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WO2018182309A1 - Composition for depositing silicon-containing thin film containing bis(aminosilyl)alkylamine compound and method for manufacturing silicon-containing thin film using the same - Google Patents

Composition for depositing silicon-containing thin film containing bis(aminosilyl)alkylamine compound and method for manufacturing silicon-containing thin film using the same Download PDF

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Publication number
WO2018182309A1
WO2018182309A1 PCT/KR2018/003655 KR2018003655W WO2018182309A1 WO 2018182309 A1 WO2018182309 A1 WO 2018182309A1 KR 2018003655 W KR2018003655 W KR 2018003655W WO 2018182309 A1 WO2018182309 A1 WO 2018182309A1
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Prior art keywords
chemical formula
silicon
thin film
composition
aminosilyl
Prior art date
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PCT/KR2018/003655
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French (fr)
Inventor
Sung Gi Kim
Jeong Joo Park
Joong Jin Park
Se Jin Jang
Byeong-Il Yang
Sang-Do Lee
Sam Dong Lee
Sang Ick Lee
Myong Woon Kim
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DNF Co Ltd
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DNF Co Ltd
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Priority claimed from KR1020180035010A external-priority patent/KR20180110612A/en
Application filed by DNF Co Ltd filed Critical DNF Co Ltd
Priority to CN201880019422.XA priority Critical patent/CN110431204B/en
Priority to US16/499,215 priority patent/US11393676B2/en
Priority to JP2019553053A priority patent/JP6876145B2/en
Publication of WO2018182309A1 publication Critical patent/WO2018182309A1/en
Anticipated expiration legal-status Critical
Priority to US17/572,509 priority patent/US11749522B2/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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    • 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
    • C23C16/345—Silicon nitride
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    • 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
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    • 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]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45536—Use of plasma, radiation or electromagnetic fields
    • C23C16/4554—Plasma being used non-continuously in between ALD reactions
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms

Definitions

  • the present invention relates to a composition for depositing a silicon-containing thin film and a method for manufacturing a silicon-containing thin film using the same, and more particularly, to a composition for depositing a silicon-containing thin film, containing a specific compound, a bis(aminosilyl)alkylamine compound as a precursor for depositing a thin film, and a method for manufacturing a silicon-containing thin film using the same.
  • a silicon-containing thin film is manufactured through various deposition processes in a semiconductor field to thereby be manufactured in various forms such as a silicon film, a silicon oxide film, a silicon nitride film, a silicon carbonitride film, and a silicon oxynitride film, and an application field of the silicon-containing thin film may be wide.
  • the silicon oxide film and the silicon nitride film have a significantly excellent barrier property and oxidation resistance
  • the silicon oxide film and the silicon nitride film are used as an insulating film, a diffusion barrier, a hard mask, an etch stop layer, a seed layer, a spacer, a trench isolation, an intermetallic dielectric material, and a passivation layer in manufacturing an apparatus.
  • TFT thin film transistor
  • MOCVD metal-organic chemical vapor deposition
  • ALD atomic layer deposition
  • LPCVD low-pressure chemical vapor deposition
  • PECVD plasma-enhanced chemical vapor deposition
  • PEALD plasma-enhanced atomic layer deposition
  • a precursor used to form the silicon-containing thin film may include silane, silane compounds, aminosilane, and alkoxysilane compounds.
  • Specific examples thereof may include silane chloride compounds such as dichlorosilane (SiH 2 Cl 2 ) and hexachlorodisilane (Cl 3 SiSiCl 3 ), trisilylamine (N(SiH 3 ) 3 ), bis-diethylaminosilane (H 2 Si(N(CH 2 CH 3 ) 2 ) 2 ), di-isopropylaminosilane (H 3 SiN(i-C 3 H 7 ) 2 ), and the like.
  • silane chloride compounds such as dichlorosilane (SiH 2 Cl 2 ) and hexachlorodisilane (Cl 3 SiSiCl 3 ), trisilylamine (N(SiH 3 ) 3 ), bis-diethylaminosilane (H 2 Si(N(CH 2 CH 3 ) 2
  • An object of the present invention is to provide a composition for depositing a silicon-containing thin film, containing a bis(aminosilyl)alkylamine compound capable of being used as a precursor of the silicon-containing thin film.
  • Another object of the present invention is to provide a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention.
  • Another object of the present invention is to provide a bis(aminosilyl)alkylamine compound capable of being used as a precursor of a silicon-containing thin film.
  • composition for depositing a silicon-containing thin film containing: a bis(aminosilyl)alkylamine compound, which has excellent physical properties as a precursor for thin film deposition, as a precursor for silicon-containing thin film deposition, wherein the bis(aminosilyl)alkylamine compound is represented by the following Chemical Formula 1.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 1 to R 4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R 1 and R 2 , and R 3 and R 4 are each independently linked to each other to form a ring; and
  • R 5 to R 8 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl.)
  • R 5 to R 7 may be each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl, and R 8 may be hydrogen.
  • the bis(aminosilyl)alkylamine compound according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 2 or 3.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 5 to R 7 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl;
  • R 11 to R 14 are each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl;
  • n and m are each independently an integer of 1 to 7.
  • R 5 to R 7 may be each independently hydrogen or (C1-C5)alkyl
  • R 11 to R 14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl
  • n and m may be each independently an integer of 1 to 4.
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 4 or 5.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 11 to R 14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl;
  • R 5 and R 6 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl;
  • n and m are each independently an integer of 1 to 7.
  • R may be (C1-C5)alkyl; R 5 and R 6 may be each independently (C1-C5)alkyl; and n and m may be each independently an integer of 1 to 4.
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 6 or 7.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 11 to R 14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl;
  • n and m are each independently an integer of 1 to 7.
  • R may be (C1-C5)alkyl; R 11 to R 14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n and m may be each independently an integer of 1 to 4.
  • the bis(aminosilyl)alkylamine compound according to the exemplary embodiment of the present invention may be selected from the following compounds, but is not limited thereto.
  • the composition for depositing a silicon-containing thin film may be deposited by an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a low-pressure chemical vapor deposition (LPCVD) method, a plasma-enhanced chemical vapor deposition (PECVD) method, or a plasma-enhanced atomic layer deposition (PEALD) method
  • the silicon-containing thin film may be a silicon oxide (SiO 2 ) film, a silicon oxy carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon carbonitride (SiCN) film, or a silicon carbide (SiC) film.
  • the method for manufacturing a silicon-containing thin film may include: a) maintaining a temperature of a substrate mounted in a chamber at 30 to 500°C;
  • composition for depositing a silicon-containing thin film described above with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate;
  • reaction gas is supplied after being activated by generating plasma with a plasma power of 50 to 1000 W.
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 may be represented by Chemical Formula 2 or 3.
  • a composition for depositing a silicon-containing thin film contains a bis(aminosilyl)alkylamine compound which is a liquid at room temperate and has high volatility and excellent thermal stability as a precursor, such that a high-quality silicon-containing thin film having a high purity and durability may be provided under lower plasma power and film formation temperature conditions.
  • a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention excellent thermal stability and deposition rate, and excellent stress intensity may be implemented even under a low film formation temperature condition, and in a silicon-containing thin film manufactured thereby, contents of impurities such as carbon, oxygen, and hydrogen are minimized, thereby making it possible to manufacture a silicon-containing thin film having a high purity, excellent physical and electrical properties, excellent resistance against hydrogen fluoride, an excellent water vapor transmission rate, and an excellent step coverage.
  • FIG. 1 is a view illustrating a result obtained by measuring vapor pressures of bis(aminosilyl)alkylamine compounds prepared in Examples 1 and 2.
  • FIG. 2 is a view illustrating results obtained by performing thermogravimetric analysis on the bis(aminosilyl)alkylamine compounds prepared in Examples 1 and 2.
  • FIG. 3 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon oxide thin films manufactured in Examples 3 to 5.
  • FIG. 4 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon nitride thin films manufactured in Examples 6 to 9.
  • the present invention provides a composition for depositing a silicon-containing thin film containing a bis(aminosilyl)alkylamine compound, which is a liquid at room temperature and has high volatility and excellent thermal stability to thereby be used as a useful precursor for forming a silicon-containing thin film, wherein the bis(aminosilyl)alkylamine compound is represented by the following Chemical Formula 1.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 1 to R 4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R 1 and R 2 , and R 3 and R 4 are each independently linked to each other to form a ring; and
  • R 5 to R 8 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl.)
  • composition for depositing a silicon-containing thin film according to the present invention contains a precursor for depositing a thin film represented by Chemical Formula 1, such that film formation may be performed at a low temperature, and at the same time, a high-quality thin film having high durability may be easily manufactured.
  • composition for depositing a silicon-containing thin film according to the present invention contains the precursor for depositing a thin film represented by Chemical Formula 1, the thin film may be deposited at a high thin film deposition rate, and the film has excellent stress properties and water vapor transmission rate.
  • the reason may be that as the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1, contained in the composition for depositing a silicon-containing thin film has two aminosilyl groups and one alkyl or alkenyl group as substituents, the bis(aminosilyl)alkylamine compound has high volatility and excellent thermal stability.
  • R 5 to R 7 may be each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl, and R 8 may be hydrogen.
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 2 or 3.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 5 to R 7 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl;
  • R 11 to R 14 are each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl;
  • n and m are each independently an integer of 1 to 7.
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 2 or 3 two aminosilyl functional groups and one alkyl or alkenyl group are substituted, such that the bis(aminosilyl)alkylamine compound is thermally stable, and at the same time, the bis(aminosilyl)alkylamine compound has a silazane backbone in which at least one hydrogen atom in at least one of two aminosilyl functional groups is substituted, such that the bis(aminosilyl)alkylamine compound has high volatility as a liquid at room temperature. Therefore, the bis(aminosilyl)alkylamine compound may be significantly usefully used to form a silicon-containing thin film.
  • the bis(aminosilyl)alkylamine compound according to the present invention which is a compound having the silazane backbone, essentially has two aminosilyl functional groups ( and or and ), and silyl in one of the aminosilyl functional groups necessarily has a functional group containing at least one hydrogen atom ( or ), such that the bis(aminosilyl)alkylamine compound may have excellent effects as the precursor for depositing a thin film.
  • R 5 to R 7 may be each independently hydrogen or (C1-C5)alkyl
  • R 11 to R 14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl
  • n and m may be each independently an integer of 1 to 4.
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the present invention may be represented by the following Chemical Formula 4 or 5.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 11 to R 14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl;
  • R 5 and R 6 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl;
  • n and m are each independently an integer of 1 to 7.
  • R may be (C1-C5)alkyl; R 5 and R 6 may be each independently (C1-C5)alkyl; and n and m may be each independently an integer of 1 to 4. More preferably, the bis(aminosilyl)alkylamine compound may be represented by Chemical Formula 4, and in Chemical Formula 4, R may be (C1-C3)alkyl; and R 5 and R 6 may be each independently (C1-C3)alkyl.
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 6 or 7.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 11 to R 14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl;
  • n and m are each independently an integer of 1 to 7.
  • R may be (C1-C5)alkyl; R 11 to R 14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; n and m may be each independently an integer of 1 to 4.
  • R may be (C1-C5)alkyl; R 11 to R 14 may be each independently (C1-C5)alkyl; and n and m may be each independently 1 to 4.
  • the bis(aminosilyl)alkylamine compound may be represented by Chemical Formula 6, wherein in Chemical Formula 6, R may be (C1-C3)alkyl; and R 11 to R 14 may be each independently (C1-C3)alkyl.
  • the bis(aminosilyl)alkylamine compound When silyl groups of two aminosilyl groups in the silazane backbone of the bis(aminosilyl)alkylamine compound according to the present invention have two or four hydrogen atoms, the bis(aminosilyl)alkylamine compound has more excellent reactivity and thermal stability as the precursor for depositing a thin film, such that a higher-quality thin film may be manufactured.
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 4 may be represented by the following Chemical Formula 4-1.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 1 and R 2 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R 1 and R 2 is each independently linked to each other to form a ring;
  • R 5 is (C1-C7)alkyl or (C2-C7)alkenyl.)
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 6 may be represented by the following Chemical Formula 6-1.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 1 and R 2 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl, or are linked to each other to form a ring.)
  • bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 may include the following compounds.
  • the composition for depositing a silicon-containing thin film according to the present invention needs to necessarily contain the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 as the precursor for depositing a thin film, and the bis(aminosilyl)alkylamine compound may be contained in the composition for depositing a silicon-containing thin film in a content range in which the content may be recognized by those skilled in the art in consideration of film formation conditions, a thickness, properties, or the like of the thin film.
  • alkyl means linear, branched, and cyclic saturated and unsaturated hydrocarbons having 1 to 7 carbon atoms, preferably, 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms, and examples thereof may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, neobutyl, pentyl, and the like.
  • halogen means a halogen element, and examples thereof include fluoro, chloro, bromo, and iodo.
  • alkenyl as a single group or a part of another group means a straight-chain, branched-chain, or cyclic hydrocarbon radical having 2 to 7 carbon atoms and one or more carbon-carbon double bonds.
  • a more preferable alkenyl radical is a lower alkenyl radical having 2 to 5 carbon atoms.
  • the most preferable lower alkenyl radical is a lower alkenyl radical having about 2 to 3 carbon atoms.
  • the alkenyl group may be substituted at a random usable attachment point. Examples of the alkenyl radical include ethenyl, propenyl, allyl, butenyl, and 4-methylbutenyl.
  • alkenyl and “lower alkenyl” include radicals having cis and trans orientations or alternatively, E and Z orientations.
  • R 1 and R 2 , and R 3 and R 4 are each independently linked to each other to form a ring
  • the phrase “R 1 and R 2 , and R 3 and R 4 are each independently linked to each other to form a ring” includes the case in which R 1 and R 2 are linked to each other to form a ring but R 3 and R 4 do not form a ring; the case in which on the contrary, R 1 and R 2 do not form a ring but R 3 and R 4 are linked to each other to form a ring; and the case in which R 1 and R 2 are linked to each other to form a ring and R 3 and R 4 are linked to each other to form a ring, wherein the formed ring may be an alicyclic or aromatic ring containing N, and preferably, an alicyclic ring.
  • alicyclic ring means a compound that is not an aromatic compound among organic compounds having a cyclic bonding structure.
  • the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the present invention may be prepared using a method as long as the method may be recognized by those skilled in the art.
  • the present invention provides a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention.
  • the composition for depositing a silicon-containing thin film according to the present invention containing the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1, which is a liquid art room temperature and normal pressure and has high volatility and excellent thermal stability, as the precursor is used, the handling may be easy, it is possible to manufacture various thin films, and it is possible to manufacture a silicon-containing thin film having a high purity, an excellent water vapor transmission rate, and excellent thin film stress properties at a high deposition rate even at a low temperature and a low power.
  • the silicon-containing thin film manufactured by the method according to the present invention has excellent durability and electric properties, and resistance against hydrogen fluoride and step coverage thereof are also excellent.
  • the silicon-containing thin film may be formed by any method as long as it may be recognized by those skilled in the art.
  • the silicon-containing thin film may be formed by an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a low-pressure chemical vapor deposition (LPCVD) method, a plasma enhanced chemical vapor deposition (PECVD) method, or a plasma enhanced atomic layer deposition (PEALD) method, but PECVD, ALD, or PEALD is more preferable in order to allow the thin film to be more easily deposited, and allow the manufactured thin film to have excellent properties.
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • MOCVD metal-organic chemical vapor deposition
  • LPCVD low-pressure chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • PEALD plasma enhanced atomic layer deposition
  • the silicon-containing thin film according to the present invention may be a silicon oxide (SiO 2 ) film, a silicon oxy carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon carbonitride (SiCN) film, or a silicon carbide (SiC) film, and various thin films having high quality, particularly, a thin film usable as an encapsulant of an organic light emitting diode (OLED), may be manufactured.
  • SiO 2 silicon oxide
  • SiOC silicon oxy carbide
  • SiN silicon nitride
  • SiON silicon oxy nitride
  • SiCN silicon carbonitride
  • SiC silicon carbide
  • the method for manufacturing a silicon-containing thin film according to the present invention may include:
  • composition for depositing a silicon-containing thin film according to the present invention contacting the composition for depositing a silicon-containing thin film according to the present invention with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate;
  • the method for manufacturing a silicon-containing thin film according to the present invention may include:
  • composition for depositing a silicon-containing thin film according to the present invention with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate;
  • reaction gas in step D) may remove a ligand of the bis(aminosilyl)alkylamine compound contained in the composition for depositing a silicon-containing thin film to form a Si-O atomic layer.
  • the reaction gas according to the exemplary embodiment of the present invention may be supplied after being activated by generating plasma at a plasma power of 50 to 1000 W.
  • a bis(aminosilyl)alkylamine compound according to the present invention is used as the precursor, such that the reaction gas may be activated at preferably 30 to 500°C, and more preferably 30 to 300°C by generating plasma at a low plasma power of 50 to 1000 W, preferably 100 to 800 W, and more preferably 400 to 600 W, thereby making it possible to manufacture the thin film.
  • deposition conditions may be adjusted depending on a structure or thermal properties of a desired thin film.
  • the deposition condition according to the exemplary embodiment of the present invention may include an injection flow rate of the composition for depositing a silicon-containing thin film containing the bis(aminosilyl)alkyl amine compound, injection flow rates of the reaction gas and a carrier gas, pressure, RF power, the temperature of the substrate, and the like.
  • the injection flow rate of the composition for depositing a silicon-containing thin film may be adjusted in a range of 10 to 1000 cc/min
  • the injection flow rate of the carrier gas may be adjusted in a range of 10 to 1000 cc/min
  • the injection flow rate of the reaction gas may be adjusted in a range of 1 to 1500 cc/min
  • the pressure may be adjusted in a range of 0.5 to 10 torr
  • the RF power may be adjusted in a range of 50 to 1000 W
  • the temperature of the substrate may be adjusted in a range of 30 to 500°C, preferably 80 to 300°C, but the deposition conditions are not limited thereto.
  • the reaction gas used in the method for manufacturing a silicon-containing thin film according to the present invention is not limited, but may be one selected from hydrogen (H 2 ), hydrazine (N 2 H 4 ), ozone (O 3 ), oxygen (O 2 ), nitrous oxide (N 2 O) ammonia (NH 3 ), nitrogen (N 2 ), silane (SiH 4 ), borane (BH 3 ), diborane (B 2 H 6 ), and phosphine (PH 3 ), or a mixed gas of one or more thereof, and the carrier gas may be one selected from nitrogen (N 2 ), argon (Ar), and helium (He), or a mixed gas of two or more thereof.
  • the substrate used in the method for manufacturing a silicon-containing thin film according to the present invention may be a substrate containing one or more semiconductor materials selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a silicon-on-insulator (SOI) substrate; a quartz substrate; a glass substrate for a display; or a flexible plastic substrate made of polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethylmethacrylate (PMMA), polycarbonate (PC), polyethersulfone(PES), polyester, and the like, but is not limited thereto.
  • SOI silicon-on-insulator
  • the silicon-containing thin film may be directly formed on the substrate.
  • a large number of conductive layers, dielectric layers, insulating layers, or the like, may also be formed between the substrate and the silicon-containing thin film.
  • the present invention provides a bis(aminosilyl)alkyl amine compound capable of being used as a precursor of a silicon-containing thin film.
  • the bis(aminosilyl)alkyl amine compound according to the present invention is represented by the following Chemical Formula 1.
  • R is (C1-C7)alkyl or (C2-C7)alkenyl
  • R 1 to R 4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R 1 and R 2 , and R 3 and R 4 are each independently linked to each other to form a ring; and
  • R 5 to R 8 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl.)
  • the bis(aminosilyl)alkyl amine compound according to the present invention represented by Chemical Formula 1 is a liquid at room temperature and has high volatility and excellent thermal stability as described above, such that the bis(aminosilyl)alkyl amine compound is used as a significantly useful precursor in forming a silicon-containing thin film.
  • the bis(aminosilyl)alkyl amine compound has excellent reactivity, such that the thin film may be deposited at a rapid deposition rate, and the thin film with a high purity may be manufactured.
  • the bis(aminosilyl)alkyl amine compound represented by Chemical Formula 1 may be represented by Chemical Formula 2, and more preferably Chemical Formula 6 or 7.
  • deposition was performed by a plasma enhanced atomic layer deposition (PEALD) method known in the art using a commercialized 200 mm single wafer shower head type ALD apparatus (CN1, Atomic Premium).
  • PEALD plasma enhanced atomic layer deposition
  • PECVD plasma enhanced chemical vapor deposition
  • CN1, Atomic Premium a commercialized 200 mm single wafer shower head type CVD apparatus
  • a thickness of a deposited silicon-containing thin film was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE), and properties of the thin film were analyzed using infrared spectroscopy (IFS66V/S & Hyperion 3000, Bruker Optics), X-ray photoelectron spectroscopy, a water vapor transmission rate (WVTR) analyzer (MOCON, Aquatran 2), and a stress analyzer (Frontier Semiconductor, FSM500TC).
  • IFS66V/S & Hyperion 3000 Bruker Optics
  • WVTR water vapor transmission rate
  • FSM500TC Frier Semiconductor
  • Film was formed using the bis(ethylmethylaminosilyl)methyl amine compound prepared in Example 2 according to the present invention as a composition for forming a silicon oxide film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art.
  • PEALD plasma enhanced atomic layer deposition
  • nitrous oxide was used together with plasma, and nitrogen corresponding to an inert gas was used for purging.
  • the film was formed at reaction gas and plasma time of 0.5 seconds.
  • a specific method for depositing a silicon oxide thin film was illustrated in Table 1.
  • Silicon oxide thin films were manufactured in the same manner as in Example 3 except for changing deposition conditions illustrated in the following Table 1 in Example 3, results obtained by analyzing the manufactured silicon oxide thin film were illustrated in the following Table 2, and results obtained by analyzing the deposited film using the infrared spectroscopy were illustrated in FIG. 3.
  • Film was formed using the bis(ethylmethylaminosilyl)methyl amine compound prepared in Example 2 according to the present invention as a composition for forming a silicon nitride film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art.
  • PEALD plasma enhanced atomic layer deposition
  • As a reaction gas nitrogen and ammonia were used together with plasma as first reaction gas, and nitrogen was used as a second reaction gas. The nitrogen corresponding to an inert gas was used for purging.
  • a specific method for depositing a silicon nitride thin film was illustrated in Table 3.
  • Silicon nitride thin films were manufactured in the same manner as in Example 6 except for changing conditions illustrated in the following Table 3 in Example 6, results obtained by analyzing the manufactured silicon oxide thin film were illustrated in the following Table 4, and results obtained by analyzing the deposited film using the infrared spectrometer were illustrated in FIG. 4.

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Abstract

Provided are a composition for depositing a silicon-containing thin film containing a bis(aminosilyl)alkylamine compound and a method for manufacturing a silicon-containing thin film using the same, and more particularly, a composition for depositing a silicon-containing thin film, containing the bis(aminosilyl)alkylamine compound capable of being usefully used as a precursor of the silicon-containing thin film, and a method for manufacturing a silicon-containing thin film using the same.

Description

COMPOSITION FOR DEPOSITING SILICON-CONTAINING THIN FILM CONTAINING BIS(AMINOSILYL)ALKYLAMINE COMPOUND AND METHOD FOR MANUFACTURING SILICON-CONTAINING THIN FILM USING THE SAME
The present invention relates to a composition for depositing a silicon-containing thin film and a method for manufacturing a silicon-containing thin film using the same, and more particularly, to a composition for depositing a silicon-containing thin film, containing a specific compound, a bis(aminosilyl)alkylamine compound as a precursor for depositing a thin film, and a method for manufacturing a silicon-containing thin film using the same.
A silicon-containing thin film is manufactured through various deposition processes in a semiconductor field to thereby be manufactured in various forms such as a silicon film, a silicon oxide film, a silicon nitride film, a silicon carbonitride film, and a silicon oxynitride film, and an application field of the silicon-containing thin film may be wide.
Particularly, since the silicon oxide film and the silicon nitride film have a significantly excellent barrier property and oxidation resistance, the silicon oxide film and the silicon nitride film are used as an insulating film, a diffusion barrier, a hard mask, an etch stop layer, a seed layer, a spacer, a trench isolation, an intermetallic dielectric material, and a passivation layer in manufacturing an apparatus.
Recently, a polycrystalline silicon thin film has been used in a thin film transistor (TFT), a solar cell, and the like, and an application field thereof has been gradually diversified.
As a representative technology for manufacturing a silicon-containing thin film known in the art, there are a metal-organic chemical vapor deposition (MOCVD) method for reacting a gas-type silicon precursor and a reaction gas with each other to form a film on a surface of a substrate or directly reacting the gas-type silicon precursor and the reaction gas with each other on the surface to form a film and an atomic layer deposition (ALD) method for physically or chemically adsorbing a gas-type silicon precursor and sequentially injecting a reaction gas to form a film. Various technologies for manufacturing a thin film such as a low-pressure chemical vapor deposition (LPCVD) method applying the above-mentioned method, a plasma-enhanced chemical vapor deposition (PECVD) method and a plasma-enhanced atomic layer deposition (PEALD) method capable of performing deposition at a low temperature, and the like, are applied to processes for manufacturing next-generation semiconductors and display devices to thereby be used to form a ultra-fine pattern and deposit an ultra-thin film having uniform and excellent properties at a nano-scale thickness.
Representative examples of a precursor used to form the silicon-containing thin film may include silane, silane compounds, aminosilane, and alkoxysilane compounds. Specific examples thereof may include silane chloride compounds such as dichlorosilane (SiH2Cl2) and hexachlorodisilane (Cl3SiSiCl3), trisilylamine (N(SiH3)3), bis-diethylaminosilane (H2Si(N(CH2CH3)2)2), di-isopropylaminosilane (H3SiN(i-C3H7)2), and the like. These precursors have been used in mass-production processes for manufacturing semiconductors and displays.
However, due to fineness of devices caused by ultra-high integration of the devices and an increase in aspect ratio, and diversification of materials of the devices, a technology of forming an ultra-fin thin film having a uniform and thin thickness and excellent electrical properties at a low temperature to be desired has been required. Therefore, a high-temperature process (600℃ or more) using an existing silicon precursor, a step coverage, etching properties, and physical and electric properties of the thin film have become problems, such that the development of a novel more excellent silicon precursor and a method for forming a thin film have been studied.
An object of the present invention is to provide a composition for depositing a silicon-containing thin film, containing a bis(aminosilyl)alkylamine compound capable of being used as a precursor of the silicon-containing thin film.
Another object of the present invention is to provide a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention.
Another object of the present invention is to provide a bis(aminosilyl)alkylamine compound capable of being used as a precursor of a silicon-containing thin film.
In one general aspect, there is provided a composition for depositing a silicon-containing thin film containing: a bis(aminosilyl)alkylamine compound, which has excellent physical properties as a precursor for thin film deposition, as a precursor for silicon-containing thin film deposition, wherein the bis(aminosilyl)alkylamine compound is represented by the following Chemical Formula 1.
[Chemical Formula 1]
Figure PCTKR2018003655-appb-I000001
(In Chemical Formula 1,
R is (C1-C7)alkyl or (C2-C7)alkenyl;
R1 to R4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R1 and R2, and R3 and R4 are each independently linked to each other to form a ring; and
R5 to R8 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl.)
Preferably, in Chemical Formula 1 according to an exemplary embodiment of the present invention, R5 to R7 may be each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl, and R8 may be hydrogen.
In order to allow the composition to have excellent properties suitable for thin film deposition, it is preferable that the bis(aminosilyl)alkylamine compound according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 2 or 3.
[Chemical Formula 2]
Figure PCTKR2018003655-appb-I000002
[Chemical Formula 3]
Figure PCTKR2018003655-appb-I000003
(In Chemical Formula 2 or 3,
R is (C1-C7)alkyl or (C2-C7)alkenyl;
R5 to R7 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl;
R11 to R14 are each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and
n and m are each independently an integer of 1 to 7.)
Preferably, in Chemical Formula 2 or 3 according to the exemplary embodiment of the present invention, R5 to R7 may be each independently hydrogen or (C1-C5)alkyl; R11 to R14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n and m may be each independently an integer of 1 to 4.
Preferably, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 4 or 5.
[Chemical Formula 4]
Figure PCTKR2018003655-appb-I000004
[Chemical Formula 5]
Figure PCTKR2018003655-appb-I000005
(In Chemical Formulas 4 and 5,
R is (C1-C7)alkyl or (C2-C7)alkenyl;
R11 to R14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl;
R5 and R6 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl; and
n and m are each independently an integer of 1 to 7.)
Preferably, in Chemical Formula 4 or 5 according to the exemplary embodiment of the present invention, R may be (C1-C5)alkyl; R5 and R6 may be each independently (C1-C5)alkyl; and n and m may be each independently an integer of 1 to 4.
Preferably, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 6 or 7.
[Chemical Formula 6]
Figure PCTKR2018003655-appb-I000006
[Chemical Formula 7]
Figure PCTKR2018003655-appb-I000007
(In Chemical Formulas 6 and 7,
R is (C1-C7)alkyl or (C2-C7)alkenyl;
R11 to R14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl; and
n and m are each independently an integer of 1 to 7.)
Preferably, in Chemical Formula 6 or 7 according to the exemplary embodiment of the present invention, R may be (C1-C5)alkyl; R11 to R14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n and m may be each independently an integer of 1 to 4.
The bis(aminosilyl)alkylamine compound according to the exemplary embodiment of the present invention may be selected from the following compounds, but is not limited thereto.
Figure PCTKR2018003655-appb-I000008
Figure PCTKR2018003655-appb-I000009
.
In another general aspect, there is provided a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film described above.
The composition for depositing a silicon-containing thin film may be deposited by an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a low-pressure chemical vapor deposition (LPCVD) method, a plasma-enhanced chemical vapor deposition (PECVD) method, or a plasma-enhanced atomic layer deposition (PEALD) method, and the silicon-containing thin film may be a silicon oxide (SiO2) film, a silicon oxy carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon carbonitride (SiCN) film, or a silicon carbide (SiC) film.
More specifically, the method for manufacturing a silicon-containing thin film may include: a) maintaining a temperature of a substrate mounted in a chamber at 30 to 500℃;
b) contacting the composition for depositing a silicon-containing thin film described above with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate; and
c) injecting a reaction gas into the substrate in which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film, wherein the reaction gas is supplied after being activated by generating plasma with a plasma power of 50 to 1000 W.
In another general aspect, there is provided a bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 described above.
In order to more efficiently deposit a high-quality thin film, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 may be represented by Chemical Formula 2 or 3.
A composition for depositing a silicon-containing thin film contains a bis(aminosilyl)alkylamine compound which is a liquid at room temperate and has high volatility and excellent thermal stability as a precursor, such that a high-quality silicon-containing thin film having a high purity and durability may be provided under lower plasma power and film formation temperature conditions.
Further, in a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention, excellent thermal stability and deposition rate, and excellent stress intensity may be implemented even under a low film formation temperature condition, and in a silicon-containing thin film manufactured thereby, contents of impurities such as carbon, oxygen, and hydrogen are minimized, thereby making it possible to manufacture a silicon-containing thin film having a high purity, excellent physical and electrical properties, excellent resistance against hydrogen fluoride, an excellent water vapor transmission rate, and an excellent step coverage.
FIG. 1 is a view illustrating a result obtained by measuring vapor pressures of bis(aminosilyl)alkylamine compounds prepared in Examples 1 and 2.
FIG. 2 is a view illustrating results obtained by performing thermogravimetric analysis on the bis(aminosilyl)alkylamine compounds prepared in Examples 1 and 2.
FIG. 3 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon oxide thin films manufactured in Examples 3 to 5.
FIG. 4 is a view illustrating results obtained by performing infrared spectroscopic analysis on deposited films of silicon nitride thin films manufactured in Examples 6 to 9.
The present invention provides a composition for depositing a silicon-containing thin film containing a bis(aminosilyl)alkylamine compound, which is a liquid at room temperature and has high volatility and excellent thermal stability to thereby be used as a useful precursor for forming a silicon-containing thin film, wherein the bis(aminosilyl)alkylamine compound is represented by the following Chemical Formula 1.
[Chemical Formula 1]
Figure PCTKR2018003655-appb-I000010
(In Chemical Formula 1,
R is (C1-C7)alkyl or (C2-C7)alkenyl;
R1 to R4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R1 and R2, and R3 and R4 are each independently linked to each other to form a ring; and
R5 to R8 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl.)
The composition for depositing a silicon-containing thin film according to the present invention contains a precursor for depositing a thin film represented by Chemical Formula 1, such that film formation may be performed at a low temperature, and at the same time, a high-quality thin film having high durability may be easily manufactured.
Further, the composition for depositing a silicon-containing thin film according to the present invention contains the precursor for depositing a thin film represented by Chemical Formula 1, the thin film may be deposited at a high thin film deposition rate, and the film has excellent stress properties and water vapor transmission rate.
The reason may be that as the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1, contained in the composition for depositing a silicon-containing thin film has two aminosilyl groups and one alkyl or alkenyl group as substituents, the bis(aminosilyl)alkylamine compound has high volatility and excellent thermal stability.
Preferably, in Chemical Formula 1 according to the exemplary embodiment, R5 to R7 may be each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl, and R8 may be hydrogen.
Preferably, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to an exemplary embodiment of the present invention may be represented by the following Chemical Formula 2 or 3.
[Chemical Formula 2]
Figure PCTKR2018003655-appb-I000011
[Chemical Formula 3]
Figure PCTKR2018003655-appb-I000012
(In Chemical Formula 2 or 3,
R is (C1-C7)alkyl or (C2-C7)alkenyl;
R5 to R7 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl;
R11 to R14 are each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and
n and m are each independently an integer of 1 to 7.)
In the bis(aminosilyl)alkylamine compound represented by Chemical Formula 2 or 3 according to the present invention, two aminosilyl functional groups and one alkyl or alkenyl group are substituted, such that the bis(aminosilyl)alkylamine compound is thermally stable, and at the same time, the bis(aminosilyl)alkylamine compound has a silazane backbone in which at least one hydrogen atom in at least one of two aminosilyl functional groups is substituted, such that the bis(aminosilyl)alkylamine compound has high volatility as a liquid at room temperature. Therefore, the bis(aminosilyl)alkylamine compound may be significantly usefully used to form a silicon-containing thin film.
More specifically, the bis(aminosilyl)alkylamine compound according to the present invention, which is a compound having the silazane backbone, essentially has two aminosilyl functional groups (
Figure PCTKR2018003655-appb-I000013
and
Figure PCTKR2018003655-appb-I000014
or
Figure PCTKR2018003655-appb-I000015
and
Figure PCTKR2018003655-appb-I000016
), and silyl in one of the aminosilyl functional groups necessarily has a functional group containing at least one hydrogen atom (
Figure PCTKR2018003655-appb-I000017
or
Figure PCTKR2018003655-appb-I000018
), such that the bis(aminosilyl)alkylamine compound may have excellent effects as the precursor for depositing a thin film.
Preferably, in Chemical Formula 2 or 3 according to the exemplary embodiment of the present invention, R5 to R7 may be each independently hydrogen or (C1-C5)alkyl; R11 to R14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; and n and m may be each independently an integer of 1 to 4.
More preferably, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the present invention may be represented by the following Chemical Formula 4 or 5.
[Chemical Formula 4]
Figure PCTKR2018003655-appb-I000019
[Chemical Formula 5]
Figure PCTKR2018003655-appb-I000020
(In Chemical Formulas 4 and 5,
R is (C1-C7)alkyl or (C2-C7)alkenyl;
R11 to R14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl; and
R5 and R6 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl; and
n and m are each independently an integer of 1 to 7.)
Preferably, in Chemical Formulas 4 and 5 according to the exemplary embodiment of the present invention, R may be (C1-C5)alkyl; R5 and R6 may be each independently (C1-C5)alkyl; and n and m may be each independently an integer of 1 to 4. More preferably, the bis(aminosilyl)alkylamine compound may be represented by Chemical Formula 4, and in Chemical Formula 4, R may be (C1-C3)alkyl; and R5 and R6 may be each independently (C1-C3)alkyl.
Preferably, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 6 or 7.
[Chemical Formula 6]
Figure PCTKR2018003655-appb-I000021
[Chemical Formula 7]
Figure PCTKR2018003655-appb-I000022
(In Chemical Formulas 6 and 7,
R is (C1-C7)alkyl or (C2-C7)alkenyl;
R11 to R14 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl; and
n and m are each independently an integer of 1 to 7.)
More preferably, in Chemical Formulas 6 and 7, R may be (C1-C5)alkyl; R11 to R14 may be each independently hydrogen, (C1-C5)alkyl, or (C2-C5)alkenyl; n and m may be each independently an integer of 1 to 4. Preferably, R may be (C1-C5)alkyl; R11 to R14 may be each independently (C1-C5)alkyl; and n and m may be each independently 1 to 4. More preferably, the bis(aminosilyl)alkylamine compound may be represented by Chemical Formula 6, wherein in Chemical Formula 6, R may be (C1-C3)alkyl; and R11 to R14 may be each independently (C1-C3)alkyl.
When silyl groups of two aminosilyl groups in the silazane backbone of the bis(aminosilyl)alkylamine compound according to the present invention have two or four hydrogen atoms, the bis(aminosilyl)alkylamine compound has more excellent reactivity and thermal stability as the precursor for depositing a thin film, such that a higher-quality thin film may be manufactured.
In view of the precursor for depositing a thin film having more excellent properties, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 4 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 4-1.
[Chemical Formula 4-1]
Figure PCTKR2018003655-appb-I000023
(In Chemical Formula 4-1,
R is (C1-C7)alkyl or (C2-C7)alkenyl;
R1 and R2 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R1 and R2 is each independently linked to each other to form a ring; and
R5 is (C1-C7)alkyl or (C2-C7)alkenyl.)
In view of the precursor for depositing a thin film having more excellent properties, the bis(aminosilyl)alkylamine compound represented by Chemical Formula 6 according to the exemplary embodiment of the present invention may be represented by the following Chemical Formula 6-1.
[Chemical Formula 6-1]
Figure PCTKR2018003655-appb-I000024
(In Chemical Formula 6-1,
R is (C1-C7)alkyl or (C2-C7)alkenyl; and
R1 and R2 are each independently (C1-C7)alkyl, or (C2-C7)alkenyl, or are linked to each other to form a ring.)
Although not limited, but a specific example of the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the exemplary embodiment of the present invention may include the following compounds.
Figure PCTKR2018003655-appb-I000025
Figure PCTKR2018003655-appb-I000026
Figure PCTKR2018003655-appb-I000027
.
The composition for depositing a silicon-containing thin film according to the present invention needs to necessarily contain the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 as the precursor for depositing a thin film, and the bis(aminosilyl)alkylamine compound may be contained in the composition for depositing a silicon-containing thin film in a content range in which the content may be recognized by those skilled in the art in consideration of film formation conditions, a thickness, properties, or the like of the thin film.
As used herein, the term "alkyl" means linear, branched, and cyclic saturated and unsaturated hydrocarbons having 1 to 7 carbon atoms, preferably, 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms, and examples thereof may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, neobutyl, pentyl, and the like.
As used herein, the term "halogen" means a halogen element, and examples thereof include fluoro, chloro, bromo, and iodo.
As used herein, the term "alkenyl" as a single group or a part of another group means a straight-chain, branched-chain, or cyclic hydrocarbon radical having 2 to 7 carbon atoms and one or more carbon-carbon double bonds. A more preferable alkenyl radical is a lower alkenyl radical having 2 to 5 carbon atoms. The most preferable lower alkenyl radical is a lower alkenyl radical having about 2 to 3 carbon atoms. Further, the alkenyl group may be substituted at a random usable attachment point. Examples of the alkenyl radical include ethenyl, propenyl, allyl, butenyl, and 4-methylbutenyl. The terms "alkenyl" and "lower alkenyl" include radicals having cis and trans orientations or alternatively, E and Z orientations.
As used herein, the phrase "R1 and R2, and R3 and R4 are each independently linked to each other to form a ring" includes the case in which R1 and R2 are linked to each other to form a ring but R3 and R4 do not form a ring; the case in which on the contrary, R1 and R2 do not form a ring but R3 and R4 are linked to each other to form a ring; and the case in which R1 and R2 are linked to each other to form a ring and R3 and R4 are linked to each other to form a ring, wherein the formed ring may be an alicyclic or aromatic ring containing N, and preferably, an alicyclic ring.
As used herein, the term "alicyclic ring" means a compound that is not an aromatic compound among organic compounds having a cyclic bonding structure.
The bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 according to the present invention may be prepared using a method as long as the method may be recognized by those skilled in the art.
In addition, the present invention provides a method for manufacturing a silicon-containing thin film using the composition for depositing a silicon-containing thin film according to the present invention.
Since in the method for manufacturing a silicon-containing thin film, the composition for depositing a silicon-containing thin film according to the present invention, containing the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1, which is a liquid art room temperature and normal pressure and has high volatility and excellent thermal stability, as the precursor is used, the handling may be easy, it is possible to manufacture various thin films, and it is possible to manufacture a silicon-containing thin film having a high purity, an excellent water vapor transmission rate, and excellent thin film stress properties at a high deposition rate even at a low temperature and a low power.
The silicon-containing thin film manufactured by the method according to the present invention has excellent durability and electric properties, and resistance against hydrogen fluoride and step coverage thereof are also excellent.
In the method for manufacturing a silicon-containing thin film according to the present invention, the silicon-containing thin film may be formed by any method as long as it may be recognized by those skilled in the art. However, preferably, the silicon-containing thin film may be formed by an atomic layer deposition (ALD) method, a chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a low-pressure chemical vapor deposition (LPCVD) method, a plasma enhanced chemical vapor deposition (PECVD) method, or a plasma enhanced atomic layer deposition (PEALD) method, but PECVD, ALD, or PEALD is more preferable in order to allow the thin film to be more easily deposited, and allow the manufactured thin film to have excellent properties.
The silicon-containing thin film according to the present invention may be a silicon oxide (SiO2) film, a silicon oxy carbide (SiOC) film, a silicon nitride (SiN) film, a silicon oxy nitride (SiON) film, a silicon carbonitride (SiCN) film, or a silicon carbide (SiC) film, and various thin films having high quality, particularly, a thin film usable as an encapsulant of an organic light emitting diode (OLED), may be manufactured.
More specifically, the method for manufacturing a silicon-containing thin film according to the present invention may include:
a) maintaining a temperature of a substrate mounted in a chamber at 30 to 500℃;
b) contacting the composition for depositing a silicon-containing thin film according to the present invention with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate; and
c) injecting a reaction gas into the substrate in which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film.
More specifically, the method for manufacturing a silicon-containing thin film according to the present invention may include:
A) maintaining a temperature of a substrate mounted in a chamber at 30 to 500℃;
B) contacting the composition for depositing a silicon-containing thin film according to the present invention with the substrate to adsorb the composition for depositing a silicon-containing thin film in the substrate;
C) purging the remaining composition for depositing a silicon-containing thin film and by-products;
D) injecting a reaction gas into the substrate in which the composition for depositing a silicon-containing thin film is adsorbed to form a silicon-containing thin film; and
E) purging the remaining reaction gas and by-products, wherein the reaction gas in step D) may remove a ligand of the bis(aminosilyl)alkylamine compound contained in the composition for depositing a silicon-containing thin film to form a Si-O atomic layer.
Preferably, the reaction gas according to the exemplary embodiment of the present invention may be supplied after being activated by generating plasma at a plasma power of 50 to 1000 W.
In the method for manufacturing a silicon-containing thin film according to the exemplary embodiment of the present invention, a bis(aminosilyl)alkylamine compound according to the present invention is used as the precursor, such that the reaction gas may be activated at preferably 30 to 500℃, and more preferably 30 to 300℃ by generating plasma at a low plasma power of 50 to 1000 W, preferably 100 to 800 W, and more preferably 400 to 600 W, thereby making it possible to manufacture the thin film.
In the method for manufacturing a silicon-containing thin film according to the exemplary embodiment of the present invention, deposition conditions may be adjusted depending on a structure or thermal properties of a desired thin film. Examples of the deposition condition according to the exemplary embodiment of the present invention may include an injection flow rate of the composition for depositing a silicon-containing thin film containing the bis(aminosilyl)alkyl amine compound, injection flow rates of the reaction gas and a carrier gas, pressure, RF power, the temperature of the substrate, and the like. As non-restrictive examples of the deposition conditions, the injection flow rate of the composition for depositing a silicon-containing thin film may be adjusted in a range of 10 to 1000 cc/min, the injection flow rate of the carrier gas may be adjusted in a range of 10 to 1000 cc/min, the injection flow rate of the reaction gas may be adjusted in a range of 1 to 1500 cc/min, the pressure may be adjusted in a range of 0.5 to 10 torr, the RF power may be adjusted in a range of 50 to 1000 W, and the temperature of the substrate may be adjusted in a range of 30 to 500℃, preferably 80 to 300℃, but the deposition conditions are not limited thereto.
The reaction gas used in the method for manufacturing a silicon-containing thin film according to the present invention is not limited, but may be one selected from hydrogen (H2), hydrazine (N2H4), ozone (O3), oxygen (O2), nitrous oxide (N2O) ammonia (NH3), nitrogen (N2), silane (SiH4), borane (BH3), diborane (B2H6), and phosphine (PH3), or a mixed gas of one or more thereof, and the carrier gas may be one selected from nitrogen (N2), argon (Ar), and helium (He), or a mixed gas of two or more thereof.
The substrate used in the method for manufacturing a silicon-containing thin film according to the present invention may be a substrate containing one or more semiconductor materials selected from Si, Ge, SiGe, GaP, GaAs, SiC, SiGeC, InAs, and InP; a silicon-on-insulator (SOI) substrate; a quartz substrate; a glass substrate for a display; or a flexible plastic substrate made of polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethylmethacrylate (PMMA), polycarbonate (PC), polyethersulfone(PES), polyester, and the like, but is not limited thereto.
Further, the silicon-containing thin film may be directly formed on the substrate. Alternatively, a large number of conductive layers, dielectric layers, insulating layers, or the like, may also be formed between the substrate and the silicon-containing thin film.
In addition, the present invention provides a bis(aminosilyl)alkyl amine compound capable of being used as a precursor of a silicon-containing thin film. The bis(aminosilyl)alkyl amine compound according to the present invention is represented by the following Chemical Formula 1.
Figure PCTKR2018003655-appb-I000028
(In Chemical Formula 1,
R is (C1-C7)alkyl or (C2-C7)alkenyl; and
R1 to R4 are each independently hydrogen, (C1-C7)alkyl, or (C2-C7)alkenyl, or R1 and R2, and R3 and R4 are each independently linked to each other to form a ring; and
R5 to R8 are each independently hydrogen, halogen, (C1-C7)alkyl, or (C2-C7)alkenyl.)
The bis(aminosilyl)alkyl amine compound according to the present invention, represented by Chemical Formula 1 is a liquid at room temperature and has high volatility and excellent thermal stability as described above, such that the bis(aminosilyl)alkyl amine compound is used as a significantly useful precursor in forming a silicon-containing thin film.
Further, since in silyl (silicon) of each aminosilyl group, four hydrogen atoms are present, the bis(aminosilyl)alkyl amine compound has excellent reactivity, such that the thin film may be deposited at a rapid deposition rate, and the thin film with a high purity may be manufactured.
Preferably, the bis(aminosilyl)alkyl amine compound represented by Chemical Formula 1 may be represented by Chemical Formula 2, and more preferably Chemical Formula 6 or 7.
The present invention will be described in detail with reference to the following Examples. The terms and words used in the present specification and claims should not be interpreted as being limited to typical meanings or dictionary definitions, but should be interpreted as having meanings and concepts relevant to the technical scope of the present invention based on the rule according to which an inventor can appropriately define the concept of the term to describe most appropriately the best method he or she knows for carrying out the present invention.
Therefore, configurations described in the embodiments and shown in the drawings of the present specification indicate only the most preferred example rather than indicating all the technical ideas of the present invention and therefore, it is to be understood that various equivalents and modifications that can replace the above configurations may be present.
Further, in all the following Examples, deposition was performed by a plasma enhanced atomic layer deposition (PEALD) method known in the art using a commercialized 200 mm single wafer shower head type ALD apparatus (CN1, Atomic Premium). In addition, deposition was performed by a plasma enhanced chemical vapor deposition (PECVD) method known in the art using a commercialized 200 mm single wafer shower head type CVD (PECVD) apparatus (CN1, Atomic Premium).
A thickness of a deposited silicon-containing thin film was measured using an ellipsometer (OPTI-PROBE 2600, THERMA-WAVE), and properties of the thin film were analyzed using infrared spectroscopy (IFS66V/S & Hyperion 3000, Bruker Optics), X-ray photoelectron spectroscopy, a water vapor transmission rate (WVTR) analyzer (MOCON, Aquatran 2), and a stress analyzer (Frontier Semiconductor, FSM500TC).
[Example 1] Preparation of Bis(methyldimethylaminosilyl)methylamine
Figure PCTKR2018003655-appb-I000029
Under an anhydrous and inert atmosphere, after putting dichloromethylsilane (SiH(CH3)Cl2, 115 g (1.0mol)) and n-pentane (577 g (8mol)) into a 1000mL flame-dried flask and slowly adding methylamine (CH3NH2, 59 g (1.9 mol)) thereto while maintaining a temperature at -25℃, the mixture was stirred for 3 hours, and methylamine hydrochloride ((CH3)NH3Cl) was removed by filtration. While stirring a recovered bis(chloromethylsilyl)methylamine ((SiH(CH3)Cl)2N(CH3)) solution with n-pentane and maintaining a temperature at -25℃, dimethylamine ((CH3)2NH, 94 g (7.13 mol)) was slowly added thereto. After the addition was completed, the reaction solution was slowly heated to room temperature and stirred at room temperature for 6 hours. After removing dimethylamine hydrochloride ((CH3)2NH2Cl, white) formed by filtering the resultant, a filtrate was obtained. A solvent was removed from this filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining bis(methyldimethylaminosilyl)methylamine ((CH3)2NSiH(CH3))2N(CH3), 71 g (0.35 mol), yield: 70 %).
1H-NMR(inCDCl3):δ 0.16(t, 6H (Si-CH3)2), 2.42(d, 3H (NCH3)), 2.48(s, 12H,((CH3)2NSi))2, 4.39(m, 2H, (-SiHN)2).
[Example 2] Preparation of Bis(ethylmethylaminosilyl)methylamine
Figure PCTKR2018003655-appb-I000030
Under an anhydrous and inert atmosphere, after putting dichlorosilane (SiH2Cl2, 360 g (3.56 mol)) and n-pentane (3,202 g (27.79 mol)) into a 5000mL flame-dried Sus reactor (a high-pressure reactor) and slowly adding methylamine (CH3NH2, 210 g (6.77 mol)) thereto while maintaining a temperature at -25℃, the mixture was stirred for 3 hours, and methylamine hydrochloride ((CH3)NH3Cl)) was removed by filtration. While stirring a recovered bischlorolsilylamine ((SiH2Cl)2N(CH3)) solution with n-pentane and maintaining a temperature at -25℃, ethylmethylamine ((CH3CH2)(CH3)NH), 421 g (7.13 mol)) was slowly added thereto. After the addition was completed, the reaction solution was slowly heated to room temperature and stirred at room temperature for 6 hours. After removing ethylmethylamine hydrochloride ((CH3CH2)(CH3)NH2Cl), white) formed by filtering the resultant, a filtrate was obtained. A solvent was removed from this filtrate under reduced pressure, followed by distillation under reduced pressure, thereby obtaining bis(ethylmethylaminosilyl)methylamine ((CH3CH2)(CH3)NSiH2)2N(CH3), 219 g (1.07 mol), yield: 60 %).
1H-NMR(inC6D6):δ 0.97(t, 6H (N-CH2-CH3)2), 2.47(s, 6H (Si-NCH3)2), 2.53(s, 3H (SiH2-NCH3)), 2.81(q, 4H (N-CH2-CH3)2, 4.77(m, 4H, (-SiH2N)2).
[Example 3] Manufacturing of Silicon Oxide Thin film by PEALD using Bis(ethylmethylaminosilyl)methylamine
Film was formed using the bis(ethylmethylaminosilyl)methyl amine compound prepared in Example 2 according to the present invention as a composition for forming a silicon oxide film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art.
As a reaction gas, nitrous oxide was used together with plasma, and nitrogen corresponding to an inert gas was used for purging. The film was formed at reaction gas and plasma time of 0.5 seconds. A specific method for depositing a silicon oxide thin film was illustrated in Table 1.
A result obtained by analyzing the manufactured silicon oxide thin film was illustrated in Table 2, and a result obtained by analyzing the deposited film using infrared spectroscopy was illustrated in FIG. 3.
[Examples 4 and 5] Manufacturing of Silicon Oxide Thin film by PEALD using Bis(ethylmethylaminosilyl)methylamine
Silicon oxide thin films were manufactured in the same manner as in Example 3 except for changing deposition conditions illustrated in the following Table 1 in Example 3, results obtained by analyzing the manufactured silicon oxide thin film were illustrated in the following Table 2, and results obtained by analyzing the deposited film using the infrared spectroscopy were illustrated in FIG. 3.
Deposition Conditions of Silicon Oxide Thin Film by PEALD
Temperature of Substrate (℃) Precursor Purge Reaction Gas and Plasma Reaction Gas Purge No. of Deposition Process Time (sec)
Heating Temperature(℃) Injection Time(sec) Flow Rate (sccm) Time (sec) Flow Rate (sccm) RF Power (W) Time (sec) Time (sec) Flow Rate (sccm) Cycle
Example 3 90 65 0.1 600 0.4 800 400 0.5 0.1 300 614 675
Example 4 90 65 0.1 600 0.4 800 400 0.7 0.1 300 603 784
Example 5 90 65 0.1 600 0.4 800 400 0.9 0.1 300 603 905
Evaluation of Properties of Silicon Oxide Thin Film
Deposition Rate Thickness of Thin Film Refractive Index O/SiComposition Ratio Stress of Film WVTR
(Å/cycle) (Å) - - (MPa) (g/[m2-day])
Example 3 1.14 700 1.46 1.72 -201 3.2E-02
Example 4 1.16 700 1.47 1.72 -231 1.5E-02
Example 5 1.16 700 1.47 1.72 -275 3.5E-03
[Example 6] Manufacturing of Silicon Nitride Thin Film by PEALD using Bis(ethylmethylaminosilyl)methylamine
Film was formed using the bis(ethylmethylaminosilyl)methyl amine compound prepared in Example 2 according to the present invention as a composition for forming a silicon nitride film in a general plasma enhanced atomic layer deposition (PEALD) apparatus using a plasma enhanced atomic layer deposition (PEALD) method known in the art. As a reaction gas, nitrogen and ammonia were used together with plasma as first reaction gas, and nitrogen was used as a second reaction gas. The nitrogen corresponding to an inert gas was used for purging. A specific method for depositing a silicon nitride thin film was illustrated in Table 3.
A specific result obtained by analyzing the silicon nitride thin film was illustrated in Table 4, and a result obtained by analyzing the deposited film using an infrared spectrometer were illustrated in FIG. 4.
[Examples 7 to 9] Manufacturing of Silicon Nitride Thin Film by PEALD using Bis(ethylmethylaminosilyl)methylamine
Silicon nitride thin films were manufactured in the same manner as in Example 6 except for changing conditions illustrated in the following Table 3 in Example 6, results obtained by analyzing the manufactured silicon oxide thin film were illustrated in the following Table 4, and results obtained by analyzing the deposited film using the infrared spectrometer were illustrated in FIG. 4.
Deposition Conditions of Silicon Nitride Thin Film by PEALD
Temperature of Substrate (℃) Precursor Purge Reaction Gas and Plasma Reaction Gas Purge No. of Deposition Process Time (sec)
Heating Temperature(℃) Injection Time(sec) Flow Rate (sccm) Time (sec) Flow Rate (sccm) RF Power (W) Time (sec) Flow Rate (sccm) RF Power (W) Time (sec) Time (sec) Flow Rate (sccm) Cycle
Example 6 300 65 0.4 6000 0.4 2000 100 1.5 6000 600 4 0.4 6000 300 2130
Example 7 300 65 0.4 6000 0.4 2000 200 1.5 6000 600 4 0.4 6000 300 2130
Example 8 300 65 0.4 6000 0.4 2000 400 1.5 6000 600 4 0.4 6000 300 2130
Example 9 300 65 0.4 6000 0.4 2000 800 1.5 6000 600 4 0.4 6000 300 2130
Evaluation of Properties of Silicon Nitride Thin Film
Variable Deposition Rate Thickness of Thin Film Refractive Index N/SiComposition Ratio Stress of Film WVTR
(Å /cycle) (Å ) - - (MPa) (g/[m2-day])
Example 6 Plasma Power of 100W 0.29 88 1.93 1.13 -301 6.2E-02
Example 7 Plasma Power of 200W 0.22 67 1.89 1.16 -350 1.1E-02
Example 8 Plasma Power of 400W 0.34 103 1.95 1.18 -416 3.5E-03
Example 9 Plasma Power of 800W 0.38 114 1.80 1.21 -517 5.3E-03

Claims (16)

  1. A composition for depositing a silicon-containing thin film, the composition comprising a bis(aminosilyl)alkylamine compound represented by the following Chemical Formula 1:
    [Chemical Formula 1]
    Figure PCTKR2018003655-appb-I000031
    in Chemical Formula 1,
    R is C1-C7alkyl or C2-C7alkenyl;
    R1 to R4 are each independently hydrogen, C1-C7alkyl, or C2-C7alkenyl, or R1 and R2, and R3 and R4 are each independently linked to each other to form a ring; and
    R5 to R8 are each independently hydrogen, halogen, C1-C7alkyl, or C2-C7alkenyl.
  2. The composition of claim 1, wherein in Chemical Formula 1, R5 to R7 are each independently hydrogen, halogen, C1-C7alkyl, or C2-C7alkenyl, and R8 is hydrogen.
  3. The composition of claim 1, wherein the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 is represented by the following Chemical Formula 2 or 3:
    [Chemical Formula 2]
    Figure PCTKR2018003655-appb-I000032
    [Chemical Formula 3]
    Figure PCTKR2018003655-appb-I000033
    in Chemical Formula 2 or 3,
    R is C1-C7alkyl or C2-C7alkenyl;
    R5 to R7 are each independently hydrogen, halogen, C1-C7alkyl, or C2-C7alkenyl;
    R11 to R14 are each independently hydrogen, C1-C5alkyl, or C2-C5alkenyl; and
    n and m are each independently an integer of 1 to 7.
  4. The composition of claim 3, wherein in Chemical Formula 2 or 3, R5 to R7 are each independently hydrogen or C1-C7alkyl;
    R11 to R14 are each independently hydrogen, C1-C5alkyl, or C2-C5alkenyl; and
    n and m are each independently an integer of 1 to 4.
  5. The composition of claim 1, wherein the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 is represented by the following Chemical Formula 4 or 5:
    [Chemical Formula 4]
    Figure PCTKR2018003655-appb-I000034
    [Chemical Formula 5]
    Figure PCTKR2018003655-appb-I000035
    in Chemical Formulas 4 and 5,
    R is C1-C7alkyl or C2-C7alkenyl;
    R11 to R14 are each independently hydrogen, C1-C7alkyl, or C2-C7alkenyl;
    R5 and R6 are each independently C1-C7alkyl, or C2-C7alkenyl; and
    n and m are each independently an integer of 1 to 7.
  6. The composition of claim 5, wherein in Chemical Formulas 4 and 5, R is C1-C5alkyl;
    R5 and R6 are each independently C1-C5alkyl; and
    n and m are each independently an integer of 1 to 4.
  7. The composition of claim 1, wherein the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 is represented by the following Chemical Formula 6 or 7:
    [Chemical Formula 6]
    Figure PCTKR2018003655-appb-I000036
    [Chemical Formula 7]
    Figure PCTKR2018003655-appb-I000037
    in Chemical Formulas 6 and 7,
    R is C1-C7alkyl or C2-C7alkenyl;
    R11 to R14 are each independently hydrogen, C1-C7alkyl, or C2-C7alkenyl; and
    n and m are each independently an integer of 1 to 7.
  8. The composition of claim 7, wherein in Chemical Formulas 6 and 7, R is C1-C5alkyl;
    R11 to R14 are each independently hydrogen, C1-C5alkyl, or C2-C5alkenyl; and
    n and m are each independently an integer of 1 to 4.
  9. The composition of claim 1, wherein the bis(aminosilyl)alkylamine compound is selected from the following compounds:
    _
    Figure PCTKR2018003655-appb-I000038
    Figure PCTKR2018003655-appb-I000039
    Figure PCTKR2018003655-appb-I000040
    Figure PCTKR2018003655-appb-I000041
    .
  10. A method for manufacturing a silicon-containing thin film, using the composition of any one of claims 1 to 9.
  11. The method of claim 10, wherein deposition is performed by an atomic layer deposition method, a chemical vapor deposition method, a metal-organic chemical vapor deposition method, a low-pressure chemical vapor deposition method, a plasma-enhanced chemical vapor deposition method, or a plasma-enhanced atomic layer deposition method.
  12. The method of claim 10, wherein the silicon-containing thin film is a silicon oxide film, a silicon oxy carbide film, a silicon nitride film, a silicon oxy nitride film, a silicon carbonitride film, or a silicon carbide film.
  13. The method of claim 10, comprising:
    a) maintaining a temperature of a substrate mounted in a chamber at 30 to 500℃;
    b) contacting the composition of any one of claims 1 to 8 with the substrate to adsorb the composition in the substrate; and
    c) injecting a reaction gas into the substrate in which the composition is adsorbed to form a silicon-containing thin film.
  14. The method of claim 13, wherein the reaction gas is supplied after being activated by generating plasma with a plasma power of 50 to 1000 W.
  15. A bis(aminosilyl)alkylamine compound represented by the following Chemical Formula 1:
    [Chemical Formula 1]
    Figure PCTKR2018003655-appb-I000042
    in Chemical Formula 1,
    R is C1-C7alkyl or C2-C7alkenyl;
    R1 to R4 are each independently hydrogen, C1-C7alkyl, or C2-C7alkenyl, or R1 and R2, and R3 and R4 are each independently linked to each other to form a ring; and
    R5 to R8 are each independently hydrogen, halogen, C1-C7alkyl, or C2-C7alkenyl.
  16. The bis(aminosilyl)alkylamine compound of claim 15, wherein the bis(aminosilyl)alkylamine compound represented by Chemical Formula 1 is represented by Chemical Formula 2 or 3:
    [Chemical Formula 2]
    Figure PCTKR2018003655-appb-I000043
    [Chemical Formula 3]
    Figure PCTKR2018003655-appb-I000044
    In Chemical Formula 2 or 3,
    R5 to R7 are each independently hydrogen, halogen, C1-C7alkyl, or C2-C7alkenyl;
    R11 to R14 are each independently hydrogen, C1-C5alkyl, or C2-C5alkenyl; and
    n and m are each independently an integer of 1 to 7.
PCT/KR2018/003655 2017-03-29 2018-03-28 Composition for depositing silicon-containing thin film containing bis(aminosilyl)alkylamine compound and method for manufacturing silicon-containing thin film using the same Ceased WO2018182309A1 (en)

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JP2019553053A JP6876145B2 (en) 2017-03-29 2018-03-28 A composition for vapor deposition of a silicon-containing thin film containing a bis (aminosilyl) alkylamine compound, and a method for producing a silicon-containing thin film using the composition.
US17/572,509 US11749522B2 (en) 2017-03-29 2022-01-10 Composition for depositing silicon-containing thin film containing bis(aminosilyl)alkylamine compound and method for manufacturing silicon-containing thin using the same

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