WO2012176988A1 - Composé organométallique, procédé pour le préparer, et procédé de préparation d'un film mince l'employant - Google Patents

Composé organométallique, procédé pour le préparer, et procédé de préparation d'un film mince l'employant Download PDF

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WO2012176988A1
WO2012176988A1 PCT/KR2012/003857 KR2012003857W WO2012176988A1 WO 2012176988 A1 WO2012176988 A1 WO 2012176988A1 KR 2012003857 W KR2012003857 W KR 2012003857W WO 2012176988 A1 WO2012176988 A1 WO 2012176988A1
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thin film
formula
metal
represented
metalloid
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PCT/KR2012/003857
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Won Seok Han
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Up Chemical Co., Ltd.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages
    • 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
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C07F13/005—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
    • C07F15/04—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
    • 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

Definitions

  • the present disclosure relates to an organometallic compound, a preparing method of the same, and a preparing method of a metal-containing thin film using the same.
  • a metal-containing thin film such as a metal silicide thin film containing metal, e.g., cobalt, nickel, manganese, magnesium, and silicon
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • a cobalt oxide thin film and a nickel oxide thin film formed by the CVD method or the ALD method can be used usefully in a sensor.
  • a manganese thin film or a manganese oxide thin film can be used as a diffusion barrier film for preventing copper diffusion in a copper wiring of a semiconductor.
  • Korean Patent No. 10-0647332 entitled “Resistive random access memory enclosing an oxide with variable resistance states” describes that a nickel oxide thin film formed by a CVD method or an ALD method is used as a memory substance of a RRAM.
  • Organometallic precursor compounds are used to prepare metal oxide thin films such as ZrO 2 for DRAM dielectric.
  • Liquid organometallic precursors are generally preferred for industrial applications. Vaporized liquid can be easily transferred to the surface of a substrate, whereas delivery of solid precursors is prone to problems such as clogging and particle generation.
  • Liquid organometallic precursors suitable for pure metal deposition are relatively rare.
  • Metal carbonyl compounds may be used for deposition of cobalt and nickel thin films.
  • carbonyl compounds of cobalt and nickel have toxicity and limited thermal stability.
  • oxygen-containing precursors for some applications because an oxygen atom in the precursor might remain in a film or at an interface between a deposited film and a substrate.
  • oxygen impurity at an interface between silicon and a deposited cobalt or nickel thin film causes defects during silicide formation.
  • Cyclopentadienyl compounds of cobalt and nickel were used for deposition of cobalt and nickel thin film with large amount of carbon impurities, which are not desirable in general.
  • the present disclosure provides an organometallic compound which can be used in a CVD method or an ALD method, a preparing method of the same, and a preparing method of a metal-containing thin film using the same.
  • an organometallic compound as represented by the following Formula 1 or 2:
  • M 1 is a metal having an oxidation number of +2
  • M 2 is a metal or metalloid having an oxidation number of +4
  • each of R 1 and R 2 is independently a linear or branched alkyl group having 1 to 5 carbon atoms, or trialkylsilyl group as represented by -SiR 7 R 8 R 9
  • each of R 3 and R 4 is independently hydrogen, a linear or branched alkyl group having 1 to 5 carbon atoms, or trialkylsilyl group as represented by -SiR 10 R 11 R 12
  • each of R 5 and R 6 is independently an allyl group
  • each of R 7 to R 12 is independently a linear or branched alkyl group having 1 to 5 carbon atoms.
  • a method for preparing the organometallic compound of a metal having an oxidation number of +2 as represented by the Formula 1, comprising: a process as represented by following Reaction Formula 1, wherein the process includes: synthesizing a diazadiene-derived bivalent anion by reacting a diazadiene neutral ligand as represented by following Formula 15 with each or mixture of R 5 MgX' and R 6 MgX' or each or mixture of R 5 M' and R 6 M'; and forming the organometallic compound as represented by the Formula 1 by reacting a bivalent metal halide compound as represented by M 1 X 2 , the diazadiene neutral ligand as represented by the Formula 15, and the diazadiene-derived bivalent anion:
  • a method for preparing the organometallic compound of a metal or metalloid having an oxidation number of +4 as represented by the Formula 2 comprising: a process as represented by following Reaction Formula 2, wherein the process includes: synthesizing a diazadiene-derived bivalent anion by reacting diazadiene neutral ligand as represented by the Formula 15 with each or mixture of R 5 MgX' and R 6 MgX' or each or mixture of R 5 M' and R 6 M'; and forming the organometallic compound as represented by the Formula 2 by reacting a tetravalent metal halide or metalloid halide compound as represented by M 2 X 4 , and the diazadiene-derived bivalent anion:
  • a method for preparing the metal-containing thin film comprising depositing the organometallic compound of the first aspect of the present disclosure on a substrate by a chemical vapor deposition method or an atomic layer deposition method.
  • a metal-containing thin film prepared from the organometallic compound of the first aspect of the present disclosure.
  • the metal-containing thin film of the fifth aspect of the present disclosure wherein the metal-containing thin film includes, but is not limited to, a metal thin film, a metalloid thin film, a metal oxide thin film, a metalloid oxide thin film, a metal silicide thin film, a metal nitride thin film, or a metalloid nitride thin film.
  • the metal thin film may include a cobalt thin film or a nickel thin film, and the cobalt thin film or the nickel thin film can be used as, but not limited to, an electrode. If the cobalt thin film or the nickel thin film is formed on silicon, these thin films can be used for preparing, but not limited to, a cobalt silicide layer or a nickel silicide layer.
  • an electrode comprising the metal-containing thin film of the fifth aspect of the present disclosure.
  • a resistive memory comprising the metal-containing thin film of the fifth aspect of the present disclosure.
  • a silicon nitride comprising the metal-containing thin film of the fifth aspect of the present disclosure.
  • An organometallic compound represented by the Formula 1 or 2 in accordance with the first aspect of the present disclosure is supplied in a gas state and a metal-containing thin film can be formed by a CVD method or an ALD method. If the organometallic compound represented by the Formula 1 or 2 in accordance with the first aspect of the present disclosure is used to form the metal-containing thin film by the CVD method or the ALD method, the organometallic compound is in a liquid state at room temperature and has a high vapor pressure, so that it can be easily vaporized, and has high thermostability and low toxicity. Therefore, as compared with conventional techniques, this organometallic compound is highly applicable.
  • the metal-containing thin film formed by supplying the organometallic compound in a gas state represented by the Formula 1 or 2 in accordance with the first aspect of the present disclosure and by using the CVD method or the ALD method may include, but is not limited to, a metal thin film, a metal oxide thin film, a metal silicide thin film, or a metal nitride thin film.
  • the metal thin film may include a cobalt thin film or a nickel thin film, and the cobalt thin film or the nickel thin film can be used as, but not limited to, an electrode in a semiconductor device.
  • the nickel thin film is highly applicable, liquid organic nickel compounds used for preparing the nickel thin film have not been known.
  • the organometallic compound represented by the Formula 1 or 2 in accordance with the first aspect of the present disclosure comprises the liquid organic nickel compound. Therefore, it is advantageous in that the nickel thin film can be formed more economically and easily by using the organometallic compound of the present disclosure.
  • cobalt thin film or the nickel thin film is formed on silicon, these thin films can be used for preparing a cobalt silicide layer or a nickel silicide layer.
  • metal silicides can be used usefully for, but not limited to, contact in a semiconductor device.
  • a cobalt oxide thin film or a nickel oxide thin film can be used as, but not limited to, an electrode substance of a thin film type battery and a memory substance of a resistance random access memory (RRAM).
  • a metal oxide thin film can be used as, but not limited to, a diffusion barrier.
  • a silicon nitride thin film can be used as, but not limited to, an insulator.
  • the metal-containing thin film formed by the CVD or the ALD method can be applied to various fields of industry in addition to the above-described application examples.
  • the metal-containing thin film can be formed more economically and easily by the CVD or the ALD method.
  • Fig. 1 is a thermogravimetric analysis graph of a cobalt compound prepared in accordance with an Example 1 of the present disclosure
  • Fig. 2 is a differential thermal analysis graph of the cobalt compound prepared in accordance with the Example 1 of the present disclosure
  • Fig. 3 is an isothermal thermogravimetric analysis graph of the cobalt compound prepared in accordance with the Example 1 of the present disclosure
  • Fig. 4 is a thermogravimetric analysis graph of a nickel compound prepared in accordance with an Example 2 of the present disclosure
  • Fig. 5 is a differential thermal analysis graph of the nickel compound prepared in accordance with the Example 2 of the present disclosure.
  • Fig. 6 is an isothermal thermogravimetric analysis graph of the nickel compound prepared in accordance with the Example 2 of the present disclosure
  • Fig. 7 is a thermogravimetric analysis graph of a manganese compound prepared in accordance with an Example 3 of the present disclosure
  • Fig. 8 is a differential thermal analysis graph of the manganese compound prepared in accordance with the Example 3 of the present disclosure.
  • Fig. 9 is a thermogravimetric analysis graph of a silicon compound prepared in accordance with an Example 4 of the present disclosure.
  • Fig. 10 is a differential thermal analysis graph of the silicon compound prepared in accordance with the Example 4 of the present disclosure.
  • Fig. 11 is a scanning electron microscope (SEM) image of a cobalt thin film prepared by using ammonia as a reaction gas in accordance with an Test Example 3 of the present disclosure
  • Fig. 12 is an Auger analysis result of the cobalt thin film prepared by using ammonia as a reaction gas in accordance with the Test Example 3 of the present disclosure
  • Fig. 13 is a SEM image of a cobalt thin film prepared by using ethanol as a reaction gas in accordance with the Test Example 3 of the present disclosure
  • Fig. 14 is an Auger analysis result of the cobalt thin film prepared by using ethanol as a reaction gas in accordance with the Test Example 3 of the present disclosure
  • Fig. 15 is a SEM image of a cobalt thin film prepared by using hydrogen as a reaction gas in accordance with the Test Example 3 of the present disclosure
  • Fig. 16 is an Auger analysis result of the cobalt thin film prepared by using hydrogen as a reaction gas in accordance with the Test Example 3 of the present disclosure
  • Fig. 17 is a SEM image of a cobalt oxide thin film prepared in accordance with the Test Example 4 of the present disclosure
  • Fig. 18 is an Auger analysis result of the cobalt oxide thin film prepared in accordance with the Test Example 4 of the present disclosure
  • Fig. 19 is a SEM image of a nickel thin film prepared by using hydrogen as a reaction gas in accordance with the Test Example 5 of the present disclosure
  • Fig. 20 is an Auger analysis result of the nickel thin film prepared by using hydrogen as a reaction gas in accordance with the Test Example 5 of the present disclosure
  • Fig. 21 is a SEM image of a nickel oxide thin film prepared in accordance with the Test Example 6 of the present disclosure.
  • Fig. 22 is an Auger analysis result of the nickel oxide thin film prepared in accordance with the Test Example 6 of the present disclosure.
  • step of does not mean “step for”.
  • the term "on” that is used to designate a position of one element with respect to another element includes both a case that the one element is adjacent to the another element and a case that any other element exists between these two elements.
  • halo may include, but is not limited to, F, Cl, Br, or I.
  • alkyl or “alkyl group” may include a linear or branched, saturated or unsaturated alkyl group having a number of carbon atoms of 1 to 10 or 1 to 5, for example, an alkyl group including, but not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, hepxyl, octyl, nonyl, decyl, or isomers thereof.
  • titanium alkylsilyl group may include, but is not limited to, a group in which silicon (Si) is bonded to three identical or different alkyl groups.
  • metal-containing thin film means a thin film containing a pure metal, metalloid, modified metal, or modified metalloid in whole or in part and may include, but is not limited to, a metal thin film, a metalloid thin film, a metal oxide thin film, a metalloid oxide thin film, a metal silicide thin film, a metal nitride thin film, or a metalloid nitride thin film.
  • metal thin film means a thin film containing metal or metalloid which is not modified by oxidation or nitrification as a principal component unlike metal oxide thin film, metal silicide thin film, or metal nitride thin film, and may include a thin film made of, for example, but not limited to, cobalt, nickel, manganese, magnesium, silicon, copper, zinc, cadmium, mercury, lead, platinum, germanium, tin, titanium, zirconium, or hafnium.
  • metal oxide thin film means a thin film containing metal oxide or metalloid oxide as a principal component instead of pure metal or metalloid, and may include, for example, but not limited to, a cobalt oxide thin film, a nickel oxide thin film, a manganese oxide thin film, and a silicon oxide thin film.
  • metal silicide thin film means a thin film containing metal silicide as a principal component instead of pure metal, and may include, for example, but not limited to, a cobalt silicide thin film and a nickel silicide thin film.
  • metal nitride thin film means a thin film containing metal nitride or metalloid nitride as a principal component instead of pure metal or metalloid, and may include, for example, but not limited to, a cobalt nitride thin film, a nickel nitride thin film, and a silicon nitride thin film.
  • an organometallic compound as represented by the following Formula 1 or 2:
  • M 1 is a metal having an oxidation number of +2
  • M 2 is a metal or metalloid having an oxidation number of +4
  • each of R 1 and R 2 is independently a linear or branched alkyl group having 1 to 5 carbon atoms, or trialkylsilyl group as represented by -SiR 7 R 8 R 9
  • each of R 3 and R 4 is independently hydrogen, a linear or branched alkyl group having 1 to 5 carbon atoms, or trialkylsilyl group as represented by -SiR 10 R 11 R 12
  • each of R 5 and R 6 is independently an allyl group
  • each of R 7 to R 12 is independently a linear or branched alkyl group having 1 to 5 carbon atoms.
  • the organometallic compound as represented by the Formula 1 or 2 may have, but not limited to, high volatility by reducing a mutual attraction between molecules.
  • each of the R 1 and R 2 may be independently, but is not limited to, an ethyl group, an isopropyl ( i Pr) group, or a tert-butyl ( t Bu) group.
  • the organometallic compound may have a high vapor pressure and can be carefully used for, but not limited to, a CVD method or an ALD method.
  • the organometallic compound as represented by the Formula 1 or 2 contains the same functional group as R 1 and R 2 , it becomes economical since a time and costs for preparing the organometallic compound can be reduced, but it is not limited thereto.
  • the organometallic compound contains the same functional group as R 3 and R 4 , it becomes economical since a time and costs for preparing the organometallic compound can be reduced, but it is not limited thereto.
  • the organometallic compound is represented by the following Formula 3 or 4 wherein each of R 1 and R 2 is an ethyl group and each of R 3 and R 4 is hydrogen; wherein the compound is represented by the following Formula 5 or 6 wherein each of R 1 and R 2 is an isopropyl group and each of R 3 and R 4 is hydrogen; or the organometallic compound is represented by the following Formula 7 or 8 wherein each of R 1 and R 2 is a tert-butyl group and each of R 3 and R 4 is hydrogen, but it is not limited thereto:
  • M 1 , M 2 , R 5 , and R 6 are as defined in the first aspect.
  • the organometallic compound as represented by the Formula 1 or 2 may contain an allyl group as R 5 and R 6 , but it is not limited thereto. If the organometallic contains the same functional group as R 5 and R 6 , it becomes economical since a time and costs for preparing the organometallic compound can be reduced, but it is not limited thereto. Further, if the organometallic compound as represented by the Formula 1 or 2 is a compound containing an allyl group as R 5 and R 6 , it is possible to form, but not limited to, a metal thin film which it is difficult or impossible to form by the conventional techniques. By way of example, a liquid organic nickel compound that can be used for forming a nickel thin film has not been known. However, in the Example 2 of the present disclosure, a liquid organic nickel compound that contains an allyl group as R 5 and R 6 and can be used for forming a nickel thin film has been disclosed, but the present disclosure is not limited thereto.
  • the organometallic compound is represented by the following Formula 9, 10, 11, 12, 13, or 14 wherein each of R 5 and R 6 of Formula 3, 4, 5, 6, 7, or 8 is an allyl group, but it is not limited thereto:
  • M 1 includes a metal selected from a group including, but not limited to, Co, Ni, Mn, Mg, Si, Cu, Zn, Cd, Hg, Pd, and Pt. In accordance with an embodiment of the present disclosure, M 1 includes, but is not limited to, Co, Ni, Mn, or Mg.
  • M 2 includes a metal or metalloid selected from a group including, but not limited to, Si, Ge, Sn, Pb, Ti, Zr, and Hf. In accordance with an embodiment of the present disclosure, wherein M 2 includes, but is not limited to, Si, or Ti.
  • the organometallic compound in accordance with the first aspect of the present disclosure can be used as, but not limited to, a precursor when a metal- or metalloid-containing thin film, such as a metal thin film, a metalloid thin film, a metal oxide thin film, a metalloid oxide thin fiml, a metal silicide thin film, a metal nitride thin film, or a metalloid nitride thin film, applied to a semiconductor device is prepared by using a CVD method or an ALD method.
  • a metal- or metalloid-containing thin film such as a metal thin film, a metalloid thin film, a metal oxide thin film, a metalloid oxide thin fiml, a metal silicide thin film, a metal nitride thin film, or a metalloid nitride thin film, applied to a semiconductor device is prepared by using a CVD method or an ALD method.
  • a method for preparing the organometallic compound of a metal having an oxidation number of +2 as represented by the Formula 1, comprising: a process as represented by following Reaction Formula 1, wherein the process includes: synthesizing a diazadiene-derived bivalent anion by reacting a diazadiene neutral ligand as represented by following Formula 15 with each or mixture of R 5 MgX' and R 6 MgX' or each or mixture of R 5 M' and R 6 M'; and forming the organometallic compound as represented by the Formula 1 by reacting a bivalent metal halide compound as represented by M 1 X 2 , the diazadiene neutral ligand as represented by the Formula 15, and the diazadiene-derived bivalent anion:
  • each of R 5 and R 6 may be, but is not limited to, the same functional group.
  • the organometallic compound as represented by the Formula 1 can be formed by, but not limited to, reacting a diazadiene neutral ligand represented by the Formula 15 with two equivalents of a R 5 MgX' or R 5 M' to synthesize a diazadiene-derived bivalent anion, and adding one equivalent of a bivalent metal halide compound as represented by M 1 X 2 and one equivalent of the diazadiene neutral ligand as represented by the Formula 15 thereto.
  • forming the organometallic compound as represented by the Formula 1 is performed by forming a reaction solution by adding the bivalent metal halide compound as represented by M 1 X 2 , and the diazadiene neutral ligand as represented by the Formula 15 to an organic solvent, cooling the reaction solution, adding the diazadiene-derived bivalent anion to the cooled reaction solution with stirring, filtering an salt insoluble in the organic solvent, and removing the organic solvent, but it is not limited thereto.
  • the bivalent metal halide compound as represented by M 1 X 2 can be dissolved in the organic solvent and powder thereof can be dispersed in the solvent, but it is not limited thereto.
  • the cooling process may be performed at temperature of from about -80°C to about 0°C, for example, but not limited to, from about -80°C to about -60°C, from about -80°C to about -40°C, from about -80°C to about -20°C, from about -80°C to about 0°C, from about -60°C to about -40°C, from about -60°C to about -20°C, from about -60°C to about 0°C, from about -40°C to about -20°C, from about -40°C to about 0°C, or from about -20°C to about 0°C.
  • the adding the diazadiene-derived bivalent anion to the cooled reaction solution with stirring may be performed at, but not limited to, a low speed.
  • the organic solvent may contain, but is not limited to, tetrahydrofuran (THF), 1,2-dimethoxyethane, or 2-methoxyethyl ether.
  • THF tetrahydrofuran
  • the organic solvent may employ various solvents which have been typically used as, but not limited to, a nonpolar organic solvent or a weakly polar organic solvent.
  • the stirring may be performed under, but not limited to, an inert gas in order to suppress a decomposition reaction.
  • the inert gas may include, but is not limited to, a nitrogen gas or an argon gas.
  • the inert gas is included in reaction conditions, but not limited to, in order to suppress a decomposition reaction caused by moisture or oxygen during the stirring reaction.
  • a method for preparing the organometallic compound of a metal or metalloid having an oxidation number of +4 as represented by the Formula 2 comprising: a process as represented by following reaction Formula 2, wherein the process includes: synthesizing a diazadiene-derived bivalent anion by reacting diazadiene neutral ligand as represented by the Formula 15 with each or mixture of R 5 MgX' and R 6 MgX' or each or mixture of R 5 M' and R 6 M'; and forming the organometallic compound as represented by the Formula 2 by reacting a tetravalent metal halide or metalloid halide compound as represented by M 2 X 4 , and the diazadiene-derived bivalent anion:
  • each of X' and X 4 is independently Cl, Br, or I
  • M' is Li, Na, or K
  • M 2 and R 1 to R 6 are as defined in the first aspect of the present disclosure.
  • each of R 5 and R 6 may be, but is not limited to, the same functional group.
  • the organometallic compound as represented by the Formula 2 can be formed by, but not limited to, reacting a diazadiene neutral ligand represented by the Formula 15 with two equivalents of a R 5 MgX' or R 5 M' to synthesize a diazadiene-derived bivalent anion, and adding a tetravalent metal halide or metalloid halide compound as represented by M 2 X 4 thereto.
  • the organometallic compound as represented by the Formula 2 is performed by forming a reaction solution by adding the tetravalent metal halide or metalloid halide compound as represented by M 2 X 4 , cooling the reaction solution, adding the diazadiene-derived bivalent anion to the cooled reaction solution with stirring, filtering an salt insoluble in the organic solvent, and removing the organic solvent, but it is not limited thereto.
  • the tetravalent metal halide or metalloid halide compound as represented by M 2 X 4 can be dissolved in the organic solvent and powder thereof can be dispersed in the solvent, but it is not limited thereto.
  • the cooling process may be performed at temperature of from about -30°C to about 0°C, for example, but not limited to, from about -30°C to about -20°C, from about -30°C to about -10°C, from about -30°C to about 0°C, from about -20°C to about -10°C, from about -20°C to about 0°C, or from about -10°C to about 0°C.
  • the adding the diazadiene-derived bivalent anion to the cooled reaction solution with stirring may be performed at, but not limited to, a low speed.
  • the organic solvent may contain, but is not limited to, tetrahydrofuran (THF), 1,2-dimethoxyethane, or 2-methoxyethyl ether.
  • THF tetrahydrofuran
  • the organic solvent may employ various solvents which have been typically used as, but not limited to, a nonpolar organic solvent or a weakly polar organic solvent.
  • the stirring may be performed under, but not limited to, an inert gas in order to suppress a decomposition reaction.
  • the inert gas may include, but is not limited to, a nitrogen gas or an argon gas.
  • the inert gas is included in reaction conditions, but not limited to, in order to suppress a decomposition reaction caused by moisture or oxygen during the stirring reaction.
  • a method for preparing the metal-containing thin film comprising depositing the organometallic compound of the first aspect of the present disclosure on a substrate by a CVD method or an ALD method.
  • the method for preparing the metal-containing thin film may further comprise, but is not limited to, forming a seed layer on the substrate before the organometallic compound is deposited on the substrate.
  • the seed layer may be prepared by, for example, but not limited to, performing from 10 to 30 cycles of ALD method alternately supplying a gas containing tetrakisdimethylamino titanium (TDMAT) and a gas containing ammonia onto the substrate.
  • TDMAT tetrakisdimethylamino titanium
  • the method comprises, but is not limited to, contacting the organometallic compound in a gaseous state with the substrate.
  • the organometallic compound in a gaseous state is supplied to the substrate by means selected from a group including, but not limited to, bubbling, gaseous phase mass flow controller (MFC), direct liquid injection (DLI), and liquid delivery system (LDS).
  • MFC gaseous phase mass flow controller
  • DLI direct liquid injection
  • LDS liquid delivery system
  • the deposition is performed at temperature of, but not limited to, from about 50°C to about 700°C.
  • the depositing process may be performed at temperature of, but not limited to, 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 200°C to about 700°C, from about 200°C to about 600°C, from about 200°C to about 500°C, from about 200°C to about 400°C, or from about 200°C to about 300°C.
  • a carrier gas for supplying the organometallic compound to the method for preparing the metal-containing thin film may include, but is not limited to, argon, nitrogen, helium, hydrogen, or a mixture gas thereof.
  • a purge gas may include, but is not limited to, argon, nitrogen, helium, hydrogen, or a mixture gas thereof.
  • the CVD method or the ALD method may further comprises using a reaction gas selected from a group including, but not limited to, hydrogen, oxygen, ozone, ammonia, water vapor, alcohols, aldehydes, carboxylic acids, silanes, and combinations thereof.
  • a reaction gas may include, but is not limited to, a gas containing an oxygen atom, such as water vapor, oxygen, or ozone.
  • a reaction gas may include, but is not limited to, a gas such as hydrogen, ammonia, alcohol gases, aldehyde gases, carboxylic acid gases, or silane gases.
  • the metal- or metalloid-containing thin film includes, but is not limited to, a metal thin film, a metalloid thin film, a metal oxide thin film, a metalloid oxide thin film, a metal silicide thin film, a metal nitride thin film, or a metalloid nitride thin film.
  • the metal or metalloid thin film may include, but is not limited to, a cobalt thin film or a nickel thin film.
  • the cobalt thin film or the nickel thin film may be used as, but not limited to, an electrode in a semiconductor device.
  • cobalt thin film or the nickel thin film is formed on silicon
  • these films may be used for, but not limited to, forming a cobalt silicide layer and a nickel silicide layer, respectively.
  • a cobalt oxide thin film or a nickel oxide thin film may be used as, but not limited to, an electrode substance of a thin film type battery and a memory substance of a resistance random access memory (RRAM).
  • RRAM resistance random access memory
  • a silicon nitride thin film may be used as, but not limited to, an insulator.
  • a metal-containing thin film prepared from the organometallic compound of the first aspect of the present disclosure.
  • the metal- or metalloid-containing thin film includes, but is not limited to, a metal thin film, a metalloid thin film, a metal oxide thin film, a metalloid oxide thin film, a metal silicide thin film, a metal nitride thin film, or a metalloid nitride thin film.
  • the metal thin film may include, but is not limited to, a cobalt thin film or a nickel thin film.
  • the cobalt thin film or the nickel thin film may be used as an electrode. If the cobalt thin film or the nickel thin film is formed on silicon, these films may be used for, but not limited to, forming a cobalt silicide layer and a nickel silicide layer, respectively.
  • an electrode comprising the metal-containing thin film of the fifth aspect of the present disclosure.
  • a resistive memory comprising the metal-containing thin film of the fifth aspect of the present disclosure.
  • a silicon nitride comprising the metal- or metalloid-containing thin film of the fifth aspect of the present disclosure.
  • bivalent anion solution was prepared by slowly adding 96 mL of allyl magnesium chloride solution (2.0 M, tetrahydrofuran solvent; 193 mmol, 2.5 eq.) to a solution in which 10.8 g of i Pr-DAD (77 mmal, 1.0 eq.) was dissolved in 30 mL of 1,2-dimetoxyethane, and then the reaction solution was slowly heated to room temperature.
  • allyl magnesium chloride solution 2.0 M, tetrahydrofuran solvent; 193 mmol, 2.5 eq.
  • the bivalent anion solution was prepared by slowly adding 57 mL of allyl magnesium chloride solution (2.0 M, tetrahydrofuran solvent; 115 mmol, 2.5 eq.) to a solution in which 6.4 g of i Pr-DAD (46 mmol, 1.0 eq.) was dissolved in 30 mL of 1,2-dimetoxyethane, and then the reaction solution was slowly heated to room temperature.
  • allyl magnesium chloride solution 2.0 M, tetrahydrofuran solvent; 115 mmol, 2.5 eq.
  • bivalent anion solution was prepared by slowly adding 99 mL of allyl magnesium chloride solution (2.0 M, tetrahydrofuran solvent; 198 mmol, 2.5 eq.) to a solution in which 11.1 g of i Pr-DAD (79 mmol, 1.0 eq.) was dissolved in 30 mL of 1,2-dimetoxyethane, and then the reaction solution was slowly heated to room temperature.
  • allyl magnesium chloride solution 2.0 M, tetrahydrofuran solvent; 198 mmol, 2.5 eq.
  • the bivalent anion solution was prepared by slowly adding 133 mL of allyl magnesium chloride solution (2.0 M, tetrahydrofuran solvent; 266 mmol, 4.5 eq.) to a solution in which 11.1 g of i Pr-DAD (130 mmol, 2.2 eq.) was dissolved in 30 mL of tetrahydrofuran, and then the reaction solution was slowly heated to room temperature.
  • allyl magnesium chloride solution 2.0 M, tetrahydrofuran solvent; 266 mmol, 4.5 eq.
  • Test Example 1 Thermogravimetric analysis and differential thermal analysis (TGA/DSC)
  • thermogravimetric analysis and a differential thermal analysis were carried out.
  • TGA/DSC thermogravimetric analysis and a differential thermal analysis
  • a weight of the cobalt compound of the example 1 was sharply decreased in a range of from about 100°C to about 230°C in a TGA graph.
  • a temperature at which a weight of the sample reaches 1/2 of the original weight, i.e. T 1/2 was 204°C.
  • the cobalt compound of the Formula 16 showed an endothermic peak caused by decomposition of the compound at 277°C.
  • a weight of the nickel compound of the example 2 was sharply decreased in a range of from about 100°C to about 230°C in a TGA graph.
  • a temperature at which a weight of the sample reaches 1/2 of the original weight, i.e. T 1/2 was 201°C.
  • the nickel compound of the Formula 17 showed an endothermic peak caused by decomposition of the compound at 230°C.
  • a weight of the manganese compound of the example 3 was sharply decreased in a range of from about 80°C to about 210°C in a TGA graph.
  • a temperature at which a weight of the sample reaches 1/2 of the original weight, i.e. T 1/2 was 163°C.
  • the manganese compound of the Formula 18 showed an endothermic peak caused by decomposition of the compound at 256°C.
  • a weight of the silicon compound of the example 4 was sharply decreased in a range of from about 70°C to about 170°C in a TGA graph.
  • a temperature at which a weight of the sample reaches 1/2 of the original weight, i.e. T 1/2 was 142°C.
  • the silicon compound of the Formula 19 showed an endothermic peak caused by decomposition of the compound at 350°C.
  • thermogravimetric analysis was carried out at 80°C, 100°C, 120°C, and 150°C.
  • 80°C 100°C
  • 120°C 120°C
  • 150°C 150°C.
  • about 5 mg of sample was placed into an alumina sample container and the sample was heated at a heating rate of about 10 °C/min.
  • a temperature of the sample was measured for 2 hours after reaching each temperature. The measured results are shown in Figs. 3 and 6.
  • the cobalt compound of the example 1 was volatilized at a temperature of about 150°C or less without modification or thermal decomposition of the compound.
  • the nickel compound of the example 2 was volatilized at a temperature of about 150°C or less without modification or thermal decomposition of the compound.
  • Test Example 3 Deposition of cobalt thin film by ALD or sequential CVD method
  • a cobalt thin film was formed by the ALD method or the CVD method.
  • An ALD cycle in which a tetrakis(dimethylamido)titanium (TDMAT) gas and an ammonia (NH 3 ) gas are supplied alternately onto a silicon wafer (001) surface heated at about 300°C in an ALD reaction container was carried out about 20 times so as to form a titanium nitride film as a seed layer on a silicon substrate. Then, the ALD method was performed by using the cobalt compound as represented by the Formula 16. In addition to the cobalt compound as represented by the Formula 16, ammonia, ethanol, and a hydrogen gas were used as reaction gases. No cobalt thin film was deposited on the silicon wafer(001) surface without the seed layer.
  • the substrate was heated at about 300°C in the ALD reaction container, and the cobalt compound as represented by the Formula 16 was placed in a bubbler container made of stainless steel. While being heated at about 100°C, the cobalt compound was bubbled and vaporized by using an argon gas having a flow rate of about 50 sccm as a carrier gas of the cobalt compound.
  • An ALD cycle in which the cobalt compound gas was supplied for about 5 seconds, the argon gas was supplied for about 5 seconds, the reaction gas was supplied for about 5 seconds, and the argon gas was supplied for about 5 seconds to the ALD reaction container in which an internal pressure was kept at about 3 torr was repeatedly carried out about 300 times.
  • a surface and a cross section of a thin film formed as described above were observed with a scanning electron microscope (SEM) and components of the thin film were analyzed by an Auger electron spectroscope (AES).
  • SEM scanning electron microscope
  • AES Auger electron spectroscope
  • Fig. 11 provides SEM images of a surface and a cross section of a thin film obtained by using ammonia as a reaction gas
  • Fig. 12 shows contents of cobalt, carbon, and oxygen analyzed by the AES.
  • Fig. 13 provides SEM images of a surface and a cross section of a thin film obtained by using ethanol as a reaction gas
  • Fig. 14 shows contents of cobalt, carbon, and oxygen analyzed by the AES.
  • Fig. 15 provides SEM images of a surface and a cross section of a thin film obtained by using hydrogen as a reaction gas
  • Fig. 16 shows contents of cobalt, carbon, and oxygen analyzed by the AES.
  • a cobalt thin film was formed by using any one of ammonia, ethanol, and hydrogen as a reaction gas.
  • Test Example 4 Deposition of cobalt oxide thin film by ALD or sequential CVD method
  • a cobalt oxide thin film was formed by the ALD method or a sequential CVD method.
  • a silicon wafer coated with a silicon oxide (SiO2) film of about 100 nm was used as a substrate.
  • the substrate was heated at about 250°C, and the cobalt compound was placed in a bubbler container made of stainless steel. While being heated at about 100°C, the cobalt compound was bubbled and vaporized by using an argon gas having a flow rate of about 50 sccm as a carrier gas of the cobalt compound.
  • An ALD cycle in which the cobalt compound gas was supplied for about 20 seconds, an argon gas was supplied for about 5 seconds, the ozone gas was supplied for about 5 seconds, and the argon gas was supplied for about 5 seconds to an ALD reaction container in which an internal pressure was kept at about 3 torr was repeatedly carried out about 300 times.
  • FIG. 17 A surface and a cross section of a thin film formed as described above were observed with a scanning electron microscope (SEM) and resultant images thereof are provided in Fig. 17 and contents of cobalt, carbon, and oxygen analyzed by an Auger electron spectroscope (AES) are shown in Fig. 18.
  • SEM scanning electron microscope
  • AES Auger electron spectroscope
  • Test Example 5 Deposition of nickel thin film by ALD or sequential CVD method
  • a nickel thin film was formed by the ALD method or the sequential CVD method.
  • An ALD method using the nickel compound as represented by the Formula 17 was performed onto a titanium nitride wafer heated at about 250°C in an ALD reaction container.
  • the substrate was heated at about 250°C in the ALD reaction container, and the nickel compound as represented by the Formula 17 was placed in a bubbler container made of stainless steel. While being heated at about 100°C, the nickel compound was bubbled and vaporized by using an argon gas having a flow rate of about 50 sccm as a carrier gas of the nickel compound.
  • An ALD cycle in which the nickel compound gas was supplied for about 5 seconds, an argon gas was supplied for about 5 seconds, the hydrogen gas was supplied for about 5 seconds, and the argon gas was supplied for about 5 seconds to the ALD reaction container in which an internal pressure was kept at about 3 torr was repeatedly carried out about 300 times.
  • a surface and a cross section of a thin film formed as described above were observed with a scanning electron microscope (SEM), and components of the thin film were analyzed by an Auger electron spectroscope (AES).
  • SEM scanning electron microscope
  • AES Auger electron spectroscope
  • Fig. 19 provides SEM images of a surface and a cross section of a thin film obtained by using a hydrogen gas as a reaction gas
  • Fig. 20 shows contents of nickel, carbon, and oxygen analyzed by the Auger electron spectroscope.
  • Test Example 6 Deposition of nickel oxide thin film by ALD or sequential CVD method
  • a nickel oxide thin film was formed by the ALD method or the sequential CVD method.
  • a silicon wafer coated with a silicon oxide (SiO 2 ) film of about 100 nm was used as a substrate.
  • the substrate was heated at about 200°C, and the nickel compound was placed in a bubbler container made of stainless steel. While being heated at about 100°C, the nickel compound was bubbled and vaporized by using an argon gas having a flow rate of about 50 sccm as a carrier gas of the nickel compound.
  • An ALD cycle in which the nickel compound gas was supplied for about 20 seconds, an argon gas was supplied for about 5 seconds, the ozone gas was supplied for about 5 seconds, and the argon gas was supplied for about 5 seconds to an ALD reaction container in which an internal pressure was kept at about 3 torr was repeatedly carried out about 300 times.
  • a surface and a cross section of a thin film formed as described above were observed with a scanning electron microscope (SEM) and resultant images thereof are provided in Fig. 21, and contents of nickel, carbon, and oxygen analyzed by an Auger electron spectroscope (AES) are shown in Fig. 22.
  • SEM scanning electron microscope
  • AES Auger electron spectroscope

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Abstract

La présente description concerne un composé organométallique, un procédé pour le préparer, et un procédé de préparation d'un film mince contenant un métal l'employant.
PCT/KR2012/003857 2011-06-24 2012-05-16 Composé organométallique, procédé pour le préparer, et procédé de préparation d'un film mince l'employant WO2012176988A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150056384A1 (en) * 2012-02-07 2015-02-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method for the deposition of a ruthenium containing film using arene diazadiene ruthenium(0) precursors
US9371338B2 (en) 2012-07-20 2016-06-21 American Air Liquide, Inc. Organosilane precursors for ALD/CVD silicon-containing film applications
US9382268B1 (en) 2013-07-19 2016-07-05 American Air Liquide, Inc. Sulfur containing organosilane precursors for ALD/CVD silicon-containing film applications
JP2016540038A (ja) * 2013-10-28 2016-12-22 エスエーエフシー ハイテック インコーポレイテッド アミドイミン配位子を含む金属複合体
US9822132B2 (en) 2013-07-19 2017-11-21 American Air Liquide, Inc. Hexacoordinate silicon-containing precursors for ALD/CVD silicon-containing film applications
WO2020006382A1 (fr) * 2018-06-30 2020-01-02 Applied Materials, Inc. Précurseurs contenant de l'étain et procédés de dépôt de films contenant de l'étain
US10570513B2 (en) 2014-12-13 2020-02-25 American Air Liquide, Inc. Organosilane precursors for ALD/CVD silicon-containing film applications and methods of using the same
CN113818026A (zh) * 2021-09-15 2021-12-21 苏州源展材料科技有限公司 一种ald源钢瓶的清洗方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012027357A2 (fr) 2010-08-24 2012-03-01 Wayne State University Précurseurs volatils thermiquement stables
US9822446B2 (en) 2010-08-24 2017-11-21 Wayne State University Thermally stable volatile precursors
US9249505B2 (en) 2013-06-28 2016-02-02 Wayne State University Bis(trimethylsilyl) six-membered ring systems and related compounds as reducing agents for forming layers on a substrate
JP6675159B2 (ja) 2015-06-17 2020-04-01 株式会社Adeka 新規な化合物、薄膜形成用原料及び薄膜の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050081300A (ko) * 2004-02-13 2005-08-19 한국화학연구원 티타늄 질화물 선구 물질 및 그 제조 방법
KR20070073636A (ko) * 2006-01-05 2007-07-10 하.체. 스타르크 게엠베하 운트 코. 카게 텅스텐 및 몰리브덴 화합물, 및 이들의 화학적증착법(ｃｖｄ)에서의 용도
KR20100061183A (ko) * 2008-11-28 2010-06-07 주식회사 유피케미칼 코발트 금속 박막 또는 코발트 함유 세라믹 박막 증착용 유기 금속 전구체 화합물 및 이를 이용한 박막 제조 방법

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5001267A (en) * 1987-12-21 1991-03-19 Texaco Chemical Company Secondary alkyl amine derivatives of ethylenediamine
US6103799A (en) * 1998-01-20 2000-08-15 Air Products And Chemicals, Inc. Surface tension reduction with N,N'-dialkylalkylenediamines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050081300A (ko) * 2004-02-13 2005-08-19 한국화학연구원 티타늄 질화물 선구 물질 및 그 제조 방법
KR20070073636A (ko) * 2006-01-05 2007-07-10 하.체. 스타르크 게엠베하 운트 코. 카게 텅스텐 및 몰리브덴 화합물, 및 이들의 화학적증착법(ｃｖｄ)에서의 용도
KR20100061183A (ko) * 2008-11-28 2010-06-07 주식회사 유피케미칼 코발트 금속 박막 또는 코발트 함유 세라믹 박막 증착용 유기 금속 전구체 화합물 및 이를 이용한 박막 제조 방법

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BUNGE, S. D. ET AL.: "Synthesis, Structural Characterization and Dynamic Behavior of Group 12 Metals Containing the Sterically Hindered Ligand [N(t-Bu)CH(t-Bu)CHN-t-Bu]", POLYHEDRON, vol. 20, 2001, pages 823 - 830 *
SCHLEIS, T. ET AL.: "Ethylene Polymerization Catalysts Based on Nickel(II) 1,4-Diazadiene Complexes: the Influence of the 1,4-Diazadiene Backbone Substituents on Structure and Reactivity", J. ORGANOMETALLIC CHEM., vol. 569, 1998, pages 159 - 167 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9416443B2 (en) * 2012-02-07 2016-08-16 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method for the deposition of a ruthenium containing film using arene diazadiene ruthenium(0) precursors
US20150056384A1 (en) * 2012-02-07 2015-02-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Method for the deposition of a ruthenium containing film using arene diazadiene ruthenium(0) precursors
US9593133B2 (en) 2012-07-20 2017-03-14 America Air Liquide, Inc. Organosilane precursors for ALD/CVD silicon-containing film applications
US9371338B2 (en) 2012-07-20 2016-06-21 American Air Liquide, Inc. Organosilane precursors for ALD/CVD silicon-containing film applications
US9938303B2 (en) 2012-07-20 2018-04-10 American Air Liquide, Inc. Organosilane precursors for ALD/CVD silicon-containing film applications
US9822132B2 (en) 2013-07-19 2017-11-21 American Air Liquide, Inc. Hexacoordinate silicon-containing precursors for ALD/CVD silicon-containing film applications
US9382268B1 (en) 2013-07-19 2016-07-05 American Air Liquide, Inc. Sulfur containing organosilane precursors for ALD/CVD silicon-containing film applications
JP2016540038A (ja) * 2013-10-28 2016-12-22 エスエーエフシー ハイテック インコーポレイテッド アミドイミン配位子を含む金属複合体
US10221481B2 (en) 2013-10-28 2019-03-05 Merck Patent Gmbh Metal complexes containing amidoimine ligands
US10570513B2 (en) 2014-12-13 2020-02-25 American Air Liquide, Inc. Organosilane precursors for ALD/CVD silicon-containing film applications and methods of using the same
WO2020006382A1 (fr) * 2018-06-30 2020-01-02 Applied Materials, Inc. Précurseurs contenant de l'étain et procédés de dépôt de films contenant de l'étain
US11286564B2 (en) 2018-06-30 2022-03-29 Applied Materials, Inc. Tin-containing precursors and methods of depositing tin-containing films
CN113818026A (zh) * 2021-09-15 2021-12-21 苏州源展材料科技有限公司 一种ald源钢瓶的清洗方法

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