Precursors containing fluorinated alkoxides and amides

Abstract

The present disclosure relates to the field of precursors, more particularly precursors containing at least one fluorinated group. In some embodiments, the precursor is a hafnium, zirconium, and titanium bis (cyclopentadienyl) precursor containing a fluorinated alkoxide and an amide. In some embodiments, the present disclosure relates to the use of precursors to deposit thin films containing Group 4, such as HfOx, ZrOx, and TiOx film applications. These films may be used in various applications including semiconductor device structures. 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 invention relates to the field of precursors, more particularly precursors containing at least one fluorinated group. Background Art

[0002] The thin films may be used in conjunction with semiconductor device structures. Summary of the invention

[0003] New precursors for applications related to 3D-NAND, DRAM and Logic are needed. Because tungsten is replaced by molybdenum in 3D-NAND, a barrier layer is needed to protect aluminum oxide (Al2O3). The present invention relates to the field of precursors, more specifically precursors containing at least one fluorinated group. In some embodiments, the precursors are hafnium, zirconium and titanium bis (cyclopentadienyl) precursors containing fluorinated alkoxides and amides. In some embodiments, the present invention relates to the use of precursors as described herein to deposit thin films containing Group 4, such as HfOx, ZrOx and TiOx film applications. These films can be used in various applications including semiconductor device structures. The compounds of the present invention have been developed and synthesized to generate improved film applications, such as compounds for HfOx, ZrOx and TiOx film applications. The improvements of the compounds of the present invention include increased molecular stability at delivery temperature and deposition temperature, improvements related to precursor film impurity levels, molecular volatility, molecular melting point and step coverage.

[0004] The precursors of the present invention have good stability and volatility. For example, bis(cyclopentadienyl)Hf compounds containing fluorinated ligands can have significantly higher volatility than compounds containing non-fluorinated ligands.

[0005] In some embodiments, the compound is a liquid at room temperature.

[0006] In some aspects, the technology described herein relates to compounds comprising the formula: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 carboxylate or F; and L2-L4 are each independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, C5-C 15 Amidinate, C5-C 15 Guanidinate, C5-C 15β-diketonate, C5-C 15 β-Ketoiminate, C5-C 15 β-Diketoimidate (diketiminate), C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 carboxylate, F, Cl, Br, I or H.

[0007] In some aspects, the technology described herein relates to a compound, wherein the compound has the formula:

[0008]

[0009] In some aspects, the technology described herein relates to compounds where L1-L4 are each independently 1,1,1,3,3,3-hexafluoro-2-propoxide, L1-L4 2,2,3,3,4,4,4-heptafluoro-1-butoxide, or 2,2,2-trifluoroethoxide.

[0010] In some aspects, the technology described herein relates to compounds where L1-L4 is a trifluoroacetate.

[0011] In some aspects, the technology described herein relates to compounds comprising the formula: Where: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C2-C 15 Amide, C2-C 15 carboxylate or F; L2 and L3 are each independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15carboxylate, F, Cl, Br, I or H; and R1-R5 are each 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.

[0012] In some aspects, the technology described herein relates to a compound having the formula:

[0013]

[0014] In some aspects, the technology described herein relates to compounds where R1-R5 is H.

[0015] In some aspects, the technology described herein relates to compounds where L1-L3 is 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 2,2,2-trifluoroethoxide.

[0016] In some aspects, the technology described herein relates to compounds where L1-L3 is a trifluoroacetate.

[0017] In some aspects, the technology described herein relates to compounds comprising the formula: Where M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F; L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15 carboxylate, F, Cl, Br, I or H; and R1-R 10Each independently is 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.

[0018] In some aspects, the technology described herein relates to a compound, wherein the compound has the formula:

[0019]

[0020] In some aspects, the technology described herein involves R1-R 10 A compound of H.

[0021] In some aspects, the technology described herein relates to compounds in which L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,2-trifluoroethoxide, or a combination thereof.

[0022] In some aspects, the technology described herein relates to a compound, wherein the compound has the formula:

[0023]

[0024] In some aspects, the technology described herein relates to compounds wherein L1 and L2 are 2,2,2-trifluoroethoxy or technical scheme 12.

[0025] In some aspects, the technology described herein relates to compounds comprising the formula: Where M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F; L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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 15Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 carboxylate, F, Cl, Br, I or H; X is each independently C or Si; and R1-R5 are each independently C1-C 15 Alkyl, C1-C 15 Fluoroalkyl or H.

[0026] In some aspects, the technology described herein relates to compounds where X is C, R1-R4 are H, and R5 is methyl.

[0027] In some aspects, the technology described herein relates to compounds where L1 and L2 are bis(2,2,2-trifluoroethyl)amide.

[0028] In some aspects, the technology described herein relates to compounds in which L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,2-trifluoroethoxide, or a combination thereof.

[0029] In some aspects, the technology described herein relates to compounds where L1 and L2 are trifluoroacetates.

[0030] In some aspects, the technology described herein relates to compounds comprising the formula: Where: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F; L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15carboxylate, F, Cl, Br, I or H; X is each independently C or Si; and R1-R4 are each independently C1-C 15 Alkyl, C1-C 15 Fluoroalkyl or H.

[0031] In some aspects, the technology described herein relates to compounds where X is C, R1-R3 are H, and R4 is methyl.

[0032] In some aspects, the technology described herein relates to compounds where L1 and L2 are bis(2,2,2-trifluoroethyl)amide.

[0033] In some aspects, the technology described herein relates to compounds where L1 and L2 are trifluoroacetates.

[0034] In some aspects, the technology described herein relates to compounds in which L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,2-trifluoroethoxide, or a combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Some embodiments of the present invention are described herein by way of example only 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 embodiments of the present invention. In this regard, the description in conjunction with the drawings makes clear to those skilled in the art the manner in which embodiments of the present invention may be practiced.

[0036] Figure 1 Fluorinated ligand compounds of the present invention according to some embodiments are shown.

[0037] Figure 2 Thermogravimetric analysis (TGA) showing the non-fluorinated compound: bis(cyclopentadienyl)Hf(NEtMe)2.

[0038] Figure 3 Shown is the TGA of bis(cyclopentadienyl)Hf(OCH(CF3)2)2 according to some embodiments.

[0039] Figure 4 Shown is the TGA of bis(cyclopentadienyl)Hf(OCH2CF3)2 according to some embodiments. DETAILED DESCRIPTION

[0040] In addition to the benefits and improvements disclosed, other objects and advantages of the present invention will be apparent from the following description and the accompanying drawings. Detailed embodiments of the present invention 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 various embodiments of the present invention is intended to be illustrative and not limiting.

[0041] All prior patents and publications mentioned herein are incorporated by reference in their entirety.

[0042] Throughout the specification and claims, unless the context clearly dictates otherwise, the following terms take the meanings explicitly associated with the present invention. 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 in a manner that does not depart from the scope or spirit of the present disclosure.

[0043] As used herein, the term "alkyl" refers to a hydrocarbon chain group having 1 to 30 carbon atoms. The alkyl group may be connected by a single bond. An alkyl group having n carbon atoms may be referred to as a "C n "C3 alkyl" may include n-propyl and isopropyl. Alkyl groups having a certain range of carbon atoms (e.g., 1 to 30 carbon atoms) may be referred to as C1-C 30 In some embodiments, the alkyl group is saturated (e.g., a single bond). In some embodiments, the alkyl group is unsaturated (e.g., a double bond and / or a triple bond). In some embodiments, the alkyl group is straight chain. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is substituted. In some embodiments, the alkyl group is unsubstituted. In some embodiments, the alkyl group may include C1-C 12 Alkyl, C1-C 11 Alkyl, C1-C 10 alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C4 alkyl, C1-C3 alkyl, or any combination thereof, consisting of, consisting essentially of, or can be selected from the group consisting of. In some embodiments, the alkyl group may include, consisting of, consisting essentially of, or can be selected from the group consisting of, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, isobutyl, sec-butyl, n-pentyl, 1,1-dimethylethyl (tert-butyl), n-pentyl, isopentyl, n-hexyl, isohexyl, 3-methylhexyl, 2-methylhexyl, octyl, decyl, dodecyl, octadecyl, or any combination thereof, consisting of, consisting essentially of, or can be selected from the group consisting of.

[0044] As used herein, unless the context clearly dictates otherwise, the term "based on" is not exclusive and allows for being based on other undescribed factors. In addition, throughout the specification, the meanings of "a", "an" and "the" include plural references. The meaning of "in..." includes "in..." and "on...".

[0045] As used herein, the term "between" does not necessarily require being arranged 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" can describe an item being next 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:

[0046] being arranged directly between two other structural elements so that the particular structural component is in direct contact with both other structural elements;

[0047] being arranged directly beside only one of the two other structural elements, so that the particular structural component is in direct contact with only one of the two other structural elements;

[0048] indirectly arranged 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;

[0049] indirectly between two other structural elements, so that a particular structural component is not in direct contact with either of the two other structural elements, and other features may be arranged therebetween; or

[0050] Any combination thereof.

[0051] As used herein, "embedded" means that a first material is distributed throughout a second material.

[0052] New precursors for applications related to 3D-NAND, DRAM and Logic are needed. Because tungsten is replaced by molybdenum in 3D-NAND, a barrier layer is needed to protect aluminum oxide (Al2O3). The present invention relates to the field of precursors, more specifically precursors containing at least one fluorinated group. In some embodiments, the precursors are hafnium, zirconium and titanium bis (cyclopentadienyl) precursors containing fluorinated alkoxides and amides. In some embodiments, the present invention relates to the use of precursors as described herein to deposit thin films containing Group 4, such as HfOx, ZrOx and TiOx film applications. These films can be used in various applications including semiconductor device structures. The compounds of the present invention have been developed and synthesized to generate improved film applications, such as compounds for HfOx, ZrOx and TiOx film applications. The improvements of the compounds of the present invention include increased molecular stability at delivery temperature and deposition temperature, improvements related to precursor film impurity levels, molecular volatility, molecular melting point and step coverage.

[0053] The precursors of the present invention have good stability and volatility. For example, bis(cyclopentadienyl)Hf compounds containing fluorinated ligands can have significantly higher volatility than compounds containing non-fluorinated ligands.

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

[0055]

[0056] In some embodiments, for Formula 1, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0057] In some embodiments, for Formula 1, L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F.

[0058] In some embodiments, for Formula 1, L2-L4 are each independently alkyl, amide, alkoxide, carboxylate, amidino, guanidino, β-diketonate, β-ketoimidate, β-diketoimidate, fluoroalkyl, alkoxide containing at least one fluorine group, amide containing at least one fluorine group, carboxylate containing at least one fluorine group, F, Cl, Br, I or H. In some embodiments, for Formula 1, L2-L4 are each independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, C5-C15 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, C2-C 15 carboxylate, F, Cl, Br, I or H. For example, L2-L4 is C1-C 15 For example, L2-L4 is C1-C 15 alkyl, wherein L2 is methyl, L3 is ethyl, and L4 is butyl. For example, L2 is C2-C 15 Amide, L3 is C1-C 15 Alkoxide, and L4 is C5-C 15 amidine group.

[0059] In some embodiments, L1-L4 are ligands of the same type (e.g., C1-C 15 In some embodiments, L1-L4 are ligands of the same type (e.g., C1-C 15 alkyl), but are different ligands (for example, L1 is methyl, L2 is ethyl, L3 is propyl, and L4 is butyl). In some embodiments, L1-L4 are all different types of ligands (for example, L1 is C1-C 15 Alkyl, L2 is C2-C 15 Amide, L3 is C1-C 15 carboxylate, and L4 is C1-C 15 In some embodiments, at least one of L1-L4 is the same type of ligand (for example, L1 and L2 are C1-C 15 Alkyl, L3 is C1-C 15 carboxylate, and L4 is C1-C 15 Alkoxide).

[0060] In some embodiments, for Formula 1, L1-L4 are C2-C 15 Amide (such as bis (2,2,2-trifluoroethyl) amide)). For example, Formula 2 represents the formula when L1-L4 in Formula 1 is bis (2,2,2-trifluoroethyl) amide), as shown below:

[0061]

[0062] In some embodiments, for Formula 1, L1-L4 are each independently 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,3,3,4,4,4-heptafluoro-1-butoxide or 2,2,2-trifluoroethoxide. For example, in some embodiments, L1-L4 are 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 2,2,2-trifluoroethoxide or a combination thereof.

[0063] In some embodiments, for Formula 1, L1-L4 are C2-C 15 Carboxylic acid esters (eg trifluoroacetate).

[0064] In some embodiments, compounds of the invention include compounds having the formula:

[0065]

[0066] In some embodiments, for Formula 3, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0067] In some embodiments, for Formula 3, L1 is C1-C 15 Fluoroalkyl, C2-C 15 Amide, C2-C 15 Carboxylate or F.

[0068] In some embodiments, for Formula 3, L2 and L3 are each independently alkyl, amide, alkoxide, carboxylate, amidino, guanidino, β-diketonate, β-ketoimidate, β-diketoimidate, fluoroalkyl, alkoxide containing at least one fluorine group, amide containing at least one fluorine group, carboxylate containing at least one fluorine group, F, Cl, Br, I or H. In some embodiments, for Formula 3, L2 and L3 are each independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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 15Amide, C2-C 15 carboxylate, F, Cl, Br, I or H.

[0069] In some embodiments, for Formula 3, L1-L3 are ligands of the same type (e.g., C1-C 15 In some embodiments, L1-L3 are ligands of the same type (e.g., C1-C 15 alkyl), but are different ligands (for example, L1 is methyl, L2 is ethyl, and L3 is propyl). In some embodiments, L1-L3 are all different types of ligands (for example, L1 is C1-C 15 Alkyl, L2 is C2-C 15 Amide, and L3 is C1-C 15 In some embodiments, at least one of L1-L3 is a ligand of the same type (for example, L1 and L2 are C1-C 15 Alkyl and L3 is C1-C 15 carboxylate).

[0070] In some embodiments, for Formula 3, R1-R5 are each 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.

[0071] In some embodiments, R1-R5 are functional groups of the same type (e.g., C1-C 15 In some embodiments, R1-R5 are functional groups of the same type (e.g., C1-C 15 alkyl), but are different functional groups (for example, R1 is methyl, R2 is ethyl, R3 is propyl, R4 is butyl, and R5 is pentyl). In some embodiments, R1-R5 are all different types of functional groups (for example, R1 is C1-C 15 Alkyl, R2 is C2-C 15 Amine, R3 is C1-C 15 Ether, R4 is C1-C 15 In some embodiments, at least one of R1-R5 is the same type of functional group (for example, R1 and R2 are C1-C 15 Alkyl and R3-R5 are C1-C 15 fluoroalkyl).

[0072] In some embodiments, for Formula 3, L1-L3 are C2-C 15 Amide (e.g., bis(2,2,2-trifluoroethyl)amide). For example, Formula 4 represents the compound when R1-R5 in Formula 3 is H and L1-L3 is bis(2,2,2-trifluoroethyl)amide, as shown below:

[0073]

[0074] In some embodiments, for Formula 3, R1-R5 are H.

[0075] In some embodiments, for Formula 3, L1-L3 are C1-C 15 Alkoxide (e.g., 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,3,3,4,4,4-heptafluoro-1-butoxide, or 2,2,2-trifluoroethoxide). In some embodiments, for Formula 3, R1-R5 is H and L1-L3 is 1,1,1,3,3,3-hexafluoro-2-propoxide. In some embodiments, for Formula 3, R1-R5 is H and L1-L3 is 2,2,3,3,4,4,4-heptafluoro-1-butoxide.

[0076] In some embodiments, for Formula 3, R1-R5 are H and L1-L3 are 2,2,2-trifluoroethoxide.

[0077] In some embodiments, for Formula 3, L1-L3 are C2-C 15 Carboxylate (eg, trifluoroacetate). In some embodiments, for Formula 3, R1-R5 are H and L1-L3 are trifluoroacetate.

[0078] In some embodiments, compounds of the invention include compounds having the formula:

[0079]

[0080] In some embodiments, for Formula 5, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0081] In some embodiments, for Formula 5, L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F.

[0082] In some embodiments, for Formula 5, L2 is alkyl, amide, alkoxide, carboxylate, amidino, guanidino, β-diketonate, β-ketoimidate, β-diketoimidate, fluoroalkyl, alkoxide containing at least one fluorine group, amide containing at least one fluorine group, carboxylate containing at least one fluorine group, F, Cl, Br, I or H. In some embodiments, for Formula 5, L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15 carboxylate, F, Cl, Br, I or H.

[0083] In some embodiments, for Formula 5, L1 and L2 are the same type of functional groups (e.g., C1-C 15 In some embodiments, L1 and L2 are ligands of the same type (e.g., C1-C 15 In some embodiments, L1 and L2 are different ligands (for example, L1 is methyl and L2 is ethyl). 15 Alkyl and L2 is C2-C 15 amide).

[0084] In some embodiments, for Formula 5, R1-R 10 Each independently is 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.

[0085] In some embodiments, R1-R 10 For the same type of functional group (e.g. C1-C 15 In some embodiments, R1-R 10For the same type of functional group (e.g. C1-C 15 alkyl), but are different functional groups (for example, R1 is methyl, R2 is ethyl, R3 is propyl, R4 is butyl, R5 is pentyl, etc.). In some embodiments, R1-R 10 are different types of functional groups (for example, R1 is C1-C 15 Alkyl, R2 is C2-C 15 Amine, R3 is C1-C 15 Ether, R4 is C1-C 15 fluoroether, R5 is H, etc.). In some embodiments, R1-R 10 At least one of them is the same type of functional group (for example, R1-R5 is C1-C 15 Alkyl and R6-R 10 C1-C 15 fluoroalkyl).

[0086] In some embodiments, for Formula 5, L1 and L2 are C2-C 15 Amide (e.g., bis(2,2,2-trifluoroethyl)amide). For example, Formula 6 represents R1-R 10 The compound when is H and L1 and L2 are bis(2,2,2-trifluoroethyl)amide groups is as shown below:

[0087]

[0088] In some embodiments, for Formula 5, R1-R 10 For H.

[0089] In some embodiments, for Formula 5, L1 and L2 are C1-C 15 Alkoxide (e.g., 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide, or 2,2,2-trifluoroethoxide. In some embodiments, for Formula 5, R1-R 10 is H, and L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide. In some embodiments, for Formula 5, R1-R 10 is H, and L1 and L2 are 1,1,1,3,3,3-hexafluoro-2-propoxide. In some embodiments, for Formula 5, R1-R 10 is H, and L1 and L2 are 2,2,2-trifluoroethoxide.

[0090] For example, Formula 7 represents R1-R in Formula 5. 10The compound when L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide is shown below and represented by Structural Formula 7:

[0091]

[0092] In some embodiments, for Formula 5, L1 and L2 are C2-C 15 Carboxylic acid esters (eg trifluoroacetate).

[0093] In some embodiments, compounds of the invention include compounds having the formula:

[0094]

[0095] In some embodiments, for Formula 8, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0096] In some embodiments, for Formula 8, L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F.

[0097] In some embodiments, for Formula 8, L2 is alkyl, amide, alkoxide, carboxylate, amidino, guanidino, β-diketonate, β-ketoimidate, β-diketoimidate, fluoroalkyl, alkoxide containing at least one fluorine group, amide containing at least one fluorine group, carboxylate containing at least one fluorine group, F, Cl, Br, I or H. In some embodiments, for Formula 8, L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15 carboxylate, F, Cl, Br, I or H.

[0098] In some embodiments, for Formula 8, L1 and L2 are the same type of ligand (e.g., C1-C 15 In some embodiments, L1 and L2 are ligands of the same type (e.g., C1-C 15 In some embodiments, L1 and L2 are different ligands (for example, L1 is methyl and L2 is ethyl). 15 Alkyl and L2 is C2-C 15 amide).

[0099] In some embodiments, for Formula 8, each X is independently C or Si. In some embodiments, for Formula 8, both X are C or Si. In some embodiments, for Formula 8, one X is C and one X is Si.

[0100] In some embodiments, for Formula 8, R1-R5 are each independently C1-C 15 Alkyl, C1-C 15 Fluoroalkyl or H.

[0101] In some embodiments, R1-R5 are functional groups of the same type (e.g., C1-C 15 In some embodiments, R1-R5 are functional groups of the same type (e.g., C1-C 15 alkyl), but are different functional groups (for example, R1 is methyl, R2 is ethyl, R3 is propyl, R4 is butyl, and R5 is pentyl). In some embodiments, R1-R5 are all different types of functional groups (for example, R1 is C1-C 15 Alkyl, R2 is C2-C 15 Amine, R3 is C1-C 15 Ether, R4 is C1-C 15 In some embodiments, at least one of R1-R5 is a functional group of the same type (for example, R1 and R2 are C1-C 15 Alkyl and R3-R5 are C1-C 15 fluoroalkyl).

[0102] In some embodiments, for Formula 8, X is C, R1-R4 are H, and R5 is methyl.

[0103] In some embodiments, for Formula 8, L1 and L2 are C2-C 15Amide (eg, bis(2,2,2-trifluoroethyl)amide). In some embodiments, for Formula 8, X is C, R1-R4 are H, R5 is methyl, and L1 and L2 are bis(2,2,2-trifluoroethyl)amide.

[0104] In some embodiments, for Formula 8, L1 and L2 are C1-C 15 Alkoxides (for example 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide or 2,2,2-trifluoroethoxide).

[0105] In some embodiments, for Formula 8, L1 and L2 are C2-C 15 Carboxylic acid esters (eg trifluoroacetate).

[0106] In some embodiments, compounds of the invention include compounds having the formula:

[0107]

[0108] In some embodiments, for Formula 9, M is titanium (Ti), zirconium (Zr), or hafnium (Hf).

[0109] In some embodiments, for Formula 9, L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F.

[0110] In some embodiments, for Formula 9, L2 is alkyl, amide, alkoxide, carboxylate, amidino, guanidino, β-diketonate, β-ketoimidate, β-diketoimidate, fluoroalkyl, alkoxide containing at least one fluorine group, amide containing at least one fluorine group, carboxylate containing at least one fluorine group, F, Cl, Br, I or H. In some embodiments, for Formula 9, L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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 15Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 carboxylate, F, Cl, Br, I or H.

[0111] In some embodiments, for Formula 9, L1 and L2 are the same type of ligand (e.g., C1-C 15 In some embodiments, L1 and L2 are ligands of the same type (e.g., C1-C 15 In some embodiments, L1 and L2 are different ligands (for example, L1 is methyl and L2 is ethyl). 15 Alkyl and L2 is C2-C 15 amide).

[0112] In some embodiments, for Formula 9, each X is independently C or Si. In some embodiments, for Formula 9, both X are C or Si. In some embodiments, for Formula 8, one X is C and one X is Si.

[0113] In some embodiments, for Formula 9, R1-R4 are each independently C1-C 15 Alkyl, C1-C 15 Fluoroalkyl or H.

[0114] In some embodiments, for Formula 9, X is C, R1-R3 are H, and R4 is methyl.

[0115] In some embodiments, for Formula 9, L1 and L2 are C2-C 15 Amide (eg, bis(2,2,2-trifluoroethyl)amide). In some embodiments, for Formula 9, X is C, R1-R3 are H, R4 is methyl, and L1 and L2 are bis(2,2,2-trifluoroethyl)amide.

[0116] In some embodiments, for Formula 9, L1 and L2 are C2-C 15 Carboxylic acid ester (eg, trifluoroacetate). In some embodiments, for Formula 9, X is C, R1-R3 are H, R4 is methyl, and L1 and L2 are trifluoroacetate.

[0117] In some embodiments, for Formula 9, L1 and L2 are C1-C 15Alkoxide (e.g., 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide or 2,2,2-trifluoroethoxide). In some embodiments, for Formula 9, X is C, R1-R3 are H, R4 is methyl, and L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide or 2,2,2-trifluoroethoxide.

[0118] Figure 1 Shown are fluorinated ligand compounds of the present invention (fluorinated L groups (eg, L1, L2, L3, and L4) of Formula 1-9) according to some embodiments.

[0119] As comparative examples of fluorinated and non-fluorinated compounds, Figure 2 Thermogravimetric analysis (TGA) showing the non-fluorinated compound: bis(cyclopentadienyl)Hf(NEtMe)2.

[0120] Figure 3 Shown is the TGA of bis(cyclopentadienyl)Hf(OCH(CF3)2)2 according to some embodiments.

[0121] Figure 4 Shown is the TGA of bis(cyclopentadienyl)Hf(OCH2CF3)2 according to some embodiments.

[0122] aspect

[0123] 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.

[0124] Aspect 1. A compound comprising the following formula: Where: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 carboxylate or F; and L2-L4 are each independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, C5-C 15 amidino, C5-C 15 Guanidine, C5-C 15 β-Diketonate, C5-C 15 β-Ketoimidate, C5-C 15β-diketoimidate, C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 carboxylate, F, Cl, Br, I or H.

[0125] Aspect 2. The compound according to aspect 1, wherein the compound has the following formula:

[0126]

[0127] Aspect 3. The compound according to aspect 1, wherein L1-L4 are each independently 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,3,3,4,4,4-heptafluoro-1-butoxide or 2,2,2-trifluoroethoxide.

[0128] Aspect 4. The compound according to aspect 1, wherein L1-L4 are trifluoroacetate.

[0129] Aspect 5. A compound comprising the following formula: Where: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C2-C 15 Amide, C2-C 15 carboxylate or F; L2 and L3 are each independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15 carboxylate, F, Cl, Br, I or H; and R1-R5 are each independently C1-C 15 Alkyl, C1-C 15 Ether, C2-C 15 Amine, C1-C 15 Fluoroether, C1-C 15Fluoroalkyl, OH, F, Cl, Br, I or H.

[0130] Aspect 6. The compound according to aspect 5, which has the following formula:

[0131]

[0132] Aspect 7. The compound according to aspect 5, wherein R1-R5 is H.

[0133] Aspect 8. The compound according to aspect 5 or 6, wherein L1-L3 is 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,3,3,4,4,4-heptafluoro-1-butoxide, or 2,2,2-trifluoroethoxide.

[0134] Aspect 9. The compound according to aspect 5 or 6, wherein L1-L3 is trifluoroacetate.

[0135] Aspect 10. A compound comprising the formula: Where: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F; L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15 carboxylate, F, Cl, Br, I or H; and R1-R 10 Each independently is 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.

[0136] Aspect 11. The compound according to aspect 10, wherein the compound has the following formula:

[0137]

[0138] Aspect 12. The compound according to aspect 10, wherein R1-R 10 For H.

[0139] Aspect 13. The compound according to aspect 10 or 12, wherein L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,2-trifluoroethoxide or a combination thereof.

[0140] Aspect 14. The compound according to aspect 10, wherein the compound has the following formula:

[0141]

[0142] Aspect 15. The compound according to aspect 10 or 12, wherein L1 and L2 are 2,2,2-trifluoroethoxide.

[0143] Aspect 16. A compound comprising the formula: Where: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F; L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15 carboxylate, F, Cl, Br, I or H; X is each independently C or Si; and R1-R5 are each independently C1-C 15 Alkyl, C1-C 15Fluoroalkyl or H.

[0144] Aspect 17. The compound according to aspect 16, wherein X is C, R1-R4 are H, and R5 is methyl.

[0145] Aspect 18. The compound according to aspect 16 or 17, wherein L1 and L2 are bis(2,2,2-trifluoroethyl)amide.

[0146] Aspect 19. The compound according to aspect 16 or 17, wherein L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,2-trifluoroethoxide, or a combination thereof.

[0147] Aspect 20. The compound according to aspect 16 or 17, wherein L1 and L2 are trifluoroacetate.

[0148] Aspect 21. A compound comprising the formula: Where: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F; L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15 carboxylate, F, Cl, Br, I or H; X is each independently C or Si; and R1-R4 are each independently C1-C 15 Alkyl, C1-C 15 Fluoroalkyl or H.

[0149] Aspect 22. The compound according to aspect 21, wherein X is C, R1-R3 are H, and R4 is methyl.

[0150] Aspect 23. The compound according to aspect 21 or 22, wherein L1 and L2 are bis(2,2,2-trifluoroethyl)amide.

[0151] Aspect 24. The compound according to aspect 21 or 22, wherein L1 and L2 are trifluoroacetate.

[0152] Aspect 25. The compound according to aspect 21 or 22, wherein L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,2-trifluoroethoxide, or a combination thereof.

[0153] It is to be understood that changes may be made in detail, particularly as to the construction materials employed and the shape, size and arrangement of parts without departing from the scope of the invention.This specification and described embodiments are examples, with the true scope and spirit of the invention being indicated by the following claims.

Claims

1. A compound comprising the formula: in: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 carboxylate or F; and L2-L4 are each independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, C5-C 15 Amidinate, C5-C 15 Guanidinate, C5-C 15 β-diketonate, C5-C 15 β-Ketoiminate, C5-C 15 β-Diketoimidate (diketiminate), C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 carboxylate, F, Cl, Br, I or H.

2. The compound according to claim 1, wherein the compound has the following formula:

3. The compound of claim 1, wherein L1-L4 are each independently 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,3,3,4,4,4-heptafluoro-1-butoxide or 2,2,2-trifluoroethoxide. The compound according to claim 1 , wherein L1-L4 is trifluoroacetate.

5. A compound comprising the formula: in: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C2-C 15 Amide, C2-C 15 Carboxylate or F; L2 and L3 are each independently C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15 carboxylate, F, Cl, Br, I or H; and R1-R5 are each 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.

6. The compound according to claim 5, which has the formula:

7. The compound according to claim 5, wherein R1-R5 is H.

8. The compound of claim 5 or claim 6, wherein L1-L3 is 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 2,2,2-trifluoroethoxide.

9. The compound according to claim 5, wherein L1-L3 is trifluoroacetate.

10. A compound comprising the formula: in: M is Ti, Zr or Hf; L1 is C1-C 15 Fluoroalkyl, C1-C 15 Alkoxides, C2-C 15 Amide, C2-C 15 Carboxylate or F; L2 is C1-C 15 Alkyl, C2-C 15 Amide, C1-C 15 Alkoxide, C1-C 15 Carboxylic acid ester, 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, C2-C 15 carboxylate, F, Cl, Br, I or H; and R1-R 10 Each independently is 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.

11. The compound according to claim 10, wherein the compound has the formula:

12. The compound according to claim 10, wherein R1-R 10 For H.

13. The compound of claim 10 or claim 12, wherein L1 and L2 are 2,2,3,3,4,4,4-heptafluoro-1-butoxide, 1,1,1,3,3,3-hexafluoro-2-propoxide, 2,2,2-trifluoroethoxide, or a combination thereof.

14. The compound of claim 10, wherein the compound has the formula:

15. The compound of claim 10 or claim 12, wherein L1 and L2 are 2,2,2-trifluoroethoxide.

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