WO2017179857A1 - Composé de métal de transition, son procédé de préparation, et composition pour le dépôt d'un film mince contenant un métal de transition contenant celui-ci - Google Patents

Composé de métal de transition, son procédé de préparation, et composition pour le dépôt d'un film mince contenant un métal de transition contenant celui-ci Download PDF

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WO2017179857A1
WO2017179857A1 PCT/KR2017/003782 KR2017003782W WO2017179857A1 WO 2017179857 A1 WO2017179857 A1 WO 2017179857A1 KR 2017003782 W KR2017003782 W KR 2017003782W WO 2017179857 A1 WO2017179857 A1 WO 2017179857A1
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group
aryl
alkyl
transition metal
alkyl group
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PCT/KR2017/003782
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English (en)
Korean (ko)
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김명운
이상익
채원묵
임상준
이강용
조아라
전상용
임행돈
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(주)디엔에프
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Priority claimed from KR1020170040141A external-priority patent/KR101959519B1/ko
Application filed by (주)디엔에프 filed Critical (주)디엔에프
Priority to CN201780023511.7A priority Critical patent/CN109071571B/zh
Priority to US16/093,012 priority patent/US10913755B2/en
Priority to EP17782612.0A priority patent/EP3444255A1/fr
Priority to JP2018552842A priority patent/JP6979032B2/ja
Publication of WO2017179857A1 publication Critical patent/WO2017179857A1/fr

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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
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N 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
    • 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

Definitions

  • the present invention relates to a novel transition metal compound, a method for preparing the same, and a composition for depositing a transition metal-containing thin film including the same, and more particularly, a novel transition metal compound that can be usefully used as a precursor of a transition metal-containing thin film, and a It relates to a manufacturing method, a transition metal-containing thin film deposition composition comprising the same, a transition metal-containing thin film and a transition metal-containing thin film using the transition metal-containing thin film deposition composition.
  • silicon oxide SiO 2
  • Such silicon oxide has a simple manufacturing process, but has a relatively low dielectric constant, so that when the thickness is thin, a gate-to-channel leakage current occurs from the gate.
  • various processes eg, atomic layer deposition (ALD) and chemical vapor deposition (CVD)
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • the preparation of a zirconium oxide thin film by atomic layer deposition using a zirconium precursor or chemical vapor deposition has been developed in various ways depending on the ligand structure of the zirconium precursor.
  • ZrCl 4, ZrI 4 the zirconium oxide thin film by atomic layer deposition or chemical vapor deposition method using an inorganic salt, such as ZrF 4 is an inorganic salt in the inner films (Cl -, F -, I -) electrical characteristics of the thin film to the remaining There is a problem that this deterioration and agglomeration of the thin film is likely to occur. In addition, the roughness of the zirconium oxide film can not be arbitrarily adjusted, and the thickness of the thin film is also difficult to adjust.
  • zirconium oxide thin film formed from a zirconium compound having an amido ligand coordinated as a precursor is known.
  • Zr (NMeEt) 4 Alternatively, all zirconium amido compounds represented by Zr (NEt 2 ) 4 exist in liquid state with low viscosity at room temperature, and have high vapor pressure and easy removal of amido ligands by ozone and water vapor. It is most used as a precursor of ZrO 2 thin film production.
  • these zirconium amido compounds have high reactivity and are not easily stored for long periods of time.
  • the zirconium amido compounds have been recently known to decompose during vaporization to greatly affect the quality of the thin film.
  • the present invention provides a transition metal compound and a method for producing the same, which can be used as a precursor for thin film deposition with excellent thermal stability in order to solve the above problems.
  • the present invention also provides a composition for depositing a transition metal-containing thin film comprising the transition metal compound of the present invention, a transition metal-containing thin film prepared using the same, and a method for producing a transition metal-containing thin film using the same.
  • the present invention provides a transition metal compound having high volatility, excellent thermal stability, and excellent cohesive force that can be used as a precursor for thin film deposition.
  • the transition metal compound of the present invention is represented by the following Chemical Formula 1.
  • M is a transition metal of Group 4 on the periodic table
  • R 1 to R 4 are each independently a hydrogen atom or a (C1-C20) alkyl group
  • R 5 And R 6 independently of one another are a hydrogen atom, a (C1-C20) alkyl group, a (C6-C20) aryl group, a (C6-C20) aryl (C1-C20) alkyl group or a (C1-C20) alkoxy group;
  • A is-(CR 11 R 12 ) a- , and R 11 and R 12 are each independently hydrogen, (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) An alkyl group or a (C1-C20) alkoxy group, a being an integer from 1 to 3;
  • D is -N (R 13 )-, R 13 is a hydrogen atom, (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20 An alkyl group, a (C1-C20) alkylcarbonyl group or a (C3-C20) cycloalkylcarbonyl group;
  • X independently of each other is substituted with a (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) alkyl group, (C1-C20) alkoxy group, (C3-C20) alkyl or Unsubstituted or unsubstituted amino group, (C1-C20) alkyl or (C6-C20) aryl, unsubstituted silyl group, (C3-C20) heterocycloalkyl group, (C1-C20) alkyl or (C6-C20) aryl Phosphyl unsubstituted or substituted with a substituted or unsubstituted amide group, (C1-C20) alkyl or (C6-C20) aryl, or a phosphine group unsubstituted with (C1-C20) alkyl or (C6-C20) aryl
  • the alkyl group, cycloalkyl group, aryl group, arylalkyl group, alkylcarbonyl group, cycloalkylcarbonyl group or alkoxy group of R 1 to R 6 , A, D and X is a (C1-C20) alkyl group, (C3-C20) cycloalkyl group, May be further substituted with a (C6-C20) aryl group or a (C6-C20) aryl (C10-C20) alkyl group;
  • n is an integer of 1 or 2.
  • M may be titanium, zirconium or hafnium
  • R 1 to R 6 may be independently a hydrogen atom or a (C1-C7) alkyl group.
  • R 11 to R 13 in the general formula 1 may be independently a hydrogen atom or a (C1-C20) alkyl group
  • X is independently of each other (C1-C20) alkyl or (C6 -C20) aryl or unsubstituted amino group, (C1-C20) alkyl or (C6-C20) aryl substituted or unsubstituted amide group, (C1-C20) alkyl group, (C3-C20) heterocycloalkyl group Or a (C1-C20) alkoxy group.
  • M in the formula 1 is zirconium, hafnium or titanium;
  • R 1 to R 6 independently represent a hydrogen atom or a (C1-C7) alkyl group and each other;
  • X may independently be an amino group substituted with (C1-C20) alkyl, a (C1-C20) alkyl group, a (C3-C20) heterocycloalkyl group or a (C1-C20) alkoxy group.
  • the transition metal compound of Formula 1 according to an embodiment of the present invention may be selected from the following compounds.
  • the present invention provides a method for preparing a transition metal compound represented by the following Chemical Formula 1, wherein the following Chemical Formula 1 is prepared by reacting Chemical Formula 2 with Chemical Formula 3 to prepare a transition metal compound represented by Chemical Formula 1. It includes.
  • M is a transition metal of Group 4 on the periodic table
  • R 1 to R 4 are each independently a hydrogen atom or a (C1-C20) alkyl group
  • R 5 And R 6 independently of one another are a hydrogen atom, a (C1-C20) alkyl group, a (C6-C20) aryl group, a (C6-C20) aryl (C1-C20) alkyl group or a (C1-C20) alkoxy group;
  • A is - (CR 11 R 12) a - , and, R 11 and R 12 are independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl (C1-C20) to each other An alkyl group or a (C1-C20) alkoxy group, a being an integer from 1 to 3;
  • D is -N (R 13 )-, R 13 is a hydrogen atom, (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20 An alkyl group, a (C1-C20) alkylcarbonyl group or a (C3-C20) cycloalkylcarbonyl group;
  • X independently of each other is substituted with a (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) alkyl group, (C1-C20) alkoxy group, (C3-C20) alkyl or Unsubstituted or unsubstituted amino group, (C1-C20) alkyl or (C6-C20) aryl, unsubstituted silyl group, (C3-C20) heterocycloalkyl group, (C1-C20) alkyl or (C6-C20) aryl Phosphyl unsubstituted or substituted with a substituted or unsubstituted amide group, (C1-C20) alkyl or (C6-C20) aryl, or a phosphine group unsubstituted with (C1-C20) alkyl or (C6-C20) aryl
  • the alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group, arylalkyl group, alkylcarbonyl group, cycloalkylcarbonyl group or alkoxy group of R 1 to R 6 , A, D and X is a (C1-C20) alkyl group, (C3-C20 A cycloalkyl group, a (C6-C20) aryl group or a (C6-C20) aryl (C10-C20) alkyl group;
  • n is an integer of 1 or 2.
  • Chemical Formula 2 may be prepared by reacting Chemical Formula 4 with Chemical Formula 5 to produce Chemical Formula 6, and then reacting Chemical Formula 6 with Chemical Formula 7.
  • M 1 is an alkali metal
  • R 1 to R 4 are each independently a hydrogen atom or a (C1-C20) alkyl group
  • R 5 And R 6 independently of one another are a hydrogen atom, a (C1-C20) alkyl group, a (C6-C20) aryl group, a (C6-C20) aryl (C1-C20) alkyl group or a (C1-C20) alkoxy group;
  • A is-(CR 11 R 12 ) a- , and R 11 and R 12 are each independently hydrogen, (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) An alkyl group or a (C1-C20) alkoxy group, a being an integer from 1 to 3;
  • D is -N (R 13 )-, R 13 is a hydrogen atom, (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20 An alkyl group, a (C1-C20) alkylcarbonyl group or a (C3-C20) cycloalkylcarbonyl group;
  • the alkyl group, cycloalkyl group, aryl group, arylalkyl group, alkylcarbonyl group, cycloalkylcarbonyl group or alkoxy group of R 1 to R 6 , A and D is a (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6 - May be further substituted with a -C20) aryl group or a (C6-C20) aryl (C10-C20) alkyl group;
  • X 1 and X 2 are independently of each other halogen
  • n is an integer of 1 or 2.
  • the present invention also provides a transition metal-containing thin film deposition composition comprising the transition metal compound of the present invention.
  • the transition metal of the transition metal compound included in the transition metal-containing thin film deposition composition of the present invention may be zirconium, hafnium or titanium.
  • the present invention provides a transition metal-containing thin film and a transition metal-containing thin film prepared by using the transition metal-containing thin film deposition composition of the present invention.
  • novel transition metal compound of the present invention can be used as a precursor of a transition metal-containing thin film due to its high volatility, excellent thermal stability and cohesion.
  • novel transition metal compound of the present invention has a low melting point and is mostly present as a liquid at room temperature, and has high thermal stability and excellent storage stability.
  • the transition metal-containing thin film deposition composition of the present invention may be applied to various thin film deposition methods by including the transition metal compound of the present invention having high thermal stability as a precursor, and the thin film prepared by using the same has high density and purity.
  • the transition metal-containing thin film deposition composition of the present invention has high volatility, excellent thermal stability and cohesion, and low melting point, so that the transition metal thin film is formed by including the transition metal compound of the present invention, which is mostly liquid at room temperature. It is possible to obtain a high purity thin film having excellent step coverage and high density.
  • FIG. 3 is a diagram showing step coverage characteristics of Experimental Example 4.
  • the present invention provides a transition metal compound represented by the following Chemical Formula 1 having high volatility, excellent thermal stability and excellent cohesion.
  • M is a transition metal of Group 4 on the periodic table
  • R 1 to R 4 are each independently a hydrogen atom or a (C1-C20) alkyl group
  • R 5 And R 6 independently of one another are a hydrogen atom, a (C1-C20) alkyl group, a (C6-C20) aryl group, a (C6-C20) aryl (C1-C20) alkyl group or a (C1-C20) alkoxy group;
  • A is-(CR 11 R 12 ) a- , and R 11 and R 12 are each independently hydrogen, (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) An alkyl group or a (C1-C20) alkoxy group, a being an integer from 1 to 3;
  • D is -N (R 13 )-, R 13 is a hydrogen atom, (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20 An alkyl group, a (C1-C20) alkylcarbonyl group or a (C3-C20) cycloalkylcarbonyl group;
  • X independently of each other is substituted with a (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) alkyl group, (C1-C20) alkoxy group, (C3-C20) alkyl or With an unsubstituted or unsubstituted amino group, (C1-C20) alkyl or (C6-C20) aryl, an unsubstituted siloxy group, (C3-C20) heterocycloalkyl group, (C1-C20) alkyl or (C6-C20) aryl Phosphyl unsubstituted or substituted with a substituted or unsubstituted amide group, (C1-C20) alkyl or (C6-C20) aryl, or a phosphine group unsubstituted with (C1-C20) alkyl or (C6-C20)
  • the alkyl group, cycloalkyl group, aryl group, arylalkyl group, alkylcarbonyl group, cycloalkylcarbonyl group or alkoxy group of R 1 to R 6 , A, D and X is a (C1-C20) alkyl group, (C3-C20) cycloalkyl group, May be further substituted with a (C6-C20) aryl group or a (C6-C20) aryl (C10-C20) alkyl group;
  • n is an integer of 1 or 2.
  • the transition metal compound represented by Chemical Formula 1 of the present invention may be easily used as a precursor for preparing a thin film containing a transition metal having high volatility and high thermal stability.
  • the transition metal compound represented by Chemical Formula 1 of the present invention has a low melting point, and thus exists in most liquids at room temperature, and thus has high storage stability. Thus, a thin film of high purity can be manufactured with high density.
  • the transition metal compound represented by the formula (1) of the present invention is one molecule of silicon and transition metal Since it is possible to manufacture a transition metal silicate thin film using only one precursor, it is economical and efficient, and the purity of the thin film is very excellent.
  • X independently of each other (C1-C20) alkyl group, (C3-C20) heterocycloalkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) Alkyl group, (C1-C20) alkoxy group, siloxy group substituted with (C3-C20) alkyl, mono (C1-C20) alkylamino group, di (C1-C20) alkylamino group, mono (C1-C20) alkylamide group, Di (C1-C20) alkylamide groups, phosphine groups substituted with (C1-C20) alkyl, or phosphido groups substituted with (C1-C20) alkyl, preferably amino groups substituted with (C1-C20) alkyl , (C1-C20) alkyl group, (C3-C20) heterocycloalkyl group or (
  • M in accordance with an embodiment of the present invention to increase the dielectric constant may be titanium, zirconium or hafnium.
  • R 1 to R 6 may be independently a hydrogen atom or a (C1-C7) alkyl group each other, independently represent a hydrogen atom specifically, methyl group, ethyl group, n- propyl group, isopropyl Propyl group, n-butyl group, sec -butyl group, tert -butyl group or n-pentyl group.
  • R 11 and R 12 of A are independently of each other a hydrogen atom, (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) It may be an alkyl group or a (C1-C20) alkoxy group, preferably a hydrogen atom or a (C1-C20) alkyl group, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec -butyl group, tert - butyl or n- pentyl group, a may be an integer from 1 to 3 of an integer, preferably from 1 to 2.
  • R 13 of D is a hydrogen atom, (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1- C20) alkyl, (C1-C20) alkyl carbonyl group or (C3-C20) cycloalkyl-carbonyl may be date, a specific example, methyl, ethyl, n- propyl, isopropyl, sec - butyl or tert - Butyl, cyclohexyl, dicyclohexylmethyl, adamantyl, phenyl, phenylmethyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, tert -butylcarbonyl or adamantylcarbon And may be a specific example, methyl, ethyl
  • X independently of each other mono (C1-C20) alkylamino group, di (C1-C20) alkylamino group, mono (C1-C20) alkylamide group, di (C1-C20) alkyl Amide group, (C1-C20) alkyl group, (C3-C20) heterocycloalkyl group or (C1-C20) alkoxy group, more preferably mono (C1-C20) alkylamino group, di (C1-C20) alkylamino group, It may be a (C1-C20) alkyl group, (C3-C20) heterocycloalkyl group or (C1-C20) alkoxy group, and examples of mono (C1-C20) alkylamino group and di (C1-C20) alkylamino group include methylamino group and ethyl Amino group, n-propylamino group, isoprop
  • a tert -butyl group, and a specific example of a (C3-C20) heterocycloalkyl group is an aziridinyl group, a pyrrolidinyl group, a peridinyl group, an azepanyl group or an azocanyl group, preferably May be a pyrrolidinyl group or a piperidinyl group, and a specific example of a (C1-C20) alkoxy group Methoxy, ethoxy, n- propoxy, iso-propoxy, n- butoxy, sec - butoxy, tert - butoxy group, n- pentoxy group, neo-pentoxy group, n- heksok group, n- oktok time Or n-dodecoxy group, of which methoxy, ethoxy, isopropoxy or tert -butoxy groups are preferred.
  • the transition metal compound according to an embodiment of the present invention is a precursor for depositing a transition metal-containing thin film, and in view of obtaining a high-quality transition metal-containing thin film having high volatility and high thermal stability, preferably, R 1 to R 6 are independently hydrogen.
  • An atom or a (C1-C7) alkyl group; X may independently be a mono (C1-C20) alkylamino group, a di (C1-C20) alkylamino group, a (C1-C20) alkyl group, a (C3-C20) heterocycloalkyl group or a (C1-C20) alkoxy group, more
  • M is zirconium, hafnium, titanium
  • R 1 to R 6 are each independently a hydrogen atom or a (C1-C7) alkyl group
  • X may independently be a di (C1-C20) alkylamino group or a (C1-C20) alkoxy group.
  • the transition metal compound represented by Chemical Formula 1 of the present invention may be selected from the following compounds, but is not limited thereto.
  • Substituents including the "alkyl”, “alkoxy” and other “alkyl” moieties described herein include all linear or pulverized forms, preferably 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 Having from 4 to 4 carbon atoms.
  • aryl described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and is a single or fused ring containing 4 to 7 ring atoms, preferably 5 or 6 ring atoms, as appropriate for each ring. It includes a ring system, a form in which a plurality of aryl is connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.
  • Cycloalkyl described in the present invention means a non-aromatic monocyclic or polycyclic ring system having 3 to 20 carbon atoms, and the monocyclic ring is, without limitation, cyclopropyl, cyclobutyl , Cyclopentyl and cyclohexyl.
  • Examples of polycyclic cycloalkyl groups include perhydronaphthyl, perhydroindenyl, and the like; Bridged polycyclic cycloalkyl groups include adamantyl, norbornyl, and the like.
  • Heterocycloalkyl described in the present invention means a substituted or unsubstituted non-aromatic 3 to 15 membered ring radical composed of carbon atoms and 1 to 5 heteroatoms selected from nitrogen, phosphorus, oxygen and sulfur, and heterocycloalkyl
  • the radical may be a monocyclic, bicyclic or tricyclic ring system which may be fused, bridged or comprise a spiro ring system and the nitrogen, phosphorus, carbon, oxygen or sulfur atoms in the heterocyclic ring radicals may May be oxidized in some cases.
  • the nitrogen atom may be quaternized in some cases.
  • the present invention provides a method for preparing a transition metal compound represented by the following Chemical Formula 1, comprising the step of preparing a transition metal compound represented by the following Chemical Formula 1 by reacting the following Chemical Formula 2 and Chemical Formula 3.
  • M is a transition metal of Group 4 on the periodic table
  • R 1 to R 4 are each independently a hydrogen atom or a (C1-C20) alkyl group
  • R 5 And R 6 independently of one another are a hydrogen atom, a (C1-C20) alkyl group, a (C6-C20) aryl group, a (C6-C20) aryl (C1-C20) alkyl group or a (C1-C20) alkoxy group;
  • A is-(CR 11 R 12 ) a- , and R 11 and R 12 are each independently hydrogen, (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) An alkyl group or a (C1-C20) alkoxy group, a being an integer from 1 to 3;
  • D is -N (R 13 )-, R 13 is a hydrogen atom, (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20 An alkyl group, a (C1-C20) alkylcarbonyl group or a (C3-C20) cycloalkylcarbonyl group;
  • X independently of each other is substituted with a (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) alkyl group, (C1-C20) alkoxy group, (C3-C20) alkyl or Unsubstituted or unsubstituted amino group, (C1-C20) alkyl or (C6-C20) aryl, unsubstituted silyl group, (C3-C20) heterocycloalkyl group, (C1-C20) alkyl or (C6-C20) aryl Phosphyl unsubstituted or substituted with a substituted or unsubstituted amide group, (C1-C20) alkyl or (C6-C20) aryl, or a phosphine group unsubstituted with (C1-C20) alkyl or (C6-C20) aryl
  • the alkyl group, cycloalkyl group, aryl group, arylalkyl group, alkylcarbonyl group, cycloalkylcarbonyl group or alkoxy group of R 1 to R 6 , A, D and X is a (C1-C20) alkyl group, (C3-C20) cycloalkyl group, May be further substituted with a (C6-C20) aryl group or a (C6-C20) aryl (C10-C20) alkyl group;
  • n is an integer of 1 or 2.
  • Formula 2 may include the step of preparing the following Chemical Formula 6 by reacting the following Chemical Formula 4 and Chemical Formula 5 and then reacting the Chemical Formula 6 with the Chemical Formula 7.
  • M 1 is an alkali metal
  • R 1 to R 4 are each independently a hydrogen atom or a (C1-C20) alkyl group
  • R 5 And R 6 independently of one another are a hydrogen atom, a (C1-C20) alkyl group, a (C6-C20) aryl group, a (C6-C20) aryl (C1-C20) alkyl group or a (C1-C20) alkoxy group;
  • A is-(CR 11 R 12 ) a- , and R 11 and R 12 are each independently hydrogen, (C1-C20) alkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20) An alkyl group or a (C1-C20) alkoxy group, a being an integer from 1 to 3;
  • D is -N (R 13 )-, R 13 is a hydrogen atom, (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6-C20) aryl group, (C6-C20) aryl (C1-C20 An alkyl group, a (C1-C20) alkylcarbonyl group or a (C3-C20) cycloalkylcarbonyl group;
  • the alkyl group, cycloalkyl group, aryl group, arylalkyl group, alkylcarbonyl group, cycloalkylcarbonyl group or alkoxy group of R 1 to R 6 , A and D is a (C1-C20) alkyl group, (C3-C20) cycloalkyl group, (C6 - May be further substituted with a -C20) aryl group or a (C6-C20) aryl (C10-C20) alkyl group;
  • X 1 and X 2 are independently of each other halogen
  • n is an integer of 1 or 2.
  • heterocycloalkyl in Chemical Formula 1 according to an embodiment of the present invention, after preparing a compound having X or a monoalkylamino group or a dialkylamino group in Chemical Formula 1, heterocycloalkyl, for example, pyrrolidine and It can be prepared by reaction with piperidine.
  • the preparation method of the present invention can be represented by the following schemes 1-3.
  • the solvent used in the production method of the present invention may be any organic solvent, but hexane, pentane, dichloromethane (DCM), dichloroethane (DCE), toluene, acetonitrile (MeCN), nitrate It is preferable to use at least one selected from the group consisting of nitromethan, tetrahydrofuran (THF), N, N -dimethyl formamide (DMF) and N, N -dimethylacetamide (DMA). Do.
  • the reaction temperature may be used at a temperature used in conventional organic synthesis, but may vary depending on the amount of reactants and starting materials.
  • the reaction of Scheme 1 is in the range of 10 to 30 ° C.
  • the reaction in Scheme 2 is in the range of 55 to 70. It may be carried out at °C °C, in the case of Scheme 3 may be carried out at 20 to 30 °C, to confirm the complete consumption of the starting material through NMR, etc. to complete the reaction.
  • the solvent may be distilled off under reduced pressure after the extraction process, and the desired product may be separated and purified through conventional methods such as column chromatography.
  • the present invention also provides a transition metal-containing thin film deposition composition comprising the transition metal compound of the present invention.
  • the transition metal-containing thin film deposition composition may include only the transition metal compound of the present invention as a precursor.
  • the transition metal compound of the present invention may be represented by the formula (1) as described above, preferably in the formula (1) M may be titanium, zirconium or hafnium.
  • the transition metal-containing thin film deposition composition according to an embodiment of the present invention may include a compound in which R 1 to R 6 and R 11 to R 13 in Formula 1 are independently a hydrogen atom or a (C1-C7) alkyl group. have.
  • X is independently a mono (C1-C20) alkylamino group, a di (C1-C20) alkylamino group, or a mono (C1-C20) It may include a compound that is an alkylamide group, a di (C1-C20) alkylamide group, a (C1-C20) alkyl group or a (C1-C20) alkoxy group.
  • the transition metal-containing thin film deposition composition according to an embodiment of the present invention may include only the transition metal compound represented by Formula 1 used as a precursor, and has high thermal stability and excellent step coverage.
  • the transition metal compound of Formula 1 is wherein R 1 to R 6 are independently a hydrogen atom or a (C1-C7) alkyl group; X may independently be a mono (C1-C20) alkylamino group, a di (C1-C20) alkylamino group, a (C1-C20) alkyl group or a (C1-C20) alkoxy group.
  • the present invention also provides a transition metal-containing thin film prepared by using the transition metal-containing thin film deposition composition comprising the transition metal compound of the present invention.
  • the transition metal-containing thin film of the present invention is excellent in thermal stability of the present invention, by using a transition metal-containing thin film deposition composition comprising a transition metal compound having a high volatility as a precursor can be produced a high quality thin film of high density and high purity. .
  • the transition metal-containing thin film of the present invention can be prepared by conventional methods used in the art, for example, organometallic chemical vapor deposition (MOCVD), atomic layer deposition (ALD) process, low pressure vapor deposition (LPCVD), plasma enhanced Vapor deposition (PECVD) or plasma enhanced atomic layer deposition (PEALD);
  • MOCVD organometallic chemical vapor deposition
  • ALD atomic layer deposition
  • LPCVD low pressure vapor deposition
  • PECVD plasma enhanced Vapor deposition
  • PEALD plasma enhanced atomic layer deposition
  • the transition metal-containing thin film of the present invention is prepared using a transition metal-containing thin film deposition composition comprising the transition metal compound of the present invention as a precursor, but is not limited to, for example, transition metal oxide film, transition metal nitride film, transition metal It may be a carbon nitride film or a transition metal silicon nitride film, and may be a gate insulating film of a transistor or a dielectric film of a capacitor.
  • the present invention also provides a method for producing a transition metal-containing thin film using the composition for depositing a transition metal-containing thin film of the present invention.
  • the method for producing a transition metal-containing thin film of the present invention may be prepared using only the transition metal compound of the present invention as a precursor for thin film deposition.
  • deposition conditions may be controlled according to the structure or thermal characteristics of the desired thin film, and the deposition conditions according to an embodiment of the present invention include a transition metal compound.
  • Input flow rate of the composition for depositing the transition metal-containing thin film containing, the flow rate of the reaction gas, carrier gas, pressure, RF power, substrate temperature and the like can be exemplified, non-limiting example of such a deposition condition is a transition metal-containing thin film
  • the flow rate of the composition for deposition is 10 to 1000 cc / min
  • the carrier gas is 10 to 1000 cc / min
  • the flow rate of the reaction gas is 1 to 1000 cc / min
  • the pressure is 0.5 to 10 torr
  • the RF power is 200 to 1000 W.
  • the substrate temperature may be adjusted in the range of 150 to 400 °C but is not limited thereto.
  • the reaction gas used in the method for producing a transition metal-containing thin film of the present invention is not limited, but hydrogen (H 2 ), hydrazine (N 2 H 4 ), ozone (O 3 ), ammonia (NH 3 ), nitrogen ( N 2 ), silane (SiH 4 ), borane (BH 3 ), diborane (B 2 H 6 ) and phosphine (PH 3 ) may be one or more mixed gas selected from, the carrier gas is nitrogen (N 2 ), argon (Ar) and helium (He) may be one or more mixed gas selected from.
  • a substrate used in the method for manufacturing a transition metal-containing thin film according to an embodiment of the present invention includes a substrate comprising at least one semiconductor material of Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs and InP; SOI (Silicon On Insulator) substrate; Quartz substrates; Or glass substrates for displays; Polyimide, Polyethylene Terephthalate (PET), Polyethylene Naphthalate (PEN, PolyEthylene Naphthalate), Polymethyl Methacrylate (PMMA), Polycarbonate (PC, PolyCarbonate), Polyethersulfone Flexible plastic substrates such as (PES) and polyester; It may be, but is not limited thereto.
  • the transition metal-containing thin film may include a plurality of conductive layers, dielectric layers, or insulating layers between the substrate and the transition metal-containing thin film.
  • Chloro (chloromethyl) dimethyl silane (228g, 1.6mol) was added to 1500ml of pentane, followed by adding methylamine (100g, 3.2mol) at -10 ° C and stirring at room temperature (25 ° C) for 24 hours. After the reaction was completed, the resultant was filtered to remove the amine salt, and then the solvent and the volatile byproduct were removed under reduced pressure, and distilled under reduced pressure to obtain 197.1 g (89.4%) of the title compound.
  • Chloro (chloromethyl) dimethyl silane (109g, 0.8mol) was added to 1000ml of pentane, followed by normalpropylamine (90g, 1.5mol) at -10 ° C, followed by stirring at room temperature (25 ° C) for 24 hours. After completion of the reaction, the mixture was filtered to remove the amine salt, and the solvent and the volatile byproducts were removed under reduced pressure and distilled under reduced pressure to obtain 100 g (79%) of the title compound.
  • Chloro (chloromethyl) dimethyl silane 130g, 0.9mol was added to 1000ml of pentane, and isopropylamine (108g, 1.8mol) was added at -10 ° C and stirred at room temperature (25 ° C) for 24 hours. After completion of the reaction, the mixture was filtered to remove the amine salt, and the solvent and the volatile byproduct were removed under reduced pressure and distilled under reduced pressure to obtain 120 g (79%) of the title compound.
  • a zirconium silicate thin film was prepared on a silicon substrate by atomic layer deposition.
  • the silicon substrate was maintained at 300 ° C., and the (C 5 H 4 ) CH 2 Si (CH 3 ) 2 N (CH 2 CH 2 CH 3 ) Zr (N (CH 3 ) 2 ) 2 precursor synthesized in Example 4 was used. Filled in a stainless steel bubbler container was maintained at 129 °C.
  • the precursor of Example 4 vaporized in a stainless steel bubbler vessel was transferred to a silicon substrate by argon gas (50 sccm) as a transfer gas to be adsorbed onto the silicon substrate.
  • the zirconium silicate precursor compound was removed using argon gas (4000 sccm) for about 15 seconds.
  • ozone gas having a concentration of about 180 g / m 3 was supplied at 500 sccm for 10 seconds to form a zirconium silicate thin film.
  • argon gas (4000 sccm) was used to remove reaction by-products and residual reaction gas for about 10 seconds.
  • the zirconium silicate thin film was formed by repeating 100 cycles using the above process as one cycle.
  • Example 1 Synthesis in Example 1 instead of (C 5 H 4 ) CH 2 Si (CH 3 ) 2 N (CH 2 CH 2 CH 3 ) Zr (N (CH 3 ) 2 ) 2 precursor synthesized in Example 4 in Example 10 Except that the temperature of the stainless bubble vessel is maintained at 120 ° C. using the prepared precursor (C 5 H 4 ) CH 2 Si (CH 3 ) 2 N (CH 3 ) Zr (N (CH 3 ) 2 ) 2 . A thin film was formed in the same manner as in Example 10.
  • a hafnium silicate thin film was prepared on a silicon substrate by atomic layer deposition.
  • the silicon substrate was maintained at 300 ° C.
  • the (C 5 H 4 ) CH 2 Si (CH 3 ) 2 N (CH 3 ) Hf (N (CH 3 ) 2 ) 2 precursor synthesized in Example 2 was subjected to a stainless steel bubbler.
  • the vessel was filled and kept at 129 ° C.
  • the hafnium silicate precursor vaporized in a stainless steel bubbler container was transferred to a silicon substrate by argon gas (50 sccm) as a transfer gas to be adsorbed onto the silicon substrate.
  • the tin precursor compound was removed for about 15 seconds using argon gas (4000 sccm).
  • hafnium silicate thin film was formed by repeating 100 cycles using the above process as one cycle.
  • Table 1 shows the composition analysis results analyzed by X-ray photoelectron spectroscopy of the thin film deposited in Examples 10 to 12 above.
  • the ratio of zirconium, silicon, and oxygen is about 1: 1: 4, and it can be confirmed that zirconium silicate (ZrSiO 4 ) or hafnium silicate (HfSiO 4 ) is formed with high purity without carbon impurities.
  • the transition metal compound of the present invention includes both the transition metal and the silyl group in one molecule, so that when the transition metal compound of the present invention is used as a precursor, a transition metal silicate film is formed. It can be seen that only the oxide film is formed.
  • a zirconium silicate thin film was formed on a trench wafer having an aspect ratio of about 1: 6 using the deposition method described in Example 10 to confirm the step coating characteristics, and the results are shown in FIG. 1.
  • a zirconium silicate thin film was formed on the trench wafer having an aspect ratio of about 1: 6 using the deposition method described in Example 11 to confirm the step coating characteristics, and the results are shown in FIG. 2.
  • FIG. 2 can also confirm high step coverage properties of 92% or more.
  • a hafnium silicate thin film was formed on a trench wafer having an aspect ratio of about 1: 6 using the deposition method described in Example 12, and the results are shown in FIG. 3.
  • DSC Differential Scanning Calorimeter, DSC3, METTLER TOLEDO
  • the thermal decomposition temperature was compared with the onset temperature of DSC, and the thermal stability was increased compared to the (C 5 H 5 ) Zr (N (CH 3 ) 2 ) 3 zirconium compound of Comparative Example 1. It can be seen that, it is possible to form a thin film at a higher temperature, it can be seen that leading to an increase in the step coverage in the fine pattern.

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Abstract

La présente invention concerne : un nouveau composé de métal de transition ; son procédé de préparation ; une composition pour le dépôt d'un film mince contenant un métal de transition contenant celui-ci ; un film mince contenant un métal de transition utilisant la composition pour le dépôt d'un film mince contenant un métal de transition ; et un procédé de préparation d'un film mince contenant un métal de transition. Le composé de métal de transition selon la présente invention a une stabilité thermique élevée, une volatilité élevée et une stabilité de stockage élevée, et ainsi un film mince contenant un métal de transition ayant une densité élevée et une pureté élevée peut être facilement préparé en utilisant ce dernier en tant que précurseur.
PCT/KR2017/003782 2016-04-12 2017-04-06 Composé de métal de transition, son procédé de préparation, et composition pour le dépôt d'un film mince contenant un métal de transition contenant celui-ci WO2017179857A1 (fr)

Priority Applications (4)

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CN201780023511.7A CN109071571B (zh) 2016-04-12 2017-04-06 过渡金属化合物、其制造方法及包含其的含过渡金属薄膜蒸镀用组合物
US16/093,012 US10913755B2 (en) 2016-04-12 2017-04-06 Transition metal compound, preparation method therefor, and composition for depositing transition metal-containing thin film, containing same
EP17782612.0A EP3444255A1 (fr) 2016-04-12 2017-04-06 Composé de métal de transition, son procédé de préparation, et composition pour le dépôt d'un film mince contenant un métal de transition contenant celui-ci
JP2018552842A JP6979032B2 (ja) 2016-04-12 2017-04-06 遷移金属化合物、その製造方法およびこれを含む遷移金属含有薄膜蒸着用組成物

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KR10-2016-0044683 2016-04-12
KR20160044683 2016-04-12
KR1020170040141A KR101959519B1 (ko) 2016-04-12 2017-03-29 전이금속 화합물, 이의 제조방법 및 이를 포함하는 전이금속함유 박막증착용 조성물
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021513539A (ja) * 2018-02-08 2021-05-27 メカロ カンパニー リミテッドＭｅｃａｒｏ Ｃｏ．，Ｌｔｄ． 有機金属化合物およびこれを用いた薄膜

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6635778B1 (en) * 1996-10-30 2003-10-21 Repsol Quimica S.A. Catalysts systems for the polymerization and copolymerization of alpha-olefins
KR20070121281A (ko) * 2006-06-21 2007-12-27 (주)디엔에프 지르코늄 산화물 박막 증착용 유기금속 선구물질 및 이의제조 방법
KR20120042971A (ko) * 2009-07-14 2012-05-03 레르 리키드 쏘시에떼 아노님 뿌르 레？드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 고온에서의 ⅳ족 금속 함유 막의 퇴적
KR20120078025A (ko) * 2010-12-31 2012-07-10 주식회사 한솔케미칼 실릴아민 리간드가 포함된 유기금속화합물, 및 이를 전구체로 이용한 금속 산화물 또는 금속-규소 산화물의 박막 증착 방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6635778B1 (en) * 1996-10-30 2003-10-21 Repsol Quimica S.A. Catalysts systems for the polymerization and copolymerization of alpha-olefins
KR20070121281A (ko) * 2006-06-21 2007-12-27 (주)디엔에프 지르코늄 산화물 박막 증착용 유기금속 선구물질 및 이의제조 방법
KR20120042971A (ko) * 2009-07-14 2012-05-03 레르 리키드 쏘시에떼 아노님 뿌르 레？드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 고온에서의 ⅳ족 금속 함유 막의 퇴적
KR20120078025A (ko) * 2010-12-31 2012-07-10 주식회사 한솔케미칼 실릴아민 리간드가 포함된 유기금속화합물, 및 이를 전구체로 이용한 금속 산화물 또는 금속-규소 산화물의 박막 증착 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
VALADE, L. ET AL.: "Evaluation of the Simultaneous Use of Cp2VMe2 and CpTiC12N (SiMe3)2 as Precursors to Ceramic: Thin Films Containing Titanium and Vanadium: towards Titanium-vanadium Carbonitride", APPLIED ORGANOMETALLIC CHEMISTRY, vol. 12, 1998, pages 173 - 187, XP055433915 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021513539A (ja) * 2018-02-08 2021-05-27 メカロ カンパニー リミテッドＭｅｃａｒｏ Ｃｏ．，Ｌｔｄ． 有機金属化合物およびこれを用いた薄膜
JP6999830B2 (ja) 2018-02-08 2022-02-04 メカロ カンパニー リミテッド 有機金属化合物およびこれを用いた薄膜

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