WO2015190871A1 - Liquid precursor compositions, preparation methods thereof, and methods for forming layer using the composition - Google Patents

Liquid precursor compositions, preparation methods thereof, and methods for forming layer using the composition Download PDF

Info

Publication number
WO2015190871A1
WO2015190871A1 PCT/KR2015/005945 KR2015005945W WO2015190871A1 WO 2015190871 A1 WO2015190871 A1 WO 2015190871A1 KR 2015005945 W KR2015005945 W KR 2015005945W WO 2015190871 A1 WO2015190871 A1 WO 2015190871A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid precursor
precursor composition
dad
metal compound
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2015/005945
Other languages
English (en)
French (fr)
Inventor
Won Seok Han
Wonyong Koh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UP Chemical Co Ltd
Original Assignee
UP Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UP Chemical Co Ltd filed Critical UP Chemical Co Ltd
Priority to KR1020167012801A priority Critical patent/KR101936162B1/ko
Priority to KR1020167001280A priority patent/KR20160017094A/ko
Priority to CN201580031286.2A priority patent/CN106460169B/zh
Priority to JP2016572630A priority patent/JP6635950B2/ja
Publication of WO2015190871A1 publication Critical patent/WO2015190871A1/en
Priority to US15/199,705 priority patent/US10014089B2/en
Anticipated expiration legal-status Critical
Priority to US16/002,304 priority patent/US10763001B2/en
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • 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
    • C23C16/06—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 metallic material
    • C23C16/18—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 metallic material from metallo-organic compounds
    • 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
    • C23C16/406—Oxides of iron group metals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • 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
    • C23C16/06—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 metallic material
    • 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
    • C23C16/44—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 method of coating
    • C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
    • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD

Definitions

  • the present disclosure relates to liquid precursor compositions, preparation methods of the liquid precursor compositions, and methods for forming layers using the liquid precursor composition.
  • Chemical vapor deposition (CVD) and atomic layer deposition (ALD) provide methods for forming metal-containing layers on target substrates by supplying gases containing metal compounds to a deposition chamber or other deposition equipment. They have been widely used to manufacture electronic devices, semiconductor devices, display devices, and so on. Particularly, the semiconductor industry needs novel metal compounds and/or compositions for depositing metal-containing layers, such as metal layers, metal silicide layers, metal oxide layers, and metal nitride layers with desirable properties.
  • Amidinate compounds of nickel or cobalt have been used as precursors for ALD [B. S. Lim, A. Rahtu, J. S. Park, and R. G. Gordon, Inorganic Chemistry, 42, 7951 (2003)].
  • compositions having a high content of the amidinate compounds are in a solid state at room temperature and thus are not suitable for volume production of semiconductor devices using CVD or ALD.
  • Carbonyl compounds of cobalt or nickel are also in solid state at room temperature and thus not suitable for volume production of semiconductor devices using CVD or ALD.
  • a few liquid cobalt precursors such as dicobalt hexacarbonyl tert-butylacetylene (CCTBA) or cyclopentadielycobalt dicarbonyl [(C 5 H 5 )Co(CO) 2 ] are available commercially; however, they have to be used at a relatively low deposition temperature because they are not thermally stable.
  • Few liquid nickel precursors are known and none is available commercially. And thus the semiconductor industry needs a liquid precursor composition for vapor deposition of cobalt- or nickel-containing layers.
  • one purpose of the present disclosure is to provide liquid precursor compositions that can be used, for example, for deposition, methods for preparing the liquid precursor compositions, and methods for forming metal or metal compound-containing layers using the liquid precursor compositions.
  • liquid precursor compositions including: metal compounds represented by the following Chemical Formula 1:
  • M denotes Co or Ni
  • DAD denotes a diazadiene ligand compound represented by R 1 NC(R 3 )C(R 4 )NR 2 , wherein each of R 1 to R 4 includes independently H; or a linear or branched C 1-5 alkyl group.
  • the methods comprise reacting a mixture containing a halogenated metal compound represented by MX 2 or a halogenated metal complex compound represented by ZMX 2 (where M is Co or Ni; X is a halogen; and Z is one or more neutral ligands), a diazadiene ligand compound represented by DAD, and an alkali metal in a solvent.
  • Z may be any neutral ligand(s) commonly known in the art, which preferably does not interfere with the synthesis of M(DAD) 2 ;
  • Z may be at least one neutral ligand selected from the group consisting of 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), 2-methoxyethyl ether, ammonia (NH 3 ), pyridine, N,N,N',N'-tetramethyl-1,2-ethylenediamine, tricyclohexylphosphine, triphenylphosphine, 1,2-Bis(diphenylphosphino)ethane, and 1,3-Bis(diphenylphosphino)propane.
  • X may be Cl, Br or I.
  • the DAD compound and alkali metal are not combined prior to the combination of either (a) the DAD compound with the halogenated metal compound or halogenated metal complex compound or (b) the alkali metal with the halogenated metal compound or halogenated metal complex compound.
  • the reaction may be followed by purification to obtain a composition containing a metal compound represented by the following Chemical Formula 1:
  • M denotes Co or Ni
  • DAD denotes diazadiene ligand compound represented by R 1 NC(R 3 )C(R 4 )NR 2 ,
  • each of R 1 to R 4 includes independently H; or a linear or branched alkyl group of C 1-5 .
  • the mixture may be obtained by mixing the halogenated metal compound or halogenated metal complex compound with the diazadiene ligand compound DAD, and then subsequently adding the alkali metal.
  • the mixture may be obtained by mixing the halogenated metal compound or halogenated metal complex compound with the alkali metal, and then adding the diazadiene ligand compound DAD.
  • methods are provided for forming a layer, such as by vapor deposition, for example by CVD or ALD.
  • the methods comprise depositing a layer containing a metal or metal compound using a liquid precursor composition in accordance with the first aspect of the present disclosure as represented by the following Chemical Formula 1:
  • M denotes Co or Ni
  • DAD denotes a diazadiene ligand compound represented by R 1 NC(R 3 )C(R 4 )NR 2 , wherein each of R 1 to R 4 includes independently H; or a linear or branched C 1-5 alkyl group.
  • the metal compound of Chemical Formula 1 is at least about 80% or more, about 85% or more, about 90% or more, or 95% or more of the liquid precursor composition.
  • the content may be determined by, for example, chromatography.
  • the chromatography may be a gas chromatography, but is not limited thereto.
  • the purity of the liquid precursor composition may be at least about 80% or more, about 85% or more, about 90% or more, or 95% or more. That is, in some embodiments, impurities (components other than the metal compound of Chemical Formula 1) may be about 20% or less, about 15% or less, about 10% or less or even about 5% or less.
  • the purity may also be determined by, for example, chromatography. In some embodiments, the chromatography may be a gas chromatography, but is not limited thereto.
  • a liquid precursor composition in accordance with some exemplary embodiments of the present disclosure, or a liquid source material prepared from the liquid precursor composition, is advantageous in forming layers containing a metal or metal compound, particularly nickel or cobalt.
  • the liquid precursor composition may be used to deposit a cobalt or nickel metallic film.
  • the metallic film may comprise at least about 80 at% nickel or cobalt.
  • liquid precursor compositions in accordance with exemplary embodiments of the present disclosure may also be used in forming layers of a cobalt compound or a nickel compound, such as a cobalt silicide layer, a cobalt oxide layer, a cobalt nitride layer, a nickel oxide layer, a nickel nitride layer, a nickel silicide layer, etc.
  • a cobalt compound or a nickel compound such as a cobalt silicide layer, a cobalt oxide layer, a cobalt nitride layer, a nickel oxide layer, a nickel nitride layer, a nickel silicide layer, etc.
  • the liquid precursor compositions in accordance with exemplary embodiments of the present disclosure have a high purity.
  • the use of high-purity compositions can increase the reproducibility of a volume production process of semiconductor devices, which is advantageous in manufacturing semiconductor devices with uniform properties.
  • the use of a high-purity composition as disclosed herein can avoid other problems associated with the use of low-purity compositions. For example, when a low-purity precursor composition containing a significant amount of impurities is used, semiconductor devices may not have uniform properties in each batch due to low reproducibility of a semiconductor device manufacturing process and a lot of defective semiconductor devices may be produced. In some embodiments such problems may be avoided using the compositions provided herein.
  • FIG. 1 is a flow chart showing a method for preparing a liquid precursor in accordance with an illustrative embodiment of the present disclosure.
  • FIG. 2 is a flow chart showing a method for preparing a liquid precursor in accordance with an illustrative embodiment of the present disclosure.
  • FIG. 3 is a flow chart showing a method for preparing a liquid precursor in accordance with an illustrative embodiment of the present disclosure.
  • FIG. 4A and FIG. 4B show a gas chromatography-flame ionization detector (GC-FID) analysis results of a liquid precursor composition containing Co( i Pr-DAD) 2 which was prepared in accordance with Example 1.
  • GC-FID gas chromatography-flame ionization detector
  • FIG. 5 shows a gas chromatography-mass spectroscopy (GC-MS) analysis result of the liquid precursor composition containing Co( i Pr-DAD) 2 which was prepared in accordance with Example 1.
  • GC-MS gas chromatography-mass spectroscopy
  • FIG. 6A and FIG. 6B show a GC-FID analysis results of a liquid precursor composition which containing Co( i Pr-DAD) 2 which was prepared in accordance with Example 2.
  • FIG. 7A and FIG. 7B show a GC-FID analysis results of a liquid precursor composition which containing Co( i Pr-DAD) 2 which was prepared in accordance with Comparative Example 1.
  • FIG. 8 shows a GC-MS analysis result of the liquid precursor composition containing Co( i Pr-DAD) 2 which was prepared in accordance with Comparative Example 1.
  • FIG. 9A and FIG. 9B show a GC-FID analysis results of a liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Example 3.
  • FIG. 10 shows a NMR spectrum of the liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Example 3.
  • FIG. 11A and FIG. 11B show a GC-FID analysis results of a liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Example 4.
  • FIG. 12 shows a NMR spectrum of the liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Example 4.
  • FIG. 13A and FIG. 13B show a GC-FID analysis results of a liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Example 5.
  • FIG. 14 shows a NMR spectrum of the liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Example 5.
  • FIG. 15A and FIG. 15B show a GC-FID analysis results of a liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Example 6.
  • FIG. 16 shows a NMR spectrum of the liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Example 6.
  • FIG. 17A and FIG. 17B show a GC-FID analysis results of a liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Comparative Example 2.
  • FIG. 18 shows a NMR spectrum of the liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Comparative Example 2.
  • FIG. 19A and FIG. 19B show a GC-FID analysis results of a liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Comparative Example 3.
  • FIG. 20 shows a NMR spectrum of the liquid precursor composition containing Ni( i Pr-DAD) 2 which was prepared in accordance with Comparative Example 3.
  • FIG. 21 shows an analysis result of an atomic composition depending on a depth of a cobalt-containing layer deposited in accordance with Example 7 using Auger electron spectroscopy.
  • FIG. 22 shows an analysis result of an atomic composition depending on a depth of a layer deposited in accordance with Comparative Example 4 using Auger electron spectroscopy.
  • FIG. 23 shows an analysis result of an atomic composition depending on a depth of a nickel-containing layer deposited in accordance with Example 8 using Auger electron spectroscopy.
  • FIG. 24A and FIG. 24B are scanning electron microscopic images of a surface and a cross section of the nickel-containing layer deposited in accordance with Example 8.
  • FIG. 25 shows a tunneling electron microscopy (TEM) diffraction pattern image of the cobalt oxide layer deposited in accordance with Example 9.
  • TEM tunneling electron microscopy
  • FIG. 26 shows a thermogravimetry analysis (TGA) result of a liquid precursor composition prepared in accordance with Example 1.
  • FIG. 27 shows a differential scanning calorimetry (DSC) analysis result of the liquid precursor composition prepared in accordance with Example 1.
  • a and/or B means "A or B, or A and B".
  • alkyl may include a linear or branched alkyl group having carbon atoms in a number ranging from 1 to 5.
  • the alkyl group may be methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, sec-butyl group, etc., but may not be limited thereto.
  • halogenated metal compound refers to a halogenated metal compound represented by MX 2 or a halogenated metal complex compound represented by ZMX 2 , where X is a halogen and Z is one or more neutral ligands such as DME, THF, 2-methoxyethyl ether, ammonia, pyridine, N,N,N',N'-tetramethyl-1,2-ethylenediamine, tricyclohexylphosphine, triphenylphosphine, 1,2-Bis(diphenylphosphino)ethane, or 1,3-Bis(diphenylphosphino)propane.
  • Z may be any other neutral ligand commonly known in the art. However, the neutral ligand preferably does not interfere the synthesis of M(DAD) 2 .
  • the halogenated metal complex compound represented by ZMX 2 may include a complex compound or its derivative, such as (DME)NiBr 2 , in which a neutral ligand such as 1,2-dimethoxyethane (DME) is combined with a halogenated metal compound.
  • a complex compound or its derivative such as (DME)NiBr 2
  • a neutral ligand such as 1,2-dimethoxyethane (DME) is combined with a halogenated metal compound.
  • it may be a complex compound or its derivative combined with a neutral ligand such as tetrahydrofuran (THF) or 2-methoxyethyl ether.
  • THF tetrahydrofuran
  • 2-methoxyethyl ether 2-methoxyethyl ether
  • it may be a complex compound or its derivative, such as Ni(NH 3 ) 6 Br 2 , in which neutral ligands, such as six ammonias, are combined with a
  • any and all conventionally known methods can be used.
  • a known chromatography method may be used to separate components and determine contents, constituents, or purity of the components.
  • the content or composition, of a liquid precursor composition or other composition with respect to a specific component can be determined on the basis of a ratio of an area of a peak for the specific component relative to the sum of areas of all the detected peaks.
  • the purity of the liquid precursor can be also be determined on the basis of a ratio of an area of a peak for the specific compound of interest, typically M(DAD) 2 , relative to all other components.
  • the content can be presented as the percentage (%) of the area of the peak for the specific component of interest (typically M(DAD) 2 ) relative to the sum of the areas of all detected peaks.
  • purity can be presented as the % of the specific component of interest relative to the total components or as the % of components (impurities) other than the component of interest (typically M(DAD) 2 ) relative to the total components.
  • Commercial chromatography devices can be used and will generally output an analysis result showing contents, constituents, or purity expressed by % together with chromatograms.
  • a gas chromatography (GC) device using a flame ionization detector (FID) can be used, as has been widely used in the art to measure contents, compositions, or purity.
  • a liquid precursor composition may be combined with one or more additional components, such as diluents, to form, for example, a liquid source material.
  • additional components such as diluents
  • the content and purity of the liquid precursor composition, with respect to the compound of interest typically M(DAD) 2
  • M(DAD) 2 may differ from the content and purity of a liquid source material.
  • liquid precursor compositions are provided.
  • the liquid precursor composition may be used for depositing a layer containing a metal, such as Ni or Co, or metal compound, such as a Ni- or Co-containing compound.
  • the liquid precursor compositions may be used for depositing a metal-containing layer, such as a Ni- or Co-containing layer, by a vapor deposition process.
  • the liquid precursor compositions may be used in metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD) processes.
  • MOCVD metal organic chemical vapor deposition
  • ALD atomic layer deposition
  • the liquid precursor compositions comprise a metal compound represented by the following Chemical Formula 1:
  • M denotes Co or Ni
  • DAD denotes a diazadiene ligand compound represented by R 1 NC(R 3 )C(R 4 )NR 2 , wherein each of R 1 to R 4 may be independently H, or a linear or branched C 1-5 alkyl group.
  • HNCHCHNH may be abbreviated as H-DAD
  • MeNCHCHNMe may be abbreviated as Me-DAD
  • EtNCHCHNEt may be abbreviated as Et-DAD
  • n PrNCHCHN n Pr may be abbreviated as n Pr-DAD
  • i PrNCHCHN i Pr may be abbreviated as i Pr-DAD
  • n BuNCHCHN n Bu may be abbreviated as n Bu-DAD
  • t BuNCHCHN t Bu may be abbreviated as t Bu-DAD
  • sec BuNCHCHN sec Bu may be abbreviated as sec Bu-DAD.
  • Me represents a methyl group
  • Et represents an ethyl group
  • n Pr represents n-propyl group
  • i Pr represents isopropyl group
  • n Bu represents n-butyl group
  • t Bu represents tert-butyl group
  • sec Bu represents a sec-butyl group.
  • the diazadiene ligand may include one in which either independently or both of R 1 and R 2 may be an isopropyl group or tert-butyl group, and both of R 3 and R 4 may be H, but is not intended to be limited thereto.
  • the diazadiene ligand may include i Pr-DAD or t Bu-DAD, but is not intended to be limited thereto.
  • a liquid precursor composition may comprise Co( i PrNCHCHN i Pr) 2 [abbreviation: Co( i Pr-DAD) 2 ], which may have a molecular weight of about 339 g/mol.
  • a liquid precursor composition may comprise compound Ni( i PrNCHCHN i Pr) 2 [abbreviation: Ni( i Pr-DAD) 2 ], which may have a molecular weight of about 339 g/mol.
  • the metal compound of Chemical Formula 1 is at least about 80% or more, about 85% or more, about 90% or more, or 95% or more of the liquid precursor composition.
  • the content may be determined by, for example, chromatography as mentioned above.
  • the chromatography may be a gas chromatography, but is not limited thereto.
  • a liquid precursor composition may consist substantially or essentially of the metal compound of Chemical Formula 1.
  • the purity of the liquid precursor composition with respect to the metal compound of Chemical Formula 1 may be at least about 80% or more, about 85% or more, about 90% or more, or 95% or more. That is, impurities (components other than the metal compound of Chemical Formula 1) are about 20% or less, about 15% or less, about 10% or less or even about 5% or less.
  • the purity may be determined by, for example, chromatography. In some embodiments, the chromatography may be a gas chromatography, but is not limited thereto.
  • the liquid precursor composition may be diluted or otherwise mixed with one or more additional components to form a liquid source material.
  • the liquid precursor composition may be mixed with one or more inert ingredients, such as an inert diluent, for storage or use.
  • a liquid source material comprising the liquid precursor composition may be used in some embodiments described herein rather than using the liquid precursor composition directly.
  • the composition and purity of the liquid precursor composition, with respect to the M(DAD) 2 compound may differ from the composition and purity of a liquid source material due to the presence of additional compounds in the liquid precursor composition.
  • the composition and purity of a liquid precursor composition is provided herein, the composition and purity is given relative to the liquid precursor composition itself and does not take into account any additional ingredients with which the liquid precursor composition may be combined, such as diluents.
  • At least about 80% or more, about 85% or more, about 90% or more, or 95% or more of the liquid precursor composition is the compound Co( i PrNCHCHN i Pr) 2 .
  • the content of the liquid precursor composition may be determined by, for example, chromatography.
  • the chromatography may be a gas chromatography, but is not limited thereto.
  • the purity of a liquid precursor composition comprising Co( i PrNCHCHN i Pr) 2 may be about 80% or more, about 85% or more, about 90% or more, or 95% or more, but is not limited thereto. That is, impurities (components other than the metal compound Co( i PrNCHCHN i Pr) 2 ) may be about 20% or less, about 15% or less, about 10% or less or even about 5% or less.
  • the purity may be determined by, for example, chromatography. In some embodiments, the chromatography may be a gas chromatography, but is not limited thereto.
  • At least about 80% or more, about 85% or more, about 90% or more, or 95% or more of a liquid precursor composition is the compound Ni( i PrNCHCHN i Pr) 2 .
  • the content of the liquid precursor composition may be determined by, for example, chromatography.
  • the chromatography may be gas chromatography, but is not limited thereto.
  • the purity of the liquid precursor composition comprising Ni( i PrNCHCHN i Pr) 2 may be about 80% or more, about 85% or more, about 90% or more, or 95% or more, but is not limited thereto. That is, impurities (components other than the metal compound Ni( i PrNCHCHN i Pr) 2 ) are about 20% or less, about 15% or less, about 10% or less or even about 5% or less.
  • the purity may be determined by, for example, chromatography. In some embodiments, the chromatography may be a gas chromatography, but is not limited thereto.
  • a liquid precursor composition may consist substantially or essentially of the metal compound represented by Co( i PrNCHCHN i Pr) 2 .
  • the liquid precursor composition may have a molecular weight of about 339 g/mol.
  • the liquid precursor composition may consist substantially or essentially of the metal compound represented by Ni( i PrNCHCHN i Pr) 2 . In some embodiments, the liquid precursor composition may have a molecular weight of about 339 g/mol.
  • the methods comprise: reacting a mixture containing a halogenated metal compound represented by MX 2 or a halogenated metal complex compound represented by ZMX 2 (where M is Ni or Co; X is a halogen; and Z is one or more neutral ligands), a diazadiene ligand compound DAD, and an alkali metal in a solvent (S100), followed by purification (S200).
  • Z may be selected from the group consisting of DME, THF, 2-methoxyethyl ether, ammonia, pyridine, N,N,N',N'-tetramethyl-1,2-ethylenediamine, tricyclohexylphosphine, triphenylphosphine, 1,2-Bis(diphenylphosphino)ethane, and 1,3-Bis(diphenylphosphino)propane.
  • Z may be any neutral ligand commonly known in the art, preferably one that does not interfere the synthesis of M(DAD) 2 .
  • the DAD and alkali metal are not combined prior to the combination of one or both of the DAD and/or alkali metal with the halogenated metal compound or halogenated metal complex compound.
  • a liquid precursor composition containing a metal compound represented by the following Chemical Formula 1 is obtained:
  • M denotes Co or Ni
  • DAD denotes a diazadiene ligand compound represented by R 1 NC(R 3 )C(R 4 )NR 2 ,
  • each of R 1 to R 4 includes independently H; or a linear or branched alkyl group of C 1-5
  • At least about 80% or more, about 85% or more, about 90% or more, or 95% or more of the liquid precursor composition obtained by the preparation methods is a metal compound of Chemical Formula 1.
  • the preparation process may produce a liquid precursor composition that includes some amount of components other than the metal compound of Chemical Formula 1.
  • the liquid precursor composition obtained by the preparation methods may have a purity with respect to Chemical Formula 1 of about 80% or more, about 85% or more, about 90% or more, or 95% or more, but may not be limited thereto. That is, impurities (components other than the metal compound of Chemical Formula 1) are about 20% or less, about 15% or less, about 10% or less or even about 5% or less.
  • the content and/or purity may be determined by, for example, chromatography.
  • the chromatography may be gas chromatography, but is not limited thereto.
  • the purification may be performed by a single or multiple step(s) of reduced-pressure distillation, but the purification is not limited thereto and may be carried out by other methods known in the art. In some embodiments, one, two or three reduced-pressure distillation steps are carried out.
  • the liquid precursor compositions obtained by the preparation methods may be used for depositing a metal-containing layer by vapor deposition, such as by organic metal chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but not limited thereto.
  • vapor deposition such as by organic metal chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but not limited thereto.
  • MOCVD organic metal chemical vapor deposition
  • ALD atomic layer deposition
  • At least about 80% or more, about 85% or more, about 90% or more, or 95% or more of the liquid precursor composition obtained by the preparation methods may be the compound Co( i PrNCHCHN i Pr) 2 .
  • the content may be determined by, for example, using chromatography.
  • the chromatography may be gas chromatography, but is not limited thereto.
  • the purity of the liquid precursor composition with respect to the metal compound Co( i PrNCHCHN i Pr) 2 and obtained by the preparation methods may be about 80% or more, about 85% or more, about 90% or more, or 95% or more, but is not limited thereto. That is, impurities (components other than the metal compound Co( i PrNCHCHN i Pr) 2 ) may be about 20% or less, about 15% or less, about 10% or less or even about 5% or less in some embodiments.
  • the purity may be determined by, for example, using chromatography. In some embodiments, the chromatography may be gas chromatography, but is not limited thereto.
  • the preparation methods are used to produce Co( i PrNCHCHN i Pr) 2 [abbreviation: Co( i Pr-DAD) 2 ], which may have a molecular weight of about 339 g/mol.
  • At least about 80% or more, about 85% or more, about 90% or more, or 95% or more of the liquid precursor composition obtained by the preparation methods may be the metal compound represented by Ni( i PrNCHCHN i Pr) 2 .
  • the content may be determined by, for example, using chromatography.
  • the chromatography may be gas chromatography, but is not limited thereto.
  • the purity of the liquid precursor composition with respect to the metal compound Ni( i PrNCHCHN i Pr) 2 and obtained by the preparation methods may be about 80% or more, about 85% or more, about 90% or more, or 95% or more, but is not limited thereto. That is, impurities (components other than the metal compound Ni( i PrNCHCHN i Pr) 2 ) are about 20% or less, about 15% or less, about 10% or less or even about 5% or less.
  • the purity may be determined by, for example, using chromatography. In some embodiments, the chromatography may be gas chromatography, but is not limited thereto.
  • the preparation methods are used to produce Ni( i PrNCHCHN i Pr) 2 [abbreviation: Ni( i Pr-DAD) 2 ], which may have a molecular weight of about 339 g/mol.
  • the liquid precursor composition formed by the preparation methods may consist substantially or essentially of the metal compound represented by Co( i PrNCHCHN i Pr) 2 .
  • the liquid precursor composition formed by the preparation methods may consist substantially or essentially of the metal compound represented by Ni( i PrNCHCHN i Pr) 2 .
  • a mixture is formed containing one equivalent of a halogenated metal compound represented by MX 2 or a halogenated metal complex compound represented by ZMX 2 (where M is Ni or Co; X is a halogen; and Z is one or more neutral ligand(s)), about two equivalents of a diazadiene ligand compound DAD, and about two equivalents of an alkali metal in a solvent.
  • the mixture is reacted to form a reaction product (S100), which can then be purified as described above to form a liquid precursor composition comprising a metal compound represented by Chemical Formula 1 (M(DAD) 2 ) (S200).
  • the metal compound makes up at least about 80%, about 85%, about 90%, about 95% or more of the liquid precursor composition.
  • the DAD compound and the alkali metal are not reacted together initially.
  • the DAD compound and alkali metal are not combined prior to the combination of either (a) the DAD compound with the halogenated metal compound or halogenated metal complex compound or (b) the alkali metal with the halogenated metal compound or halogenated metal complex compound.
  • the mixture is obtained by mixing the halogenated metal compound represented by MX 2 or halogenated metal complex compound represented by ZMX 2 with the diazadiene ligand compound DAD (S50), and then subsequently adding the alkali metal (S60).
  • the alkali metal is not dissolved but remains in a solid state until it is added to the mixture.
  • the alkali metal may be dissolved while adding the alkali metal; or the alkali metal may be dissolved after completely adding the alkali metal.
  • the alkali metal may be added at a very low temperature at which no dissolution of the alkali metal occurs (S60), and then subsequently the mixture warms up to be reacted while the dissolution of the alkali metal occurs (S100).
  • the alkali metal may be added at a temperature at which the dissolution of the alkali metal occurs and thus the reaction of the mixture occurs while adding the alkali metal, which means that S60 and S100 in FIG. 2 occur concurrently.
  • the mixture may be obtained by mixing the halogenated metal compound represented by MX 2 or halogenated metal complex compound represented by ZMX 2 with the alkali metal (S70), and then subsequently adding the diazadiene ligand compound DAD (S80).
  • the alkali metal is not dissolved but remains in a solid state.
  • a dissolution reaction of the alkali metal occurs (S100).
  • the dissolution of the alkali metal may occur while adding the DAD compound; or it may occur after completely adding the DAD compound.
  • the DAD compound may be added at a very low temperature at which no dissolution of the alkali metal occurs (S80), and then subsequently the mixture warms up to be reacted while the dissolution of the alkali metal occurs (S100).
  • the DAD compound may be added at a temperature at which the dissolution of the alkali metal occurs and thus the reaction of the mixture occurs while adding the alkali metal, which means that S80 and S100 in FIG. 3 occur concurrently.
  • a composition which is prepared by mixing two equivalents of an alkali metal with two equivalents of a diazadiene ligand compound DAD to completely dissolve the alkali metal, and then, subsequently adding one equivalent of the halogenated metal compound represented by MX 2 or halogenated metal complex compound represented by ZMX 2 , is greatly different from a composition prepared in accordance with the exemplary embodiments disclosed above, both in terms of gas chromatography analysis results and deposition results of a layer containing a metal or metal compound by CVD or ALD.
  • a liquid precursor composition wherein at least about 80% or more of the liquid precursor composition is a metal compound represented by the Chemical Formula 1 is not produced.
  • such a process does not produce a composition which has a purity of at least about 80%.
  • a preparation process for preparing a liquid precursor composition comprising a compound of Chemical Formula 1 comprises a reaction scheme as represented by the following Reaction Formula 1 or 2.
  • Reaction Formula 1 a mixture is formed of a diazadiene ligand DAD represented by the following Chemical Formula 2 and the halogenated metal compound represented by MX 2 or halogenated metal complex compound represented by ZMX 2 .
  • an alkali metal (M') is added to the mixture to allow a reaction therebetween and the production of the M(DAD) 2 product.
  • a single or multiple step(s) of reduced-pressure distillation may then be carried out for purification. For example, one, two or three reduced-pressure distillations may be carried out.
  • a mixture of a halogenated metal compound represented by MX 2 or halogenated metal complex compound represented by ZMX 2 and an alkali metal (M') diazadiene is prepared.
  • the ligand DAD represented by the following Chemical Formula 2 is added to the mixture to allow reaction there between, which produces M(DAD) 2 .
  • a single or multiple step(s) of reduced-pressure distillation can then be performed for purification. For example, one, two or three reduced-pressure distillations may be carried out.
  • M denotes Co or Ni
  • DAD denotes a diazadiene ligand compound represented by R 1 NC(R 3 )C(R 4 )NR 2 , wherein each of R 1 to R 4 includes independently H, or a linear or branched C 1-5 alkyl group
  • X is a halogen and in some embodiments may be Cl, Br, or I
  • M' is an alkali metal and in some embodiments may be selected from the group consisting of Li, Na, K, Rb, and Cs
  • Z is one or more neutral ligands and in some embodiments may be at least one selected from the group consisting of DME, THF, 2-methoxyethyl ether, ammonia, pyridine, N,N,N',N'-tetramethyl-1,2-ethylenediamine, tricyclohexylphosphine, triphenylphosphine, 1,2-Bis(diphenylphosphino)ethane, 1,3-Bis(diphen
  • a reaction mixture is prepared by mixing a diazadiene ligand compound and a halogenated metal compound represented by MX 2 or halogenated metal complex compound represented by ZMX 2 in an organic solvent.
  • the halogenated metal compound or halogenated metal complex compound may be dissolved in the organic solvent or may be dispersed in the form of powder in the organic solvent.
  • an alkali metal may be added with stirring.
  • the added alkali metal may be dissolved while causing an exothermic reaction.
  • a salt insoluble in the organic solvent is removed by filtering.
  • a liquid precursor composition is obtained by purification such as by a single or multiple step(s) of reduced-pressure distillation.
  • a different order of the addition of the reactants is utilized as in Reaction Formula 2.
  • the halogenated metal compound represented by MX 2 or halogenated metal complex compound represented by ZMX 2 can be mixed with an alkali metal in an organic solvent.
  • the halogenated metal compound represented by MX 2 or halogenated metal complex compound represented by ZMX 2 may be dissolved in the organic solvent or may be dispersed in the form of powder in the organic solvent.
  • the alkali metal is not dissolved but remains in a solid hen, a diazadiene ligand DAD may be slowly added to the mixture with stirring.
  • the alkali metal may be dissolved while causing an exothermic reaction.
  • a salt insoluble in the organic solvent is removed by filtering.
  • a liquid precursor composition may be obtained by purification, such as by a single or multiple step(s) of reduced-pressure distillation.
  • the organic solvent may be a non-polar or weakly polar organic solvent, without limitation.
  • the organic solvent may include tetrahydrofuran (THF), 1, 2-dimethoxyethane (DME), or 2-methoxyethyl ether, but is not limited thereto.
  • the reaction may be performed in the presence of an inert gas such as a nitrogen gas (N 2 ) or an argon gas (Ar) in order to suppress a reaction with atmospheric moisture or, but may not be limited thereto.
  • an inert gas such as a nitrogen gas (N 2 ) or an argon gas (Ar) in order to suppress a reaction with atmospheric moisture or, but may not be limited thereto.
  • liquid precursor compositions such as vapor deposition methods.
  • the liquid precursor composition can be used in CVD or ALD processes.
  • a layer comprising nickel or cobalt is deposited by CVD or ALD.
  • a metallic layer containing about 80 at% or more of nickel or cobalt is deposited in some embodiments.
  • a layer containing a metal or metal compound is deposited using a liquid precursor composition comprising a metal compound represented by the following Chemical Formula 1:
  • M denotes Co or Ni
  • DAD denotes a diazadiene ligand compound represented by R 1 NC(R 3 )C(R 4 )NR 2 , wherein each of R 1 to R 4 includes independently H; or a linear or branched C 1-5 alkyl group.
  • a layer may be deposited by metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but deposition methods are not limited thereto.
  • MOCVD metal organic chemical vapor deposition
  • ALD atomic layer deposition
  • a layer containing Co or Ni may be formed using a liquid precursor composition in accordance with the first aspect of the present disclosure by CVD or ALD, but not limited thereto.
  • the liquid precursor composition or a liquid source material as discussed above
  • the liquid precursor composition is vaporized and introduced in the deposition chamber of a CVD or ALD equipment.
  • One or more additional appropriate reactant gases may also be introduced into the deposition chamber. The vapor of the liquid precursor composition and the reactant gases are introduced onto the surface of the substrates concurrently (in the case of CVD) or alternately (in the case of ALD).
  • a metal-containing layer is deposited on a substrate, for example by a vapor deposition process, at a deposition temperature of from about 50°C to about 700°C, but may not be limited thereto.
  • the deposition temperature may be from about 50°C to about 700°C, from about 50°C to about 600°C, from about 50°C to about 500°C, from about 50°C to about 400°C, from about 50°C to about 300°C, from about 50°C to about 200°C, from about 50°C to about 100°C, from about 50°C to about 80°C, from about 80°C to about 700°C, from about 100°C to about 700°C, from about 200°C to about 700°C, from about 300°C to about 700°C, from about 400°C to about 700°C, from about 500°C to about 700°C, from about 600°C to about 700°C, from about 100°C to about 600°C, from about 100°C to about 500°C, from
  • the liquid precursor composition may be vaporized by any of a variety of ways known in the arts such as by flowing a carrier gas through a bubbler containing the liquid precursor composition, or by direct liquid injection (DLI) into a vaporizer.
  • the carrier gas flow may be controlled, for example, by a mass flow controller (MFC).
  • MFC mass flow controller
  • a liquid deliver system (LDS) may be used with DLI.
  • argon (Ar), helium (He), nitrogen (N 2 ), hydrogen (H 2 ) or a gaseous mixture thereof may be used as a carrier gas for delivering the vapor of the liquid precursor composition on the substrate, and/or as a purge gas.
  • various gases may be used as a reactant gas in combination with vapor of the liquid precursor composition disclosed herein.
  • oxygen reactants such as water vapor (H 2 O), oxygen (O 2 ) or ozone (O 3 ) may be used to deposit a metal oxide layer.
  • Hydrogen (H 2 ), ammonia (NH 3 ), or silanes may be used as a reactant gas in order to deposit metal or metal silicide layers.
  • Ammonia with or without plasma may be used as a reactant gas in order to deposit a metal nitride layer. But the reactant gases may not be limited thereto.
  • second reactants may be selected by the skilled artisan based on the particular circumstances and the nature of the layers to be deposited. Additional reactants may also be included in order to form more complex films.
  • one or more plasma reactants may be used, such as in a plasma chemical vapor deposition or plasma atomic layer deposition process, but not limited thereto.
  • a vapor phase reactant is prepared from a liquid precursor composition wherein about 80% or more, about 85% or more, about 90% or more, or about 95% or more of the liquid precursor composition is a metal compound of Chemical Formula 1.
  • the composition may be determined, for example, by chromatography, such as gas chromatography.
  • a vapor phase reactant may be prepared from a liquid source material which comprises a liquid precursor composition as described herein.
  • a vapor phase reactant is prepared from a liquid precursor composition comprising a metal compound of Chemical Formula 1 and having a purity of about 80% or more, about 85% or more, about 90% or more, or 95% or more, but may not be limited thereto. That is, impurities (components other than the metal compound of Chemical Formula 1) are about 20% or less, about 15% or less, about 10% or less or even about 5% or less. The purity may be determined, for example, by chromatography, such as gas chromatography.
  • a vapor phase reactant is prepared from a liquid precursor composition wherein about 80% or more, about 85% or more, about 90% or more, or 95% or more of the liquid precursor composition is the metal compound Co( i PrNCHCHN i Pr) 2 .
  • the liquid precursor composition is at least about 80%, about 90%, about 95% or more pure. That is, impurities (components other than the metal compound Co( i PrNCHCHN i Pr) 2 ) are about 20% or less, about 15% or less, about 10% or less or even about 5% or less.
  • a vapor phase reactant is prepared from a liquid source material comprising a liquid precursor composition of Co( i PrNCHCHN i Pr) 2 as described.
  • Co( i PrNCHCHN i Pr) 2 [abbreviation: Co( i Pr-DAD) 2 ] may have a molecular weight of about 339 g/mol, but may not be limited thereto.
  • a vapor phase reactant may be prepared from a liquid precursor composition wherein about 80% or more about 85% or more, about 90% or more, or 95% or more, of the liquid precursor composition is the metal compound Ni( i PrNCHCHN i Pr) 2 .
  • the liquid precursor composition is at least about 80%, about 90%, or about 95% or more pure. That is, impurities (components other than the metal compound of Ni( i PrNCHCHN i Pr) 2 ) are about 20% or less, 15% or less, about 10% or less or even about 5% or less.
  • a vapor phase reactant is prepared from a liquid source material comprising a liquid precursor composition of Ni( i PrNCHCHN i Pr) 2 as described.
  • Ni( i PrNCHCHN i Pr) 2 [abbreviation: Ni( i Pr-DAD) 2 ] may have a molecular weight of about 339 g/mol, but may not be limited thereto.
  • a vapor phase reactant may be prepared from a liquid precursor composition that substantially or essentially consists of the metal compound represented by Co( i PrNCHCHN i Pr) 2 , but may not be limited thereto.
  • a vapor phase reactant may be prepared from a liquid precursor composition that substantially or essentially consists of the metal compound represented by Ni( i PrNCHCHN i Pr) 2 , but may not be limited thereto.
  • the liquid precursor composition may form part of a liquid source material.
  • the liquid precursor composition may be diluted to form a liquid source material that is vaporized for the deposition reactions.
  • the content and purity of the liquid precursor compositions discussed above are given in relation to the liquid precursor composition and thus are given without consideration for any diluent, solvent, carrier or the like.
  • a Co-containing thin film is deposited by CVD or ALD using a vapor phase reactant prepared from a liquid precursor composition containing metal compound represented by Co( i PrNCHCHN i Pr) 2 .
  • the film comprises greater than 80% Co.
  • a CVD process for forming a Co-containing thin film comprises contacting a substrate with a vapor phase reactant comprising Co( i PrNCHCHN i Pr) 2 at an appropriate deposition temperature.
  • a vapor phase reactant comprising Co( i PrNCHCHN i Pr) 2 at an appropriate deposition temperature.
  • One or more additional reactants may be included in order to deposit the desired film.
  • an ALD process for forming a Co-containing thin film comprises alternately and sequentially contacting a substrate with a vapor phase reactant comprising Co( i PrNCHCHN i Pr) 2 and at least one additional reactant at an appropriate deposition temperature.
  • a cobalt oxide film may be deposited by ALD by alternately and sequentially containing a substrate with vapor phase Co( i Pr-DAD) 2 prepared from a liquid precursor composition described herein and ozone or a different oxygen reactant.
  • the cobalt oxide film may be a Co 3 O 4 film.
  • a cobalt nitride film may be deposited by ALD by alternately and sequentially containing a substrate with vapor phase Co( i Pr-DAD) 2 prepared from a liquid precursor composition described herein and ammonia or a different nitrogen reactant.
  • a Ni-containing thin film is deposited by CVD or ALD using a vapor phase reactant prepared from a liquid precursor composition containing metal compound represented by Ni( i PrNCHCHN i Pr) 2 .
  • the film comprises greater than 80% Ni.
  • a CVD process for forming a Ni-containing thin film comprises contacting a substrate with a vapor phase reactant comprising Ni( i PrNCHCHN i Pr) 2 at an appropriate deposition temperature.
  • a vapor phase reactant comprising Ni( i PrNCHCHN i Pr) 2 at an appropriate deposition temperature.
  • One or more additional reactants may be included in order to deposit the desired film.
  • an ALD process for forming a Ni-containing thin film comprises alternately and sequentially contacting a substrate with a vapor phase reactant comprising Ni( i PrNCHCHN i Pr) 2 and at least one additional reactant at an appropriate deposition temperature.
  • a nickel oxide film may be deposited by ALD by alternately and sequentially contacting a substrate with vapor phase Ni( i Pr-DAD) 2 prepared from a liquid precursor composition described herein and ozone or a different oxygen reactant.
  • a nickel nitride film may be deposited by ALD by alternately and sequentially contacting a substrate with vapor phase Ni( i Pr-DAD) 2 prepared from a liquid precursor composition described herein and ammonia or a different nitrogen reactant.
  • a chromatography method may be used to separate the components and determine contents of the components.
  • contents of the components were determined by comparing the areas of the peaks of chromatograms measured by a gas chromatography (GC) using a flame ionization detector (FID).
  • Example 1 Preparation 1 of liquid precursor composition containing 90% or more of Co( i Pr-DAD) 2 (via addition of 2 equivalents of Na first and then addition of 2 equivalents of i Pr-DAD, using DME solvent)
  • Pieces of sodium 70.8 g (3.08 mol, 2 equivalents) were added into 1 liter(L) of 1,2-dimethoxyethane (DME) in a 10 L Schlenk flask under N 2 atmosphere.
  • Anhydrous CoCl 2 200 g (1.54 mol, 1 equivalent) was dispersed in 2 L of DME in another 5 L Schlenk flask to prepare a suspension.
  • the CoCl 2 suspension was slowly added using a cannula into the 10 L flask containing the sodium pieces with stirring.
  • a i Pr-DAD solution was prepared by dissolving 432 g (3.08 mol, 2 equivalents) of i Pr-DAD in 1 L of DME, which was slowly added into the above 10 L flask in which stirring was being performed at room temperature, to prepare a mixed solution. The mixed solution was further stirred for 24 hours at room temperature, and the DME solvent and other volatile components were removed under reduced pressure. Then, the resultant mixture was dissolved by adding 3 L of anhydrous n-hexane. The mixture dissolved in the n-hexane was filtered through Celite pad and glass frit. The n-hexane was removed from the filtrate under reduced pressure, and 333 g of a dark brown liquid was obtained. Reduced-pressure distillation at 0.3 torr was performed three (3) times to finally obtain 235 g [45.5% yield as Co( i Pr-DAD) 2 ] of a yellow-brown liquid as the liquid precursor composition.
  • the resulting liquid precursor composition containing Co( i Pr-DAD) 2 was analyzed using a gas chromatography - flame ionization detector (GC-FID), and a gas chromatography - mass spectroscopy (GC-MS), and the resulting chromatogram and mass spectrum obtained by analysis were as shown in FIG. 4A and FIG. 4B and FIG. 5, respectively.
  • GC-FID gas chromatography - flame ionization detector
  • GC-MS gas chromatography - mass spectroscopy
  • FIG. 4A and FIG. 4B show the chromatogram and the area% of the peaks in the chromatogram according to the retention time obtained from a gas chromatography-flame ionization detector (GC-FID) analysis of a liquid precursor composition prepared in accordance with Example 1, and FIG. 5 shows a gas chromatography-mass spectroscopy (GC-MS) analysis result of the liquid precursor composition prepared in accordance with Example 1.
  • GC-FID gas chromatography-flame ionization detector
  • FIG. 5 shows a gas chromatography-mass spectroscopy (GC-MS) analysis result of the liquid precursor composition prepared in accordance with Example 1.
  • GC-MS gas chromatography-mass spectroscopy
  • Mass spectrum value (m/z): 32.1, 43.2, 56.2, 70.2, 86.0, 100.0, 116.1, 125.2, 133.6, 142.1, 157.1, 169.3, 183.1, 199.1, 214.1, 226.1, 239.1, 253.1, 268.1, 281.1, 296.1, 309.2, 324.3, 339.3, 353.2, 362.1, 378.3, 394.2, 405.2.
  • Example 2 Preparation 2 of liquid precursor composition containing 90% or more of Co( i Pr-DAD) 2 (via addition of 2 equivalents of Li first and then addition of 2 equivalents of i Pr-DAD, using DME solvent)
  • Lithium (Li) 5.3 g (0.770 mol, 2 equivalents) was added into 500 mL of DME in a 3 L Schlenk flask under N 2 atmosphere.
  • Anhydrous CoCl 2 50 g (0.385 mol, 1 equivalent) was dispersed in 200 mL of DME in another Schlenk flask to prepare a suspension.
  • the CoCl 2 suspension was slowly added using a cannula into the 3 L flask containing lithium with stirring.
  • i Pr-DAD solution was prepared by dissolving 108 g (0.770 mol, 2 equivalents) of i Pr-DAD in 500 mL of DME, which was slowly added with stirring into the 3 L flask in which stirring was being performed at room temperature, to prepare a mixed solution. The mixed solution was further stirred for 12 hours at room temperature, and the DME solvent and other volatile components were removed under reduced pressure. Then, the resultant mixture was dissolved by adding 1.5 L of anhydrous n-hexane. The mixture dissolved in the n-hexane was filtered through Celite pad and glass frit. The n-hexane was removed from the filtrate under reduced pressure, and 110 g of a dark brown liquid was obtained. Reduced-pressure distillation at 0.3 torr was performed 3 times to finally obtain 60 g [46.2% yield as Co( i Pr-DAD) 2 ] of a yellow-brown liquid.
  • the finally obtained liquid precursor composition containing Co( i Pr-DAD) 2 was analyzed using the same GC-FID as used in Example 1, and the analysis results were as shown in FIG. 6A and FIG. 6B. It could be seen from the results shown in FIG. 6A and FIG. 6B that in the liquid precursor composition prepared in accordance with Example 2, the content of the main component is 93.9% of the total with respect to the areas of the chromatogram peaks.
  • Comparative Example 1 Preparation of liquid precursor composition containing less than 60% of Co( i Pr-DAD) 2 (via first reaction between 2 equivalents of Li and 2 equivalents of i Pr-DAD, using THF solvent)
  • i Pr-DAD 432 g (3.08 mol, 2 equivalents) and lithium (Li) 21.38 g (3.08 mol, 2 equivalents) were added into 3 L of THF in a 10 L Schlenk flask under N 2 atmosphere for reaction to prepare an in-situ prepared solution.
  • Anhydrous CoCl 2 200 g (1.54 mol, 1 equivalent) was dispersed in 1 L of THF in another Schlenk flask to prepare a suspension.
  • the suspension was slowly added using a cannula into the 10 L flask containing the in-situ prepared solution with stirring to prepare a mixed solution.
  • the mixed solution was further stirred for 12 hours at room temperature, and the THF solvent and other volatile components were removed under reduced pressure.
  • the resultant mixture was dissolved by adding 3 L of anhydrous n-hexane.
  • the mixture dissolved in the n-hexane was filtered through Celite pad and glass frit.
  • the n-hexane was removed from the filtrate reduced pressure, and 420 g of a dark brown liquid was obtained.
  • Reduced-pressure distillation at 0.3 torr was performed 5 times to finally obtain 37 g [7.1% yield as Co( i Pr-DAD) 2 ] of a yellow-brown liquid.
  • the finally obtained liquid precursor composition containing Co( i Pr-DAD) 2 was analyzed using the same GC-FID and GC-MS as used in Example 1, and the analysis results were as shown in FIG. 7A and FIG. 7B and FIG. 8, respectively. It could be seen from the GC-MS result shown in FIG. 8 that the molecular mass of the main component is 339 g/mol, which corresponds to that of Co( i Pr-DAD) 2 . However, it could be seen from the GC-FID results shown in FIG. 7A and FIG. 7B that the liquid precursor composition obtained in accordance with Comparative Example 1 contains the metal compound, as the main element, in a content of 52.4% of the total and contains a lot of impurities despite reduced-pressure distillation repeated 5 times.
  • Mass spectrum value (m/z): 43.1, 56.1, 70.1, 86.0, 100.0, 116.0, 129.1, 142.0, 157.1, 169.2, 183.1, 199.1, 214.1, 226.1, 239.1, 253.1, 268.1, 281.1, 296.1, 309.2, 324.3, 339.3, 355.2, 378.0, 394.2, 405.1, 415.0, 429.1, 479.2, 508.9.
  • Example 3 Preparation 1 of liquid precursor composition containing 90% or more of Ni( i Pr-DAD) 2 (via addition of 2 equivalents of i Pr-DAD first and then addition of 2 equivalents of Li, using THF solvent)
  • the finally obtained liquid precursor composition containing Ni( i Pr-DAD) 2 was analyzed using the same GC-FID as used in Example 1, and the analysis result was as shown in FIG. 9A and FIG. 9B. It could be seen from the result shown in FIG. 9A and FIG. 9B that the liquid precursor composition contains a single compound represented by Ni( i Pr-DAD) 2 as a main component in a content of 98.3% of the total.
  • a nuclear magnetic resonance (NMR) spectrum of the liquid precursor composition is shown in FIG. 10. NMR signals other than those of Ni( i Pr-DAD) 2 are hardly observed.
  • Example 4 Preparation 2 of liquid precursor composition containing 90% or more of Ni( i Pr-DAD) 2 (via addition of 2 equivalents of Na first and then addition of 2 equivalents of i Pr-DAD, using THF solvent)
  • Sodium (Na) 21.1 g (0.915 mol, 2 equivalents) was added into 1 L of THF in a 3 L Schlenk flask under N 2 atmosphere.
  • Anhydrous NiBr 2 100 g (0.458 mol, 1 equivalent) was dispersed in 500 mL of THF in another Schlenk flask to prepare a suspension.
  • the suspension was slowly added using a cannula into the 3 L flask containing sodium with stirring.
  • a i Pr-DAD solution was prepared by dissolving 128.3 g (0.915 mol, 2 equivalents) of i Pr-DAD in 500 mL of THF, which was slowly added with stirring into the 3 L flask in which stirring was being performed at room temperature, to prepare a mixed solution.
  • the mixed solution was stirred at room temperature for 12 hours, and the THF solvent and other volatile components were removed under reduced pressure. Then, the resultant mixture was dissolved by adding 1 L of anhydrous n-hexane. The mixture dissolved in the n-hexane was filtered through Celite pad and glass frit. The n-hexane was removed from the filtrate under reduced pressure, and 110 g of a dark brown liquid was obtained. Reduced-pressure distillation at 0.3 torr was performed 3 times to finally obtain 45 g [28.9% yield as Ni ( i Pr-DAD) 2 ] of a dark brown liquid.
  • the finally obtained liquid precursor composition containing Ni( i Pr-DAD) 2 was analyzed using the same GC-FID as used in Example 1, and the analysis result is shown in FIG. 11A and FIG. 11B. It can be seen from the result shown in FIG. 11A and FIG. 11B that the liquid precursor composition contains a main component in a content of 97.8% of the total. An NMR spectrum of the liquid precursor composition is shown in FIG. 12. NMR signals other than those of Ni( i Pr-DAD) 2 are hardly observed.
  • Example 5 Preparation 3 of liquid precursor composition containing 90% or more of Ni( i Pr-DAD) 2 (via addition of 2 equivalents of Li first and then addition of 2 equivalents of i Pr-DAD, using THF solvent
  • Lithium (Li) 6.4 g (0.92 mol, 2 equivalents) was added into 1 L of THF in a 3 L Schlenk flask under N 2 atmosphere.
  • Anhydrous NiBr 2 100 g (0.458 mol, 1 equivalent) was dispersed in 500 mL of THF in another Schlenk flask to prepare a suspension.
  • the suspension was slowly added using a cannula into the 3 L flask containing lithium with stirring.
  • An i Pr-DAD solution was prepared by dissolving 128.3 g (0.915 mol, 2 equivalents) of i Pr-DAD in 500 mL of THF, which was slowly added with stirring into the 3 L flask in which stirring was being performed at room temperature, to prepare a mixed solution.
  • the mixed solution was stirred at room temperature for 12 hours, and the THF solvent and other volatile components were removed under reduced pressure. Then, the resultant mixture was dissolved by adding 1 L of anhydrous n-hexane. The mixture dissolved in the n-hexane was filtered through Celite pad and glass frit. The n-hexane was removed from the filtrate under reduced pressure, and 102 g of a dark brown liquid was obtained. Reduced-pressure distillation at 0.3 torr was performed 3 times to finally obtain 85 g [55.1% yield as Ni ( i Pr-DAD) 2 ] of a dark brown liquid.
  • the finally obtained liquid precursor composition containing Ni( i Pr-DAD) 2 was analyzed using the same GC-FID as used in Example 1, and the analysis result was as shown in FIG. 13A and FIG. 13B. It could be seen from the result shown in FIG. 13A and FIG. 13B that the liquid precursor composition contains a main component in a content of 96.5% of the total. An NMR spectrum of the liquid precursor composition is shown in FIG. 14. NMR signals other than those of Ni( i Pr-DAD) 2 are hardly observed.
  • Example 6 Preparation 4 of liquid precursor composition containing 90% or more of Ni( i Pr-DAD) 2 (via addition of 2 equivalents of Li first and then addition of 2 equivalents weight of i Pr-DAD, using DME solvent)
  • Lithium (Li) 6.4 g (0.92 mol, 2 equivalents) was added into 1 L of DME in a 2 L Schlenk flask under N 2 atmosphere.
  • Anhydrous NiBr 2 100 g (0.458 mol, 1 equivalent) was dispersed in 500 mL of DME in another Schlenk flask to prepare a suspension.
  • the suspension was slowly added using a cannula into the 2 L flask containing lithium with stirring.
  • a i Pr-DAD solution was prepared by dissolving 128.3 g (0.915 mol, 2 equivalents) of i Pr-DAD in 500 mL of DME, which was slowly added with stirring into the 2 L flask in which stirring was being performed at room temperature, to prepare a mixed solution.
  • the mixed solution was stirred at room temperature for 12 hours, and the DME solvent and other volatile components were removed under reduced pressure. Then, the resultant mixture was dissolved by adding 1 L of anhydrous n-hexane. The mixture dissolved in the n-hexane was filtered through Celite pad and glass frit. The n-hexane was removed from the filtrate under reduced pressure, and 150 g of a dark brown liquid was obtained. Reduced-pressure distillation at 0.3 torr was performed 2 times to finally obtain 106 g [68.3% yield as Ni ( i Pr-DAD) 2 ] of a dark brown liquid.
  • the finally obtained liquid precursor composition containing Ni( i Pr-DAD) 2 was analyzed using the same GC-FID as used in Example 1, and the analysis result is shown in FIG. 15A and FIG. 15B. It could be seen from the result shown in FIG. 15A and FIG. 15B that the liquid precursor composition contains a main component in a content of 98.1% of the total. An NMR spectrum of the liquid precursor composition is shown in FIG. 16. NMR signals other than those of Ni( i Pr-DAD) 2 are hardly observed.
  • Comparative Example 2 Preparation of liquid precursor composition containing less than 60% of Ni( i Pr-DAD) 2 (via first reaction between 2 equivalents of Na and 2 equivalents of i Pr-DAD, using NiBr 2 )
  • i Pr-DAD 40 g (0.28 mol, 2 equivalents) and sodium (Na) 6.6 g (0.28 mol, 2 equivalents) were added into 0.3 L of THF in a 1 L Schlenk flask under N 2 atmosphere for reaction to prepare an in-situ prepared solution.
  • NiBr 2 31 g (0.14 mol, 1 equivalent) was dispersed in 0.2 L of THF in another 1L Schlenk flask to prepare a suspension.
  • the suspension was slowly added using a cannula into the 1 L flask containing the in-situ prepared solution with stirring to prepare a mixed solution.
  • the mixed solution was further stirred for 12 hours at room temperature, and the THF solvent and other volatile components were removed under reduced pressure.
  • the resultant mixture was dissolved by adding 0.2 L of anhydrous n-hexane.
  • the mixture dissolved in the n-hexane was filtered through Celite pad and glass frit.
  • the n-hexane was removed from the filtrate under reduced pressure, and 44 g of a dark brown liquid was obtained.
  • Reduced-pressure distillation at 0.5 torr was performed once and 5.5 g of a dark brown liquid was obtained. Because GC-FID and NMR spectrum indicate only a minute content of Ni( i Pr-DAD) 2 in the liquid precursor composition, further purification was not performed.
  • the obtained liquid precursor composition was analyzed using the same GC-FID as used in Example 1, and the analysis result is shown in FIG. 17A and FIG. 17B.
  • An NMR spectrum of the liquid precursor compositions is shown in FIG. 18.
  • An NMR signal of Ni( i Pr-DAD) 2 is indicated by the arrow. It could be seen that the content of Ni( i Pr-DAD) 2 in this liquid composition is insignificant since the area of the peak for the signal of Ni( i Pr-DAD) 2 in the NMR spectrum is much smaller than the other peak areas.
  • the content of Ni( i Pr-DAD) 2 is less than 2% since an area of any peak around 26 (min) where the signal of Ni( i Pr-DAD) 2 appears in the gas chromatogram is less than 2% of the total peak areas.
  • Comparative Example 3 Preparation of liquid precursor composition containing less than 60% of Ni( i Pr-DAD) 2 (via first reaction between 2 equivalents of Na and 2 equivalents of i Pr-DAD, using (DME)NiBr 2 )
  • i Pr-DAD 36 g (0.26 mol, 2 equivalents) and sodium (Na) 6.0 g (0.26 mol, 2 equivalents) were added into 0.3 L of THF in a 1 L Schlenk flask under N 2 atmosphere for reaction to prepare an in-situ prepared solution.
  • (DME)NiBr 2 40 g (0.129 mol, 1 equivalent) was dispersed in 0.2 L of THF in another 1L Schlenk flask to prepare a suspension. The suspension was slowly added using a cannula into the 1 L flask containing the in-situ prepared solution with stirring to prepare a mixed solution. The mixed solution was further stirred for 12 hours at room temperature, and the THF solvent and other volatile components were removed under reduced pressure.
  • the resultant mixture was dissolved by adding 0.2 L of anhydrous n-hexane.
  • the mixture dissolved in the n-hexane was filtered through Celite pad and glass frit.
  • the n-hexane was removed from the filtrate under reduced pressure, and 40.5 g of a dark brown liquid was obtained. Reduced-pressure distillation at 0.5 torr was performed once and 9 g of a dark brown liquid was obtained.
  • the obtained liquid precursor composition was analyzed using the same GC-FID as used in Example 1, and the analysis result was as shown in FIG. 19A and FIG. 19B.
  • An NMR spectrum of the liquid precursor composition is shown in FIG. 20, and a NMR signal of Ni( i Pr-DAD) 2 was as indicated by the arrow. It can be seen that the content of Ni( i Pr-DAD) 2 in this composition is less than 30% because the areas of the most significant peaks at 25.634 (min) and 26.162 (min) in the gas chromatogram are measured as 23.9% and 24.4%, respectively, of the total peak areas, even though it is not known which of the two peaks at 25.634 (min) and 26.162 (min) is for Ni( i Pr-DAD) 2 . Further, such materials, of which peaks are so close to each other in retention time in the gas chromatogram, cannot be substantially separated by fractional distillation.
  • a liquid precursor composition substantially or essentially consisting of Ni( i Pr-DAD) 2 only has not been reported previously.
  • the methods of the present invention is advantageous in obtaining a liquid composition substantially or essentially consisting of Ni( i Pr-DAD) 2 .
  • Example 7 Layer deposition by CVD using liquid precursor composition containing Co( i Pr-DAD) 2 prepared by Example 2
  • Film deposition was performed by CVD using a liquid precursor composition containing Co( i Pr-DAD) 2 as prepared by Example 2.
  • a silicon wafer covered by a titanium nitride (TiN) film was used as a substrate.
  • the substrate was placed in a deposition chamber of a reactor, and a temperature of a substrate heater, on which the substrate was placed, was maintained in a range of from 240°C to 300°C.
  • the liquid precursor composition was placed in a stainless steel container. While the container was heated at 100°C, the liquid precursor composition was evaporated using argon (Ar) as a carrier gas having a flow rate of 60 standard cubic centimeters per minute (sccm). The pressure of the deposition chamber was maintained at 0.5 torr.
  • Ar argon
  • the vapor of the liquid precursor composition carried by Ar and an ammonia (NH 3 ) gas at a flow rate of 60 sccm were alternatively supplied into the deposition chamber to be brought onto the heated substrate.
  • a gas supply cycle consisting of the liquid precursor composition supply for 20 seconds, Ar gas flow for 10 seconds, NH 3 gas flow for 10 seconds, and Ar gas flow for 10 seconds was repeated 300 times to deposit a cobalt-containing layer.
  • the cobalt-containing layer deposited at the substrate heater temperature of 240°C was analyzed by Auger electron spectroscopy to measure an atomic content depending on a depth of the film.
  • the depth-profile analysis result was shown in FIG. 21.
  • Comparative Example 4 Layer deposition by CVD using liquid precursor composition containing Co( i Pr-DAD) 2 prepared by Comparative Example 1
  • Film deposition was performed by CVD using the liquid precursor composition prepared by Comparative Example 1.
  • a deposition condition was the same as Example 7.
  • the prepared layer was analyzed by Auger electron spectroscopy to measure an atomic content depending on a depth of the film.
  • the depth-profile analysis result was as shown in FIG. 22.
  • Example 8 Layer deposition by CVD using liquid precursor composition containing Ni( i Pr-DAD) 2 prepared by Example 4
  • Film deposition was performed by CVD using the liquid precursor composition containing Ni( i Pr-DAD) 2 and prepared by Example 4.
  • a silicon wafer covered by a titanium (Ti) film and a gold (Au) film was used as a substrate.
  • the substrate was placed in a deposition chamber of a reactor, and a temperature of a substrate heater, on which the substrate was placed, was maintained in a range of from 160°C to 200°C.
  • the liquid precursor composition was placed in a stainless steel container. While the container was heated at 90°C, the liquid precursor composition was evaporated using Ar as a carrier gas having a flow rate of 60 sccm. The pressure of the deposition chamber was maintained at 0.5 torr.
  • the vapor of the liquid precursor composition carried by Ar and a hydrogen (H 2 ) gas at a flow rate of 60 sccm were alternatively supplied into the deposition chamber to be brought into contact with the heated substrate.
  • a gas supply cycle consisting of the liquid precursor composition supply 20 seconds, Ar gas flow 10 seconds, H 2 gas flow 10 seconds, and Ar gas flow 10 seconds was repeated 100 times to deposit a layer.
  • the nickel-containing layer deposited at the substrate heater temperature of 160°C was analyzed by Auger electron spectroscopy to measure an atomic content depending on a depth.
  • the depth-profile analysis result was shown in FIG. 23.
  • a surface and a cross section of the nickel-containing layer deposited at the substrate heater temperature of 200°C was observed by scanning electron microscopy (SEM), and the results thereof were as shown in FIG. 24A and FIG. 24B.
  • Comparative Example 5 Layer deposition by CVD using liquid precursor composition containing Ni( i Pr-DAD) 2 prepared by Comparative Example 2
  • Film deposition was performed by CVD using the liquid precursor composition prepared by Comparative Example 2. A deposition condition was the same as Example 8. No deposition of any layer was observed.
  • Example 9 Cobalt oxide layer deposited by ALD using liquid precursor composition containing Co( i Pr-DAD) 2 prepared by Example 2
  • Cobalt oxide film was deposited by ALD using the liquid precursor composition containing Co( i Pr-DAD) 2 as prepared by Example 2 and ozone (O 3 ) gas inside a hot wall tube furnace reactor.
  • the liquid precursor composition was vaporized at 65°C and the vapor was delivered into the chamber with an Ar carrier gas at a flow rate of 50 sccm.
  • the temperature of the gas delivery line was gradually increased from 80 to 110°C.
  • the concentration of O 3 generated by an ozone generator was 11%.
  • Ar gas was used as the purge gas at a flow rate of 500 sccm.
  • the ALD window region of constant growth per cycle was found between 120 to 250°C and the growth-per-cycle is 0.12 nm/cycle.
  • FIG. 25 shows a tunneling electron microscopy (TEM) diffraction pattern image of the cobalt oxide film prepared at 250°C.
  • the interplanar spacings of the cobalt oxide film were 0.464, 0.283, 0.246, and 0.164 nm, each corresponding to the (111), (220), (311), and (422) planes of Co 3 O 4 (JCPDS No. 80-1534). No peaks corresponding to the planes of CoO (JCPDS No. 75-0533) were observed.
  • a liquid precursor composition containing Co( i Pr-DAD) 2 enables ALD of Co 3 O 4 , which was not been reported previously.
  • FIG. 21 shows an analysis result of an atomic composition depending on a depth of the cobalt-containing layer deposited in accordance with Example 7 using Auger electron spectroscopy
  • FIG. 22 shows an analysis result of an atomic composition depending on a depth of the layer deposited in accordance with Comparative Example 4 using Auger electron spectroscopy.
  • Ti titanium
  • N nitrogen
  • Example 7 it can be seen that the layer deposited in Example 7 is much thicker even though the deposition conditions were the same. Thus, it can be concluded that a liquid precursor composition containing 90% or more of Co( i Pr-DAD) 2 in accordance with the present disclosure is superior to form a cobalt-containing layer compared to a liquid precursor composition containing less than 60% of Co( i Pr-DAD) 2 with respect to the layer growth rate and the Co content in the deposited layer.
  • FIG. 23 showing an Auger depth-profile analysis result a nickel-containing layer deposited in accordance with Example 8, it can be seen that a layer having a nickel content of about 80 at% is formed on the substrate.
  • FIG. 24A and FIG. 24B showing SEM images of a surface and a cross section of the deposited layer, it can be seen that the substrate is completely covered by a metallic nickel layer having a thickness of 181 nm. Accordingly, it can be seen that a liquid precursor composition according to the present disclosure is suitable to form a nickel-containing layer.
  • a metal oxide layer can be formed using a reactive gas including oxygen and a metal nitride layer can be formed using a reactive gas including nitrogen.
  • a cobalt oxide layer or a nickel oxide layer can be formed using the liquid precursor composition of the present disclosure and an oxygen (O 2 ) gas.
  • a cobalt oxide layer or a nickel oxide layer can be formed using the liquid precursor composition of the present disclosure and an ozone (O 3 ) gas.
  • a cobalt nitride layer or a nickel nitride layer can be formed using the liquid precursor composition of the present disclosure and an ammonia (NH 3 ) gas.
  • plasma CVD or plasma ALD using plasma may be used.
  • thermogravimetry (TG) analysis result and a differential scanning calorimetry (DSC) analysis result of the liquid precursor composition prepared in accordance with Example 1 were as shown in FIG. 26 and FIG. 27, respectively.
  • FIG. 26 shows a thermogravimetry analysis result of the liquid precursor composition prepared in accordance with Example 1
  • FIG. 27 shows a differential scanning calorimetry analysis result of the liquid precursor composition prepared in accordance with Example 1.
  • the liquid precursor composition prepared by Example 1 shows abrupt mass decrease at a temperature range of from about 150°C and about 220°C, and T 1/2 corresponding to a temperature at which a mass decrease depending on a temperature reaches half the mass of an original sample is 205°C.
  • the liquid precursor composition prepared by Example 1 shows a heat-absorption (endothermic) peak at 293°C caused by decomposition of the compound in the DSC graph.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
PCT/KR2015/005945 2014-06-13 2015-06-12 Liquid precursor compositions, preparation methods thereof, and methods for forming layer using the composition Ceased WO2015190871A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
KR1020167012801A KR101936162B1 (ko) 2014-06-13 2015-06-12 액체 전구체 조성물, 이의 제조 방법, 및 상기 조성물을 이용한 막의 형성 방법
KR1020167001280A KR20160017094A (ko) 2014-06-13 2015-06-12 액체 전구체 조성물, 이의 제조 방법, 및 상기 조성물을 이용한 막의 형성 방법
CN201580031286.2A CN106460169B (zh) 2014-06-13 2015-06-12 液体前体组合物、其制备方法和使用该组合物形成层的方法
JP2016572630A JP6635950B2 (ja) 2014-06-13 2015-06-12 液体前駆体組成物、その製造方法、及び前記組成物を利用した膜の形成方法
US15/199,705 US10014089B2 (en) 2014-06-13 2016-06-30 Liquid precursor compositions, preparation methods thereof, and methods for forming layer using the composition
US16/002,304 US10763001B2 (en) 2014-06-13 2018-06-07 Liquid precursor compositions, preparation methods thereof, and methods for forming layer using the composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20140072274 2014-06-13
KR10-2014-0072274 2014-06-13

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/199,705 Continuation US10014089B2 (en) 2014-06-13 2016-06-30 Liquid precursor compositions, preparation methods thereof, and methods for forming layer using the composition

Publications (1)

Publication Number Publication Date
WO2015190871A1 true WO2015190871A1 (en) 2015-12-17

Family

ID=54833872

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/005945 Ceased WO2015190871A1 (en) 2014-06-13 2015-06-12 Liquid precursor compositions, preparation methods thereof, and methods for forming layer using the composition

Country Status (6)

Country Link
US (2) US10014089B2 (enExample)
JP (1) JP6635950B2 (enExample)
KR (2) KR101936162B1 (enExample)
CN (1) CN106460169B (enExample)
TW (1) TWI682051B (enExample)
WO (1) WO2015190871A1 (enExample)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017214088A1 (en) 2016-06-06 2017-12-14 Wayne State University Reaction of diazadiene complexes with amines

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11476158B2 (en) * 2014-09-14 2022-10-18 Entegris, Inc. Cobalt deposition selectivity on copper and dielectrics
US11078224B2 (en) * 2017-04-07 2021-08-03 Applied Materials, Inc. Precursors for the atomic layer deposition of transition metals and methods of use
KR102103346B1 (ko) * 2017-11-15 2020-04-22 에스케이트리켐 주식회사 박막 증착용 전구체 용액 및 이를 이용한 박막 형성 방법.
KR102123331B1 (ko) * 2018-12-19 2020-06-17 주식회사 한솔케미칼 코발트 전구체, 이의 제조방법 및 이를 이용한 박막의 제조방법
WO2022211218A1 (ko) 2021-04-02 2022-10-06 한국과학기술원 액체금속 전구체 용액, 이를 이용한 금속막 제조방법 및 이를 포함하는 전자소자

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070160761A1 (en) * 2006-01-05 2007-07-12 H.C. Starck Gmbh & Co. Kg Tungsten and molybdenum compounds and thier use for chemical vapour deposition (CVD)
WO2013046157A1 (en) * 2011-09-27 2013-04-04 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Nickel bis diazabutadiene precursors, their synthesis, and their use for nickel containing film depositions
US20130251903A1 (en) * 2010-11-17 2013-09-26 Up Chemical Co., Ltd. Diazadiene-based metal compound, method for preparing same and method for forming a thin film using same
KR20140067147A (ko) * 2011-09-27 2014-06-03 레르 리키드 쏘시에떼 아노님 뿌르 레？드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 텅스텐 디아자부타디엔 전구체, 그들의 합성, 및 텅스텐 함유 필름 침착을 위한 그들의 용도

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8636845B2 (en) * 2008-06-25 2014-01-28 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Metal heterocyclic compounds for deposition of thin films
US8485738B2 (en) * 2009-07-31 2013-07-16 Hewlett-Packard Development Company, L.P. Optical fiber connector
US9822446B2 (en) * 2010-08-24 2017-11-21 Wayne State University Thermally stable volatile precursors
US9255327B2 (en) * 2010-08-24 2016-02-09 Wayne State University Thermally stable volatile precursors
CN105392917A (zh) 2013-05-24 2016-03-09 Up化学株式会社 使用钨化合物沉积含钨膜的方法和用于沉积含钨膜的包含钨化合物的前体组合物
US9067958B2 (en) * 2013-10-14 2015-06-30 Intel Corporation Scalable and high yield synthesis of transition metal bis-diazabutadienes
US9236292B2 (en) * 2013-12-18 2016-01-12 Intel Corporation Selective area deposition of metal films by atomic layer deposition (ALD) and chemical vapor deposition (CVD)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070160761A1 (en) * 2006-01-05 2007-07-12 H.C. Starck Gmbh & Co. Kg Tungsten and molybdenum compounds and thier use for chemical vapour deposition (CVD)
US20130251903A1 (en) * 2010-11-17 2013-09-26 Up Chemical Co., Ltd. Diazadiene-based metal compound, method for preparing same and method for forming a thin film using same
WO2013046157A1 (en) * 2011-09-27 2013-04-04 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Nickel bis diazabutadiene precursors, their synthesis, and their use for nickel containing film depositions
KR20140067147A (ko) * 2011-09-27 2014-06-03 레르 리키드 쏘시에떼 아노님 뿌르 레？드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 텅스텐 디아자부타디엔 전구체, 그들의 합성, 및 텅스텐 함유 필름 침착을 위한 그들의 용도

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIRCHMANN, MARIUS ET AL.: "Octahedral Coordination Compounds of the Ni, Pd, Pt Triad", ANGEW. CHEM. INT. ED., vol. 47, no. 5, 18 January 2008 (2008-01-18), pages 963 - 966, XP055242203 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017214088A1 (en) 2016-06-06 2017-12-14 Wayne State University Reaction of diazadiene complexes with amines
CN109563621A (zh) * 2016-06-06 2019-04-02 韦恩州立大学 二氮杂二烯络合物与胺的反应
EP3464676A4 (en) * 2016-06-06 2019-12-25 Wayne State University REACTION OF DIAZADIA COMPLEXES WITH AMINES
US11015241B2 (en) 2016-06-06 2021-05-25 Wayne State University Reaction of diazadiene complexes with amines
CN109563621B (zh) * 2016-06-06 2021-07-20 韦恩州立大学 二氮杂二烯络合物与胺的反应

Also Published As

Publication number Publication date
KR20160017094A (ko) 2016-02-15
KR101936162B1 (ko) 2019-01-08
CN106460169A (zh) 2017-02-22
US20160314980A1 (en) 2016-10-27
US20180286529A1 (en) 2018-10-04
US10014089B2 (en) 2018-07-03
KR20170008715A (ko) 2017-01-24
CN106460169B (zh) 2019-04-23
TW201604305A (zh) 2016-02-01
US10763001B2 (en) 2020-09-01
TWI682051B (zh) 2020-01-11
JP6635950B2 (ja) 2020-01-29
JP2017525840A (ja) 2017-09-07

Similar Documents

Publication Publication Date Title
WO2015190871A1 (en) Liquid precursor compositions, preparation methods thereof, and methods for forming layer using the composition
WO2012067439A2 (ko) 다이아자다이엔계 금속 화합물, 이의 제조 방법 및 이를 이용한 박막 형성 방법
WO2012176989A1 (en) A diamine compound or its salt, preparing method of the same, and uses of the same
WO2010071364A9 (ko) 금속 박막 또는 금속 산화물 박막 증착용 유기금속 전구체 화합물 및 이를 이용한 박막 증착 방법
WO2022019712A1 (ko) 니오븀 전구체 화합물, 이를 포함하는 막 형성용 전구체 조성물, 및 니오븀-함유 막 형성 방법
WO2018048124A1 (ko) 5족 금속 화합물, 이의 제조 방법, 이를 포함하는 막 증착용 전구체 조성물, 및 이를 이용하는 막의 증착 방법
WO2019203407A1 (ko) 원자층 증착용(ald), 화학 기상 증착용(cvd) 전구체 화합물 및 이를 이용한 ald/cvd 증착법
WO2015190900A1 (ko) 성막용 전구체 화합물 및 이를 이용한 박막 형성 방법
WO2019088722A1 (ko) 루테늄함유 박막의 제조방법 및 이로부터 제조된 루테늄함유 박막
WO2023121383A1 (ko) 몰리브데늄 전구체 화합물, 이의 제조방법, 및 이를 이용한 몰리브데늄-함유 막의 증착 방법
WO2023282615A1 (ko) 몰리브데늄 전구체 화합물, 이의 제조방법, 및 이를 이용한 몰리브데늄-함유 박막의 증착 방법
WO2020101437A1 (ko) 실리콘 전구체 화합물, 제조 방법, 및 이를 이용하는 실리콘-함유 막 형성 방법
WO2020027552A1 (en) Aluminum compounds and methods of forming aluminum-containing film using the same
US11999756B2 (en) Method for producing organometallic compound and thin film fabricated using organometallic compound obtained thereby
WO2023068629A1 (ko) 3족 금속 전구체, 이의 제조방법 및 이를 이용하는 박막의 제조방법
WO2023200154A1 (ko) 루테늄 전구체 조성물, 이의 제조방법, 및 이를 이용한 루테늄-함유 막의 형성 방법
WO2024058431A1 (ko) 이트륨 또는 스칸듐 함유 박막 형성용 전구체, 이를 이용한 이트륨 또는 스칸듐 함유 박막 형성 방법 및 상기 이트륨 또는 스칸듐 함유 박막을 포함하는 반도체 소자
WO2018199642A1 (ko) 금속 트리아민 화합물, 이의 제조방법 및 이를 포함하는 금속 함유 박막증착용 조성물
WO2022114782A1 (ko) 탄탈 화합물, 이의 제조방법 및 이를 포함하는 탄탈 함유 박막증착용 조성물
WO2021145661A2 (ko) 원자층 증착용(ald), 화학 기상 증착용(cvd) 전구체 화합물 및 이를 이용한 ald/cvd 증착법
WO2014168312A1 (ko) 4 족 전이금속-함유 전구체 화합물 및 이를 이용하는 박막의 증착 방법
WO2022055201A1 (ko) 4족 금속 원소-함유 화합물, 이를 포함하는 전구체 조성물, 및 이를 이용한 박막의 제조 방법
WO2023239152A1 (ko) 박막 전구체 화합물, 이를 이용한 박막 형성 방법 및 이로부터 제조된 반도체 기판
WO2023113308A1 (ko) 몰리브데넘 화합물, 이의 제조방법 및 이를 포함하는 박막 증착용 조성물
WO2024049150A1 (ko) 금속 화합물을 포함하는 박막증착용 조성물, 이를 이용한 금속 함유 박막의 제조방법 및 이를 이용하여 제조된 금속 함유 박막

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 20167001280

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15806804

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016572630

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15806804

Country of ref document: EP

Kind code of ref document: A1