WO2014168312A1 - Composé précurseur contenant un métal de transition du groupe iv, et procédé pour déposer une couche mince utilisant celui-ci - Google Patents

Composé précurseur contenant un métal de transition du groupe iv, et procédé pour déposer une couche mince utilisant celui-ci Download PDF

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WO2014168312A1
WO2014168312A1 PCT/KR2013/011370 KR2013011370W WO2014168312A1 WO 2014168312 A1 WO2014168312 A1 WO 2014168312A1 KR 2013011370 W KR2013011370 W KR 2013011370W WO 2014168312 A1 WO2014168312 A1 WO 2014168312A1
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group
transition metal
formula
precursor compound
containing precursor
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PCT/KR2013/011370
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Korean (ko)
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한원석
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주식회사 유피케미칼
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    • 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
    • C23C16/44—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
    • 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
    • C07F17/00—Metallocenes
    • 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
    • C23C16/308—Oxynitrides
    • 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
    • C23C16/34—Nitrides

Definitions

  • the present application relates to a Group 4 transition metal-containing precursor compound, a method for preparing the precursor compound, a precursor composition for thin film deposition including the precursor compound, and a method for depositing a thin film using the precursor compound.
  • Korean Patent Laid-Open No. 10-2012-0038369 “Method for Manufacturing Semiconductor Device, Substrate Processing Device and Semiconductor Device” discloses forming a ZrO 2 dielectric layer included in a semiconductor DRAM using TEMAZ.
  • cyclopentadienyltris (dimethylamido) zirconium [CpZr (NMe 2 ) 3 ] having a pyrolysis temperature higher than TEMAZ may also be used to deposit a zirconium oxide film.
  • a high dielectric constant oxide film having a low aspect current in a structure having a higher aspect ratio.
  • a zirconium oxide film or a hafnium oxide film can be formed using an atomic layer deposition method at a high temperature.
  • the zirconium raw material or hafnium raw material used for a liquid vaporization apparatus is a liquid at normal temperature.
  • Raw materials that are solid at room temperature may also be heated to liquefy by melting above their melting point, or may be used in liquid vaporization devices in the form of solutions dissolved in a suitable solvent.
  • the vapor pressure of the solvent should be less than the raw material to prevent the problem that the solvent evaporates in the liquid vaporization device to block the passage of the solution as a solid raw material.
  • cyclopentadienyltris (dimethylamido) zirconium [CpZr (NMe 2 ) 3 ] compounds can be used for this purpose.
  • the zirconium oxide film or the hafnium oxide film may differ in permittivity, leakage current, step coverage, etc., so that a new zirconium raw material compound or a new hafnium raw material can be selected so as to select the most suitable raw material for the desired purpose.
  • the demand for compounds still exists in the semiconductor industry.
  • the present application is to provide a Group 4 transition metal-containing precursor compound represented by Formula 1 or Formula 2, a method for preparing the same, and a thin film deposition use thereof.
  • M 1 comprises Zr or Hf
  • Cp ' comprises a cyclopentadienyl group which may be substituted by a C 1-4 alkyl group
  • n 1 or 2
  • the two Cp's may be the same or different from each other
  • L includes a C 1-3 alkyl group, a C 1-6 alkoxide group or -NHR 3 , wherein R 3 is a C 1-6 alkyl group, and when two or more L are two or more L, they may be the same or different from each other,
  • M 1 is bonded to Cp ';
  • M 1 comprises Zr or Hf
  • Cp 'and Cp each independently include a cyclopentadienyl group which may be substituted by a C 1-4 alkyl group,
  • L 1 and L 2 each independently include a C 1-3 alkyl group, a C 1-6 alkoxide group, or —NHR 3 , wherein R 3 is a C 1-6 alkyl group,
  • R 1 and R 2 each independently include hydrogen or a C 1-4 alkyl group
  • M 1 is bonded to Cp 'and Cp ".
  • a first aspect of the present application provides a Group 4 transition metal-containing precursor compound represented by Formula 1 or Formula 2 below:
  • M 1 comprises Zr or Hf
  • Cp ' comprises a cyclopentadienyl group which may be substituted by a C 1-4 alkyl group
  • n 1 or 2
  • the two Cp's may be the same or different from each other
  • L includes a C 1-3 alkyl group, a C 1-6 alkoxide group or -NHR 3 , wherein R 3 is a C 1-6 alkyl group, and when two or more L are two or more L, they may be the same or different from each other,
  • M 1 is bonded to Cp ';
  • M 1 comprises Zr or Hf
  • Cp 'and Cp each independently include a cyclopentadienyl group which may be substituted by a C 1-4 alkyl group,
  • L 1 and L 2 each independently include a C 1-3 alkyl group, a C 1-6 alkoxide group, or —NHR 3 , wherein R 3 is a C 1-6 alkyl group,
  • R 1 and R 2 each independently include hydrogen or a C 1-4 alkyl group
  • M 1 is bonded to Cp 'and Cp ".
  • a second aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:
  • M 1 X 4 and Cp'M 2 are reacted in an organic solvent to form M 1 (Cp ′) n (X) 4-n ;
  • M 1 X 4 and Cp'M 2 X includes a halo group
  • M 2 and M 3 each independently include an alkali metal
  • M 1 , Cp ′, and L are each of the agent of the present application. Same as defined in 1 aspect.
  • a third aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:
  • a fourth aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:
  • a fifth aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:
  • R ′ and R ′′ are each independently C 1- 4 alkyl group
  • M 1 , Cp ', Cp ", R 1 , R 2 , L 1 and L 2 are the same as defined above in the first aspect of the present application.
  • a sixth aspect of the present application provides a precursor composition for depositing a Group 4 transition metal-containing thin film, comprising a Group 4 transition metal-containing precursor compound according to the first aspect of the present application.
  • a seventh aspect of the present application provides a method for depositing a Group 4 transition metal-containing thin film using the Group 4 transition metal-containing precursor compound according to the first aspect of the present application.
  • an oxide of Group 4 transition metal is included in a uniform thickness on a surface having a high aspect ratio using an organometallic chemical vapor deposition method or an atomic layer deposition method at a high temperature.
  • a thin film can be formed, and the recording density of the semiconductor DRAM can be improved by using the thin film for manufacturing a semiconductor DRAM.
  • Group 4 transition metal-containing precursor compound As a raw material and forming a thin film containing an oxide of Group 4 transition metal by organometallic chemical vapor deposition or atomic layer deposition, For example, even at a high temperature of about 320 °C to about 360 °C can exhibit an excellent step coverage effect.
  • Group 4 transition metal-containing precursor compound for example, (EtCp) 2 Zr (Me) 2 , ( i PrCp) 2 Zr (Me) 2 , CpZr (O sec Bu) 3 , CpZr (O 3 Pen) 3 , CpZr (NH t Bu) 3 , Cp (EtCp) Zr (OMe) 2 , Cp ( i PrCp) Zr (OMe) 2 , (MeCp) (EtCp) Zr (OMe) 2 , (EtCp ) 2 Zr (OMe) 2 , and Cp (EtCp) Zr (OEt) 2 , and (MeCp) 2 Zr (OEt) 2 , and (MeCp) 2 Zr (OEt) 2 are liquid at room temperature, Cp (MeCp) Zr (OMe) 2 , (MeCp) 2 Zr (OMe) 2 , Cp (MeCp) Zr (
  • 1 is a graph showing the results of thermogravimetric analysis of a Group 4 transition metal-containing precursor compound prepared according to one embodiment of the present application.
  • Figure 2 is a graph showing the results of thermogravimetric analysis of Group 4 transition metal-containing precursor compound prepared according to an embodiment of the present application.
  • FIG 3 is a graph showing film growth per atomic layer deposition cycle of a zirconium oxide thin film formed according to an embodiment of the present application.
  • 4A to 4F are transmission electron micrographs showing a cross section of a zirconium oxide thin film formed on a narrow, deep grooved substrate according to one embodiment of the present application.
  • 5A to 5F are transmission electron micrographs showing a cross section of a zirconium oxide thin film formed on a narrow, deep grooved substrate according to one embodiment of the present application.
  • FIG. 6 is a graph showing film growth per atomic layer deposition cycle of a zirconium oxide thin film formed according to an embodiment of the present application.
  • step to or “step of” does not mean “step for.”
  • the term "combination (s) thereof" included in the representation of a makushi form refers to one or more mixtures or combinations selected from the group consisting of the components described in the representation of makushi form, It means to include one or more selected from the group consisting of the above components.
  • alkyl group includes a linear or branched C 1-10 alkyl group, C 1-6 alkyl group, C 1-4 alkyl group, C 1-3 alkyl group, or C 3-6 alkyl group, respectively. It may be, for example, may include, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or all possible isomers thereof.
  • alkoxide group is a form in which the alkyl group and the oxygen atom as defined above are bonded, and may include a C 1-10 alkoxide group, a C 1-6 alkoxide group or a C 3-6 alkoxide group, eg For example, methoxide, ethoxide, propoxide, butoxide, pentoxide, hexoxide, hexoxide, octoside, nonoxide, desoxide, or all possible isomers thereof may be included, but is not limited thereto. You may not.
  • halo group means that a halogen element belonging to Group 17 of the periodic table is included in the compound in the form of a functional group, and the halogen element is, for example, F, Cl, Br, or I It may be, but may not be limited thereto.
  • alkali metal refers to a metal belonging to Group 1 of the periodic table, and may be Li, Na, Ca, Rb, or Cs, but may not be limited thereto.
  • Group 4 transition metal refers to a transition metal belonging to Group 4 of the periodic table, which may for example be Ti, Zr, or Hf, and in particular herein may mean Zr or Hf. However, this may not be limited. It is generally known that among Group 4 transition metals, especially Zr and Hf are almost indistinguishable from each other and the properties of Zr and Hf compounds are very similar. It is common sense for organometallic chemists that a compound in which Zr is substituted with Hf in a Zr compound can be synthesized in the same manner as the Zr compound, and that the properties of the synthesized Hf compound are very similar to that of the Zr compound.
  • cyclopentadienyl (group) may be abbreviated as Cp and refers to a 5-membered ring aromatic cyclic substituent of -C 5 H 5 .
  • a first aspect of the present application provides a Group 4 transition metal-containing precursor compound represented by Formula 1 or Formula 2 below:
  • M 1 comprises Zr or Hf
  • Cp ' comprises a cyclopentadienyl group which may be substituted by a C 1-4 alkyl group
  • n 1 or 2
  • the two Cp's may be the same or different from each other
  • L comprises a C 1-3 alkyl group, a C 1-6 alkoxide group or —NHR 3 , wherein said R 3 is a C 1-6 alkyl group and when two or more L are two or more L they may be the same or different from each other;
  • M 1 is bonded to Cp ';
  • M 1 comprises Zr or Hf;
  • L 1 and L 2 each independently represent a C 1-3 alkyl group, C 1- 6 alkoxide group, or —NHR 3 , wherein R 3 is a C 1-6 alkyl group, R 1 and R 2 each independently comprise hydrogen or a C 1-4 alkyl group; and
  • M 1 is Bound to Cp 'and Cp ".
  • the C 1-3 alkyl group may be a methyl group, an ethyl group, an n-propyl group, or an iso-propyl group, but may not be limited thereto.
  • the C 1-6 alkoxide group is a methoxy, ethoxy, n-propoxide group, iso-propoxide group, n-butoxide group, iso-butoxide group, sec-butoxide group , but may include tert-butoxide group, 1-pentoxide group, 2-pentoxide group, or 3-pentoxide group, but may not be limited thereto.
  • the n-propoxide group may be abbreviated as O n Pr as CH 3 (CH 2 ) 2 O— and the iso-propoxide group is referred to as O i Pr as (CH 3 ) 2 CHO-.
  • n-butoxide group may be abbreviated to O n Bu as CH 3 (CH 2 ) 3 O— and the iso-butoxide group is referred to as O i Bu as (CH 3 ) 2 CHCH 2 O—
  • O i Bu as (CH 3 ) 2 CHCH 2 O—
  • sec-butoxide group may be abbreviated to O sec Bu as CH 3 CH 2 CH (CH 3 ) O— and the tert-butoxide group is referred to as O t Bu as (CH 3 ) 3 CO— It may be abbreviated, but may not be limited thereto.
  • the 1-pentoxide group is abbreviated O 1 Pen as CH 3 (CH 2 ) 4 O— and the 2-pentoxide group is CH 3 [CH 3 (CH 2 ) 2 ] CHO— It is abbreviated as O 2 Pen and the 3-pentoxide group may be abbreviated as O 3 Pen as (CH 3 CH 2 ) 2 CHO-, but may not be limited thereto.
  • R 3 in -NHR 3 may include a C 1-6 alkyl group or a C 3-6 alkyl group, for example, methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, An n-butylamino group, iso-butylamino group, sec-butylamino group, tert-butylamino group, 1-pentylamino group, 2-pentylamino group, or may include 3-pentylamino group, but may not be limited thereto.
  • the n-propylamino group may be abbreviated as NH n Pr as CH 3 (CH 2 ) 2 NH—
  • the iso-propylamino group may be abbreviated as NH i Pr as (CH 3 ) 2 CHNH-
  • the n-butylamino group may be abbreviated NH n Bu as CH 3 (CH 2 ) 3 NH—
  • the iso-butylamino group may be abbreviated NH i Bu as (CH 3 ) 2 CHCH 2 NH—
  • the sec -butylamino group may be abbreviated as NH sec Bu as CH 3 CH 2 CH (CH 3 ) NH-
  • the tert-butylamino group may be abbreviated as NH t Bu as (CH 3 ) 3 CNH- It may be, but may not be limited thereto.
  • the 1-pentylamino group is abbreviated NH 1 Pen as CH 3 (CH 2 ) 4 NH-
  • the 2-pentylamino group is abbreviated NH 2 Pen as CH 3 [CH 3 (CH 2 ) 2 ] CHNH-
  • the 3-pentylamino group may be abbreviated as NH 3 Pen as (CH 3 CH 2 ) 2 CHNH-, but may not be limited thereto.
  • L, L 1 and L 2 are each independently a methyl group, an ethyl group, a propyl group, an iso-propyl group, a methoxide group, an ethoxide group, an n-propoxide group, and iso It may include, but is not limited to, a propoxide group, an iso-butoxide group, a sec-butoxide group, a 3-pentoxide group, or a tert-butylamino group.
  • L when L is two or more, they may be the same or different from each other, but may not be limited thereto.
  • Cp 'and Cp each independently comprise a cyclopentadienyl group which may be substituted by a C 1-4 alkyl group, wherein Cp' or Cp" is 1 to 5 substituents It may include, wherein 1 to 5 hydrogen atoms of the Cp 'or Cp "may be independently substituted by the C 1-4 alkyl group.
  • Cp ie, C 5 H 5
  • a substituent C 5 H 4 (CH 3 ) comprising one methyl group C 5 H 4 (C 2 H 5 ) comprising one ethyl group, C 5 H 4 (CH 2 containing one n-propyl group as a substituent) CH 2 CH 3
  • C 5 H 4 (C 2 H 5 ), which is a kind of Cp ′, may be abbreviated as EtCp
  • C 5 H 4 (CH 2 CH 2 CH 3 ) may be abbreviated as n PrCp
  • the C 5 H 4 (CH (CH 3 ) 2 ) may be abbreviated as i PrCp, but may not be limited thereto.
  • Cp ′ and Cp ′′ may be each independently Cp, MeCp, EtCp, n PrCp, i PrCp, i BuCp, sec BuCp, or t BuCp, but may not be limited thereto.
  • n 2 in Formula 1
  • the two Cp's may be the same or different from each other.
  • Cp ′ and Cp ′′ may be the same as or different from each other.
  • R 1 and R 2 may be the same or different from each other, and may include ones selected from the group consisting of methyl group, ethyl group, n-propyl group, and iso-propyl group, respectively. This may not be limited.
  • the Group 4 transition metal-containing precursor compound may include (EtCp) 2 Zr (Me) 2 , ( i PrCp) 2 Zr (Me) 2 , CpZr (O sec Bu) 3 , CpZr ( O 3 Pen) 3 , CpZr (NH t Bu) 3 , Cp (MeCp) Zr (OMe) 2 , (MeCp) 2 Zr (OMe) 2 , Cp (EtCp) Zr (OMe) 2 , Cp ( i PrCp) Zr (OMe) 2 , (MeCp) (EtCp) Zr (OMe) 2 , (EtCp) 2 Zr (OMe) 2 , Cp (MeCp) Zr (OEt) 2 , Cp (EtCp) Zr (OEt) 2 , Cp (EtCp) Zr (OEt) 2 , Cp (EtCp) Zr (OEt) 2 ,
  • the Group 4 transition metal-containing precursor compound may include, but is not limited to, a liquid at room temperature or a liquid at a volatilization temperature. Accordingly, (EtCp) 2 Zr (Me) 2 , ( i PrCp) 2 Zr (Me) 2 , CpZr (O sec Bu) 3 , CpZr (O 3 Pen) 3 , CpZr (NH t Bu) which are liquid at room temperature ) 3 , ( n PrCp) 2 Zr (Me) 2 , Cp (MeCp) Zr (OMe) 2 , (MeCp) 2 Zr (OMe) 2 , Cp (EtCp) Zr (OMe) 2 , Cp ( i PrCp) Zr (OMe) 2 , (MeCp) (EtCp) Zr (OMe) 2 , (EtCp) 2 Zr (OMe) 2 , Cp (MeCp) 2 Zr (OMe
  • a second aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:
  • M 1 X 4 and Cp'M 2 are reacted in an organic solvent to form M 1 (Cp ′) n (X) 4-n ; And reacting the M 1 (Cp ′) n (X) 4-n and M 3 L in an organic solvent to form a Group 4 transition metal-containing precursor compound represented by Formula 1:
  • M 1 , Cp ′, n, and L in Formula 1 are the same as defined in the first aspect of the present application, respectively;
  • X includes a halo group, and M 2 and M 3 each independently include an alkali metal.
  • a third aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:
  • R 'and R" may be the same or different from each other, and each independently include a C 1-4 alkyl group; M 1 , Cp ′, and L are the same as defined above in the first aspect of the present application, respectively.
  • a fourth aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:
  • R 'and R may be the same or different from each other, and each independently And C 1-4 alkyl group, M 1 , Cp ′, n, and L are the same as defined above in the first aspect of the present application.
  • a fifth aspect of the present application provides a method of preparing a Group 4 transition metal-containing precursor compound according to the first aspect, comprising:
  • R ′ and R ′′ may be the same as or different from each other.
  • M 1 , Cp ′, Cp ′′, R 1 , R 2 , L 1 and L 2 are the same as defined above in each of the first aspects herein.
  • the organic solvent may be one selected from the group consisting of toluene, benzene, hexane, pentane, tetrahydrofuran, dichloromethane, chloroform, ether, and combinations thereof, but It may not be limited.
  • a sixth aspect of the present application provides a precursor composition for depositing a Group 4 transition metal-containing thin film including a Group 4 transition metal-containing precursor compound according to the first aspect of the present application.
  • a seventh aspect of the present application provides a method for depositing a Group 4 transition metal-containing thin film using the Group 4 transition metal-containing precursor compound according to the first aspect of the present application.
  • the second to seventh aspects of the present application are each a method for producing a Group 4 transition metal-containing precursor compound according to the first aspect of the present application, a precursor composition for thin film deposition including the precursor compound, and the precursor compound
  • a method of depositing a thin film detailed descriptions of parts overlapping with the first aspect of the present application have been omitted, but the descriptions of the first aspect of the present disclosure are not described in each of the second to seventh aspects of the present application. The same may be applied even if omitted.
  • depositing the thin film may be performed by organometallic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), but may not be limited thereto.
  • MOCVD organometallic chemical vapor deposition
  • ALD atomic layer deposition
  • the thin film may include, but may not be limited to, a Group 4 transition metal-containing oxide, nitride, or oxynitride.
  • the thin film in each of the sixth and seventh aspects of the present application includes a ZAZ multilayer film in which zirconium oxide (ZrO 2 ) / aluminum oxide (Al 2 O 3 ) / zirconium oxide (ZrO 2 ) is sequentially formed. It may be, but may not be limited thereto.
  • Figure 1 is a graph showing the thermal weight analysis results of CpZr (O sec Bu) 3 , a Group 4 transition metal-containing precursor compound according to Example 3.
  • CpZr (O sec Bu) 3 which is a Group 4 transition metal-containing precursor compound of the present application, can be confirmed that a rapid weight loss occurs at 150 ° C. to 280 ° C. in a thermogravimetric analysis (TGA) graph.
  • TGA thermogravimetric analysis
  • FIG. 2 is a graph showing the thermal weight analysis results of CpZr (O 3 Pen) 3 which is a Group 4 transition metal-containing precursor compound according to the fourth embodiment.
  • CpZr (O 3 Pen) 3 which is a Group 4 transition metal-containing precursor compound of the present application, was found to have a rapid weight loss at 150 ° C. to 250 ° C. in a thermogravimetric analysis (TGA) graph.
  • TGA thermogravimetric analysis
  • Example 2 An experiment was performed in which a zirconium oxide film was formed using atomic layer deposition (ALD) using ( i PrCp) 2 Zr (Me) 2 obtained in Example 2 as a precursor.
  • the substrate was a silicon wafer on which titanium nitride (TiN) was deposited.
  • the substrate was heated to 300 ° C to 350 ° C.
  • the precursor compound contained in a stainless steel vessel was heated to a temperature of 120 °C, the precursor compound was fed to the ALD reactor for performing atomic layer deposition by passing argon (Ar) gas at a flow rate of 50 sccm through the vessel. .
  • the internal pressure of the ALD reactor was maintained at 3 torr.
  • FIG. 3 is a graph showing film growth per atomic layer deposition cycle of a zirconium oxide thin film formed according to the present embodiment. As shown in FIG. 3, it was confirmed that a zirconium oxide film was formed with a constant film thickness within the temperature range applied to the substrate.
  • the internal pressure of the ALD reactor was maintained at 3 torr.
  • the precursor compound gas was supplied to the ALD reactor for 15 seconds, and then argon gas was supplied for 5 seconds, then ozone (O 3 ) gas was supplied for 14 seconds, and then ALD was supplied again by supplying argon gas for 5 seconds.
  • One cycle was completed and this was repeated 200 times.
  • the cross section of the zirconium oxide thin film formed according to the above process was measured using a transmission electron microscope (TEM), and the results are shown in FIGS. 4A to 4F.
  • 4A to 4C are observations of the upper end, the middle end, and the lower end of the hole pattern, respectively, and the TEM analysis results of the zirconium oxide film formed by heating the temperature of the substrate to 300 ° C., and FIGS.
  • 4D to 4F are hole patterns, respectively.
  • the upper end, the stop part and the lower end of the film were observed, and the TEM analysis result of the zirconium oxide film formed by heating the temperature of the base material to 350 ° C. 4A to 4F, it was confirmed that a film was formed evenly on both the surface of the substrate and the inside of the hole.
  • Example 19 Zirconium Oxide Formation Using (Cp 2 CMe 2 ) Zr (OMe) 2 and Atomic Layer Deposition
  • the internal pressure of the ALD reactor was maintained at 3 torr.
  • the precursor compound gas was supplied to the ALD reactor for 15 seconds, and then argon gas was supplied for 5 seconds, then ozone (O 3 ) gas was supplied for 14 seconds, and then ALD was supplied again by supplying argon gas for 5 seconds.
  • One cycle was completed and this was repeated 200 times.
  • the cross section of the zirconium oxide thin film formed according to the above process was measured using a transmission electron microscope (TEM), and the results are shown in FIGS. 5A to 5F.
  • 5A to 5C are observations of the upper end, the middle end, and the lower end of the hole pattern, respectively, and are results of TEM analysis of a zirconium oxide film formed by heating the temperature of the substrate to 300 ° C.
  • the precursor compound gas was supplied to the ALD reactor for 9 seconds, and then argon gas was supplied for 5 seconds, and then ozone (O 3 ) gas was supplied for 14 seconds, and then ALD was supplied with argon gas for 5 seconds.
  • the cycle was repeated to form a zirconium oxide film on a flat wafer heated to 300 ° C, 320 ° C, and 350 ° C.
  • the film growth per ALD cycle with temperature is shown in FIG. 6. In the temperature range of 300 °C to 350 °C it can be seen that almost no change in film growth per ALD cycle.

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Abstract

La présente invention concerne un composé précurseur contenant un métal de transition du groupe IV, un procédé pour préparer le composé précurseur, une composition de précurseur pour le dépôt d'un film mince comprenant le composé précurseur, et un procédé pour déposer le film mince au moyen du composé précurseur.
PCT/KR2013/011370 2013-04-08 2013-12-09 Composé précurseur contenant un métal de transition du groupe iv, et procédé pour déposer une couche mince utilisant celui-ci WO2014168312A1 (fr)

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KR1020130038326A KR20140074162A (ko) 2012-12-07 2013-04-08 4 족 전이금속-함유 전구체 화합물, 및 이를 이용하는 박막의 증착 방법
KR10-2013-0038326 2013-04-08
KR10-2013-0152574 2013-12-09
KR1020130152574A KR20140121761A (ko) 2013-04-08 2013-12-09 4 족 전이금속-함유 전구체 화합물 및 이를 이용하는 박막의 증착 방법

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024030616A1 (fr) * 2022-08-05 2024-02-08 Dow Global Technologies Llc Métallocènes d'hafnium asymétriques

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Publication number Priority date Publication date Assignee Title
US20080292783A1 (en) * 2007-04-13 2008-11-27 Samsung Electronics Co., Ltd. Method of manufacturing a thin layer and methods of manufacturing gate structures and capacitors using the same
KR20090018080A (ko) * 2006-06-02 2009-02-19 레르 리키드 쏘시에떼 아노님 뿌르 레드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 유전체 필름의 형성 방법, 신규 전구체 및 그의 반도체 제조에서의 용도
WO2009036046A1 (fr) * 2007-09-14 2009-03-19 Sigma-Aldrich Co. Procédés de préparation de films minces par dépôt de couches atomiques à l'aide de précurseurs de monocyclopentadiényl trialcoxy hafnium et zirconium

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KR20090018080A (ko) * 2006-06-02 2009-02-19 레르 리키드 쏘시에떼 아노님 뿌르 레드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 유전체 필름의 형성 방법, 신규 전구체 및 그의 반도체 제조에서의 용도
US20080292783A1 (en) * 2007-04-13 2008-11-27 Samsung Electronics Co., Ltd. Method of manufacturing a thin layer and methods of manufacturing gate structures and capacitors using the same
WO2009036046A1 (fr) * 2007-09-14 2009-03-19 Sigma-Aldrich Co. Procédés de préparation de films minces par dépôt de couches atomiques à l'aide de précurseurs de monocyclopentadiényl trialcoxy hafnium et zirconium

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024030616A1 (fr) * 2022-08-05 2024-02-08 Dow Global Technologies Llc Métallocènes d'hafnium asymétriques

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