WO2012176989A1 - Composé diamine ou son sel, procédé pour le préparer, et ses utilisations - Google Patents

Composé diamine ou son sel, procédé pour le préparer, et ses utilisations Download PDF

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WO2012176989A1
WO2012176989A1 PCT/KR2012/003866 KR2012003866W WO2012176989A1 WO 2012176989 A1 WO2012176989 A1 WO 2012176989A1 KR 2012003866 W KR2012003866 W KR 2012003866W WO 2012176989 A1 WO2012176989 A1 WO 2012176989A1
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formula
represented
salt
compound
diamine compound
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PCT/KR2012/003866
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Wonyong Koh
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 a diamine compound or its salt having utility for preparing an organometallic compound suitable for vapor phase deposition processes such as a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • 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 a diamine compound and its salt having utility for preparing an organometallic compound suitable for vapor phase deposition processes such as a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • 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 or vinyl 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 salt of the diamine compound as represented by the Formula 1 comprising: a process as represented by following Reaction Formula 1, wherein the process includes: reacting a diazadiene neutral ligand represented by following Formula 2 with each or mixture of R 5 MgX' and R 6 MgX' or each or mixture of R 5 M' and R 6 M':
  • X' is Cl, Br, or I
  • M' is Li, Na, or K
  • the conjugated cation contains a cation as represented by [M 3 ] + or [M 4 X] + in which M 3 is an alkali metal, M 4 is an alkali earth metal, and X is Cl, Br, or I, and R 1 to R 6 are as defined in the first aspect of the present disclosure.
  • a method for preparing the diamine compound as represented by the Formula 1 comprising: forming the salt of the diamine compound as represented by the Formula 1 via the Reaction Formula 1; and converting the salt of the diamine compound into the diamine compound as represented by the Formula 1.
  • a method for preparing a organometallic compound of a metal having an oxidation number of +2 as represented by following Formula 12, comprising: a process as represented by following Reaction Formula 2, wherein the process includes: reacting a bivalent metal halide compound as represented by M 1 X 2 , the diazadiene neutral ligand as represented by the Formula 2, and the salt of the diamine compound as represented by the Formula 1:
  • M 1 is a metal having an oxidation number of +2
  • X is Cl, Br, or I
  • R 1 to R 6 are as defined in the first aspect of the present disclosure.
  • a method for preparing a organometallic compound of a metal or metalloid having an oxidation number of +4 as represented by following Formula 13, comprising: a process as represented by following Reaction Formula 3, wherein the process includes: reacting a tetravalent metal halide compound as represented by M 2 X 4 , and the salt of the diamine compound as represented by the Formula 1:
  • M 2 is a metal having an oxidation number of +4, X is Cl, Br, or I, and R 1 to R 6 are as defined in the first aspect of the present disclosure.
  • the diamine compound as represented by the Formula 1 or its salt can be used to prepare an organometallic compound suitable for vapor phase deposition processes such as a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • the organometallic compound prepared by using the diamine compound or its salt can be used to deposit metal-containing thin films including, but not limited to, a metal thin film, a metal oxide thin film, and a metal nitride thin film.
  • a liquid organometallic compound prepared by using the diamine compound or its salt is useful for industrial applications due to its ease of transport. Further, the organometallic compound is useful for film deposition where oxygen incorporation into a deposited film or at an interface between a substrate and the deposited film needs to be avoided.
  • the metal thin film may be a cobalt or nickel thin film, which may be used as an electrode in a semiconductor device.
  • a cobalt or nickel thin film deposited on silicon may be used to form cobalt silicide or nickel silicide thin film by a heat treatment.
  • the metal oxide thin film may be a cobalt oxide thin film or nickel oxide thin film, which may be used as a resistive ramdom access memory (RRAM).
  • RRAM resistive ramdom access memory
  • the metal nitride thin film may be a silicon nitride thin film, which may be used as a dielectric layer in a semiconductor device.
  • Figure 1 is an Auger electron spectroscope (AES) depth profile of a Co thin film deposited by a sequential CVD method using a Co precursor as represented by the Formula 15; and
  • AES Auger electron spectroscope
  • Figure 2 is an AES depth profile of a Ni oxide thin film deposited by a sequential CVD method using a Ni precursor as represented by the Formula 14.
  • 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, the alkyl or 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 or modified metal in whole or in part and 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.
  • metal thin film means a thin film containing metal 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 a bivalent or tetravalent metal or metalloid, for example, but not limited to, cobalt, nickel, manganese, magnesium, silicon, copper, zinc, cadmium, mercury, lead, platinum, germanium, tin, titanium, zirconium, or hafnium.
  • a bivalent or tetravalent metal or metalloid 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 as a principal component instead of pure metal, and may include, for example, but not limited to, a cobalt oxide thin film and a nickel 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 nitride of a metal or metalloid as a principal component instead of pure metal, 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.
  • the present disclosure relates to various aspects of diamine compounds or their salts, which have utility for preparing organometallic compounds suitable for CVD or ALD method.
  • 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 or vinyl group
  • each of R 7 to R 12 is independently a linear or branched alkyl group having 1 to 5 carbon atoms.
  • R 1 and R 2 may be the alkyl group having 1 to 5 carbon atoms in order for the organometallic compounds prepared from the diamine compound to have high volatility.
  • R 1 and R 2 may be, but is not limited to, independently ethyl group, isopropyl group, or tert-butyl group.
  • the diamine compound in which R 1 and R 2 are independently ethyl group, isopropyl group, or tert-butyl group, and R 3 and R 4 are hydrogen is useful for CVD or ALD method due to its high volatility.
  • Preparing the diamine compound or its salt in which R 1 and R 2 are the same group can save time and efforts, and thus, it is more economical as compared with preparing the diamine compound or its salt in which R 1 and R 2 are different.
  • preparing the diamine compound or its salt in which R 3 and R 4 are the same group can save time and efforts, and thus, it is more economical as compared with preparing the diamine compound or its salt in which R 3 and R 4 are different.
  • the diamine compound is represented by following Formula 3 in which each of R 1 and R 2 is an ethyl group and each of R 3 and R 4 is hydrogen; the diamine compound is represented by following Formula 4 in which each of R 1 and R 2 is an isopropyl group and each of R 3 and R 4 is hydrogen; or the diamine compound is represented by following Formula 5 in which 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:
  • R 5 and R 6 are as defined in the first aspect of the present disclosure.
  • each of R 5 and R 6 may be an allyl group. Preparing the diamine compound or its salt in which R 5 and R 6 are the same group can save time and efforts, and thus, it is more economical as compared with preparing the diamine compound or its salt in which R 5 and R 6 are different.
  • the diamine compound is represented by following Formula 6, 7, or 8 in which each of R 5 and R 6 of Formula 3, 4, or 5 is an allyl group:
  • the diamine compound or its salt may be a compound represented by the Formula 6 or its salt in which both of R 1 and R 2 are ethyl group, both of R 3 and R 4 are hydrogen, and both of R 5 and R 6 are allyl group; a compound represented by the Formula 7 or its salt in which both of R 1 and R 2 are isopropyl group, both of R 3 and R 4 are hydrogen, and both of R 5 and R 6 are allyl group; and a compound represented by the Formula 8 or its salt in which both of R 1 and R 2 are tert-butyl group, both of R 3 and R 4 are hydrogen, and both of R 5 and R 6 are allyl group, but it is not limited thereto.
  • the diamine compound is represented by following Formula 9, 10, or 11 in which each of R 5 and R 6 of Formula 3, 4, or 5 is a vinyl group:
  • the diamine compound or its salt may be a compound represented by the Formula 9 or its salt in which both of R 1 and R 2 are ethyl group, both of R 3 and R 4 are hydrogen, and both of R 5 and R 6 are vinyl group; a compound represented by the Formula 10 or its salt in which both of R 1 and R 2 are isopropyl group, both of R 3 and R 4 are hydrogen, and both of R 5 and R 6 are vinyl group; and a compound represented by the Formula 11 or its salt in which both of R 1 and R 2 are tert-butyl group, both of R 3 and R 4 are hydrogen, and both of R 5 and R 6 are vinyl group, but it is not limited thereto.
  • the salt of the diamine compound contains a dianion of the compound as represented by the Formula 1 and a cation as represented by [M 3 ] + or [M 4 X] + in which M 3 is an alkali metal, M 4 is an alkali earth metal, and X is Cl, Br, or I, but it is not limited thereto.
  • the cation as represented by [M 3 ] + or [M 4 X] + contains Li + , Na + , K + , Rb + , [MgCl] + , [MgBr] + , or [MgI] + , but it is not limited thereto.
  • a method for preparing the salt of the diamine compound as represented by the Formula 1 comprising: a process as represented by following Reaction Formula 1, wherein the process includes: reacting a diazadiene neutral ligand represented by following Formula 2 with each or mixture of R 5 MgX' and R 6 MgX' or each or mixture of R 5 M' and R 6 M':
  • X' is Cl, Br, or I
  • M' is Li, Na, or K
  • the conjugated cation contains a cation as represented by [M 3 ] + or [M 4 X] + in which M 3 is an alkali metal, M 4 is an alkali earth metal, and X is Cl, Br, or I, and R 1 to R 6 are as defined in the first aspect of the present disclosure.
  • a method for preparing the diamine compound as represented by the Formula 1 comprising: forming the salt of the diamine compound as represented by the Formula 1 via the Reaction Formula 1; and converting the salt of the diamine compound into the diamine compound as represented by the Formula 1.
  • converting the salt of the diamine compound into the diamine compound may be performed by work-up procedure, but it is not limited thereto.
  • the work-up procedure known to organic chemists may be utilized including, but not limited to, a use of NH 4 Cl or dilute HCl.
  • a method for preparing a organometallic compound of a metal having an oxidation number of +2 as represented by following Formula 12, comprising: a process as represented by following Reaction Formula 2, wherein the process includes: reacting a bivalent metal halide compound as represented by M 1 X 2 , the diazadiene neutral ligand as represented by the Formula 2, and the salt of the diamine compound as represented by the Formula 1:
  • M 1 is a metal having an oxidation number of +2
  • X is Cl, Br, or I
  • R 1 to R 6 are as defined in the first aspect of the present disclosure.
  • a method for preparing a organometallic compound of a metal or metalloid having an oxidation number of +4 as represented by following Formula 13, comprising: a process as represented by following Reaction Formula 3, wherein the process includes: reacting a tetravalent metal halide compound as represented by M 2 X 4 , and the salt of the diamine compound as represented by the Formula 1:
  • M 2 is a metal having an oxidation number of +4, X is Cl, Br, or I, and R 1 to R 6 are as defined in the first aspect of the present disclosure.
  • the product of the Reaction Formula 1, the salt of the diamine compound may be used without further separation or purification and may provide a dianion of the diamine compound shown in the Reaction Formula 2 and the Reaction Formula 3.
  • the dianion of the diamine compound may be generated by a reaction of the diamine compound and a strong base such as n-butyllithium, but it is not limited thereto.
  • 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 12 can be formed by, but not limited to, making a reaction between a diazadiene neutral ligand represented by the Formula 2 and a two equivalents of the R 5 MgX' or R 5 M' to synthesize the salt of the diamine compound as represented by the Formula 1 and adding one equivalent of the bivalent metal halide compound as represented by M 1 X 2 and one equivalent of the diazadiene neutral ligand as represented by the Formula 2 thereto.
  • forming the organometallic compound as represented by the Formula 12 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 2 to an organic solvent, cooling the reaction solution, adding the salt of the diamine compound as represented by the Formula 1 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 -60°C to about -20°C, from about -60°C to about 0°C, from -40°C to about -20°C, from -40°C to about 0°C, or from about -20°C to about 0°C.
  • the adding the salt of the diamine compound as represented by the Formula 1 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.
  • 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.
  • 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 13 can be formed by, but not limited to, making a reaction between a diazadiene neutral ligand represented by the Formula 2 and two equivalents of the R 5 MgX' or R 5 M' to synthesize a salt of the diamine compound as represented by the Formula 1, and adding a tetravalent metal halide compound as represented by M 2 X 4 thereto.
  • the organometallic compound as represented by the Formula 13 is performed by forming a reaction solution by adding the tetravalent metal halide compound as represented by M 2 X 4 , cooling the reaction solution, adding the salt of the diamine compound as represented by the Formula 1 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 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 -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 salt of the diamine compound as represented by the Formula 1 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.
  • 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.
  • Boiling point 60°C at 0.3 torr
  • the flask was slowly heated to room temperature and stirred for 24 hours at room temperature. Then, the DME solvent and volatile by-products were removed under vacuum. The residue was then dissolved in 200 mL of n-hexane. The n-hexane solution was filtered through a Celite pad and a glass frit. The filtrate was vacuum distilled after removing n-hexane under vacuum. The dark red liquid product of 7.11 g as represented by the Formula 14 was obtained.
  • Example 5 Preparing organic cobalt compound as represented by the Formula 15 from i Pr-DAD and allylmagnesium chloride
  • Test Example 1 Deposition of cobalt thin film by ALD method or sequential CVD method using a Co precursor as represented by the Formula 15
  • a seed layer was prepared on a silicon substrate heated to 300°C in an ALD reactor by alternately supplying tetrakis(dimethylamido)titanium (TDMAT) and ammonia (NH 3 ). No cobalt film was deposited on the silicon substrate (001) without the seed layer.
  • TDMAT tetrakis(dimethylamido)titanium
  • NH 3 ammonia
  • the silicon substrate with the seed layer was heated to 300°C in the ALD reactor.
  • a stainless steel bubbler containing a cobalt precursor represented by the Formula 15 was heated to 100°C.
  • the cobalt precursor was vaporized and delivered to the ALD reactor by Ar carrier gas having a flow rate of about 50 sccm.
  • a pressure inside the ALD reactor was maintained at 3 torr.
  • a gas supply sequence includes a Co precursor carried by Ar for 5 sec, an Ar gas purge for 5 sec, ammonia gas for 5 sec, and an Ar gas purge for 5 sec. After performing 300 cycles of the gas supply sequence, the film was analyzed by a scanning electron microscope (SEM) and an Auger electron spectroscope (AES). An AES depth profile of a Co film deposited by using ammonia as a reaction gas was shown in Fig. 1, which indicates that a Co metal film was deposited. Similar AES depth profiles were obtained when a H 2 gas was used as a reaction gas.
  • Test Example 2 Deposition of nickel oxide thin film by ALD method or sequential CVD method using a Ni precursor as represented by Formula 14
  • a stainless steel bubbler containing a Ni precursor as represented by the Formula 14 was heated to 100°C.
  • the Ni precursor was vaporized and delivered to the ALD reactor by an Ar carrier gas having a flow velocity of about 50 sccm.
  • a pressure inside the ALD reactor was maintained at 3 torr.
  • a gas supply sequence includes a Ni precursor carried by Ar for 20 sec, an Ar gas purge for 5 sec, an ozone (O3) gas flow for 5 sec, and an Ar gas purge for 5 sec. After performing 300 cycles of the gas supply sequence, the film was analyzed by a scanning electron microscope (SEM) and an Auger electron spectroscopy (AES). An AES depth profile of a Ni film deposited by using ammonia as a reaction gas was shown in Fig. 2, which indicates that a Ni oxide thin film was deposited.
  • SEM scanning electron microscope
  • AES Auger electron spectroscopy
  • the substrate was examined by a SEM and an energy-dispersive X-ray spectroscope (EDX). It was observed that a Co-containing thin film was not deposited.
  • EDX energy-dispersive X-ray spectroscope
  • the substrate was examined by a SEM and an energy-dispersive X-ray spectroscope (EDX). It was observed that a Ni-containing film was not deposited.
  • EDX energy-dispersive X-ray spectroscope
  • Diamine represented by the Formula 1 or its salt can be used to prepare an organometallic compound suitable for vapor phase deposition processes such as a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method.
  • Organometallic precursors with allyl-containing diamine ligands are highly suitable to deposit metal thin films or metal oxide thin films, which can be used as electrodes and various other functional layers in a semiconductor device.

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Abstract

La présente description concerne un composé diamine ou son sel, présentant une utilité pour préparer un composé organométallique approprié à des procédés de dépôt en phase vapeur comme un procédé de dépôt chimique en phase vapeur (CVD) ou un procédé de dépôt de couches atomiques (ALD).
PCT/KR2012/003866 2011-06-24 2012-05-16 Composé diamine ou son sel, procédé pour le préparer, et ses utilisations WO2012176989A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9255327B2 (en) 2010-08-24 2016-02-09 Wayne State University Thermally stable volatile precursors
WO2016203887A1 (fr) * 2015-06-17 2016-12-22 株式会社Adeka Procédé de fabrication d'un nouveau composé, matière première pour la formation de film fin, et film fin
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US10533023B2 (en) 2013-06-28 2020-01-14 Wayne State University Bis(trimethylsilyl) six-membered ring systems and related compounds as reducing agents for forming layers on a substrate

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US9255327B2 (en) 2010-08-24 2016-02-09 Wayne State University Thermally stable volatile precursors
US9822446B2 (en) 2010-08-24 2017-11-21 Wayne State University Thermally stable volatile precursors
US9982344B2 (en) 2010-08-24 2018-05-29 Wayne State University Thermally stable volatile precursors
US10533023B2 (en) 2013-06-28 2020-01-14 Wayne State University Bis(trimethylsilyl) six-membered ring systems and related compounds as reducing agents for forming layers on a substrate
WO2016203887A1 (fr) * 2015-06-17 2016-12-22 株式会社Adeka Procédé de fabrication d'un nouveau composé, matière première pour la formation de film fin, et film fin
JP2017007952A (ja) * 2015-06-17 2017-01-12 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
US10253408B2 (en) 2015-06-17 2019-04-09 Adeka Corporation Compound, thin film-forming material, and thin film manufacturing method

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