TW201241224A - Hafnium-containing or zirconium-containing precursors for vapor deposition - Google Patents

Abstract

Disclosed are hafnium-containing and zirconium-containing precursors and methods of synthesizing the same. The compounds may be used to deposit hafnium, zirconium, hafnium oxide, and zirconium oxide containing layers using vapor deposition methods such as chemical vapor deposition or atomic layer deposition.

Description

201241224, the invention description: [Technical Field] The invention discloses a method for containing a bell and a zirconium-containing precursor, a method, and a method for using a mixed precursor and a miscible precursor. Synthesis of conjugated and precursor-containing precursors for deposition using vapor deposition processes [Prior Art] One of the serious challenges facing the semiconductor industry is the development of new gate dielectric materials for DRAMs and valleys. . For decades, dioxide (SA) is a reliable dielectric, but as the transistor continues to shrink and the technology moves from a "all-si" transistor to a "metal gate/high-k" transistor, based on si〇 The reliability of the gate dielectric of 2 reaches its physical limit. As the size shrinkage for current technology, the need for new high dielectric constant materials and processes has increased and become more critical. U.S. Patent Application Publication No. 2005/277223 discloses an ALD method for forming a metal oxide using a metal-containing precursor having the formula M(Ll)x(L2)y, wherein ruthenium is a metal, and L1 and L2 may be a halide. Diketone, alkoxide, amine group, alkoxyamine, phosphonium salt or polydentate ligand. However, the exemplary precursors are only Hf(〇tBu)2(NEtMe)2, Hf(OtBu)2(NEt2)2, Hf(NEt2)2(DMAMP)2, Hf(NEtMe)2(DMAMP)2, Ti (OtBu) 3C, Ti(OtBU)3Me, Ti(OtBu)2(NEt2)2, Ti(NEt2)2(DMAMP)2, Ti(OtBu)2(DMAMP)2, and TiCl2(DMAMP)2. U.S. Patent No. 7,491,654 discloses an ALD process for forming a ZrO 2 film using a ginseng (N-ethyl-N-nonylamino) (t-butoxy)zirconium precursor. Other sources and methods for Hf and Zr-containing materials 201241224 are being searched for for a new generation of integrated circuit devices. A new precursor is needed. SUMMARY OF THE INVENTION A molecule having the following formula is disclosed:

Md-N-CiD-N-RdJORddNRsDAOzCRdz Formula I or

M(R1-N-(C(R3)2)mN-R2)v(〇R4)x(NR5R6)y(〇2CR7)2 Formula II wherein: Μ is Hf or Zr; _ Ri ' R2, R5, R6 And R7 are independently selected from the group consisting of hydrazine and a C1-C6 ray group; R3 = Η, C1-C6 alkyl, or NMe2; • R4 is a C1-C6 alkyl group; • m = 2 to 4; • u = 0 To 2; v = 〇 to 1; x = 1 to 3; • y = 0 to 2; z = 〇 to 1; in Equation I, u+x+y+z == 4; • In Equation II, 2v+x+y+z = 4; and u, v or zk 1 〇 these revealed molecules are further comprising one or more of the following: .- • The molecule has the formula I, where u= l, x=3, y=0, and z=〇; 201241224 • The molecule is selected from the group consisting of: M(iPr-NC(Me)-N-iPr)!(OiPr)3 ' M(iPr -NC(Me)-N-iPr)!(OMe)3 ' M(iPr-NC(Me)-N-iPr)!(OEt)3 ' M(iPr-NC(Me)-N-iPr)!( OnPr)3 ' M(iPr-NC(Me)-N-iPr)!(OsBu)3 > M(iPr-NC(Me)-N-iPr)!(OiBu)3 ' M(iPr-NC(Me )-N-iPr)!(OtBu)3 ' M(Et-NC(Me)-N-Et),(OEt)3 ' M(Et-NC(Me)-N-Et)!(OMe)3, M(Et-NC(Me)-N-Et)!(OnPr)3, M(Et-NC(Me)-N-Et)!(OsBu)3 ' M(Et-NC(Me)-N-Et )!(OiBu)3 > MCEt-NC^MehN-EthCOtBuV And M(iPr-NC(NMe2)-N-iPr)(OiPr)3 • The molecule has the formula II' wherein v=l, x=2, y=0, and z = 0; • the molecule is selected from the following Group consisting of: M(iPr-N-(CH2)2-N-iPr)1(OiPr)2 ' M(iPr-N-(CH2)2-N-iPr)1(OMe)2, M(iPr -N-(CH2)2-N-iPr) 1 (0Et)2, M(iPr-N-(CH2)2-N-iPr)1(OsBu)2 M(iPr-N-(CH2)2-N -iPr), (OtBu) 2 M(Et-N-(CH2)2-N-Et)i(OMe)2 , M(Et-N-(CH2)2-N-Et), (OnPr)2 ' M(Et-N-(CH2)2-N-Et)1(OiBu)2 ' M(iPr-N-(CH2)3-N-iPr)1(OiPr)2 ' M(iPr-N-(CH2 )3-N-iPr)1(OEt)2 ' M(iPr-N-(CH2)3-N-iPr)1(OsBu)2 M(iPr-N-(CH2)2-N-iPr)1( OnPr)2 ' • M(iPr-N-(CH2)2-N-iPr)1(OiBu)2 ' ' M(Et-N-(CH2)2-N-Et), (OiPr)2 ' M( Et-N-(CH2)2-N-Et)i(OEt)2, M(Et-N-(CH2)2-N-Et)1(OsBu)2 ' M(Et-N-(CH2)2 -N-Et),(OtBu)2 ' M(iPr-N-(CH2)3-N-iPr)1(OMe)2 ' M(iPr-N-(CH2)3-N-iPr)1(OnPr ) 2 ' • M(iPr-N-(CH2)3-N-iPr), (OiBu)2 ' M(iPr-N-(CH2)3-N-iPr)1(OtBu)2 ' M(Et- N-(CH2)3-N-Et),(OiPr)2 ' M(Et-N-(CH2)3-N-Et)i(OMe)2 , M(Et-N-(CH2)3-N -Et)i(OEt)2, M(Et-N-(CH2)3-N-Et)1(OnPr)2 ' M(Et-N-(CH2)3-N-Et)l(OsBu)2 ' MCEt-N-CCHA-N-EOKOiBuh, and IVKEt-N-CC HA-N-EtMOtBuh ; 201241224 • The molecule has the formula I, where u = 2, x = 2, y = 0, and z = 0; • The molecule is selected from the group consisting of the following M (iPr-NC (H )-N-iPr)2(OiPr)2 M(iPr-NC(H)-N-iPr)2(OEt)2 M(iPr-NC(H)-N-iPr)2(OsBu)2 M(iPr -NC(H)-N-iPr)2(OtBu)2 M(Et-NC(H)-N-Et)2(OMe)2 M(Et-NC(H)-N-Et)2(OnPr) 2, M(iPr-NC(H)-N-iPr)2(〇Me)2, M(iPr-NC(H)-N-iPr)2(OnPr)2, M(iPr-NC(H)- N-iPr)2(OiBu)2, M(Et-NC(H)-N-Et)2(〇iPr)2, M(Et-NC(H)-N-Et)2(OEt)2, M (Et-NC(H)-N-Et)2(OsBu)2 M(Et-NC(H)-N-Et)2(OiBu)2, M(Et-NC(H)-N-Et)2 (OtBu)2, M(iPr-NC(Me)-N-iPr)2(OiPr)2, M(iPr-NC(Me)-N-iPr)2(OMe)2, M(iPr-NC(Me )-N-iPr)2(OEt)2, M(iPr-NC(Me)-N-iPr)2(OnPr)2, M(iPr-NC(Me)-N-iPr)2(OsBu)2 M(iPr-NC(Me)-N-iPr)2(OiBu)2, M(iPr-NC(Me)-N-iPr)2(OtBu)2, M(Et-NC(Me)-N-Et 2(OiPr)2, M(Et-NC(Me)-N-Et)2(OMe)2, M(Et-NC(Me)-N-Et)2(〇Et)2, M(Et- NC(Me)-N-Et)2(OnPr)2, M(Et-NC(Me)-N-Et)2(OsBu)2, M(Et-NC(Me)-N-Et)2(OiBu 2, and M (Et-NC(Me)-N-Et) 2(OtBu) 2 ; • The molecule has the formula I, where u= l, x = 2, y = l, and z = 0; • The molecule is selected from the group consisting of: M(iPr-NC(Me)-N-iPr)(OiPr)2(NMe2), M( iPr-NC(Me)-N-iPr)(OiPr)2(NEt2), M(iPr-NC(Me)-N-iPr)(OiPr)2(NEtMe), M(Et-NC(Me)-N -Et)(OiPr)2(NMe2), M(Et-NC(Me)-N-Et)(OiPr)2(NEt2), M(Et-NC(Me)-N-Et)(OiPr)2( NEtMe) , 6 201241224 M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NMe2) M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NEt2) , M(iPr- NC(NMe2)-N-iPr)(OiPr)2(NEtMe) M(iPr-NC(Me)-N-iPr)(OiPr)2(NMeiPr) M(iPr-NC(Me)-N-iPr)( OiPr)2(NiPr2) M(iPr-NC(Me)-N-iPr)(OiPr)2(NMetBu) M(iPr-NC(Me)-N-iPr)(OiPr)2(NneoPentyl2) M(Et- NC(Me)-N-Et)(OiPr)2(NMeiPr) M(Et-NC(Me)-N-Et)(OiPr)2(NiPr2) M(Et-NC(Me)-N-Et)( OiPr)2(NneoPentyl2) M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NMeiPr) M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NiPr2) M(iPr- NC(NMe2)-N-iPr)(OiPr)2(NneoPentyl2) M(iPr-!NC(NMe2)-N-iPr)(OiPr)2(NMeiPr); • The molecule has the formula I, where u=l, x = 2, y = 0, and • The molecule is selected from the group consisting of M(iPr-NC(Me)-N-iPr)(0iPr)2(02CMe) M(Et-NC(Me)-N-Et )(0iPr)2(02CM e); • The molecule has the formula II, where v=l, x=l, y=0, and • the molecule is selected from the group consisting of M(iPr-N-(CH2)2-N-iPr) (0iPr (02CMe) M(iPr-N-(CH2)2-N-iPr)(0Me)(02CMe) M(iPr-N-(CH2)2-N-iPr)(0Et)(02CMe) M(iPr- N-(CH2)2-N-iPr)(0nPr)(02CMe) 201241224 M(iPr-N-(CH2)2-N-iPr)(0sBu)(02CMe) , M(iPr-N-(CH2)2 -N-iPr)(0iBu)(02CMe) , M(iPr-N-(CH2)2-N-iPr)(0tBu)(02CMe) , M(Et-N-(CH2)2-N-Et)( 0iPr)(02CMe), M(Et-N-(CH2)2-N-Et)(0Me)(02CMe), M(Et-N-(CH2)2-N-Et)(0Et)(02CMe), M(Et-N-(CH2)2-N-Et)(0nPr)(02CMe), M(Et-N-(CH2)2-N-Et)(0sBu)(02CMe), M(Et-N- (CH2)2-N-Et)(0iBu)(02CMe), and M(Et-N-(CH2)2-N-Et)(0tBu)(02CMe); • The molecule has the formula I or formula, wherein u, v, y = 〇, χ = 2, and z = 2; • The molecule is M(0iPr) 2(02CMe) 2 ; • The molecule has the formula I or Π, where u, v, y = 〇, χ=3, and ζ=1; and • The molecule is M(0iPr)3(02CMe). A method of forming a Hf-containing or Zr-containing layer on a substrate is also disclosed. Providing a & chamber, at least one substrate disposed within the reaction chamber. Vapor of at least one of the molecules disclosed above is introduced into the reaction chamber. The vapor is brought into contact with the substrate to form an Hf-containing or Zr-containing layer on at least one surface of the substrate using a vapor deposition process. The methods disclosed herein may include one or more of the following: Symbols and nomenclature specific abbreviations, symbols, and terms are used throughout the following description and patent application No. 8 201241224 Displacement lead titanate; Used and included: the abbreviation "PZT" means the abbreviation "Ri-NCd"! ^-!^"

The abbreviation "R丨-N(C(R3)2)m_N-R2J refers to the following chemical structure:

The abbreviation "〇2CR_7" refers to the following chemical structure:

The abbreviation "Cy" refers to cyclohexyl; the abbreviation "Cp" refers to cyclopentadiene; the term "aliphatic" refers to a C1-C6 straight or branched alkyl group; the term "alkyl j refers to a carbon atom only And a saturated functional group of a hydrogen atom and includes a linear alkyl group, a branched alkyl group or a cycloalkyl group. Examples of the linear alkyl group include (not limited to 201241224) methyl, ethyl, n-propyl 'n-butyl, and the like. Examples of branched alkyl groups include, without limitation, a third butyl group. Examples of cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. The abbreviation "Me" refers to a The abbreviation "Et" refers to an ethyl group; the abbreviation "pr" refers to a propyl group; the abbreviation "hear" refers to isopropyl; the abbreviation "iBu" refers to an isobutyl group; the abbreviation "iBu" refers to an isobutyl group; Base, the abbreviation "sBu" refers to the second butyl; the abbreviation "_" refers to the second butyl; the abbreviation "Nz-amd" refers to Rl_NC(R3) n_r2, where R; = C1-C6 alkyl and R丨And r2 = z, z is defined as heart, y, b, listen, iBu sBu or tBu, for example NMe-amd is Me-NC(Me)N-Me; the abbreviation "Nz-fmd" refers to Rl_Nc(R3) N_R2 , where & = H and &及; and R2 = z,z is defined as Me, Et, Pr, ipr or the abbreviation "nz_(4) refers to r|-nc(R3)n-R2, where l = nr5r6, where Rs and R6 = ^ lPr, nBu, iBu, sBl^tBu; the abbreviation "talk" refers to the abbreviation "TMA" refers to trimethyl sulphate; the abbreviation "" refers to atomic layer characterization, the abbreviation "CVD" refers to chemical vapor deposition; "Cafes

Generation of low pressure chemical vapor deposition; the abbreviation "P 円r LVD" refers to pulsed chemical vapor identification 'abbreviation PE-ALD' refers to the difficult to throw

Electric table a strong atomic layer deposition; the abbreviation "MIM is the metal insulator metal (for capacitance refers to dynamic random access memory (4). II. Structure) 'abbreviation _ 匕 hidden body, the abbreviation "FeRAM" refers to the ferroelectric Access memory; the abbreviation "CMOS" refers to # $i Γ ^ "daily complementary MOS; tailed TGA" refers to thermogravimetric analysis. Solution In this paper, we use the periodic table of elements, which can be referred to by the abbreviations (the standard abbreviations of the elements, for example, Hf refers to .., Zr refers to 10 201241224 zirconium, etc.). [Embodiment] A novel method for synthesizing cerium-containing and cerium-containing precursors, synthesizing cerium-containing and zirconium-containing precursors, and a method using cerium-containing and erroneous precursors are disclosed. The disclosed mixed ruthenium-containing and mis-containing precursors are derived from different classes of ligand systems, such as sulfonium salts, formamidine salts, sulfonium salts, decylamines, and/or chelating guanamine ligands, plus Alkoxide ligand. The precursor design helps to improve the volatility of 'reducing the melting point (liquid or very low melting solids), increasing the reactivity with water, and increasing the thermal stability for wider process window applications. The yttrium-containing and zirconium-containing precursors disclosed herein have the following formula:

M(Rl'Nc(R3) N-R2)u(〇R4)x(NR5R6)y(02CR7)z Formula I or M(Rl-N'(C(R3)2)mN.R2)v(0R4) x(NRsR6)y(02CR7)z Formula: wherein: M is Hf or Zr; R], R2, R5, Han 6 and R7 are independently selected from the group consisting of ruthenium and C1-C6 alkyl; Κ·3 = Η , C1-C6 alkyl, or NMe2; R4 is C1-C6 alkyl; m = 2 to 4; u = :0 to 2; V = 0 to 1; X = 1 to 3; y = 0 to 2; 201241224 z = 〇 to 1; in the formula I, u+x+y+z = 4; in the formula II, 2v+x+y+z = 4; and u, v or z >1. As defined above, the C1-C6 alkyl group includes any linear alkyl group, branched bond group or cyclohexyl group having from 1 to 6 carbon atoms, including but not limited to Me, tBu or cyclohexyl. In Formula 1, the R^NC^RON-R2 ligand has the following chemical structure:

R2 is in Formula II 'The ligand has the following chemical structure: /4) (C(R3)2)m

Ri therefore 'although the same element is maintained in the backbone of the ligand (ie, N CN-)' but the ligand itself has a non-疋 domain negative charge between the -N_c-N backbones_ The i-ligand is turned to a _2 ligand having a negative charge localized to each gas atom. In addition, the formula has a structure which is harder than the ligand of the formula II 2012122424. When Ri and R3 are C1-C6 straight or branched alkyl groups of formula I, Ri and R3 may be independent substituents or they may be joined together to form a single ring structure extending from Ri to Rule 3, as follows Argument. c 13⁄4

\ I

Ri-NC-N-R2 Similarly, when R, R3 and R2 are C1-C6 straight or branched alkyl groups of formula I, they may be independent substituents or they may be joined together to form a bicyclic structure, As demonstrated below.

R1-NQN-R2 selects the configuration of the precursors disclosed in order to optimize the reactivity (especially with H2〇) and at the same time optimize the stability ^ μ-N bond is weak It will react quickly on this surface. At the same time, the M-0 bond is much stronger and will help stabilize the molecule to avoid rapid decomposition. The precursor is obtained by adjusting this molecule, which precursor reacts well on the substrate due to the weaker sites. When u = 1, χ = 3, y = 0 and z = 0 in the formula I, and R2 is preferably Et or ipr ' R3 is preferably η, Me or NMe2, and R4 is preferably C1-C4 13 201241224 Linear or branched chain base chain. Exemplary precursors include: M(iPr-NC(H)-N-iPr)!(OiPr)3 ' M(iPr-NC(H)-N-iPr)i(OMe)3 ' M(iPr-NC( H)-N-iPr)i(OEt)3, M(iPr-NC(H)-N-iPr)!(OnPr)3, M(iPr-NC(H)-N-iPr)i(OsBu)3 ' M(iPr-NC(H)-N-iPr)i(OiBu)3 ' M(iPr-NC(H)-N-iPr)1(OtBu)3 ' M(iPr-NC(Me)-N- iPr),(OiPr)3 ' M(iPr-NC(Me)-N-iPr)i(OMe)3 ' M(iPr-NC(Me)-N-iPr)i(OEt)3 ' M(iPr- NC(Me)-N-iPr)i(OnPr)3 ' M(iPr-NC(Me)-N-iPr)i(OsBu)3 ' M(iPr-NC(Me)-N-iPr)i(OiBu ) 3 ' M(iPr-NC(Me)-N-iPr)i(OtBu)3 ' M(Et-NC(Me)-N-Et)!(OEt)3 , M(Et-NC(Me)- N-Et)i(OMe)3, M(Et-NC(Me)-N-Et)i(OnPr)3 ' M(Et-NC(Me)-N-Et)i(OsBu)3 ' MCEt- NC^MehN-EQ^OiBuh, MiEt-NC^MehN-EOKOtBuh, or M(iPr-NC(NMe2)-N-iPr)(OiPr)3 When M is Hf, the exemplary precursors include: Hf (iPr-NC(H)-N-iPr)!(OiPr)3 'Hf(iPr-NC(H)-N-iPr)!(OMe)3 ' Hf(iPr-NC(H)-N-iPr) ,(OEt)3,HfOPr-N-CTO-N-iPOKOnP^s 'Hf(iPr-NC(H)-N-iPr)i(OsBu)3 ' Hf(iPr-NC(H)-N-iPr) i(OiBu)3 ' Hf(iPr-NC(H)-N-iPr)!(OtBu)3 ' Hf(iPr-NC(Me)-N-iPr)i(OiPr)3 ' Hf(iPr-NC( Me)-N-iPr)i(OMe)3 ' Hf(iPr-NC(Me)-N -iPr),(OEt)3 'Hf(iPr-NC(Me)-N-iPr)i(OnPr)3' Hf(iPr-NC(Me)-N-iPr)i(OsBu)3 ' Hf(iPr -NC(Me)-N-iPr)i(OiBu)3' Hf(iPr-NC(Me)-N-iPr)i(OtBu)3 ' Hf(Et-NC(Me)-N-Et)i( OEt)3 ' Hf(Et-NC(Me)-N-Et)!(OMe)3 , Hf(Et-NC(Me)-N-Et)!(OnPr)3 ' Hf(Et-NC(Me) -N-Et)1(OsBu)3 'HfXEt-NC^MehN-EtMOiBuh, HfXEt-NC^MehN-EtMOtBuh, or Hf(iPr-NC(NMe2)-N-iPr)(OiPr)3. 14 201241224 • When Μ is Zr, these exemplary precursors include:

Zr(iPr-NC(H)-N-iPr)!(OiPr)3, Zr(iPr-NC(H)-N-iPr), (OMe)3, Zr(iPr-NC(H)-N-iPr )!(OEt)3 , Zr(iPr-NC(H)-N-iPr)!(OnPr)3 , Zr(iPr-NC(H)-N-iPr)!(OsBu)3, Zr(iPr-NC (H)-N-iPr)!(OiBu)3 ' Zr(iPr-NC(H)-N-iPr)!(OtBu)3 ' Zr(iPr-NC(Me)-N-iPr)i(OiPr) 3 ' Zr(iPr-NC(Me)-N-iPr)!(OMe)3 ' Zr(iPr-NC(Me)-N-iPr)!(OEt)3 ' Zr(iPr-NC(Me)-N -iPr)!(OnPr)3 ' Zr(iPr-NC(Me)-N-iPr)i(OsBu)3 ' Zr(iPr-NC(Me)-N-iPr)!(OiBu)3 ' Zr(iPr -NC(Me)-N-iPr)!(OtBu)3 ' Zr(Et-NC(Me)-N-Et)!(OEt)3 , Zr(Et-NC(Me)-N-Et)i( OMe)3, Zr(Et-NC(Me)-N-Et), (OnPr)3 ' Zr(Et-NC(Me)-N-Et), (OsBu)3 ' Zi^Et-N-CXMeyN- EthCOiBuh, ZrCEt-NC^MeVN-EOKOtBuh, or Zr(iPr-NC(NMe2)-N-iPr)(OiPr)3. In this particular embodiment, the preferred exemplary precursors are HfCiPr-iN-C^MehN-iPOKOiPrh or ZrGPr-N-C^MeyN-iPrMOiPrh. When m=2 or 3, v=l, x=2, y=0 and z=0 in formula II, I and R2 are preferably Et or iPr, R3 is preferably Η, and R4 is preferably C1. -C4 linear or branched bond base chain. More preferably, when m = 2, R! and R2 are not Me. Exemplary precursors include: MCiPr-N-CCHzh-N-iPrhCOiPrh, M(iPr-N-(CH2)2-N-iPr)i(OMe)2 > M(iPr-N-(CH2)2-N -iPr)i(OEt)2 ' M(iPr-N-(CH2)2-N-iPr)1(OnPr)2 ' M(iPr-N-(CH2)2-N-iPr)1(OsBu)2 ' M(iPr-N-(CH2)2-N-iPr)i(OiBu)2 ' M(iPr-N-(CH2)2-N-iPr)i(OtBu)2 ' M(Et-N-( CH2)2-N-Et)1(OiPr)2, M(Et-N-(CH2)2-N-Et), (OMe)2, M(Et-N-(CH2)2-N-Et) 1(OEt)2 , M(Et-N-(CH2)2-N-Et)1(OnPr)2 , M(Et-N-(CH2)2-N-Et)i(OsBu)2 ' M( Et-N-(CH2)2-N-Et)1(OiBu)2 ' 15 Hit* 201241224 M(Et-N-(CH2)2-N-Et)1(OtBu)2 ' M(iPr-N- (CH2)3-N-iPr)1(OiPr)2 ' M(iPr-N-(CH2)3-N-iPr)i(OMe)2 ' M(iPr-N-(CH2)3-N-iPr )1(OEt)2 ' M(iPr-N-(CH2)3-N-iPr)1(OnPr)2 ' M(iPr-N-(CH2)3-N-iPr)1(OsBu)2 ' M (iPr-N-(CH2)3-N-iPr)i(OiBu)2 ' M(iPr-N-(CH2)3-N-iPr), (OtBu)2 ' M(Et-N-(CH2) 3-N-Et), (OiPr)2, M(Et-N-(CH2)3-N-Et), (OMe)2, M(Et-N-(CH2)3-N-Et)i( OEt)2, M(Et-N-(CH2)3-N-Et)1(OnPr)2,

Mpt-N-CCHA-N-EthCOsBuh, MCEt-N-CCHA-N-EthCOiBuh, or JV^Et-NJCHA-N-EtMOtBuh. When M is Hf, the exemplary precursors include: Hf(iPr-N-(CH2)2-N-iPr), (OiPr)2 'Hf(iPr-N-(CH2)2-N-iPr) 1(OMe)2 'Hf(iPr-N-(CH2)2-N-iPr)1(OEt)2 'Hf(iPr-N-(CH2)2-N-iPr)1(OnPr)2 ' Hf( iPr-N-(CH2)2-N-iPr),(OsBu)2 'Hf(iPr-N-(CH2)2-N-iPr)i(OiBu)2 'Hf(iPr-N-(CH2)2 -N-iPr)i(OtBu)2 'Hf(Et-N-(CH2)2-N-Et), (OiPr)2 'Hf(Et-N-(CH2)2-N-Et), (OMe 2, Hf(Et-N-(CH2)2-N-Et)1(OEt)2,

Hf(Et-N-(CH2)2-N-Et)1(OnPr)2 'Hf(Et-N-(CH2)2-N-Et)1(OsBu)2 '

Hf(Et-N-(CH2)2-N-Et)1(OiBu)2, Hf(iPr-N-(CH2)3-N-iPr)1(OiPr)2, Hf(iPr-N-(CH2) )3-N-iPr)1(OEt)2 'Hf(iPr-N-(CH2)3-N-iPr)1(OsBu)2 Hf(iPr-N-(CH2)3-N-iPr), ( OtBu)2 Hf(Et-N-(CH2)3-N-Et)i(OMe)2 , Hf(Et-N-(CH2)3-N-Et)i(OnPr)2 '

Hf(Et-N-(CH2)2-N-Et)i(OtBu)2 Hf(iPr-N-(CH2)3-N-iPr)1(OMe)2 Hf(iPr-N-(CH2)3 -N-iPr)1(OnPr)2 'Hf(iPr-N-(CH2)3-N-iPr)i(OiBu) > Hf(Et-N-(CH2)3-N-Et)i(OiPr 2 Hf(Et-N-(CH2)3-N-Et)1(OEt)2 Hf(Et-N-(CH2)3-N-Et)1(OsBu)2

Hf^Et-N-CCHA-N-EtMOiBuh, or HiXEt-NJCHA-N-EtMOtBuh. When M is Zr, the exemplary precursors include: 16 201241224

Zr(iPr-N-(CH2)2-N-iPr)1(OiPr)2 ' Zr(iPr-N-(CH2)2-N-iPr)1(OMe)2 ' Zr(iPr-N-(CH2 )2-N-iPr)1(OEt)2 ' Zr(iPr-N-(CH2)2-N-iPr)1(OnPr)2 ' Zr(iPr-N-(CH2)2-N-iPr)1 (OsBu)2' Zr(iPr-N-(CH2)2-N-iPr)1(OiBu)2 ' Zr(iPr-N-(CH2)2-N-iPr)1(OtBu)2 ' Zr(Et -N-(CH2)2-N-Et)1(OiPr)2 ' Zr(Et-N-(CH2)2-N-Et)1(OMe)2 , Zr(Et-N-(CH2)2- N-Et), (OEt)2, Zr(Et-N-(CH2)2-N-Et)1(OnPr)2 ' Zr(Et-N-(CH2)2-N-Et)i(OsBu) 2 ' Zr(Et-N-(CH2)2-N-Et)1(OiBu)2 ' Zr(Et-N-(CH2)2-N-Et)1(OtBu)2 ' Zr(iPr-N- (CH2)3-N-iPr)1(OiPr)2 ' Zr(iPr-N-(CH2)3-N-iPr)1(OMe)2 ' Zr(iPr-N-(CH2)3-N-iPr )1(OEt)2 ' Zr(iPr-N-(CH2)3-N-iPr)1(OnPr)2 ' Zr(iPr-N-(CH2)3-N-iPr), (OsBu)2' Zr (iPr-N-(CH2)3-N-iPr)1(OiBu)2 ' Zr(iPr-N-(CH2)3-N-iPr)1(OtBu)2 > Zr(Et-N-(CH2 )3-N-Et)i(OiPr)2 ' Zr(Et-N-(CH2)3-N-Et)1(OMe)2 , Zr(Et-N-(CH2)3-N-Et)1 (OEt)2, Zi^Et-N-CCHzh-N-EthCOnPrh, ZrCEt-NJCHA-N-EtMOsBuh, ZKEt-N-CCHA-N-EtMOiBuh, or ZMEt-N-CCH^-N-EtMOtBuh. In this particular example, the preferred exemplary precursors are: Hf(iPr-N-(CH2)2-N-iPr)1(OiPr)2' Hf(Et-N-(CH2)3-N- Et)1(OiPr)2 'Hf(Et-N-(CH2)2-N-Et)1(OiPr)2 ' Zr(iPr-N-(CH2)2-N-iPr)1(OiPr)2 ' Zi^Et-N-CCH^-N-EthCOiPrh, or Zi^Et-N-CCHdrN-EthCOiPrh. When u = 2, x = 2, y = 0 and z = 0 in formula I, the precursor has the following chemical structure:

17 201241224 In this embodiment, R, and R2 are preferably Et or iPr, R3 is preferably Η or Me, and R4 is preferably a C1-C4 linear or branched alkyl chain. More preferably, R_3 is not NMe2. Exemplary precursors include: M(iPr-NC(H)-N-iPr)2(OiPr)2, M(iPr-NC(H)-N-iPr)2(OMe)2, M(iPr-NC( H)-N-iPr)2(OEt)2, M(iPr-NC(H)-N-iPr)2(OnPr)2, M(iPr-NC(H)-N-iPr)2(OsBu)2 , M(iPr-NC(H)-N-iPr)2(OiBu)2, M(iPr-NC(H)-N-iPr)2(OtBu)2, M(Et-NC(H)-N- Et)2(OiPr)2, M(Et-NC(H)-N-Et)2(OMe)2, M(Et-NC(H)-N-Et)2(〇Et)2, M(Et -NC(H)-N-Et)2(OnPr)2, M(Et-NC(H)-N-Et)2(〇sBu)2, M(Et-NC(H)-N-Et)2 (OiBu)2, M(Et-NC(H)-N-Et)2(OtBu)2, M(iPr-NC(Me)-N-iPr)2(OiPr)2, M(iPr-NC(Me )-N-iPr)2(OMe)2, M(iPr-NC(Me)-N_iPr)2(OEt)2, M(iPr_N-C(Me)-N-iPr)2(OnPr)2, M( iPr-NC(Me)-N-iPr)2(OsBu)2, M(iPr-NC(Me)-N-iPr)2(OiBu)2, M(iPr-NC(Me)-N-iPr)2 (OtBu)2, M(Et-NC(Me)-N-Et)2(OiPr)2 'M(Et-NC(Me)-N-Et)2(OMe)2, M(Et-NC(Me )-N-Et)2(〇Et)2, M(Et-NC(Me)-N-Et)2(OnPr)2, M(Et-NC(Me)-N-Et)2(OsBu)2 M(Et-NC(Me)-N-Et)2(OiBu)2, and M(Et-NC(Me)-N-Et)2(OtBu)2. When M is Hf, the exemplary precursors include: Hf(iPr-NC(H)-N-iPr)2(OiPr)2 'Hf(iPr-NC(H)-N-iPr)2(OMe) 2. Hf(iPr-NC(H)-N-iPr)2(OEt)2, Hf(iPr-NC(H)-N-iPr)2(OnPr)2, Hf(iPr-NC(H)-N -iPr)2(OsBu)2, Hf(iPr-NC(H)-N-iPr)2(OiBu)2 'Hf(iPr-NC(H)-N-iPr)2(OtBu)2, Hf(Et -NC(H)-N-Et)2(OiPr)2, Hf(Et-NC(H)-N-Et)2(OMe)2, Hf(Et-NC(H)-N-Et)2( 〇Et)2, 201241224

Hf(Et-NC(H)-N-Et)2(OnPr)2, Hf(Et-NC(H)-N-Et)2(〇sBu)2, Hf(Et-NC(H)-N- Et)2(OiBu)2, Hf(Et-NC(H)-N-Et)2(〇tBu)2, Hf(iPr-NC(Me)-N-iPr)2(OiPr)2, Hf(iPr -NC(Me)-N-iPr)2(OMe)2, Hf(iPr-NC(Me)-N-iPr)2(OEt)2, Hf(iPr-NC(Me)-N-iPr)2( OnPr)2, Hf(iPr-NC(Me)-N-iPr)2(OsBu)2, Hf(iPr-NC(Me)-N-iPr)2(OiBu)2, Hf(iPr-NC(Me) -N-iPr)2(OtBu)2, Hf(Et-NC(Me)-N-Et)2(OiPr)2, Hf(Et-NC(Me)-N-Et)2(OMe)2, Hf (Et-NC(Me)-N-Et)2(〇Et)2, Hf(Et-NC(Me)-N-Et)2(OnPr)2, Hf(Et-NC(Me)-N-Et 2(OsBu)2, Hf(Et-NC(Me)-N-Et)2(OiBu)2, and Hf(Et-NC(Me)-N-Et)2(OtBu)2. When M is Zr, the exemplary precursors include: Zr(iPr-NC(H)-N-iPr)2(OiPr)2, Zr(iPr-NC(H)-N-iPr)2(OMe) 2, Zr(iPr-NC(H)-N-iPr)2(OEt)2, Zr(iPr-NC(H)-N-iPr)2(OnPr)2, Zr(iPr-NC(H)-N -iPr)2(OsBu)2 ' Zr(iPr-NC(H)-N-iPr)2(OiBu)2 ' < Zr(iPr-NC(H)-N-iPr)2(OtBu)2, Zr (Et_N-C(H)-N-Et)2(OiPr)2, Zr(Et-NC(H)-N-Et)2(OMe)2, Zr(Et-NC(H)-N-Et) 2(OEt)2, Zr(Et-NC(H)-N-Et)2(OnPr)2, Zr(Et-NC(H)-N-Et)2(OsBu)2, Zr(Et-NC( H)-N-Et)2(〇iBu)2, Zr(Et-NC(H)-N-Et)2(〇tBu)2, Zr(iPr-NC(Me)-N-iPr)2(OiPr 2' Zr(iPr-NC(Me)-N-iPr)2(OMe)2 ' Zr(iPr-NC(Me)-N-iPr)2(〇Et)2 ' Zr(iPr-NC(Me) -N-iPr)2(OnPr)2 > Zr(iPr-NC(Me)-N-iPr)2(OsBu)2, Zr(iPr-NC(Me)-N-iPr)2(OiBu)2 Zr(iPr-NC(Me)-N-iPr)2(OtBu)2, Zr(Et-NC(Me)-N-Et)2(OiPr)2, Zr(Et-NC(Me)-N-Et 2(OMe)2, Zr(Et-NC(Me)-N-Et)2(OEt)2, Zr(Et-NC(Me)-N-Et)2(OnPr)2, Zr(Et-NC (Me)-N-Et)2(OsBu)2, Zr(Et-NC(Me)-N-Et)2(OiBu)2, and Zr(Et-NC(Me)-N-Et)2(OtBu )2. 19 201241224 In this particular example, the preferred exemplary precursor is Hf(iPr-NC(H)-N-iPr)2(OiPr)2, Hf(iPr-NC(Me)-N-iPr)2 ( OiPr)2, Zr(iPr-NC(H)-N-iPr)2(OiPr)2, or Zr(iPr-NC(Me)-N-iPr)2(OiPr)2. When u = 1 ' x = 2 ' y = 1 and z = 0 in the formula I, the precursor has the following chemical structure:

In this embodiment, Ri and R2 are preferably Et or iPr; I is preferably Η, Me or NMe2; R4 is preferably iPr; and R5 and R6 are preferably independently Me or Et. Exemplary precursors include: M(iPr-NC(Me)-N-iPr)(OiPr)2(NMe2), M(iPr-NC(Me)-N-iPr)(OiPr)2(NEt2), M( iPr-NC(Me)-N-iPr)(OiPr)2(NEtMe), M(Et-NC(Me)-N-Et)(OiPr)2(NMe2), M(Et-NC(Me)-N -Et)(OiPr)2(NEt2) , M(Et-NC(Me)-N-Et)(OiPr)2(NEtMe) , M(iPr-NC(NMe2)-N-iPr)(OiPr)2( NMe2), M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NEt2), M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NEtMe), M(iPr-NC (Me)-N-iPr)(OiPr)2(NMeiPr), M(iPr-NC(Me)-N-iPr)(OiPr)2(NiPr2), 201241224 M(iPr-NC(Me)-N-iPr )(OiPr)2(NMetBu) , M(iPr-NC(Me)-N-iPr)(OiPr)2(NneoPentyl2) M(Et-NC(Me)-N-Et)(OiPr)2(NMeiPr) , M(Et-NC(Me)-N-Et)(OiPr)2(NiPr2), M(Et-NC(Me)-N-Et)(OiPr)2(NneoPentyl2), M(iPr-NC(NMe2) -N-iPr)(OiPr)2(NMeiPr), M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NiPr2), M(iPr-NC(NMe2)-N-iPr)(OiPr) 2 (NneoPentyl2) and M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NMeiPr). When M is Hf, the exemplary precursors include: Hf(iPr-N-C(Me)-N-iPr)(OiPr)2(NMe2),

Hf(iPr-N-C(Me)-N-iPr)(OiPr)2(NEt2),

Hf(iPr-N-C(Me)-N-iPr)(OiPr)2(NEtMe),

Hf(Et-N-C(Me)-N-Et)(OiPr)2(NMe2),

Hf(Et-N-C(Me)-N-Et)(OiPr)2(NEt2),

Hf(Et-N-C(Me)-N-Et)(OiPr)2(NEtMe),

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NMe2),

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NEt2),

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NEtMe),

Hf(iPr-N-C(Me)-N-iPr)(OiPr)2(NMeiPr),

Hf(iPr-N-C(Me)-N-iPr)(OiPr)2(NiPr2),

Hf(iPr-N-C(Me)-N-iPr)(OiPr)2(NMetBu),

Hf(iPr-N-C(Me)-N-iPr)(OiPr)2(NneoPentyl2),

Hf(Et-N-C(Me)-N-Et)(OiPr)2(NMeiPr), 21 201241224

Hf(Et-N-C(Me)-N-Et)(OiPr)2(NiPr2),

Hf(Et-N-C(Me)-N-Et)(OiPr)2(NneoPentyl2),

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NMeiPr),

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NiPr2),

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NneoPentyl2) and

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)2 (NMeiPr). When M is Zr, the exemplary precursors include: Zr(iPr-N-C(Me)-N-iPr)(OiPr)2(NMe2),

Zr(iPr-N-C(Me)-N-iPr)(OiPr)2(NEt2),

Zr(iPr-N-C(Me)-N-iPr)(OiPr)2(NEtMe),

Zr(Et-N-C(Me)-N-Et)(OiPr)2(NMe2),

Zr(Et-N-C(Me)-N-Et)(OiPr)2(NEt2),

Zr(Et-N-C(Me)-N-Et)(OiPr)2(NEtMe),

Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NMe2),

Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NEt2),

Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NEtMe),

Zr(iPr-N-C(Me)-N-iPr)(OiPr)2(NMeiPr),

Zr(iPr-N-C(Me)-N-iPr)(OiPr)2(NiPr2),

Zr(iPr-N-C(Me)-N-iPr)(OiPr)2(NMetBu),

Zr(iPr-N-C(Me)-N-iPr)(OiPr)2(NneoPentyl2),

Zr(Et-N-C(Me)-N-Et)(OiPr)2(NMeiPr),

Zr(Et-N-C(Me)-N-Et)(OiPr)2(NiPr2),

Zr(Et-N-C(Me)-N-Et)(OiPr)2(NneoPentyl2),

Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NMeiPr) , 22 201241224

Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NiPr2),

Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NneoPentyl2), and Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NMeiPr). In this particular example, the preferred exemplary precursor is

Hf(iPr-N-C(Me)-N-iPr)(OiPr)2(NMe2) or

Zr(iPr-N-C(Me)-N-iPr)(OiPr)2(NMe2). When in the formula I, u = 1, x = 2, y = 0 and z = 1, the precursor has the following chemical structure:

QR4

OR4 In this embodiment, Ri and R2 are preferably Et or iPr; R3 is preferably Η or Me; R4 is preferably iPr; and R7 is preferably Me. Exemplary precursors include: M(iPr-N-C(Me)-N-iPr)(0iPr)2(02CMe) and M(Et-N-C(Me)-N-Et)(0iPr)2(02CMe). When Μ is Hf, the exemplary precursors include: Hf(iPr-NC(Me)-N-iPr)(0iPr)2(02CMe) and Hf(Et-NC(Me)-N-Et) (0iPr) ) 2 (02CMe). When Μ is Zr, the exemplary precursors include: Zr(iPr-NC(Me)-N-iPr)(0iPr)2(02CMe) and Zr(Et-NC(Me)-N-Et) (0iPr) ) 2 (02CMe). When v = l, x = 1, y = 0 and z = 1 in formula II, the precursor has the following chemical structure: 23 201241224

I Ri When m=2, v=l, χ = 1, y=0, z=l and R_3=H, the precursor has the following chemical structure:

R2 I

Ri When m=3, v=l, x=l, y=0, z=l and R3 = H, the precursor has the following chemical structure:

In these specific examples, m is preferably 2 or 3, R! and R2 are preferably Et or iPr; R3 is preferably Η; R4 is preferably C1-C4 straight or branched alkane 24 201241224 precursor includes Base bond; and R7 is preferably Me. Illustrative M(iPr-N-(CH2)2-N-iPr)(0iPr)(02CMe) M(iPr-N-(CH2)2-N-iPr)(0Me)(02CMe) M(iPr-N- (CH2)2-N-iPr)(0Et)(02CMe) M(iPr-N-(CH2)2-N-iPr)(0nPr)(02CMe) M(iPr-N-(CH2)2-N-iPr )(0sBu)(02CMe) M(iPr-N-(CH2)2-N-iPr)(OiBu)(02CMe) M(iPr-N-(CH2)2-N-iPr)(0tBu)(02CMe) M (Et-N-(CH2)2-N-Et)(OiPr)(02CMe) M(Et-N-(CH2)2-N-Et)(0Me)(02CMe) M(Et-N-(CH2) 2-N-Et)(0Et)(02CMe) M(Et-N-(CH2)2-N-Et)(0nPr)(02CMe) M(Et-N-(CH2)2-N-Et)(0sBu (02CMe), and the precursors include: M(Et-N-(CH2)2-N-Et)(OiBu)(02CMe) M(Et-N-(CH2)2-N-Et)(0tBu)( 02CMe). When M is Hf, the exemplary Hf(iPr-N-(CH2)2-N-iPr)(OiPr)(02CMe)Hf(iPr-N-(CH2)2-N-iPr)(0Me)( 02CMe) Hf(iPr-N-(CH2)2-N-iPr)(0Et)(02CMe) Hf(iPr-N-(CH2)2-N-iPr)(0nPr)(02CMe) Hf(iPr-N- (CH2)2-N-iPr)(0sBu)(02CMe) Hf(iPr-N-(CH2)2-N-iPr)(0iBu)(02CMe) Hf(iPr-N-(CH2)2-N-iPr )(OtBu)(02CMe) Hf(Et-N-(CH2)2-N-Et)(0iPr)(02CMe) 25 201241224

Hf(Et-N-(CH2)2-N-Et)(0Me)(02CMe)

Hf(Et-N-(CH2)2-N-Et)(0Et)(02CMe)

Hf(Et-N-(CH2)2-N-Et)(0nPr)(02CMe)

Hf(Et-N-(CH2)2-N-Et)(OsBu)(02CMe) , and the drive include:

Hf(Et-N-(CH2)2-N-Et)(OiBu)(02CMe)

Hf(Et-N-(CH2)2-N-Et) (0tBu) (02CMe). When M is Zr, the exemplary pre-Zr(iPr-N-(CH2)2-N-iPr)(OiPr)(02CMe) Zr(iPr-N-(CH2)2-N-iPr)(0Me) (02CMe) Zr(iPr-N-(CH2)2-N-iPr)(0Et)(02CMe)

Zr(iPr-N-(CH2)2-N-iPr)(0nPr)(02CMe)

Zr(iPr-N-(CH2)2-N-iPr)(0sBu)(02CMe)

Zr(iPr-N-(CH2)2-N-iPr)(0iBu)(02CMe)

Zr(iPr-N-(CH2)2-N-iPr)(0tBu)(02CMe)

Zr(Et-N-(CH2)2-N-Et)(OiPr)(02CMe)

Zr(Et-N-(CH2)2-N-Et)(0Me)(02CMe), and , an exemplary precursor (NMe2)2,

Zr(Et-N-(CH2)2-N-Et)(0Et)(02CMe) Zr(Et-N-(CH2)2-N-Et)(0nPr)(02CMe) Zr(Et-N-(CH2) ) 2-N-Et)(0sBu)(02CMe) Zr(Et-N-(CH2)2-N-Et)(0iBu)(02CMe) Zr(Et-N-(CH2)2-N-Et)( OtBu) (02CMe). When u=l, x=l, y=2 and z=0 in the formula I, it includes: M(iPr-NC(Me)-N-iPr)(OiPr) M(iPr-NC(Me)-N- iPr)(OiPr)(NEt2)2 26 201241224 M(iPr-NC(Me)-N-iPr)(OiPr)(NEtMe)2 M(Et-NC(Me)-N-Et)(OiPr)(NMe2) 2 M(Et-NC(Me)-N-Et)(OiPr)(NEt2)2 M(Et-NC(Me)-N-Et)(OiPr)(NEtMe)2 , M(iPr-NC(NMe2) -N-iPr)(OiPr)(NMe2)2 , M(iPr-NC(NMe2)-N-iPr)(OiPr)(NEt2)2 , and M(iPr-NC(NMe2)-N-iPr)(OiPr) ) (NEtMe) 2. When M is Hf, the exemplary precursors include: Hf(iPr-N-C(Me)-N-iPr)(OiPr)(NMe2)2 ,

Hf(iPr-N-C(Me)-N-iPr)(OiPr)(NEt2)2 ,

Hf(iPr-N-C(Me)-N-iPr)(OiPr)(NEtMe)2 ,

Hf(Et-N-C(Me)-N-Et)(OiPr)(NMe2)2 ,

Hf(Et-N-C(Me)-N-Et)(OiPr)(NEt2)2 ,

Hf(Et-N-C(Me)-N-Et)(OiPr)(NEtMe)2 ,

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)(NMe2)2 ,

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)(NEt2)2 , and

Hf(iPr-N-C(NMe2)-N-iPr)(OiPr)(NEtMe)2. When M is Zr, the exemplary precursors include: Zr(iPr-N-C(Me)-N-iPr)(OiPr)(NMe2)2 ,

Zr(iPr-N-C(Me)-N-iPr)(OiPr)(NEt2)2 ,

Zr(iPr-N-C(Me)-N-iPr)(OiPr)(NEtMe)

Zr(Et-N-C(Me)-N-Et)(OiPr)(NMe2)2

Zr(Et-N-C(Me)-N-Et)(OiPr)(NEt2)2

Zr(Et-N-C(Me)-N-Et)(OiPr)(NEtMe)2 27 201241224

Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)(NMe2)2 ,

Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)(NEt2)2 , and

Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)(NEtMe)2. When v = l, x = 1, y = 1, and z = 0 in Formula II, exemplary precursors include: M(iPr-N-(CH2)2-N-iPr)(OiPr)(NMe2) ' M(iPr-N_(CH2)2-N-iPr)(OiPr)(NEt2) , M(iPr-N-(CH2)2-N-iPr)(OiPr)(NEtMe) , M(Et-N-( CH2)2-N-Et)(OiPr)(NMe2) , M(Et-N-(CH2)2-N-Et)(OiPr)(NEt2) , and M(Et-N-(CH2)2-N -Et)(OiPr)(NEtMe). When M is Hf, the exemplary precursors include: Hf(iPr-N-(CH2)2-N-iPr)(OiPr)(NMe2), Hf(iPr-N-(CH2)2-N-iPr )(OiPr)(NEt2) ,

Hf(iPr-N-(CH2)2-N-iPr)(OiPr)(NEtMe) '

Hf(Et-N-(CH2)2-N-Et)(OiPr)(NMe2),

Hf(Et-N-(CH2)2-N-Et)(OiPr)(NEt2), and

Hf(Et-N-(CH2)2-N-Et)(OiPr)(NEtMe). When M is Zr, the exemplary precursors include: Zr(iPr-N-(CH2)2-N-iPr)(OiPr)(NMe2), Zr(iPr-N-(CH2)2-N-iPr )(OiPr)(NEt2) '

Zr(iPr-N-(CH2)2-N-iPr)(OiPr)(NEtMe),

Zr(Et-N-(CH2)2-N-Et)(OiPr)(NMe2),

Zr(Et-N-(CH2)2-N-Et)(OiPr)(NEt2), and

Zr(Et-N-(CH2)2-N-Et)(OiPr)(NEtMe). When u = l, x = 1, y = 0, and z = 2 in Formula I, exemplary precursors include: M(iPr-NC(Me)-N-iPr)(OiPr) (02CMe)2 and 28 201241224 M(Et-NC(Me)-N-Et)(0iPr)(02CMe)2. When Μ is Hf, the exemplary precursors include: Hf(iPr-NC(Me)-N-iPr)(OiPr) (02CMe)2 and Hf(Et-NC(Me)-N-Et) (0iPr) ) (02CMe) 2. When Μ is Zr, the exemplary precursors include: Zr(iPr-NC(Me)-N-iPr; K〇iPr;) (02CMe)2 and Zr(Et-NC(Me)-N-Et) (0iPr)(02CMe)2. When u, v, y = 0, χ = 2, and z = 2 in either of Formula I or Formula II, the exemplary precursor includes M(0iPr)2(02CMe)2, or when Μ is Hf When the exemplary precursor includes Hf(OiPr)2(〇2CMe)2, and when Μ is Zr, the exemplary precursor includes Zr(OiPr)2(〇2CMe)2 » when in Formula I or Formula II In any of u, v, y = 0, χ = 3 and z = 1, 'exemplary precursors include M(OiPr) 3 (〇2CMe), or when μ is Hf, the exemplary precursors include Hf ( OiPr)3 (〇2CMe), and when Μ is Zr, the exemplary precursor includes Zr(OiPr)3(〇2C]VIe). A hydrocarbon solution of ruthenium (Ι^_Ν-(:(Ι13)-Ν-Ι12) can be combined with a ruthenium or zirconium compound (such as Hf(〇R4)3(NR5R6), Hf(OR4)2 by a nitrogen atmosphere. (NR5R6)2, Zr(OR4)3(NR5R6), or a pure solution or hydrocarbon solution of Zr(〇R4)2(NR5R6)2) to synthesize the precursors disclosed, and the outlet of the mixing flask is connected to the oil. The exemplary hydrocarbon solution of the bubbler includes pentane.

-'^ % · Knife - Do not perform the liquid obtained by distillation or sublimation

29 201241224 Precursors are used for the deposition of tantalum-containing and zirconium-containing films, respectively. The methods disclosed herein can be used in the fabrication of semiconductors, photovoltaic devices, LCD-TFT or flat panel devices. The method includes: providing a substrate; providing a vapor comprising at least one of the disclosed germanium- or germanium-containing precursors; and contacting the vapor with the substrate (and typically directing the vapor to the substrate) A donor layer or a miscible layer is formed on at least one surface of the substrate. The method disclosed by shai et al. also provides for forming a bimetallic-containing layer on a substrate using a vapor deposition process. The methods disclosed herein can be used in the manufacture of semiconductors, photovoltaic devices, LCD-TFT or flat-type devices, the method comprising: providing a substrate; providing at least one of the disclosed cerium- or zirconium-containing precursors The vapor of the person; and contacting the vapor with the substrate (and typically directing the vapor to the substrate) to form a bimetallic-containing layer on at least one surface of the substrate. Oxygen sources such as 〇3, 〇2, h2〇 and N〇 may also be provided, preferably h2o. The disclosed cerium-containing and zirconium-containing precursors can be used to deposit cerium-containing and cerium-containing films using any deposition method known to those skilled in the art. Examples of suitable deposition methods include, without limitation, conventional chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), atomic layer deposition (ALD), pulsed chemical vapor deposition (P-CVD), plasma enhanced Atomic layer deposition (pE_ALD), or a combination thereof. Preferably, the deposition method is ALD or pE_ALD. The ruthenium- or zirconium-containing precursor vapor is introduced into the reaction chamber containing at least one substrate. Maintaining the temperature and pressure within the reaction chamber and the temperature of the substrate under suitable conditions such that contact between the ruthenium- or ruthenium-containing precursor and the substrate results in the formation of Hf-containing or inclusions on at least one surface of the substrate 30 201241224

Zr layer. Reactants can also be used to help form the Hf-containing or Zr-containing layer. The reaction chamber can be any housing or chamber for the deposition method of the device to 'such as (without limitation) parallel plate type reactor, cold wall type reactor, hot wall type reactor, single wafer reactor, multi wafer Reactors, or other such types of '/product systems. All such exemplary reaction chambers can be used as an Ald reaction chamber. The reaction chamber can be maintained at a pressure ranging from about 毫5 mTorr (〇7 Pa) to about 20 Torr (2700 Pa). Additionally, the beta octave in the reaction chamber can range from about 200 C to about 600 °C. Those of ordinary skill in the art will recognize that the temperature can be optimized by a pure experiment to achieve the desired result. The temperature of the reaction chamber can be controlled by controlling the temperature of the substrate holder or controlling the temperature of the reactor wall. Apparatus for heating the substrate is known in the art. The reactor wall is heated to a temperature sufficient to obtain the desired film at a sufficient growth rate and the desired film has the desired physical state and composition. The reactor wall can be heated to one of a non-limiting exemplary temperature range including from about 200 C to about 600 °C. When utilizing an electropolymer deposition process, the deposition temperature can be about 200. (: to a range of about 55 CTC. Or, when performing a thermal process, the deposition temperature may be in the range of about 400 ° C to about 6 ° C. Or 'the substrate can be heated to a sufficient temperature to grow enough The desired ruthenium or ruthenium containing film is obtained at a rate and the desired ruthenium or ruthenium containing film has the desired physical state and composition. The substrate can be heated to one of the non-limiting exemplary temperature ranges including from 15 〇. Preferably, the temperature of the substrate is maintained to be less than or equal to 45 (TC. The type of substrate on which the cerium- or zirconium-containing film will be deposited will vary depending on the end use of 31 201241224. In some embodiments, the substrate can be selected from the group consisting of oxides used as dielectric materials in MIM, DRAM, or FeRam technology (eg, work-based materials, Ti〇2-based materials, based on Zr〇2) Materials, materials based on rare earth oxides, materials based on ternary oxides, 胄#), or nitride-based films (eg 'TaN) used as oxygen barriers between copper and low-k layers. Other substrates are available For semiconductors, photovoltaic devices, LC In the manufacture of D-TFT s-go plate devices, examples of such substrates include, but are not limited to, solid substrates, such as metal-containing nitride substrates (eg, TaN, TiN 'WN, TaCN, TiCN, TaSiN, and TiSiN); Insulators (eg, SiO 2 , Si 3 N 4 , SiON, HfO 2 , Ta 2 〇 5, Zr 〇 2, Ti 〇 2, Al 2 〇 3 ′ and barium titanate); or other substrates, including any number of combinations of such materials. The actual substrate utilized may also depend on the particular precursor embodiment utilized. However, in many instances, the preferred substrate utilized will be selected from the group consisting of TiN, SRO, Ru, and Si-type substrates. The cerium- or zirconium-containing precursor may be fed in a liquid state to a vaporizer in which the cerium-containing or cerium-containing precursor is introduced before or after the precursor is introduced into the reaction chamber. Vaporization. Before the ruthenium or ruthenium containing precursor is oxidized, the fused or misproducible precursor may be optionally mixed with one or more solvents, one or more metal sources, and one or more solvents and - or a mixture of multiple metal sources. These solvents can be selected from the following The group consisting of: 曱本,乙本,一曱 benzene 'all triterpene benzene, 癸 、, 十二烧 ' octane, hexane, pentane, or others. The concentration can be obtained in about 〇.〇5 M to a range of about 2 。. The metal source may include any metal-containing precursor now known or later developed. 32 201241224 Alternatively, it may be cut into the containing precursor containing or containing the wrong precursor by The contained or misproducible precursor is vaporized in a vessel or by bubbling the carrier gas to the ruthenium containing or misproducing precursor. The carrier gas and the containing or containing precursor are then The vapor form is introduced into the reaction chamber. The carrier gas can include, but is not limited to, Ar, He, ν2, and mixtures thereof. The ruthenium containing or ruthenium containing precursor may optionally be combined with one or more solvents, metal containing precursors or mixtures thereof in the vessel. If necessary, the vessel can be heated to a temperature which permits the containing or containing hammer precursor to be in its liquid phase and has a sufficient vapor pressure. The container can be maintained at, for example, about 〇. . To a temperature in the range of about 15 (TC), those skilled in the art recognize that the temperature of the vessel can be adjusted in a known manner to control the amount of vaporization of the ruthenium containing or ruthenium containing precursor. The chamber may optionally be combined with a solvent, a metal-containing precursor, and a stable precursor prior to the chamber, and the reactant containing or containing the precursor may be reacted with the interior of the reaction chamber. Mixing. Examples of inactive reactants include, without limitation, metal-containing precursors, such as aluminum-containing precursors (such as 'TMA) or sand-containing precursors (such as bis(diethylamino) sulphur). These or other metal-containing precursors are incorporated into the resulting film as a replacement agent' or as a second or third metal in the resulting film, such as PZT. The field containing or containing the wrong film also contains Oxygen (such as (and without limitation) = 〇). The reactants may include one selected from the group consisting of: 2 〇3 H2〇, ^2〇2, acetic acid, formalin, secondary Formaldehyde, and combinations thereof, preferably, when the ALD process is performed, the reactant is H2〇. Slurry to treat the reactants to decompose the reactants into their 33 201241224 free radical form. The plasma can be produced or present in its own reaction chamber. Or 'the plasma can be substantially from the reaction chamber at the location Discharge in the chamber, for example, in a remotely located plasma system. Those skilled in the art will recognize methods and apparatus suitable for such plasma processing. For example, the reactants can be introduced into direct plasma In the reactor (the direct plasma reactor produces a plasma in the reaction chamber) to produce the electrically treated reactant in the reaction chamber. The exemplary direct electricity reactor includes a production by Trion Technologies. a TitanTM PECVD system that can be introduced and held in the reaction chamber prior to plasma treatment. Alternatively, the plasma treatment can occur simultaneously with the introduction of the reactants. In situ plasma is typically A 13.56 MHz RF capacitively coupled plasma is produced between the showerhead and the δH substrate holder. The substrate or showerhead can be a supply electrode depending on whether a positive ion impact occurs. Typical applied power in the device is from about 1 〇〇w to about 1 〇〇〇w. Dissociation of the reactants achieved using in-situ plasma is typically less than that achieved with a remote plasma source for the same power input. The dissociation, and therefore the dissociation of the reactants, is less efficient than the dissociation of the reactants in the remote plasma system, which may be beneficial for depositing a metal-containing nitride crucible that is susceptible to damage by the plasma on the substrate. Alternatively, in the reaction chamber The plasma treated reactant is externally generated. The reactant can be treated with MKS Instruments' antron® i reactive gas generator prior to loading into the reaction chamber. Plasma at 2 45 GHz, 7 kW The power and operation at a pressure in the range of from about 3 Torr to about 1 Torr can decompose the reactant 〇3 into three 〇· radicals. Preferably, the remote power is generated in a range from about 1 kW to about 10 kW, more preferably from about 25 kW to about 34 201241224 7.5 kW. §3Hai must contain or contain a film. The film also contains another metal (such as V is not limited) Ta, Hf, Zr, Nb, Mg, Al, Sr, Y, Ba, Γη * ' As '

When Sb, Bi, Sn, Pb, Co, a lanthanide element (such as Eu), or a combination thereof, the reactants may include a metal-containing 1 drive selected from, but not limited to, the following: a metal alkane, such as Ln(RCp)3 or Co(RCp)2; a metal alkane, such as Ti(Cp)(OMe)3; and any combination thereof. The vapor containing the metal precursor is introduced into the reaction chamber. The temperature and pressure within the reaction chamber and the temperature of the substrate are maintained under suitable conditions such that contact between the metal-containing precursor and the substrate results in the formation of a metal-containing layer on at least one surface of the substrate. Reactants can also be used to help form the metal containing layer. Those of ordinary skill in the art will recognize that additional reactants may be utilized in such disclosed deposition processes. The ruthenium containing or erroneous precursor and one or more (iv) reactants can be introduced into the reaction chamber simultaneously (chemical vapor deposition), sequentially (atomic layer deposition) or in other combinations. For example, the containing or containing precursors may be introduced in one pulse and may be introduced in separate pulses to introduce two additional metal sources [modified atomic layer deposition]. Alternatively, the reaction chamber may already contain the reactants prior to introduction of the containing or containing precursor. The reverse can be passed through a plasma system localized to the distal end of the reaction chamber, and the reactants can be separated into free s or continuously introduced by pulse into other metal sources (pulsed chemical vapor deposition). The containing or misproducing precursor is directed to the "Reaction" chamber. In each of the examples, the pulse may be followed by a purge or 35 201241224 evacuation step to remove the excess component introduced. In each embodiment, the pulse may last for a period of time ranging from about 0.01 s to about 10 s or from about 0.3 s to about 38, or from about 0.5 S to about 2 Within the scope of s. In a non-limiting exemplary atomic layer deposition process, a vapor phase containing a ruthenium- or precursor-containing precursor is introduced into the reaction chamber, and the vapor containing the ruthenium or the precursor is contained in the reaction chamber I The phase is in contact with a suitable substrate. Excess ruthenium or ruthenium containing precursor can then be removed from the reaction chamber by purging and/or evacuating the reaction chamber. Introducing an oxygen source into the reaction chamber in which the oxygen source reacts with the absorbed ruthenium or ruthenium containing precursor in a self-limiting manner by purging and/or evacuating the reaction chamber The chamber removes any excess oxygen from the reaction chamber. If the desired film is a yttria or zirconia film, the two-step process can provide the desired film thickness, or the two-step process can be repeated until a film having the necessary thickness is obtained. Alternatively, if the desired film is a germanium or a metal oxide film, a second vapor containing a metal precursor may be introduced into the reaction chamber after the two-step process. The metal-containing precursor will be selected based on the nature of the ruthenium metal oxide or metal oxide film being deposited. After introduction into the reaction chamber, the ?-metal precursor is brought into contact with the substrate. Any excess metal-containing precursor is removed from the reaction chamber by purging and/or evacuating the reaction chamber. Further, an oxygen source can be introduced into the reaction chamber to react with the metal-containing precursor. Excess oxygen is removed from the S-reaction chamber by removing it by purging and/or evacuating the reaction chamber. If the desired film thickness has been achieved, the S-Hail process can be terminated. However, if a thicker film is required, the entire four-step process can be repeated. The film having the desired composition and thickness can be alternately supplied by alternately supplying the supplied or contained precursor, the metal-containing precursor, and the ?-oxygen source. Further, by changing the number of pulses, a film having a desired stoichiometric amount of Hf: metal or Zr: metal ratio can be obtained. For example, a ruthenium film (Pb[ZrxTii χ] 〇3, where 0 0<lt<>> can be obtained by having one pulse of the zirconium containing precursor, one pulse of the titanium-containing precursor, and two pulses of the lead-containing precursor ; 1), wherein each pulse is followed by a pulse of the oxygen source. However, those of ordinary skill in the art will recognize that the number of pulses required to obtain the desired film may not be the same as the stoichiometric ratio of the resulting film. The ruthenium containing or ruthenium containing films produced by the processes discussed above may include ruthenium. Those of ordinary skill in the art will recognize that the desired film composition can be obtained by careful selection of the appropriate ruthenium or ruthenium containing precursor and reactants. EXAMPLES The following non-limiting examples are provided to further illustrate specific examples of the invention. However, the embodiments are not intended to be all inclusive and are not intended to limit the scope of the invention described herein. Prophetic Example 1

Hf(N -amd)(〇ipr)3 or Zr(NiPr_amd)(〇ipr)3: The pentane solution was cooled to -30 ° C for 1 hour. Hf(〇ipr)3(NMe2) or Zr(OiPr)3(NMe2) was added to the cooled pentane solution. The mixture was stirred at a temperature under a nitrogen atmosphere. The NiPr_amd_H pentane solution was slowly added to the above mixture. The outlet of the flask was connected to an oil bubbler and the oil bubbler was connected to the acid scrubber. The resulting solution was stirred at room temperature overnight. The solvent and volatiles are removed from the reaction mixture under vacuum to yield the target 37 201241224 molecule (Hf(NiPr-amd)(OiPr)3 or Zr(NiPr-amd)(OiPr)3). Prophetic Example 2

Hf(NiPl"-amd)2(OiPr)2 or Zr(NlPr-amd)2(〇iPr)2 : will be net

Hf(OiPr)2(NMe2)2 or neat Zr(OiPr)2(NMe2)2 is added to a solution containing NlPr-amd-H, which is stirred at room temperature under a nitrogen atmosphere, and the outlet of the flask is connected to the oil. Bubbler. The resulting solution was stirred at room temperature overnight. The solvent and volatiles are removed from the reaction mixture under vacuum to produce the target molecule (Hf(NlPr-amd)2(OiPr)2 or Zr(NlPr-amd)2(OiPr)2). Prophetic Example 3

Hf(NlPr-fmd)2(OiPr)2 or Zr(NiPr-fmd)2(〇iPr)2 : will be net

Hf(OiPr)2(NMe2)2 or neat Zr(OiPr)2(NMe2)2 is added to a solution containing NiPr-fmd-H in pentane stirred at room temperature under a nitrogen atmosphere, and the outlet of the flask is connected to the oil. Bubbler. The resulting solution was stirred at room temperature overnight. The solvent and volatiles are removed from the reaction mixture under vacuum to produce the target molecule (Hf(NiPr-fmd)2(OiPr)2 or Zr(NiPr-fmd)2(OiPr)2). Prophetic Example 4

Hf(NiPr-gmd)2(OiPr)2 or Zr(NiPr-gmd)2(OiPr)2 : will be net

Hf(〇iPr)2(NMe2)2 or net Zr(OiPr)2(NMe2)2 was added to a solution containing iPr-N=C=N-iPr in pentane stirred at room temperature under a nitrogen atmosphere. The outlet is connected to the oil bubbler. The resulting solution was stirred at room temperature overnight. The solvent and volatiles are removed from the reaction mixture under vacuum to yield the target molecule (Hf(NlPr-gmd)2(OiPr)2 or Zr(NlPr-gmd)2(OiPr)2). Prophetic Example 5

Hf(NiPr-amd)(OiPr)2(NMe2) or 38 201241224

Zr(NlPl"-amd)(OiPr)2(NMe2): Slowly add NiPr-amd-H pentane solution to Hf(OiPr)2(NMe2) mixed at room temperature under nitrogen atmosphere 2 or a solution of Zr(OiPr)2(NMe2)2 in pentane. The outlet of the flask was connected to an oil bubbler and the oil bubbler was connected to the pickler. The resulting solution was mixed at room temperature. The solvent and volatiles are removed from the reaction mixture under vacuum to yield the target molecule (Hf(NlPr-amd)(OiPr)2(NMe2) or Zr(NiPr-amd)(OiPr)2(NMe2)). Prophetic Example 6

Hf(Et-N-(CH2)2-N-Et)(OiPr)2 or

Zr(Et-N-(CH2)2-N-Et)(OiPr)2: Slowly add a net of Et-NH-(CH2)2-NH-Et to the room temperature under nitrogen atmosphere at room temperature A mixed solution of Hf(OiPr)2(NMe2)2 or Zr(OiPr)2(NMe2)2 was prepared. Connect the flask outlet " to the oil bubbler' and connect the oil bubbler to the pickling dispenser. The resulting solution was scrambled at room temperature. The solvent and volatiles are removed from the reaction mixture under vacuum to produce the target molecule (Hf(Et-N-(CH2)2-N-Et)(OiPr)2 or Zr(Et-N-(CH2)2 -N-Et)(〇iPr)2). Prophetic Example 7

Ti(Me-N-(CH2)2-N-Me)(OiPr)2: A synthesis similar to that of Example 6 will be carried out in which the reactants have a suitable ligand. Prophetic Example 8

Ti(Me2CH-N-(CH2)3-N-CHMe2)(〇iPr)2: A synthesis similar to that of Example 6 will be carried out in which the reactants have a suitable ligand. Prophetic Example 9 An HfO 2 or ZrO 2 film was deposited on a SiOVSi substrate using the cerium- or zirconium-containing precursor of any of Examples 1 to 8 and 39 201241224 reactant 〇3. The SiO 2 /Si substrate was maintained at a temperature of 250 ° C. The precursor was maintained at 5 Torr. (: vaporization in the lower bubbler. The ALD cycle will include the precursor pulse 5 seconds before, followed by a 5 second purge followed by a 2 second reactant pulse followed by a 5 second purge. Expected Hf〇2 or The Zr〇2 growth rate is 0.5 A/cycle or greater than 〇5 A/cycle. At the deposition rate, the analytical ALD mechanism will be as high as 350 ° C. Prophetic Example 1 〇 Using any of Examples 1 to 8 The HfCh or ZrO 2 film is deposited on the SiOVSi substrate with a ruthenium or ruthenium containing precursor and a reactant KbO. The SiC^/Si substrate is maintained at a temperature of 250 ° C. The precursor is maintained in a bubbler maintained at 50 ° C. Vaporization. The ALD cycle will include a precursor pulse of 20 seconds, followed by a 5 second purge followed by a 2 second reactant pulse followed by a 1 second purge. The expected growth rate of Hf〇2 or Zr〇2 is 〇 • 5 A/cycle or greater than 〇5 A/cycle. The analytical ALD mechanism will be as high as 350 ° C. It is to be understood that the skilled person can understand the principles and scope of the invention as expressed in the appended claims. The details, materials, steps, and proportions of the configurations that have been described and described herein to explain the nature of the present invention are made. Multi extra changes. Accordingly 'the present invention is not intended to be limited to the above and to the penetration / Specific embodiments or examples of specific drawings. Brief Description of the drawings [] [] No major components SIGNS LIST 40

Claims (1)

201241224 VII. Patent application scope: 1. A molecule having the following formula: M(R1-NC(R3)-N-R2)u(〇R4)x(NR5R6)y(〇2CR7)z Formula 1 or wherein: Μ Rf or Zr; Ri, R2, R5, R6 and R7 are independently selected from the group consisting of ruthenium and C1-C6 ray; Han 3 = Η, C1-C6 thermal group, or NMe2; R4 is C1-C6 alkyl m = 2 to 4; u = 0 to 2; 'v 2 0 to 1; x = 1 to 3; y = 0 to 2; z = 0 to 1; in Equation I, u + x+y+ζ = 4 ; In Formula II, 2v+x+y+z = 4; and u, v or z > 1 〇2. As claimed in the first item of the patent scope, the molecule has the formula I 'χχ3 , y=〇, and z=〇〇3. The molecule of claim 2, wherein the molecule is selected from the group consisting of: K(iPr-NC(Me)-N-iPr)丨(OiPr) 3, 201241224 M(iPr-NC(Me)-N-iPr)1(OMe)3 ' M(iPr-NC(Me)-N-iPr)!(OEt)3 > M(iPr-NC(Me )-N-iPr), (OnPr)3 ' M(iPr-NC(Me)-N-iPr), (OsBu)3 ' M(iPr-NC(Me)-N-iPr)i(OiBu)3 ' M(iPr-NC(Me)-N-iPr)!(OtBu)3 ' M(Et-NC(Me)-N-Et)i(OEt)3 , M(Et-NC(Me)-N-Et ), (OMe)3, M(Et-NC(Me)-N-Et), (OnPr)3 'M(Et-NC(Me) -N-Et), (OsBu)3 'MCEt-N-C^MeVN-EOKOiBu):», MiEt-N-C^MeyN-EtMOtBuh, and M(iPr-N-C(NMe2)-N-iPr)(OiPr)3. 4_, as in the numerator of claim 1, the molecule has the formula II, wherein v = l, x = 2, y = 0, and z = 0 ° 5 · The molecule of claim 4, wherein The molecule is selected from the group consisting of M(iPr-N-(CH2)2-N-iPr)丨(OiPr)2, M(iPr-N-(CH2)2-N-iPr)1(OMe) 2 ' M(iPr-N-(CH2)2-N-iPr),(OEt)2 ' M(iPr-N-(CH2)2-N-iPr)1(OnPr)2 ' M(iPr-N- (CH2)2-N-iPr)i(OsBu)2 ' M(iPr-N-(CH2)2-N-iPr)1(OiBu)2 ' M(iPr-N-(CH2)2-N-iPr ),(OtBu)2 ' M(Et-N-(CH2)2-N-Et)i(OiPr)2, M(Et-N-(CH2)2-N-Et), (OMe)2, M (Et-N-(CH2)2-N-Et)1(OEt)2, M(Et-N-(CH2)2-N-Et), (OnPr)2, M(Et-N-(CH2) 2-N-Et)i(OsBu)2 ' M(Et-N-(CH2)2-N-Et), (OiBu)2 ' M(Et-N-(CH2)2-N-Et),( OtBu)2 ' M(iPr-N-(CH2)3-N-iPr)1(OiPr)2 ' M(iPr-N-(CH2)3-N-iPr), (OMe)2 ' M(iPr- N-(CH2)3-N-iPr)i(OEt)2 ' M(iPr-N-(CH2)3-N-iPr)i(OnPr)2 ' M(iPr-N-(CH2)3-N -iPr)i(OsBu)2 ' M(iPr-N-(CH2)3-N-iPr),(OiBu)2 ' M(iPr-N-(CH2)3-N-iPr)1(OtBu)2 'M(Et-N-(CH2)3-N-Et)1(OiPr)2, M(Et-N-(CH2)3-N-Et)i(OMe)2, M(Et-N-( CH2)3-N-Et)i(OEt)2, M(Et-N-(CH2)3-N-Et)i(OnPr)2, IVUEt-lSKCHA- N-EtMOsBuh, MCEt-NJCH^-N-EtMOiBuh, and 42 201241224 MCEt-N-CCHA-N-EthCOtBuh. 6. For the numerator of claim 1 of the patent, the molecule has the formula I, where u=2, x=2, y=0, and z=0. 7. A molecule according to claim 6 wherein the molecule is selected from the group consisting of M(iPr-NC(H)-N-iPr)2(OiPr)2, M(iPr-NC(H) )-N-iPr)2(OMe)2, M(iPr-NC(H)-N-iPr)2(OEt)2, M(iPr-NC(H)-N-iPr)2(OnPr)2 M(iPr-NC(H)-N-iPr)2(OsBu)2, M(iPr-NC(H)-N-iPr)2(OiBu)2, M(iPr-NC(H)-N-iPr 2(OtBu)2, M(Et-NC(H)-N-Et)2(OiPr)2, M(Et-NC(H)-N-Et)2(〇Me)2, M(Et- NC(H)-N-Et)2(OEt)2, M(Et-NC(H)-N-Et)2(〇nPr)2, M(Et-NC(H)-N-Et)2( OsBu)2, M(Et-NC(H)-N-Et)2(〇iBu)2, M(Et-NC(H)-N-Et)2(〇tBu)2, M(iPr-NC( Me)-N-iPr)2(OiPr)2, M(iPr-NC(Me)-N-iPr)2(OMe)2, M(iPr-NC(Me)-N-iPr)2(OEt)2 , M(iPr-NC(Me)-N-iPr)2(0nPr)2, M(iPr-NC(Me)-N-iPr)2(OsBu)2, M(iPr-NC(Me)-N- iPr)2(OiBu)2, M(iPr-NC(Me)-N-iPr)2(OtBu)2, M(Et-NC(Me)-N-Et)2(OiPr)2, M(Et- NC(Me)-N-Et)2(〇Me)2, M(Et-NC(Me)-N-Et)2(OEt)2, M(Et-NC(Me)-N-Et)2( OnPr)2, M(Et-NC(Me)-N-Et)2(OsBu)2, M(Et-NC(Me)-N-Et)2(OiBu)2, and M(Et-NC(Me )-N-Et) 2 (OtBu) 2. 8. As claimed in the first paragraph of the patent scope, the molecule has the formula I, wherein u = l, x = 2, y = l, and z = 0. 9. A molecule according to claim 8 wherein the molecule is selected from the group consisting of M(iPr-NC(Me)-N-iPr)(OiPr)2(NMe2), M(iPr-NC (Me)-N-iPr)(OiPr)2(NEt2), 43 201241224 M(iPr-NC(Me)-N-iPr)(OiPr)2(NEtMe) , M(Et-NC(Me)-N- Et)(OiPr)2(NMe2), M(Et-NC(Me)-N-Et)(OiPr)2(NEt2), M(Et-NC(Me)-N-Et)(OiPr)2(NEtMe ), M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NMe2), M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NEt2), M(iPr-NC( NMe2)-N-iPr)(OiPr)2(NEtMe), M(iPr-NC(Me)-N-iPr)(OiPr)2(NMeiPr), M(iPr-NC(Me)-N-iPr)( OiPr)2(NiPr2), M(iPr-NC(Me)-N-iPr)(OiPr)2(NMetBu), M(iPr-NC(Me)-N-iPr)(OiPr)2(NneoPentyl2), M (Et-NC(Me)-N-Et)(OiPr)2(NMeiPr), M(Et-NC(Me)-N-Et)(OiPr)2(NiPr2), M(Et-NC(Me)- N-Et)(OiPr)2(NneoPentyl2), M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NMeiPr), M(iPr-NC(NMe2)-N-iPr)(OiPr)2 (NiPr2), M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NneoPentyl2) and M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NMeiPr). 10. The molecule of claim 1, wherein the molecule has the formula I, wherein U-1' χ = 2, y = 〇, and z = l. 11. A molecule according to claim 10, wherein the molecule is selected from the group consisting of M(iPr-NC(Me)-N-iPr)(0iPr)2(02CMe) and M(Et-NC) (Me)-N-Et) (0iPr) 2 (02CMe). 12. The molecule of claim 1, wherein the molecule has the formula π, 201241224 wherein V=1, χ=1, y=〇, and z=l. 13. The molecule of claim 12, wherein the molecule is selected from the group consisting of M(iPr_N_(CH2)2-N-iPr)(0iPr)(02CMe), M(iPr-N-( CH2)2-N-iPr)(OMe)(02CMe) , M(iPr-N-(CH2)2-N-iPr)(0Et)(02CMe) , M(iPr-N-(CH2)2-N- iPr)(0nPr)(02CMe) , M(iPr-N-(CH2)2-N-iPr)(0sBu)(02CMe) , M(iPr-N-(CH2)2-N-iPr)(0iBu)( 02CMe) , M(iPr-N-(CH2)2-N-iPr)(0tBu)(02CMe) , M(Et-N-(CH2)2-N-Et)(0iPr)(02CMe) , M(Et -N-(CH2)2-N-Et)(0Me)(02CMe), M(Et-N-(CH2)2-N-Et)(0Et)(02CMe), M(Et-N-(CH2) 2-N-Et)(0nPr)(02CMe) , M(Et-N-(CH2)2-N-Et)(0sBu)(02CMe) , M(Et-N-(CH2)2-N-Et) (0iBu)(02CMe), and M(Et-N-(CH2)2-N-Et)(0tBu)(02CMe). 14. The molecule of claim i, wherein the molecule has the formula I or formula II' wherein u, v, y = 〇, χ = 2, and ζ = 2. 15_ If the molecule of claim 14 is a molecule, the molecule is M(OiPr)2(〇2CMe)2 〇1 6. As the molecule of claim 1, the molecule has formula I or formula II' where u , v, y=〇, χ=3, and ζ=1. 17_如_ The molecule of the 16th patent range, the molecule is M(OiPr)3(〇2CMe). 45 201241224 18· A method of forming a Hf-containing or Zr-containing layer on a substrate, the method comprising: providing a reaction chamber in which at least one substrate is disposed; steam comprising at least one precursor having the following formula Introduced into the reaction chamber: M(R1-NC(R3)-N-R2)u(〇R4)x(NR5R6)y(〇2CR7)2 Formula I or wherein: Μ is Hf or Zr; Ri, R2 , R5, R6 and R7 are independently selected from the group consisting of hydrazine and CM-C6 alkyl; R3 = hydrazine, C1-C6 alkyl group or NMe2; R4 is C1-C6 alkyl; m = 2 to 4; = 〇 to 2 ; v = 〇 to 1 ; X = 1 to 3 ; y = 0 to 2 ; z = 0 to 1 ; in Equation I, u + x + y + z = 4 ; In Equation II, 2v +x+y+z = 4; and u, v or z 2 1 ; contacting the vapor with the substrate to form the Hf-containing or Zr-containing layer on at least one surface of the substrate 46 201241224 using a vapor deposition process . 19. The object of claim 18 is selected from the group consisting of M(iPr-NC(Me)-N-iPr)! (OMe)3, M(iPr-NC(Me)-N-iPr)1 (OnPr)3 ' M(iPr-NC(Me)-N-iPr)1(OiBu)3 ' M(Et-NC(Me)-N-Et)i(OEt)3 , M(Et-NC(Me )-N-Et)i(OnPr)3, M(Et-NC(Me)-N-Et)i(OiBu)3, M(iPr-NC(NMe2)-N-iPr)(OiPr)3, M (iPr-N-(CH2)2-N-iPr)1(OMe)2 ' M(iPr-N-(CH2)2-N-iPr)1(OnPr)2 ' M(iPr-N-(CH2) 2-N-iPr)i(OiBu)2 ' M(Et-N-(CH2)2-N-Et)1(OiPr)2 , M(Et-N-(CH2)2-N-Et)i( OEt)2, M(Et-N-(CH2)2-N-Et)1(OsBu)2, M(Et-N-(CH2)2-N-Et)1(OtBu)2 'M(iPr- N-(CH2)3-N-iPr)1(OMe)2 > M(iPr-N-(CH2)3-N-iPr)1(OnPr)2 ' M(iPr-N-(CH2)3- N-iPr)1(OiBu)2 ' M(Et-N-(CH2)3-N-Et)i(OiPr)2 , M(Et-N-(CH2)3-N-Et)1(OEt) 2, M(Et-N-(CH2)3-N-Et)1(OsBu)2, M(Et-N-(CH2)3-N-Et)i(OtBu)2, the method of the item, wherein At least one precursor M (iPr-NC(Me)-N-iPr)!(OiPr)3 'M(iPr-NC(Me)-N-iPr), (OEt)3, M(iPr-NC(Me)- N-iPr)!(OsBu)3 ' M(iPr-NC(Me)-N-iPr)!(OtBu)3 ' M(Et-NC(Me)-N-Et)!(OMe)3 , M( Et-NC(Me)-N-Et), (OsBu)3, M(Et-NC(Me)-N-Et)i(OtBu)3, M(iPr-N-(CH2) 2-N-iPr),(OiPr)2 ' M(iPr-N-(CH2)2-N-iPr)1(OEt)2 ' M(iPr-N-(CH2)2-N-iPr)1( OsBu)2 ' M(iPr-N-(CH2)2-N-iPr)1(OtBu)2 ' M(Et-N-(CH2)2-N-Et)1(OMe)2 , M(Et- N-(CH2)2-N-Et)i(OnPr)2, M(Et-N-(CH2)2-N-Et)](OiBu)2, M(iPr-N-(CH2)3-N -iPr)1(OiPr)2 ' M(iPr-N-(CH2)3-N-iPr)1(OEt)2 ' M(iPr-N-(CH2)3-N-iPr)1(OsBu)2 ' M(iPr-N-(CH2)3-N-iPr)1(OtBu)2 ' M(Et-N-(CH2)3-N-Et)i(OMe)2 , M(Et-N-( CH2)3-N-Et)1(OnPr)2, M(Et-N-(CH2)3-N-Et)i(OiBu)2, M(iPr-NC(H)-N-iPr)2( OiPr)2, 47 201241224 M(iPr-NC(H)-N-iPr)2(OMe)2, M(iPr-NC(H)-N-iPr)2(OEt)2, M(iPr-NC( H)-N-iPr)2(OnPr)2, M(iPr-NC(H)-N-iPr)2(OsBu)2, M(iPr-NC(H)-N-iPr)2(OiBu)2 , M(iPr-NC(H)-N-iPr)2(OtBu)2, M(Et-NC(H)-N-Et)2(OiPr)2, M(Et-NC(H)-N- Et)2(OMe)2, M(Et-NC(H)-N-Et)2(OEt)2, M(Et-NC(H)-N-Et)2(OnPr)2, M(Et- NC(H)-N-Et)2(OsBu)2, M(Et-NC(H)-N-Et)2(OiBu)2, M(Et-NC(H)-N-Et)2(OtBu 2, M(iPr-NC(Me)-N-iPr)2(OiPr)2, M(iPr-NC(Me)-N-iPr)2(OMe)2, M(iPr-NC(Me)- N-iPr)2(OEt)2, M(iPr-NC(Me)-N-iPr)2(OnPr)2, M(iPr -NC(Me)-N-iPr)2(OsBu)2, M(iPr-NC(Me)-N-iPr)2(OiBu)2, M(iPr-NC(Me)-N-iPr)2( OtBu)2, M(Et-NC(Me)-N-Et)2(OiPr)2, M(Et-NC(Me)-N-Et)2(OMe)2, M(Et-NC(Me) -N-Et)2(OEt)2, M(Et-NC(Me)-N-Et)2(〇nPr)2, M(Et-NC(Me)-N-Et)2(OsBu)2, .M(Et-NC(Me)-N-Et)2(OiBu)2 , M(Et-NC(Me)-N-Et)2(OtBu)2 , M(iPr-NC(Me)-N- iPr)(OiPr)2(NMe2), M(iPr-NC(Me)-N-iPr)(OiPr)2(NEt2), M(iPr-NC(Me)-N-iPr)(OiPr)2(NEtMe ), M(Et-NC(Me)-N-Et)(OiPr)2(NMe2), M(Et-NC(Me)-N-Et)(OiPr)2(NEt2), M(Et-NC( Me)-N-Et)(OiPr)2(NEtMe), M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NMe2), M(iPr-NC(NMe2)-N-iPr)( OiPr)2(NEt2), M(iPr-NC(NMe2)-N-iPr)(OiPr)2(NEtMe), M(iPr-NC(Me)-N-iPr)(0iPr)2(02CMe), 48 201241224 M(Et-NC(Me)-N-Et)(0iPr)2(02CMe) M(iPr-N-(CH2)2-N-iPr)(0iPr)(02CMe) M(iPr-N-(CH2 )2-N-iPr)(0Me)(02CMe) M(iPr-N-(CH2)2-N-iPr)(0Et)(02CMe) M(iPr-N-(CH2)2-N-iPr)( 0nPr)(02CMe) M(iPr-N-(CH2)2-N-iPr)(OsBu)(02CMe) M(iPr-N-(CH2)2-N-iPr)(0iBu)(02CMe) M(iPr -N-(CH2)2-N-iPr)(0tBu)(02CMe) M(Et-N-(CH2)2-N-Et)(0iPr)(02CMe) M(Et-N-(CH2)2-N-Et)(0Me)(02CMe) M(Et-N-(CH2) ))(Nt-N-(CH2)2-N-Et)(0nPr)(02CMe) M(Et-N-(CH2)2-N-Et)( 0sBu)(02CMe) M(Et-N-(CH2)2-N-Et)(0iBu)(02CMe) M(0iPr)2(02CMe)2 , and M(Et-N-(CH2)2-N- Et) (0tBu) (02CMe), M (0iPr) 3 (02CMe). Eight, schema: (none) 49