WO2012138332A1 - Hafnium-containing or zirconium-containing precursors for vapor deposition - Google Patents

Hafnium-containing or zirconium-containing precursors for vapor deposition Download PDF

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WO2012138332A1
WO2012138332A1 PCT/US2011/031360 US2011031360W WO2012138332A1 WO 2012138332 A1 WO2012138332 A1 WO 2012138332A1 US 2011031360 W US2011031360 W US 2011031360W WO 2012138332 A1 WO2012138332 A1 WO 2012138332A1
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ipr
oipr
cme
molecule
nme
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Venkateswara R. Pallem
Christian Dussarrat
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Priority to KR1020137029037A priority Critical patent/KR101721294B1/en
Priority to PCT/US2011/031360 priority patent/WO2012138332A1/en
Priority to US14/009,812 priority patent/US9087690B2/en
Publication of WO2012138332A1 publication Critical patent/WO2012138332A1/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • H10P14/69392—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing hafnium, e.g. HfO2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
    • H10P14/6326—Deposition processes
    • H10P14/6328—Deposition from the gas or vapour phase
    • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H10P14/6339—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
    • H10P14/69—Inorganic materials
    • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
    • H10P14/6938—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
    • H10P14/6939—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
    • H10P14/69395—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing zirconium, e.g. ZrO2

Definitions

  • SiO 2 silicon dioxide
  • M(L1 )x(L2)y wherein M is a metal, L1 and L2 may be halide, diketonate, alkoxide, amino, a!koxyamine, amidinate, or multidentate ligands.
  • the exemplary precursors however are only Hf ⁇ OtBu) 2 (NEtMe)2, Hf(OtBu)2 ⁇ NEt 2 )2, Hf(NEt 2 ) 2 (DMAMP) 2 , Hf(NEtMe) 2 (DMAMP) 2 , Ti(OtBu) 3 CI, Ti(OtBu) 3 Me, Ti(OtBu) 2 (NEt 2 ) 2 , Ti(NEt 2 ) 2 (DMAMP) 2! Ti(OtBu) 2 (DMAMP) 2 , and
  • US Pat. No. 7,491 ,654 discloses ALD methods of forming ZrO 2 thin films using a tris(N-ethyl-N-methylamino)(tertbutoxy)zirconium precursor.
  • M is Hf or Zr
  • Ri , R 2l e, and R 7 are independently selected from the group consisting of H and C1-C6 alkyl group;
  • R 3 H, C1 -C6 alkyl group, or NMe 2 ;
  • R is a C1 -C6 alkyl group
  • the disclosed molecules may further include one or more of the following aspects:
  • the molecule being selected from the group consisting of M(iPr-N- C(Me)-N-iPr)i(OiPr) 3 , M(iPr-N-C(Me)-N-iPr)i(OMe) 3l (iPr-N-C(Me)-N- IPr)i(OEt) 3 , MflPr-N-C-iMeJ-N-iPrMOnPrk, M(iPr-N-C(Me)-N- iPrJ ⁇ OsBuJa, M(iPr-N-C(Me)-N-iPr)i(OiBu) 3 , M(iPr-N-C(Me)-N- iPr) 1 (OtBu ⁇ 3 , M(Et-N-C(Me)-N-Et) ⁇ i(OEt) 3 , M(Et-N-C(Me)-N-Et)i(
  • the mo!ecu!e being selected from the group consisting of M(iPr-N-C(H) N-iPr) 2 (OiPr) 2 , M(iPr-N-C(H)-N-iPr) 2 ⁇ OMe) 2 , M(iPr-N-C(H)-N-iPr) 2 (OEt) M(iPr-N-C(H)-N-iPr) 2 (OnPr) 2 , M(iPr-N-C(H)-N-iPr) 2 (OsBu) 2 , M(iPr-N- C(H)-N-iPr) 2 (OiBu) 2 , ⁇ iPr-N-C(H)-N-iPr) 2 (OtBu) 2 , (Et-N-C(H)-N- Et) 2 (OiPr) 2 , M(Et-N-C(H)-N-Et) 2 (OMe)
  • the molecule being selected from the group consisting of M(iPr-N- C(Me)-N-iPr)(OiPr) 2 ⁇ NMe 2 ), M(iPr-N-C( e)-N-iPr)(OiPr) 2 (NEt 2 ), M(iPr- N-C(Me)-N-iPr)(OiPr) 2 (NEtMe), M(Et-N-C(Me)-N-Et)(OiPr) 2 (NMe 2 ), M(Et-N-C ⁇ Me)-N-Et)(OiPr) 2 (NEt 2 ), (Et-N-C( e)-N-Et)(OiPr) 2 (NEiMe), M(iPr-N-C(NMe 2 )-N-iPr)(0!Pr) 2 (NMe 2 ), M(iPr-N-C(NMe 2 )-
  • the molecule being selected from the group consisting of M(iPr-N- (CH 2 ) 2 -N-iPr)(OiPr) ⁇ 0 2 CMe), M ⁇ iPr-N-(CH 2 ) 2 -N-iPr)(OMe)(0 2 CMe), M ⁇ iPr-N-(CH 2 ) 2 -N-iPr)(OEt)(0 2 CMe ⁇ , M(iPr-N-(CH 2 ) 2 -N- iPr) ⁇ OnPr)(0 2 CMe), M(iPr-N-(CH 2 ) 2 -N-iPr)(OsBu)(0 2 CMe), M(iPr-N- (CH 2 ) 2 -N-iPr)(OiBu)(0 2 C e), (iPr-N-(CH 2 )2-N-iPr)(OtBu)(0 2 CMe), M ⁇ Et-N-
  • a Hf-containing or Zr-containing Iayer on a substrate.
  • a reaction chamber is provided having at least one substrate disposed within it.
  • the vapor of at least one of the molecules disclosed above is introduced into the reaction chamber.
  • the vapor is contacted with the substrate to form a Hf-containing or Zr-containing iayer on at least one surface of the substrate using a vapor deposition process.
  • the disclosed methods may further include one or more of the following aspects:
  • PZT lead zirconium titanates
  • RrNCiF ⁇ N-F refers to the following chemical structure:
  • R 1 -N(C(R 3 ) 2 )m-N-R2 refers to the following chemical structure
  • the abbreviation O 2 CR 7 " refers to the followin chemical structure: the abbreviation “Cy” refers to cyclohexyi; the abbreviation “Cp” refers to cyclopentadiene; the term “aliphatic group” refers to a C1 -C6 linear or branched chain alkyl group; the term “alkyl group” refers to saturated functional groups containing exclusively carbon and hydrogen atoms and includes linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, n-propyl groups, n-butyl groups, etc.
  • Examples of branched aikyls groups include without limitation, t-butyl.
  • Examples of cyclic alkyl groups include without limitation, cyc!opropyi groups, cyciobutyl groups, cyciopentyl groups, cyclohexyl groups, etc.
  • Me refers to a methyl group
  • Et refers to an ethyl group
  • Pr refers to a propyl group
  • iPr refers to an isopropyl group
  • iBu refers to an isobutyl group
  • nBu refers to a n-butyl group
  • sBu refers to a sec-butyl group
  • ⁇ Bu refers to a tertiary butyl group
  • novel hafnium-containing and zirconium-containing precursors Disclosed are novel hafnium-containing and zirconium-containing precursors, methods of synthesizing the same, and methods of using the same.
  • the disclosed heteroleptic hafnium-containing and zirconium- containing precursors are derived from different classes of !igand systems, such as amidinate, formamidinate, guanidinate, amide, and/or chelating amide ligands, plus aikoxide ligands.
  • Precursor design may help improve volatility, reduce the melting point (liquids or very low melting " solids), increase reactivity with water, and increase thermal stability for wider process window applications.
  • hafnium-containing and zirconium-containing precursors have the following formulae:
  • ⁇ Hf or Zr
  • ⁇ Ri , R 2 , R5, R6, and R 7 are independently selected from the group consisting of H and C1 -C6 alkyl group;
  • R 4 is a C1 -C6 alkyl group
  • the C1 -C6 alkyl group includes any linear, branched, or cyclic alkyl groups having from 1 to 6 carbon atoms, including but not limited to Me, tBu, or cyciohexyi groups.
  • RrNC(R 3 )N-R 2 ligand has the following chemical structure:
  • R 1 -N-(C(R 3 )2) m -N-R2 ligand has the following chemical structure:
  • the ligand itself has gone from a -1 ligand having one delocaiized negative charge between the -N-C-N- backbone to a -2 ligand having a negative charge localized at each nitrogen atom.
  • the Formula I ligand has a more rigid structure than the Formula !S ligand.
  • Ri and R 3 are C1 -C6 linear or branched alkyl groups in Formula I, Ri and R 3 may be independent substituents or they may be linked together to form a monocyclic structure extending from R-i to R3, as demonstrated below.
  • R-i , R 3 and f3 ⁇ 4 are C1-C6 linear or branched alkyl groups in Formula I
  • R-i , R3 and R2 may be independent substituents or they may be linked together to form a bicyc!ic structure, as demonstrated below.
  • the configuration of the disclosed precursors was selected in order to optimize the reactivity (especially with H 2 0) and, at the same time, the stability.
  • the M-N bond is weak and will react rapidly on the surface.
  • the M-0 bond is much stronger and will help stabilize the molecule to avoid fast decomposition.
  • R-i and R 2 are preferably Et or iPr, R 3 is preferably H, Me, or NMe 2l and R 4 is preferably a C1 -C4 linear or branched alkyl chain.
  • Exemplary precursors include M(iPr-N-C(H)-N- iPr)i(OiPr) 3 , M(iPr-N-C(H)-N-iPr)i(OMe) 3 , M(iPr-N-C(H)-N-iPr)i(OEt) 3 , M(iPr- N-CiHJ-N-iPrMOnPrk, M(iPr-N-C(H)-N-iPr ⁇ 1 (OsBu) 3!
  • the exemplary precursors include Hf(iPr-N-C(H)-N- iPr) 1 ⁇ OiPr> 3l Hf Pr-N-CCHJ-N-iPrMOMek, Hf(iPr-N-C(H)-N-iPr) 1 (OEt) 3 , Hf(iPr- N-C ⁇ -N-iPrMOnPr HfiiPr-N-CiHJ-N-iPrJ ⁇ OsBu ⁇ , Hf(iPr-N-C(H)-N- iP ⁇ OiBuJa, HfiiPr-N-CiHJ-N-iPrJ ⁇ OtBuJa, Hf(iPr-N-C(Me)-N-iPr) 1 ⁇ OiPr) 3 , Hf(iPr-N-C(Me)-N-iPr)i(OMe) 3 , Hf(iPr-
  • the exemplary precursors include Zr(iPr-N-C ⁇ H)-N- iPr)-,(OiPr)3, Zr(iPr-N-C(H)-N-iPr)i(OMe) 3 , Zr(iPr-N-C(H)-N-iPr) 1 (OEt) 3 , Zr(iPr- N-C(H)-N-iPr)i(OnPr) 3 , Zr(iPr-N-C(H)-N-iPr)i(OsBu) 3 , Zr(iPr-N-C(H)-N- iP ⁇ OiBuJa, ZrOPr-N-C(H)-N-iPr)-i(OtBu) 3 , ZriiPr- -CiMeJ-N-iPrJ ⁇ OiP s, Zr(iPr-N-C(Me)-N-iPrJ ⁇ O
  • the preferred exemplary precursors are Hf ⁇ iPr-N- CtMeJ-N-iPrMOiPr ⁇ or Zr Pr-N-CtMeJ-N-iPrMOiPrJs.
  • Exemplary precursors include M(iPr-N-(CH 2 ) 2 -N-iPr) (OiPr) 2 , M(iPr-N-(CH 2 ) 2 - N-iPr)i(OMe)2, M(iPr-N- ⁇ CH 2 )2-N-iPr) (OEt)2, M(iPr-N-(CH 2 )2-N-iPr) 1 (OnPr) 2 l M(iPr-N-(CH 2 ) 2 -N-iPr)i(OsBu) 2 , M(iPr-N- ⁇ CH 2 ) 2 -N-iPr) 1 (OiBu) 2 , M(iPr-N- (CH 2 ) 2 -N-iPr)i(OtBu) 2 l M(Et-N-(CH 2 ) 2 -N-Et)i(OiPr) 2 , M(Et-N-(CH 2 ) 2
  • the exemplary precursors include Hf(iPr-N-(CH 2 ) 2 -N- iPr)i(OiPr) 2 , Hf(iPr-N-(CH 2 ) 2 -N-iPr)i(OMe) 2 , Hf(iPr-N-(CH 2 ) 2 -N-iPr).,(OEt) 2 , Hf(iPr-N-(CH 2 ) 2 -N-iPr)i(OnPr) 2 , Hf(iPr-N-(CH 2 ) 2 -N-iPr)i(OsBu) 2l Hf(iPr-N- (CH 2 ) 2 -N-iPr)i(OiBu) 2 , Hf(iPr-N-(CH 2 ) 2 -N-iPr) (OtBu) 2 , Hf(Et-N-(CH 2 ) 2 -N- Et)i
  • the exemplary precursors include Zr(iPr-N-(CH 2 ) 2 -N- iPr)i(OiPr) 2 , Zr(iPr-N-(CH 2 ) 2 -N-iPr)i(OMe) 2 , Zr(iPr-N-(CH 2 ) 2 -N-iPr)i ⁇ OEt) 2 l Zr(iPr-N-(CH 2 ) z -N-iPr) 1 (OnPr) 2 , Zr(iPr-N-(CH 2 ) 2 -N-iPr)i(OsBu) 2 , Zr(iPr-N- (CH 2 ) 2 -N-iPr)i(OiBu) 2l Zr(iPr-N-(CH 2 ) 2 -N-iPr)i(OtBu) 2 , Zr(Et-N-(CH 2 ) 2 -N- Et
  • the preferred exemplary precursors are Hf(iPr-N- (CHa ⁇ -N-iP ⁇ OiP s, Hf(Et-N-(CH 2 ) 3 -N-Et)i(OiPr) 2 , Hf(Et-N-(CH 2 ) 2 -N- Et)i(OiPr) 2l Zr(iPr-N-(CH 2 )2-N-iPr)i(OrPr) 2l Zr(Et-N-(CH 2 ) 3 -N-Et) 1 (OiPr) 2 , or Zr(Et-N-(CH 2 ) 2 -N-Et) 1 (OiPr ⁇ 2 .
  • the precursor has the following chemical structure:
  • Ri and R 2 are preferably Et or iPr
  • R 3 is preferably H or Me
  • R 4 is preferably a C1 -C4 linear or branched alkyi chain. More preferably, R3 is not NMe 2 .
  • Exemplary precursors include M(iPr-N-C(H)-N- iPr) 2 (OiPr) 2!
  • the exemplary precursors include Hf(iPr-N-C(H)-N- iPr) 2 (OiPr) 2 , Hf(iPr-N-C(H)-N-iPr) 2 (OMe) 2 , Hf(iPr-N-C(H)-N-iPr) 2 (OEt) 2l Hf(iPr- N-C(H)-N-iPr) 2 (OnPr) 2 , Hf(iPr-N-C(H)-N-iPr) 2 (OsBu) 2 , Hf(iPr-N-C ⁇ H)-N- iPr) 2 (OiBu) 2 , Hf(iPr-N-C(H)-N-iPr) 2 (OtBu) 2 , Hf ⁇ Et-N-C(H)-N-Et) 2 (OiPr) 2!
  • the exemplary precursors include Zr ⁇ iPr-N-C(H)-N- iPr) 2 (OiPr) 2 , Zr(iPr-N-C(H)-N-iPr) 2 (OMe) 2 , Zr(iPr-N-C(H)-N-iPr) 2 (OEt) 2 , Zr(IPr- N-C(H)-N-iPr) 2 (OnPr) 2 , Zr(iPr-N-C(H)-N-iPr) 2 (OsBu) 2 , Zr(iPr-N-C(H)-N- iPr) 2 (OiBu) 2 , Zr(iPr-N-C(H)-N-iPr) 2 (OtBu) 2) Zr(Et-N-C(H)-N-Et) 2 (OiPr) 2 , Zr(Et- N-C(H)-N-N-N-
  • Zr(iPr-N-C(Me)-N-iPr) 2 (OMe) 2 , Zr(iPr-N ⁇ C(Me)-N-iPr) 2 (OEt) 2 , Zr(iPr-N-C(Me)-N-iPr) 2 (OnPr) 2 , Zr(iPr-N-C(Me)- N-iPr) 2 (OsBu) 2 , Zr(iPr-N-C(Me)-N-iPr) 2 (OiBu) 2; Zr(iPr-N-C(Me)-N-iPr) 2 (OtBu) 2 , Zr(Et-N-C(Me)-N-Et) 2 (OiPr) 2 , Zr(Et-N-C(Me)-N-Et) 2 (OMe) 2 , Z ' r(Et-N-C(Me)-N- Et)
  • the preferred exemplary precursor is Hf ⁇ iPr-N- C ⁇ H)-N-iPr) 2 (OiPr) 2 , Hf(iPr-N-C(Me)-N-iPr) 2 (OiPr) 2 , Zr(iPr-N-C(H)-N- iPr) 2 (OiPr) 2 , or Zr(iPr-N-C(Me)-N-iPr) 2 (OiPr) 2 .
  • Ri and R 2 are preferably Et or iPr; R 3 is preferabiy H, Me, or NMe 2 ; R 4 is preferabiy iPr; and R 5 and R 6 preferably are independently Me or Et.
  • Exemplary precursors include M(iPr-N-C(Me)-N-iPr)(OiPr) 2 (NMe 2 ), M(iPr-N-C(Me)-N-iPr)(OiPr) 2 ⁇ NEt 2 ), M(iPr-N-C(Me)-N-iPr)(OiPr) 2 (NEtMe), M(Et-N-C(Me)-N-Et)(OiPr)2(NMe 2 ), M(Et-N-C(Me)-N-Et)(OiPr) 2 (NEt 2 ), M(Et-N- C(Me)-N-Et)(OiPr) 2 (NEt 2
  • the exemplary precursors include Hf(iPr-N-C(Me)-N- iPr)(OiPr) 2 (NMe 2 ) ( Hf(iPr-N-C(Me)-N-iPr) ⁇ OiPr) 2 (NEt 2 ), Hf(iPr-N-C(Me)-N- iPr)(OiPr) 2 (NEt e), Hf(Et-N-C(Me)-N-Et)(OiPr) 2 ⁇ NMe 2 ), Hf(Et-N-C(Me)-N- Et) ⁇ OiPr) 2 (NEt 2 ), Hf(Et-N-C(Me)-N-Et) ⁇ OiPr) 2 (NEtMe), Hf(iPr-N-C(NMe 2 )-N- iPr)(OiPr) 2 (NMe 2 ), Hf(iPr-N-C
  • the exemplary precursors include Zr(iPr-N-C(Me)-N- iPr)(OiPr) 2 (NMe 2 ), Zr(iPr-N-C(Me)-N-iPr)(OiPr) 2 (NEt 2 ), Zr(iPr-N-C(Me)-N- iPr)(OiPr) 2 (NEtMe), Zr ⁇ Et-N-C(Me)-N-Et)(OiPr) 2 (NMe 2 ) !
  • the preferred exemplary precursor is Hf(iPr-N- C(Me)-N-iPr)(OiPr) 2 (NMe 2 ) or Zr(iPr-N-C( e)-N-iPr)(OiPr) 2 (NMe 2 ).
  • the precursor has the following chemical structure:
  • Ri and R 2 are preferably Et or iPr; R 3 is preferably H or Me; R 4 is preferably iPr; and R 7 is preferably Me.
  • Exemplary precursors include M(iPr-N-C(Me)-N-iPr)(OiPr) 2 (0 2 CMe) and M(Et-N-C(Me)-N- Et)(OiPr) 2 (0 2 CMe).
  • the exemplary precursors include Hf ⁇ iPr-N- C(Me)-N-iPr)(OiPr) 2 (0 2 CMe) and Hf(Et-N-C(Me)-N-Et)(OiPr) 2 (0 2 CMe).
  • M Hf
  • the exemplary precursors include Zr(iPr-N-C(Me)-N- iPr)(OiPr) 2 ⁇ 0 2 CMe) and Zr(Et-N-C(Me)-N-Et)(OiPr) 2 (0 2 CMe).
  • the precursor has the following chemical structure:
  • the precursor has the following chemical structure:
  • the precursor has the following chemical structure:
  • m is preferabiy 2 or 3
  • Ri and R 2 are preferably Et or iPr
  • R 3 is preferabiy H
  • R 4 is preferably a C1 -C4 linear or branched alkyl chain
  • R 7 is preferably Me.
  • Exemplary precursors include M(iPr-N-(CH 2 ) 2 -N- iPr)(OiPr)(0 2 CMe), M ⁇ !Pr-N-(CH 2 )2-N-iPr ⁇ (OMe)(0 2 CMe), M(iPr-N-(CH 2 ) 2 -N- iPr)(OEt)(0 2 CMe) !
  • the exemplary precursors include Hf(iPr-N-(CH 2 )2-N- iPr) ⁇ OiPr)(0 2 CMe), Hf(iPr-N-(CH 2 ) 2 -N-iPr)(OMe)(0 2 CMe), Hf(iPr-N-(CH 2 ) 2 -N- iPr)(OEt)(0 2 CMe), Hf(iPr-N-(CH 2 ) 2 -N-iPr)(OnPr)(0 2 CMe), Hf(iPr-N-(CH 2 ) 2 -N- iPr)(OsBu)(0 2 CMe), Hf(iPr-N-(CH 2 )2-N-iPr)(OiBu)(0 2 CMe), Hf(iPr-N-(CH 2 )2-N-iPr)(OiBu)(0 2 CMe), Hf(iPr-
  • the exemplary precursors include Zr(iPr-N-(CH 2 ) 2 -N- iPr)(OiPr)(0 2 CMe), Zr(iPr-N-(CH 2 ) 2 -N-iPr)(OMe)(0 2 CMe), Zr ⁇ iPr-N-(CH 2 ) 2 -N- iPr)(OEt)(0 2 CMe), Zr(iPr-N-(CH 2 ) 2 -N-iPr) ⁇ OnPr)(0 2 CMe) I Zr(iPr-N-(CH 2 ) 2 -N- iPr)(OsBu) ⁇ 0 2 CMe), Zr ⁇ iPr-N- ⁇ CH 2 ) 2 -N-iPr)(OiBu) ⁇ 0 2 CMe) !
  • exemplary precursors include M(iPr-N-C(Me)-N-iPr)(OiPr) (NMe 2 ) 2 , M(iPr-N-C(Me)-N- !Pr)(OiPr)(NEt 2 ) 2 , M(iPr-N-C(Me)-N-iPr)(OiPr)(NEtMe) 2!
  • the exemplary precursors include Hf(iPr-N-C( e)-N- iPr)(OiPr) (NMe 2 ) 2 , Hf(iPr-N-C(Me)-N-iPr)(OiPr)(NEt 2 ) 2[ Hf(iPr-N-C(Me)-N- iPr)(OiPr)(NEtMe) 2l Hf(t ⁇ t-N-C(Me)-N-Et)(OiPr)(NMe 2 )2, Hf(Et-N-C(Me)-N- Et)(OiPr)(NEt 2 ) 2l Hf(Et-N-C(Me)-N-Et)(OiPr)(NEtMe) 2 , Hf(iPr-N-C(NMe 2 )-N- iPr)(OiPr)(NMe 2 )
  • the exemplary precursors include Zr(iPr-N-C(Me)-N- iPr)(OiPr) (NMe 2 ) 2 , Zr(iPr-N-C(Me)-N-iPr)(OiPr)(NEt 2 ) 2 , Zr(iPr-N-C(Me)-N- iPr)(OiPr)(NEtMe) 2 , Zr(Et-N-C(Me)-N-Et)(OiPr)(NMe 2 ) 2 , Zr ⁇ Et-N-C(Me)-N- Et)(OiPr)(NEt 2 ) 2 , Zr(Et-N-C(Me)-N-Et)(OiPr)(NEtMe) 2 , Zr(iPr-N-C(NMe 2 )-N- iPr)(OiPr)(NMe 2 ) 2
  • exemplary precursors inciude M(iPr-N-(CH 2 ) 2 -N-iPr) ⁇ OiPr)(NMe 2 ), M(iPr-N-(CH 2 )2-N-iPr)(OiPr)(NEt2), M(iPr-N-(CH 2 ) 2 -N-iPr)(OiPr)(NEtMe), (Et-N-(CH 2 ) 2 -N-Et)(OiPr)(NMe 2 ), M(Et-N-(CH 2 ) 2 -N-Et)(OiPr)(NEt 2 ), and M(Et-N-(CH 2 ) 2 -N-Et)(OiPr)(NEtMe).
  • the exemplary precursors include Hf(iPr-N-(CH 2 ) 2 -N- iPr)(OiPr)(NMe 2 ), Hf(iPr-N-(CH 2 ) 2 -N-iPr) ⁇ OiPr)(NEt 2 ), Hf(iPr-N-(CH 2 ) 2 -N- iPr)(OiPr)(NEtMe), Hf(Et-N-(CH 2 ) 2 -N-Et) ⁇ OiPr)(NMe 2 ), Hf(Et-N-(CH 2 ) 2 -N- Et)(OiPr) ⁇ NEt 2 ) !
  • exemplary precursors include M(iPr-N-C(Me)-N-iPr)(OiPr) (0 2 CMe) 2 and ⁇ Et-N-C(Me)-N- Et)(OiPr) ⁇ 0 2 CMe) 2 .
  • M is Hf
  • the exemplary precursors include Hf(iPr-N- C(Me)-N-iPr)(OiPr) (0 2 CMe) 2 and Hf(Et-N-C(Me)-N-Et)(OiPr)(0 2 CMe) 2 .
  • the exemplary precursors include Zr(iPr-N-C(Me)-N-iPr) ⁇ OiPr) (0 2 CMe) 2 and Zr(Et-N-C(Me)-N-Et)(OiPr)(0 2 CMe) 2 .
  • exemplary precursors include M(OiPr)2 ⁇ 0 2 CMe) 2 , or Hf(OiPr) 2 ⁇ 0 2 CMe)2 when M is Hf and Zr(OiPr) 2 (0 2 CMe) 2 when M is Zr.
  • exemplary precursors include M(OiPr) 3 (0 2 CMe), or Hf(OiPr) 3 (0 2 CMe) when M is Hf and Zr(OiPr) 3 (0 2 C e) when M is Zr.
  • the disclosed precursors may be synthesized by combining a hydrocarbon solution of H(R r N-C(R 3 )-N-R 2 ) with a neat or hydrocarbon solution of a hafnium or zirconium compound, such as Hf(OR 4 ) 3 (NR 5 R 6 ), Hf(OR ) 2 (NR 5 R 6 )2, Zr(OR 4 )3( R 5 R6) I or Zr(OR4)2(NR 5 R 6 )2, under atmosphere of nitrogen, the outlet of the mixing flask being connected to an oil bubbler.
  • Exemplary hydrocarbon solutions include pentane.
  • the resulting solution is stirred at room temperature overnight. Where applicable, H0 2 CR 7 may be added and further stirred for 6-12 hours.
  • Solvent and vo!atiies are removed from the reaction mixture under vacuum. Purification of the resulting liquid or solid is carried out by distillation or sublimation, respectively. Additional synthesis details are provided in the Examples.
  • the disclosed methods provide for the use of the hafnium-containing and zirconium-containing precursors for deposition of hafnium-containing and zirconium-containing films, respectively.
  • the disclosed methods may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, or flat panel type devices.
  • the method includes: providing a substrate; providing a vapor including at least one of the disclosed hafnium-containing or zirconium- containing precursors: and contacting the vapor with the substrate (and typically directing the vapor to the substrate) to form a hafnium-containing or zirconium-containing layer on at least one surface of the substrate.
  • the disclosed methods also provide for forming a bimetal-containing layer on a substrate using a vapor deposition process.
  • the disclosed methods may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, or flat panel type devices.
  • the method includes: providing a substrate; providing a vapor including at least one of the disclosed hafnium- containing or zirconium-containing precursors and contacting the vapor with the substrate (and typicaily directing the vapor to the substrate) to form a bi meta!-containing layer on at least one surface of the substrate.
  • An oxygen source such as 0 3 , O 2 , H 2 O, and NO, preferably H 2 O, may also be provided.
  • hafnium-containing and zirconium-containing precursors may be used to deposit hafnium-containing and zirconium-contianing films using any deposition methods known to those of skill in the art.
  • 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), p!asma enhanced atomic layer deposition (PE-ALD), or combinations thereof.
  • the deposition method is ALD or PE-ALD.
  • the vapor of the hafnium-containing or zirconium-containing precursor is introduced into a reaction chamber containing at least one substrate.
  • a Hf-containing or Zr-containing layer on at least one surface of the substrate are held at suitable conditions so that contact between the hafnium-containing or zirconium-containnig precursor and substrate results in formation of a Hf-containing or Zr-containing layer on at least one surface of the substrate.
  • a reactant may also be used to help in formation of the Hf-containing or Zr-containing layer.
  • the reaction chamber may be any enclosure or chamber of a device in which deposition methods take place, such as, without limitation, a parailel- plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a sing!e- wafer reactor, a multi-wafer reactor, or other such types of deposition systems.
  • Ail of these exemplary reaction chambers are capable of serving as an ALD reaction chamber.
  • the reaction chamber may be maintained at a pressure ranging from about 0.5 mTorr (0.07 Pa) to about 20 Torr (2700 Pa).
  • the temperature within the reaction chamber may range from about 200°C to about 600°C.
  • the temperature may be optimized through mere experimentation to achieve the desired result.
  • the temperature of the reaction chamber may be controlled by either controlling the temperature of the substrate holder or controlling the temperature of the reactor wall. Devices used to heat the substrate are known in the art.
  • the reactor wall is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with desired physical state and composition.
  • a non-limiting exemplary temperature range to which the reactor wall may be heated includes from approximately 200°C to approximately 600°C, When a plasma deposition process is utilized, the deposition temperature may range from approximately 200°C to approximately 550°C. Alternatively, when a thermal process is performed, the deposition temperature may range from approximately 400°C to approximately 600°C.
  • the substrate may be heated to a sufficient temperature to obtain the desired hafnium-containing or zirconium-containing film at a sufficient growth rate and with desired physical state and composition.
  • a non- limiting exemplary temperature range to which the substrate may be heated includes from 150°C to 600°C.
  • the temperature of the substrate remains less than or equal to 450°C.
  • the substrate upon which the hafnium-containing or zirconium- containing film will be deposited will vary depending on the final use intended.
  • the substrate may be chosen from oxides which are used as dielectric materials in iM, DRAM, or FeRam technologies (for example, HfO 2 based materials, TiO 2 based materials, ZrO 2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or from nitride-based films (for example, TaN) that are used as an oxygen barrier between copper and the low-k layer.
  • Other substrates may be used in the manufacture of semiconductors, photovoitaics, LCD-TFT, or flat panel devices. Examples of such substrates include, but are not limited to, solid substrates such as metal nitride containing substrates (for example, TaN, TiN, WN,
  • insulators for example, SiO 2l Si 3 N 4 , SiON, HfO 2 , Ta 2 0 5 , ZrO 2 , TiO 2 , AI 2 O 3 , and barium strontium titanate; or other substrates that include any number of combinations of these materials.
  • the actual substrate utilized may also depend upon the specific precursor embodiment utilized. In many instances though, the preferred substrate utilized will be selected from TiN, SRO, Ru, and Si type substrates.
  • the hafnium-containing or zirconium-containing prec rsor may be fed in liquid state to a vaporizer where it is vaporized before it is introduced into the reaction chamber.
  • the hafnium-containing or zirconium-containing precursor Prior to its vaporization, the hafnium-containing or zirconium-containing precursor may optionally be mixed with one or more solvents, one or more metal sources, and a mixture of one or more solvents and one or more metal sources.
  • the solvents may be selected from the group consisting of toluene, ethyl benzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane, or others.
  • the resulting concentration may range from approximately 0.05 M to approximately 2 M.
  • the metal source may include any metal-containing precursors now known or later developed.
  • the hafnium-containing or zirconium-containing precursor may be vaporized by passing a carrier gas into a container containing the hafnium-containing or zirconium-containing precursor or by bubbling the carrier gas into the hafnium-containing or zirconium-containing precursor.
  • the carrier gas and hafnium-containing or zirconium-containing precursor are then introduced into the reaction chamber as a vapor.
  • the carrier gas may include, but is not limited to, Ar, He, N 2 ,and mixtures thereof.
  • the hafnium- containing or zirconium-containing precursor may optionally be mixed in the container with one or more solvents, metal-containing precursors, or mixtures thereof.
  • the container may be heated to a temperature that permits the hafnium-containing or zirconium-containing precursor to be in its liquid phase and to have a sufficient vapor pressure.
  • the container may be maintained at temperatures in the range of, for examp!e, approximately 0°C to approximately 150°C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of hafnium-containing or zirconium-containing precursor vaporized.
  • the hafnium-containing or zirconium-containing precursor may be mixed with reactants inside the reaction chamber.
  • exemplary reactants include, without limitation, metal-containing precursors such as aiuminum-containing precursors such as TMA or silicon-containing precursors such as bis(diethylamino)silane.
  • metal-containing precursors such as aiuminum-containing precursors such as TMA or silicon-containing precursors such as bis(diethylamino)silane.
  • aiuminum-containing precursors such as TMA
  • silicon-containing precursors such as bis(diethylamino)silane.
  • the reactants may include an oxygen source which is selected from, but not limited to, O2, O3, H 2 O, H 2 O 2l acetic acid, formalin, para-formaldehyde, and combinations thereof.
  • the reactant is H 2 O.
  • the reactant may be treated by plasma in order to decompose the reactant into its radical form.
  • the p!asma may be generated or present within the reaction chamber itself. Alternatively, the p!asma may generally be at a location removed from the reaction chamber, for instance, in a remotely located plasma system.
  • One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
  • the reactant may be introduced into a direct plasma reactor, which generates a plasma in the reaction chamber, to produce the plasma-treated reactant in the reaction chamber.
  • direct plasma reactors include the TitanTM PECVD System produced by Trion Technologies.
  • the reactant may be introduced and he!d in the reaction chamber prior to plasma processing.
  • the plasma processing may occur simultaneously with the introduction of reactant.
  • In-situ plasma is typically a 13.56 MHz RF capacitively coupled plasma that is generated between the showerhead and the substrate holder.
  • the substrate or the showerhead may be the powered electrode depending on whether positive ion impact occurs.
  • Typical applied powers in in-situ plasma generators are from approximately 100 W to approximately 1000 W.
  • the disassociation of the reactant using in-situ plasma is typically less than achieved using a remote plasma source for the same power input and is therefore not as efficient in reactant disassociation as a remote plasma system, which may be beneficial for the deposition of metal-nitride-containing films on substrates easily damaged by plasma.
  • the plasma-treated reactant may be produced outside of the reaction chamber.
  • the MKS Instruments' ASTRON ® i reactive gas generator may be used to treat the reactant prior to passage into the reaction chamber.
  • the reactant 0 3 Operated at 2.45 GHz, 7kW plasma power, and a pressure ranging from approximately 3 Torr to approximately 10 Torr, the reactant 0 3 may be decomposed into three O " radicals.
  • the remote plasma may be generated with a power ranging from about 1 kW to about 10 kW, more preferably from about 2.5 kW to about 7.5 kW.
  • the reactants may include a metal-containing precursor which is selected from, but not limited to, metal alkyls, such as Ln(RCp) 3 or Co(RCp) 2 , metal alkoxies, such as Ti(Cp)(OMe) 3 , and any combination thereof.
  • the vapor of the metai-containing precursor is introduced into a reaction chamber.
  • the temperature and the pressure within the reaction chamber and the temperature of the substrate are held at suitable conditions so that contact between the metal-containing precursor and substrate results in formation of a metal-containing layer on at least one surface of the substrate.
  • a reactant may also be used to help in formation of the metal- containing layer.
  • the hafnium-containing or zirconium-containing precursor and one or more reactants may be introduced into the reaction chamber simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in other combinations.
  • the hafnium-containing or zirconium-containing precursor may be introduced in one pulse and two additional metal sources may be introduced together in a separate pulse [modified atomic layer deposition].
  • the reaction chamber may already contain the reactant prior to introduction of the hafnium-containing or zirconium-containing precursor.
  • the reactant may be passed through a plasma system localized remotely from the reaction chamber, and decomposed to radicals.
  • the hafnium-containing or zirconium-containing precursor may be introduced to the reaction chamber continuously while other metal sources are introduced by pulse (pulsed-chemica! vapor deposition).
  • a pulse may be followed by a purge or evacuation step to remove excess amounts of the component introduced.
  • the pulse may last for a time period ranging from about 0.01 s to about 10 s, alternatively from about 0.3 s to about 3 s, alternatively from about 0.5 s to about 2 s.
  • the vapor phase of a hafnium-containing or zirconium-containing precursor is introduced into the reaction chamber, where it is contacted with a suitable substrate. Excess hafnium-containing or zirconium-containing precursor may then be removed from the reaction chamber by purging and/or evacuating the reaction chamber.
  • An oxygen source is introduced into the reaction chamber where it reacts with the absorbed hafnium-containing or zirconium-containing precursor in a self-limiting manner. Any excess oxygen source is removed from the reaction chamber by purging and/or evacuating the reaction chamber. If the desired film is a hafnium oxide or zirconium oxide film, this two-step process may provide the desired fiim thickness or may be repeated until a fi!m having the necessary thickness has been obtained.
  • the two-step process above may be followed by introduction of a second vapor of a metal-containing precursor into the reaction chamber.
  • the metal- containing precursor will be selected based on the nature of the hafnium metal oxide or zirconium metal oxide film being deposited.
  • the metal-containing precursor is contacted with the substrate. Any excess metal-containing precursor is removed from the reaction chamber by purging and/or evacuating the reaction chamber.
  • an oxygen source may be introduced into the reaction chamber to react with the metal-containing precursor. Excess oxygen source is removed from the reaction chamber by purging and/or evacuating the reaction chamber.
  • the process may be terminated. However, if a thicker film is desired, the entire four-step process may be repeated. By alternating the provision of the hafnium-containing or zirconium- containing precursor, metal-containing precursor, and oxygen source, a fi!m of desired composition and thickness can be deposited.
  • films having a desired stoichiometric Hf: metal or Zrmetal ratio may be obtained.
  • a PZT film (Pb[Zr x T!i -x ]O3 with 0 ⁇ x ⁇ 1 ) may be obtained by having oneactue of the zirconium-containing precursor, one pulse of a titanium-containing precursor, and two pulses of the lead-containing precursor, with each pulse being followed by pulses of the oxygen source.
  • the number of pulses required to obtain the desired film may not be identical to the stoichiometric ratio of the resulting film.
  • hafnium-containing or zirconium-containing films resulting from the processes discussed above may include PZT.
  • PZT zirconium-containing precursor and reactants
  • Hf(N iPr -amd)(OiPr) 3 or Zr(N iPr -amd)(OiPr) 3 A pentane solution will be chilled to -30°C for 1 hour. Hf(OiPr) 3 (NMe 2 ) or Zr(OiPr) 3 (NMe 2 ) will be added to the chilled pentane solution. The mixture will be stirred at room temperature under atmosphere of nitrogen. A solution of N lPr -amd-H in pentane will slowly be added to the above mixture. The outlet of the flask will be ' connected to an oil bubbler, which in turn will be connected to an acid scrubber. The resulting solution will be stirred at room temperature overnight.
  • Solvent and volatiles will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(N iPr -amd)(OiPr) 3 or Zr(N iPr -amd)(OiPr) 3 ).
  • Hf(N ipr -amd) 2 (OiPr) 2 or Zr(N ipr -amd) 2 (OiPr) 2 Neat Hf(OiPr) 2 (NMe 2 ) 2 or neat Zr(OiPr)2(NMe 2 ) 2 will be added to a pentane solution containing N lPr -amd-H stirring at room temperature under atmosphere of nitrogen, the outlet of the flask will be connected to an oil bubbler.
  • Hf ⁇ N iPr -fmd) 2 (OiPr) 2 or Zr(N iPr -fmd) 2 (OiPr) 2 Neat Hf(OiPr) 2 (NMe 2 ) 2 or neat Zr(OiPr) 2 (NMe 2 ) 2 will be added to a pentane solution containing N iPr -fmd-H stirring at room temperature under atmosphere of nitrogen, the outlet of the flask will be connected to an oil bubbler. The resulting solution will be stirred at room temperature overnight.
  • Solvent and volatiles will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(N lPr - fmd) 2 (OiPr) 2 or Zr(N iPr -fmd) 2 (OiPr) 2 ).
  • Solvent and volatiies will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(N iPr -gmd) 2 (OiPr) 2 or Zr(N iPr -gmd) 2 (OiPr) 2 ).
  • a solution of N iPr - amd-H in pentane will be added slowly dropwise to a pentane solution containing Hf(OiPr) 2 (NMe 2 ) 2 or Zr(OiPr) 2 (NMe 2 ) 2 stirring at room temperature under atmosphere of nitrogen.
  • the outlet of the flask will be connected to an oil bubbler, which in turn will be connected to an acid scrubber.
  • the resulting solution will be stirred at room temperature overnight.
  • Solvent and volatiies will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(N iPr -amd)(OiPr) 2 (NMe 2 ) or Zr(N iPr -amd)(OiPr) 2 (NMe 2 )).
  • Hf(Et-N-(CH 2 ) 2 -N-Et) ⁇ OiPr) 2 or Zr(Et-N- ⁇ CH 2 ) 2 -N-Et)(OiPr) 2 To a pentane solution containing Hf(OiPr) 2 (NMe 2 ) 2 or Zr(0!Pr) 2 (N e 2 ) 2 stirring at room temperature under atmosphere of nitrogen will be added slowly drop wise neat liquid of Et-NH-(CH 2 ) 2 -NH-Et. The outlet of the flask will be connected to an oil bubbler, which in turn will be connected to an acid scrubber. The resulting solution will be stirred at room temperature overnight.
  • Examples 1 to 8 and the reactant 0 3 will be used to deposit a film of Hf0 2 or Zr0 2 on a Si0 2 /Si substrate.
  • the Si0 2 /Si substrate will be maintained at a temperature of 250 ° C.
  • the precursor will be vaporized in a bubbler maintained at 50°C.
  • the ALD cycle will include a precursor pulse of 5 seconds, followed by a 5 second purge, followed by a reactant pulse of 2 seconds, followed by a 5 second purge.
  • the Hf02 or Zr02 growth rate is expected to be 0.5 A/cycle or greater.
  • the ALD regime will be assessed up to 350°C with a deposition rate.
  • the hafnium-containing or zirconium-containing precursor of any one of Examples 1 to 8 and the reactant H 2 0 will be used to deposit a film of Hf0 2 or Zr0 2 on a Si0 2 /Si substrate.
  • the Si0 2 /Si substrate will be maintained at a temperature of 250 ° C.
  • the precursor will be vaporized in a bubbler maintained at 50°C.
  • the ALD cycle will include a precursor pulse of 20 seconds, followed by a 5 second purge, followed by a reactant pulse of 2 seconds, followed by a 10 second purge.
  • the Hf0 2 or Zr0 2 growth rate is expected to be 0.5 A/cycle or greater.
  • the ALD regime will be assessed up to 350°C.

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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

HAFNIUM-CONTAINING OR ZIRCONIUM-CONTAINING PRECURSORS
FOR VAPOR DEPOSITION
Technical Field
Disclosed are hafnium-containing and zirconium-containing
precursors, methods of synthesizing the same, and methods of using the same to deposit hafnium-containing and zirconium-containing layers using vapor deposition processes.
Background
One of the serious challenges the semiconductor industry faces is developing new gate dielectric materials for DRAM and capacitors. For decades, silicon dioxide (SiO2) was a reliable dielectric, but as transistors have continued to shrink and the technology has moved from "Full Si" transistors to "Metal Gate/High-k" transistors, the reliability of the Si02-based gate dielectric is reaching its physical !imits. The need for new high dielectric constant materials and processes is increasing and becoming more and more critical as the size for current technology shrinks.
US Pat App Pub No 2005/277223 discloses ALD methods of forming metal oxides using metal-containing precursors having the formula
M(L1 )x(L2)y, wherein M is a metal, L1 and L2 may be halide, diketonate, alkoxide, amino, a!koxyamine, amidinate, or multidentate ligands. The exemplary precursors however are only Hf{OtBu)2(NEtMe)2, Hf(OtBu)2{NEt2)2, Hf(NEt2)2(DMAMP)2, Hf(NEtMe)2(DMAMP)2, Ti(OtBu)3CI, Ti(OtBu)3Me, Ti(OtBu)2(NEt2)2, Ti(NEt2)2(DMAMP)2! Ti(OtBu)2(DMAMP)2, and
TiCI2(DMAMP)2.
US Pat. No. 7,491 ,654 discloses ALD methods of forming ZrO2 thin films using a tris(N-ethyl-N-methylamino)(tertbutoxy)zirconium precursor.
Other sources and methods of incorporating Hf-containing and Zr- containing materials are being sought for new generations of integrated circuit devices. Novel precursors are needed. Summary
Disclosed are molecules having the following formula:
{R N-C(R3)- -R2)u(OR4)xi R5 e)y(02CR7)z Formula I
or
{Ri-N-(C(R3)2)m-N-R2)v(OR4)x(NRsR6)y(02CR7)z Formula II wherein:
M is Hf or Zr;
Ri , R2l
Figure imgf000003_0001
e, and R7 are independently selected from the group consisting of H and C1-C6 alkyl group;
R3 = H, C1 -C6 alkyl group, or NMe2;
R is a C1 -C6 alkyl group;
m = 2-4;
u = 0-2;
v = 0-1 ;
x = 1 -3;
y = 0-2;
z = 0-1 ;
in Formula I, u+x+y+z = 4;
in Formula II, 2v+x+y+z = 4; and
u, v, or z >1 .
The disclosed molecules may further include one or more of the following aspects:
• the molecule having Formula I, wherein u=1 , x=3, y=0, and z=0;
• the molecule being selected from the group consisting of M(iPr-N- C(Me)-N-iPr)i(OiPr)3, M(iPr-N-C(Me)-N-iPr)i(OMe)3l (iPr-N-C(Me)-N- IPr)i(OEt)3, MflPr-N-C-iMeJ-N-iPrMOnPrk, M(iPr-N-C(Me)-N- iPrJ^OsBuJa, M(iPr-N-C(Me)-N-iPr)i(OiBu)3, M(iPr-N-C(Me)-N- iPr)1(OtBu}3, M(Et-N-C(Me)-N-Et)<i(OEt)3, M(Et-N-C(Me)-N-Et)i(OMe)3 M(Et-N-C(Me)-N-Et)i(OnPr)3, M(Et-N-C(Me)-N-Et)1(OsBu)3, M(Et-N- C(Me)-N-Et)i(OiBu)3l M(Et-N-C(Me)-N-Et)i(OtBu)3, and M(iPr-N- C(NMe2)-N-iPr)(OiPr)3;
• the molecule having Formula II , wherein v=1 , x=2, y=0, and z=0; The moiecule being selected from the group consisting of M{iPr-N- (CH2)2-N-iPr)i{OiPr)2, M(iPr-N-(CH2)2-N-iPr)1(OIVIe)2, M(iPr-N-(CH2)2-N- iPr)i(OEt)2, M(iPr-N-(CH2)2-N-iPr)i(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)i(OtBu)2, M(Et-N-(CH2)2-N-Et)i(OiPr)2, M(Et-N-(CH2)2-N-Et)i(OMe)- M(Et-N-(CH2)2-N-Et)i(OEt)2, (Et-N-(CH2)2-N-Et)1(OnPr)2, M(Et-N- {CH2)2-N-Et)i(OsBu)2, M(Et-N-(CH2) -N"Et)i(OiBu)2) M(Et-N-(CH2)2-N- Et)i(OtBu)2 l M(iPr-N-(CH2)3-N-iPr)1(OiPr)2t M(iPr-N-(CH2)3-N- iPr)-i{OMe)2l M(iPr-N-(CH2)3-N-iPr)1(OEt)2, M(iPr-N-(CH2)3-N- iPr)i(OnPr)2, (iPr-N-(CH2)3-N-iPr)i(OsBu)2l M(iPr-N-(CH2)3-N- \Pr),{0\Bu)2, M(iPr-N-(CH2)3-N-iPr)1(OtBu)2, M(Et-N-(CH2)3-N- Et)i(OiPr)2, M(Et-N-(CH2)3-N-Et)i(OMe)2> M(Et-N-(CH2)3-N-Ei)1{OEt)2> M(Et-N-(CH2)3-N-Et)1(OnPr)2[ M(Et-N-(CH2)3-N-Et)i(OsBu)2, M(Et-N~ (CH2)3-N-Et)i(OiBu)2, and M(Et-N-(CH2)3-N-Et)i(OtBu)2;
the molecule having Formula !, wherein u=2 , x=2 , y=0, and z=0 ;
the mo!ecu!e being selected from the group consisting of M(iPr-N-C(H) N-iPr)2(OiPr)2, M(iPr-N-C(H)-N-iPr)2{OMe)2, M(iPr-N-C(H)-N-iPr)2(OEt) M(iPr-N-C(H)-N-iPr)2(OnPr)2, M(iPr-N-C(H)-N-iPr)2(OsBu)2, M(iPr-N- C(H)-N-iPr)2(OiBu)2, {iPr-N-C(H)-N-iPr)2(OtBu)2, (Et-N-C(H)-N- Et)2(OiPr)2, M(Et-N-C(H)-N-Et)2(OMe)2, M(Et-N-C(H)-N-Et)2(OEt)2l M(Et-N-C(H)-N-Et)2(OnPr)2, M(Et-N-C(H)-N-Et)2(OsBu)2, M(Et-N-C(H)- N-Et)2(OiBu)2, M(Et-N-C(H)-N-Et)2(OtBu)2, (iPr-N-C(Me)-N- iPr)2(OiPr)2, M(iPr-N-C(Me)-N-iPr)2(OMe)2, M(iPr-N-C(Me)-N- iPr)2(OEt)2, M(iPr-N-C(Me)-N-iPr)2{OnPr)2j M(iPr-N-C(Me)-N- iPr)2(OsBu)2, (iPr-N-C(Me)-N-iPr)2{OiBu)2, M(iPr~N-C(Me)-N- iPr)2(OtBu)2, M(Et"N~C(Me)-N"Et)2(OiPr)2, M(Et-N-C(Me)-N-Et)2(OMe)2, M(Et-N-C(Me)-N-Et)2(OEt)2, (Et-N-C(Me)-N-Et)2(OnPr)2, M{Et-N- C(Me)-N-Et)2(OsBu)2, M(Et-N-C( e)-N-Et)2(OiBu)2, and M(Et-N-C(Me) N-Et)2(OtBu)2;
the molecule having Formula !, wherein u=1 , x=2, y— 1 , and z=0;
the molecule being selected from the group consisting of M(iPr-N- C(Me)-N-iPr)(OiPr)2{NMe2), M(iPr-N-C( e)-N-iPr)(OiPr)2(NEt2), M(iPr- N-C(Me)-N-iPr)(OiPr)2(NEtMe), M(Et-N-C(Me)-N-Et)(OiPr)2(NMe2), M(Et-N-C{Me)-N-Et)(OiPr)2(NEt2), (Et-N-C( e)-N-Et)(OiPr)2(NEiMe), M(iPr-N-C(NMe2)-N-iPr)(0!Pr)2(NMe2), M(iPr-N-C(NMe2)-N- iPr)(OiPr)2{NEt2), and !Vl(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NEtMe), M(iPr-N- C(Me)-N-iPr)(OiPr)2(NMeiPr), M(iPr-N-C(Me)-N-iPrXOiPr)2(NiPr2), M(iPr-N-C(Me)-N-iPr)(0iPr)2(NMetBu), M(iPr-N-C( e)-N- iPr)(OiPr)2(NneoPentyi2), M(Et-N-C(Me)-N-Et)(OiPr)2(NMeiPr), M(Et- N-C(Me)-N-Et)(OiPr)2(NiPr2), M(Et-N-C(Me)-N-Et)(OiPr)2(NneoPentyl2), M(iPr-N-C(NMe2)-N-iPr)(OiPr)2{NMeiPr), M(iPr-N-C(NMe2)-N- iPr)(OiPr)2(NiPr2)! M(iPr-N-C(NMe2)-N-iPr){OiPr)2{NneoPeniyl2) and M(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NMeiPr);
the molecule having Formula I, wherein u=1 , x=2, y=0, and z=1 ;
the molecule being selected from the group consisting of M(iPr-N- C{Me)-N-iPr)(OiPr)2(02CMe) and M(Et-N-C(Me)-N-Et)(OiPr)2(02CMe); the molecule having Formula II, wherein v=1 , x=1 , y=0, and 2=1 ;
The molecule being selected from the group consisting of M(iPr-N- (CH2)2-N-iPr)(OiPr)<02CMe), M{iPr-N-(CH2)2-N-iPr)(OMe)(02CMe), M{iPr-N-(CH2)2-N-iPr)(OEt)(02CMe}, M(iPr-N-(CH2)2-N- iPr){OnPr)(02CMe), M(iPr-N-(CH2)2-N-iPr)(OsBu)(02CMe), M(iPr-N- (CH2)2-N-iPr)(OiBu)(02C e), (iPr-N-(CH2)2-N-iPr)(OtBu)(02CMe), M{Et-N-(CH2)2-N-Et)(OiPr)(02CMe), M(Et-N-(CH2)2-N- Et)(OMe)(02CMe), M(Et-N-(CH2)2-N-Et)(OEt)(02CMe), M(Et-N-(CH2)2- N-Et)(OnPr)(02CMe), M(Et-N-(CH2)2-N-Et)(OsBu){02CMe), M(Et-N- (CH2}2-N-Et){OiBu)(02CMe), and M(Et-N-(CH2)2-N-Et)(OtBu)(02CMe); the molecule having either Formula I or Formula I I, wherein u, v, y=0, x=2, and z=2;
the molecule being M{OiPr)2(02CMe)2;
the molecule having either Formula I or Formula II, wherein u, v, y=0, x=3, and z=1 ; and
the molecule being M(OiPr)3(02CMe). Also disclosed are methods of forming a Hf-containing or Zr-containing Iayer on a substrate. A reaction chamber is provided having at least one substrate disposed within it. The vapor of at least one of the molecules disclosed above is introduced into the reaction chamber. The vapor is contacted with the substrate to form a Hf-containing or Zr-containing iayer on at least one surface of the substrate using a vapor deposition process. The disclosed methods may further include one or more of the following aspects:
Notation and Nomenclature
Certain abbreviations, symbols, and terms are used throughout the following description and claims and include: the abbreviation "PZT" refers to lead zirconium titanates;
the abbreviation "RrNCiF^N-F refers to the following chemical structure:
Figure imgf000006_0001
abbreviation "R1-N(C(R3)2)m-N-R2" refers to the following chemical structure
Figure imgf000006_0002
the abbreviation O2CR7" refers to the followin chemical structure:
Figure imgf000006_0003
the abbreviation "Cy" refers to cyclohexyi; the abbreviation "Cp" refers to cyclopentadiene; the term "aliphatic group" refers to a C1 -C6 linear or branched chain alkyl group; the term "alkyl group" refers to saturated functional groups containing exclusively carbon and hydrogen atoms and includes linear, branched, or cyclic alkyl groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, n-propyl groups, n-butyl groups, etc. Examples of branched aikyls groups include without limitation, t-butyl. Examples of cyclic alkyl groups include without limitation, cyc!opropyi groups, cyciobutyl groups, cyciopentyl groups, cyclohexyl groups, etc. The abbreviation "Me" refers to a methyl group; the abbreviation "Et" refers to an ethyl group; the abbreviation "Pr" refers to a propyl group; the abbreviation "iPr" refers to an isopropyl group; the abbreviation "iBu" refers to an isobutyl group; the abbreviation "nBu" refers to a n-butyl group; the abbreviation "sBu" refers to a sec-butyl group; the abbreviation "†Bu" refers to a tertiary butyl group; the abbreviation "Nz-amd" refers to R NC(R3) N-R2, wherein R3 = a C1 -C6 alkyl group and Ri and R2 = Z, which is defined as Me, Et, Pr, iPr, nBu, iBu, sBu, or tBu, for example N e-amd is Me-NC(Me)N-Me; the abbreviation "Nz-fmd" refers to R NC(R3) N-R2, wherein R3 = H and R-i and R2 = Z, which is defined as Me, Et, Pr, iPr, or tBu; the abbreviation "Nz-gmd" refers to R NC(R3)N-R2 wherein R3 = NR5R6 with R5 and R6 = H or a C1-C6 alkyl group, and and R2 = Z, which is defined as Me, Et, Pr, iPr, nBu, iBu, sBu, or tBu; the abbreviation "THF" refers to tetrahydrofuran; the abbreviation "TMA " refers to trimethyl aluminum; the abbreviation "ALD" refers to atomic layer deposition; the abbreviation "CVD" refers to chemical vapor deposition; the abbreviation "LPCVD" refers to low pressure chemical vapor deposition; the abbreviation "P- CVD" refers to pulsed chemical vapor deposition; the abbreviation "PE-ALD" refers to plasma enhanced atomic layer deposition; the abbreviation "MiM" refers to Metal Insulator Metal (a structure used in capacitors); the abbreviation "DRAM" refers to dynamic random access memory; the abbreviation "FeRAM" refers to ferroelectric random access memory; the abbreviation "CMOS" refers to complementary metai-oxide-semiconductor; the abbreviation "TGA" refers to thermogravimetnc analysis.
The standard abbreviations of the elements from the periodic table of elements are used herein. It should be understood that elements may be referred to by these abbreviations (e.g., Hf refers to hafnium, Zr refers to zirconium, etc.).
Description of Preferred Embodiments
Disclosed are novel hafnium-containing and zirconium-containing precursors, methods of synthesizing the same, and methods of using the same.
The disclosed heteroleptic hafnium-containing and zirconium- containing precursors are derived from different classes of !igand systems, such as amidinate, formamidinate, guanidinate, amide, and/or chelating amide ligands, plus aikoxide ligands. Precursor design may help improve volatility, reduce the melting point (liquids or very low melting" solids), increase reactivity with water, and increase thermal stability for wider process window applications.
The disclosed hafnium-containing and zirconium-containing precursors have the following formulae:
iyi{RrN-C(R3)-N- 2)u(OR4)x(N 5R6)y(02CR7)z Formula I
or
M{RrN-{C( R3)2)m-N-R2)v(OR4)x{NR5R6)y(02CR7)z Formula II wherein:
■ is Hf or Zr;
■ Ri , R2, R5, R6, and R7 are independently selected from the group consisting of H and C1 -C6 alkyl group;
R3 - H, C1 -C6 alkyl group, or NMe2;
■ R4 is a C1 -C6 alkyl group;
m = 2-4;
u = 0-2;
v = 0-1 ;
x = 1 -3;
y = 0-2;
z = 0-1 ;
■ in Formula I, u+x+y+z = 4; ■ in Formula II, 2v+x+y+z = 4; and
■ u, v, or z >1.
As defined above, the C1 -C6 alkyl group includes any linear, branched, or cyclic alkyl groups having from 1 to 6 carbon atoms, including but not limited to Me, tBu, or cyciohexyi groups.
In Formula I, the RrNC(R3)N-R2 ligand has the following chemical structure:
Figure imgf000009_0001
In Formula II, the R1-N-(C(R3)2)m-N-R2 ligand has the following chemical structure:
Figure imgf000009_0002
Therefore, although the same elements have been maintained in the backbone of the iigand (i.e., -N-C-N-), the ligand itself has gone from a -1 ligand having one delocaiized negative charge between the -N-C-N- backbone to a -2 ligand having a negative charge localized at each nitrogen atom. Additionally, the Formula I ligand has a more rigid structure than the Formula !S ligand.
When Ri and R3 are C1 -C6 linear or branched alkyl groups in Formula I, Ri and R3 may be independent substituents or they may be linked together to form a monocyclic structure extending from R-i to R3, as demonstrated below. R N-C-N-R2
Similarly, when R-i , R3 and f¾ are C1-C6 linear or branched alkyl groups in Formula I, R-i , R3 and R2 may be independent substituents or they may be linked together to form a bicyc!ic structure, as demonstrated below.
Figure imgf000010_0001
The configuration of the disclosed precursors was selected in order to optimize the reactivity (especially with H20) and, at the same time, the stability. The M-N bond is weak and will react rapidly on the surface. At the same time, the M-0 bond is much stronger and will help stabilize the molecule to avoid fast decomposition. By tuning this molecule, a precursor is obtained that reacts well on the substrate thanks to a weaker site
When u=1 , x=3, y=0, and z=0 in Formula I, R-i and R2 are preferably Et or iPr, R3 is preferably H, Me, or NMe2l and R4 is preferably a C1 -C4 linear or branched alkyl chain. Exemplary precursors include M(iPr-N-C(H)-N- iPr)i(OiPr)3, M(iPr-N-C(H)-N-iPr)i(OMe)3, M(iPr-N-C(H)-N-iPr)i(OEt)3, M(iPr- N-CiHJ-N-iPrMOnPrk, M(iPr-N-C(H)-N-iPr}1(OsBu)3! M(iPr-N-C(H)-N- iPr)i(OiBu)3l (iPr-N-C(H)-N-iPr)i(OtBu)3, M(iPr-N-C(Me)-N-iPr)i(OiPr)3, M(iPr-N-C(Me)-N-iPr;h(OMe)3, M(iPr-N-C(Me)-N-iPr)1(OEt)3, M(iPr-N-C(Me)- N-iPr)-,(OnPr)3, M(iPr-N-C(Me)-N-sPr)1(OsBu)3, MflPr-N-CiMeJ-N-iPrMOiBi s, M(iPr-N-C(Me)-N-iPr;h(OtBu)3, M(Et-N-C(Me)-N-Et)i(OEt)3, M{Et-N-C(Me)-N- EtJifOMeJs, M(Et-N-C( e)-N-Et)i(OnPr)3, M(Et-N-C(Me)-N-Et)1(OsBu)3, M(Et- N-C(Me)-N-Et)i(OiBu)3l M(Et-N-C(Me)-N-Et)1(OtBu)3, or M(iPr-N-C(NMe2)-N- iPr)(OiPr)3.
When M is Hf, the exemplary precursors include Hf(iPr-N-C(H)-N- iPr)1<OiPr>3l Hf Pr-N-CCHJ-N-iPrMOMek, Hf(iPr-N-C(H)-N-iPr)1(OEt)3, Hf(iPr- N-C^-N-iPrMOnPr HfiiPr-N-CiHJ-N-iPrJ^OsBu^, Hf(iPr-N-C(H)-N- iP ^OiBuJa, HfiiPr-N-CiHJ-N-iPrJ^OtBuJa, Hf(iPr-N-C(Me)-N-iPr)1{OiPr)3, Hf(iPr-N-C(Me)-N-iPr)i(OMe)3, Hf(iPr-N-C(Me)-N-iPr)i(OEt)3, Hf(iPr-N-C(Me)- N-iPrMOnPrfe, HfiiPr-N-Ci eJ-N-iPrJ^OsBuJa, Hf(iPr-N-C( e)-N-iPr)i(OiBu)3 Hf(iPr-N-C( e)-N-iPr)1(OtBu)3, Hf(Et-N-C(Me)-N-Et)i(OEt)3, Hf(Et-N-C( e)-N Et)i(OMe)3, Hf(Et-N-C(Me)-N-Et)i(OnPr)3, Hf(Et-N-C(Me)-N-Et)i(OsBu)3, Hf(Et-N-C{Me)-N-Et)1(OiBu)3! Hf(Et-N-C(Me)-N-Et)1(OtBu)3, or Hf(iPr-N- C(NMe2)-N-iPr)(OiPr)3.
When is Zr, the exemplary precursors include Zr(iPr-N-C{H)-N- iPr)-,(OiPr)3, Zr(iPr-N-C(H)-N-iPr)i(OMe)3, Zr(iPr-N-C(H)-N-iPr)1(OEt)3, Zr(iPr- N-C(H)-N-iPr)i(OnPr)3, Zr(iPr-N-C(H)-N-iPr)i(OsBu)3, Zr(iPr-N-C(H)-N- iP ^OiBuJa, ZrOPr-N-C(H)-N-iPr)-i(OtBu)3, ZriiPr- -CiMeJ-N-iPrJ^OiP s, Zr(iPr-N-C(Me)-N-iPr)1(OMe)3, Zr(iPr-N-C(Me)-N-iPr)1(OEt)3[ Zr(iPr-N-C(Me)~ N-iPrMOnPrfe, Zr(iPr-N-C(Me)-N-iPr)-i{OsBu)3, Zr(iPr-N-C(Me)-N-iPr)i{OiBu)3 Zr(iPr-N-C(Me)-N-iPr)i(OtBu)3, Zr(Et-N-C(Me)-N-Et)i(OEt)3, Zr(Et-N-C(Me)-N- Et)1(O e)3, Zr(Et-N-C(Me)-N-Et)1(OnPr)3, Zr(Et-N-C(Me)-N-Et)i(OsBu)3l Zr{Et-N-C( e)-N-Et)1(OiBu)3, Zr(Et-N-C(Me)-N-Et)i(OtBu)3, or Zr(iPr-N- C(NMe2)-N-iPr)(OiPr)3.
In this embodiment, the preferred exemplary precursors are Hf{iPr-N- CtMeJ-N-iPrMOiPr^ or Zr Pr-N-CtMeJ-N-iPrMOiPrJs.
When m=2 or 3, v=1 , x=2, y=0, and z=0 in Formula II, Ri and R2 are preferably Et or iPr, R3 is preferabiy H, and R4 is preferabiy a C1 -C4 linear or branched alkyl chain. More preferably, R-, and R2 are not Me when m=2. Exemplary precursors include M(iPr-N-(CH2)2-N-iPr) (OiPr)2, M(iPr-N-(CH2)2- N-iPr)i(OMe)2, M(iPr-N-{CH2)2-N-iPr) (OEt)2, M(iPr-N-(CH2)2-N-iPr)1(OnPr)2 l 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)i(OtBu)2 l M(Et-N-(CH2)2-N-Et)i(OiPr)2, M(Et-N-(CH2)2-N- Et)i(OMe)2, MfEt-N-iCHzfe-N-EtMOEtk, M(Et-N-(CH2)2-N-Et)1(OnPr)2, M(Et- N-(CH2)2-N-Et)i(OsBu)2l M(Et-N~(CH2)2-N-Et)t(OiBu)2, M(Et-N-(CH2)2-N- Et)i(OtBu)2l {iPr-N-(CH2)3-N-iPr).|(OiPr)2, M(iPr-N-(CH2)3-N-iPr)1(OMe)2, M(iPr-N-(CH2)3-N-iPr)1(OEt)2 l 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)i(OiBu)2l M(iPr-N-(CH2)3-N-iPr)i(OtBu)2 M(Ei-N-(CH2)3-N-Et)1{OiPr)2, M(Et-N-(CH2)3-N-Et)1(OMe)2, M(Et-N-(CH2)3-N- EtMOEtfe, M{Et-N-(CH2)3-N-Et)1(OnPr)2, M(Et-N-(CH2)3-N-Et)1(OsBu)2, M(Et- N-{CH2)3-N-Et)i(OiBu)2, or M(Et-N-(CH2)3-N-Et)i(OtBu)2.
When M is Hf, the exemplary precursors include Hf(iPr-N-(CH2)2-N- iPr)i(OiPr)2, Hf(iPr-N-(CH2)2-N-iPr)i(OMe)2, Hf(iPr-N-(CH2)2-N-iPr).,(OEt)2, Hf(iPr-N-(CH2)2-N-iPr)i(OnPr)2, Hf(iPr-N-(CH2)2-N-iPr)i(OsBu)2l Hf(iPr-N- (CH2)2-N-iPr)i(OiBu)2, Hf(iPr-N-(CH2)2-N-iPr) (OtBu)2, Hf(Et-N-(CH2)2-N- Et)i(OiPr)2, Hf(Et-N-(CH2)2-N-Et)i(O e)2, Hf(Et-N-(CH2)2-N-Et)1(OEt)2, Hf(Et-
Figure imgf000012_0001
Hf(Et-N-(CH2)2-N-Et)i(OsBu)2, Hf(Et-N-(CH2)2-N- Et)1(OiBu)2l Hf(Et-N-(CH2)2-N-Et)i(OtBu)2f HfiiPr-N-iC^Js-N-iPrJ^OiPr^, Hf(iPr-N-(CH2)3-N-iPr)1(OMe)2, Hf(iPr-N-{CH2)3-N-iPr)i{OEt)2j Hf(iPr-N-(CH2)3- N-iPrMOnPr)2, Hf(iPr-N-(CH2)3-N-iPr)i(OsBu)2 l Hf Pr-N^CH^-N-iPrMOiBu^
Figure imgf000012_0002
Hf(Et-N-(CH2)3-N-Et)1(OiPr)2 '; Hf(Et-N-(CH2)3- N-Et)i(OMe)2, Hf(Et-N-(CH2)3-N-Et)i(OEt)2, HftEt-N-tCHzfe-N-EtMOnPrk, Hf(Et-N-(CH2)3-N-Et)1(OsBu)2l Hf(Et-N-(CH2)3-N-Et)1(OiBu)2, or Hf(Et-N- (CH2)3-N-Et)1(OtBu)2.
When M is Zr, the exemplary precursors include Zr(iPr-N-(CH2)2-N- iPr)i(OiPr)2, Zr(iPr-N-(CH2)2-N-iPr)i(OMe)2, Zr(iPr-N-(CH2)2-N-iPr)i{OEt)2 l Zr(iPr-N-(CH2)z-N-iPr)1(OnPr)2, Zr(iPr-N-(CH2)2-N-iPr)i(OsBu)2, Zr(iPr-N- (CH2)2-N-iPr)i(OiBu)2l Zr(iPr-N-(CH2)2-N-iPr)i(OtBu)2, Zr(Et-N-(CH2)2-N- Et)i{OiPr)2l Zr(Et-N-(CH2)2-N-Et)i(OMe)2, Zr(Et-N-(CH2)2-N-Et;h(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-
Figure imgf000012_0003
Zr(Et-N-(CH2)2-N-Et;h(OtBu)2! Zr(iPr-N-(CH2)3-N-iPr)i(OiPr)2, Zr(iPr-N-(CH2}3-N-iPr)1{OMe)2, Zr(iPr-N-(CH2)3-N-iPr)1(OEt)2j Zr(iPr-N-(CH2)3- N-iP ^OnPr^, Zr(iPr-N-(CH2)3-N-iPr)i(OsBu)2, Zr(iPr-N-(CH2)3-N-iPr)i(OiBu)2 Zr(iPr-N-(CH2)3-N-iPr)1(OtBu)2, Zr(Et-N-(CH2)3-N-Et)1(OiPr)2! Zr(Et-N-(CH2)3-
Figure imgf000012_0004
Figure imgf000012_0005
Zr(Et-N-(CH2)3-N-Et)i(OiBu)2l or Zr(Et-N- (CH2)3-N-EtMOtBu)2.
In this embodiment, the preferred exemplary precursors are Hf(iPr-N- (CHa^-N-iP ^OiP s, Hf(Et-N-(CH2)3-N-Et)i(OiPr)2, Hf(Et-N-(CH2)2-N- Et)i(OiPr)2l Zr(iPr-N-(CH2)2-N-iPr)i(OrPr)2l Zr(Et-N-(CH2)3-N-Et)1(OiPr)2, or Zr(Et-N-(CH2)2-N-Et)1(OiPr}2. When u=2, x=2, y=0, and z=0 in Formula I, the precursor has the following chemical structure:
Figure imgf000013_0001
In this embodiment, Ri and R2 are preferably Et or iPr, R3 is preferably H or Me, and R4 is preferably a C1 -C4 linear or branched alkyi chain. More preferably, R3 is not NMe2. Exemplary precursors include M(iPr-N-C(H)-N- iPr)2(OiPr)2! M(iPr-N-C(H)-N-iPr)2(OMe)2, M(iPr-N-C{H)-N-iPr)2(OEt)2s M(iPr- N-C(H)-N-iPr)2(OnPr)2, M(iPr-N-C(H)-N-iPr)2(OsBu)2, M(iPr-N-C(H)-N- iPr)2(OiBu)2l M{iPr-N-C(H)-N-iPr)2(OtBu)2, M(Et-N-C(H)-N-Et)2(OiPr)2, M(Et-N- C(H)-N-Et)2(OMe)2, M(Et-N-C(H)-N-Et)2(OEt)2! (Et-N-C(H)-N-Et)2(OnPr)2, M(Et-N-C(H)-N-Et)2(OsBu)2l M(Et-N-C(H)-N-Et)2(OiBu)2, M(Et-N-C(H)-N- Et)2(OtBu)2, M(iPr-N-C(Me)-N-iPr)2(OiPr)2, M{iPr-N-C(Me)-N-iPr)2(OMe)2, M(iPr-N-C(Me)-N-iPr)2(OEt)2, M(iPr-N-C(Me)-N-iPr)2(OnPr)2, M(iPr-N-C(Me)- N-iPr)2{OsBu)2, M(iPr-N-C(Me)-N-iPr)2(OiBu)2t M(iPr-N-C(Me)-N-iPr)2(OtBu)2, M(Et-N-C(Me)-N-Et)2(OiPr)2, M(Et-N-C(Me)-N-Et)2(OMe)2, M(Et-N-C(Me)-N- Et)2{OEt)2, M(Et-N-C(Me)-N-Et)2(OnPr)2, M(Et-N-C(Me)-N-Et)2(OsBu)2, (Et- N-C{Me)-N-Et)2(OiBu)2, and M(Et-N-C(Me)-N-Et)2(OtBu)2.
When M is Hf, the exemplary precursors include Hf(iPr-N-C(H)-N- iPr)2(OiPr)2, Hf(iPr-N-C(H)-N-iPr)2(OMe)2, Hf(iPr-N-C(H)-N-iPr)2(OEt)2l Hf(iPr- N-C(H)-N-iPr)2(OnPr)2, Hf(iPr-N-C(H)-N-iPr)2(OsBu)2, Hf(iPr-N-C{H)-N- iPr)2(OiBu)2, Hf(iPr-N-C(H)-N-iPr)2(OtBu)2, Hf{Et-N-C(H)-N-Et)2(OiPr)2! Hf(Et- N-C(H)-N-Et)2(OMe)2, Hf(Et-N-C(H)-N-Et)2(OEt)2[ Hf(Et-N-C(H)-N-Et)2(OnPr)2, Hf(Et-N-C(H)-N-Et)2(OsBu)2, Hf(Et-N-C(H)-N-Et)2(OiBu)2, Hf{Et-N-C(H)-N- Et)2(OtBu)2, Hf(iPr-N~C(Me)-N-iPr)2(OiPr)2, Hf(iPr-N-C(Me)-N-iPr)2(OMe)2, Hf(iPr-N-C(Me)"N-iPr)2(OEt)2, Hf(iPr-N"C(Me)-N-iPr)2(OnPr)2l Hf{iPr-N-C(Me)- N"iPr)2(OsBu)2l Hf(iPr-N-C(Me)-N-iPr)2(OiBu)2, Hf(iPr-N-C(Me)-N-iPr)2(OtBu)2j Hf(Et-N-C(Me)-N-Et)2(OiPr)2, Hf(Et-N-C(Me)-N-Et)2(OMe)2, Hf(Et-N-C(Me)-N- Et)2(OEt)2, Hf(Et-N-C(Me)-N-Et)2(OnPr)2l Hf(Et-N-C(Me)-N-Et)2(OsBu)2, Hf(Et- N-C(Me)-N-Et)2(OiBu)2, and Hf(Et-N-C{Me)-N-Et)2(OtBu)2.
When M is Zr, the exemplary precursors include Zr{iPr-N-C(H)-N- iPr)2(OiPr)2, Zr(iPr-N-C(H)-N-iPr)2(OMe)2, Zr(iPr-N-C(H)-N-iPr)2(OEt)2, Zr(IPr- N-C(H)-N-iPr)2(OnPr)2, Zr(iPr-N-C(H)-N-iPr)2(OsBu)2, Zr(iPr-N-C(H)-N- iPr)2(OiBu)2, Zr(iPr-N-C(H)-N-iPr)2(OtBu)2) Zr(Et-N-C(H)-N-Et)2(OiPr)2, Zr(Et- N-C(H)-N-Et)2(OMe)2 l Zr(Et-N-C(H)-N-Et)2(OEt)2, Zr(Et-N-C(H)-N-Et)2(OnPr)2, Zr(Et-N-C(H)-N-Et)2(OsBu)2, Zr(Et-N-C(H)-N-Et)2(OiBu)2l Zr(Et-N-C(H)-N- Et)2{OtBu)2, Zr(iPr-N-C(Me)-N-iPr)2(OiPr)2! Zr(iPr-N-C(Me)-N-iPr)2(OMe)2, Zr(iPr-N~C(Me)-N-iPr)2(OEt)2, Zr(iPr-N-C(Me)-N-iPr)2(OnPr)2, Zr(iPr-N-C(Me)- N-iPr)2(OsBu)2, Zr(iPr-N-C(Me)-N-iPr)2(OiBu)2; Zr(iPr-N-C(Me)-N-iPr)2(OtBu)2, Zr(Et-N-C(Me)-N-Et)2(OiPr)2, Zr(Et-N-C(Me)-N-Et)2(OMe)2, Z'r(Et-N-C(Me)-N- Et)2(OEt)2, Zr(Et-N-C(Me)-N-Et)2(OnPr)2, Zr(Et-N-C(Me)-N-Et)2(OsBu)2, Zr(Et- N-C(Me)-N-Et)2(OiBu)2j and Zr(Et-N-C(Me)-N-Et)2(OtBu)2.
in this embodiment, the preferred exemplary precursor is Hf{iPr-N- C{H)-N-iPr)2(OiPr)2, Hf(iPr-N-C(Me)-N-iPr)2(OiPr)2, Zr(iPr-N-C(H)-N- iPr)2(OiPr)2, or Zr(iPr-N-C(Me)-N-iPr)2(OiPr)2.
When u=1 , x=2, y= , and z=0 in Formula I, the precursor has the following chemical structur
Figure imgf000014_0001
In this embodiment, Ri and R2 are preferably Et or iPr; R3 is preferabiy H, Me, or NMe2; R4 is preferabiy iPr; and R5 and R6 preferably are independently Me or Et. Exemplary precursors include M(iPr-N-C(Me)-N-iPr)(OiPr)2(NMe2), M(iPr-N-C(Me)-N-iPr)(OiPr)2{NEt2), M(iPr-N-C(Me)-N-iPr)(OiPr)2(NEtMe), M(Et-N-C(Me)-N-Et)(OiPr)2(NMe2), M(Et-N-C(Me)-N-Et)(OiPr)2(NEt2), M(Et-N- C(Me)-N-Et)(OiPr)2(NEtMe), M(iPr-N-C(NMe2)-N-iPr)(OiPr)2{NMe2), M(iPr-N- C(NMe2)-N-iPr)(OiPr)2(NEt2), M(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NEtMe), M(iPr- N-C(Me)-N-iPr)(OiPr)2(NMeiPr), M(iPr-N-C(Me)-N-iPr)(OiPr)2(NiPr2)( M(iPr-N- C(Me)-N-iPr)(OiPr)2(NMetBu), M(iPr-N-C(Me)-N-iPr)(OiPr)2(NneoPentyl2), M(Et-N-C(Me)-N-Et)(OiPr)2<NMeiPr), M(Et-N-C(Me)-N-Et)(OiPr)2(NiPr2), M(Et N-C(Me)-N-Et)(OiPr)2(NneoPenty!2), M(iPr-N-C(NMe2)-N-iPr)(OiPr)2(N eiPr) M(iPr-N-C{NMe2)-N-!Pr)(OiPr)2(NiPr2), (iPr-N-C(NMe2)-N- iPr)(OiPr)2(NneoPentyi2) and (iPr-N-C(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(NEt e), 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(NEt e), Hf(iPr-N-C(Me)-N-iPr)(OiPr)2(N eiPr), 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(NneoPeniyl2), Hf(Et-N-C(Me)-N-Et)(OiPr)2(N eiPr), Hf(Et-N- C( e)-N-E†)(OiPr)2(NiPr2), Hf(Et-N-C(Me)-N-Et)(OiPr)2(NneoPentyl2), Hf(iPr- N-C(N e2)-N-iPr)(OiPr)2(NMeiPr), Ηί(ίΡΓ-Ν-0{ΝΜθ2)-Ν-ΪΡΓ){ΟίΡΓ)2(ΝϊΡΓ2), Hf(iPr-N-C(N e2)-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(N e2), 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(N etBu), Zr(iPr-N-C(Me)-N- iPr)(OiPr)2(NneoPenty!2), 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), Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NiPr2), Zr(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NneoPentyi2), and Zr(iPr-N-C(NMe2)-N- iPr)(OiPr)2(N eiPr).
In this embodiment, the preferred exemplary precursor is Hf(iPr-N- C(Me)-N-iPr)(OiPr)2(NMe2) or Zr(iPr-N-C( e)-N-iPr)(OiPr)2(NMe2). When u=1 , x-2, y=0, and z=1 in Formula I, the precursor has the following chemical structure:
Figure imgf000016_0001
In this embodiment, Ri and R2 are preferably Et or iPr; R3 is preferably H or Me; R4 is preferably iPr; and R7 is preferably Me. Exemplary precursors include M(iPr-N-C(Me)-N-iPr)(OiPr)2(02CMe) and M(Et-N-C(Me)-N- Et)(OiPr)2(02CMe). When M is Hf, the exemplary precursors include Hf{iPr-N- C(Me)-N-iPr)(OiPr)2(02CMe) and Hf(Et-N-C(Me)-N-Et)(OiPr)2(02CMe). When M is Zr, the exemplary precursors include Zr(iPr-N-C(Me)-N- iPr)(OiPr)2{02CMe) and Zr(Et-N-C(Me)-N-Et)(OiPr)2(02CMe).
When v = 1 , x = 1 , y=0, and z - 1 in Formula II, the precursor has the following chemical structure:
R2
I
Ri
When m=2,
Figure imgf000016_0002
the precursor has the following chemical structure:
Figure imgf000016_0003
When m=3, v=1 , x=1 , y=0, z=1 , and R3=H, the precursor has the following chemical structure:
Figure imgf000017_0001
In these embodiments, m is preferabiy 2 or 3, Ri and R2 are preferably Et or iPr; R3 is preferabiy H; R4 is preferably a C1 -C4 linear or branched alkyl chain; and R7 is preferably Me. Exemplary precursors include M(iPr-N-(CH2)2-N- iPr)(OiPr)(02CMe), M{!Pr-N-(CH2)2-N-iPr}(OMe)(02CMe), M(iPr-N-(CH2)2-N- iPr)(OEt)(02CMe)! M(iPr-N-(CH2)2-N-iPr)(OnPr){02CMe), M(iPr-N-(CH2)2-N- iPr)(OsBu)(02CMe), M(iPr-N CH2)2-N-iPr)(OiBu)(02CMe), M(iPr-N-(CH2)2-N- iPr)(OtBu)(02CMe)t (Et-N-(CH2)2-N-Et)(OiPr){02CMe), M(Et-N-(CH2)2-N- Et)(OMe)(02CMe), M(Et-N-(CH2)2-N-Et)(OEt)(02CMe), M(Et-N-(CH2)2-N- Et)(OnPr)(02CMe), M(Et-N-(CH2)2-N-Et)(OsBu)(02CMe), M(Et-N-(CH2)2-N- Et)(OiBu)(02CMe), and M(Et-N-(CH2)2-N-Et)(OtBu)(02CMe).
When M is Hf, the exemplary precursors include Hf(iPr-N-(CH2)2-N- iPr){OiPr)(02CMe), Hf(iPr-N-(CH2)2-N-iPr)(OMe)(02CMe), Hf(iPr-N-(CH2)2-N- iPr)(OEt)(02CMe), Hf(iPr-N-(CH2)2-N-iPr)(OnPr)(02CMe), Hf(iPr-N-(CH2)2-N- iPr)(OsBu)(02CMe), Hf(iPr-N-(CH2)2-N-iPr)(OiBu)(02CMe), Hf(iPr-N-(CH2)2-N- iPr)(OtBu)(02CMe), Hf(Et-N-(CH2)2-N-Et)(OiPr)(02CMe)! Hf(Et-N-(CH2)2-N- Et)(OMe)(02CMe), Hf(Et-N-(CH2)2-N-Et)(OEt)(02CMe), Hf(Et-N-(CH2)2-N- Et)(OnPr)(02CMe), Hf(Et-N-(CH2)2-N-Et)(OsBu)(02CMe), Hf(Et-N-(CH2)2-N- Et)(OiBu}(02CiVie), and Hf(Et-N-(CH2)2-N-Et)(OtBu)(02CMe).
When M is Zr, the exemplary precursors include Zr(iPr-N-(CH2)2-N- iPr)(OiPr)(02CMe), Zr(iPr-N-(CH2)2-N-iPr)(OMe)(02CMe), Zr{iPr-N-(CH2)2-N- iPr)(OEt)(02CMe), Zr(iPr-N-(CH2)2-N-iPr){OnPr)(02CMe)I Zr(iPr-N-(CH2)2-N- iPr)(OsBu){02CMe), Zr{iPr-N-{CH2)2-N-iPr)(OiBu){02CMe)! Zr(iPr-N-(CH2)2-N- iPr)(OtBu)(02CMe), Zr(Et-N-(CH2)2-N-Et)(OiPr)(02CMe), Zr(Et-N-(CH2)2-N- Ei)(O e)(02CMe)t Zr(Et-N-(CH2)2-N-Et)(OEt)(02CMe), Zr(E†-N-(CH2)2-N- Et)(OnPr)(02CMe), Zr(Et-N-(CH2)2-N-Et){OsBu){02CMe), Zr(Et-N-(CH2)2-N- Et)(OiBu)(02CMe), and Zr(Et-N-(CH2)2-N-Et)(OtBu)(02CMe).
When u=1 , x=1 , y=2, and z=0 in Formula I, exemplary precursors include M(iPr-N-C(Me)-N-iPr)(OiPr) (NMe2)2, M(iPr-N-C(Me)-N- !Pr)(OiPr)(NEt2)2, M(iPr-N-C(Me)-N-iPr)(OiPr)(NEtMe)2! M(Et-N-C(Me)-N- Et)(OiPr)(NMe2)2, M(Et-N-C(Me)-N-Et){OiPr)(NEt2)2, M(Et-N-C(Me)-N- Et)(OiPr)(NEtMe)2, M(iPr-N-C(N e2)-N-iPr){OiPr)(NMe2)2, M(iPr-N-C(NMe2)- N-iPr)(OiPr)(NEt2)2, and M(iPr-N-C(NMe2)-N-iPr)(OiPr)(NEtMe)2.
When M is Hf, the exemplary precursors include Hf(iPr-N-C( e)-N- iPr)(OiPr) (NMe2)2, Hf(iPr-N-C(Me)-N-iPr)(OiPr)(NEt2)2[ Hf(iPr-N-C(Me)-N- iPr)(OiPr)(NEtMe)2l Hf(t≡t-N-C(Me)-N-Et)(OiPr)(NMe2)2, Hf(Et-N-C(Me)-N- Et)(OiPr)(NEt2)2l 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)2, 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, 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=1 , x-1 , y=1 , and z=0 in Formula Π, exemplary precursors inciude 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), (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 inciude 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=1 , x=1 , y-0, and z=2 in Formula I, exemplary precursors include M(iPr-N-C(Me)-N-iPr)(OiPr) (02CMe)2 and <Et-N-C(Me)-N- Et)(OiPr){02CMe)2. When M is Hf, the exemplary precursors include Hf(iPr-N- C(Me)-N-iPr)(OiPr) (02CMe)2 and Hf(Et-N-C(Me)-N-Et)(OiPr)(02CMe)2.
When M is Zr, the exemplary precursors include Zr(iPr-N-C(Me)-N-iPr){OiPr) (02CMe)2 and Zr(Et-N-C(Me)-N-Et)(OiPr)(02CMe)2.
When u, v, y=0, x=2, and z=2 in either of Formula I or Formula II, exemplary precursors include M(OiPr)2{02CMe)2, or Hf(OiPr)2{02CMe)2 when M is Hf and Zr(OiPr)2(02CMe)2 when M is Zr.
When u, v, y=0, x=3, and z=1 in either of Formula I or'Formula li, exemplary precursors include M(OiPr)3(02CMe), or Hf(OiPr)3(02CMe) when M is Hf and Zr(OiPr)3(02C e) when M is Zr.
The disclosed precursors may be synthesized by combining a hydrocarbon solution of H(RrN-C(R3)-N-R2) with a neat or hydrocarbon solution of a hafnium or zirconium compound, such as Hf(OR4)3(NR5R6), Hf(OR )2(NR5R6)2, Zr(OR4)3( R5R6)I or Zr(OR4)2(NR5R6)2, under atmosphere of nitrogen, the outlet of the mixing flask being connected to an oil bubbler. Exemplary hydrocarbon solutions include pentane. The resulting solution is stirred at room temperature overnight. Where applicable, H02CR7 may be added and further stirred for 6-12 hours. Solvent and vo!atiies are removed from the reaction mixture under vacuum. Purification of the resulting liquid or solid is carried out by distillation or sublimation, respectively. Additional synthesis details are provided in the Examples.
Also disclosed are methods of using the disclosed hafnium-containing and zirconium-containing precursors for vapor deposition methods. The disclosed methods provide for the use of the hafnium-containing and zirconium-containing precursors for deposition of hafnium-containing and zirconium-containing films, respectively. The disclosed methods may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, or flat panel type devices. The method includes: providing a substrate; providing a vapor including at least one of the disclosed hafnium-containing or zirconium- containing precursors: and contacting the vapor with the substrate (and typically directing the vapor to the substrate) to form a hafnium-containing or zirconium-containing layer on at least one surface of the substrate.
The disclosed methods also provide for forming a bimetal-containing layer on a substrate using a vapor deposition process. The disclosed methods may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, or flat panel type devices. The method includes: providing a substrate; providing a vapor including at least one of the disclosed hafnium- containing or zirconium-containing precursors and contacting the vapor with the substrate (and typicaily directing the vapor to the substrate) to form a bi meta!-containing layer on at least one surface of the substrate. An oxygen source, such as 03, O2, H2O, and NO, preferably H2O, may also be provided.
The disclosed hafnium-containing and zirconium-containing precursors may be used to deposit hafnium-containing and zirconium-contianing films using any deposition methods known to those of skill 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), p!asma enhanced atomic layer deposition (PE-ALD), or combinations thereof. Preferably, the deposition method is ALD or PE-ALD.
The vapor of the hafnium-containing or zirconium-containing precursor is introduced into a reaction chamber containing at least one substrate. The temperature and the pressure within the reaction chamber and the
temperature of the substrate are held at suitable conditions so that contact between the hafnium-containing or zirconium-containnig precursor and substrate results in formation of a Hf-containing or Zr-containing layer on at least one surface of the substrate. A reactant may also be used to help in formation of the Hf-containing or Zr-containing layer.
The reaction chamber may be any enclosure or chamber of a device in which deposition methods take place, such as, without limitation, a parailel- plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a sing!e- wafer reactor, a multi-wafer reactor, or other such types of deposition systems. Ail of these exemplary reaction chambers are capable of serving as an ALD reaction chamber. The reaction chamber may be maintained at a pressure ranging from about 0.5 mTorr (0.07 Pa) to about 20 Torr (2700 Pa). In addition, the temperature within the reaction chamber may range from about 200°C to about 600°C. One of ordinary skill in the art will recognize that the temperature may be optimized through mere experimentation to achieve the desired result.
The temperature of the reaction chamber may be controlled by either controlling the temperature of the substrate holder or controlling the temperature of the reactor wall. Devices used to heat the substrate are known in the art. The reactor wall is heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with desired physical state and composition. A non-limiting exemplary temperature range to which the reactor wall may be heated includes from approximately 200°C to approximately 600°C, When a plasma deposition process is utilized, the deposition temperature may range from approximately 200°C to approximately 550°C. Alternatively, when a thermal process is performed, the deposition temperature may range from approximately 400°C to approximately 600°C.
Alternatively, the substrate may be heated to a sufficient temperature to obtain the desired hafnium-containing or zirconium-containing film at a sufficient growth rate and with desired physical state and composition. A non- limiting exemplary temperature range to which the substrate may be heated includes from 150°C to 600°C. Preferably, the temperature of the substrate remains less than or equal to 450°C.
The type of substrate upon which the hafnium-containing or zirconium- containing film will be deposited will vary depending on the final use intended. In some embodiments, the substrate may be chosen from oxides which are used as dielectric materials in iM, DRAM, or FeRam technologies (for example, HfO2 based materials, TiO2 based materials, ZrO2 based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or from nitride-based films (for example, TaN) that are used as an oxygen barrier between copper and the low-k layer. Other substrates may be used in the manufacture of semiconductors, photovoitaics, LCD-TFT, or flat panel devices. Examples of such substrates include, but are not limited to, solid substrates such as metal nitride containing substrates (for example, TaN, TiN, WN,
TaCN, TiCN, TaSiN, and TiSiN); insulators (for example, SiO2l Si3N4, SiON, HfO2, Ta205, ZrO2, TiO2, AI2O3, and barium strontium titanate); or other substrates that include any number of combinations of these materials. The actual substrate utilized may also depend upon the specific precursor embodiment utilized. In many instances though, the preferred substrate utilized will be selected from TiN, SRO, Ru, and Si type substrates.
The hafnium-containing or zirconium-containing prec rsor may be fed in liquid state to a vaporizer where it is vaporized before it is introduced into the reaction chamber. Prior to its vaporization, the hafnium-containing or zirconium-containing precursor may optionally be mixed with one or more solvents, one or more metal sources, and a mixture of one or more solvents and one or more metal sources. The solvents may be selected from the group consisting of toluene, ethyl benzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane, or others. The resulting concentration may range from approximately 0.05 M to approximately 2 M. The metal source may include any metal-containing precursors now known or later developed.
Alternatively, the hafnium-containing or zirconium-containing precursor may be vaporized by passing a carrier gas into a container containing the hafnium-containing or zirconium-containing precursor or by bubbling the carrier gas into the hafnium-containing or zirconium-containing precursor.
The carrier gas and hafnium-containing or zirconium-containing precursor are then introduced into the reaction chamber as a vapor. The carrier gas may include, but is not limited to, Ar, He, N2,and mixtures thereof. The hafnium- containing or zirconium-containing precursor may optionally be mixed in the container with one or more solvents, metal-containing precursors, or mixtures thereof. If necessary, the container may be heated to a temperature that permits the hafnium-containing or zirconium-containing precursor to be in its liquid phase and to have a sufficient vapor pressure. The container may be maintained at temperatures in the range of, for examp!e, approximately 0°C to approximately 150°C. Those skilled in the art recognize that the temperature of the container may be adjusted in a known manner to control the amount of hafnium-containing or zirconium-containing precursor vaporized.
In addition to the optional mixing of the hafnium-containing or zirconium-containing precursor with solvents, metal-containing precursors, and stabilizers prior to introduction into the reaction chamber, the hafnium- containing or zirconium-containing precursor may be mixed with reactants inside the reaction chamber. Exemplary reactants include, without limitation, metal-containing precursors such as aiuminum-containing precursors such as TMA or silicon-containing precursors such as bis(diethylamino)silane. These or other meta!-containing precursors may be incorporated into the resultant film in small quantities, as a dopant, or as a second or third metal in the resulting film, such as PZT,
When the desired hafnium-containing or zirconium-containing film also contains oxygen, such as, for example and without limitation, ZrO, the reactants may include an oxygen source which is selected from, but not limited to, O2, O3, H2O, H2O2l acetic acid, formalin, para-formaldehyde, and combinations thereof. Preferably, when an ALD process is performed, the reactant is H2O.
The reactant may be treated by plasma in order to decompose the reactant into its radical form. The p!asma may be generated or present within the reaction chamber itself. Alternatively, the p!asma may generally be at a location removed from the reaction chamber, for instance, in a remotely located plasma system. One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.
For example, the reactant may be introduced into a direct plasma reactor, which generates a plasma in the reaction chamber, to produce the plasma-treated reactant in the reaction chamber. Exemplary direct plasma reactors include the Titan™ PECVD System produced by Trion Technologies. The reactant may be introduced and he!d in the reaction chamber prior to plasma processing. Alternativeiy, the plasma processing may occur simultaneously with the introduction of reactant. In-situ plasma is typically a 13.56 MHz RF capacitively coupled plasma that is generated between the showerhead and the substrate holder. The substrate or the showerhead may be the powered electrode depending on whether positive ion impact occurs. Typical applied powers in in-situ plasma generators are from approximately 100 W to approximately 1000 W. The disassociation of the reactant using in-situ plasma is typically less than achieved using a remote plasma source for the same power input and is therefore not as efficient in reactant disassociation as a remote plasma system, which may be beneficial for the deposition of metal-nitride-containing films on substrates easily damaged by plasma.
Alternativeiy, the plasma-treated reactant may be produced outside of the reaction chamber. The MKS Instruments' ASTRON®i reactive gas generator may be used to treat the reactant prior to passage into the reaction chamber. Operated at 2.45 GHz, 7kW plasma power, and a pressure ranging from approximately 3 Torr to approximately 10 Torr, the reactant 03 may be decomposed into three O" radicals. Preferably, the remote plasma may be generated with a power ranging from about 1 kW to about 10 kW, more preferably from about 2.5 kW to about 7.5 kW.
When the desired hafnium-containing or zirconium-containing film also contains another metal, such as, for example and without limitation, Ta, Hf, Zr, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co, lanthanides (such as Eu), or combinations thereof, the reactants may include a metal-containing precursor which is selected from, but not limited to, metal alkyls, such as Ln(RCp)3 or Co(RCp)2, metal alkoxies, such as Ti(Cp)(OMe)3, and any combination thereof.
The vapor of the metai-containing precursor is introduced into a reaction chamber. The temperature and the pressure within the reaction chamber and the temperature of the substrate are held at suitable conditions so that contact between the metal-containing precursor and substrate results in formation of a metal-containing layer on at least one surface of the substrate. A reactant may also be used to help in formation of the metal- containing layer.
One of ordinary skill in the art will recognize that additional reactants may be used in the disclosed deposition processes.
The hafnium-containing or zirconium-containing precursor and one or more reactants may be introduced into the reaction chamber simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in other combinations. For example, the hafnium-containing or zirconium-containing precursor may be introduced in one pulse and two additional metal sources may be introduced together in a separate pulse [modified atomic layer deposition]. Alternatively, the reaction chamber may already contain the reactant prior to introduction of the hafnium-containing or zirconium-containing precursor. The reactant may be passed through a plasma system localized remotely from the reaction chamber, and decomposed to radicals.
Alternatively, the hafnium-containing or zirconium-containing precursor may be introduced to the reaction chamber continuously while other metal sources are introduced by pulse (pulsed-chemica! vapor deposition). In each example, a pulse may be followed by a purge or evacuation step to remove excess amounts of the component introduced. In each example, the pulse may last for a time period ranging from about 0.01 s to about 10 s, alternatively from about 0.3 s to about 3 s, alternatively from about 0.5 s to about 2 s.
In one non-limiting exemplary atomic layer deposition type process, the vapor phase of a hafnium-containing or zirconium-containing precursor is introduced into the reaction chamber, where it is contacted with a suitable substrate. Excess hafnium-containing or zirconium-containing precursor may then be removed from the reaction chamber by purging and/or evacuating the reaction chamber. An oxygen source is introduced into the reaction chamber where it reacts with the absorbed hafnium-containing or zirconium-containing precursor in a self-limiting manner. Any excess oxygen source is removed from the reaction chamber by purging and/or evacuating the reaction chamber. If the desired film is a hafnium oxide or zirconium oxide film, this two-step process may provide the desired fiim thickness or may be repeated until a fi!m having the necessary thickness has been obtained.
Alternatively, if the desired fiim is a hafnium or zirconium metal oxide film, the two-step process above may be followed by introduction of a second vapor of a metal-containing precursor into the reaction chamber. The metal- containing precursor will be selected based on the nature of the hafnium metal oxide or zirconium metal oxide film being deposited. After introduction into the reaction chamber, the metal-containing precursor is contacted with the substrate. Any excess metal-containing precursor is removed from the reaction chamber by purging and/or evacuating the reaction chamber. Once again, an oxygen source may be introduced into the reaction chamber to react with the metal-containing precursor. Excess oxygen source is removed from the reaction chamber by purging and/or evacuating the reaction chamber. If a desired film thickness has been achieved, the process may be terminated. However, if a thicker film is desired, the entire four-step process may be repeated. By alternating the provision of the hafnium-containing or zirconium- containing precursor, metal-containing precursor, and oxygen source, a fi!m of desired composition and thickness can be deposited.
Additionally, by varying the number of pulses, films having a desired stoichiometric Hf: metal or Zrmetal ratio may be obtained. For example, a PZT film (Pb[ZrxT!i-x]O3 with 0<x<1 ) may be obtained by having one puise of the zirconium-containing precursor, one pulse of a titanium-containing precursor, and two pulses of the lead-containing precursor, with each pulse being followed by pulses of the oxygen source. However, one of ordinary skill in the art will recognize that the number of pulses required to obtain the desired film may not be identical to the stoichiometric ratio of the resulting film.
The hafnium-containing or zirconium-containing films resulting from the processes discussed above may include PZT. One of ordinary ski!l in the art will recognize that by judicial selection of the appropriate hafnium-containing or zirconium-containing precursor and reactants, the desired fiim composition may be obtained. Examples
The following non-limiting examples are provided to further illustrate embodiments of the invention. However, the examples are not intended to be all inclusive and are not intended to limit the scope of the inventions described herein.
Prophetic Example 1
Hf(NiPr-amd)(OiPr)3 or Zr(NiPr-amd)(OiPr)3: A pentane solution will be chilled to -30°C for 1 hour. Hf(OiPr)3(NMe2) or Zr(OiPr)3(NMe2) will be added to the chilled pentane solution. The mixture will be stirred at room temperature under atmosphere of nitrogen. A solution of NlPr-amd-H in pentane will slowly be added to the above mixture. The outlet of the flask will be'connected to an oil bubbler, which in turn will be connected to an acid scrubber. The resulting solution will be stirred at room temperature overnight. Solvent and volatiles will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(NiPr-amd)(OiPr)3 or Zr(NiPr-amd)(OiPr)3).
Prophetic Example 2
Hf(Nipr-amd)2(OiPr)2 or Zr(Nipr-amd)2(OiPr)2: Neat Hf(OiPr)2(NMe2)2 or neat Zr(OiPr)2(NMe2)2 will be added to a pentane solution containing NlPr-amd-H stirring at room temperature under atmosphere of nitrogen, the outlet of the flask will be connected to an oil bubbler. The resulting solution will be stirred at room temperature overnight Solvent and volatiles will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(N'pr- amd)2(OiPr)2 orZr(NiPr-amd)2(OiPr)2).
Prophetic Example 3
Hf{NiPr-fmd)2(OiPr)2 or Zr(NiPr-fmd)2(OiPr)2: Neat Hf(OiPr)2(NMe2)2 or neat Zr(OiPr)2(NMe2)2 will be added to a pentane solution containing NiPr-fmd-H stirring at room temperature under atmosphere of nitrogen, the outlet of the flask will be connected to an oil bubbler. The resulting solution will be stirred at room temperature overnight. Solvent and volatiles will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(NlPr- 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: Neat Hf(OiPr)2(NMe2)2 or neat Zr(OiPr)2(NMe2)2 will be added to a pentane solution containing iPr-N=C=N- iPr stirring at room temperature under atmosphere of nitrogen, the outlet of the flask will be connected to an oil bubbler. The resulting solution will be stirred at room temperature overnight. Solvent and volatiies will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(NiPr-gmd)2(OiPr)2 or Zr(NiPr-gmd)2(OiPr)2).
Prophetic Example 5
Hf(NiPr-amd)(OiPr)2(NMe2) or Zr(NiPr-amd)(OiPr)2(N e2): A solution of NiPr- amd-H in pentane will be added slowly dropwise to a pentane solution containing Hf(OiPr)2(NMe2)2 or Zr(OiPr)2(NMe2)2 stirring at room temperature under atmosphere of nitrogen. The outlet of the flask will be connected to an oil bubbler, which in turn will be connected to an acid scrubber. The resulting solution will be stirred at room temperature overnight. Solvent and volatiies will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(NiPr-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: To a pentane solution containing Hf(OiPr)2(NMe2)2 or Zr(0!Pr)2(N e2)2 stirring at room temperature under atmosphere of nitrogen will be added slowly drop wise neat liquid of Et-NH-(CH2)2-NH-Et. The outlet of the flask will be connected to an oil bubbler, which in turn will be connected to an acid scrubber. The resulting solution will be stirred at room temperature overnight. Solvent and volatiies will be removed from the reaction mixture under vacuum, resulting in the target molecule (Hf(Et-N-(CH2)2-N-Et)(OiPr)2 or Zr(Et-N-(CH2)2-N- Et)(OiPr)2). Prophetic Example 7
Ti( e-N-(CH2)2-N- e)(OiPr)2: Synthesis will be carried out similar to Example 6 with reactants having the appropriate ligands. Prophetic Example 8
Ti(Me2CH-N-{CH2)3-N-CHMe2)(OiPr)2: Synthesis will be carried out similar to Example 6 with reactants having the appropriate ligands.
Prophetic Example 9
The hafnium-containing or zirconium-containing precursor of any one of
Examples 1 to 8 and the reactant 03 will be used to deposit a film of Hf02 or Zr02 on a Si02/Si substrate. The Si02/Si substrate will be maintained at a temperature of 250°C. The precursor will be vaporized in a bubbler maintained at 50°C. The ALD cycle will include a precursor pulse of 5 seconds, followed by a 5 second purge, followed by a reactant pulse of 2 seconds, followed by a 5 second purge. The Hf02 or Zr02 growth rate is expected to be 0.5 A/cycle or greater. The ALD regime will be assessed up to 350°C with a deposition rate. Prophetic Example 10
The hafnium-containing or zirconium-containing precursor of any one of Examples 1 to 8 and the reactant H20 will be used to deposit a film of Hf02 or Zr02 on a Si02/Si substrate. The Si02/Si substrate will be maintained at a temperature of 250°C. The precursor will be vaporized in a bubbler maintained at 50°C. The ALD cycle will include a precursor pulse of 20 seconds, followed by a 5 second purge, followed by a reactant pulse of 2 seconds, followed by a 10 second purge. The Hf02 or Zr02 growth rate is expected to be 0.5 A/cycle or greater. The ALD regime will be assessed up to 350°C.
It will be understood that many additional changes in the details, materials, steps, and arrangement of parts, which have been herein described and iliustrated in order to explain the nature of the invention, may be made by those skiiled in the art within the principle and scope of the invention as expressed in the appended claims. Thus, the present invention is not intended to be limited to the specific embodiments in the examples given above and/or the attached drawings.

Claims

What is claimed is;
1 . A molecule having the following formula:
M(Ri-N-C(R3)- -R2)u(OR4)x(NR5R6)y(02CR7)z Formula I
or
WI(Ri- -(C(R3)2)m"N-R2)v(OR4)x{NR5R6)y(02C 7)z Formula II wherein:
M is Hf or Zr;
Ri , R2, R5, Re, and R7 are independently selected from the group consisting of H and C1 -C6 alkyl group;
R3 = H, C1 -C6 alkyl group, or NMe2;
■ R4 is a C1 -C6 alkyl group;
m = 2-4;
u = 0-2;
v = 0-1 ;
x = 1-3;
y = 0-2;
z = 0-1 ;
in Formula I, u+x+y+z = 4;
■ in Formula II, 2v+x-t-y÷z = 4; and
u, v, or z >1 .
2. The molecule of claim 1 , the molecule having Formula S, wherein u=1 , x=3, y=0, and z=0.
3. The molecule of claim 2, wherein the molecule is selected from the group consisting of MOPr-N-CfMeJ-N-iPrJ-iiOiPrk, M{iPr-N-C(Me)-N- iPr)i(OMe)3, M(iPr-N-C(Me)-N-iPr)i(OEt)3, MO r-N-CiMeJ-N-iPrMOnPrk, M Pr-N-CiMeJ-N-iPrMOsBu^, M(iPr-N-C(Me)-N-iPr).|{OiBu)3, M(iPr-N-C(Me)- N-iPr)t(OtBu)3, M(Et-N-C( e)-N-Et)i(OEt)3, M(Et-N-C(Me)-N-Et)1(OMe)3l M(Et-N-C(Me)-N-Et)i(OnPr)3, M(Et-N-C(Me)-N-Et)i(OsBu)3, M(Et-N-C(Me)-N- EtMOiBu)^ M(Et-N-C(Me)-N-Et)1(OtBu)3l and M(iPr-N-C(NMe2)-N-iPr)(OiPr)3.
4. The molecule of claim 1 , the molecule having Formula II, wherein v=1 , 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)1(OiPr)2, 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)i{OnPr)2l M(iPr-N-(CH2)2-N-iPr)1(OsBu)2( M(iPr-N-(CH2)2-N-!Pr)1{0!Bu)2, M(iPr-N- (CH2)2-N-iPr)1{OtBu)2, M(Et-N-(CH2)2-N-Et)i(OiPr)2, M(Et-N-(CH2)2-N- Et) (OMe)2, {Et-N-{CH2)2-N-Et)1(OEt)2, M(Et-N-(CH2)2-N-Et)i(OnPr)2, M(Et- N-(CH2)2-N-Et)i(OsBu)2j M(Et-N-(CH2)2-N-Et)i(OiBu)2l M(E†-N-(CH2)2-N- Et)-,(OtBu)2,
Figure imgf000032_0001
(iPr-N-(CH2)3-N-iPr)1(OIvle)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-iPrMOsBufe, M(iPr-N-(CH2)3-N-iPr)i{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)t(OnPr)2, M(Et-N-(CH2)3-N-Et)i(OsBu)2, M(Et- N-(CH2)3-N-Et)1(OiBu)2, and M(Et-N-(CH2)3-N-Et)i(OtBu)2.
6. The molecule of claim 1 , the molecule having Formula I, wherein u=2, x=2, y=0, and z=0.
7. The molecule of claim 6, wherein the molecule is selected from the group consisting of M(iPr-N-C(H)-N-iPr)2(OiPr)2, M(iPr-N-C(H)-N-iPr)2(OMe)2, (iPr-N-C(H)-N-iPr)2(OEt)2, M(iPr-N-C(H)-N-IPr)2(OnPr)2l {iPr-N-C(H)-N- iPr)2(OsBu)2, M(iPr-N-C{H)-N-iPr)2(OiBu)2, (iPr-N-C{H)-N-iPr)2(OtBu)2, M(Et- N-C(H)-N-Et)2(OiPr)2, M(Et-N-C(H)-N-Et)2(OMe)2, M(Et-N-C{H)-N-Et)2(OEt)2, (Et-N-C(H)-N-Et)2(OnPr)2, M(Et-N-C(H)-N-Et)2(OsBu)2l M(Et-N-C(H)-N- Et)2(OiBu)2, M(Et-N-C(H)-N-Et)2(OtBu)2, M(iPr-N-C(Me)-N-iPr)2(OiPr)2l M(iPr- N-C(Me)-N-iPr)2(OMe)2, M(iPr-N-C(Me)-N-iPr)2(OEt)2, M(iPr-N-C(Me)-N- iPr)2(OnPr)2, (iPr-N-C(Me)-N-iPr)2{OsBu)2j M(iPr-N-C(Me)-N-iPr)2(OiBu)2, (iPr-N-C(Me)-N-iPr)2(OtBu)2, M(Et-N-C(Me)-N-Et)2(OiPr)2, M(Et-N-C(Me)-N- Et)2(OMe)2i M(Et-N-C(Me)-N-Et)2(OEt)2, M(Et-N-C(Me)-N-Et)2(OnPr)2, M(Et- N-C(Me)-N-Et)2(OsBu)2, M(Et-N-C{Me)-N-Et)2(OiBu)2, and M(Et-N-C{Me)-N- Et)2(OtBu)2.
8. The molecu!e of claim 1 , the molecule having Formula I, wherein u=1 , x=2, y=1 , and z-0.
9. The molecule of claim 8, wherein the molecule is selected from the group consisting of M(iPr-N-C(Me)-N-iPr)(OiPr)2(NMe2), M(iPr-N-C(Me)-N- iPr)(OiPr)2(NEt2), M{iPr-N-C(Me)-N-iPr)(OiPr)2(NEtMe), M(Et-N-C(Me)-N- Et)(OiPr)2(NMe2)I M(Et-N-C(Me)-N-Et)(OiPr)2(NEt2), M(Et-N-C(Me)-N- Et)(OiPr)2(NEtMe), M(iPr-N-C(NMe2)-N-iPr){OiPr)2(NMe2), M(iPr-N-C{NMe2)- N-iPr)(OiPr)2(NEt2), M(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NEtMe), M(iPr-N-C(Me)- N-iPr)(OiPr)2(N eiPr), M(iPr-N-C(Me)-N-iPr)(OiPr)2(NiPr2), M(iPr-N-C(Me)-N- iPr)(OiPr)2(NMetBu), M(iPr-N-C(Me)-NHPr)(OiPr)2(NneoPentyl2), M(Et-N- C{Me)-N-Et)(OiPr)2(NMeiPr), M(Et-N-C(Me)-N-Et)(OiPr)2(NiPr2), M(Et-N- C(Me)-N-Et)(OiPr)2(NneoPentyl2), M(iPr-N-C(NMe2)-N-iPr){OiPr)2(NMeiPr), M(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NiPr2), M(iPr-N-C(NMe2)-N- iPr)(OiPr)2(NneoPentyl2) and M(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NMeiPr).
10. The molecule of claim 1 , the molecule having Formula I, wherein u=1 , x=2, y=0, and z=1 .
1 1 . The molecule of claim 10, wherein the molecule is selected from the group consisting of M(iPr-N-C(Me)-N-iPr)(OiPr)2(02CMe) and M(Et-N-C(Me)- N-Et){OiPr)2(02CMe).
12. The molecule of claim , the molecule having Formula II, wherein v=1 , x-1 , y=0, and z=1 .
13. The molecule of claim 12, wherein the molecule is selected from the group consisting of M(iPr-N-<CH2}2-N-iPr)(OiPr)(02CMe), M(iPr-N-(CH2)2-N- iPr)(OMe){02CMe), M(iPr-N-(CH2)2-N-iPr)(OEt)(02CMe), M(iPr-N-(CH2)2-N- iPr)(OnPr)(02CMe), (iPr-N-(CH2)2-N-iPr)(OsBu)(02CMe), M(iPr-N-(CH2)2-N- iPr)(OiBu)(02CMe), M(iPr-N-(CH2)2-N-iPr)(OtBu)(02C e), M(Et-N-{CH2)2-N- Et)(OiPr)(02CMe), M(Et-N-(CH2)2-N-Et)(OMe)(02CMe), M(Et-N-(CH2)2-N- Et)(OEt)(02CMe), M(Et-N-(CH2)2-N-Et)(OnPr)(02CMe), M(Et-N-(CH2)2-N- Et)(OsBu){02CMe), {Et-N-(CH2)2-N-Et)(OiBu)(02C e)1 and M(Et-N-<CH2)2- N-Et)(0†Bu)(02CMe).
14. The molecule of claim 1 , the molecule having either Formula ί or Formula II, wherein u, v, y=0, x-2, and z=2.
15. The molecule of claim 14, the molecule being M(OiPr)2(02CMe)2.
16. The molecule of claim , the molecule having either Formula I or Formula II, wherein u, v, y=0, x=3, and z=1 .
17. The molecule of claim 16, the molecule being M(OiPr)3(02CMe).
18. A method of forming a Hf-containing or Zr-containing layer on a substrate, the method comprising:
providing a reaction chamber having at least one substrate disposed therein;
introducing into the reaction chamber a vapor including at least one precursor having the formula:
!VI(R1-N-C(R3)-N-R2)tl(OR4))4(NR5 6)y(02CR7)z Formula I
or
M(RrN-{C( R3)2)m-N-R2)v(OR4)x(NR5R6)y(02CR7)z Formula II wherein:
M is Hf or Zr;
Ri , R2, R5, Re, and R7 are independently selected from the group consisting of H and C1 -C6 alkyl group;
R3 = H, C1-C6 alkyi group, or NMe2;
R4 is a C1-C6 alkyl group; ■ m = 2-4;
u = 0-2;
v = 0-1 ;
x = 1 -3;
y = 0-2;
z = 0-1 ;
■ in Formula i, u+x+y+z = 4;
■ in Formula II, 2v+x+y+z = 4; and
■ u, v, or z >1 ;
contacting the vapor with the substrate to form the Hf-containing or Zr- containing iayer on at Ieast one surface of the substrate using a vapor deposition process.
19. The method of ciaim 18, wherein the at ieast one precursor is selected from the group consisting of M Pr-N-Cf Me^N-iPrMOiPrh, M(iPr-N-C(Me)-N- iPr)1(OMe)3, M(iPr-N-C(Me)-N-iPr)i(OEt)3, MOPr-N-CtMeJ-N-iPrMOnPrk, M(iPr-N-C{Me)-N-iPr)i(OsBu)3, M(iPr-N-C(Me)-N-iPr).|{OiBu)3l M(iPr-N-C(Me)- N-iPr)i(OtBu)3, (Et-N-C(Me)-N-Et)i(OEt)3, M(Et-N-C(Me)-N-Et)1(OMe)3, (Et-N-C(Me)-N-Et)i(OnPr)3l IV Et- -CiMey-N-EtMOsBu)^ (Et-N-C(Me)-N- EtMOiBu)3, (Et-N-C(Me)-N-Et)-i(OtBu)3l M(iPr-N-C(NMe2)-N-iPr)(OiPr)3, M(!Pr-N-(CH2)2-N-iPr)1(OiPr)2, M(iPr-N-(CH2)2-N-iPr)1(OMe)2! M(iPr-N-(CH2)2- N-iPrMOEtfe, M Pr-N^CH^-N-iPrMOnPr , M(iPr-N-(CH2)2-N-iPr)1(OsBu)2, M(iPr-N-(CH2)2-N-iPr)1(OiBu)2, M(iPr-N-(CH2)2-N-iPr)i(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)2l M(Et- N-(CH2)2-N-Et)i(OnPr)2, (Et-N-(CH2)2-N-Et)i(OsBu)2, M(Et-N-(CH2)2-N- Et)1(OiBu)2, M(Et-N-(CH2)2-N-Et)i(OtBu)2, M(iPr-N-(CH2)3-N-iPr)1(OiPr)2i M(iPr-N-(CH2)3-N-iPr)l(OMe)2, (iPr-N-(CH2)3-N-iPr)1(OEt)2j 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)i(OiBu)2, M(iPr-N-(CH2)3-N-iPr)1(OtBu)2, M(Et-N-{CH2)3-N-Et)1(OiPr)2l M(Et-N-(CH2)3-N- Et)i(O e)2 l M(Et-N-(CH2)3-N-Et)i(OEt)2l M(Et-N-{CH2)3-N-Et)1(OnPr)2, M(Et- N-(CH2)3-N-Et)i(OsBu)2, (Et-N-(CH2)3-N-Et)1(OiBu)2, M(Et-N-{CH2)3-N- Et)i(OtBu)2 l M(iPr-N-C(H)-N-iPr)2(OiPr)2, M(iPr-N-C(H)-N-iPr)2(OMe)2! M(iPr- N-C(H)-N-iPr)2(OEt)2, (iPr-N-C{H)-N-iPr)2(OnPr)2, M(iPr-N-C(H)-N- iPr)2(OsBu)2, M(iPr-N-C(H)-N-iPr)2(OiBu)2, M(iPr-N-C(H)-N-iPr)2(OtBu)2> (Et- N-C(H)-N-Et)2(OiPr)2> M{Et-N-C(H)-N-Et)2(OMe)2l M(Ei-N-C(H)-N-Et)2(OEt)2, (Et-N-C(H)-N-Et)2(OnPr)2, M(Et-N-C(H)-N-Et)2(OsBu)2, M(Et-N-C(H)-N- Et)2{OiBu)2, M(Et-N-C(H)-N-Et)2(OtBu)2l M(iPr-N-C(Me)-N-iPr)2(OiPr)2, M(iPr- N-C{Me)-N-iPr)2(OMe)2, M(iPr-N-C(Me)-N-iPr)2(OEt)2) M(iPr-N-C(Me)-N- iPr)2(OnPr)2, M(iPr-N-C(Me)-N-iPr)2(OsBu)2l M(iPr-N-C(Me)-N-iPr)2(OiBu)2, M(iPr-N-C(Me)-N-iPr)2(OtBu)2> M(Ei-N-C(Me)-N-Ei)2(OiPr)2! (Et-N-C(Me)-N- Et)2(OMe)2, M(Et-N-C(Me)-N-Et)2(OEt)2, M(Et-N-C(Me)-N-Et)2(OnPr)2, M(Et- N-C(Me)-N-Et)2{OsBu)2! M(Et-N-C(Me)-N-Et)2(OiBu)2l M(Et-N-C(Me)-N- Et)2(OtBu)2, M(iPr-N-C(Me)-N-iPr)(OiPr)2(NMe2), M(iPr-N-C(Me)-N- iPr)(OiPr)2(NEt2), M{iPr-N-C(Me}-N-iPr)(OiPr)2(NEt e), M(Et-N-C(Me)-N- Et)(OiPr)2(NMe2), M<Et-N-C(Me)-N-Et)(OiPr)2(NE†2), M(Et-N-C(Me)-N- Et)(OiPr)2(NEtMe), M(iPr-N-C(NMe2)-N-iPr)(OiPr)2(NMe2), M(iPr-N-C(NMe2)- N-iPr)(OiPr)2{NEt2), M(iPr-N-C(N e2)-N-iPr)(OiPr)2(NEiMe), M(iPr-N-C(Me)- N-iPr)(OiPr)2{02CMe), M(Et-N-C(Me)-N-Et)(OiPr)2(02CMe), (iPr-N-(CH2)2-N- iPr)(OiPr)(02C e), M(iPr-N-(CH2)2-N-iPr)(OMe)(02CMe), (iPr-N-{CH2)2-N- iPr)(OEt)(02CMe), M(iPr-N-{CH2)2-N-iPr)(OnPr)(02CMe), M(iPr-N-(CH2)2-N- iPr)<OsBu)(02CMe), M{iPr-N-(CH2)2-N-iPr)(OiBu)(02CMe), M(IPr-N-(CH2)2-N- iPr)(OtBu)(02CMe)( M(Et-N-(CH2)2-N-Et)(OiPr)(02CMe), M(Et-N-(CH2)2-N- Ei)(OMe)(02CMe), M(Et-N-(CH2)2-N-Et)(OEt)(02CMe), M(Et-N-(CH2)2-N- Et)(OnPr)(02CMe), M(Et-N-(CH2)2-N-Et)(OsBu)(02C e), M{Et-N-(CH2)2-N- Et)(OiBu)(02C e)1 M(Et-N-(CH2)2-N-Et)(OtBu)(02CMe), M(OiPr)2(02CMe)2, and M(OiPr)3(02CMe).
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019507750A (en) * 2016-02-12 2019-03-22 シースター ケミカルズ ユーエルシー Organometallic compounds and methods
JP2023545900A (en) * 2020-09-08 2023-11-01 ハンソル ケミカル カンパニー リミテッド Group 4 metal element-containing compound, precursor composition containing the same, and method for producing a thin film using the same

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* Cited by examiner, † Cited by third party
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CN105284188B (en) * 2013-06-11 2017-04-26 柯尼卡美能达株式会社 Method for manufacturing organic electroluminescent element
US9666593B2 (en) 2014-09-29 2017-05-30 Sandisk Technologies Llc Alternating refractive index in charge-trapping film in three-dimensional memory
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006045083A (en) * 2004-08-02 2006-02-16 Asahi Denka Kogyo Kk Thin film forming raw material, thin film manufacturing method and metal compound
US20080280455A1 (en) * 2005-06-28 2008-11-13 Micron Technology, Inc. Atomic layer deposition systems and methods including metal beta-diketiminate compounds
US20090275199A1 (en) * 2005-06-28 2009-11-05 Micron Technology, Inc. Unsymmetrical ligand sources, reduced symmetry metal-containing compounds, and systems and methods including same
US20100003532A1 (en) * 2008-06-06 2010-01-07 Feist Benjamin J Beta-diketiminate precursors for metal containing film deposition
KR20100016477A (en) * 2007-04-12 2010-02-12 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 Zirconium, hafnuim, titanium, and silicon precursors for ald/cvd

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6511936B1 (en) 1998-02-12 2003-01-28 University Of Delaware Catalyst compounds with β-diminate anionic ligands and processes for polymerizing olefins
KR100584200B1 (en) 2004-02-13 2006-05-29 한국화학연구원 Titanium oxide precursor and its manufacturing method
KR100581993B1 (en) * 2004-06-09 2006-05-22 삼성전자주식회사 Material formation method using atomic layer deposition
WO2006012052A2 (en) 2004-06-25 2006-02-02 Arkema, Inc. Amidinate ligand containing chemical vapor deposition precursors
KR100640654B1 (en) 2005-07-16 2006-11-01 삼성전자주식회사 Method of forming a rho2 thin film and a method of manufacturing a capacitor of a semiconductor memory device including the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006045083A (en) * 2004-08-02 2006-02-16 Asahi Denka Kogyo Kk Thin film forming raw material, thin film manufacturing method and metal compound
US20080280455A1 (en) * 2005-06-28 2008-11-13 Micron Technology, Inc. Atomic layer deposition systems and methods including metal beta-diketiminate compounds
US20090275199A1 (en) * 2005-06-28 2009-11-05 Micron Technology, Inc. Unsymmetrical ligand sources, reduced symmetry metal-containing compounds, and systems and methods including same
KR20100016477A (en) * 2007-04-12 2010-02-12 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 Zirconium, hafnuim, titanium, and silicon precursors for ald/cvd
US20100003532A1 (en) * 2008-06-06 2010-01-07 Feist Benjamin J Beta-diketiminate precursors for metal containing film deposition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019507750A (en) * 2016-02-12 2019-03-22 シースター ケミカルズ ユーエルシー Organometallic compounds and methods
JP7072511B2 (en) 2016-02-12 2022-05-20 シースター ケミカルズ ユーエルシー Organometallic compounds
US11802134B2 (en) 2016-02-12 2023-10-31 Seastar Chemicals Ulc Organometallic compound and method
JP2023545900A (en) * 2020-09-08 2023-11-01 ハンソル ケミカル カンパニー リミテッド Group 4 metal element-containing compound, precursor composition containing the same, and method for producing a thin film using the same
JP7636525B2 (en) 2020-09-08 2025-02-26 ハンソル ケミカル カンパニー リミテッド Group 4 metal element-containing compound, precursor composition containing same, and method for producing thin film using same
US12365700B2 (en) 2020-09-08 2025-07-22 Hansol Chemical Co., Ltd. Group 4 metal element-containing compound, precursor composition including same, and method for manufacturing thin film using same

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