WO2021085810A2 - Composé de métal de transition du groupe 4, son procédé de préparation et composition comprenant celui-ci pour le dépôt d'un film mince - Google Patents

Composé de métal de transition du groupe 4, son procédé de préparation et composition comprenant celui-ci pour le dépôt d'un film mince Download PDF

Info

Publication number
WO2021085810A2
WO2021085810A2 PCT/KR2020/010113 KR2020010113W WO2021085810A2 WO 2021085810 A2 WO2021085810 A2 WO 2021085810A2 KR 2020010113 W KR2020010113 W KR 2020010113W WO 2021085810 A2 WO2021085810 A2 WO 2021085810A2
Authority
WO
WIPO (PCT)
Prior art keywords
transition metal
group
thin film
alkyl
formula
Prior art date
Application number
PCT/KR2020/010113
Other languages
English (en)
Korean (ko)
Other versions
WO2021085810A3 (fr
Inventor
정택모
박보근
이가연
엄태용
여승민
김건환
이영국
Original Assignee
한국화학연구원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국화학연구원 filed Critical 한국화학연구원
Publication of WO2021085810A2 publication Critical patent/WO2021085810A2/fr
Publication of WO2021085810A3 publication Critical patent/WO2021085810A3/fr

Links

Images

Classifications

    • 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
    • C07F7/28—Titanium compounds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD

Definitions

  • the present invention relates to a group 4 transition metal compound, a method for preparing the same, and a composition for thin film deposition including the same, and more particularly, a group 4 transition metal compound useful as a group 4 transition metal thin film precursor, a method for preparing the same, and a thin film comprising the same It relates to a vapor deposition composition and a method of manufacturing a group 4 transition metal-containing thin film using the same.
  • the deposition process of a thin film is classified into a physical deposition method and a chemical deposition method.
  • a physical deposition method In order to manufacture a high-quality thin film by chemical vapor deposition, not only the thin film itself, that is, the chemical properties of the compound forming the thin film must be excellent, but also the thin film forming compound can be easily introduced into the deposition chamber of the thin film manufacturing equipment.
  • Physical properties such as thermal stability and vapor pressure of the compound for forming a thin film must be excellent.
  • a method of introducing the compound for thin film formation into the deposition chamber a method of directly transferring the compound for thin film formation by using its own vapor pressure, a method using an inert gas as a transfer gas, etc. have been used.
  • a method of directly transferring and spraying into the deposition chamber using an injector (Liquid delivery system) is being used.
  • the compound for forming a thin film In the process of transporting and vaporizing the liquid compound for forming a thin film, the compound for forming a thin film is continuously heated and exposed to heat. In this process, if the compound for forming a thin film is decomposed or the viscosity of the compound for forming a thin film is excessively decreased, the transport of the compound for forming a thin film is difficult or spraying into the chamber is not smoothly performed, so that the thickness of the formed thin film is reduced. There is a problem that it becomes uneven and the quality is deteriorated.
  • the semiconductor structure is directly refined and refined, it is applied to various processes (e.g., atomic layer deposition (ALD), chemical vapor deposition (CVD)) that have excellent step coverage even in fine patterns.
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • the Group 4 transition metal compound may include a titanium precursor, a zirconium precursor, and a hafnium precursor, and the preparation of a Group 4 transition metal oxide thin film through an atomic layer deposition method or a chemical vapor deposition method using the same depends on the ligand structure of these precursors. It has developed in various ways.
  • group 4 transition metal inorganic salts such as ZrCl 4 , ZrI 4 , and ZrF 4 are known.
  • the inorganic salt in the inner films (Cl -, F -, I -) is to remain in the electric characteristics of the thin film degradation and aggregation (aggromeration) of the thin film differs generated Had an easy problem.
  • Chem. Mater., 2002, 14, 4350 discloses a zirconium compound in which an amido ligand is coordinated, and a zirconium oxide thin film using the same as a precursor.
  • the precursors represented by the zirconium compound e.g., Zr(NMeEt) 4 or Zr(NEt 2 ) 4
  • Zr(NMeEt) 4 or Zr(NEt 2 ) 4 all exist in a liquid state with low viscosity at room temperature, and the vapor pressure is very high, and the amido ligand is caused by ozone and water vapor. It is easy to remove the zirconium oxide thin film through the atomic layer deposition method.
  • the zirconium compound is very reactive, it is not easy to store for a long period of time. In particular, the zirconium compound is decomposed during evaporation due to low thermal stability, resulting in deterioration of the quality of the thin film.
  • the present invention provides a novel Group 4 transition metal compound and a method for preparing the same.
  • the present invention provides a composition for depositing a thin film containing a group 4 transition metal comprising the group 4 transition metal compound of the present invention and a method for manufacturing a thin film containing a group 4 transition metal using the same.
  • the present invention provides a Group 4 transition metal compound which is very useful as a precursor for thin film deposition due to its excellent thermal stability and volatility, and the Group 4 transition metal compound of the present invention is represented by the following formula (1).
  • M is a Group 4 transition metal
  • R 1 to R 6 are independently of each other C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl;
  • R 11 to R 15 are each independently hydrogen or C 1 -C 10 alkyl.
  • M is titanium, zirconium or hafnium
  • R 1 to R 6 are independently of each other C 1 -C 7 alkyl
  • R 11 to R 15 are independently hydrogen or It may be C 1 -C 7 alkyl
  • M is zirconium or hafnium
  • R 1 to R 3 are the same as each other C 1 -C 4 alkyl
  • R 4 to R 6 are the same as each other C 1- It may be C 4 alkyl.
  • the Group 4 transition metal compound according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.
  • M is titanium, zirconium, or hafnium.
  • the present invention provides a method for preparing a Group 4 transition metal compound of the present invention.
  • the method for preparing a Group 4 transition metal compound of the present invention is represented by the following Chemical Formula 2 by reacting a compound of Chemical Formula 3 with a compound of Chemical Formula 4. And preparing a Group 4 transition metal compound.
  • M is a Group 4 transition metal
  • R 1 and R 4 are independently of each other C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl;
  • R 11 to R 15 are each independently hydrogen or C 1 -C 10 alkyl
  • R 21 to R 26 are each independently C 1 -C 10 alkyl.
  • the present invention provides a composition for depositing a group 4 transition metal-containing thin film comprising the group 4 transition metal compound of the present invention represented by Formula 1 above.
  • M is titanium, zirconium or hafnium
  • R 1 to R 6 are independently of each other C 1 -C 7 alkyl
  • R 11 to R 15 are independently hydrogen or C It may be 1 -C 7 alkyl, more preferably M is zirconium or hafnium
  • R 1 to R 3 are the same as each other C 1 -C 4 alkyl
  • R 4 to R 6 are the same as each other C 1 -C 4 may be alkyl.
  • the present invention provides a method of manufacturing a group 4 transition metal-containing thin film using the composition for depositing a transition metal-containing thin film of the present invention.
  • the novel Group 4 transition metal compound of the present invention has high thermal stability and excellent volatility, so it is very useful as a precursor for a group 4 transition metal-containing thin film. Manufacturing is possible.
  • novel Group 4 transition metal compound of the present invention is very easy to handle as a liquid at room temperature, has excellent thermal stability and volatility, and thus can be applied to various thin film deposition methods, and has the advantage of producing a high-quality thin film with a fast deposition rate. Have.
  • composition for depositing a group 4 transition metal thin film of the present invention includes the novel group 4 transition metal compound of the present invention, it is possible to manufacture a thin film having high density and purity of the thin film and very excellent physical and electrical properties.
  • Example 1 shows a TGA graph of Zr(cp)(edpa) 3 prepared in Example 1 according to the present invention.
  • Example 2 shows a TGA graph of Hf(cp)(edpa) 3 prepared in Example 2 according to the present invention.
  • Figure 3 is a graph showing the change in the growth rate of the thin film according to the supply time using the Hf (cp) (edpa) 3 precursor of the present invention and the reaction gas H 2 O gas.
  • Example 4 is a graph showing a change in thickness according to a deposition cycle of a hafnium oxide thin film prepared in Example 4 of the present invention.
  • Example 5 is a graph showing the XPS analysis results of the hafnium oxide thin film prepared in Example 4 of the present invention.
  • alkyl includes both straight-chain or branched-chain forms, and may have 1 to 10 carbon atoms, preferably 1 to 7, more preferably 1 to 4 carbon atoms.
  • cycloalkyl is a substituent derived by the removal of one hydrogen from a fully saturated or partially unsaturated hydrocarbon ring, and as a specific example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentenyl , Cyclohexenyl, cycloheptenyl, cyclopentadiene, cyclohexadiene, cycloheptadiene, bicycloheptyl or bicycloheptenyl, and the like, but is not limited thereto.
  • the present invention provides a group 4 transition metal compound that is very useful as a precursor of a high-k thin film, and the group 4 transition metal compound of the present invention is represented by the following formula (1).
  • M is a Group 4 transition metal
  • R 1 to R 6 are independently of each other C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl;
  • R 11 to R 15 are each independently hydrogen or C 1 -C 10 alkyl.
  • the Group 4 transition metal compound of Formula 1 according to an embodiment of the present invention exists as a liquid at room temperature, so it is easy to handle and has excellent thermal stability, so that it is not decomposed even in a continuous heating process, so that a high quality thin film can be manufactured.
  • the Group 4 transition metal compound of the present invention can produce a high-quality thin film having a high dielectric constant by simultaneously employing one cyclopentadienyl derivative and an alkoxyamide ligand.
  • the Group 4 transition metal compound of the present invention since the Group 4 transition metal compound of the present invention has excellent thermal stability, volatility and reactivity, it can be deposited by various deposition methods, and a high density, high purity group 4 transition metal-containing thin film can be prepared at a high deposition rate.
  • M is titanium, zirconium or hafnium
  • R 1 to R 6 are independently of each other C 1 -C 7 alkyl
  • R 11 to R 15 are independently hydrogen or It may be a C 1 -C 7 alkyl.
  • M is more preferably zirconium or hafnium in Formula 1
  • R 1 to R 3 are the same as each other C 1 -C 4 alkyl
  • R 4 to Like each other R 6 may be C 1 -C 4 alkyl.
  • Formula 1 according to an embodiment of the present invention may be represented by the following Formula 2.
  • M is a Group 4 transition metal
  • R 1 and R 4 are independently of each other C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl;
  • R 11 to R 15 are each independently hydrogen or C 1 -C 10 alkyl.
  • M is zirconium or hafnium
  • R 1 and R 4 are independently of each other C 1 -C 4 alkyl
  • R 11 to R 15 are independently hydrogen or C It may be 1 -C 4 alkyl.
  • R 1 and R 4 in Formula 2 according to an embodiment of the present invention are independently of each other methyl, ethyl, n -propyl, i -propyl, n -butyl, i -butyl, s -butyl or t -butylyl I can.
  • the Group 4 transition metal compound according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.
  • M is titanium, zirconium, or hafnium.
  • the present invention provides a method for preparing a Group 4 transition metal compound.
  • the method for preparing a Group 4 transition metal compound of the present invention comprises reacting a compound of Formula 3 with a compound of Formula 4, And preparing a group transition metal compound.
  • M is a Group 4 transition metal
  • R 1 and R 4 are independently of each other C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl;
  • R 11 to R 15 are each independently hydrogen or C 1 -C 10 alkyl
  • R 21 to R 26 are each independently C 1 -C 10 alkyl.
  • the reaction according to an embodiment of the present invention may be performed at room temperature (10 to 35°C) for 8 to 24 hours.
  • It may be used in an amount of 2 to 5 moles, preferably 2 to 4 moles, per 1 mole of the compound of Formula 3 according to an embodiment of the present invention.
  • the reaction according to an embodiment of the present invention may be carried out under an organic solvent, and the organic solvent usable is not limited, but an organic solvent having high solubility in the reactants may be used, and specifically, hexane (n -Hexane), diethylether, toluene (toluene), tetrahydrofuran (THF) one or more selected from one or more organic solvents can be used.
  • organic solvent usable is not limited, but an organic solvent having high solubility in the reactants may be used, and specifically, hexane (n -Hexane), diethylether, toluene (toluene), tetrahydrofuran (THF) one or more selected from one or more organic solvents can be used.
  • reaction according to an embodiment of the present invention may be carried out in an inert gas atmosphere such as nitrogen or argon.
  • Group 4 transition metal compound of Formula 1 according to an embodiment of the present invention can be prepared in a variety of ways possible within the range recognized by those skilled in the art.
  • the present invention provides a composition for thin film deposition containing a Group 4 transition metal comprising a Group 4 transition metal compound represented by the following Formula 1 of the present invention.
  • M is a Group 4 transition metal
  • R 1 to R 6 are independently of each other C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl;
  • R 11 to R 15 are each independently hydrogen or C 1 -C 10 alkyl.
  • M is titanium, zirconium or hafnium; R 1 to R 6 are each independently C 1 -C 7 alkyl, and R 11 to R 15 may each independently be hydrogen or C 1 -C 7 alkyl.
  • R 1 to R 3 are independently C 3 -C 7 alkyl, and R 4 to R 6 may be C 1 -C 4 alkyl independently of each other. have.
  • R 11 to R 15 in Formula 1 may be hydrogen independently of each other.
  • R 1 to R 3 in Formula 1 may be C 1 -C 7 alkyl with the same substituent
  • R 4 to R 6 may be C 1 -C 7 alkyl with the same substituent, preferably R 1 To R 3 may be C 3 -C 7 alkyl with the same substituent, and R 4 to R 6 may be C 1 -C 4 alkyl with the same substituent.
  • composition for depositing a thin film containing a group 4 transition metal can produce a high-quality thin film by using the group 4 transition metal compound of the present invention having extremely improved thermal stability and volatility as a precursor.
  • the composition for depositing a thin film containing a group 4 transition metal includes a linear, branched or cyclic alkane compound having 5 to 10 carbon atoms; Aromatic hydrocarbon compounds having 6 to 12 carbon atoms; An alkylamine compound having 2 to 10 carbon atoms; Heterocycloalkyl compounds containing oxygen, nitrogen, and the like; It may further include one solvent selected from, or a mixed solvent of two or more.
  • the alkane compound may include hexane, heptane, octane cyclohexane, neopentane, and the like
  • the aromatic hydrocarbon compound may include benzene, toluene, xylene, and the like
  • the alkylamine compound is dimethylamine, diethyl Amine, ethylmethylamine, triethylamine, tributylamine, tetramethylethylenediamine, and the like.
  • the heterocycloalkyl compound may include tetrahydrofuran and pyridine.
  • composition for depositing a thin film containing a Group 4 transition metal may include 0.1 to 10 moles of the solvent based on 1 mole of the Group 4 transition metal compound.
  • the solvent may be specifically contained in an amount of 0.2 to 5 moles, more specifically 0.5 to 3 moles.
  • the group 4 transition metal-containing thin film deposition composition may be used for thin film deposition through a conventional solution process.
  • the composition for thin film deposition containing a group 4 transition metal is a mixture of the group 4 transition metal compound and a solvent in a 1:1 molar ratio
  • its viscosity (Viscosity, Cp, measured at 28.3°C) is 1 to 50 Cp. It may be, specifically 1 to 30Cp, more specifically it may be 1 to 20Cp.
  • the R 1 to R 3 of the Group 4 transition metal compound are pulverized alkyl (for example, C 3-7 alkyl), more It is possible to implement a low viscosity, and it is possible to manufacture a high-density thin film having excellent step coverage and crystallinity.
  • the present invention provides a method of manufacturing a group 4 transition metal-containing thin film using the composition for depositing a group 4 transition metal-containing thin film of the present invention.
  • the Group 4 transition metal-containing thin film according to an embodiment of the present invention can be any known method that can be recognized by those skilled in the art, but examples include chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD). , Atomic layer deposition (ALD), low pressure vapor deposition, plasma enhanced atomic layer deposition, and the like.
  • CVD chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • ALD Atomic layer deposition
  • low pressure vapor deposition low pressure vapor deposition
  • plasma enhanced atomic layer deposition and the like.
  • the group 4 transition metal-containing thin film prepared by the above deposition method is a titanium oxide thin film, a zirconium oxide thin film, a hafnium oxide thin film, a titanium oxynitride thin film, a zirconium oxynitride thin film, a hafnium oxynitride thin film, or a group 4 transition metal-containing composite. It may be an oxynitride thin film.
  • the substrate used for the group 4 transition metal-containing thin film in one embodiment of the present invention is not limited as long as it is a conventional substrate, and non-limiting examples thereof include Ru, TiN, Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs and InP, a substrate containing at least one semiconductor material, a silicon on insulator (SOI) substrate, a rigid substrate such as a quartz substrate or a glass substrate for a display, or a polyimide, polyethylene terephthalate (PET, PolyEthylene Terephthalate), PolyEthylene Naphthalate (PEN), Poly Methyl MethAcrylate (PMMA), Polycarbonate (PC, PolyCarbonate), Polyethersulfone (PES), Polyester, etc. It may be a plastic substrate.
  • SOI silicon on insulator
  • PEN polyethylene terephthalate
  • PEN PolyEthylene Naphthalate
  • PMMA Poly Methyl MethAcrylate
  • the method of manufacturing a group 4 transition metal-containing thin film through the composition for depositing a group 4 transition metal according to an embodiment of the present invention is specifically, performed by chemical vapor deposition (CVD) or atomic layer deposition (ALD). I can.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • a method of manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention includes the steps of maintaining a temperature of a substrate mounted in a chamber at 80 to 400°C; And supplying energy to the substrate.
  • the step of supplying energy is to activate a reaction for deposition, and may be a step of supplying energy by plasma, light, heat, voltage, or the like.
  • the temperature of the substrate may be in the range of 100 to 350°C, more specifically 200 to 325°C.
  • a deposition source derived from the composition for depositing a thin film containing a group 4 transition metal at the temperature of the substrate may be provided.
  • the deposition source may be provided with an additional reaction gas.
  • the reaction gases used in the method for manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention are oxygen (O 2 ), ozone (O 3 ), nitrous oxide (N 2 O), carbon dioxide (CO 2 ), and water.
  • Oxygen plasma, ozone plasma, water plasma, and the like may be one or two or more mixed gases selected from.
  • the reaction gas is not limited, but may be provided at a flow rate of 1 sccm to 1,000 sccm, specifically 100 sccm to 500 sccm, more specifically 150 to 400 sccm.
  • each step of the method of manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention may further include a purge step.
  • the purge gas in the purge step is not limited as long as it is a conventional one that does not react with the group 4 transition metal compound of the present invention, and non-limiting examples thereof include nitrogen, helium, neon, argon, krypton, xenon, and radon. It may be one or a mixed gas of two or more selected from and the like.
  • the deposition source and the purge gas may be provided at a flow rate of 1 sccm to 3,000 sccm, specifically 100 sccm to 1,500 sccm, and more specifically 300 to 1,300 sccm.
  • the pressure in the chamber may be 0.1 to 10 torr, specifically 0.1 to 5 torr, and more specifically 0.5 to 3 torr.
  • An additional heat treatment step may be further performed on the Group 4 transition metal-containing thin film obtained through the method for producing a Group 4 transition metal-containing thin film according to an embodiment of the present invention.
  • the group 4 transition metal-containing thin film manufactured according to the method of manufacturing a group 4 transition metal-containing thin film according to an embodiment of the present invention is a high dielectric thin film material having a high density and high dielectric constant.
  • the high dielectric constant thin film material having a high density and high dielectric constant is easily supplied through an ALD process or a CVD process, and thus the wiring of a semiconductor device, It can be used in various ways to form a gate insulating film of a transistor, a dielectric film of a capacitor, or a coating film of an electronic component.
  • examples of the Group 4 transition metal compound according to the present invention were performed under an inert argon or nitrogen atmosphere using a glove box or a Schlenk line, and the structural analysis of the obtained title compound was 1 H and 13 C NMR. It was measured through spectrum (Bruker Advance 400 NMR) and elemental analysis (Thermo Scientific Flash 2000).
  • a thermogravimetric analysis (TGA) method was used in order to measure the thermal stability, volatility, and decomposition temperature of the Group 4 transition metal compound.
  • the TGA method was measured under nitrogen gas injection at a pressure of 1.5 bar/min while heating the obtained title compound to 800°C at a rate of 10°C/min.
  • Tris(dimethylamino)cyclopentadienylzirconium (0.50g, 1.73mmol) was dissolved in 100 mL of n-hexane, and then N-ethoxy-2,2-dimethylpropanamide (edpaH) (0.75 g, 5.20 mmol) was added dropwise. After stirring at room temperature for 12 hours, n-hexane was removed under reduced pressure. Purification by distillation (150° C./300 mtorr) gave about 0.75 g (74%) of the title compound as a pale yellow liquid.
  • Tris(dimethylamino)cyclopentadienylhafnium (1.00 g, 2.66 mmol) was dissolved in 150 mL of hexane, and then N-ethoxy-2,2-dimethylpropanamide (edpaH) (1.16 g, 7.98 mmol) was added dropwise. After stirring at room temperature for 12 hours, hexane was removed under reduced pressure. Purification by distillation (180° C./300 mtorr) gave about 1.2 g (67 %) of the title compound as a pale yellow liquid.
  • edpaH N-ethoxy-2,2-dimethylpropanamide
  • Example 2 As a result of TG analysis of Hf(Cp)(edpa) 3 prepared in Example 1, a mass decrease began to occur around 110°C, and a mass of 95% or more decreased at about 250°C. From this, it can be seen that the compound prepared in Example 2 of the present invention also has high thermal stability.
  • a hafnium oxide thin film was prepared on a silicon substrate by atomic layer deposition.
  • the silicon substrate was maintained at 300°C, and the Hf(cp)(edpa) 3 precursor synthesized in Example 2 was filled in a stainless steel bubbler container and maintained at 110°C.
  • the Hf(cp)(edpa) 3 precursor vaporized in a stainless steel bubbler container is supplied to the silicon substrate using argon gas (50 sccm) as a transfer gas, but the supply time is increased from 1 second to 7 seconds.
  • the deposition rate of was measured and shown in FIG. 3.
  • the H 2 O reaction gas was supplied by increasing the supply time from 1 second to 5 seconds, and the thin film deposition rate according to the supply time was measured and shown in FIG. 3.
  • the thin film deposition rate remains constant. After 5 seconds, the Hf It can be seen that the (cp)(edpa) 3 precursor is included in the substrate, and the H 2 O reaction gas is saturated after 3 seconds as the thickness of the thin film is constant after 3 seconds. From this, the supply time of the Hf(cp)(edpa) 3 precursor was set to 5 seconds, and the supply time of H 2 O was set to 3 seconds.
  • Example 3 the supply time of the Hf(cp)(edpa) 3 precursor was 5 seconds, and the supply time of H 2 O was 3 seconds, and then reaction by-products and residual reaction gas were removed for about 10 seconds using argon gas (1000 sccm). Removed. Using the above process as one cycle, 100 cycles were repeated to form a hafnium oxide thin film, and the results are shown in FIG. 4.
  • the thickness of the thin film linearly increased as the deposition cycle increased, and the deposition rate was about 0.9 ⁇ /cycle.
  • XPS analysis results of the hafnium oxide thin film deposited in Example 4 are shown in FIG. 5.
  • the peaks of Hf 4f 7/2 and 4f 5/2 of FIG. 5 and the peaks from O1s it can be seen that the binding energy of Hf-O is shown in the hafnium oxide thin film.
  • the purity of the hafnium oxide thin film is excellent because there is almost no carbon as an impurity in the hafnium oxide thin film.
  • the hafnium oxide thin film deposited in Example 4 was analyzed by XRF. As a result, Hf was present in the thin film, indicating that a hafnium oxide thin film was prepared.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

La présente invention concerne un composé de métal de transition du groupe 4, son procédé de préparation et un procédé de formation d'un film mince l'utilisant. Un composé de métal de transition du groupe 4, selon la présente invention présente une excellente volatilité et est thermiquement stable, et peut ainsi être utilisé en tant que précurseur pour préparer un film mince contenant du métal de transition du groupe 4 de densité et de pureté élevées.
PCT/KR2020/010113 2019-10-29 2020-07-31 Composé de métal de transition du groupe 4, son procédé de préparation et composition comprenant celui-ci pour le dépôt d'un film mince WO2021085810A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2019-0135051 2019-10-29
KR1020190135051A KR102327450B1 (ko) 2019-10-29 2019-10-29 4족 전이금속 화합물, 이의 제조방법 및 이를 포함하는 박막증착용 조성물

Publications (2)

Publication Number Publication Date
WO2021085810A2 true WO2021085810A2 (fr) 2021-05-06
WO2021085810A3 WO2021085810A3 (fr) 2021-06-24

Family

ID=75715262

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2020/010113 WO2021085810A2 (fr) 2019-10-29 2020-07-31 Composé de métal de transition du groupe 4, son procédé de préparation et composition comprenant celui-ci pour le dépôt d'un film mince

Country Status (2)

Country Link
KR (1) KR102327450B1 (fr)
WO (1) WO2021085810A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102548034B1 (ko) * 2023-01-17 2023-06-28 한국화학연구원 신규한 유기 비스무트 화합물, 이의 제조방법 및 이를 이용하여 박막을 제조하는 방법

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013501815A (ja) * 2009-08-14 2013-01-17 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード ハフニウム含有前駆体およびジルコニウム含有前駆体ならびにそれを使用する方法
WO2013157901A1 (fr) * 2012-04-20 2013-10-24 주식회사 유피케미칼 Composé précurseur contenant un métal de transition du groupe 4, procédé de préparation correspondant, composition de précurseur le contenant, et procédé de dépôt de film mince l'utilisant
WO2017082541A1 (fr) * 2015-11-11 2017-05-18 한국화학연구원 Précurseur de métal, procédé de préparation associé, et procédé de formation de film mince au moyen de celui-ci
KR101806987B1 (ko) * 2016-02-03 2017-12-08 주식회사 유피케미칼 4 족 금속 원소-함유 화합물, 이의 제조 방법, 이를 포함하는 막 증착용 전구체 조성물, 및 이를 이용하는 막의 증착 방법
US10364259B2 (en) * 2016-12-30 2019-07-30 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same

Also Published As

Publication number Publication date
KR20210050689A (ko) 2021-05-10
KR102327450B1 (ko) 2021-11-17
WO2021085810A3 (fr) 2021-06-24

Similar Documents

Publication Publication Date Title
WO2015105350A1 (fr) Nouveau dérivé de cyclodisilazane, son procédé de préparation et film mince contenant du silicium l'utilisant
WO2021133080A1 (fr) Composé précurseur de métal yttrium/lanthanide, composition le comprenant pour former un film, et procédé de formation d'un film contenant un métal yttrium/lanthanide à l'aide de la composition
WO2019103500A1 (fr) Composition pour déposer un film mince contenant du silicium et procédé de production d'un film mince contenant du silicium l'utilisant
WO2012176989A1 (fr) Composé diamine ou son sel, procédé pour le préparer, et ses utilisations
WO2015142053A1 (fr) Composé aminé de germanium organique et procédé de dépôt de film mince l'utilisant
WO2018048124A1 (fr) Composé métallique du groupe 5, son procédé de préparation, composition de précurseur de dépôt de film le comprenant, et procédé de dépôt de film l'utilisant
WO2015130108A1 (fr) Composition de précurseur pour formation de pellicule contenant du zirconium et procédé de formation de pellicule contenant du zirconium à l'aide de celle-ci
WO2019203407A1 (fr) Composé précurseur pour dépôt de couche atomique (ald) ou dépôt chimique en phase vapeur (cvd), et procédé d'ald/cvd l'utilisant
WO2019088722A1 (fr) Procédé de production d'un film mince contenant du ruthénium, et film mince contenant du ruthénium produit par celui-ci
WO2020116770A1 (fr) Composé de métal de transition du groupe 4, procédé de préparation d'un tel composé et procédé de formation d'un film mince mettant en œuvre un tel composé
WO2021085810A2 (fr) Composé de métal de transition du groupe 4, son procédé de préparation et composition comprenant celui-ci pour le dépôt d'un film mince
WO2020101437A1 (fr) Composé précurseur de silicium, son procédé de préparation et procédé de formation de film contenant du silicium l'utilisant
WO2017135715A1 (fr) Composé contenant un métal du groupe 4, son procédé de préparation, composition de précurseur contenant celui-ci pour le dépôt de film, et procédé de dépôt de film l'utilisant
WO2023068629A1 (fr) Précurseur de métal du groupe 3, procédé de préparation de celui-ci et procédé de fabrication d'un e film mince à l'aide de celui-ci
WO2018182309A1 (fr) Composition pour déposer un film mince contenant du silicium contenant un composé bis(aminosilyl)alkylamine et procédé de fabrication de film mince contenant du silicium l'utilisant
WO2022169232A1 (fr) Composé de métal de transition du groupe 4, procédé de fabrication d'un tel composé et procédé de formation d'un film mince l'utilisant
WO2021261890A1 (fr) Précurseur pour la formation d'un film mince, son procédé de préparation, et procédé de formation d'un film mince le comprenant
WO2021153986A1 (fr) Composé précurseur de silicium, composition pour former un film contenant du silicium comprenant celui-ci, et procédé de formation d'un film contenant du silicium
WO2018182305A9 (fr) Composé silylamine, composition de dépôt de film mince contenant du silicium le contenant, et procédé de fabrication d'un film mince contenant du silicium à l'aide de la composition
WO2023113308A1 (fr) Composé de molybdène, son procédé de préparation et composition le comprenant pour un dépôt de film mince
WO2024058431A1 (fr) Précurseur pour la formation d'un film mince contenant de l'yttrium ou du scandium, procédé de formation d'un film mince contenant de l'yttrium ou du scandium l'utilisant et élément semi-conducteur comprenant un film mince contenant de l'yttrium ou du scandium
WO2017082541A1 (fr) Précurseur de métal, procédé de préparation associé, et procédé de formation de film mince au moyen de celui-ci
WO2021034014A1 (fr) Nouveau composé de silylcyclodisilazane et procédé de fabrication de couche mince contenant du silicium à l'aide de celui-ci
WO2023113309A1 (fr) Composé de molybdène, son procédé de préparation et procédé de fabrication d'une couche mince le comprenant
WO2022114782A1 (fr) Composé à base de tantale, son procédé de préparation, et composition de dépôt de film fin contenant du tantale le comprenant

Legal Events

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

Ref document number: 20881008

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20881008

Country of ref document: EP

Kind code of ref document: A2