Metal complex containing a cyclopentadienyl ligand

Abstract

To provide metal complexes including cyclopentadienyl ligands and methods for preparing metal-containing films using the metal complexes.SOLUTION: There is provided a metal complex corresponding in structure to Formula I: [(R1)nCp]2M1 L1...(I), wherein M1 is yttrium or lanthanum; each R1 is independently C1 to C5-alkyl; n is 1, 2, 3, 4, or 5; Cp is cyclopentadienyl ring; and L1 is R35, or R36-C3HO2, wherein R35 and R36 are each independently C1 to C4-alkyl.SELECTED DRAWING: None

Description

Detailed Invention of the Invention

[0001] 〔Technical Field〕 The present technology generally relates to a metal complex containing a cyclopentadienyl ligand, a method for preparing the complex, and a method for preparing a metal-containing thin film using the complex.

[0002] 〔Background Art〕 Various precursors have been used and various deposition techniques have been employed to form thin films. Such techniques include reactive sputtering, ion-assisted deposition, sol-gel deposition, chemical vapor deposition (CVD) (also known as metalorganic CVD or MOCVD), and atomic layer deposition (ALD) (also known as atomic layer epitaxy). CVD and ALD processes are increasingly used because they have advantages such as improved synthesis control, high film uniformity, and effective control of doping. Further, CVD and ALD processes provide excellent conformal step coverage in the highly non-planar structures associated with modern ultra-small devices.

[0003] CVD is a chemical process that uses precursors to form a thin film on the surface of a substrate. In a typical CVD process, the precursors pass over the surface of a substrate (e.g., a wafer) in a low-pressure or atmospheric-pressure reaction chamber. The precursors react and / or decompose on the substrate surface to form a thin film of the deposited material. Volatile by-products are removed by a gas flow through the reaction chamber. Control of the deposited film thickness can be difficult because it depends on a combination of many parameters such as temperature, pressure, gas flow volume and uniformity, chemical depletion effects, and time.

[0004] ALD is also a method of depositing thin films. ALD is a self-limiting, sequential, and unique film growth technique based on surface reactions. This surface reaction enables precise thickness control and allows conformal thin films of precursor-derived materials to be deposited on substrate surfaces of various compositions. In ALD, the precursors are separated during the reaction. The first precursor passes over the substrate surface and forms a monolayer on the substrate surface. Excess unreacted precursor is pumped out of the reaction chamber. Then, the second precursor passes over the substrate surface and reacts with the first precursor. And a second monolayer film is formed on the first formed monolayer film on the substrate surface. This cycle is repeated until a film of the desired thickness is formed.

[0005] Thin films, especially thin metal-containing films, have various important applications such as in the manufacture of nanotechnology and semiconductor devices. Examples of such applications include high refractive index optical coatings, corrosion protection coatings, photocatalytic self-cleaning glass coatings, biocompatible coatings, dielectric capacitor layers and gate dielectric insulating films in field effect transistors (FETs), capacitor electrodes, gate electrodes, adhesion dispersion barriers, and integrated circuits. Dielectric thin films are also used in high-κ dielectric oxides for dynamic random access memories (DRAMs) and in ultraminiature electronic applications such as ferroelectric perovskites used in infrared detectors and non-volatile ferroelectric random access memories (NV-FeRAMs). The continuous reduction in the size of ultraminiature electronic components has increased the need for improvement in such thin film technologies.

[0006] Techniques related to the preparation of scandium-containing thin films and yttrium-containing thin films (e.g., scandium oxide, yttrium oxide, etc.) are of particular interest. For example, scandium-containing films have found many practical applications in fields such as catalysts, batteries, memory devices, displays, sensors, and ultrafine and miniature electronics and semiconductor devices. In the case of electronic applications, a commercially viable vapor deposition method using scandium-containing precursors and yttrium-containing precursors having appropriate properties including volatility, low melting point, reactivity, and stability is required. However, the number of available scandium-containing compounds and yttrium-containing compounds having such appropriate properties is limited. Therefore, there is great interest in the development of scandium complexes and yttrium complexes having performance characteristics suitable for use as precursor materials in vapor deposition processes for preparing scandium-containing films and yttrium-containing films. For example, scandium-containing precursors and yttrium-containing precursors having improved performance characteristics (e.g., thermal stability, vapor pressure, and deposition rate) are needed, and a method for depositing thin films from such precursors is also needed.

[0007] 〔Summary of the Invention〕 According to one aspect, a metal complex of formula I is provided: [(R 1 ) n Cp]2M 1 L 1 (I); wherein M 1 is a Group 3 metal or a lanthanide (e.g., scandium, yttrium, and lanthanum); R 1 are each independently hydrogen, C1-C5-alkyl or silyl; n is 1, 2, 3, 4, or 5; Cp is a cyclopentadienyl ring; and L 1 is 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 selected from the group consisting of -C3HO2; wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen or C1-C5-alkyl, and R 32 , R 33 , R 34 , R 35 and R 36 are each independently alkyl or silyl; wherein M 1 is yttrium, and L 1 is 3,5-R 7 R 8 -C3HN2, R 1 is C1-C5-alkyl or silyl; wherein M 1 is yttrium, and L 1 is N(SiR 4 R 5 R 6 )2, n is 1, 2, 3, or 4.

[0008] In another aspect, a metal complex of formula II is provided: [((R 9 )) n Cp)2M 2 L 2 2 (II); wherein M 2 is a Group 3 metal or a lanthanide (e.g., scandium, yttrium and lanthanum); R 9 are each independently hydrogen or C1-C5-alkyl; n is 1, 2, 3, 4 or 5; Cp is a cyclopentadienyl ring; L 2 is selected from the group consisting of Cl, F, Br, I and 3,5-R 10 R 11 -C3HN2; wherein R 10 and R 11 are each independently hydrogen or C1-C5-alkyl; wherein M 2 is scandium, and L 2When it is Cl, R 9 is C1-C5-alkyl.

[0009] In other embodiments, methods of forming metal-containing films by vapor deposition such as CVD and ALD are provided herein. The method includes evaporating at least one metal complex having a structure corresponding to formula I: (R 1 Cp)2M 1 L 1 (I), wherein M 1 is a Group 3 metal or a lanthanide (e.g., scandium, yttrium, and lanthanum), R 1 are each independently hydrogen, C1-C5-alkyl, or silyl; Cp is a cyclopentadienyl ring; L 1 is 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, selected from the group consisting of; wherein R 2 、R 3 、R 4 、R 5 、R 6 、R 7 and R 8 are each independently hydrogen or C1-C5-alkyl, and R 32 、R 33 、R 34 、R 35 and R 36 are each independently alkyl or silyl.

[0010] Other embodiments including the specific embodiments of the present embodiment summarized above will become apparent from the following detailed description.

[0011] [Brief Description of the Drawings] Figure 1 shows the XPS (X-ray photoelectron spectroscopy) analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0012] Figure 2 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0013] Figure 3 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0014] Figure 4 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0015] Figure 5 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0016] Figure 6 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0017] Figure 7 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0018] Figure 8 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0019] Figure 9 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0020] Figure 10 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0021] Figure 11 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0022] Figure 12 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0023] Figure 13 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0024] Figure 14 shows the XPS analysis of the Sc2O3 film using Sc(MeCp)2(3,5-dimethyl-pyrazolate).

[0025] Figure 15 shows the dependence of the growth rate of Y2O3 per cycle on the deposition temperature when [Y(MeCp)2(3,5-MePn-C3HN2)]2 is deposited in ALD.

[0026] Figure 16 shows the dependence of the growth rate of Y2O3 per cycle on the H2O purge time when [Y(MeCp)2(3,5-MePn-C3HN2)]2 is deposited at 125 °C, 150 °C, and 200 °C in ALD.

[0027] Figure 17 shows the growth rate of Y2O3 per cycle in ALD at three different positions in the cross-flow reactor along the precursor / carrier gas flow direction: the precursor inlet, the reactor center, and the precursor outlet.

[0028] 〔Detailed Description〕 Before describing examples of some embodiments of the present technology, it should be understood that the present technology is not limited to the details of the configurations or process steps described in the following description. The present technology can have other embodiments and can be implemented or executed in various ways. It should also be understood that metal complexes and other compounds can be exemplified herein using structural formulas having specific stereochemical arrangements. These exemplifications are intended only as examples and should not be construed as limiting the disclosed structures to specific stereochemical arrangements. Rather, the described structures are intended to encompass all metal complexes and compounds having the indicated chemical formulas.

[0029] In various aspects, there are provided metal complexes, methods for manufacturing such metal complexes, and methods of using such metal complexes to form thin metal-containing films by a vapor deposition process.

[0030] As used herein, the terms “metal complex” (or more simply “complex”) and “precursor” are used interchangeably and refer to metal-containing molecules or compounds that can be used to prepare metal-containing films by a vapor deposition process such as, for example, ALD or CVD. The metal complex can be deposited, adsorbed, decomposed, delivered, and / or passed over a substrate or its surface so as 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 elemental metal films as more fully defined below, but also films that include one or more elements and a metal, such as, for example, metal oxide films, metal nitride films, metal silicide films, etc. As used herein, the terms “elemental metal film” and “pure metal film” are used interchangeably and refer to a film consisting of, or consisting essentially of, a pure metal. For example, an elemental metal film may contain 100% pure metal, or an elemental 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%, or at least about 99.99% pure metal along with one or more impurities. Unless the context indicates otherwise, the term “metal film” should be construed to mean an elemental metal film. In some embodiments, the metal-containing film is an elemental scandium film or an elemental 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. These scandium-containing films and yttrium-containing films can be prepared from the various scandium complexes and yttrium complexes described herein.

[0032] As used herein, the term "vapor deposition process" is used to refer to any kind of vapor deposition technique, including but not limited to CVD and ALD. In various embodiments, CVD can take the form of conventional (i.e., continuous flow) CVD, liquid injection CVD, or photo-assisted CVD. CVD can also take the form of a pulsed technique, i.e., pulsed CVD. In other embodiments, ALD can take the form of conventional (i.e., pulsed injection) ALD, liquid injection ALD, photo-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. The term "vapor deposition process" further includes the various vapor deposition techniques described in Chemical Vapour Deposition: Precursors, Processes, and Applications; Jones, A. C.; Hitchman, M. L., Eds. The Royal Society of Chemistry: Cambridge, 2009; Chapter 1, pp 1-36.

[0033] (Alone or in combination with another term(s)) The term "alkyl" refers to a saturated hydrocarbon chain of 1 to about 12 carbon atoms, such as, but not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc. The alkyl group may be straight-chain or branched-chain. "Alkyl" is intended to encompass all structural isomers of the alkyl group. For example, as used herein, propyl encompasses both n-propyl and isopropyl; butyl encompasses n-butyl, sec-butyl, isobutyl and tert-butyl; pentyl encompasses n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl and 3-pentyl. Further, as used herein, "Me" refers to methyl, "Et" refers to ethyl, "Pr" refers to propyl, "i-Pr" refers to isopropyl, "Bu" refers to butyl, "t-Bu" refers to tert-butyl, "iBu" refers to isobutyl, and "Pn" and "Npn" refer to neopentyl. In some embodiments, the alkyl group is a C1-C5- or 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 resonance double bond and all three carbon atoms of the allyl ligand are bonded to the metal center by η 3 -coordination by a π bond. Thus, the complexes of the present invention are π-complexes. Both of these features are represented by a dashed bond. When the allyl moiety is substituted with one X group, the X 1 group replaces an allyl hydrogen to form [X 1 C3H4], and when substituted with two X groups X 1 and X 2 , it forms [X 1 X 2 C3H3], where X 1 and X 2 are the same or different, and the same applies hereinafter.

[0035] The term "silyl" refers to -SiZ 1 Z 2 Z3 refers to a group, where Z 1 , Z 2 , and Z 3 each independently is 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 group, where Z 5 , Z 6 , and Z 7 are alkyl, and Z 5 , Z 6 , and Z 7 may be the same or different alkyls. Non-limiting examples of trialkylsilyl include trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), and tert-butyldimethylsilyl (TBDMS).

[0037] The deposition of some metals including scandium and yttrium can be difficult to achieve due to thermal stability issues, unstable with respect to deposition, or too stable. The organometallic complexes disclosed in this embodiment enable control of physical properties and provide improved stability and simple and high-yield synthesis. In this regard, the metal complexes provided herein are excellent candidates for preparing thin metal-containing films in various vapor deposition processes.

[0038] Thus, according to one aspect, a metal complex of the following formula I is provided: [(R 1 ) n Cp]2M 1 L 1 (I); wherein M 1 is a Group 3 metal or a lanthanide; R 1 are each independently hydrogen, C1-C5-alkyl or silyl; n is 1, 2, 3, 4, or 5; Cp is a cyclopentadienyl ring; and L1 is 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; R 35 、R 36 -C3HO2; R 12 N = C - C - 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 selected from the group consisting of; wherein 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 is each independently hydrogen or C1 - C5 - alkyl, and R 32 、R 33 、R 34 、R 35 and R 36 is each independently alkyl or silyl.

[0039] In some embodiments, M 1 can be selected from the group consisting of scandium, yttrium, and lanthanum. In other embodiments, M 1 can be selected from the group consisting of scandium and yttrium. In particular, M 1can be scandium.

[0040] In another embodiment, M 1 is yttrium, L 1 is 3,5-R 7 R 8 -C3HN2, R 1 is C1-C5-alkyl or silyl, and / or M 1 is yttrium, L 1 is N(SiR 4 R 5 R 6 )2, n is 1, 2, 3 or 4.

[0041] In some embodiments, L 1 is 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 is selected from the group consisting of -C3HO2.

[0042] In some embodiments, L 1 is NR 2 R 3 ; N(SiR 4 R 5 R 6 )2; 3,5-R 7 R 8 -C3HN2; 1-(SiMe3)C3H4 (trimethylsilylallyl); 1,3-bis-(SiMe3)2C3H3 (bis-trimethylsilylallyl), 6-methyl-2,4-heptanedionate.

[0043] Each R present 1 may be the same or different. For example, if n is 2, 3, 4 or 5, each R 1may all be hydrogen, or may all be alkyl (e.g., C1-C5-alkyl), or may all be silyl. Alternatively, when n is 2, 3, 4, or 5, each R 1 may be different. For example, if n is 2, the first R 1 may be hydrogen, and the second R 1 may be alkyl (e.g., C1-C5-alkyl) or silyl.

[0044] Each R that exists 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 may be the same or different. 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 may all be hydrogen, or may all be alkyl (e.g., C1-C5-alkyl).

[0045] In one embodiment, R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 12 R 13 R14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 Up to 16 of them can each 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 Among them, at least 1, at least 2, at least 3, at least 4 or at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, at least 13, at least 14, at least 15, or at least 16 can be hydrogen.

[0046] 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 Up to 16 of them can each independently be alkyl. For example, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 Of these, at least 1, at least 2, at least 3, at least 4, or at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 12, at least 13, at least 14, at least 15, or at least 16 may be alkyl.

[0047] Each R present 32 , R 33 and R 34 may be the same or different. For example, R 32 , R 33 and R 34 may all be alkyl (e.g., C1-C5-alkyl) or may all be silyl (e.g., SiMe3).

[0048] Each R present 35 and R 36 may be the same or different. For example, R 35 and R 36 may all be the same or different alkyl (e.g., C1-C5-alkyl), R 35 and R 36 may all be the same or different silyl (e.g., SiMe3), or R 35 and R 36 may be alkyl (e.g., C1-C5-alkyl) and silyl (e.g., SiMe3).

[0049] In one embodiment, up to 2 of R 32 , R 33 , R 34 , R 35 and R 36 may each independently be alkyl. For example, R 32 , R33 , R 34 , R 35 and R 36 Among them, at least one or at least two may be alkyl.

[0050] In another embodiment, R 32 , R 33 , R 34 , R 35 and R 36 Up to two of them may each independently be silyl. For example, among R 32 , R 33 , R 34 , R 35 and R 36 , at least one or at least two may be silyl.

[0051] The alkyl groups discussed herein may be 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 a further embodiment, the alkyl is C1-C5-alkyl, C1-C4-alkyl, C1-C3-alkyl, C1-C2-alkyl or C1-alkyl. The alkyl group may be straight-chain or branched. In particular, the alkyl is straight-chain. In a further embodiment, the alkyl 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 herein may be Si(alkyl)3, Si(alkyl)2H, and Si(alkyl)H2, but are not limited thereto, where alkyl is as defined above. For example, examples of silyl include, but are not limited to, SiH3, SiMeH2, SiMe2H, SiMe3, SiEtH2, SiEt2H, SiEt3, SiPrH2, SiPr2H, SiPr3, SiBuH2, SiBu2H, SiBu3, where "Pr" includes i-Pr and "Bu" includes t-Bu.

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

[0054] In some embodiments, 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 can each independently be hydrogen or C1-C4-alkyl. In other embodiments, 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 can each independently be hydrogen, methyl, ethyl or propyl. In other embodiments, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 12 , R13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 may each independently be hydrogen, methyl or ethyl. In particular, 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 may each independently be hydrogen or methyl.

[0055] In some embodiments, R 1 may each independently be 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 may each independently be hydrogen, C1-C4-alkyl.

[0056] In other embodiments, R 1 may each independently be hydrogen, methyl, ethyl, propyl or silyl; R 2 , R 3 , R 4 , R 5 , R6 and R 7 and R 8 and R 12 and R 13 and R 14 and R 15 and R 16 and R 17 and R 18 and R 19 and R 20 and R 21 may each independently be hydrogen, methyl, ethyl or propyl.

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

[0058] In some embodiments, R 32 and R33 , R 34 , R 35 and R 36 may each independently be C1-C5-alkyl or silyl. In other embodiments, R 32 , R 33 , R 34 , R 35 and R 36 may each independently be C1-C4-alkyl or silyl. In other embodiments, R 32 , R 33 , R 34 , R 35 and R 36 may each independently be methyl, ethyl, propyl or silyl. In other embodiments, R 32 , R 33 , R 34 , R 35 and R 36 may each independently be methyl, ethyl or silyl. In other embodiments, R 32 , R 33 , R 34 , R 35 and R 36 may each independently be a silyl such as, but not limited to, SiH3, SiMeH2, SiMe2H, SiMe3, SiEtH2, SiEt2H, SiEt3, SiPrH2, SiPr2H, SiPr3, SiBuH2, SiBu2H, SiBu3, etc. In particular, R 32 , R 33 , R 34 , R 35 and R 36 may each independently be SiMe2. In particular, R 32 , R 33 and R 34 may each independently be SiMe3. In other embodiments, R 35 and R 36 may each independently be C1-C4-alkyl, particularly methyl and / or butyl.

[0059] In some embodiments, L 1 is NR 2 R3 ; N(SiR 4 R 5 R 6 )2; 1-(R 32 )C3H4; and 1-R 33 -3-R 34 -C3H3 is selected from the group consisting of.

[0060] In another embodiment, L 1 is 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 -C3HO2 may be selected from the group consisting of.

[0061] In another embodiment, R 1 can each independently be hydrogen, C1-C4-alkyl or silyl; and L 1 is NR 2 R 3 where R 2 and R 3 can each independently be hydrogen or C1-C4-alkyl. In another embodiment, R 1 can each independently be hydrogen, methyl, ethyl, propyl or silyl; R 2 and R 3 can each independently be hydrogen, methyl, ethyl or propyl. In another embodiment, R 1 can each independently be hydrogen, methyl, or ethyl; R 2 and R 3 can each independently be hydrogen, methyl, or ethyl. In particular, R 1 can each be methyl; R 2 and R 3 can each independently be hydrogen, methyl, or ethyl.

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

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

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

[0065] In other embodiments, R 1 can each independently be hydrogen, C1-C4-alkyl or silyl; L 1 can be 1-R 33 -3-R 34 -C3H3, where R 33 and R 34 can be C1-C5-alkyl or silyl. In another embodiment, R 1can each independently be hydrogen, methyl, ethyl or silyl, R 33 and R 34 can each independently be C1-C4-alkyl or silyl, R 32 can be silyl. In another embodiment, R 1 can each independently be hydrogen, methyl or ethyl, R 33 and R 34 can each independently be silyl such as SiH3, SiMeH2, SiMe2H, SiMe3, SiEtH2, SiEt2H, SiEt3, SiPrH2, SiPr2H, SiPr3, SiBuH2, SiBu2H, SiBu3, etc., but are not limited thereto. In particular, R 1 can each independently be methyl or ethyl, R 33 and R 34 can be SiMe3.

[0066] In other embodiments, R 1 can each independently be hydrogen, C1-C4-alkyl or silyl; L 1 can be R 35 , R 36 -C3HO2, where R 35 and R 36 can be C1-C5-alkyl or silyl. In another embodiment, R 1 can each independently be hydrogen, methyl, ethyl or silyl, R 35 and R 36 can each independently be C1-C4-alkyl or silyl. In another embodiment, R 1 can each independently be hydrogen, methyl or ethyl, R 35 and R 36 can each independently be silyl such as SiH3, SiMeH2, SiMe2H, SiMe3, SiEtH2, SiEt2H, SiEt3, SiPrH2, SiPr2H, SiPr3, SiBuH2, SiBu2H, SiBu3, etc., but are not limited thereto. In another embodiment, R 1 can each independently be hydrogen, methyl or ethyl, R35 and R 36 may each independently be C1-C4-alkyl, and in particular may be methyl and / or butyl. In particular, R 1 may each independently be methyl or ethyl, R 35 and R 36 may each independently be methyl or butyl. In particular, R 1 may each independently be methyl or ethyl, R 35 and R 36 may be SiMe3.

[0067] Examples of metal complexes having a structure corresponding to formula I are shown in Table 1.

[0068]

Table 1

[0069] In one embodiment, a mixture of two or more organometallic complexes of formula I is provided.

[0070] In another embodiment, a metal complex of formula II is provided: [((R 9 )) n Cp)2M 2 L 2 2 (II), wherein M 2 is a Group 3 metal or a lanthanide; R 9 are each independently hydrogen or C1-C5-alkyl; n is 1, 2, 3, 4 or 5; Cp is a cyclopentadienyl ring; and L 2 is Cl; F; Br; I; 3,5-R 10 R 11 -C3HN2; R 22 N=C-C-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 is selected from the group consisting of, wherein R10 , R 11 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , and R 31 are each independently hydrogen or C1-C5-alkyl.

[0071] In some embodiments, M 2 can be selected from the group consisting of scandium, yttrium, and lanthanum. In other embodiments, M 2 can be selected from the group consisting of scandium and yttrium. In particular, M 2 can be scandium.

[0072] In other embodiments, when M 2 is scandium and L 2 is Cl, R 9 is C1-C5-alkyl.

[0073] In some embodiments, L 2 is selected from the group consisting of Cl; F; Br; I; and 3,5-R 10 R 11 -C3HN2.

[0074] Each R present 9 can be the same or different. For example, when n is 2, 3, 4, or 5, each R 9 can all be hydrogen, or all can be alkyl (e.g., C1-C5-alkyl). Alternatively, when n is 2, 3, 4, or 5, R 1 can each be different. For example, when n is 2, the first R 9 can be hydrogen, and the second R 9 can be alkyl (e.g., C1-C5-alkyl).

[0075] Each R present10 , R 11 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R 30 , and R 31 may be the same or different. 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 may all be hydrogen or may all be alkyl (e.g., C1-C5-alkyl).

[0076] In one 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 of them may each be hydrogen. 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 1, at least 2, at least 3, at least 4 or at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11 of them may be hydrogen.

[0077] 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 of up to 11 of them can each independently be alkyl. 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 of at least 1, at least 2, at least 3, at least 4 or at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 11 can be alkyl.

[0078] The alkyl groups discussed herein may be 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 a further embodiment, the alkyl is 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 is straight-chain. In a further embodiment, the alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and neopentyl.

[0079] In some embodiments, R 9 can each independently be C1-C5-alkyl. In other embodiments, R 9can each independently be hydrogen or C1-C4-alkyl. In another embodiment, R 9 can each independently be hydrogen, methyl, ethyl, or propyl. In another embodiment, R 9 can each independently be hydrogen, methyl, or ethyl. In particular, R 9 can each be methyl.

[0080] In certain embodiments, M 2 can be scandium, and R 9 can each independently be C1-C4-alkyl. In another embodiment, M 2 can be scandium, L 2 can be Cl, and R 9 can each independently be methyl, ethyl or propyl. In particular, R 9 can each independently be methyl or ethyl.

[0081] In another certain embodiment, M 2 can be yttrium, and R 9 can each independently be C1-C4-alkyl. In another embodiment, M 2 can be yttrium, L 2 can be 3,5-R 10 R 11 -C3HN2, and R 9 can each independently be methyl, ethyl or propyl, and R 10 and R 9 can each independently be C1-C5-alkyl. In particular, R 9 can each independently be methyl or ethyl.

[0082] Examples of metal complexes whose structures correspond to Formula II are shown in Table 2.

[0083]

Table 2

[0084] Additional other metal complexes provided herein 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). As used herein, "THF" refers to tetrahydrofuran.

[0085] The metal complexes provided herein can be prepared, for example, as shown in Scheme A below.

[0086]

Chemical formula

[0087] The metal complexes provided herein can be used to prepare metal-containing films, such as films of elemental scandium, elemental yttrium, scandium oxide, yttrium oxide, scandium nitride, yttrium nitride, and scandium silicate and yttrium silicate. Thus, in another aspect, a method of forming a metal-containing film by a vapor deposition process is provided. The method includes evaporating at least one organometallic complex whose structure corresponds to formula (I), formula (II), or a combination thereof, as disclosed herein. For example, this may include (1) evaporating at least one complex, and (2) delivering at least one complex to the surface of a substrate or passing at least one complex over the substrate (and / or decomposing at least one complex on the surface of the substrate).

[0088] In the vapor deposition method disclosed in this specification, various substrates can be used. For example, metal complexes such as those disclosed herein can be delivered, passed through, or vapor deposited on substrates or their surfaces, including 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 commonly encountered in nanoscale device manufacturing processes (e.g., semiconductor manufacturing processes). As will be understood by those skilled in the art, the substrate can be subjected to a pretreatment process 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.

[0089] In certain embodiments, the metal complex can be dissolved in a suitable solvent, such as a hydrocarbon solvent or an amine solvent, to facilitate a vapor deposition process. Suitable hydrocarbon solvents include aliphatic hydrocarbons such as hexane, heptane, and nonane; aromatic hydrocarbons such as toluene and xylene; and aliphatic and cyclic ethers such as diglyme, triglyme, and tetraglyme, but are not limited thereto. 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 produce a solution having a concentration of from about 0.05 M to about 1 M.

[0090] In another embodiment, at least one metal complex can be delivered to the substrate surface "neat" (not diluted with a carrier gas).

[0091] In one embodiment, the vapor deposition process is chemical vapor deposition.

[0092] In another embodiment, the vapor deposition process is atomic layer deposition.

[0093] The ALD and CVD methods are not limited, but include various types of ALD and CVD processes such as continuous or pulsed injection processes, liquid injection processes, photo-assisted processes, plasma-assisted processes, and plasma-enhanced processes. For clarity, the method of the present technology particularly includes a direct liquid injection process. For example, in direct liquid injection CVD (DLI-CVD), a solid or liquid metal complex is dissolved in a suitable solvent, and the solution formed therefrom can be injected into the deposition chamber to evaporate the metal complex. The evaporated metal complex is then transported / delivered to the substrate surface. Generally, DLI-CVD can be particularly useful when the metal complex exhibits relatively low volatility or is otherwise difficult to evaporate.

[0094] In one embodiment, at least one metal complex is evaporated and / or passed over the substrate surface using conventional CVD or pulsed CVD to form a metal-containing film. For conventional CVD processes, see, for example, Smith, Donald (1995) Thin-Film Depotion: Principles and Practice. McGraw-Hill.

[0095] In one embodiment, the CVD growth conditions of the metal complexes disclosed herein include, but are not limited to: a. Substrate temperature: 50 - 600 °C b. Evaporator temperature (metal precursor temperature): 0 - 200 °C c. Reactor pressure: 0 - 100 Torr d. Flow rate of argon or nitrogen carrier gas: 0 - 500 sccm e. Oxygen flow rate: 0 - 500 sccm f. Hydrogen flow rate: 0 - 500 sccm g. Execution time: Varies depending on the desired film thickness In another embodiment, photo-assisted CVD is used to form a metal-containing film by evaporating and / or passing at least one metal complex disclosed herein over a substrate surface.

[0096] In a further embodiment, conventional (i.e., pulse injection) ALD is used to form a metal-containing film by evaporating and / or passing at least one metal complex disclosed herein over a substrate surface. For conventional ALD processes, see, e.g., George SM., et al J. Phys. Chem., 1996, 100, 13121-13131.

[0097] In another embodiment, liquid injection ALD is used to form a metal-containing film by evaporating and / or passing at least one metal complex disclosed herein over a substrate surface, and the at least one metal complex is delivered to the reaction chamber by direct liquid injection as opposed to vapor suction by a bubbler. For liquid injection ALD processes, see, e.g., Potter R. J., et al., Chem. Vap. Deposition, 2005, 11(3), 159-169.

[0098] Examples of ALD growth conditions for the metal complexes disclosed herein include, but are not limited to: a. Substrate temperature: 0 to 400 °C b. Evaporator temperature (metal precursor temperature): 0 to 200 °C c. Reactor pressure: 0 to 100 Torr d. Flow rate of argon or nitrogen carrier gas: 0 to 500 sccm e. Flow rate of reaction gas: 0 to 500 sccm f. Pulse sequence (metal complex / purge / reaction gas / purge): varies depending on the size of the chamber g. Number of cycles: varies depending on the desired film thickness In another embodiment, photo-assisted ALD is used to form a metal-containing film by evaporating and / or passing at least one metal complex disclosed herein over a substrate surface. For a photo-assisted ALD process, see, for example, U.S. Patent No. 4,581,249.

[0099] In another embodiment, plasma-assisted ALD or plasma-enhanced ALD is used to form a metal-containing film by evaporating and / or passing at least one metal complex disclosed herein over a substrate surface.

[0100] In another embodiment, a method of forming a metal-containing film on a substrate surface includes: during an ALD process, exposing the substrate to a vapor-phase metal complex according to one or more of the embodiments described herein to form a layer on the surface that includes a metal complex bound to the surface by a metal center (e.g., nickel); during the ALD process, exposing the substrate having a metal complex bound to a co-reactant to cause an exchange reaction between the bound metal complex and the co-reactant, thereby dissociating the bound metal complex and producing a first layer of elemental metal on the substrate surface; and sequentially repeating the ALD process and the treatment.

[0101] The reaction time, temperature, and pressure are selected to produce metal surface interactions and form a layer on the surface of the substrate. The reaction conditions for the ALD reaction are selected based on the properties of the metal complex. The deposition can be carried out at atmospheric pressure, but more commonly it is carried out under reduced pressure. The vapor pressure of the metal complex should be low enough to be practical for such applications. The substrate temperature should be high enough to maintain the bonds between the metal atoms on the surface and prevent thermal decomposition of the gas reactants. However, the substrate temperature should be high enough to keep the source materials (i.e., reactants) in the gas phase and provide sufficient activation energy for the surface reaction. The appropriate temperature depends on various parameters including the specific metal complex and pressure used. The properties of the specific metal complexes for use in the ALD deposition methods disclosed herein can be evaluated using methods known in the art and enable the selection of appropriate temperatures and pressures for the reaction. Generally, the presence of functional groups that increase the rotational entropy of the ligand sphere and lower molecular weight results in a melting point that gives rise to a liquid at typical delivery temperatures and increased vapor pressure.

[0102] Metal complexes for use in deposition methods will have all of the requirements of sufficient vapor pressure, sufficient thermal stability at the selected substrate temperature, and sufficient reactivity to cause a reaction on the substrate surface without including undesirable impurities in the thin film. Sufficient vapor pressure ensures that the molecules of the source compound are present on the substrate surface at a concentration sufficient to allow a complete self-saturation reaction. Sufficient thermal stability ensures that the source compound does not undergo thermal decomposition that produces impurities in the thin film.

[0103] Thus, the metal complexes disclosed herein that are utilized in these methods may be liquids, solids, or gases. Typically, the metal complex is a liquid or solid at ambient temperature having a vapor pressure sufficient to allow consistent transport of the vapor into the process chamber.

[0104] In one embodiment, a film of elemental metal, metal nitride, metal oxide, or metal silicide can be formed by delivering at least one metal complex as disclosed herein, either independently or in combination with a co-reactant, for vapor deposition. In this regard, the co-reactant can be vapor deposited or delivered or passed over the substrate surface either independently or in combination with at least one metal complex. As will be readily appreciated, the particular 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, alcohol, 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, t-butanol, etc. Examples of suitable boranes include, but are not limited to, hydrogenated (i.e., reduced) boranes such as borane, diborane, triborane, etc. Examples of suitable silanes include, but are not limited to, hydrogenated silanes such as silane, disilane, trisilane, etc. Examples of suitable hydrazines include, but are not limited to, hydrazine (N2H4), hydrazine optionally substituted with one or more alkyl groups such as methylhydrazine, tert-butylhydrazine, N,N- or N,N'-dimethylhydrazine (i.e., alkyl-substituted hydrazine), hydrazine optionally substituted with one or more aryl groups such as phenylhydrazine (i.e., aryl-substituted hydrazine), etc.

[0105] In one embodiment, the metal complex disclosed herein is delivered to the substrate surface in pulses alternating with pulses of an oxygen-containing co-reactant to provide a metal oxide film. Examples of such oxygen-containing co-reactants include, but are not limited to, H2O, H2O2, O2, ozone, air, i-PrOH, t-BuOH, or N2O, etc.

[0106] In other embodiments, the co-reactant includes a reducing agent, such as hydrogen. In this embodiment, an elemental metal film is obtained. In certain embodiments, the elemental metal film consists of, or consists essentially of, a pure metal. Such a pure metal film may contain more than about 80, 85, 90, 95, or 98% metal. In even more specific embodiments, the elemental metal film is a scandium film or a yttrium film.

[0107] In other embodiments, at least one metal complex disclosed herein is delivered to a reaction chamber for vapor deposition, either alone or in combination with a co-reactant such as, but not limited to, ammonia, hydrazine, and / or other nitrogen-containing compounds (e.g., amines), to form a metal nitride film. A plurality of such co-reactants may be used. In a further embodiment, the metal nitride film is a nickel nitride film.

[0108] In another embodiment, the mixed metal film can be formed by a vapor deposition process in which at least one metal complex disclosed herein is evaporated in combination with a second metal complex containing a metal other than the metal of the at least one metal complex disclosed herein, but not necessarily simultaneously.

[0109] In certain embodiments, the methods of the present technology are utilized for applications such as complementary metal oxide semiconductor (CMOS) for memory and logic applications on substrates such as dynamic random access memory (DRAM) and silicon chips.

[0110] Any of the metal complexes disclosed herein can be used to prepare thin films of elemental metals, metal oxides, metal nitrides, and / or metal silicides. Such films can find use as oxidation catalysts, anode materials (e.g., SOFC or LIB anodes), conductive layers, sensors, diffusion barriers / c coatings, superconducting and non-superconducting materials / c coatings, friction coatings, and / or protective coatings. It will be understood by those skilled in the art that film properties (e.g., conductivity) depend on many factors such as the metals, co-reactants and / or co-complexes used in the deposition, the thickness of the film produced, the parameters used during growth and subsequent processes, and the substrate.

[0111] There are fundamental differences between thermally driven CVD processes and reactively driven ALD processes. The requirements for precursor properties to achieve optimal performance are very different. In CVD, clean thermal decomposition of the complex to deposit the necessary chemical species on the substrate is important. However, in ALD, such thermal decomposition must be avoided at all costs. In ALD, the reaction between the incoming reagents must be rapid on the surface, resulting in the formation of the target substance on the substrate. However, in CVD, such reactions between chemical species are detrimental due to their gas-phase mixing before reaching the substrate and can lead to particle formation. In general, it has been recognized that good CVD precursors do not necessarily form good ALD precursors due to the relaxed thermal stability requirements for CVD precursors. In the present invention, the metal complexes of formula I have sufficient thermal stability and reactivity towards selected co-reactants to function as ALD precursors, and they also have a clean decomposition pathway at higher temperatures to form the desired material through a CVD process. Therefore, the metal complexes described in formula I are advantageously useful as viable ALD and CVD precursors.

[0112] Throughout this specification, references to "one embodiment", "a particular embodiment", "one or more embodiments" or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the technology. Thus, the appearances of the phrases "in one or more embodiments", "in a particular embodiment", "in one embodiment", or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0113] Although the technology herein has been described with reference to particular embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the technology. It will be apparent to those skilled in the art that various modifications and variations can be made to the methods and apparatuses of the technology without departing from the spirit and scope of the technology. Accordingly, the technology is intended to include modifications and variations that are within the scope of the appended claims and their equivalents. Accordingly, the technology will be more readily understood by reference to the following examples, which are generally described but provided for illustrative purposes and are not intended to be limiting.

[0114] In addition to, or in place of, this, the invention can include one or more of the following embodiments.

[0115] Embodiment 1. A metal complex whose structure corresponds to formula I: [(R 1 ) n Cp]2M 1 L 1 (I); In the formula, M 1 is a Group 3 metal or a lanthanide (e.g., scandium, yttrium, and lanthanum); R 1 are each independently hydrogen, C1-C5-alkyl, or silyl; n is 1, 2, 3, 4, or 5; Cp is a cyclopentadienyl ring; and L 1 is NR2 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=C-C-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 selected from the group consisting of; wherein 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 is each independently hydrogen or C1-C5-alkyl, and R 32 、R 33 、R 34 、R 35 and R 36 is each independently alkyl or silyl; optionally, wherein M 1 is yttrium and L 1 is 3,5-R 7 R 8 -C3HN2, then R 1 is C1-C5-alkyl or silyl; and optionally, wherein M 1 is yttrium and L 1 is N(SiR4 R 5 R 6 When it is 2, n is 1, 2, 3, or 4.

[0116] Embodiment 2. R 1 is, independently of one another, hydrogen, C1-C4-alkyl or silyl; and R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is, independently of one another, hydrogen or C1-C4-alkyl; and R 32 , R 33 , R 34 , R 35 and R 36 is, independently of one another, C1-C5-alkyl or silyl, the metal complex of Embodiment 1.

[0117] Embodiment 3. R 1 is, independently of one another, 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 is, independently of one another, 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 is, independently of one another, C1-C4-alkyl or silyl, preferably methyl, ethyl, propyl or silyl, more preferably SiMe3, the metal complex according to Embodiment 1 or 2.

[0118] Embodiment 4. R 1 is, independently of one another, hydrogen, C1-C4-alkyl or silyl; L1 is NR 2 R 3 and R 2 and R 3 are each independently hydrogen or C1-C4-alkyl, the metal complex according to any one of the above embodiments.

[0119] Embodiment 5. R 1 are each independently hydrogen, methyl, ethyl, propyl or silyl, preferably hydrogen, methyl or ethyl, more preferably methyl; R 2 and R 3 are each independently hydrogen, methyl, ethyl or propyl, preferably hydrogen, methyl or ethyl, the metal complex according to Embodiment 4.

[0120] Embodiment 6. R 1 are each independently hydrogen, C1-C4-alkyl or silyl; and, L 1 is N(SiR 4 R 5 R 6 )2, R 4 , R 5 and R 6 are each independently hydrogen or C1-C4-alkyl, the metal complex according to any one of the above embodiments.

[0121] Embodiment 7. R 1 are each independently hydrogen, methyl, ethyl, propyl or silyl, preferably hydrogen, methyl or ethyl, more preferably methyl; and, R 4 , R 5 and R 6 are each independently hydrogen, methyl, ethyl or propyl, preferably hydrogen, methyl or ethyl, the metal complex according to Embodiment 6.

[0122] Embodiment 8. R 1 are each independently hydrogen, C1-C4-alkyl or silyl; and, L 1 is 3,5-R 7R 8 is - C3HN2, and R 7 and R 8 are each independently hydrogen or C1 - C5 - alkyl, the metal complex according to any one of the above embodiments.

[0123] Embodiment 9. R 1 are each independently hydrogen, methyl, ethyl, propyl or silyl, preferably hydrogen, methyl or ethyl, more preferably methyl, the metal complex according to Embodiment 8.

[0124] Embodiment 10. R 1 are each independently hydrogen, C1 - C4 - alkyl or silyl, preferably hydrogen, methyl, ethyl or silyl; and, L 1 is 1-(R 32 )C3H4, and R 32 is C1 - C5 - alkyl or silyl, preferably R 32 is methyl, ethyl or silyl, more preferably L 1 is 1-(SiMe3)C3H4, the metal complex according to any one of the above embodiments.

[0125] Embodiment 11. R 1 are each independently hydrogen, C1 - C4 - alkyl or silyl, preferably hydrogen, methyl, ethyl or silyl; and, L 1 is 1 - R 33 -3 - R 34 -C3H3, and R 33 and R 34 are each independently C1 - C5 - alkyl or silyl, preferably R 33 and R 34 are each independently methyl, ethyl or silyl, more preferably L 1 is 1,3 - bis-(SiMe3)2C3H3, the metal complex according to any one of the above embodiments.

[0126] Embodiment 12. R 1is, independently of one another, hydrogen, C1-C4-alkyl or silyl, preferably hydrogen, methyl, ethyl or silyl; and L 1 is R 35 、R 36 -C3HO2, and R 35 and R 36 are, independently of one another, C1-C5-alkyl or silyl, preferably R 35 and R 36 are, independently of one another, methyl, ethyl, propyl, butyl or silyl, more preferably L 1 is 6-methyl-2,4-heptanedionate, i.e., Me,iBu-C3HO2, the metal complex according to any one of the above embodiments.

[0127] Embodiment 13. 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(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]; Sc(MeCp)2(3,5-Me2-C3HN2), the metal complex according to any one of the above embodiments.

[0128] Embodiment 14. The metal complex whose structure corresponds to formula II: [((R 9 ) n Cp)2M 2 L 2 2 (II), wherein M 2 is a Group 3 metal or a lanthanide (e.g., scandium, yttrium and lanthanum); R 9 are, independently of one another, hydrogen, or C1-C5-alkyl; n is 1, 2, 3, 4, or 5; Cp is a cyclopentadienyl ring; and L 2 is Cl; F; Br; I; 3,5-R 10 R 11 -C3HN2; R22 N=C-C-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 selected from 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 are each independently hydrogen or C1-C5-alkyl, and optionally, M 2 is scandium, and L 2 is Cl, then R 9 is C1-C5-alkyl.

[0129] Embodiment 15. The metal complex according to Embodiment 14, wherein R 9 is each independently C1-C5-alkyl.

[0130] Embodiment 16. The metal complex according to Embodiment 14 or 15, wherein R 9 is each independently hydrogen or C1-C4-alkyl, preferably hydrogen, methyl, ethyl or propyl, more preferably hydrogen, methyl or ethyl, and even more preferably methyl.

[0131] Embodiment 17. The metal complex according to Embodiment 14, 15 or 16, wherein M 2 is scandium; R 9 is each independently C1-C4-alkyl, preferably methyl, ethyl or propyl, more preferably methyl; and preferably, L 2 is Cl.

[0132] Embodiment 18. M 2 is yttrium; R 9 is each independently C1-C5-alkyl, preferably methyl, ethyl or propyl; more preferably methyl or ethyl; and preferably, L 2 is 3,5-R 10 R 11 -C3HN2, and R 9 are each independent, a metal complex according to Embodiment 14, 15 or 16.

[0133] Embodiment 19. A metal complex according to Embodiment 14, 15, 16, 17 or 18, wherein the complex is [Sc(MeCp)2Cl]]2; and [Y(MeCp)2(3,5-MePn-C3HN2)]2.

[0134] Embodiment 20. A method for forming a metal-containing film by a vapor deposition process, the method comprising the step of evaporating at least one metal complex according to any one of the above embodiments.

[0135] Embodiment 21. The method according to Embodiment 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.

[0136] Embodiment 22. The method according to Embodiment 20, wherein the vapor deposition process is atomic layer deposition, preferably liquid injection atomic layer deposition or plasma-enhanced atomic layer deposition.

[0137] Embodiment 23. The metal complex is delivered to the substrate in pulses alternating with pulses of an oxygen source, preferably the oxygen source is selected from the group consisting of H2O, H2O2, O2, ozone, air, i-PrOH, t-BuOH, and N2O, according to any one of Embodiments 20, 21 or 22.

[0138] Embodiment 24. The method according to any one of Embodiments 20, 21, 22, or 23, further comprising a step of evaporating at least one co-reactant 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, preferably, at least one co-reactant is hydrazine (e.g., hydrazine (N2H4), N,N-dimethylhydrazine).

[0139] Embodiment 25. The method according to any one of Embodiments 20, 21, 22, 23, or 24, which is used for DRAM or CMOS applications.

[0140] 〔Examples〕 Unless otherwise specified, all synthetic operations are carried out in an inert atmosphere (e.g., purified nitrogen or argon) using techniques for handling air-reactive substances generally known in the art (e.g., Schlenk techniques).

[0141] 〔Example 1: Preparation of Complex 11 ([Sc(MeCp)2Cl]2)〕 A 500 mL Schlenk flask equipped with a magnetic stirrer was charged with ScCl3 (15.5 g, 0.102 mol) and KMeCp (24.2 g, 0.205 mol), followed by anhydrous diethyl ether (200 mL). The mixture was stirred at room temperature (18 °C to 24 °C) for 12 hours under a nitrogen atmosphere to obtain a maroon suspension. The solvent was removed under pressure, and the resulting solid was extracted with 5 × 50 mL of toluene and filtered through a medium frit. The solvent was removed from the filtrate under reduced pressure to obtain the final product as a yellow powder (16.4 g, 0.0344 mol, 67% yield). The 1 H NMR (C6D6): δ 2.02 (12H, MeC5H4), 6.09 (8H, MeC5H4), 6.24 (8H, MeC5H4). The 13 C NMR (C6D6): δ 15.4 (MeC5H4), 114.4 (MeC5H4), 116.0 (MeC5H4), 124.9 (MeC5H4).

[0142] 〔Example 2: Preparation of Complex 3 (Sc(MeCp)2[N(SiMe3)2])〕 A 250 mL Schlenk flask equipped with a magnetic stirrer was charged with [Sc(MeCp)2Cl]2 (4.6 g, 0.0098 mol) and KN(SiMe3)2 (3.9 g, 0.020 mol), and then anhydrous diethyl ether (100 mL) was added. The mixture was stirred at room temperature (18 °C to 24 °C) for 12 hours under a nitrogen atmosphere to obtain a pink suspension. The solvent was removed under pressure, and the resulting solid was extracted with 3 × 30 mL of hexane and filtered through a medium frit. The solvent was removed from the filtrate under reduced pressure, and the final product was obtained as a yellow powder (6.7 g, 0.018 mol, 90% yield). The 1 1H NMR (C6D6): δ 1.10 (18H, SiMe3), 2.04 (6H, MeC5H4), 5.85 (4H, MeC5H4), 6.00 (4H, MeC5H4). The 13 13C NMR (C6D6): δ 4.2 (SiMe3), 15.7 (MeC5H4), 114.3 (MeC5H4), 115.9 (MeC5H4), 125.0 (MeC5H4).

[0143] 〔Example 3: Synthesis of Complex 2 (Sc(MeCp)2[1,3-bis(trimethylsilyl)allyl])〕 A 250 mL Schlenk flask equipped with a magnetic stirrer was charged with [Sc(MeCp)2Cl]2 (1.0 g, 2.1 mmol) and K(1,3-bis-trimethylsilyl-allyl) (1.05 g, 4.7 mmol), and then anhydrous diethyl ether (100 mL) was added. The mixture was stirred at room temperature (18 °C to 24 °C) for 12 hours under a nitrogen atmosphere to obtain an orange suspension. The solvent was removed under reduced pressure, and the resulting solid was extracted with 3 × 30 mL of hexane and filtered through a medium frit. The solvent was removed from the filtrate under reduced pressure, and the final product was obtained as a red liquid (1.0 g, 2.6 mmol, 62% yield). The 11H NMR (C6D6), δ 0.04 (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).

[0144] 〔Example 4: Synthesis of Complex 1 (Sc(MeCp)2(1-trimethylsilylallyl))〕 A 250 mL Schlenk flask equipped with a magnetic stirrer was charged with [Sc(MeCp)2Cl]2 (5.2 g, 10.9 mmol) and K(trimethylsilyl-allyl) (3.3 g, 21.8 mmol), and then anhydrous diethyl ether (100 mL) was added. The mixture was stirred at room temperature (18 °C to 24 °C) for 12 hours under a nitrogen atmosphere to obtain an orange suspension. The solvent was removed under reduced pressure, and the resulting solid was extracted with 3 × 30 mL of pentane and filtered through a medium frit. The solvent was removed from the filtrate under reduced pressure to obtain the final product as a red liquid (3.7 g, 11.7 mmol, 54% yield). The 1 1H NMR (C6D6): δ -0.02 (9H, SiMe3), 1.82 (6H, MeC5H4), 2.29 (1H, allyl CH2), 4.15 (1H, allyl CH2), 4.73 (1H, allyl CH(TMS)), 5.94 (8H, MeC5H4), 7.47 (1H, allyl CH).

[0145] 〔Example 5: Synthesis of Complex 4 (Sc(MeCp)2(3,5-dimethylpyrazolate))〕 A 500 mL Schlenk flask equipped with a magnetic stirrer was charged with [Sc(MeCp)2Cl]2 (12.0 g, 25.1 mmol) and KMe2Pz (6.75 g, 50.3 mmol), and then anhydrous THF (150 mL) was added. The mixture was stirred at room temperature (18 °C to 24 °C) for 12 hours under a nitrogen atmosphere. The solvent was removed under reduced pressure, and the resulting yellow sticky solid was extracted with 5 × 20 mL of toluene and filtered through a medium frit. The solvent was removed from the filtrate under reduced pressure to obtain a red oil. Further distillation under vacuum gave the final product as a pale yellow liquid (10.7 g, 35.9 mmol, 72% yield). 1 1H NMR (C6D6): δ 1.85 (6H, MeC5H4), 2.28 (6H, Me2Pz), 5.84 (4H, MeC5H4), 5.96 (1H, Me2Pz), 6.20 (4H, MeC5H4).

[0146] Example 6: Synthesis of Complex 8 (Y(MeCp)2(3-methyl-5-pentyl-pyrazolate)) A 500 mL Schlenk flask equipped with a magnetic stirrer was charged with [Y(MeCp)2Cl]2 (9.33 g, 16.5 mmol) and K(Me,Pn)Pz (6.28 g, 33.0 mmol), and then anhydrous THF (150 mL) was added. The mixture was stirred at room temperature (18 °C to 24 °C) for 12 hours under a nitrogen atmosphere. The solvent was removed under reduced pressure, and the resulting yellow sticky solid was extracted with 5 × 20 mL of toluene and filtered through a medium frit. The solvent was removed from the filtrate under reduced pressure to obtain a red oil. Further distillation under vacuum gave the final product as a pale yellow liquid (7.7 g, 19.3 mmol, 58% yield). 1 1H NMR (C6D6): δ 0.94 (3H, pentyl), 1.40 (4H, pentyl), 1.75 (2H, pentyl), 2.16 (6H, MeC5H4), 2.17 (3H, Me,Pn Pz), 2.65 (2H, pentyl), 5.66 (4H, MeC5H4), 5.90 (1H, Me,Pn Pz), 5.96 (4H, MeC5H4).

[0147] 〔Example 7: Synthesis of Complex 9 (Sc(MeCp)2(6-methyl-2,4-heptanedionate))〕 A 500 mL Schlenk flask equipped with a magnetic stirrer was charged with [Sc(MeCp)2Cl]2 (1.0 g, 1.8 mmol) and K(6-methyl-2,4-heptanedionate) (0.67 g, 3.7 mmol), and then anhydrous THF (150 mL) was added. The mixture was stirred at room temperature (18 °C to 24 °C) for 12 hours under a nitrogen atmosphere. The solvent was removed under reduced pressure, and the resulting yellow sticky solid was extracted with 3 × 20 mL of toluene and filtered through a medium frit. The solvent was removed from the filtrate under reduced pressure to obtain an orange oil (0.8 g, 2.1 mmol, 58% yield). The 1 1H NMR (C6D6): δ 0.89 (6H, i Bu), 1.71 (3H, Me), 1.89 (2H, i Bu), 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).

[0148] 〔Example 8: Synthesis of Complex 10 (Y(MeCp)2(6-methyl-2,4-heptanedionate))〕 A 500 mL Schlenk flask equipped with a magnetic stirrer was charged with [Y(MeCp)2Cl]2 (1.5 g, 2.4 mmol) and K(6-methyl-2,4-heptanedionate) (0.89 g, 4.9 mmol), and then anhydrous THF (150 mL) was added. The mixture was stirred at room temperature (18 °C to 24 °C) for 12 hours under a nitrogen atmosphere. The solvent was removed under reduced pressure, and the resulting yellow sticky solid was extracted with 3 × 20 mL of toluene and filtered through a medium frit. The solvent was removed from the filtrate under reduced pressure to obtain an orange oil (1.2 g, 2.9 mmol, 60% yield). The 1 1H NMR (C6D6): δ 0.89 (6H, i Bu), 1.72 (3H, Me), 1.91 (2H, i Bu), 2.04 (1H, iBu), 2.10 (6H, MeC5H4), 5.25 (1H, diketonate), 5.95 (4H, MeC5H4), 6.10 (2H, MeC5H4), 6.15 (2H, MeC5H4).

[0149] [Example 9: ALD of Sc2O3 film using complex 4 (Sc(MeCp)2(3,5-dimethyl-pyrazolate)) and water] Sc(MeCp)2(3,5-dimethyl-pyrazolate) was heated in a stainless steel bubbler at 100 - 115 °C and delivered into the ALD reactor using about 20 sccm of nitrogen as the carrier gas, pulsed for about 2 seconds, and then purged for about 28 - 58 seconds. Subsequently, a pulse of water vapor (1 second) was sent from a water cylinder at room temperature, followed by a 60-second nitrogen purge. A needle valve was present between the deposition chamber and the water cylinder and was adjusted to obtain an appropriate amount of water vapor. Scandium oxide was deposited on a silicon chip having a thin layer of native oxide SiO2 at about 175 - 300 °C up to 300 cycles. After cooling the reactor to about 60 °C under vacuum while purging with nitrogen, the film was taken out. A film thickness of 60 - 260 Å was obtained, and preliminary results showed a growth rate of 1 Å / cycle or less. XPS (X-ray photoelectron spectroscopy) analysis confirmed that scandium oxide with N and C contaminants removed during XPS analysis was present on the top surface. The XPS data in Figures 1 - 14 show that once the surface contamination is removed by sputtering, the film contains less than 1% of any element other than the desired scandium and oxygen. Only Sc and O were detected in the bulk, and the measured stoichiometry matched the theoretical composition of Sc2O3.

[0150] [Example 10: ALD of Y2O3 film using complex 12 ([Y(MeCp)2(3,5-MePn-C3HN2)]2)] [Outline of the method] [Y(MeCp)2(3,5-MePn-C3HN2)]2 was heated in a stainless-steel bubbler at 130 - 180 °C and delivered to a cross-flow ALD reactor using nitrogen as the carrier gas, and deposited by ALD using water. H2O was delivered by vapor suction from a stainless-steel ampoule at room temperature. A silicon chip with a native SiO2 layer 14 - 17 Å thick was used as the substrate. The as-deposited film was used for thickness and optical property measurements using an optical ellipsometer. Selected samples were analyzed by XPS for film composition and impurity concentration.

[0151] <Example 10a> [Y(MeCp)2(3,5-MePn-C3HN2)]2 was heated to 170 °C and delivered to the ALD reactor using 20 sccm of nitrogen as the carrier gas, pulsed from the bubbler for 7 seconds, followed by a 20-second N2 purge, and then pulsed with H2O for 0.015 seconds and purged with N2 for 90 seconds in each ALD cycle, and deposited at multiple temperatures from 125 - 250 °C for 200 cycles or more. The as-deposited film was cooled to 80 °C or less in the reactor under N2 purge and then removed. A thin film with a thickness of 150 - 420 Å was deposited. The data of the growth rate per cycle at a fixed reactor inlet position were plotted in Figure 15.

[0152] The curve in Figure 15 shows that the growth rate of Y2O3 from an unoptimized H2O ALD process appears to be temperature-dependent under the same deposition conditions. The higher the temperature, the faster the growth rate. Further tests revealed that the growth rate at higher temperatures seems to be affected by the H2O purge time. This may be due to the initial formation of Y(OH)3 and / or strong adsorption of H2O by the Y2O3 film at higher temperatures. For example, even when purging with H2O for 120 seconds at 200 °C, saturation was not reached, but the dependence on the H2O purge time was much smaller at 150 °C or lower, as shown in Figure 16.

[0153] <Example 10b> [Y(MeCp)2(3,5-MePn-C3HN2)]2 was heated to 170 - 176 °C and delivered to an ALD reactor using 20 sccm of nitrogen as the carrier gas, pulsed from the bubbler for 3 - 13 seconds to generate various precursor doses, followed by a 60-second N2 purge, then a 0.015-second H2O pulse and a 30-second N2 purge for each ALD cycle, and deposited at 135 °C for 350 cycles. Along the precursor / carrier gas flow direction, the film thickness was monitored at three different positions: the precursor inlet, the reactor center, and the precursor outlet in a cross-flow reactor. The growth rate data per cycle was plotted in Figure 17.

[0154] The saturation of the growth rate at approximately 0.79 Å / cycle (GPC) with increasing precursor amount, and the convergence of the growth rates at the three different positions, suggest that the process at 135 °C is a true ALD process with a minor CVD component contribution to the growth rate. Under the optimized saturation growth conditions, excellent thickness uniformity of ≤ ±1.3% was achieved over the 6 - 7-inch diameter region of the cross-flow reactor.

[0155] The complete ALD window, including the deposition temperature, has not yet been determined. This precursor was thermally stable at high temperatures ≥ 250 °C.

[0156] All publications, patent applications, issued patents, and other documents referred to herein are incorporated herein by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in incorporated references are excluded to the extent they conflict with the definitions in the present disclosure.

[0157] The terms "comprise", "comprises", and "comprising" are to be construed inclusively rather than exclusively.

Brief Description of the Drawings

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Claims

1. Use of a metal complex in the production of a metal-containing film by a vapor deposition process, wherein the structure of the metal complex is represented by Formula I: [[(R １ ) ｎ Cp] ２ M １ L １ (I) In the formula, M １ is yttrium or lanthanum; Each R １ is, independently of one another, C １ to C ５ -alkyl; n is 1, 2, 3, 4, or 5; Cp is a cyclopentadienyl ring; and L １ is R represented by the following formula ３５ , R ３６ -C ３ HO ２ and R ３５ and R ３６ are each independently C １ ~C ４ -alkyl; 【Chemical 1】 Use of the metal complex.

2. R ３５ and R ３６ is each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl, for use of the metal complex according to claim 1.

3. Each R １ is, independently of one another, C １ to C ４ -alkyl, use of the metal complex according to claim 1.

4. Each R １ is methyl or ethyl, use of the metal complex according to Claim 1.

5. A metal complex whose structure corresponds to Formula I: [(R1)nCp]2M1L1 (I) In the formula, M1 is yttrium or lanthanum; Each R1 is independently C1-C5-alkyl; n is 1, 2, 3, 4, or 5; Cp is a cyclopentadienyl ring; and L1 is R35, R36-C3HO2 represented by the following formula, R35 and R36 are each independently C1-C4-alkyl, and L1 is not 6-methyl-2,4-heptanedionate; [Chemical Formula 2] The metal complex is not (Cp*)2Y(acac) (Cp* is 1,2,3,4,5-pentamethylcyclopentadienyl, acac means acetylacetonate). Metal complex.

6. The metal complex according to Claim 5, wherein R35 and R36 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl.

7. The metal complex according to Claim 5, wherein each R1 is independently C1-C4-alkyl.

8. The metal complex according to Claim 5, wherein each R1 is methyl or ethyl.

9. A method for forming a metal-containing film by a vapor deposition process, comprising the step of evaporating at least one metal complex whose structure corresponds to Formula I: (R1Cp)2M1L1 (I) In the formula, M1 is yttrium or lanthanum; Each R1 is independently C1-C5-alkyl; Cp is a cyclopentadienyl ring; and L1 is R35, R36-C3HO2 represented by the following formula, R35 and R36 are each independently C1-C4-alkyl, and L1 is not 6-methyl-2,4-heptanedionate; 【Chemical Formula 3】 Method. **Claim 10**: The method according to claim 9, wherein R35 and R36 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl. **Claim 11**: The method according to claim 9, wherein each R1 is independently C1-C4-alkyl. **Claim 12**: The method according to claim 9, wherein each R1 is methyl or ethyl. **Claim 13**: The method according to claim 9, wherein the vapor deposition process is chemical vapor deposition or the vapor deposition process is atomic layer deposition. **Claim 14**: The method according to claim 9, wherein the metal complex is delivered to the substrate in pulses alternating with pulses of an oxygen source, and the oxygen source is selected from the group consisting of H2O, H2O2, O2, ozone, air, i-PrOH, t-BuOH, and N2O. **Claim 15**: The method according to claim 9, further comprising the step of evaporating at least one co-reactant 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, wherein the hydrazine is hydrazine (N2H4) or N,N-dimethylhydrazine. **Claim 16**: A metal complex having a structure corresponding to formula I: [(R1)nCp]2M1L1 (I) wherein: M1 is yttrium or lanthanum; each R1 is independently C1-C5-alkyl; n is 1, 2, 3, 4, or 5; Cp is a cyclopentadienyl ring; and L1 is R35, R36-C3HO2 represented by the following formula, and R35 and R36 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl; 【Chemical 4】 the metal complex is not (Cp*)2Y(acac) (Cp* means 1,2,3,4,5-pentamethylcyclopentadienyl, and acac means acetylacetonate). A metal complex. **Claim 17**: The metal complex according to claim 16, wherein each R1 is independently C1-C4-alkyl. **Claim 18**: The metal complex according to claim 16, wherein each R1 is methyl or ethyl. A method of forming a metal-containing film by a vapor deposition process, comprising the step of evaporating at least one metal complex whose structure corresponds to formula I: (R1Cp)2M1L1 (I) wherein M1 is yttrium or lanthanum; each R1 is independently C1-C5-alkyl; Cp is a cyclopentadienyl ring; and L1 is R35, R36-C3HO2 represented by the following formula, and R35 and R36 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl, 【Chemical Formula 5】 Method. The method according to claim 19, wherein each R1 is independently C1-C4-alkyl. The method according to claim 19, wherein each R1 is methyl or ethyl. The method according to claim 19, wherein the vapor deposition process is chemical vapor deposition or the vapor deposition process is atomic layer deposition. The method according to claim 19, wherein the metal complex is delivered to the substrate in pulses alternating with pulses of an oxygen source, and the oxygen source is selected from the group consisting of H2O, H2O2, O2, ozone, air, i-PrOH, t-BuOH, and N2O. The method according to claim 19, further comprising the step of evaporating at least one co-reactant 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, wherein the hydrazine is hydrazine (N2H4) or N,N-dimethylhydrazine.

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