deposition of some metals, including scandium and yttrium, is difficult to achieve due to thermal stability issues that prevent deposition, either due to instability or excessive stability. The organometallic complexes disclosed in this invention allow for control over physical properties and provide increased stability and simple, high-yield synthesis. In this regard, the metal complexes provided herein are promising candidates for preparing metal-containing thin films in various vapor deposition processes.

[0038] Therefore, according to one aspect, a metal complex of formula I is provided: [(R 1 ) n Cp]2M 1 L 1 (I), where M 1 It is a Group 3 metal or a lanthanide element; each R 1 Independently hydrogen, C1-C5 alkyl or silyl; n is 1, 2, 3, 4 or 5; Cp is a cyclopentadienyl ring; L 1 Choose Free NR 2 R 3 , N(SiR 4 R 5 R 6 )2, 3, 5-R 7 R 8 -C3HN2、1-(R 32C3H4, 1-R 33 -3-R 34 -C3H3、R 35 ,R 36 -C3HO2、R 12 N = CC - NR 13 R 14 R 15 N-CH2-CH2-NR 16 -CH2-CH2-NR 17 R 18 and R 19 O-CH2-CH2-NR 20 -CH2-CH2-OR 21 The group consisting of R; 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Each is independently hydrogen or a C1-C5 alkyl group; and R 32 R 33 R 34 R 35 and R 36 Each is independently an alkyl or silyl group.

[0039] In some implementations, M 1 The group consisting of scandium, yttrium, and lanthanum can be selected. In other embodiments, M 1 The group can be composed of free scandium and yttrium. Specifically, M 1 It can be scandium.

[0040] In some implementations, when M 1 It is yttrium and L 1 It is 3,5-R 7 R 8 When -C3HN2, R 1 It is a C1-C5 alkyl or silyl group, and / or wherein when M 1 It is yttrium and L 1 It is N(SiR) 4 R 5 R 6 When n = 2, n is 1, 2, 3 or 4.

[0041] In some implementations, L 1 Choose Free NR 2 R 3 , N(SiR 4 R 5 R 6 )2, 3, 5-R 7 R 8 -C3HN2、1-(R 32 C3H4, 1-R 33 -3-R 34 -C3H3 and R 35 ,R 36 The group consists of -C3HO2.

[0042] In some implementations, L 1 Choose Free NR 2 R 3 , N(SiR 4 R 5 R 6 )2, 3, 5-R 7 R 8 The group consists of -C3HN2, 1-(SiMe3)C3H4 (trimethylsilyl allyl), 1,3-bis(SiMe3)2C3H3 (bis(trimethylsilyl) allyl) and 6-methyl-2,4-heptadecyl ester.

[0043] R 1 It can be the same or different each time it appears. For example, if n is 2, 3, 4, or 5, each R 1 They can all be hydrogen, all be alkyl (such as C1-C5 alkyl), or all be silyl. Alternatively, if n is 2, 3, 4, or 5, each R 1 They can be different. For example, if n is 2, the first R... 1 But hydrogen and the second R 1 However, it can be alkyl (such as C1-C5 alkyl) or silyl.

[0044] R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20and R 21 It can be the same or different each time it appears. For example, R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 They can all be hydrogen or all be alkyl (such as C1-C5 alkyl groups).

[0045] In one implementation, R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Up to 16 (inclusive) of the atoms in the R group can all be hydrogen. For example, R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 At least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine, at least ten, at least eleven, at least twelve, at least thirteen, at least fourteen, at least fifteen, or at least sixteen of them may be hydrogen.

[0046] In another embodiment, R2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Up to 16 (inclusive) of them can each be an alkyl group independently. For example, R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 At least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine, at least ten, at least eleven, at least twelve, at least thirteen, at least fourteen, at least fifteen, or at least sixteen of them may be alkyl groups.

[0047] R 32 R 33 and R 34 It can be the same or different each time it appears. For example, R 32 R 33 and R 34 They can all be alkyl (such as C1-C5 alkyl) or all be silyl (such as SiMe3).

[0048] R 35 and R 36 It can be the same or different each time it appears. For example, R 35 and R 36 They can all be the same or different alkyl groups (such as C1-C5 alkyl groups), or R 35 and R 36 They can all be the same or different silyl groups (such as SiMe3), or R 35 and R 36It can be alkyl (such as C1-C5 alkyl) and silyl (such as SiMe3).

[0049] In one implementation, R 32 R 33 R 34 R 35 and R 36 At most two (inclusive) of them can be alkyl groups independently. For example, R 32 R 33 R 34 R 35 and R 36 At least one or at least two of them may be alkyl groups.

[0050] In another embodiment, R 32 R 33 R 34 R 35 and R 36 At most two (inclusive) of them can be silyl groups, each independently. For example, R 32 R 33 R 34 R 35 and R 36 At least one or at least two of them may be silyl groups.

[0051] The alkyl group discussed herein can be a C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl. In another embodiment, the alkyl group is a C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl. The alkyl group can be straight-chain or branched. In particular, the alkyl group is straight-chain. In another embodiment, the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and neopentyl.

[0052] The silyl groups discussed in this article can be Si(alkyl)3, Si(alkyl)2H, and Si(alkyl)H2, wherein the alkyl group is as described above, but is not limited thereto. Examples of silyl groups include, but are not limited to, SiH3, SiMeH2, SiMe2H, SiMe3, SiEtH2, SiEt2H, SiEt3, SiPrH2, SiPr2H, SiPr3, SiBuH2, SiBu2H, and SiBu3, wherein “Pr” includes “i-Pr” and “Bu” includes “t-Bu”.

[0053] In some implementations, each R 1It can be independently hydrogen, C1-C4 alkyl, or silyl. In another embodiment, each R 1 It can be independently hydrogen, methyl, ethyl, propyl, or silyl. In another embodiment, each R 1 It can be independently hydrogen, methyl, or ethyl. Specifically, each R... 1 It can be methyl.

[0054] In some implementations, R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Each can be independently hydrogen or a C1-C4 alkyl group. In another embodiment, R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Each can be independently hydrogen, methyl, ethyl, or propyl. In another embodiment, R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21Each can be independently hydrogen, methyl, or ethyl. Specifically, R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Each can be either hydrogen or methyl.

[0055] In some implementations, each R 1 It can be independently hydrogen, C1-C4 alkyl, or silyl; and R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 and R 18 Each can be independently hydrogen or a C1-C4 alkyl group.

[0056] In other implementations, each R 1 It can be independently hydrogen, methyl, ethyl, propyl, or silyl; and R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Each can be hydrogen, methyl, ethyl, or propyl, independently.

[0057] In some implementations, each R 1 It can be hydrogen, methyl, or ethyl independently; and R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Each can be independently hydrogen, methyl, or ethyl. In another embodiment, each R 1 It can be methyl and R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Each can be either hydrogen or methyl.

[0058] In some implementations, R 32 R 33 R 34 R 35 and R 36 Each can be an alkyl or silyl group, each of which can be independently C1-C5. In other embodiments, R 32 R 33 R 34 R 35 and R 36 Each can be an alkyl or silyl group, each of which can be independently C1-C4. In other embodiments, R 32 R 33 R 34 R 35 and R 36 Each can be independently methyl, ethyl, propyl, or silyl. In other embodiments, R 32 R 33 R 34 R35 and R 36 Each can be independently methyl, ethyl, or silyl. In other embodiments, R 32 R 33 R 34 R 35 and R 36 Each of these can be independently silyl group, such as, but not limited to, SiH3, SiMeH2, SiMe2H, SiMe3, SiEtH2, SiEt2H, SiEt3, SiPrH2, SiPr2H, SiPr3, SiBuH2, SiBu2H, and SiBu3. In particular, R... 32 R 33 R 34 R 35 and R 36 Each can be independently SiMe3. Specifically, R 32 R 33 and R 34 Each can be independently SiMe3. In other embodiments, R 35 and R 36 Each can be an alkyl group, C1-C4, particularly methyl and / or butyl.

[0059] In some implementations, L 1 Choose Free NR 2 R 3 , N(SiR 4 R 5 R 6 )2、1-(R 32 C3H4 and 1-R 33 -3-R 34 The group consists of -C3H3.

[0060] In another embodiment, L 1 Choose Free NR 2 R 3 , N(SiR 4 R 5 R 6 )2, 1-(SiMe3)C3H4, 1,3-bis(SiMe3)2C3H3 and R 35 ,R 36 The group consists of -C3HO2.

[0061] In another implementation, each R 1 It can be independently hydrogen, C1-C4 alkyl, or silyl; and L 1 For NR 2 R 3 , where R 2 and R 3Each can be independently hydrogen or a C1-C4 alkyl group. In another embodiment, each R 1 It can be independently hydrogen, methyl, ethyl, propyl, or silyl; and R 2 R 3 Each can be independently hydrogen, methyl, ethyl, or propyl. In another embodiment, each R... 1 It can be hydrogen, methyl, or ethyl independently; and R 2 R 3 Each can be independently hydrogen, methyl, or ethyl. Specifically, each R... 1 It can be methyl; and R 2 R 3 Each can be hydrogen, methyl, or ethyl independently.

[0062] In another implementation, each R 1 It can be independently hydrogen, C1-C4 alkyl, or silyl; and L 1 N(SiR) 4 R 5 R 6 )2, where R 4 R 5 and R 6 Each can be independently hydrogen or a C1-C4 alkyl group. In another embodiment, each R 1 It can be independently hydrogen, methyl, ethyl, propyl, or silyl; and R 4 R 5 and R 6 Each can be independently hydrogen, methyl, ethyl, or propyl. In another embodiment, each R... 1 It can be hydrogen, methyl, or ethyl independently; and R 4 R 5 and R 6 Each can be independently hydrogen, methyl, or ethyl. Specifically, each R... 1 It can be methyl; and R 4 R 5 and R 6 Each can be hydrogen, methyl, or ethyl independently.

[0063] In some implementations, each R 1 It can be independently hydrogen, C1-C4 alkyl, or silyl; and L 1 It can be 3,5-R 7 R 8 -C3HN2, where R 7 and R 8 Each can be independently hydrogen or a C1-C5 alkyl group. In other embodiments, each R... 1 It can be independently hydrogen, methyl, ethyl, propyl, or silyl. In other embodiments, each R1 It can be hydrogen, methyl, or ethyl independently. Specifically, each R... 1 It can be methyl. In other embodiments, R 7 and R 8 Each can be independently hydrogen or a C1-C4 alkyl group or hydrogen. In other embodiments, R 7 and R 8 Each can be independently methyl, ethyl, propyl, or hydrogen. In particular, R 7 and R 8 Each can be either methyl or ethyl.

[0064] In some implementations, each R 1 It can be independently hydrogen, C1-C4 alkyl, or silyl; and L 1 It can be 1-(R) 32 C3H4, where R 32 It can be a C1-C5 alkyl or silyl group. In another embodiment, R 32 It can be a C1-C4 alkyl or silyl group. In other embodiments, each R 1 It can be independently hydrogen, methyl, ethyl, propyl or silyl and R 32 It can be silyl alkyl. In another embodiment, each R... 1 It can be independently hydrogen, methyl, or ethyl and R 32 It can be a silyl group, such as, but not limited to, SiH3, SiMeH2, SiMe2H, SiMe3, SiEtH2, SiEt2H, SiEt3, SiPrH2, SiPr2H, SiPr3, SiBuH2, SiBu2H, and SiBu3. Specifically, each R... 1 It can be independently methyl or ethyl and R 32 It could be SiMe3.

[0065] In other implementations, each R 1 It can be independently hydrogen, C1-C4 alkyl, or silyl; and L 1 It can be 1-R 33 -3-R 34 -C3H3, where R 33 and R 34 It can be a C1-C5 alkyl or silyl group. In another embodiment, each R 1 It can be independently hydrogen, methyl, ethyl, propyl, or silyl, and R 33 and R 34 Each can be independently a C1-C4 alkyl or silyl group and R 32 It can be silyl alkyl. In another embodiment, each R... 1 It can be independently hydrogen, methyl, or ethyl, and R33 and R 34 Each can be independently silyl group, such as, but not limited to, SiH3, SiMeH2, SiMe2H, SiMe3, SiEtH2, SiEt2H, SiEt3, SiPrH2, SiPr2H, SiPr3, SiBuH2, SiBu2H, and SiBu3. Specifically, each R... 1 It can be independently methyl or ethyl, and R 33 and R 34 It could be SiMe3.

[0066] In other implementations, each R 1 It can be independently hydrogen, C1-C4 alkyl, or silyl; and L 1 It can be R 35 ,R 36 -C3HO2, where R 35 and R 36 It can be a C1-C5 alkyl or silyl group. In another embodiment, each R 1 It can be independently hydrogen, methyl, ethyl or silyl and R 35 and R 36 Each can be an alkyl or silyl group, each of which can be independently C1-C4. In another embodiment, each R 1 It can be independently hydrogen, methyl, or ethyl and R 35 and R 36 Each can be independently silyl group, such as, but not limited to, SiH3, SiMeH2, SiMe2H, SiMe3, SiEtH2, SiEt2H, SiEt3, SiPrH2, SiPr2H, SiPr3, SiBuH2, SiBu2H, and SiBu3. In another embodiment, each R 1 It can be independently hydrogen, methyl, or ethyl and R 35 and R 36 Each can be an alkyl group of C1-C4, particularly methyl and / or butyl. Specifically, each R... 1 It can be independently methyl or ethyl and R 35 and R 36 Each can be independently methyl or butyl. Specifically, each R... 1 It can be independently methyl or ethyl and R 35 and R 36 It can be SiM e3 .

[0067] Table 1 below provides examples of metal complexes that structurally correspond to Formula I.

[0068] Table 1

[0069]

[0070] In one embodiment, a mixture of two or more organometallic complexes of Formula I is provided.

[0071] In another embodiment, a metal complex of formula II is provided: [((R 9 ) n Cp)2M 2 L 2 ]2(II), where M 2 It is a Group 3 metal or a lanthanide element; each R 9 Independently hydrogen or a C1-C5 alkyl group; n is 1, 2, 3, 4 or 5; Cp is a cyclopentadienyl ring; and L 2 Choose freely Cl, F, Br, I, 3,5-R 10 R 11 -C3HN2、R 22 N = CC - NR 23 R 24 R 25 N-CH2-NR 26 -CH2-NR 27 R 28 and R 29 O-CH2-NR 30 -CH2-OR 31 The group consisting of R; 10 R 11 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 29 R 30 and R 31 Each is independently hydrogen or a C1-C5 alkyl group.

[0072] In some implementations, M 2 The group consisting of scandium, yttrium, and lanthanum is selected. In other embodiments, M... 2 The group can be composed of free scandium and yttrium. Specifically, M 2 It can be scandium.

[0073] In other embodiments, where M 2 For scandium and L 2 When it is Cl, R 9 It is a C1-C5 alkyl group.

[0074] In some implementations, L 2 Choose freely from Cl, F, Br, I and 3,5-R 10R 11 The group consists of -C3HN2.

[0075] R 9 It can be the same or different each time it appears. For example, if n is 2, 3, 4, or 5, each R 9 They can all be hydrogen or all be alkyl (e.g., C1-C5 alkyl). Alternatively, if n is 2, 3, 4, or 5, each R 1 They can be different. For example, if n is 2, the first R... 9 But hydrogen and the second R 9 However, it can be an alkyl group (such as C1-C5 alkyl groups).

[0076] R 10 R 11 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 29 R 30 and R 31 It can be the same or different each time it appears. For example, R 10 R 11 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 29 R 30 and R 31 They can all be hydrogen or all be alkyl (such as C1-C5 alkyl groups).

[0077] In one implementation, R 10 R 11 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 29 R 30 and R 31 Up to 11 (inclusive) of them can each be hydrogen. For example, R 10 R 11 R 22 R 23 R 24 R 25 R 26 R27 R 28 R 29 R 30 and R 31 At least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine, at least ten, or at least eleven of them can be hydrogen.

[0078] In another embodiment, R 10 R 11 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 29 R 30 and R 31 Up to 11 (inclusive) of them can each be an alkyl group independently. For example, R 10 R 11 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 29 R 30 and R 31 At least one, at least two, at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine, at least ten, or at least eleven of them may be alkyl groups.

[0079] The alkyl group discussed herein can be a C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl. In another embodiment, the alkyl group is a C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl. The alkyl group can be straight-chain or branched. In particular, the alkyl group is straight-chain. In another embodiment, the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and neopentyl.

[0080] In some implementations, each R 9 It can be an alkyl group of C1-C5 independently. In other embodiments, each R 9 It can be hydrogen or a C1-C4 alkyl group independently. In another embodiment, each R 9It can be hydrogen, methyl, ethyl, or propyl independently. In another embodiment, each R 9 It can be hydrogen, methyl, or ethyl independently. Specifically, each R... 9 It can be methyl.

[0081] In one particular implementation, M 2 Can be scandium and each R 9 It can be an alkyl group of C1-C4 independently. In another embodiment, M 2 Can be scandium, L 2 It can be Cl and each R 9 It can be methyl, ethyl, or propyl independently. Specifically, each R... 9 It can be methyl or ethyl independently.

[0082] In another specific implementation, M 2 It can be yttrium and each R 9 It can be an alkyl group of C1-C4 independently. In another embodiment, M 2 It can be yttrium, L 2 It can be 3,5-R 10 R 11 -C3HN2, each R 9 It can be independently methyl, ethyl, or propyl and R 10 and R 9 Each is independently a C1-C5 alkyl group. Specifically, each R... 9 It can be methyl or ethyl independently.

[0083] Table 2 below provides examples of metal complexes that structurally correspond to Formula II.

[0084] Table 2

[0085]

[0086] Other metal complexes provided in this article include Y(MeCp)2(3,5-tBu2-C3HN2)(THF), Y(MeCp)2(3,5-MePn-C3HN2)(THF), and Y(MeCp)2(3,5-tBu,iBu-C3HN2)(THF), where "THF" refers to tetrahydrofuran as used herein.

[0087] For example, the metal complexes provided in this article can be prepared as shown in Scheme A below.

[0088]

[0089] Option A

[0090] The metal complexes provided herein can be used to prepare metal-containing films, such as basic scandium films, basic yttrium films, scandium oxide films, yttrium oxide films, scandium nitride films, yttrium nitride films, scandium silicide films, and yttrium silicide films. Therefore, according to another aspect, the present invention provides a method for forming metal-containing films by a vapor deposition process. As disclosed herein, the method includes vaporizing at least one organometallic complex structurally corresponding to formula I, formula II, or a combination thereof. For example, this may include (1) vaporizing at least one complex and (2) transferring at least one complex to a substrate surface or passing at least one complex through a substrate (and / or decomposing at least one complex on the substrate surface).

[0091] A variety of substrates can be used in the deposition methods disclosed herein. For example, the metal complexes disclosed herein can be transported, passed through, or deposited on a variety of substrates or their surfaces, such as, but not limited to, silicon, crystalline silicon, Si(100), Si(111), silicon oxide, glass, strained silicon, silicon on insulator (SOI), doped silicon or silicon oxide (e.g., carbon-doped silicon oxide), silicon nitride, germanium, gallium arsenide, tantalum, tantalum nitride, aluminum, copper, ruthenium, titanium, titanium nitride, tungsten, tungsten nitride, and any number of other substrates common in nanoscale device fabrication processes (e.g., semiconductor manufacturing processes). As those skilled in the art will understand, the substrate may be exposed to pretreatment processes to polish, etch, reduce, oxidize, hydroxylate, anneal, and / or bake the substrate surface. In one or more embodiments, the substrate surface includes a hydrogen-terminated surface.

[0092] In certain embodiments, the metal complex can be dissolved in suitable solvents such as hydrocarbon or amine solvents to facilitate the vapor deposition process. Suitable hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as hexane, heptane, and nonane; aromatic hydrocarbons such as toluene and xylene; and alicyclic ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Examples of suitable amine solvents include, but are not limited to, octylamine and N,N-dimethyldodecylamine. For example, the metal complex can be dissolved in toluene to obtain a solution with a concentration between about 0.05 M and about 1 M.

[0093] In another embodiment, at least one metal complex can be delivered to the substrate surface "purely" (without being diluted by a carrier gas).

[0094] In one implementation, the vapor deposition process is chemical vapor deposition.

[0095] In another embodiment, the vapor deposition process is atomic layer deposition.

[0096] ALD and CVD methods encompass various types of ALD and CVD processes, such as, but not limited to, continuous or pulsed injection processes, liquid injection processes, light-assisted processes, plasma-assisted processes, and plasma-enhanced processes. For clarity, the methods of this technique specifically include direct liquid injection processes. For example, in direct liquid injection CVD (“DLI-CVD”), a solid or liquid metal complex is dissolved in a suitable solvent and the resulting solution is injected into a vaporization chamber as a means of vaporizing the metal complex. The vaporized metal complex is then transported / delivered to the substrate surface. Generally, DLI-CVD is particularly useful when the metal complex exhibits relatively low volatility or is difficult to vaporize.

[0097] In one embodiment, conventional or pulsed CVD is used to vaporize at least one metal complex and / or pass at least one metal complex through a substrate surface to form a metal-containing film. For example, conventional CVD processes can be found in: Smith, Donald (1995). Thin-Film Deposition: Principles and Practice. McGraw-Hill.

[0098] In one embodiment, the CVD growth conditions for the metal complexes disclosed herein include, but are not limited to:

[0099] a. Substrate temperature: 50~600℃

[0100] b. Carburetor temperature (metal precursor temperature): 0~200℃

[0101] c. Reactor pressure: 0–100 Torr

[0102] d. Argon or nitrogen carrier gas flow rate: 0–500 sccm

[0103] e. Oxygen flow rate: 0–500 sccm

[0104] f. Hydrogen flow rate: 0–500 sccm

[0105] g. Running time: will vary depending on the desired film thickness.

[0106] In another embodiment, photo-assisted CVD is used to vaporize at least one metal complex disclosed herein and / or to form a metal-containing film by passing at least one metal complex disclosed herein through a substrate surface.

[0107] In another embodiment, conventional (e.g., pulse injection) ALD is used to vaporize at least one metal complex disclosed herein and / or to form a metal-containing film by passing at least one metal complex disclosed herein through a substrate surface. For example, conventional ALD processes can be found in: George SM, et al. J. Phys. Chem., 1996, 100, 13121–13131.

[0108] In another embodiment, liquid injection ALD is employed to vaporize at least one metal complex disclosed herein and / or to form a metal-containing film by passing at least one metal complex disclosed herein through a substrate surface, wherein at least one metal complex is delivered to the reaction chamber by direct liquid injection, in contrast to vapor drawn in by a bubbler. For example, the liquid injection ALD process can be found in: Potter RJ, et al., Chem. Vap. Deposition, 2005, 11(3), 159–169.

[0109] Examples of ALD growth conditions for metal complexes disclosed in this paper include, but are not limited to:

[0110] a. Substrate temperature: 0~400℃

[0111] b. Carburetor temperature (metal precursor temperature): 0~200℃

[0112] c. Reactor pressure: 0–100 Torr

[0113] d. Argon or nitrogen carrier gas flow rate: 0–500 sccm

[0114] e. Reaction gas flow rate: 0–500 sccm

[0115] f. Pulse sequence (metal complex / purge / reactive gas / purge): will vary depending on the size of the reaction chamber.

[0116] g. Number of cycles: will vary depending on the desired film thickness.

[0117] In another embodiment, photo-assisted ALD is employed to vaporize at least one metal complex disclosed herein and / or to form a metal-containing film by passing at least one metal complex disclosed herein through a substrate surface. For example, a photo-assisted ALD process can be found in U.S. Patent No. 4,581,249.

[0118] In another embodiment, plasma-assisted or plasma-enhanced ALD is used to vaporize at least one metal complex disclosed herein and / or to form a metal-containing film by passing at least one metal complex disclosed herein through a substrate surface.

[0119] In another embodiment, the method of forming a metal-containing film on a substrate surface includes: in an ALD process, exposing the substrate to a vapor phase metal complex according to one or more embodiments described herein to form a layer on the surface comprising a metal complex bonded to the surface using a metal center (e.g., nickel); in an ALD process, exposing the substrate with the bonded metal complex to a co-reactant to allow an exchange reaction to occur between the bonded metal complex and the co-reactant, thereby dissociating the bonded metal complex and generating a first basic metal layer on the substrate surface; and repeating the ALD process and treatment sequentially.

[0120] The reaction time, temperature, and pressure are selected to form a metal-surface interaction and obtain a layer on the substrate surface. The reaction conditions for the ALD reaction are selected based on the properties of the metal complex. Deposition can be carried out at atmospheric pressure, but is typically performed under reduced pressure. The vapor pressure of the metal complex should be low enough to be practical for this application. The substrate temperature should be high enough to maintain the integrity of the bonds between the metal atoms on the surface and prevent the thermal decomposition of the gaseous reactants. However, the substrate temperature should also be high enough to keep the source material (e.g., reactants) in the gas phase and to provide sufficient activation energy for the surface reaction. The appropriate temperature depends on various parameters, including the specific metal complex used and the pressure. The properties of the specific metal complex used in the ALD deposition method disclosed herein can be evaluated using methods known in the art, allowing for the selection of appropriate temperatures and pressures for the reaction. Generally, the presence of functional groups with lower molecular weights and increased rotational entropy of the ligand spheres results in a melting point that yields a liquid at typical transport temperatures and increased vapor pressures.

[0121] The metal complex used in the deposition method must meet all the requirements of sufficient vapor pressure, sufficient thermal stability at the selected substrate temperature, and sufficient reactivity to react on the substrate surface without unwanted impurities in the film. Sufficient vapor pressure ensures that the source compound molecules are present at a sufficient concentration on the substrate surface to allow for a complete self-saturation reaction. Sufficient thermal stability ensures that the source compound does not undergo thermal decomposition that produces impurities in the film.

[0122] Therefore, the metal complexes disclosed herein for use in these methods can be liquids, solids, or gases. Typically, the metal complexes are liquids or solids at room temperature, with a vapor pressure sufficient to allow for continuous vapor delivery to the processing chamber.

[0123] In one embodiment, a base metal, metal nitride, metal oxide, or metal silicide film can be formed by deposition using at least one metal complex disclosed herein, which can be independent or in combination with a co-reactant. In this regard, the co-reactant can be deposited, transported, or passed through a substrate surface, either independently or in combination with at least one metal complex. As will be readily apparent, the specific co-reactant used will determine the type of metal-containing film obtained. Examples of such co-reactants include, but are not limited to, hydrogen, hydrogen plasma, oxygen, air, water, alcohols, H₂O₂, N₂O, ammonia, hydrazine, borane, silane, ozone, or any combination of two or more thereof. Examples of suitable alcohols include, but are not limited to, methanol, ethanol, propanol, isopropanol, tert-butanol, etc. Examples of suitable boranes include, but are not limited to, negatively charged (i.e., reduced) boranes such as borane, diborane, triborane, etc. Examples of suitable silanes include, but are not limited to, negatively charged silanes such as silane, disilane, propane, etc. Suitable examples of hydrazine include, but are not limited to, hydrazine (N2H4), hydrazine optionally substituted with one or more alkyl groups (i.e., alkyl-substituted hydrazine), such as methylhydrazine, tert-butylhydrazine, N,N- or N,N'-dimethylhydrazine, and hydrazine optionally substituted with one or more aryl groups (i.e., aryl-substituted hydrazine), such as phenylhydrazine, etc.

[0124] In one embodiment, the metal complexes disclosed herein are pulsed and alternately pulsed with oxygen-containing co-reactants to the substrate surface to provide a metal oxide film. Examples of such oxygen-containing co-reactants include, but are not limited to, H2O, H2O2, O2, ozone, air, isopropanol, tert-butanol, or N2O.

[0125] In other embodiments, the co-reactants include a reducing agent, such as hydrogen. In these embodiments, a basic metal film is obtained. In certain embodiments, the basic metal film is composed of pure metal, or substantially pure metal. Such a pure metal film may contain more than about 80, 85, 90, 95, or 98% metal. In more specific embodiments, the basic metal film is a scandium film or a yttrium film.

[0126] In other embodiments, a metal nitride film is formed using a co-reactant, either independently or in combination with a co-reactant, to a reaction chamber for deposition. The co-reactants are, for example, but not limited to, ammonia, hydrazine, and / or other nitrogen-containing compounds (e.g., amines). A variety of such co-reactants can be used. In a further embodiment, the metal nitride film is a nickel nitride film.

[0127] In another embodiment, a hybrid metal film is formed by a vapor deposition process, wherein the vapor deposition process vaporizes a combination of at least one metal complex disclosed herein and a second metal complex, wherein the vaporization of the at least one metal complex and the second metal complex need not be performed simultaneously, and the second metal complex includes metals other than the at least one metal complex disclosed herein.

[0128] In certain implementations, this technique is used in applications on substrates such as silicon chips, for example, dynamic random access memory (DRAM) and complementary metal-oxide-semiconductor (CMOS) for storage and logic applications.

[0129] Any metal complexes disclosed herein can be used to prepare basic metal films, metal oxide films, metal nitride films, and / or metal silicide films. These films can be used as oxidation catalysts, anode materials (such as solid oxide fuel cells or lithium-ion battery anodes), conductive layers, sensors, diffusion barrier layers / coatings, superconducting and non-superconducting materials / coatings, triboelectric coatings, and / or protective coatings. It will be understood by one of ordinary skill in the art that film properties (e.g., conductivity) depend on multiple factors, such as the metal used for deposition, the presence or absence of co-reactants and / or co-complexes, the thickness of the resulting film, the parameters used in growth and subsequent processing, and the substrate.

[0130] There are fundamental differences between thermally driven CVD processes and reaction-driven ALD processes. The requirements for precursor properties differ significantly for optimal performance. In CVD, clean thermal decomposition of the complexes is crucial to deposit the desired species onto the substrate. However, such thermal decomposition must be avoided in ALD. In ALD, the reaction between input reagents must be rapid at the surface to form the target material on the substrate. However, any such reaction between species in CVD is detrimental because they mix in the gas phase before reaching the substrate, potentially leading to particle formation. Due to the less stringent thermal stability requirements of CVD precursors, it is generally accepted that a good CVD precursor is not necessarily a good ALD precursor. In this invention, the metal complexes of Formula I possess sufficient thermal stability and reactivity with selected co-reactants to be used as ALD precursors, and they have clean decomposition pathways at higher temperatures to similarly form the desired material via the CVD process. Therefore, the metal complexes of Formula I are advantageous for use as viable ALD and CVD precursors.

[0131] Throughout this specification, the terms "one embodiment," "some embodiments," "one or more embodiments," or "embodiment" refer to a specific feature, structure, material, or property described in connection with that embodiment, which is included in at least one embodiment of the present invention. Therefore, the appearance of phrases such as "in one or more embodiments," "in some embodiments," "in one embodiment," or "in an embodiment" throughout this specification does not necessarily refer to the same embodiment of the present invention. Furthermore, specific features, structures, materials, or properties may be combined in any suitable manner in one or more embodiments.

[0132] Although the present technology has been described with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the present technology. Various modifications and alterations to the methods and apparatus of the present technology can be made without departing from the spirit and scope of the present technology, and will be apparent to those skilled in the art. Therefore, the present technology is intended to include various modifications and alterations within the scope of the appended claims and their equivalents. The present technology, as generally described below, will be more readily understood by referring to the embodiments provided below in an illustrative rather than limiting manner.

[0133] The present invention may additionally or alternatively include one or more of the following embodiments.

[0134] Implementation Method 1. A metal complex structurally corresponding to Formula I: [(R 1 ) n Cp]2M 1 L 1 (I), where M 1 It is a Group 3 metal or a lanthanide element (e.g., scandium, yttrium, and lanthanum); each R 1 Independently hydrogen, C1-C5 alkyl or silyl; n is 1, 2, 3, 4 or 5; Cp is a cyclopentadienyl ring; L 1 Choose Free NR 2 R 3 , N(SiR 4 R 5 R 6 )2, 3, 5-R 7 R 8 -C3HN2、1-(R 32 C3H4, 1-R 33 -3-R 34 -C3H3 and R 35 ,R 36 -C3HO2、R 12 N = CC - NR 13 R 14 R 15 N-CH2-CH2-NR16 -CH2-CH2-NR 17 R 18 and R 19 O-CH2-CH2-NR 20 -CH 2- CH2-OR 21 The group consisting of R; 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 19 R 20 and R 21 Each is independently hydrogen or a C1-C5 alkyl group; and R 32 R 33 R 34 R 35 and R 36 Each is independently an alkyl or silyl group; optionally, when M 1 It is yttrium and L 1 It is 3,5-R 7 R 8 When -C3HN2, R 1 It is a C1-C5 alkyl or silyl group; and optionally, when M 1 It is yttrium and L 1 It is N(SiR) 4 R 5 R 6 When n = 2, n is 1, 2, 3 or 4.

[0135] Implementation Method 2. The metal complex according to Implementation Method 1, wherein each R 1 Independently hydrogen, C1-C4 alkyl or silyl; and R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each is independently a C1-C4 alkyl group; and R 32 R 33 R 34 R 35 and R 36 Each is independently a C1-C5 alkyl or silyl group.

[0136] Implementation Method 3. The metal complex according to Implementation Method 1 or 2, wherein each R 1 Independently, it is hydrogen, methyl, ethyl, propyl, or silyl, preferably hydrogen, methyl, or ethyl, more preferably methyl; and R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each is independently hydrogen, methyl, ethyl, or propyl, preferably hydrogen, methyl, or ethyl, more preferably hydrogen or methyl; and R 32 R 33 R 34 R 35 and R 36 Each of the components is an alkyl or silyl group, which is C1-C4, preferably methyl, ethyl, propyl or silyl, and more preferably SiMe3.

[0137] Implementation Method 4. According to any of the metal complexes in the previous embodiments, wherein each R 1 Independently hydrogen, C1-C4 alkyl or silyl, and L 1 For NR 2 R 3 , where R 2 and R 3 Each is independently hydrogen or a C1-C4 alkyl group.

[0138] Implementation Method 5. The metal complex according to Implementation Method 4, wherein each R 1 Independently, it is hydrogen, methyl, ethyl, propyl, or silyl, preferably hydrogen, methyl, or ethyl, more preferably methyl; and R 2 and R 3 Each of them is independently hydrogen, methyl, ethyl or propyl, preferably hydrogen, methyl or ethyl.

[0139] Implementation Method 6. According to any of the metal complexes in the previous embodiments, wherein each R 1 Independently hydrogen, C1-C4 alkyl or silyl, and L 1 N(SiR) 4 R 5 R 6 )2, where R 4 R 5 and R 6 Each is independently hydrogen or a C1-C4 alkyl group.

[0140] Embodiment 7. The metal complex according to Embodiment 6, wherein each R 1Independently, it is hydrogen, methyl, ethyl, propyl, or silyl, preferably hydrogen, methyl, or ethyl, more preferably methyl; and R 4 R 5 and R 6 Each of them is independently hydrogen, methyl, ethyl or propyl, preferably hydrogen, methyl or ethyl.

[0141] Implementation Method 8. According to any of the metal complexes in the previous embodiments, wherein each R 1 Independently hydrogen, C1-C4 alkyl or silyl, and L 1 For 3,5-R 7 R 8 -C3HN2, where R 7 and R 8 Each is independently hydrogen or a C1-C5 alkyl group.

[0142] Embodiment 9. The metal complex according to Embodiment 8, wherein each R 1 It is independently hydrogen, methyl, ethyl, propyl or silyl, preferably hydrogen, methyl or ethyl, more preferably methyl.

[0143] Implementation Method 10. According to any of the metal complexes in the previous embodiments, wherein each R 1 Independently hydrogen, C1-C4 alkyl or silyl, preferably hydrogen, methyl, ethyl or silyl; and L 1 1-(R) 32 C3H4, where R 32 It is a C1-C5 alkyl or silyl group, preferably R 32 It is methyl, ethyl or silyl, more preferably L 1 It is 1-(SiMe3)C3H4.

[0144] Implementation Method 11. According to any of the metal complexes in the previous embodiments, wherein each R 1 Independently hydrogen, C1-C4 alkyl or silyl, preferably hydrogen, methyl, ethyl or silyl; and L 1 For 1-R 33 -3-R 34 -C3H3, where R 33 and R 34 Each is independently a C1-C5 alkyl or silyl group, preferably R. 33 and R 34 Each is independently methyl, ethyl, or silyl, more preferably L 1 It is 1,3-bis(SiMe3)2C3H3.

[0145] Implementation Method 12. According to any of the metal complexes in the previous embodiments, wherein each R1 Independently hydrogen, C1-C4 alkyl or silyl, preferably hydrogen, methyl, ethyl or silyl; and L 1 For R 35 ,R 36 -C3HO2, where R 35 and R 36 Each is independently a C1-C5 alkyl or silyl group, preferably R. 35 and R 36 Each is independently methyl, ethyl, propyl, butyl, or silyl, more preferably L. 1 It is 6-methyl-2,4-heptadecyl ester, also known as Me,iBu-C3HO2.

[0146] Embodiment 13. According to any of the metal complexes in the previous embodiments, wherein the complex is: Sc(MeCp)2[1-(SiMe3)C3H4], Sc(MeCp)2[1,3-bis(SiMe3)2C3H3], Sc(MeCp)2[N(SiMe3)2], Sc(MeCp)2(3,5-Me2-C3HN2), Sc(MeCp)2(Me,iBu-C3HO2), preferably Sc(MeCp)2[1-(SiMe3)C3H4], Sc(MeCp)2[1,3-bis(SiMe3)2C3H3], Sc(MeCp)2[N(SiMe3)2] and Sc(MeCp)2(3,5-Me2-C3HN2).

[0147] Implementation method 14. A metal complex structurally corresponding to formula II: [((R 9 ) n Cp)2M 2 L 2 ]2(II), where M 2 It is a Group 3 metal or a lanthanide element (e.g., scandium, yttrium, and lanthanum); each R 9 Independently hydrogen or a C1-C5 alkyl group; n is 1, 2, 3, 4 or 5; Cp is a cyclopentadienyl ring; and L 2 Choose freely Cl, F, Br, I, 3,5-R 10 R 11 -C3HN2、R 22 N = CC - NR 23 R 24 R 25 N-CH2-NR 26 -CH2-NR 27 R 28 and R 29 O-CH2-NR 30 -CH2-OR 31 The group consisting of R;10 R 11 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 29 R 30 and R 31 Each is independently hydrogen or a C1-C5 alkyl group; optionally, when M 2 For scandium and L 2 When it is Cl, R 9 It is a C1-C5 alkyl group.

[0148] Embodiment 15. The metal complex according to Embodiment 14, wherein each R 9 It is an alkyl group that is independently C1-C5.

[0149] Embodiment 16. The metal complex according to Embodiment 14 or 15, wherein each R 9 It is independently hydrogen or a C1-C4 alkyl group, preferably hydrogen, methyl, ethyl or propyl, preferably hydrogen, methyl or ethyl, more preferably methyl.

[0150] Embodiment 17. The metal complex according to Embodiment 14, 15 or 16, wherein M 2 For scandium, each R 9 Independently a C1-C4 alkyl group, preferably methyl, ethyl, or propyl, more preferably methyl; and preferably L 2 It is Cl.

[0151] Embodiment 18. The metal complex according to Embodiment 14, 15 or 16, wherein M 2 For yttrium, each R 9 Independently a C1-C5 alkyl group, preferably methyl, ethyl, or propyl, more preferably methyl or ethyl; preferably L 2 For 3,5-R 10 R 11 -C3HN2 and each R 9 It is independent.

[0152] Embodiment 19. A metal complex according to Embodiments 14, 15, 16, 17 or 18, wherein the complex is [Sc(MeCp)2]Cl]2; and [Y(MeCp)2(3,5-MePn-C3HN2)]2.

[0153] Implementation 20. A method for forming a metal-containing film by a vapor deposition process, the method comprising vaporizing at least one metal complex according to any of the preceding embodiments.

[0154] Implementation Method 21. The method according to Implementation Method 20, wherein the vapor deposition process is chemical vapor deposition, preferably pulsed chemical vapor deposition, continuous flow chemical vapor deposition and / or liquid injection chemical vapor deposition.

[0155] Implementation Method 22. The method according to Implementation Method 20, wherein the vapor deposition process is atomic layer deposition, preferably liquid injection atomic layer deposition or plasma-enhanced atomic layer deposition.

[0156] Embodiment 23. According to any one of Embodiments 20, 21 or 22, wherein the metal complex is alternately delivered to the substrate in a pulsed form with a pulse of oxygen source, preferably the oxygen source being selected from the group consisting of H2O, H2O2, O2, ozone, air, isopropanol, tert-butanol or N2O.

[0157] Embodiment 24. The method according to any one of Embodiments 20, 21, 22 or 23 further includes vaporizing at least one co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazine, borane, silane, ozone and any two or more combinations thereof, preferably the at least one co-reactant is hydrazine (e.g. hydrazine (N2H4), N,N-dimethylhydrazine).

[0158] Implementation 25. The method according to any one of Implementation 20, 21, 22, 23 or 24, wherein the method is used in applications of dynamic random access memory or complementary metal-oxide-semiconductor.

[0159] Example

[0160] Unless otherwise stated, all synthesis operations are carried out in an inert atmosphere (e.g., pure nitrogen or argon) using techniques known in the art for handling air-sensitive materials (e.g., Schranke technique).

[0161] Example 1: Preparation of Complex 11 ([Sc(MeCp)2Cl]2)

[0162] ScCl3 (15.5 g, 0.102 mol) and KMeCp (24.2 g, 0.205 mol) were placed in a 500 mL Schrank flask equipped with a magnetic stirrer, followed by the addition of anhydrous diethyl ether (200 mL). The mixture was stirred for 12 hours under a nitrogen atmosphere at room temperature (~18°C to ~24°C) to obtain a brownish-red suspension. The solvent was removed under pressure, and the resulting solid was extracted with 5 × 50 mL toluene, followed by filtration through a medium glass frit. The solvent was removed from the filtrate under reduced pressure to give the final product as a yellow powder (16.4 g, 0.0344 mol, 67% yield). 1¹H NMR (C6D6): δ 2.02 (¹²H, MeC₅H₄), 6.09 (⁸H, MeC₅H₄), 6.24 (⁸H, MeC₅H₄). Product 13 C NMR (C6D6): δ15.4(MeC5H4), 114.4(MeC5H4), 116.0(MeC5H4), 124.9(MeC5H4).

[0163] Example 2: Preparation of Complex 3 (Sc(MeCp)2[N(SiMe3)2])

[0164] [Sc(MeCp)₂Cl]₂ (4.6 g, 0.0098 mol) and KN(SiMe₃)₂ (3.9 g, 0.020 mol) were placed in a 250 mL Schrank flask equipped with a magnetic stirrer, followed by the addition of anhydrous diethyl ether (100 mL). The mixture was stirred for 12 hours under a nitrogen atmosphere at room temperature (~18°C to ~24°C) to obtain a pink suspension. The solvent was removed under pressure, and the resulting solid was extracted with 3 × 30 mL of hexane, followed by filtration through a medium glass frit. The solvent was removed from the filtrate under reduced pressure to give the final product as a yellow powder (6.7 g, 0.018 mol, 90% yield). 1 ¹H NMR (C6D6): δ 1.10 (¹⁸H, SiMe₃), 2.04 (⁶H, MeC₅H₄), 5.85 (⁴H, MeC₅H₄), 6.00 (⁴H, MeC₅H₄). Product 13 C NMR (C6D6): δ4.2(SiMe3), 15.7(MeC5H4), 114.3(MeC5H4), 115.9(MeC5H4), 125.0(MeC5H4).

[0165] Example 3: Preparation of Complex 2 (Sc(MeCp)2[1,3-bis(trimethylsilyl)allyl])

[0166] [Sc(MeCp)₂Cl]₂ (1.0 g, 2.1 mmol) and 1,3-bis(trimethylsilyl-allyl)potassium (1.05 g, 4.7 mmol) were placed in a 250 mL Schrank flask equipped with a magnetic stirrer, followed by the addition of anhydrous diethyl ether (100 mL). The mixture was stirred for 12 hours under a nitrogen atmosphere at room temperature (~18 °C to ~24 °C) to obtain an orange suspension. The solvent was removed under pressure, and the resulting solid was extracted with 3 × 30 mL of hexane, followed by filtration through a medium glass frit. The solvent was removed from the filtrate under reduced pressure to give the final product as a red liquid (1.0 g, 2.6 mmol, 62% yield). 1H NMR(C6D6): δ0.04(18H,SiMe3),1.84(3H,MeC5H4),1.94(3H,MeC5H4),4.90(2H,allyl CH(TMS)), 5.97(2H,MeC5H4), 6.04(4H,MeC5H4), 6.29(2H,MeC5H4), 7.67(1H,allyl CH).

[0167] Example 4: Preparation of Complex 1 (Sc(MeCp)2(1-trimethylsilylallyl))

[0168] [Sc(MeCp)₂Cl]₂ (5.2 g, 10.9 mmol) and (trimethylsilylallyl)potassium (3.3 g, 21.8 mmol) were placed in a 250 mL Schrank flask equipped with a magnetic stirrer, followed by the addition of anhydrous diethyl ether (100 mL). The mixture was stirred for 12 hours under a nitrogen atmosphere at room temperature (~18°C to ~24°C) to obtain an orange suspension. The solvent was removed under pressure, and the resulting solid was extracted with 3 × 30 mL of pentane, followed by filtration through a medium glass frit. The solvent was removed from the filtrate under reduced pressure to give the final product, a red liquid (3.7 g, 11.7 mmol, 54% yield). 1 H NMR(C6D6): δ-0.02(9H,SiMe3),1.82(6H,MeC5H4),2.29(1H,allyl CH2),4.15(1H,allylCH2),4.73(1H,allyl CH(TMS)),5.94(8H,MeC5H4),7.47(1H,allyl CH).

[0169] Example 5: Preparation of Complex 4 (Sc(MeCp)2(3,5-dimethylpyrazolite))

[0170] [Sc(MeCp)₂Cl]₂ (12.0 g, 25.1 mmol) and KMe₂Pz (6.75 g, 50.3 mmol) were placed in a 500 mL Schrank flask equipped with a magnetic stirrer, followed by the addition of anhydrous tetrahydrofuran (150 mL). The mixture was stirred for 12 hours under a nitrogen atmosphere at room temperature (~18 °C to ~24 °C). The solvent was removed under reduced pressure, and the resulting yellow viscous solid was extracted with 5 × 20 mL toluene, followed by filtration through a medium glass frit. The solvent was removed from the filtrate under reduced pressure to give a red oil. Further distillation under vacuum gave a pale yellow liquid final product (10.7 g, 35.9 mmol, 72% yield). 1H NMR (C6D6): δ1.85 (6H, MeC5H4), 2.28 (6H, Me2Pz), 5.84 (4H, MeC5H4), 5.96 (1H, Me2Pz), 6.20 (4H, MeC5H4).

[0171] Example 6: Preparation of Complex 8 (Y(MeCp)2(3-methyl-5-pentylpyrazolite))

[0172] [Y(MeCp)₂Cl]₂ (9.33 g, 16.5 mmol) and K(Me,Pn)Pz (6.28 g, 33.0 mmol) were placed in a 500 mL Schrank flask equipped with a magnetic stirrer, followed by the addition of anhydrous tetrahydrofuran (150 mL). The mixture was stirred for 12 hours under a nitrogen atmosphere at room temperature (~18 °C to ~24 °C). The solvent was removed under reduced pressure, and the resulting yellow viscous solid was extracted with 5 × 20 mL toluene, followed by filtration through a medium glass frit. The solvent was removed from the filtrate under reduced pressure to give a red oil. Further distillation under vacuum gave a pale yellow liquid final product (7.7 g, 19.3 mmol, 58% yield). 1 H NMR(C6D6): δ0.94(3H,Pentyl),1.40(4H,Pentyl),1.75(2H,Pentyl),2.16(6H,MeC5H4),2.17(3H, M e, P nPz),2.65(2H,Pentyl),5.66(4H,MeC5H4),5.90(1H, M e, P nPz),5.96(4H,MeC5H4).

[0173] Example 7: Preparation of Complex 9 (Sc(MeCp)2(6-methyl-2,4-heptanediol acid))

[0174] [Sc(MeCp)₂Cl]₂ (1.0 g, 1.8 mmol) and potassium (6-methyl-2,4-heptanediketin) (0.67 g, 3.7 mmol) were placed in a 500 mL Schrank flask equipped with a magnetic stirrer, followed by the addition of anhydrous tetrahydrofuran (150 mL). The mixture was stirred for 12 hours under a nitrogen atmosphere at room temperature (~18 °C to ~24 °C). The solvent was removed under reduced pressure, and the resulting yellow viscous solid was extracted with 3 × 20 mL toluene, followed by filtration through a medium glass frit. The solvent was removed from the filtrate under reduced pressure to give an orange oil (0.8 g, 2.1 mmol, 58% yield). 1 H NMR (C6D6): δ 0.89 (6H, i Bu), 1.71(3H,Me), 1.89(2H, iBu), 2.03(6H,MeC5H4), 2.04(1H, i Bu),5.24(1H,diketonate),5.85(4H,MeC5H4),6.05(2H,MeC5H4),6.14(2H,MeC5H4).

[0175] Example 8: Preparation of Complex 10 (Y(MeCp)2(6-methyl-2,4-heptanediol acid))

[0176] [Y(MeCp)₂Cl]₂ (1.5 g, 2.4 mmol) and potassium (6-methyl-2,4-heptanediketin) (0.89 g, 4.9 mmol) were placed in a 500 mL Schrank flask equipped with a magnetic stirrer, followed by the addition of anhydrous tetrahydrofuran (150 mL). The mixture was stirred for 12 hours under a nitrogen atmosphere at room temperature (~18°C to ~24°C). The solvent was removed under reduced pressure, and the resulting yellow viscous solid was extracted with 3 × 20 mL toluene, followed by filtration through a medium glass frit. The solvent was removed from the filtrate under reduced pressure to give an orange oil (1.2 g, 2.9 mmol, 60% yield). [Product] 1 H NMR (C6D6): δ 0.89 (6H, i Bu), 1.72(3H,Me), 1.91(2H, i Bu), 2.04(1H, i Bu), 2.10 (6H, MeC5H4), 5.25 (1H, diketonate), 5.95 (4H, MeC5H4), 6.10 (2H, MeC5H4), 6.15 (2H, MeC5H4).

[0177] Example 9: ALD using Sc2O3 membranes with complex 4 (Sc(MeCp)2(3,5-dimethylpyrazol)) and water

[0178] Sc(MeCp)₂(3,5-dimethylpyrazolite) was heated to 100–115°C in a stainless steel bubbler, then transferred to the ALD reactor using 20 sccm of nitrogen as a carrier gas, pulsed for approximately 2 seconds, followed by a purging process of approximately 28–58 seconds. Water vapor was pulsed (1 second) from a water tank at room temperature, followed by a 60-second nitrogen purging. A needle valve was used between the deposition chamber and the water tank, and adjusted to obtain a sufficient water vapor dose. Scandium oxide was deposited onto a silicon chip with a thin layer of SiO₂ containing natural oxide at approximately 175–300°C for up to 300 cycles. Before unloading, the film was cooled to approximately 60°C in the reactor under a nitrogen-purged vacuum. The resulting film thickness was [not specified in the original text]. Within the specified range, preliminary results indicate that the film growth rate is approximately 1 Å / cycle. X-ray photoelectron spectroscopy (XPS) analysis confirmed the presence of scandium oxide with N and C contaminants on the top surface, which were removed during XPS analysis. Figure 1-14 XPS data showed that once surface contaminants were removed by sputtering, these films contained no more than 1% of any other elements besides the required scandium and oxygen. In most samples, only Sc and O were detected, and the measured stoichiometry matched the theoretical composition of Sc₂O₃.

[0179] Example 10: ALD using Sc2O3 film with complex 12 ([Y(MeCp)2(3,5-MePn-C3HN2)]2)

[0180] Holistic approach

[0181] [Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂ was heated to 130–180°C in a stainless steel bubbler, then conveyed to a cross-flow ALD reactor using nitrogen as a carrier gas, and water was used for deposition through the ALD. H₂O was supplied by steam drawn from a stainless steel ampoule at room temperature. [The remaining text appears to be incomplete and requires further context.] Silicon chips with natural SiO2 layers of varying thicknesses were used as substrates. The thickness and optical properties of the deposited films were measured using an optical ellipsometer. Selected samples were analyzed for film composition and impurity concentration using XPS.

[0182] Example 10a

[0183] In each ALD cycle, [Y(MeCp)₂(3,5-MePn-C₃HN₂)]₂ was heated to 170°C and then fed into the ALD reactor using 20 sccm of nitrogen as the carrier gas. It was then pulsed by a bubbler for 7 seconds, followed by a 20-second N₂ purging, and subsequently a 0.015-second H₂O pulse and a 90-second N₂ purging. Deposition was performed for 200 or more cycles at multiple temperatures ranging from 125 to 250°C. Before unloading, the deposited film was cooled to approximately 80°C in the reactor under nitrogen purging. The deposited film thickness was... Within the scope. Figure 15 The data shows the growth rate at a fixed reactor inlet position for each cycle.

[0184] Figure 15 The curves in the figure indicate that, under the same deposition conditions, the growth rate of Y2O3 from the unoptimized H2O ALD process appears to be temperature-dependent. Higher temperatures result in higher growth rates. Further testing shows that the growth rate at higher temperatures appears to be affected by the water purging time, possibly due to the initial formation of Y(OH)3 and / or the strong absorption of H2O by the Y2O3 film at higher temperatures. For example, as... Figure 16As shown, saturation was not reached at 200°C even after 120 seconds of H2O purging, while at around 150°C or lower, the dependence on H2O purging time was much smaller.

[0185] Example 10b

[0186] In each ALD cycle, [Y(MeCp)2(3,5-MePn-C3HN2)]2 was heated to 170–176 °C and then fed into the ALD reactor using 20 sccm of nitrogen as the carrier gas. Various precursor doses were generated by a 3–13 second bubbling pulse, followed by a 60-second N2 purging, then a 0.015-second H2O pulse and a 30-second N2 purging, and deposition was carried out at 135 °C for 350 cycles. The film thickness was monitored at three different locations along the precursor / carrier gas flow direction: the precursor inlet, the reactor center, and the precursor outlet of the cross-flow reactor. Figure 17 The growth rate data for each cycle is plotted in the image.

[0187] The growth rate (GPC) per cycle is approximately [value missing] based on the precursor dose. The convergence of saturation and growth rate at three different locations during the cycle indicates that the process at 135°C is indeed an ALD process, and the contribution of any CVD component to the growth rate is not significant. Under optimal saturated growth conditions, excellent thickness uniformity ≤±1.3% can be obtained within a 6–7” diameter region throughout the cross-flow reactor.

[0188] The complete ALD deposition temperature window has not yet been determined. The precursor is thermally stable at higher temperatures ≥250°C.

[0189] Just as each individual publication, patent application, published patent, or other document is specifically and individually designated to be incorporated herein by reference in its entirety, all publications, patent applications, published patents, and other documents referred to in this specification are incorporated herein by reference. Definitions incorporated herein by reference that conflict with definitions in this disclosure are excluded.

[0190] The words “comprise”, “comprises”, and “comprising” should be interpreted as open-ended, not closed-ended.

Claims

1. A metal complex that structurally corresponds to Formula I: [(R 1 ) n Cp]2M 1 L 1 (I) in, M 1 Scandium; Each R 1 Independently, it is a C1-C5 alkyl or silyl group; n is 1, 2, 3, 4 or 5; Cp is a cyclopentadienyl ring; and L 1 For 3,5-R 7 R 8 -C3HN2, where R 7 and R 8 Each is an alkyl group that is independently C1-C5.

2. The metal complex as described in claim 1, wherein, Each R 1 Independently a C1-C4 alkyl or silyl group, wherein R 7 and R 8 Each is an alkyl group that is independently C1-C5.

3. The metal complex as described in claim 2, wherein, Each R 1 It can be methyl, ethyl, propyl or silyl by itself.

4. The metal complex as described in claim 2 or 3, wherein, Each R 1 It can be methyl or ethyl on its own.

5. The metal complex as described in claim 4, wherein, Each R 1 It is a methyl group.

6. The metal complex as described in claim 1, wherein, The complex is Sc(MeCp)2(3,5-Me2-C3HN2).

7. A method for forming a metal-containing film by a vapor deposition process, the method comprising vaporizing at least one metal complex that structurally corresponds to Formula I: (R 1 Cp)2M 1 L 1 (I) in, M 1 Scandium; Each R 1 Independently, it is a C1-C5 alkyl or silyl group; Cp is a cyclopentadienyl ring; and L 1 For 3,5-R 7 R 8 -C3HN2, where R 7 and R 8 Each is an alkyl group that is independently C1-C5.

8. The method of claim 7, wherein, Each R 1 Independently C1-C4 alkyl or silyl groups, wherein R 7 and R 8 Each is an alkyl group that is independently C1-C5.

9. The method of claim 8, wherein, Each R 1 It can be methyl, ethyl, propyl or silyl by itself.

10. The method of claim 8 or 9, wherein, Each R 1 It can be methyl or ethyl on its own.

11. The method of claim 10, wherein, Each R 1 It is a methyl group.

12. The method of claim 7, wherein, The complex is Sc(MeCp)2(3,5-Me2-C3HN2).

13. The method of claim 7, wherein, The vapor deposition process is chemical vapor deposition.

14. The method of claim 13, wherein, The chemical vapor deposition process is either pulsed chemical vapor deposition or continuous flow chemical vapor deposition.

15. The method of claim 13, wherein, The chemical vapor deposition process is liquid injection chemical vapor deposition.

16. The method of claim 7, wherein, The vapor deposition process is atomic layer deposition.

17. The method of claim 16, wherein, The atomic layer deposition is either liquid injection atomic layer deposition or plasma-enhanced atomic layer deposition.

18. The method of claim 7, wherein, The metal complex is delivered to the substrate in a pulsed manner, alternating with pulses from the oxygen source.

19. The method of claim 18, wherein, The oxygen source is selected from the group consisting of H2O, H2O2, O2, ozone, air, isopropanol, tert-butanol and N2O.

20. The method of claim 7, further comprising: At least one co-reactant is vaporized, said co-reactant being selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazine, borane, silane, ozone, and any combination of two or more thereof.

21. The method of claim 20, wherein, The at least one co-reactant is hydrazine.

22. The method of claim 21, wherein, The hydrazine is hydrazine (N2H4) or N,N-dimethylhydrazine.

23. The method of claim 7, wherein, The method is used in DRAM or CMOS applications.

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