Indenyl precursors

Abstract

The compounds have been developed and synthetically disclosed to produce compounds that improve film applications, such as HfOx, ZrOx, and TiOx film applications. The improvements in compounds of the present disclosure include improvements relating to increased molecular stability at delivery and deposition temperatures, precursor film impurity levels, molecular volatility, molecular melting point, and step coverage.

Description

Technical Field

[0001] The present disclosure relates to the field of precursors, more particularly indenyl precursors (eg, indenyl substituted precursors). Background Art

[0002] Thin films are used in semiconductor device structures. Summary of the invention

[0003] The present disclosure relates to compounds of hafnium (Hf), zirconium (Zr) and titanium (Ti) indenyl (Ind) substituted precursors for depositing Group 4 containing thin films, including HfOx, ZrOx and TiOx. These thin films can be used in various applications including semiconductor device structures. The disclosed compounds have been developed and synthesized to generate improved film applications, such as compounds for HfOx, ZrOx and TiOx film applications. The improvements of the disclosed compounds include increased molecular stability at delivery and deposition temperatures, improvements related to precursor film impurity levels, molecular volatility, molecular melting point and step coverage.

[0004] Since tungsten is replaced by molybdenum in 3D-NAND, a barrier layer is needed to protect the aluminum oxide (Al 2 O 3 ). The indenyl compounds of the present disclosure can be used as precursors with good stability and volatility. The indenyl compounds can be used for large-scale production because indene can be used directly. Other compounds cannot be used directly. For example, cyclopentadiene (Cp) compounds may first need to be cracked.

[0005] In some embodiments, the disclosed compounds can be used to grow Group 4 metal oxide films. In some embodiments, the oxide films can be used in DRAM, NAND, gate, and hard mask applications. In some embodiments, the disclosure relates to indenyl-substituted Group 4 compounds to be used as precursors to high-K metal oxide films.

[0006] The indenyl compounds disclosed herein have good volatility, stability and may be a good match for 3D-NAND applications. In some embodiments, precursors with good volatility are compatible with standard ALD equipment (i.e., valves that can be roughly correlated with TGA data). For example, in some embodiments, if the TGA of the compound has a T50 of less than 250°C, it is generally considered good. Precursors with good stability can be used for a long time with standard ALD equipment and can be roughly correlated with TGA data. For example, in some embodiments, if the TGA of the compound has a residual mass of less than 10%, it is generally considered good. Indenyl Hf compounds can be made from bulk chemicals with high purity. In some embodiments, high purity is defined as greater than 99% pure (according to NMR analysis).

[0007] In some aspects, the technology described herein involves comprising: wherein M is titanium, zirconium or hafnium, and wherein L is independently C 1 -C 15 Alkyl, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-Diketoimidate, C 1 -C 15 Fluoroalkyl, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 Amide, F, Cl, Br, I or H.

[0008] In some aspects, the technology described herein relates to compounds where M is hafnium.

[0009] In some aspects, the technology described herein relates to compounds where L is Cl, bis(2,2,2-trifluoroethyl)amide, 1,1,1,3,3,3-hexafluoro-2-propoxide, or 2,2,2-trifluoroethoxide.

[0010] In some aspects, the technology described herein relates to compounds wherein L consists of one cyclopentadienyl group and two amide groups.

[0011] In some aspects, the technology described herein relates to compounds in which the two amide groups comprise dimethylamide groups, ethylmethylamide groups, or diethylamide groups.

[0012] In some aspects, the technology described herein involves comprising: A compound wherein M is titanium, zirconium or hafnium, wherein L is independently C 1 -C 15 Alkyl, C 2 -C 15 Amide, C 1 -C 15 Alkoxide, C 1-C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-diketoimidate, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 amide, F, Cl, Br, I or H, and wherein R 1 -R 7 Independently for C 1 -C 15 Alkyl, C 1 -C 15 Ether, C 2 -C 15 Amine, C 1 -C 15 Fluoroether, C 1 -C 15 fluoroalkyl, OH, F, Cl, Br, I or H, wherein at least one R 1 -R 7 Groups containing C 1 -C 15 Alkyl, C 1 -C 15 Ether, C 2 -C 15 Amine, C 1 -C 15 Fluoroether, C 1 -C 15 Fluoroalkyl, OH, F, Cl, Br or I.

[0013] In some aspects, the technology described herein relates to compounds where M is hafnium and L is dimethylamido, ethylmethylamido, diethylamido, or bis(2,2,2-trifluoroethyl)amido.

[0014] In some aspects, the technology described herein involves R 2 is methyl or ethyl and R 1 , R 3 , R 4 , R 5 , R 6 and R 7A compound of H.

[0015] In some aspects, the technology described herein involves R 4 and R 7 is methyl and R 1 , R 2 , R 3 , R 5 and R 6 A compound of H.

[0016] In some aspects, the technology described herein involves R 1 For CF 3 And R 2 -R 7 A compound of H.

[0017] In some aspects, the technology described herein involves R 1 is methyl or ethyl and R 2 -R 7 A compound of H.

[0018] In some aspects, the technology described herein involves comprising: A compound wherein M is titanium, zirconium or hafnium, wherein L is independently C 1 -C 15 Alkyl, C 2 -C 15 Amide, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-Diketoimidate, C 1 -C 15 Fluoroalkyl, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 Amide, F, Cl, Br, I or H, where R 1 -R 5 Independently for C 1 -C 15 Alkyl, C1 -C 15 fluoroalkyl or H, and wherein X is independently C or Si.

[0019] In some aspects, the technology described herein relates to compounds where M is hafnium and L is dimethylamido, ethylmethylamido, diethylamido, or bis(2,2,2-trifluoroethyl)amido.

[0020] In some aspects, the technology described herein involves R 5 is methyl or ethyl, R 1 -R 4 The compound wherein X is H and C.

[0021] In some aspects, the technology described herein involves comprising: A compound wherein M is titanium, zirconium or hafnium, wherein L is independently C 1 -C 15 Alkyl, C 2 -C 15 Amide, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-Diketoimidate, C 1 -C 15 Fluoroalkyl, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 Amide, F, Cl, Br, I or H, where R 1 -R 4 Independently for C 1 -C 15 Alkyl, C 1 -C 15 fluoroalkyl or H, and wherein X is independently C or Si.

[0022] In some aspects, the technology described herein relates to compounds where M is hafnium and L is dimethylamido, ethylmethylamido, diethylamido, or bis(2,2,2-trifluoroethyl)amido.

[0023] In some aspects, the technology described herein involves R 1 -R 3 H, R 4 The compound wherein X is C and R is methyl or ethyl.

[0024] In some aspects, the technology described herein relates to a method of depositing a film, comprising: applying a compound to a substrate.

[0025] In some aspects, the technology described herein relates to methods wherein the compound is a compound of formula (1).

[0026] In some aspects, the technology described herein relates to methods wherein the compound is a compound of formula (2).

[0027] In some aspects, the technology described herein relates to methods wherein the compound is a compound of formula (3).

[0028] In some aspects, the technology described herein relates to methods wherein the compound is a compound of formula (4). BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Some embodiments of the present disclosure are described herein only by way of example and with reference to the accompanying drawings. With particular reference now to the drawings in detail, it should be emphasized that the embodiments shown are given by way of example and for the purpose of illustrative discussion of the embodiments of the present disclosure. In this regard, the description in conjunction with the drawings makes it clear to those skilled in the art how the embodiments of the present disclosure can be practiced.

[0030] Figure 1A Shown are compounds of Formula 1 according to some embodiments.

[0031] Figure 1B Shown are compounds of Formula 1 according to some embodiments.

[0032] Figure 1C Shown are compounds of Formula 1 according to some embodiments.

[0033] Figure 2 Shown are compounds of Formula 2 according to some embodiments.

[0034] Figure 3 Shown are compounds of Formula 3 according to some embodiments.

[0035] Figure 4 Shown are compounds of Formula 4 according to some embodiments.

[0036] Figure 5Shown are compounds of the present disclosure according to some embodiments.

[0037] Figure 6 IndHf(Cl) according to some embodiments is shown 3 Thermogravimetric analysis (TGA) of

[0038] Figure 7 2-MeIndHf(NMe 2 ) 3 TGA.

[0039] Figure 8 2-MeIndHf(NMe 2 ) 3 of 1 H-NMR spectrum. DETAILED DESCRIPTION

[0040] In addition to the benefits and improvements disclosed, other objects and advantages of the present disclosure may be apparent from the following description and the accompanying drawings. Detailed embodiments of the present disclosure are disclosed herein; however, it should be understood that the disclosed embodiments are merely illustrative of the disclosure that can be embodied in various forms. In addition, each example given for each embodiment of the present disclosure is intended to be illustrative and not limiting.

[0041] Throughout the specification and claims, unless the context clearly dictates otherwise, the following terms adopt the meanings clearly associated with this document. The phrases "in one embodiment," "in an embodiment," and "in some embodiments" as used herein do not necessarily refer to the same embodiment, but they may. In addition, the phrases "in another embodiment" and "in some other embodiments" as used herein do not necessarily refer to different embodiments, but they may. All embodiments of the present disclosure are intended to be combined without departing from the scope or spirit of the present disclosure.

[0042] As used herein, unless the context clearly dictates otherwise, the term "based on" is not exclusive and allows for being based on other unstated factors. In addition, throughout the specification, the meanings of "a, an" and "the" include plural references. The meaning of "in..." includes "in..." and "on...".

[0043] As used herein, the term "between" does not necessarily require being arranged directly next to other elements. Generally, this term means a configuration in which an item is sandwiched between two or more other items. At the same time, the term "between" may describe an item being directly adjacent to two opposing items. Therefore, in any one or more embodiments disclosed herein, a specific structural component being arranged between two other structural elements may be the following:

[0044] Directly disposed between two other structural elements, such that the particular structural component is in direct contact with both other structural elements;

[0045] being arranged directly next to only one of the two other structural elements, such that the particular structural component is in direct contact with only one of the two other structural elements;

[0046] indirectly disposed beside only one of the two other structural elements, such that the particular structural component is not in direct contact with only one of the two other structural elements, and there is another element juxtaposed with the particular structural component and one of the two other structural elements;

[0047] indirectly disposed between two other structural elements, so that a particular structural component is not in direct contact with both other structural elements, and other features may be disposed therebetween; or

[0048] Any combination thereof.

[0049] As used herein, "embedded" means that a first material is distributed throughout a second material.

[0050] The present disclosure relates to indenyl hafnium, zirconium and titanium precursors for depositing HfOx, ZrOx and TiOx thin films. These films can be used in a variety of applications, including semiconductor device structures. For example, compounds disclosed herein have been developed and synthesized to generate improved film applications, such as HfOx, ZrOx and TiOx film applications. The improvements in the disclosed compounds include increased molecular stability at delivery and deposition temperatures, improvements related to precursor film impurity levels, molecular volatility, molecular melting point and step coverage.

[0051] Since tungsten is replaced by molybdenum in 3D-NAND, a barrier layer is needed to protect the aluminum oxide (Al 2 O 3 ). Indenyl compounds (e.g., indenyl Hf compounds) can be used as precursors with good stability and volatility. Indenyl compounds (e.g., indenyl Hf compounds) can be used for large-scale production because indene can be used directly. Other compounds cannot be used directly. For example, cyclopentadiene (Cp) compounds may first need to be cracked. In addition, other compounds may form potentially explosive solutions.

[0052] In some embodiments, the disclosed compounds can be used to grow Group 4 metal oxide films. In some embodiments, the oxide films can be used in DRAM, NAND, gate, and hard mask applications. In some embodiments, the disclosure relates to indenyl-substituted Group 4 compounds to be used as precursors to high-K metal oxide films.

[0053] Indenyl Hf compounds have good volatility, stability and may be a good match for 3D-NAND applications. Indenyl Hf compounds can be prepared from bulk chemicals in high purity.

[0054] In some embodiments, compounds of the present disclosure include compounds having the formula:

[0055]

[0056] In some embodiments, for Formula 1, M is titanium, zirconium, or hafnium. In some embodiments, for Formula 1, L is independently C 1 -C 15 Alkyl, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-Diketoimidate, C 1 -C 15 Fluoroalkyl, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 Amide, F, Cl, Br, I or H.

[0057] In some embodiments, for Formula 1, M is hafnium.

[0058] In some embodiments, for Formula 1, L is Cl (chloro), bis(2,2,2-trifluoroethyl)amide, 1,1,1,3,3,3-hexafluoro-2-propoxide, or 2,2,2-trifluoroethoxide.

[0059] In some embodiments, for Formula 1, L consists of one cyclopentadienyl group and two amide groups. In some embodiments, the two amide groups include dimethylamide, ethylmethylamide, or diethylamide.

[0060] Figure 1A Shown are compounds of Formula 1 according to some embodiments. In some embodiments, Figure 1AThe compound of formula 1 IndHf(Cl) is shown when M is Hf and L is Cl 3 .

[0061] In some embodiments, for Formula 1, M is Hf and L is bis(2,2,2-trifluoroethyl)amide.

[0062] In some embodiments, for Formula 1, M is Hf and L is 1,1,1,3,3,3-hexafluoro-2-propoxide or 2,2,2-trifluoroethoxide. Figure 1B Shown are compounds of Formula 1 according to some embodiments. Figure 1B The compound shown is when M is Hf and L is 2,2,2-trifluoroethoxide.

[0063] In some embodiments, for Formula 1, M is Hf and L is OMe. Figure 1C Compounds of Formula 1 are shown where M is Hf and L is OMe.

[0064] In some embodiments, M is Hf and L consists of one cyclopentadienyl group and two amide groups, specifically dimethylamide, ethylmethylamide, or diethylamide.

[0065] In some embodiments, compounds of the present disclosure include compounds having the formula:

[0066]

[0067] In some embodiments, M is titanium, zirconium, or hafnium.

[0068] In some embodiments, L is independently C 1 -C 15 Alkyl, C 2 -C 15 Amide, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-diketoimidate, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group2 -C 15 Amide, F, Cl, Br, I or H.

[0069] In some embodiments, R 1 -R 7 Independently for C 1 -C 15 Alkyl, C 1 -C 15 Ether, C 2 -C 15 Amine, C 1 -C 15 Fluoroether, C 1 -C 15 fluoroalkyl, OH, F, Cl, Br, I or H, wherein at least one R 1 -R 7 Groups containing C 1 -C 15 Alkyl, C 1 -C 15 Ether, C 2 -C 15 Amine, C 1 -C 15 Fluoroether, C 1 -C 15 Fluoroalkyl, OH, F, Cl, Br or I.

[0070] In some embodiments, M is hafnium, and L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0071] In some embodiments, R 2 is methyl or ethyl, and R 1 , R 3 , R 4 , R 5 , R 6 and R 7 For H. Figure 2 Shown are compounds of Formula 2 according to some embodiments. Figure 2 Display M is Hf, R 2 is methyl and R 1 , R 3 , R 4 , R 5 , R 6 and R 7 The compound of formula 2 when is H.

[0072] In some embodiments, R 4 and R 7 is methyl, and R 1 , R 2 , R 3 , R5 and R 6 For H.

[0073] In some embodiments, R 1 For CF 3 , and R 2 -R 7 For H.

[0074] In some embodiments, R 1 is methyl or ethyl, and R 2 -R 7 For H.

[0075] In some embodiments, M is hafnium; L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide; R 2 is methyl or ethyl; and R 1 , R 3 , R 4 , R 5 , R 6 and R 7 For H.

[0076] In some embodiments, M is hafnium; L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide; R 4 and R 7 is methyl; and R 1 , R 2 , R 3 , R 5 and R 6 For H.

[0077] In some embodiments, M is hafnium; L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide; R 1 For CF 3 ; and R 2 -R 7 For H.

[0078] In some embodiments, M is hafnium; L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide; R 1 is methyl or ethyl; and R 2 -R 7 For H.

[0079] In some embodiments, compounds of the present disclosure include compounds having the formula:

[0080]

[0081] In some embodiments, M is titanium, zirconium, or hafnium.

[0082] In some embodiments, L is independently C 1 -C 15 Alkyl, C 2 -C 15 Amide, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-Diketoimidate, C 1 -C 15 Fluoroalkyl, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 Amide, F, Cl, Br, I or H.

[0083] In some embodiments, R 1 -R 5 Independently for C 1 -C 15 Alkyl, C 1 -C 15 Fluoroalkyl or H.

[0084] In some embodiments, X is independently C or Si.

[0085] In some embodiments, M is hafnium, and L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0086] In some embodiments, R 5 is methyl or ethyl; R 1 -R 4 is H; and X is C. Figure 3 Shown are compounds of Formula 3 according to some embodiments. Figure 3 Display M is Hf, R 5 Methyl, R 1 -R 4 The compound of formula 3 when is H and X is C.

[0087] In some embodiments, M is hafnium; L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide; R 5 is methyl or ethyl; R 1 -R 4 is H; and X is C.

[0088] In some embodiments, compounds of the present disclosure include compounds having the formula:

[0089]

[0090] In some embodiments, M is titanium, zirconium, or hafnium.

[0091] In some embodiments, L is independently C 1 -C 15 Alkyl, C 2 -C 15 Amide, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-Diketoimidate, C 1 -C 15 Fluoroalkyl, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 Amide, F, Cl, Br, I or H.

[0092] In some embodiments, R 1 -R 4 Independently for C 1 -C 15 Alkyl, C 1 -C 15 fluoroalkyl or H, and

[0093] In some embodiments, X is independently C or Si.

[0094] In some embodiments, M is hafnium, and L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0095] In some embodiments, R 1 -R 3 H; R 4 is methyl or ethyl; and X is C. Figure 4 Shown are compounds of Formula 4 according to some embodiments. Figure 4 Display M is Hf, R 1 -R 3 H, R 4 The compound of formula 4 when X is C and R is methyl.

[0096] In some embodiments, M is hafnium; L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide; R 1 -R 3 H; R 4 is methyl or ethyl; and X is C.

[0097] In some embodiments, the disclosed methods involve depositing a film comprising applying a compound as described herein to a substrate. In some embodiments, the compound is a disclosed compound of Formula 1. In some embodiments, the compound is a disclosed compound of Formula 2. In some embodiments, the compound is a disclosed compound of Formula 3. In some embodiments, the compound is a disclosed compound of Formula 4.

[0098] Figure 5 Compounds of the present disclosure according to some embodiments are shown. Figure 5 In this case, the metal is hafnium. Figure 5 For the compounds shown in 2 、NEtMe、NEt 2 , OMe, OEt, Oi-Pr, Ot-Bu, Cl, Br, I, Cp, Me, H, amide, alkoxide, formates, fluorinated alkoxides, fluorinated amides, substituted Cp, amidino, guanidino, β-diketonate, β-ketoimidate or β-diketoimidate.

[0099] Figure 6 IndHf(Cl) according to some embodiments is shown 3 Thermogravimetric analysis TGA. Figure 6 show Figure 1A Compound IndHf(Cl) 3 TGA of 200 mg / mL. The temperature at which 50% of the residual mass was present was 205.98° C. The residue was 4.662% (0.1882 mg).

[0100] Figure 7 2-MeIndHf(NMe 2 ) 3 TGA. For 2-MeIndHf(NMe 2 ) 3 For example, the temperature at which 50% of the residual mass was present was 200.98° C. The residue was 7.437% (0.6868 mg).

[0101] Figure 8 2-MeIndHf(NMe 2 ) 3 NMR.

[0102] aspect

[0103] Different aspects are described below. It should be understood that any one or more of the recited features in the following aspects may be combined with any one or more of the other aspects.

[0104] Aspect 1. A compound comprising: wherein M is titanium, zirconium or hafnium, and wherein L is independently C 1 -C 15 Alkyl, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-Diketoimidate, C 1 -C 15 Fluoroalkyl, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 Amide, F, Cl, Br, I or H.

[0105] Aspect 2. The compound according to aspect 1, wherein M is hafnium.

[0106] Aspect 3. The compound according to aspect 1 or 2, wherein L is Cl, bis(2,2,2-trifluoroethyl)amide, 1,1,1,3,3,3-hexafluoro-2-propoxide or 2,2,2-trifluoroethoxide.

[0107] Aspect 4. The compound according to aspect 1 or 2, wherein L consists of one cyclopentadienyl group and two amide groups.

[0108] Aspect 5. The compound according to aspect 4, wherein the two amide groups include dimethylamide, ethylmethylamide or diethylamide.

[0109] Aspect 6. A compound comprising: Where M is titanium, zirconium or hafnium, and where L is independently C 1 -C 15 Alkyl, C 2 -C 15 Amide, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-diketoimidate, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 amide, F, Cl, Br, I or H, and wherein R 1 -R 7 Independently for C 1 -C 15 Alkyl, C 1 -C 15 Ether, C 2 -C 15 Amine, C 1 -C 15 Fluoroether, C 1 -C 15 fluoroalkyl, OH, F, Cl, Br, I or H, wherein at least one R 1 -R 7 Groups containing C 1 -C15 Alkyl, C 1 -C 15 Ether, C 2 -C 15 Amine, C 1 -C 15 Fluoroether, C 1 -C 15 Fluoroalkyl, OH, F, Cl, Br or I.

[0110] Aspect 7. The compound according to aspect 6, wherein M is hafnium, and wherein L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0111] Aspect 8. The compound according to aspect 6 or 7, wherein R 2 is methyl or ethyl, and R 1 , R 3 , R 4 , R 5 , R 6 and R 7 For H.

[0112] Aspect 9. The compound according to aspect 6 or 7, wherein R 4 and R 7 is methyl, and R 1 , R 2 , R 3 , R 5 and R 6 For H.

[0113] Aspect 10. The compound according to aspect 6 or 7, wherein R 1 For CF 3 , and R 2 -R 7 For H.

[0114] Aspect 11. The compound according to aspect 6 or 7, wherein R 1 is methyl or ethyl, and R 2 -R 7 For H.

[0115] Aspect 12. A compound comprising: Where M is titanium, zirconium or hafnium, and where L is independently C 1 -C 15 Alkyl, C 2 -C 15 Amide, C 1 -C 15 Alkoxide, C 1 -C 15Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15 β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-Diketoimidate, C 1 -C 15 Fluoroalkyl, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 Amide, F, Cl, Br, I or H, where R 1 -R 5 Independently for C 1 -C 15 Alkyl, C 1 -C 15 fluoroalkyl or H, and wherein X is independently C or Si.

[0116] Aspect 13. The compound according to aspect 12, wherein M is hafnium, and wherein L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0117] Aspect 14. The compound according to aspect 12 or 13, wherein R 5 is methyl or ethyl, wherein R 1 -R 4 is H, and wherein X is C.

[0118] Aspect 15. A compound comprising: Where M is titanium, zirconium or hafnium, and where L is independently C 1 -C 15 Alkyl, C 2 -C 15 Amide, C 1 -C 15 Alkoxide, C 1 -C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C 5 -C 15 Amidino, C 5 -C 15 Guanidine, C 5 -C 15β-diketonate, C 5 -C 15 β-Ketoimidate, C 5 -C 15 β-Diketoimidate, C 1 -C 15 Fluoroalkyl, C containing at least one fluorine group 1 -C 15 Alkoxides, C containing at least one fluorine group 2 -C 15 Amide, F, Cl, Br, I or H, where R 1 -R 4 Independently for C 1 -C 15 Alkyl, C 1 -C 15 fluoroalkyl or H, and wherein X is independently C or Si.

[0119] Aspect 16. The compound according to aspect 15, wherein M is hafnium, and wherein L is dimethylamide, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0120] Aspect 17. The compound according to aspect 15 or 16, wherein R 1 -R 3 is H, where R 4 is methyl or ethyl, and X is C.

[0121] Aspect 18. A method of depositing a film, comprising: applying the compound according to aspects 1 to 17 to a substrate.

[0122] Aspect 19. The method according to aspect 18, wherein the compound is the compound according to aspect 1.

[0123] Aspect 20. The method according to aspect 18, wherein the compound is the compound according to aspect 6.

[0124] Aspect 21. The method according to aspect 18, wherein the compound is the compound according to aspect 12.

[0125] Aspect 22. The method according to aspect 18, wherein the compound is the compound according to aspect 15.

[0126] It is to be understood that changes may be made in detail, particularly as to the materials of construction employed and the shape, size and arrangement of parts without departing from the scope of the present disclosure.This specification and described embodiments are examples, with the true scope and spirit of the disclosure being indicated by the following claims.

Claims

1. A compound comprising: wherein M is titanium, zirconium or hafnium, and Where L is independently C1-C 15 Alkyl, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 amidino, C5-C 15 Guanidine, C5-C 15 β-Diketonate, C5-C 15 β-Ketoimidate, C5-C 15 β-Diketoimidate, C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, F, Cl, Br, I or H.

2. The compound according to claim 1, Wherein M is hafnium.

3. A compound according to claim 1 or claim 2, Wherein L is Cl, bis(2,2,2-trifluoroethyl)amide, 1,1,1,3,3,3-hexafluoro-2-propoxide or 2,2,2-trifluoroethoxide.

4. The compound according to claim 1 or claim 2, Wherein L is composed of a cyclopentadienyl group and two amide groups.

5. The compound according to claim 4, The two amide groups include dimethylamide, ethylmethylamide or diethylamide.

6. A compound comprising: Wherein M is titanium, zirconium or hafnium, Where L is independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 amidino, C5-C 15 Guanidine, C5-C 15 β-Diketonate, C5-C 15 β-Ketoimidate, C5-C 15 β-diketoimidate, C1-C2-diketoimidate containing at least one fluorine group 15 Alkoxides, C2-C 15 amide, F, Cl, Br, I or H, and Wherein R1-R7 are independently C1-C 15 Alkyl, C1-C 15 Ether, C2-C 15 Amine, C1-C 15 Fluoroether, C1-C 15 fluoroalkyl, OH, F, Cl, Br, I or H, wherein at least one R1-R7 group contains C1-C 15 Alkyl, C1-C 15 Ether, C2-C 15 Amine, C1-C 15 Fluoroether, C1-C 15 Fluoroalkyl, OH, F, Cl, Br or I.

7. The compound according to claim 6, Where M is hafnium, and Wherein L is dimethylamide, ethylmethylamide, diethylamide or bis(2,2,2-trifluoroethyl)amide.

8. A compound according to claim 6 or claim 7, Wherein R2 is methyl or ethyl, and Wherein R1, R3, R4, R5, R6 and R7 are H.

9. A compound according to claim 6 or claim 7, wherein R4 and R7 are methyl groups, and Wherein R1, R2, R3, R5 and R6 are H.

10. The compound according to claim 6 or claim 7, Where R1 is CF3, and Wherein R2-R7 is H.

11. The compound according to claim 6 or claim 7, Wherein R1 is methyl or ethyl, and Wherein R2-R7 is H.

12. A compound comprising: Wherein M is titanium, zirconium or hafnium, Where L is independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 amidino, C5-C 15 Guanidine, C5-C 15 β-Diketonate, C5-C 15 β-Ketoimidate, C5-C 15 β-Diketoimidate, C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, F, Cl, Br, I or H, Wherein R1-R5 are independently C1-C 15 Alkyl, C1-C 15 fluoroalkyl or H, and wherein X is independently C or Si.

13. The compound according to claim 12, Where M is hafnium, and Wherein L is dimethylamide, ethylmethylamide, diethylamide or bis(2,2,2-trifluoroethyl)amide.

14. A compound according to claim 12 or claim 13, Wherein R5 is methyl or ethyl, Wherein R1-R4 are H, and Where X is C.

15. A compound comprising: Wherein M is titanium, zirconium or hafnium, Where L is independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid esters, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 amidino, C5-C 15 Guanidine, C5-C 15 β-Diketonate, C5-C 15 β-Ketoimidate, C5-C 15 β-Diketoimidate, C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, F, Cl, Br, I or H, Wherein R1-R4 are independently C1-C 15 Alkyl, C1-C 15 fluoroalkyl or H, and wherein X is independently C or Si.

16. The compound according to claim 15, Where M is hafnium, and Wherein L is dimethylamide, ethylmethylamide, diethylamide or bis(2,2,2-trifluoroethyl)amide.

17. A compound according to claim 15 or claim 16, Where R1-R3 are H, Wherein R4 is methyl or ethyl, and X is C.

18. A method of depositing a film, comprising: A compound according to claims 1 to 17 is applied to a substrate.

19. The method according to claim 18, The compound is according to claim 1.

20. The method according to claim 18, The compound is according to claim 6.

21. The method according to claim 18, The compound is according to claim 12.

22. The method according to claim 18, The compound is according to claim 15.

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