Indenyl precursors

Abstract

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

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to the technical field of precursors, more particularly indenyl precursors, such as indenyl-substituted precursors. [Background technology]

[0002] Thin films are used on semiconductor device structures. Summary of the Invention

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

[0004] Because tungsten is replaced by molybdenum in 3D-NAND, a blocking layer is required to protect aluminum oxide (Al2O3). The indenyl compounds of the present disclosure can be used as precursors with good stability and volatility. 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 need to be crushed first.

[0005] In some embodiments, the compounds of the present disclosure 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 present disclosure relates to indenyl-substituted 4 compounds used as precursors for high-K metal oxide films.

[0006] The indenyl compounds of the present disclosure have good volatility and stability, and may be well suited for 3D-NAND applications. In some embodiments, precursors with good volatility are compatible with standard ALD equipment, i.e., valves that can be closely correlated with TGA data. For example, in some embodiments, a compound's TGA is generally considered to be good if it has a T50 of less than 250°C. A precursor with good stability can be used for extended periods in standard ALD equipment and can be closely correlated with TGA data. For example, in some embodiments, a compound's TGA is generally considered to be good if it has less than 10% residual material. Indenyl Hf compounds can be produced with high purity from commodity chemicals. In some embodiments, high purity is defined as greater than 99% purity by NMR analysis.

[0007] In some aspects, the technology described herein relates to a compound comprising: TIFF2025529197000002.tif37170 [wherein M is titanium, zirconium, or hafnium; and L is independently C1 to C 15 Alkyl, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminate, C1-C 15Fluoroalkyl, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H].

[0008] In some embodiments, 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 where L consists of one cyclopentadienyl and two amide groups.

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

[0012] In some aspects, the technology described herein relates to a compound comprising: TIFF2025529197000003.tif40170 [wherein M is titanium, zirconium, or hafnium; and L is independently C1 to C 15 Alkyl, C2-C 15 Amides, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15β-diketiminates, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H; and R1 to R7 are independently C1 to C 15 Alkyl, C1-C 15 Ether, C2-C 15 Amines, C1-C 15 Fluoroethers, C1-C 15 fluoroalkyl, OH, F, Cl, Br, I, or H. At least one R1-R7 group is C1-C 15 Alkyl, C1-C 15 Ether, C2-C 15 Amines, C1-C 15 Fluoroethers, C1-C 15 fluoroalkyl, containing OH, F, Cl, Br, or I].

[0013] In some aspects, the technology described herein relates to compounds where M is hafnium and L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0014] In some aspects, the technology described herein relates to compounds where R2 is methyl or ethyl, and R1, R3, R4, R5, R6, and R7 are H.

[0015] In some aspects, the technology described herein provides a method for preparing a methyl group in which R4 and R7 are methyl and R1, R2, R3, R 5、 and compounds where R6 is H.

[0016] In some embodiments, the technology described herein relates to compounds where R1 is CF3 and R2-R7 are H.

[0017] In some embodiments, the technology described herein relates to compounds where R1 is methyl or ethyl and R2-R7 are H.

[0018] In some aspects, the technology described herein relates to a compound comprising: TIFF2025529197000004.tif45170 [wherein M is titanium, zirconium, or hafnium; L is independently C1 to C 15 Alkyl, C2-C 15 Amides, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminate, C1-C 15 Fluoroalkyl, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H; and R1 to R5 are independently C1 to C 15 Alkyl, C1-C 15 fluoroalkyl, or H, and X is independently C or Si.

[0019] In some aspects, the technology described herein relates to compounds where M is hafnium and L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0020] In some embodiments, the technology described herein relates to compounds where R5 is methyl or ethyl, R1-R4 are H, and X is C.

[0021] In some aspects, the technology described herein relates to a compound comprising: TIFF2025529197000005.tif38170 [wherein M is titanium, zirconium, or hafnium; and L is independently C1 to C 15 Alkyl, C2-C 15 Amides, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminate, C1-C 15 Fluoroalkyl, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H, and R1 to R4 are independently C1 to C 15 Alkyl, C1-C 15 fluoroalkyl, or H, and X is independently C or Si.

[0022] In some aspects, the technology described herein relates to compounds where M is hafnium and L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0023] In some embodiments, the technology described herein relates to compounds where R1-R3 are H, R4 is methyl or ethyl, and X is C.

[0024] In some aspects, the technology described herein relates to a method of depositing a film, the method 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).

[0029] Several embodiments of the present disclosure are described herein, by way of example only, with reference to the accompanying drawings. With specific reference now to the drawings in detail, it is emphasized that the illustrated embodiments are by way of example and illustrative illustration of embodiments of the present disclosure. In this regard, the description made with the drawings will make apparent to those skilled in the art how embodiments of the present disclosure may be practiced. [Brief explanation of the drawings]

[0030] [Figure 1A] FIG. 1 shows a compound according to Formula 1, according to some embodiments. [Figure 1B] FIG. 1 shows a compound according to Formula 1, according to some embodiments. [Figure 1C] FIG. 1 shows a compound according to Formula 1, according to some embodiments. [Figure 2] FIG. 1 shows a compound according to Formula 2, according to some embodiments. [Figure 3] FIG. 1 shows a compound according to Formula 3, according to some embodiments. [Figure 4] FIG. 1 shows a compound according to Formula 4, according to some embodiments. [Figure 5] FIG. 1 illustrates a compound according to the present disclosure, according to some embodiments. [Figure 6] FIG. 1 shows a thermogravimetric analysis (TGA) of IndHf(Cl) according to some embodiments. [Figure 7]FIG. 1 shows a TGA of 2-MeIndHf(NMe2)3 according to some embodiments. [Figure 8] 1 shows the H-NMR spectrum of 2-MeIndHf(NMe) according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0031] Among these disclosed benefits and improvements, other objects and advantages of the present disclosure will become apparent from the following description taken in conjunction with the accompanying drawings. Detailed embodiments of the present disclosure are disclosed herein. However, it should be understood that the disclosed embodiments are merely exemplary of the present disclosure, which may be embodied in various forms. Furthermore, each of the examples given with respect to the various embodiments of the present disclosure is intended to be illustrative and not limiting.

[0032] Throughout the specification and claims, the following terms take the meanings explicitly associated therewith, unless the context clearly dictates otherwise. As used herein, the phrases "in one embodiment," "in an embodiment," and "in some embodiments" do not necessarily refer to the same embodiments, but may. Furthermore, as used herein, the phrases "in another embodiment" and "in some other embodiments" do not necessarily refer to different embodiments, but may. It is intended that all embodiments of the present disclosure can be combined without departing from the scope or spirit of the disclosure.

[0033] As used herein, the term "based on" is not exclusive and allows for based on additional unrecited factors unless the context clearly dictates otherwise. Furthermore, throughout this specification, the meanings of "a," "an," and "the" include plural references. The meaning of "in" includes "in" and "on."

[0034] As used herein, the term "between" does not necessarily require being located immediately adjacent to another element. Generally, the term refers to a configuration in which something is sandwiched between two or more other things. At the same time, the term "between" can refer to something that is immediately adjacent to two opposing things. Thus, in any one or more of the embodiments disclosed herein, a particular structural element that is disposed between two other structural components may be: A particular structural component may be disposed directly between two other structural elements such that the structural component is in direct contact with both of the two other structural elements; A particular structural component may be disposed immediately adjacent to only one of two other structural elements, such that the particular structural component is in direct contact with only one of the two other structural elements; A particular structural element may be disposed indirectly adjacent to only one of the two other structural elements such that the particular structural element is not in direct contact with only one of the two other structural elements, and there is another element that juxtaposes the particular structural element and one of the two other structural elements; A particular structural component may be indirectly disposed between two other structural elements such that it is not in direct contact with both of the two other structural elements, and other features may be disposed between them; or Any combination of them It could be.

[0035] As used herein, "embedded" means that a first material is dispersed throughout a second material.

[0036] The present disclosure relates to indenyl hafnium, zirconium, and titanium precursors for the deposition of HfOx, ZrOx, and TiOx thin films. These thin films can be used in a variety of applications, including semiconductor device structures. For example, compounds of the present disclosure have been developed and synthesized to produce compounds that improve film applications, such as HfOx, ZrOx, and TiOx film applications. Improvements in the disclosed compounds include increased molecular stability at delivery and deposition temperatures, precursor film impurity levels, molecular volatility, molecular melting points, and step coverage.

[0037] Because tungsten is replaced by molybdenum in 3D-NAND, a blocking layer is required to protect the aluminum oxide (Al2O3). Indenyl compounds, such as indenyl Hf compounds, can be used as precursors with good stability and volatility. Indenyl compounds, such as 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 need to be crushed first. Furthermore, other compounds can form potentially explosive solutions.

[0038] In some embodiments, the compounds of the present disclosure 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 present disclosure relates to indenyl-substituted 4 compounds used as precursors for high-K metal oxide films.

[0039] Indenyl Hf compounds have good volatility and stability, making them well suited for 3D-NAND applications. They can be produced with high purity from commodity chemicals.

[0040] In some embodiments, compounds of the present disclosure include compounds having the following formula: TIFF2025529197000006.tif37170

[0041] In some embodiments, for Formula 1, M is titanium, zirconium, or hafnium. In some embodiments, for Formula 1, L is independently C1-C 15 Alkyl, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminate, C1-C 15 Fluoroalkyl, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H.

[0042] In some embodiments, for Formula 1, M is hafnium.

[0043] In some embodiments, for Formula 1, L is Cl (chlorine), bis(2,2,2-trifluoroethyl)amide, 1,1,1,3,3,3-hexafluoro-2-propoxide, or 2,2,2-trifluoroethoxide.

[0044] In some embodiments, for Formula 1, L consists of one cyclopentadienyl and two amide groups. In some embodiments, the two amide groups contain dimethylamdio, ethylmethylamide, or diethylamide.

[0045] 1A shows a compound according to Formula 1, according to some embodiments. In some embodiments, FIG. 1A shows a compound of Formula 1, IndHf(Cl), where M is Hf and L is Cl.

[0046] In some embodiments, for Formula 1, M is Hf and L is bis(2,2,2-trifluoroethyl)amide.

[0047] 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 shows a compound according to Formula 1, according to some embodiments. Figure 1B shows a compound where M is Hf and L is 2,2,2-trifluoroethoxide.

[0048] In some embodiments, for formula 1, M is Hf and L is OMe. Figure 1C shows a compound of formula 1 where M is Hf and L is OMe.

[0049] In some embodiments, M is Hf and L consists of one cyclopentadienyl and two amide groups, specifically dimethylamdio, ethylmethylamide, or diethylamide.

[0050] In some embodiments, compounds of the present disclosure include compounds having the following formula: TIFF2025529197000007.tif40170

[0051] In some embodiments, M is titanium, zirconium, or hafnium.

[0052] In some embodiments, L is independently C1 to C 15 Alkyl, C2-C 15 Amides, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminates, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H.

[0053] In some embodiments, R1-R7 are independently C1-C 15 Alkyl, C1-C 15 Ether, C2-C 15 Amines, C1-C 15 Fluoroethers, C1-C 15 fluoroalkyl, OH, F, Cl, Br, I, or H. At least one R1-R7 group is C1-C 15 Alkyl, C1-C 15 Ether, C2-C 15 Amines, C1-C 15 Fluoroethers, C1-C 15 Fluoroalkyl, containing OH, F, Cl, Br, or I.

[0054] In some embodiments, M is hafnium and L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0055] In some embodiments, R2 is methyl or ethyl, and R1, R3, R4, R5, R6, and R7 are H. Figure 2 shows a compound according to Formula 2 according to some embodiments. Figure 2 shows a compound of Formula 2 where M is Hf, R2 is methyl, and R1, R3, R4, R5, R6, and R7 are H.

[0056] In some embodiments, R4 and R7 are methyl, and R1, R2, R3, R5, and R6 are H.

[0057] In some embodiments, R1 is CF3 and R2-R7 are H.

[0058] In some embodiments, R1 is methyl or ethyl and R2-R7 are H.

[0059] In some embodiments, M is hafnium, L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide, R2 is methyl or ethyl, and R1, R3, R4, R5, R6, and R7 are H.

[0060] In some embodiments, M is hafnium, L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide, R4 and R7 are methyl, and R1, R2, R3, R5, and R6 are H.

[0061] In some embodiments, M is hafnium, L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide, R1 is CF3, and R2-R7 are H.

[0062] In some embodiments, M is hafnium, L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide, R1 is methyl or ethyl, and R2-R7 are H.

[0063] In some embodiments, compounds of the present disclosure include compounds having the following formula: TIFF2025529197000008.tif45170

[0064] In some embodiments, M is titanium, zirconium, or hafnium.

[0065] In some embodiments, L is independently C1 to C 15Alkyl, C2-C 15 Amides, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminate, C1-C 15 Fluoroalkyl, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H.

[0066] In some embodiments, R1-R5 are independently C1-C 15 Alkyl, C1-C 15 fluoroalkyl, or H.

[0067] In some embodiments, X is independently C or Si.

[0068] In some embodiments, M is hafnium and L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0069] In some embodiments, R5 is methyl or ethyl, R1-R4 are H, and X is C. Figure 3 shows a compound according to Formula 3 according to some embodiments. Figure 3 shows a compound of Formula 3 where M is Hf, R5 is methyl, R1-R4 are H, and X is C.

[0070] In some embodiments, M is hafnium, L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide, R5 is methyl or ethyl, R1-R4 are H, and X is C.

[0071] In some embodiments, compounds of the present disclosure include compounds having the following formula: TIFF2025529197000009.tif38170

[0072] In some embodiments, M is titanium, zirconium, or hafnium.

[0073] In some embodiments, L is independently C1 to C 15 Alkyl, C2-C 15 Amides, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminate, C1-C 15 Fluoroalkyl, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H.

[0074] In some embodiments, R1-R4 are independently C1-C 15 Alkyl, C1-C 15 fluoroalkyl, or H, and

[0075] In some embodiments, X is independently C or Si.

[0076] In some embodiments, M is hafnium and L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0077] In some embodiments, R1-R3 are H, R4 is methyl or ethyl, and X is C. Figure 4 shows a compound according to Formula 4 according to some embodiments. Figure 4 shows a compound of Formula 4 where M is Hf, R1-R3 are H, R4 is methyl, and X is C.

[0078] In some embodiments, M is hafnium, L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide, R1-R3 are H, R4 is methyl or ethyl, and X is C.

[0079] In some embodiments, the methods of the present disclosure relate to depositing a film, comprising applying a compound described herein to a substrate. In some embodiments, the compound is a compound having Formula 1 of the present disclosure. In some embodiments, the compound is a compound having Formula 2 of the present disclosure. In some embodiments, the compound is a compound having Formula 3 of the present disclosure. In some embodiments, the compound is a compound having Formula 4 of the present disclosure.

[0080] Figure 5 shows a compound according to the present disclosure, according to some embodiments. In Figure 5, the metal is hafnium. For the compounds shown in Figure 5, each L can independently be NMe2, NEtMe, NEt2, OMe, OEt, Oi-Pr, Ot-Bu, Cl, Br, I, Cp, Me, H, amide, alkoxide, carboxylate, fluorinated alkoxide, fluorinated amide, substituted Cp, amidinate, guanidinate, β-diketonate, β-ketoiminate, or β-diketiminate.

[0081] Figure 6 shows a thermogravimetric analysis (TGA) of IndHf(Cl)3, the compound of Figure 1A, according to some embodiments. The temperature at 50% residual material is 205.98 degrees Celsius. The residual is 4.662% (0.1882 mg).

[0082] 7 shows a TGA of 2-MeIndHf(NMe2)3 according to some embodiments. For 2-MeIndHf(NMe2)3, the temperature at 50% residual material is 200.98 degrees Celsius. The residual is 7.437% (0.6868 mg).

[0083] FIG. 8 shows the NMR of 2-MeIndHf(NMe2)3, according to some embodiments.

[0084] Aspects Various aspects are described below, and it should be understood that any one or more of the features described in the following aspects can be combined with any one or more of the other aspects.

[0085] Aspect 1. TIFF2025529197000010.tif37170 [wherein M is titanium, zirconium, or hafnium; and L is independently C1 to C 15 Alkyl, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminate, C1-C 15 Fluoroalkyl, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15amide, F, Cl, Br, I, or H].

[0086] Aspect 2. The compound of aspect 1, wherein M is hafnium.

[0087] Aspect 3. The compound of 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.

[0088] Aspect 4. The compound of aspect 1 or 2, wherein L consists of one cyclopentadienyl group and two amide groups.

[0089] Embodiment 5. The compound of embodiment 4, wherein the two amide groups comprise dimethylamdio, ethylmethylamide, or diethylamide.

[0090] Aspect 6. TIFF2025529197000011.tif40170 [wherein M is titanium, zirconium, or hafnium; and L is independently C1 to C 15 Alkyl, C2-C 15 Amides, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminates, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H; and R1 to R7 are independently C1 to C 15 Alkyl, C1-C 15Ether, C2-C 15 Amines, C1-C 15 Fluoroethers, C1-C 15 fluoroalkyl, OH, F, Cl, Br, I, or H. At least one R1-R7 group is C1-C 15 Alkyl, C1-C 15 Ether, C2-C 15 Amines, C1-C 15 Fluoroethers, C1-C 15 fluoroalkyl, containing OH, F, Cl, Br, or I] A compound comprising:

[0091] Aspect 7. The compound of aspect 6, wherein M is hafnium and L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0092] Aspect 8. A compound according to aspect 6 or 7, wherein R2 is methyl or ethyl, and R1, R3, R4, R5, R6, and R7 are H.

[0093] Aspect 9. A compound according to aspect 6 or 7, wherein R4 and R7 are methyl, and R1, R2, R3, R5, and R6 are H.

[0094] Aspect 10. A compound according to aspect 6 or 7, wherein R1 is CF3 and R2-R7 are H.

[0095] Aspect 11. A compound according to aspect 6 or 7, wherein R1 is methyl or ethyl, and R2-R7 are H.

[0096] Aspect 12. TIFF2025529197000012.tif45170 [wherein M is titanium, zirconium, or hafnium; L is independently C1 to C 15 Alkyl, C2-C 15 Amides, C1-C 15 Alkoxides, C1-C 15Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15 Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminate, C1-C 15 Fluoroalkyl, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H; and R1 to R5 are independently C1 to C 15 Alkyl, C1-C 15 fluoroalkyl, or H, and X is independently C or Si. A compound comprising:

[0097] Aspect 13. The compound of aspect 12, wherein M is hafnium and L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0098] Aspect 14. A compound according to aspect 12 or 13, wherein R5 is methyl or ethyl, R1 to R4 are H, and X is C.

[0099] Aspect 15. TIFF2025529197000013.tif38170 [wherein M is titanium, zirconium, or hafnium; and L is independently C1 to C 15 Alkyl, C2-C 15 Amides, C1-C 15 Alkoxides, C1-C 15 Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C5-C 15 Amidinates, C5-C 15Guanidinate, C5-C 15 β-diketonates, C5-C 15 β-Ketoiminate, C5-C 15 β-diketiminate, C1-C 15 Fluoroalkyl, C1-C containing at least one fluoro group 15 Alkoxides, C2-C containing at least one fluoro group 15 amide, F, Cl, Br, I, or H, and R1 to R4 are independently C1 to C 15 Alkyl, C1-C 15 fluoroalkyl, or H, and X is independently C or Si. A compound comprising:

[0100] Aspect 16. The compound of aspect 15, wherein M is hafnium and L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide.

[0101] Aspect 17. A compound according to aspect 15 or 16, wherein R1 to R3 are H, R4 is methyl or ethyl, and X is C.

[0102] Embodiment 18. A method for depositing a film, comprising applying a compound according to any one of embodiments 1 to 17 to a substrate.

[0103] Embodiment 19 The method of embodiment 18, wherein the compound is a compound of embodiment 1.

[0104] Embodiment 20 The method of embodiment 18, wherein the compound is a compound of embodiment 6.

[0105] Embodiment 21 The method of embodiment 18, wherein the compound is the compound of embodiment 12.

[0106] Embodiment 22 The method of embodiment 18, wherein the compound is the compound of embodiment 15.

[0107] It should be understood that changes may be made in details, particularly in matters of construction materials used and shape, size and arrangement of parts without departing from the scope of the present disclosure. The specification and described embodiments are examples, the true scope and spirit of the present disclosure being indicated by the following claims.

Claims

1. [Wherein M is titanium, zirconium, or hafnium, L is independently C １ ~C １５ Alkyl, C １ ~C １５ Alkoxide, C １ ~C １５ Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C ５ ~C １５ Amidinate, C ５ ~C １５ Guanidinate, C ５ ~C １５ β-diketonate, C ５ ~C １５ β-ketoiminate, C ５ ~C １５ β-diketiminate, C １ ~C １５ Fluoroalkyl, C containing at least one fluoro group １ ~C １５ Alkoxides, C containing at least one fluoro group ２ ~C １５ amide, F, Cl, Br, I, or H. A compound comprising:

2. M is hafnium; The compound of claim 1.

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

4. L consists of one cyclopentadienyl and two amide groups; 3. The compound according to claim 1 or 2.

5. The two amide groups include dimethylamdio, ethylmethylamide, or diethylamide; The compound of claim 4.

6. [Wherein M is titanium, zirconium, or hafnium, L is independently C １ ~C １５ Alkyl, C ２ ~C １５ Amide, C １ ~C １５ Alkoxide, C １ ~C １５ Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C ５ ~C １５ Amidinate, C ５ ~C １５ Guanidinate, C ５ ~C １５ β-diketonate, C ５ ~C １５ β-ketoiminate, C ５ ~C １５ β-diketiminate, C containing at least one fluoro group １ ~C １５ Alkoxides, C containing at least one fluoro group ２ ~C １５ amide, F, Cl, Br, I, or H; R １ ~R ７ are independently 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; At least one R １ ~R ７ The group is 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, containing OH, F, Cl, Br, or I; A compound comprising:

7. M is hafnium; L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide; The compound of claim 6.

8. R ２ is methyl or ethyl, R １ , R ３ , R ４ , R ５ , R ６ , and R ７ is H, 8. The compound according to claim 6 or 7.

9. R ４ and R ７ is methyl, R １ , R ２ , R ３ , R ５ , and R ６ is H, 8. The compound according to claim 6 or 7.

10. R １ is CF ３ and R ２ ~R ７ is H, 8. The compound according to claim 6 or 7.

11. R １ is methyl or ethyl, R ２ ~R ７ is H, 8. The compound according to claim 6 or 7.

12. [Wherein M is titanium, zirconium, or hafnium, L is independently C １ ~C １５ Alkyl, C ２ ~C １５ Amide, C １ ~C １５ Alkoxide, C １ ~C １５ Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C ５ ~C １５ Amidinate, C ５ ~C １５ Guanidinate, C ５ ~C １５ β-diketonate, C ５ ~C １５ β-ketoiminate, C ５ ~C １５ β-diketiminate, C １ ~C １５ Fluoroalkyl, C containing at least one fluoro group １ ~C １５ Alkoxides, C containing at least one fluoro group ２ ~C １５ amide, F, Cl, Br, I, or H; R １ ~R ５ are independently １ ~C １５ Alkyl, C １ ~C １５ fluoroalkyl, or H; X is independently C or Si. A compound comprising:

13. M is hafnium; L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide; The compound of claim 12.

14. R ５ is methyl or ethyl, R １ ~R ４ is H, X is C; 14. A compound according to claim 12 or 13.

15. [Wherein M is titanium, zirconium, or hafnium, L is independently C １ ~C １５ Alkyl, C ２ ~C １５ Amide, C １ ~C １５ Alkoxide, C １ ~C １５ Carboxylate, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, pentamethylcyclopentadienyl, C ５ ~C １５ Amidinate, C ５ ~C １５ Guanidinate, C ５ ~C １５ β-diketonate, C ５ ~C １５ β-ketoiminate, C ５ ~C １５ β-diketiminate, C １ ~C １５ Fluoroalkyl, C containing at least one fluoro group １ ~C １５ Alkoxides, C containing at least one fluoro group ２ ~C １５ amide, F, Cl, Br, I, or H; R １ ~R ４ are independently １ ~C １５ Alkyl, C １ ~C １５ fluoroalkyl, or H; X is independently C or Si. A compound comprising:

16. M is hafnium; L is dimethylamdio, ethylmethylamide, diethylamide, or bis(2,2,2-trifluoroethyl)amide; 16. The compound of claim 15.

17. R １ ~R ３ is H, R ４ is methyl or ethyl, X is C; 17. A compound according to claim 15 or 16.

18. 1. A method for depositing a film, comprising: Applying a compound according to claims 1 to 17 to a substrate. A method comprising:

19. The compound is a compound according to claim 1.

20. The method of claim 18.

20. The compound is a compound according to claim 6.

20. The method of claim 18.

21. The compound is a compound according to claim 12.

20. The method of claim 18.

22. The compound is a compound according to claim 15.

20. The method of claim 18.

Images