WO2017030346A1 - Ge(ii)-containing precursor composition and method for forming germanium-containing film using precursor composition - Google Patents

Ge(ii)-containing precursor composition and method for forming germanium-containing film using precursor composition Download PDF

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WO2017030346A1
WO2017030346A1 PCT/KR2016/008986 KR2016008986W WO2017030346A1 WO 2017030346 A1 WO2017030346 A1 WO 2017030346A1 KR 2016008986 W KR2016008986 W KR 2016008986W WO 2017030346 A1 WO2017030346 A1 WO 2017030346A1
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film
precursor composition
precursor
compound
deposition
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Korean (ko)
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한원석
김대영
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주식회사 유피케미칼
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
    • H10N70/8828—Tellurides, e.g. GeSbTe
    • 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
    • C07F7/30—Germanium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of switching materials, e.g. deposition of layers
    • H10N70/023—Formation of switching materials, e.g. deposition of layers by chemical vapor deposition, e.g. MOCVD, 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • 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
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

Definitions

  • Ge 2 + - relates to membrane-containing vapor deposition precursor compositions and Ge- containing film forming method using the precursor composition of germanium (Ge), including a containing precursor compound.
  • a film containing germanium is used for manufacturing a semiconductor device, and an alloy (Si-Ge) film of silicon and germanium is used for manufacturing a semiconductor device for various purposes.
  • alloys of germanium, antimony, and tellurium are used for optical recording media and phase change memory storage materials capable of writing films or thin films.
  • GST materials of various compositions can be used as optical recording media and phase change memory memory materials.
  • Ge 2 Sb 2 Te 5 phase has been studied.
  • Solid solutions of the bicomponent compounds GeTe, GeTe 2 , and Sb 2 Te 3 consisting of germanium, antimony, and tellurium can form GST materials of various compositions. It is possible to form a solid solution in which GeTe and Sb 2 Te 3 in the germanium 2+ state are mixed in various ratios and use them to form a Ge 2 Sb 2 Te 5 phase. Solid solutions in which GeTe 2 and Sb 2 Te 3 in germanium 4+ are mixed in various ratios are also possible. However, although the GeSb 2 Te 5 phase can be formed from the solid solution mixed with GeTe 2 and Sb 2 Te 3 in this way, the Ge 2 Sb 2 Te 5 phase cannot be formed. In a solid solution containing both Ge and Ge 2 + 4 + a may form a GST materials of various compositions.
  • Chemical vapor deposition in particular, a method of forming a GST film by atomic layer deposition (ALD) in which a raw material supplied in a gaseous state sequentially contacts the substrate forming the film is also known.
  • a number of 4+ germanium (Ge 4 +) precursor (precursor) has been known.
  • GeCl 4 , Ge (OCH 3 ) 4 , Ge (OC 2 H 5 ) 4 , Ge [N (CH 3 ) 2 ] 4, etc., are all liquid at room temperature and have high vapor pressure, which can be applied to CVD and ALD.
  • GeCl 2 (dioxane) is difficult to use in mass production of semiconductor devices because it is solid at room temperature and has low vapor pressure.
  • a precursor composition for film deposition containing 2+ germanium-containing compounds is required.
  • precursor compositions having high vapor pressure and liquid at room temperature are advantageous for mass production of semiconductor devices.
  • Ge 2 + - relates to a film forming method comprising germanium (Ge) using a Ge- containing film vapor deposition precursor composition and the precursor composition including a precursor containing compound.
  • chemical vapor deposition chemical vapor deposition; CVD
  • atomic layer deposition by (atomic layer deposition ALD) method Ge 2 + - containing films, Ge 2 + - containing films, GST film or GST available Ge 2 to deposit a thin film +-containing precursor composition and the Ge + 2 using the precursor composition-containing film-forming method.
  • a first aspect of the present application is to Ge 2 + represented as formula (1) provides a precursor comprising a compound containing, Ge- containing film vapor deposition precursor composition:
  • R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
  • Ge + 2 according to the first aspect of the present-precursor composition including a precursor-containing compound to a Ge- containing film forming method using a precursor composition containing, Ge 2 + represented as formula (I) Provided is a method of forming a Ge-containing film, including vapor deposition using:
  • R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
  • germanium 2+ precursors used to make germanium containing films or thin films for example GeCl 2 (dioxane)
  • GeCl 2 dioxane
  • the liquid precursor composition comprising the germanium 2+ compound of the present application is a liquid at room temperature and has a high vapor pressure, so that it is easy to vaporize and may be supplied at a uniform concentration to a large area substrate.
  • liquid precursor composition according to an embodiment of the present application is particularly advantageous for mass production of semiconductor devices including a Ge 2 Sb 2 Te 5 composition and other compositions of GST film due to the liquid and high vapor pressure properties at room temperature.
  • Figure 5 shows the results of X-ray diffraction (XRD) analysis of the heat-treated GST film prepared according to one embodiment of the present application.
  • step to or “step of” does not mean “step for.”
  • membrane is used to mean a film of all possible thicknesses, and means to include a thin film.
  • a first aspect of the present application is to Ge 2 + represented as formula (1) provides a precursor comprising a compound containing, Ge- containing film vapor deposition precursor composition:
  • R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
  • the present application of the first aspect is Ge 2 + - is contained using a precursor compound to find a new use, which may contain film deposition Ge- completed.
  • R 1 and R 2 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or Alkyl groups which are isomers thereof.
  • R 1 and R 2 may be the same or different from each other and may be methyl, ethyl, propyl, isopropyl (or i Pr), butyl, isobutyl, or t-butyl (or t Bu) , Pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, or isomers thereof.
  • the Ge 2 + -containing precursor compound or the composition may be used to deposit a Ge-containing film by vapor deposition, but may not be limited thereto.
  • the vapor deposition may be performed by ALD or CVD, but may not be limited thereto.
  • the Ge 2 + -containing compound may be a liquid at room temperature
  • the precursor composition for deposition of a Ge-containing film including the Ge 2 + -containing precursor compound may also be liquid at room temperature.
  • the Ge 2 + - to to indicate that contained (R 1 NCH CHNR 2)
  • R 1 and R 2 are liquid properties at room temperature the above compound in the Ge (II) represents a compound having 1 to 6 carbon atoms Linear or branched alkyl groups or isomers thereof.
  • R 1 and R 2 include, but may not be limited to, isopropyl ( i Pr).
  • the problems of the prior art have been solved by inventing a liquid precursor composition comprising a liquid at room temperature and having a high vapor pressure (i PrNCHCHN i Pr) Ge (II) compound.
  • germanium-containing films, in particular conventional Ge (II) compounds, which have been considered for use in forming GST films are liquids with high vapor pressure at room temperature, compared to those that were difficult to use in semiconductor manufacturing processes because they are solid at room temperature. It is particularly advantageous for use in the process.
  • the liquid precursor composition comprising the ( i PrNCH 2 CH 2 N i Pr) Ge (II) compound for the purpose of depositing a film or a thin film
  • the liquid precursor composition may be a solvent as needed Etc. can also be added.
  • ( i PrNCH 2 CH 2 N i Pr) Ge (II) is a hydrocarbon with similar vapor pressure
  • ( i PrNCH 2 CH 2 N i Pr) Ge (II) is similar to vapor (ether),
  • i PrNCH 2 CH 2 N Tertiary amines having similar vapor pressures to i Pr) Ge (II) can be used as such solvents.
  • the precursor composition for the deposition of the Ge-containing film is substantially composed of ( i PrNCH 2 CH 2 N i Pr) Ge (II) compound or comprises only the compound, which is a conventional chemical analysis method such as NMR or chromatography. by the Ge 2 + - means that the compound contains minor amounts of other substances than several% or not the detection of non-detection.
  • Second aspect of the present application is to Ge 2 + represented as the formula (1) provides a contained, Ge- containing film-forming method which comprises vapor deposition using a precursor composition including a precursor compound.
  • R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
  • R 1 and R 2 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or Alkyl groups which are isomers thereof.
  • R 1 and R 2 may be the same or different from each other and may be methyl, ethyl, propyl, isopropyl (or i Pr), butyl, isobutyl, or t-butyl (or t Bu) , Pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, or isomers thereof.
  • the vapor deposition may be performed by ALD or CVD.
  • the germanium-containing film or thin film may include a Ge metal film, a Ge oxide film, a Ge-Sb-Te (GST) film, a film of silicon-germanium alloy (SiGe), or the like. However, this may not be limited.
  • the Ge-Sb-Te (GST) membrane may include a solid solution mixture containing GeTe and Sb 2 Te 3 , but may not be limited thereto.
  • the Ge-Sb-Te (GST) film may include (GeTe) x (Sb 2 Te 3 ) y which is a solid solution mixture of GeTe and Sb 2 Te 3 .
  • the GST film may include Ge 2 Sb 2 Te 5 , which is a 2: 1 solid solution mixture of GeTe and Sb 2 Te 3 , but may not be limited thereto.
  • the GST film may be doped with other elements such as N and Si, but may not be limited thereto.
  • the Ge 2 + -containing precursor composition when using the Ge 2 + -containing precursor composition for the purpose of depositing a Ge-Sb-Te (GST) film or thin film, the Ge 2 + -containing precursor composition, antimony of the GST film Ge-Sb-Te containing GeTe composition and Sb 2 Te 3 composition simultaneously or sequentially supplied together with Sb-containing precursor compound and Te-containing precursor compound for depositing (Sb) component and tellurium (Te) component, respectively It may include but not limited to forming a film of the alloy.
  • a Ge-Sb-Te alloy comprising the GeTe composition and the Sb 2 Te 3 composition may be (GeTe) x (Sb 2 Te 3 ) y [where x and y are known using a known phase change diagram of a GST film. Determined] may be displayed as, but may not be limited thereto.
  • the Ge 4 + -containing precursor composition may be supplied simultaneously or sequentially with the Ge 2 + -containing precursor composition, the Sb-containing precursor composition, and the Te-containing precursor composition to include the GeTe 2 , GeTe, and Sb 2 Te 3 compositions. It may be to include forming a Ge-Sb-Te alloy, but may not be limited thereto.
  • the Ge-Sb-Te alloy comprising the GeTe 2 , GeTe, and Sb 2 Te 3 compositions may comprise (GeTe 2 ) z (GeTe) x (Sb 2 Te 3 ) y [where x, y, and z may be determined using a known phase change diagram of the GST film], but may not be limited thereto.
  • the Ge 4 + - containing precursor composition and Sb- containing precursor composition and the Te- containing precursor compositions can be used in those skilled in the art are properly selected from those known in the art.
  • the deposition temperature of the GST film or thin film may be about 50 °C to about 700 °C or room temperature to about 700 °C, but may not be limited thereto.
  • the deposition temperature may be about 50 ° C to about 700 ° C, about 50 ° C to about 600 ° C, about 50 ° C to about 500 ° C, about 50 ° C to about 400 ° C, about 50 ° C to about 300 ° C, about 50 ° C.
  • °C to about 200 °C about 50 to about 100 °C, about 50 to about 80 °C, about 80 to about 700 °C, about 100 to about 700 °C, about 200 to about 700 °C, about 300 to About 700 ° C., about 400 ° C. to about 700 ° C., about 500 ° C. to about 700 ° C., about 600 ° C. to about 700 ° C., or about 100 ° C. to about 700 ° C., about 100 ° C. to about 600 ° C., about 100 ° C.
  • argon (Ar), helium (He), nitrogen ( N 2 ), hydrogen (H 2 ), or a mixed gas thereof may be used, but may not be limited thereto.
  • a reaction gas for depositing a metal or metal compound-containing film especially a metal oxide film using chemical vapor deposition or atomic layer deposition, water vapor (H 2 O), oxygen (O 2 ), or ozone (O 3).
  • reaction gas for depositing a metal or metal silicide film hydrogen, ammonia (NH 3 ), alcohols, aldehydes, carboxylic acids, silanes (silanes), and combinations thereof may be used, but may not be limited thereto.
  • NH 3 ammonia
  • alcohols, aldehydes, carboxylic acids, silanes (silanes), and combinations thereof may be used, but may not be limited thereto.
  • a plasma chemical vapor deposition method or a plasma atomic layer deposition method using plasma may be used, but may not be limited thereto.
  • a bubbling method in order to transport the Ge 2 + -containing precursor composition to the substrate surface in a gaseous state, a bubbling method, a vapor phase flow control (MFC) method, direct liquid injection
  • MFC vapor phase flow control
  • Various feeding methods including a direct liquid injection (DLI) method or a liquid delivery system (LDS) for dissolving and transferring a precursor composition in an organic solvent may be applied, but the present invention may not be limited thereto.
  • Boiling point (bp) 33 (0.25 torr);
  • the substrate temperature was maintained at 80 ° C. in the atomic layer deposition apparatus.
  • the film formed at 80 ° C. showed no XRD peaks indicating that an amorphous film was formed.
  • XRD diffraction peaks were observed in the film heat-treated at 150 ° C, 250 ° C and 350 ° C. It was found from the position of the diffraction peaks that a GST film containing GeTe and GeSb 2 Te 4 crystals was formed.

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Abstract

The present invention relates to a precursor composition for depositing a Ge(II)-containing film, the precursor composition comprising a Ge2+-containing precursor compound, and to a method for forming a Ge-containing film, the method comprising vapor deposition using the precursor composition.

Description

Ｇｅ(Ⅱ)-함유 전구체 조성물 및 상기 전구체 조성물을 이용하는 게르마늄-함유 막의 형성 방법VIII (II) -containing precursor composition and method of forming a germanium-containing film using the precursor composition
본원은 Ge2 +-함유 전구체 화합물을 포함하는 게르마늄(Ge)-함유 막 증착용 전구체 조성물 및 상기 전구체 조성물을 이용하는 Ge-함유 막의 형성 방법에 관한 것이다.Herein is Ge 2 + - relates to membrane-containing vapor deposition precursor compositions and Ge- containing film forming method using the precursor composition of germanium (Ge), including a containing precursor compound.
게르마늄을 포함한 막이 반도체 소자 제조에 사용되며, 실리콘과 게르마늄의 합금(Si-Ge) 막이 다양한 목적의 반도체 소자 제조에 사용되고 있다. 또한, 게르마늄, 안티모니, 및 텔루륨의 합금(Ge-Sb-Te, GST)이 막 또는 박막이 쓰기 가능한 광학기록매체, 상변화 메모리 기억 물질에 사용된다. 다양한 조성의 GST 물질이 광학기록매체, 상변화 메모리 기억 물질로 사용될 수 있고, 특히 Ge2Sb2Te5 상(phase)이 많이 연구되었다. A film containing germanium is used for manufacturing a semiconductor device, and an alloy (Si-Ge) film of silicon and germanium is used for manufacturing a semiconductor device for various purposes. In addition, alloys of germanium, antimony, and tellurium (Ge-Sb-Te, GST) are used for optical recording media and phase change memory storage materials capable of writing films or thin films. GST materials of various compositions can be used as optical recording media and phase change memory memory materials. In particular, Ge 2 Sb 2 Te 5 phase has been studied.
게르마늄, 안티모니, 및 텔루륨으로 이루어진 2성분 화합물 GeTe, GeTe2, 및 Sb2Te3의 고용체(solid solution)로 다양한 조성의 GST 물질을 형성할 수 있다. 게르마늄이 2+ 상태에 있는 GeTe와 Sb2Te3가 다양한 비율로 섞인 고용체가 가능하고 이를 이용하여 Ge2Sb2Te5 상을 형성할 수 있다. 게르마늄이 4+ 상태에 있는 GeTe2와 Sb2Te3가 다양한 비율로 섞인 고용체도 또한 가능하다. 그러나, 이와 같이 GeTe2와 Sb2Te3가 섞인 고용체로 GeSb2Te5 상은 형성할 수 있지만, Ge2Sb2Te5 상은 형성할 수 없다. Ge2 +와 Ge4 +가 모두 포함된 고용체로 다양한 조성의 GST 물질을 형성할 수 있다.Solid solutions of the bicomponent compounds GeTe, GeTe 2 , and Sb 2 Te 3 consisting of germanium, antimony, and tellurium can form GST materials of various compositions. It is possible to form a solid solution in which GeTe and Sb 2 Te 3 in the germanium 2+ state are mixed in various ratios and use them to form a Ge 2 Sb 2 Te 5 phase. Solid solutions in which GeTe 2 and Sb 2 Te 3 in germanium 4+ are mixed in various ratios are also possible. However, although the GeSb 2 Te 5 phase can be formed from the solid solution mixed with GeTe 2 and Sb 2 Te 3 in this way, the Ge 2 Sb 2 Te 5 phase cannot be formed. In a solid solution containing both Ge and Ge 2 + 4 + a may form a GST materials of various compositions.
GST 막을 화학 기상 증착법(chemical vapor deposition, CVD), 특히 기체 상태로 공급하는 원료 물질이 막을 형성하는 기질에 순차적으로 접촉하는 원자층 증착법(atomic layer deposition, ALD)으로 형성하는 방법도 알려져 있다. 여러 가지 4+ 게르마늄(Ge4 +) 전구체(precursor)가 알려져 있다. GeCl4, Ge(OCH3)4, Ge(OC2H5)4, Ge[N(CH3)2] 4 등은 모두 상온에서 액체이고 증기압이 높으므로 CVD, ALD에 적용할 수 있다. 그에 비해 2+ 게르마늄(Ge2 +) 전구체는 알려진 것이 별로 없고, 특히 상온에서 액체이고 증기압이 높은 2+ 게르마늄(Ge2 +) 전구체 조성물을 사용하여 화학 기상 증착법이나 원자층 증착법으로 GST 막을 형성한 결과는 알려진 것이 없다. GeCl2(다이옥세인)과 SbCl3, [(C2H5)3Si]2Te를 사용하여 GeSb2Te5 조성을 포함하는 GeTe와 Sb2Te3의 고용체를 원자층 증착법으로 형성하는 방법이 보고되었다 [V. Pore et al., "Atomic Layer Deposition of Metal Tellurides and Selenides Using Alkylsilyl Compounds of Tellurium and Selenium," Journal of American Chemical Society, Volume 131, Pages 3478-3480 (2009)]. 상온에서 고체인 GeCl2(다이옥세인)과 SbCl3 대신 상온에서 액체인 Ge(OCH3)4, Sb(OC2H5)3와 [(CH3)3Si]2Te를 사용하여 GeTe2와 Sb2Te3의 고용체를 원자층 증착법으로 형성하는 방법도 보고되었지만 Ge(OCH3)4는 4+ 게르마늄 전구체이기 때문에 GeSb2Te5 막을 형성할 수 없었다 [T. Eom et. al, "Conformal Formation of (GeTe2)(1-x)(Sb2Te3)x Layers by Atomic Layer Deposition for Nanoscale Phase Change Memories," Chemistry of Materials, Volume 24, Pages 2099-2110 (2012)]. Chemical vapor deposition (CVD), in particular, a method of forming a GST film by atomic layer deposition (ALD) in which a raw material supplied in a gaseous state sequentially contacts the substrate forming the film is also known. A number of 4+ germanium (Ge 4 +) precursor (precursor) has been known. GeCl 4 , Ge (OCH 3 ) 4 , Ge (OC 2 H 5 ) 4 , Ge [N (CH 3 ) 2 ] 4, etc., are all liquid at room temperature and have high vapor pressure, which can be applied to CVD and ALD. By comparison 2+ germanium (Ge 2 +) precursors are not much is known, in particular, liquid at room temperature and the vapor pressure of a film formed of a high GST 2+ germanium (Ge 2 +) chemical vapor deposition or atomic layer deposition using a precursor composition The result is unknown. A method for forming a solid solution of GeTe and Sb 2 Te 3 including GeSb 2 Te 5 composition using GeCl 2 (dioxane) and SbCl 3 , [(C 2 H 5 ) 3 Si] 2 Te has been reported. [V. Pore et al., "Atomic Layer Deposition of Metal Tellurides and Selenides Using Alkylsilyl Compounds of Tellurium and Selenium," Journal of American Chemical Society, Volume 131, Pages 3478-3480 (2009)]. In solid GeCl 2 (dioxane) and SbCl 3 instead of room temperature, at room temperature, liquid, Ge (OCH 3) 4, and Sb (OC 2 H 5) 3 and [(CH 3) 3 Si] GeTe 2 using 2 Te A method of forming a solid solution of Sb 2 Te 3 by atomic layer deposition has also been reported, but since Ge (OCH 3 ) 4 is a 4+ germanium precursor, a GeSb 2 Te 5 film could not be formed [T. Eom et. al, "Conformal Formation of (GeTe 2 ) (1-x) (Sb 2 Te 3 ) x Layers by Atomic Layer Deposition for Nanoscale Phase Change Memories," Chemistry of Materials, Volume 24, Pages 2099-2110 (2012).
GeCl2(다이옥세인)은 상온에서 고체이고 증기압이 낮기 때문에 반도체 소자의 대량 생산에 사용하기 곤란하다. 다양한 조성의 GST 막, 특히 GeSb2Te5 막을 반도체 소자 대량 생산에 적용하기 위해서는, 2+ 게르마늄-함유 화합물을 포함하는 막 증착용 전구체 조성물이 필요하다. 특히 증기압이 높고 상온에서 액체인 전구체 조성물이 반도체 소자 대량 생산에 유리하다.GeCl 2 (dioxane) is difficult to use in mass production of semiconductor devices because it is solid at room temperature and has low vapor pressure. In order to apply GST films of various compositions, especially GeSb 2 Te 5 films, to mass production of semiconductor devices, a precursor composition for film deposition containing 2+ germanium-containing compounds is required. In particular, precursor compositions having high vapor pressure and liquid at room temperature are advantageous for mass production of semiconductor devices.
본원은 Ge2 +-함유 전구체 화합물을 포함하는 Ge-함유 막의 증착용 전구체 조성물 및 상기 전구체 조성물을 이용하는 게르마늄(Ge)-함유 막의 형성 방법에 관한 것이다.Herein is Ge 2 + - relates to a film forming method comprising germanium (Ge) using a Ge- containing film vapor deposition precursor composition and the precursor composition including a precursor containing compound.
본원의 구현예들에 있어서, 화학 기상 증착법(chemical vapor deposition; CVD) 또는 원자층 증착법(atomic layer deposition; ALD) 방법에 의하여 Ge2 +-함유 막, Ge2 +-함유 박막, GST 막 또는 GST 박막을 증착하는데 사용 가능한 Ge2 +-함유 전구체 조성물 및 상기 전구체 조성물을 이용하는 Ge2 +-함유 막의 형성 방법이 제공된다.In implementation of the present embodiment, chemical vapor deposition (chemical vapor deposition; CVD) or atomic layer deposition; by (atomic layer deposition ALD) method Ge 2 + - containing films, Ge 2 + - containing films, GST film or GST available Ge 2 to deposit a thin film +-containing precursor composition and the Ge + 2 using the precursor composition-containing film-forming method is provided.
그러나, 본원이 해결하고자 하는 과제는 이상에서 언급한 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.
본원의 제 1 측면은, 하기 화학식 1로서 표시되는 Ge2 +-함유 전구체 화합물을 포함하는, Ge-함유 막의 증착용 전구체 조성물을 제공한다:A first aspect of the present application is to Ge 2 + represented as formula (1) provides a precursor comprising a compound containing, Ge- containing film vapor deposition precursor composition:
[화학식 1][Formula 1]
(R1NCH=CHNR2)Ge(II);(R 1 NCH═CHNR 2 ) Ge (II);
상기 화학식 1에 있어서, R1과 R2는 각각 독립적으로 탄소수 1 내지 6의 선형 또는 분지형 알킬기 또는 이들의 이성질체인 알킬기를 포함한다.In Formula 1, R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
본원의 제 2 측면은, 상기 본원의 제 1 측면에 따른 Ge2 +-함유 전구체 조성물을 이용하는 Ge-함유 막의 형성 방법으로서, 하기 화학식 1로서 표시되는 Ge2 +-함유 전구체 화합물을 포함하는 전구체 조성물을 이용하여 기상 증착하는 것을 포함하는, Ge-함유 막의 형성 방법을 제공한다:Second aspect of the present application, Ge + 2 according to the first aspect of the present-precursor composition including a precursor-containing compound to a Ge- containing film forming method using a precursor composition containing, Ge 2 + represented as formula (I) Provided is a method of forming a Ge-containing film, including vapor deposition using:
[화학식 1][Formula 1]
(R1NCH=CHNR2)Ge(II);(R 1 NCH═CHNR 2 ) Ge (II);
상기 화학식 1에 있어서, R1과 R2는 각각 독립적으로 탄소수 1 내지 6의 선형 또는 분지형 알킬기 또는 이들의 이성질체인 알킬기를 포함한다.In Formula 1, R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
게르마늄을 함유하는 막 또는 박막을 제조하기 위해 사용된 종래의 게르마늄 2+ 전구체, 예를 들어, GeCl2(다이옥세인)은 상온에서 고체 상태이므로, 막 제조 시 기체 상태로 공급하기 위해서는 고온으로 가열해야 하며, 또한 고체를 기화시켜 대면적 기재에 균일한 농도로 공급하기 어렵다. 본원의 게르마늄 2+ 화합물을 포함하는 액체 전구체 조성물은 상온에서 액체로서, 증기압이 높으므로 기화가 용이하고 대면적 기재에 균일한 농도로 공급될 수 있다. Conventional germanium 2+ precursors used to make germanium containing films or thin films, for example GeCl 2 (dioxane), are solid at room temperature, so they must be heated to a high temperature in order to supply them in a gaseous state during film preparation. In addition, it is difficult to vaporize the solid and supply it to the large-area substrate at a uniform concentration. The liquid precursor composition comprising the germanium 2+ compound of the present application is a liquid at room temperature and has a high vapor pressure, so that it is easy to vaporize and may be supplied at a uniform concentration to a large area substrate.
또한, 본원의 일 구현예에 따른 상기 액체 전구체 조성물은 상온에서 액체이고 증기압이 높은 성질로 인해, Ge2Sb2Te5 조성 및 다른 조성의 GST 막을 포함하는 반도체 소자 대량 생산에 특히 유리하다. In addition, the liquid precursor composition according to an embodiment of the present application is particularly advantageous for mass production of semiconductor devices including a Ge 2 Sb 2 Te 5 composition and other compositions of GST film due to the liquid and high vapor pressure properties at room temperature.
도 1은, 본원의 일 실시예에 따라 제조된, (iPrNCH=CHNiPr)Ge(II) 화합물을 포함하는 막 증착용 액체 전구체 조성물의 NMR 스펙트럼이다.1 is an NMR spectrum of a liquid precursor composition for film deposition comprising ( i PrNCH = CHN i Pr) Ge (II) compound, prepared according to one embodiment of the present application.
도 2는, 본원의 일 실시예에 따라 제조된, (iPrNCH=CHNiPr)Ge(II) 화합물을 포함하는 막 증착용 액체 전구체 조성물 열 무게 분석 결과를 나타낸 것이다.FIG. 2 shows the results of thermogravimetric analysis of a liquid precursor composition for film deposition comprising ( i PrNCH = CHN i Pr) Ge (II) compound, prepared according to one embodiment of the present disclosure.
도 3은, 본원의 일 실시예에 따라 제조된, (iPrNCH=CHNiPr)Ge(II) 화합물을 포함하는 막 증착용 액체 전구체 조성물의 시차 주사 열량계 분석 결과를 나타낸 것이다.Figure 3 shows the results of the differential scanning calorimetry analysis of the liquid precursor composition for film deposition comprising ( i PrNCH = CHN i Pr) Ge (II) compound prepared according to an embodiment of the present application.
도 4는, 본원의 일 실시예에 따라 제조된, (iPrNCH=CHNiPr)Ge(II)와 [(C2H5)3Si]2Te를 이용하여 원자층 증착법으로 형성된 Ge-함유 막의 오제 전자 분광법(AES) 분석 결과를 나타낸 것이다.4 is Ge-containing formed by atomic layer deposition using ( i PrNCH = CHN i Pr) Ge (II) and [(C 2 H 5 ) 3 Si] 2 Te, prepared according to one embodiment of the present disclosure. The result of Auger Electron Spectroscopy (AES) analysis of the membrane is shown.
도 5는, 본원의 일 실시예에 따라 제조된, 열처리한 GST 막의 X-선 회절 (XRD) 분석 결과를 나타낸 것이다. Figure 5 shows the results of X-ray diffraction (XRD) analysis of the heat-treated GST film prepared according to one embodiment of the present application.
이하, 첨부한 도면을 참조하여 본원이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본원의 실시예를 상세히 설명한다. 그러나 본원은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. 그리고 도면에서 본원을 명확하게 설명하기 위해서 설명과 관계없는 부분은 생략하였으며, 명세서 전체를 통하여 유사한 부분에 대해서는 유사한 도면 부호를 붙였다.Hereinafter, exemplary embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.
본원 명세서 전체에서, 어떤 부분이 다른 부분과 "연결"되어 있다고 할 때, 이는 "직접적으로 연결"되어 있는 경우뿐 아니라, 그 중간에 다른 소자를 사이에 두고 "전기적으로 연결"되어 있는 경우도 포함한다. Throughout this specification, when a portion is "connected" to another portion, this includes not only "directly connected" but also "electrically connected" with another element in between. do.
본원 명세서 전체에서, 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다. Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise.
본원 명세서 전체에서 사용되는 정도의 용어 "약", "실질적으로" 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본원의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다. As used throughout this specification, the terms "about", "substantially" and the like are used at, or in the sense of, numerical values when a manufacturing and material tolerance inherent in the stated meanings is indicated, Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.
본원 명세서 전체에서 사용되는 정도의 용어 "~(하는) 단계" 또는 "~의 단계"는 "~를 위한 단계"를 의미하지 않는다.As used throughout this specification, the term "step to" or "step of" does not mean "step for."
본원 명세서 전체에서, "A 및/또는 B"의 기재는, "A 또는 B, 또는 A 및 B"를 의미한다. Throughout this specification, the description of "A and / or B" means "A or B, or A and B."
본원 명세서 전체에서, "막"은 모든 가능한 두께의 막을 포함하는 의미로 사용되며, 박막을 포함하는 것을 의미한다.Throughout this specification, "membrane" is used to mean a film of all possible thicknesses, and means to include a thin film.
이하, 본원의 구현예를 상세히 설명하였으나, 본원이 이에 제한되지 않을 수 있다.Hereinafter, embodiments of the present disclosure have been described in detail, but the present disclosure may not be limited thereto.
본원의 제 1 측면은, 하기 화학식 1로서 표시되는 Ge2 +-함유 전구체 화합물을 포함하는, Ge-함유 막의 증착용 전구체 조성물을 제공한다:A first aspect of the present application is to Ge 2 + represented as formula (1) provides a precursor comprising a compound containing, Ge- containing film vapor deposition precursor composition:
[화학식 1][Formula 1]
(R1NCH=CHNR2)Ge(II);(R 1 NCH═CHNR 2 ) Ge (II);
상기 화학식 1에 있어서, R1과 R2는 각각 독립적으로 탄소수 1 내지 6의 선형 또는 분지형 알킬기 또는 이들의 이성질체인 알킬기를 포함한다.In Formula 1, R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
즉, 본원의 제 1 측면은 Ge2 +-함유 전구체 화합물을 이용하여 Ge-함유 막을 증착할 수 있는 신규 용도를 발견하여 완성된 것이다.That is, the present application of the first aspect is Ge 2 + - is contained using a precursor compound to find a new use, which may contain film deposition Ge- completed.
본원의 일 구현예에 있어서, 상기 Ge2 +-함유 화합물을 나타내는 (R1NCH=CHNR2)Ge(II)에서 R1과 R2는 각각 독립적으로 탄소수 1 내지 6의 선형 또는 분지형 알킬기 또는 이들의 이성질체인 알킬기를 포함한다. 예를 들어, 상기 R1과 R2는 서로 동일하거나 상이할 수 있으며 메틸, 에틸, 프로필, 이소프로필 (또는 iPr로 표시됨), 부틸, 이소부틸, 또는 t-부틸 (또는 tBu로 표시됨), 펜틸, 이소펜틸, 네오펜틸, 헥실, 이소헥실, 네오헥실, 또는 이들의 이성질체를 포함할 수 있다.In one embodiment of the present application, in the (R 1 NCH = CHNR 2 ) Ge (II) representing the Ge 2 + -containing compound, R 1 and R 2 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or Alkyl groups which are isomers thereof. For example, R 1 and R 2 may be the same or different from each other and may be methyl, ethyl, propyl, isopropyl (or i Pr), butyl, isobutyl, or t-butyl (or t Bu) , Pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, or isomers thereof.
본원의 일 구현예에 있어서, 상기 Ge2 +-함유 전구체 화합물 또는 상기 조성물은 기상 증착에 의하여 Ge-함유 막을 증착하는 데 사용되는 것일 수 있으나, 이에 제한되지 않을 수 있다. 예를 들어, 상기 기상 증착은 ALD 또는 CVD에 의하여 수행되는 것일 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present application, the Ge 2 + -containing precursor compound or the composition may be used to deposit a Ge-containing film by vapor deposition, but may not be limited thereto. For example, the vapor deposition may be performed by ALD or CVD, but may not be limited thereto.
본원의 일 구현예에 있어서, 상기 Ge2 +-함유 화합물은 상온에서 액체일 수 있으며, 상기 Ge2 +-함유 전구체 화합물을 포함하는 Ge-함유 막의 증착용 전구체 조성물 또한 상온에서 액체일 수 있다. 예를 들어, 상기 Ge2 +-함유 화합물을 나타내는 (R1NCH=CHNR2)Ge(II)에서 R1과 R2는 상기 화합물이 상온에서 액체인 특성을 나타내도록 하는, 탄소수 1 내지 6의 선형 또는 분지형 알킬기 또는 이들의 이성질체인 알킬기를 포함한다. 비제한적 예로서, R1과 R2는 이소프로필(iPr)을 포함하지만, 이에 제한되지 않을 수 있다.In one embodiment of the present application, the Ge 2 + -containing compound may be a liquid at room temperature, and the precursor composition for deposition of a Ge-containing film including the Ge 2 + -containing precursor compound may also be liquid at room temperature. For example, the Ge 2 + - to to indicate that contained (R 1 NCH = CHNR 2) R 1 and R 2 are liquid properties at room temperature the above compound in the Ge (II) represents a compound having 1 to 6 carbon atoms Linear or branched alkyl groups or isomers thereof. By way of non-limiting example, R 1 and R 2 include, but may not be limited to, isopropyl ( i Pr).
본원의 일 구현예에 있어서, 상기 Ge-함유 막의 증착용 전구체 조성물은 (iPrNCH=CHNiPr)Ge(II) 또는 (tBuNCH=CHNtBu)Ge(II) 인 Ge2 +-함유 화합물을 포함할 수 있다.In one embodiment of the present application, the precursor composition for deposition of the Ge-containing film is a Ge 2 + -containing compound ( i PrNCH = CHN i Pr) Ge (II) or ( t BuNCH = CHN t Bu) Ge (II) It may include.
상기 Ge2 +-함유 화합물 (iPrNCH=CHNiPr)Ge(II)은 하기 구조를 갖는다:The Ge 2 + - containing compounds (i PrNCH = CHN i Pr) Ge (II) has the following structure:
Figure PCTKR2016008986-appb-I000001
.
Figure PCTKR2016008986-appb-I000001
.
본원의 일 구현예에 있어서, 상온에서 액체이고 증기압이 높은 (iPrNCHCHNiPr)Ge(II) 화합물을 포함하는 액체 전구체 조성물을 발명함으로써 종래 기술의 문제점들을 해결하였다.In one embodiment of the present application, the problems of the prior art have been solved by inventing a liquid precursor composition comprising a liquid at room temperature and having a high vapor pressure ( i PrNCHCHN i Pr) Ge (II) compound.
본원의 일 구현예에 있어서, 상기 (iPrNCH=CHNiPr)Ge(II) 화합물은 상온에서 액체 상태로서, 증기압이 높아 기화가 용이하다. 예를 들어, 게르마늄-함유 막, 특히 GST 막 형성 용도로 검토되었던 종래의 Ge(II) 화합물들이 상온에서 고체이기 때문에 반도체 제조 공정에 사용하기 어려웠던 것에 비해, 상온에서 증기압이 높은 액체이기 때문에 반도체 제조 공정에 사용하는 데에 특히 유리하다.In one embodiment of the present application, the ( i PrNCH = CHN i Pr) Ge (II) compound is a liquid state at room temperature, it is easy to vaporize the high vapor pressure. For example, semiconductor production is possible because germanium-containing films, in particular conventional Ge (II) compounds, which have been considered for use in forming GST films, are liquids with high vapor pressure at room temperature, compared to those that were difficult to use in semiconductor manufacturing processes because they are solid at room temperature. It is particularly advantageous for use in the process.
본원의 일 구현예에 있어서, 상기 (iPrNCH2CH2NiPr)Ge(II) 화합물을 포함하는 액체 전구체 조성물을 막 또는 박막의 증착 목적으로 사용할 때, 상기 액체 전구체 조성물에는 필요에 따라 용매 등을 첨가할 수도 있다. (iPrNCH2CH2NiPr)Ge(II) 와 증기압이 비슷한 탄화수소, (iPrNCH2CH2NiPr)Ge(II)와 증기압이 비슷한 에테르(ether), (iPrNCH2CH2NiPr)Ge(II)와 증기압이 비슷한 3차 아민 등을 이러한 용매로 사용할 수 있다. In one embodiment of the present application, when the liquid precursor composition comprising the ( i PrNCH 2 CH 2 N i Pr) Ge (II) compound for the purpose of depositing a film or a thin film, the liquid precursor composition may be a solvent as needed Etc. can also be added. ( i PrNCH 2 CH 2 N i Pr) Ge (II) is a hydrocarbon with similar vapor pressure, ( i PrNCH 2 CH 2 N i Pr) Ge (II) is similar to vapor (ether), ( i PrNCH 2 CH 2 N Tertiary amines having similar vapor pressures to i Pr) Ge (II) can be used as such solvents.
본원의 일 구현예에 있어서, 상기 Ge-함유 막의 증착용 전구체 조성물이 (iPrNCH=CHNiPr)Ge(II) 인 Ge2 +-함유 화합물로 실질적으로 이루어질 수 있다. 이와 관련하여, 상기 액체 전구체 조성물에 다른 물질을 첨가하지 않은 경우, (iPrNCH=CHNiPr)Ge(II) 인 Ge2 +-함유 화합물로 실질적으로 이루어지거나 또는 상기 화합물만을 포함하는 상기 전구체 조성물을 막 증착 목적에 사용할 수 있다. 상기 Ge-함유 막의 증착용 전구체 조성물이 (iPrNCH2CH2NiPr)Ge(II) 화합물로 실질적으로 이루어진다는 것 또는 상기 화합물만을 포함한다는 것은, NMR이나 크로마토그래피와 같은 통상의 화학분석 방법에 의하여 상기 Ge2 +-함유 화합물 이외의 다른 물질이 검출되지 않거나 수 % 미만의 미미한 양이 검출된다는 것을 의미한다.In one embodiment of the present application, the precursor composition for deposition of the Ge-containing film may be substantially made of a Ge 2 + -containing compound ( i PrNCH = CHN i Pr) Ge (II). In this regard, when no other substance is added to the liquid precursor composition, the precursor composition substantially consisting of or containing only the compound, wherein the compound is Ge 2 + -( i PrNCH = CHN i Pr) Ge (II) Can be used for film deposition purposes. The precursor composition for the deposition of the Ge-containing film is substantially composed of ( i PrNCH 2 CH 2 N i Pr) Ge (II) compound or comprises only the compound, which is a conventional chemical analysis method such as NMR or chromatography. by the Ge 2 + - means that the compound contains minor amounts of other substances than several% or not the detection of non-detection.
본원의 제 2 측면은, 하기 화학식 1로서 표시되는 Ge2 +-함유 전구체 화합물을 포함하는 전구체 조성물을 이용하여 기상 증착하는 것을 포함하는, Ge-함유 막의 형성 방법을 제공한다.Second aspect of the present application is to Ge 2 + represented as the formula (1) provides a contained, Ge- containing film-forming method which comprises vapor deposition using a precursor composition including a precursor compound.
[화학식 1][Formula 1]
(R1NCH=CHNR2)Ge(II);(R 1 NCH═CHNR 2 ) Ge (II);
상기 화학식 1에 있어서, R1과 R2는 각각 독립적으로 탄소수 1 내지 6의 선형 또는 분지형 알킬기 또는 이들의 이성질체인 알킬기를 포함한다.In Formula 1, R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
본원의 일 구현예에 있어서, 상기 Ge2 +-함유 화합물을 나타내는 (R1NCH=CHNR2)Ge(II)에서 R1과 R2는 각각 독립적으로 탄소수 1 내지 6의 선형 또는 분지형 알킬기 또는 이들의 이성질체인 알킬기를 포함한다. 예를 들어, 상기 R1과 R2는 서로 동일하거나 상이할 수 있으며 메틸, 에틸, 프로필, 이소프로필 (또는 iPr로 표시됨), 부틸, 이소부틸, 또는 t-부틸 (또는 tBu로 표시됨), 펜틸, 이소펜틸, 네오펜틸, 헥실, 이소헥실, 네오헥실, 또는 이들의 이성질체를 포함할 수 있다.In one embodiment of the present application, in the (R 1 NCH = CHNR 2 ) Ge (II) representing the Ge 2 + -containing compound, R 1 and R 2 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or Alkyl groups which are isomers thereof. For example, R 1 and R 2 may be the same or different from each other and may be methyl, ethyl, propyl, isopropyl (or i Pr), butyl, isobutyl, or t-butyl (or t Bu) , Pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, or isomers thereof.
본원의 일 구현예에 있어서, 상기 Ge2 +-함유 전구체 조성물은 기상 증착에 의하여 Ge-함유 막을 형성하는 데 사용되는 것일 수 있으며, 상기 Ge2 +-함유 전구체 화합물은 (iPrNCH=CHNiPr)Ge(II) 또는 (tBuNCH=CHNtBu)Ge(II)에서 선택되는 것일 수 있다.In one embodiment of the present application, the Ge 2 + -containing precursor composition may be used to form a Ge-containing film by vapor deposition, the Ge 2 + -containing precursor compound is ( i PrNCH = CHN i Pr ) Ge (II) or ( t BuNCH = CHN t Bu) Ge (II).
본원의 일 구현예에 있어서, 상기 기상 증착은 ALD 또는 CVD에 의하여 수행되는 것일 수 있다.In one embodiment of the present application, the vapor deposition may be performed by ALD or CVD.
본원의 일 구현예에 있어서, 상기 게르마늄-함유 막 또는 박막은 Ge 금속 막, Ge 산화물 막, Ge-Sb-Te(GST) 막, 또는 실리콘-게르마늄 합금(SiGe)의 막 등을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present application, the germanium-containing film or thin film may include a Ge metal film, a Ge oxide film, a Ge-Sb-Te (GST) film, a film of silicon-germanium alloy (SiGe), or the like. However, this may not be limited.
본원의 일 구현예에 있어서, 상기 Ge-Sb-Te(GST) 막은 GeTe 및 Sb2Te3을 함유하는 고체 용액 혼합물(solid solution mixture)을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다. 예를 들어, 상기 Ge-Sb-Te(GST) 막은 GeTe 및 Sb2Te3의 고체 용액 혼합물인 (GeTe)x(Sb2Te3)y를 포함하는 것일 수 있다. 예를 들어, 상기 GST 막은 GeTe 및 Sb2Te3의 2:1 고체 용액 혼합물인 Ge2Sb2Te5를 포함하는 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다. 또한, 상기 GST 막은 N, Si 등 다른 원소들에 의하여 도핑될 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present application, the Ge-Sb-Te (GST) membrane may include a solid solution mixture containing GeTe and Sb 2 Te 3 , but may not be limited thereto. For example, the Ge-Sb-Te (GST) film may include (GeTe) x (Sb 2 Te 3 ) y which is a solid solution mixture of GeTe and Sb 2 Te 3 . For example, the GST film may include Ge 2 Sb 2 Te 5 , which is a 2: 1 solid solution mixture of GeTe and Sb 2 Te 3 , but may not be limited thereto. In addition, the GST film may be doped with other elements such as N and Si, but may not be limited thereto.
본원의 일 구현예에 있어서, 상기 Ge2 +-함유 전구체 조성물을 Ge-Sb-Te(GST) 막 또는 박막의 증착 목적으로 사용할 때, 상기 Ge2 +-함유 전구체 조성물을, 상기 GST 막의 안티모니 (Sb) 성분과 텔루륨 (Te) 성분 각각을 증착하기 위한 Sb-함유 전구체 화합물과 Te-함유 전구체 화합물과 함께 동시에 또는 순차적으로 공급하여 GeTe 조성과 Sb2Te3 조성을 포함하는 Ge-Sb-Te 합금의 막을 형성하는 것을 포함하는 것이나, 이에 제한되지 않을 수 있다. 예를 들어, 상기 GeTe 조성과 Sb2Te3 조성을 포함하는 Ge-Sb-Te 합금은 (GeTe)x(Sb2Te3)y [여기서, 상기 x 및 y는 GST 막의 공지된 상변화 다이어그램을 이용하여 결정됨]로서 표시되는 것일 수 있으나, 이에 제한되지 않을 수 있다. 또한, Ge4 +-함유 전구체 조성물을 Ge2 +-함유 전구체 조성물, Sb-함유 전구체 조성물, Te-함유 전구체 조성물과 함께 동시에 또는 순차적으로 공급하여 GeTe2, GeTe, 및 Sb2Te3 조성을 포함하는 Ge-Sb-Te 합금을 형성하는 것을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다. 예를 들어, 상기 GeTe2, GeTe, 및 Sb2Te3 조성을 포함하는 Ge-Sb-Te 합금은 (GeTe2)z(GeTe)x(Sb2Te3)y [여기서, 상기 x, y, 및 z는 GST 막의 공지된 상변화 다이어그램을 이용하여 결정됨]로서 표시되는 것일 수 있으나, 이에 제한되지 않을 수 있다. 상기 Ge4 +-함유 전구체 조성물과 Sb-함유 전구체 조성물과 상기 Te-함유 전구체 조성물은 당업계에 공지된 것들 중에서 당업자가 적절히 선택하여 사용할 수 있다.In one embodiment of the present application, when using the Ge 2 + -containing precursor composition for the purpose of depositing a Ge-Sb-Te (GST) film or thin film, the Ge 2 + -containing precursor composition, antimony of the GST film Ge-Sb-Te containing GeTe composition and Sb 2 Te 3 composition simultaneously or sequentially supplied together with Sb-containing precursor compound and Te-containing precursor compound for depositing (Sb) component and tellurium (Te) component, respectively It may include but not limited to forming a film of the alloy. For example, a Ge-Sb-Te alloy comprising the GeTe composition and the Sb 2 Te 3 composition may be (GeTe) x (Sb 2 Te 3 ) y [where x and y are known using a known phase change diagram of a GST film. Determined] may be displayed as, but may not be limited thereto. In addition, the Ge 4 + -containing precursor composition may be supplied simultaneously or sequentially with the Ge 2 + -containing precursor composition, the Sb-containing precursor composition, and the Te-containing precursor composition to include the GeTe 2 , GeTe, and Sb 2 Te 3 compositions. It may be to include forming a Ge-Sb-Te alloy, but may not be limited thereto. For example, the Ge-Sb-Te alloy comprising the GeTe 2 , GeTe, and Sb 2 Te 3 compositions may comprise (GeTe 2 ) z (GeTe) x (Sb 2 Te 3 ) y [where x, y, and z may be determined using a known phase change diagram of the GST film], but may not be limited thereto. The Ge 4 + - containing precursor composition and Sb- containing precursor composition and the Te- containing precursor compositions can be used in those skilled in the art are properly selected from those known in the art.
본원의 일 구현예에 있어서, 상기 GST 막 또는 박막의 증착 온도는 약 50℃ 내지 약 700℃ 또는 상온 내지 약 700℃ 일 수 있으나, 이에 제한되지 않을 수 있다. 예를 들어, 상기 증착 온도는 약 50℃ 내지 약 700℃, 약 50℃ 내지 약 600℃, 약 50℃ 내지 약 500℃, 약 50℃ 내지 약 400℃, 약 50℃ 내지 약 300℃, 약 50℃ 내지 약 200℃, 약 50℃ 내지 약 100℃, 약 50℃ 내지 약 80℃, 약 80℃ 내지 약 700℃, 약 100℃ 내지 약 700℃, 약 200℃ 내지 약 700℃, 약 300℃ 내지 약 700℃, 약 400℃ 내지 약 700℃, 약 500℃ 내지 약 700℃, 약 600℃ 내지 약 700℃, 또는 약 100℃ 내지 약 700℃, 약 100℃ 내지 약 600℃, 약 100℃ 내지 약 500℃, 약 100℃ 내지 약 400℃, 약 100℃ 내지 약 300℃, 약 150℃ 내지 약 700℃, 약 150℃ 내지 약 600℃, 약 150℃ 내지 약 500℃, 약 150℃ 내지 약 400℃, 또는 약 150℃ 내지 약 300℃일 수 있으나, 이에 제한되지 않을 수 있다. In one embodiment of the present application, the deposition temperature of the GST film or thin film may be about 50 ℃ to about 700 ℃ or room temperature to about 700 ℃, but may not be limited thereto. For example, the deposition temperature may be about 50 ° C to about 700 ° C, about 50 ° C to about 600 ° C, about 50 ° C to about 500 ° C, about 50 ° C to about 400 ° C, about 50 ° C to about 300 ° C, about 50 ° C. ℃ to about 200 ℃, about 50 to about 100 ℃, about 50 to about 80 ℃, about 80 to about 700 ℃, about 100 to about 700 ℃, about 200 to about 700 ℃, about 300 to About 700 ° C., about 400 ° C. to about 700 ° C., about 500 ° C. to about 700 ° C., about 600 ° C. to about 700 ° C., or about 100 ° C. to about 700 ° C., about 100 ° C. to about 600 ° C., about 100 ° C. to about 500 ° C, about 100 ° C to about 400 ° C, about 100 ° C to about 300 ° C, about 150 ° C to about 700 ° C, about 150 ° C to about 600 ° C, about 150 ° C to about 500 ° C, about 150 ° C to about 400 ° C , Or about 150 ° C. to about 300 ° C., but may not be limited thereto.
본원의 일 구현예에 있어서, 상기 Ge2 +-함유 전구체 조성물을 기재 표면에 운반하기 위한 운송 기체(carrier gas) 및 퍼지 기체(purge gas)로는, 아르곤(Ar), 헬륨(He), 질소(N2), 수소(H2), 또는 이들의 혼합 기체를 사용할 수 있으나, 이에 제한되지 않을 수 있다. 아울러, 화학 기상 증착법 또는 원자층 증착법을 이용하여 금속 또는 금속 화합물-함유 막, 특히 금속 산화물 막을 증착하기 위한 반응 기체로는, 수증기(H2O), 산소(O2), 또는 오존(O3)을 사용할 수 있으며, 특히, 금속 또는 금속 실리사이드 막을 증착하기 위한 반응 기체로는, 수소, 암모니아(NH3), 알코올류(alcohols), 알데히드류(aldehydes), 카르복시산류(carboxylic acids), 실란류(silanes), 및 이들의 조합들로 이루어진 군으로부터 선택된 것을 사용할 수 있으나, 이에 제한되지 않을 수 있다. 플라즈마를 사용하는 플라즈마 화학기상증착법 또는 플라즈마 원자층 증착법을 사용할 수 있으나, 이에 제한되지 않을 수 있다.In one embodiment of the present application, as a carrier gas and a purge gas for transporting the Ge 2 + -containing precursor composition to the substrate surface, argon (Ar), helium (He), nitrogen ( N 2 ), hydrogen (H 2 ), or a mixed gas thereof may be used, but may not be limited thereto. In addition, as a reaction gas for depositing a metal or metal compound-containing film, especially a metal oxide film using chemical vapor deposition or atomic layer deposition, water vapor (H 2 O), oxygen (O 2 ), or ozone (O 3). ), And in particular, as a reaction gas for depositing a metal or metal silicide film, hydrogen, ammonia (NH 3 ), alcohols, aldehydes, carboxylic acids, silanes (silanes), and combinations thereof may be used, but may not be limited thereto. A plasma chemical vapor deposition method or a plasma atomic layer deposition method using plasma may be used, but may not be limited thereto.
본원의 일 구현예에 있어서, 상기 Ge2 +-함유 전구체 조성물을 기체 상태로 기재 표면에 운반하기 위해서는 버블링 방식, 기체상(vapor phase) 유량제어(MFC: mass flow controller) 방법, 직접 액체 주입(DLI: direct liquid injection) 방법 또는 전구체 조성물을 유기용매에 용해시켜 이송하는 액체 이송방법(LDS: liquid delivery system)을 포함하는 다양한 공급방식이 적용될 수 있으나, 이에 제한되지 않을 수 있다. In one embodiment of the present application, in order to transport the Ge 2 + -containing precursor composition to the substrate surface in a gaseous state, a bubbling method, a vapor phase flow control (MFC) method, direct liquid injection Various feeding methods including a direct liquid injection (DLI) method or a liquid delivery system (LDS) for dissolving and transferring a precursor composition in an organic solvent may be applied, but the present invention may not be limited thereto.
이하, 본원에 대하여 실시예를 이용하여 좀더 자세히 설명하지만, 본원이 이들 실시예에 의하여 제한되지 않는다.Hereinafter, the present application will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[실시예]EXAMPLE
<실시예 1> (iPrNCH=CHNiPr)Ge(II)을 포함하는 막 증착용 액체 전구체 조성물의 제조<Example 1> Preparation of the liquid precursor composition for film deposition containing ( i PrNCH = CHN i Pr) Ge (II)
불꽃 건조된 500 mL 슐렝크 플라스크에서, N,N '-다이아이소프로필-1,4-다이아자-1,3-부타디엔 (N,N '-diisopropyl-1,4-diaza-1,3-butadiene, iPrN=CHCH=NiPr) 21.2 g (0.151 mol)을 테트라히드로퓨란(tetrahydropuran, THF) 150 mL에 녹인 후 10℃로 유지시켰다. 상기 플라스크에 리튬(Li) 2.1 g (0.302 mol)를 첨가시킨 후, 반응 용액을 실온까지 천천히 승온시키며 15 시간 동안 교반시켰다. 이후, 상기 플라스크의 내부 온도를 다시 0℃로 냉각시키고, THF 200 mL에 혼합한 GeCl2(다이옥세인) [GeCl2(C4H8O2)] 34.3 g (0.147 mol)을 천천히 적가한 후, 반응 용액을 실온까지 천천히 승온시키며 18시간 동안 교반시켰다.In a flame dried 500 mL flask Herr Lenk, N, N '- diisopropyl-1,4-diaza-1,3-butadiene (N, N' -diisopropyl-1,4 -diaza-1,3-butadiene 21.2 g (0.151 mol) of i PrN = CHCH = N i Pr) was dissolved in 150 mL of tetrahydropuran (THF) and maintained at 10 ° C. After adding 2.1 g (0.302 mol) of lithium (Li) to the flask, the reaction solution was slowly heated to room temperature and stirred for 15 hours. The flask was then cooled to 0 ° C. again and slowly added dropwise to 34.3 g (0.147 mol) of GeCl 2 (dioxane) [GeCl 2 (C 4 H 8 O 2 )] mixed with 200 mL of THF. The reaction solution was slowly heated to room temperature and stirred for 18 hours.
상기 반응이 완료된 후 감압 하에서 용매 및 휘발성 부반응물을 제거한 뒤 n-헥산(n-hexane, C6H14) 500 mL로 추출하였다. n-헥산 추출물을 셀라이트 (Celite) 패드와 유리 프릿 (frit)을 통해 여과한 뒤 얻은 여과액을 감압 하에서 용매를 제거하고 감압 하에서 증류하여 하기 구조식으로서 표시되는 붉은색 액체 22.5g (70%)인 (iPrNCH=CHNiPr)Ge(II)를 수득하였다. 이 액체 전구체 조성물의 NMR 스펙트럼을 도 1에, 열무게 분석 결과를 도 2에, 시차 주사 열량계 분석 결과를 도 3에 나타내었다. 도 2의 열무게 분석 결과에 따르면, 상온에서 액체 상태인 (iPrNCH=CHNiPr)Ge(II)는 거의 완전한 열분해를 나타내었다(잔여량: 1.03% 이하).After the reaction was completed, the solvent and the volatile side reactions were removed under reduced pressure and extracted with 500 mL of n-hexane (n-hexane, C 6 H 14 ). The n-hexane extract was filtered through a pad of Celite and a glass frit, and then the filtrate was removed under reduced pressure and distilled under reduced pressure to give 22.5 g (70%) of a red liquid represented by the following structural formula. Phosphorus ( i PrNCH = CHN i Pr) Ge (II) was obtained. The NMR spectrum of this liquid precursor composition is shown in FIG. 1, the thermal weight analysis result is shown in FIG. 2, and the differential scanning calorimeter analysis result is shown in FIG. According to the thermogravimetric analysis of FIG. 2, the liquid phase ( i PrNCH = CHN i Pr) Ge (II) at room temperature showed almost complete pyrolysis (residue: 1.03% or less).
Figure PCTKR2016008986-appb-I000002
Figure PCTKR2016008986-appb-I000002
끓는점(bp) 33 (0.25 torr);Boiling point (bp) 33 (0.25 torr);
원소분석(elemental analysis) 계산치 (C8H16N2Ge): C 45.14, H 7.58, N 13.16; 실측치 C 45.05, H 7.38, N 13.25;Elemental analysis calculated (C 8 H 16 N 2 Ge): C 45.14, H 7.58, N 13.16; Found C 45.05, H 7.38, N 13.25;
1H-NMR (400 MHz, C6D6, 25) δ 6.840 (s, 2H, NCH), 3.984 (septet, 2H, NH(CH3)3), 1.354 (d, 12H, NH(CH 3)3). 1 H-NMR (400 MHz, C 6 D 6 , 25) δ 6.840 (s, 2H, NC H ), 3.984 (septet, 2H, N H (CH 3 ) 3 ), 1.354 (d, 12H, NH (C H 3 ) 3 ).
<실시예 2> (iPrNCH=CHNiPr)Ge(II)을 포함하는 막 증착용 액체 전구체 조성물을 사용한 Ge-Te 막 형성<Example 2> Ge-Te film formation using the liquid precursor composition for film deposition containing ( i PrNCH = CHN i Pr) Ge (II)
(iPrNCH=CHNiPr)Ge(II)을 포함하는 증착용 전구체 조성물과 [(C2H5)3Si]2Te의 기체를 교대로 기판 표면에 접촉시키는 원자층 증착법으로 Ge-Te 막을 형성하였다. 원자층 증착 장치에 기판 온도를 80ºC, 100ºC, 120ºC 각각에서 유지하였다. (iPrNCH=CHNiPr)Ge(II)의 기체를 10 초 동안 공급하고, [(C2H5)3Si]2Te의 기체를 20 초 동안 공급하는 기체 공급 주기를 800 회 반복하였다. 80℃에서 형성한 막을 오제전자분광법(AES)으로 분석한 결과를 도 4에 나타내었다. 이 결과로부터 조성이 Ge:Te = 1:1인 GeTe 막이 형성된 것을 확인할 수 있었다. 주사전자현미경(SEM)으로 기판 온도 80℃, 100℃, 및 120℃ 각각에서 형성한 막을 관찰하여 모두 표면이 평탄한 막이 형성된 것을 확인하였다.The Ge-Te film was formed by atomic layer deposition in which a vapor deposition precursor composition ( i PrNCH = CHN i Pr) Ge (II) and a gas of [(C 2 H 5 ) 3 Si] 2 Te were alternately brought into contact with the substrate surface. Formed. Substrate temperatures were maintained at 80 ° C, 100 ° C, and 120 ° C, respectively, in the atomic layer deposition apparatus. The gas supply cycle of supplying a gas of ( i PrNCH = CHN i Pr) Ge (II) for 10 seconds and a gas of [(C 2 H 5 ) 3 Si] 2 Te for 20 seconds was repeated 800 times. The film formed at 80 ° C. was analyzed by Auger Electron Spectroscopy (AES). From this result, it was confirmed that a GeTe film having a composition of Ge: Te = 1: 1 was formed. The films formed at the substrate temperatures of 80 ° C., 100 ° C. and 120 ° C. were observed with a scanning electron microscope (SEM) to confirm that all of the films had a flat surface.
<실시예 3> (iPrNCH=CHNiPr)Ge(II)을 포함하는 막 증착용 액체 전구체 조성물을 사용한 GST 막 형성<Example 3> GST film formation using the liquid precursor composition for film deposition containing ( i PrNCH = CHN i Pr) Ge (II)
(iPrNCH=CHNiPr)Ge(II)을 포함하는 증착용 전구체 조성물, SbCl3, [(C2H5)3Si]2Te을 사용한 원자층 증착법으로 GST 막을 형성하였다. 원자층 증착 장치에 기판 온도를 80ºC로 유지하였다. (iPrNCH=CHNiPr)Ge(II)의 기체를 10 초 동안 공급하고, [(C2H5)3Si]2Te의 기체를 20초 동안 공급하는 제 1 기체 공급 주기와, SbCl3의 기체를 3 초 동안 공급하고, [(C2H5)3Si]2Te의 기체를 10초 동안 공급하는 제 2 기체 공급 주기를 2:1의 비율로 조합한 초주기(supercycle)을 반복하여 GST 막을 형성하였다. 주사전자현미경(SEM)으로 관찰한 막의 표면은 실시예 2에서 형성한 막의 표면보다 거칠어서 결정질을 포함한 막이 형성된 것을 알았다. 80℃에서 형성한 막과 이를 각각 150℃, 250℃, 및 350℃에서 열처리한 막의 X-선 회절(XRD) 분석 결과를 도 5에 나타내었다. 80℃에서 형성한 막은 XRD 봉우리가 보이지 않아서 비정질의 막이 형성되었음을 나타내었다. 150℃, 250℃, 350℃에서 열처리한 막에서는 XRD 회절 봉우리가 관찰되었다. 회절 봉우리의 위치로부터 GeTe, GeSb2Te4 결정이 포함된 GST 막이 형성된 것을 알았다.A GST film was formed by an atomic layer deposition method using ( i PrNCH = CHN i Pr) Ge (II) precursor composition for deposition, SbCl 3 , [(C 2 H 5 ) 3 Si] 2 Te. The substrate temperature was maintained at 80 ° C. in the atomic layer deposition apparatus. a first gas supply cycle for supplying a gas of ( i PrNCH = CHN i Pr) Ge (II) for 10 seconds, a gas of [(C 2 H 5 ) 3 Si] 2 Te for 20 seconds, and SbCl 3 Is supplied for 3 seconds, and a second cycle of a second gas supply cycle for supplying a gas of [(C 2 H 5 ) 3 Si] 2 Te for 10 seconds is repeated at a ratio of 2: 1. To form a GST film. It was found that the surface of the film observed by the scanning electron microscope (SEM) was rougher than the surface of the film formed in Example 2, so that a film containing crystalline was formed. 5 shows X-ray diffraction (XRD) analysis results of a film formed at 80 ° C. and a film heat-treated at 150 ° C., 250 ° C., and 350 ° C., respectively. The film formed at 80 ° C. showed no XRD peaks indicating that an amorphous film was formed. XRD diffraction peaks were observed in the film heat-treated at 150 ° C, 250 ° C and 350 ° C. It was found from the position of the diffraction peaks that a GST film containing GeTe and GeSb 2 Te 4 crystals was formed.
전술한 본원의 설명은 예시를 위한 것이며, 본원이 속하는 기술분야의 통상의 지식을 가진 자는 본원의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다. 예를 들어, 단일형으로 설명되어 있는 각 구성 요소는 분산되어 실시될 수도 있으며, 마찬가지로 분산된 것으로 설명되어 있는 구성 요소들도 결합된 형태로 실시될 수 있다.The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.
본원의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위, 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본원의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application. .

Claims (13)

  1. 하기 화학식 1로서 표시되는 Ge2 +-함유 전구체 화합물을 포함하는, Ge-함유 막의 증착용 전구체 조성물:To Ge 2 + represented as formula I-containing precursor compound, Ge- containing film vapor deposition precursor composition comprising:
    [화학식 1][Formula 1]
    (R1NCH=CHNR2)Ge(II);(R 1 NCH═CHNR 2 ) Ge (II);
    상기 화학식 1에 있어서, R1과 R2는 각각 독립적으로 탄소수 1 내지 6의 선형 또는 분지형 알킬기 또는 이들의 이성질체인 알킬기를 포함함.In Chemical Formula 1, R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 Ge2 +-함유 전구체 화합물은 상온에서 액체인 것인, Ge-함유 막의 증착용 전구체 조성물.The Ge 2 + -containing precursor compound is a liquid at room temperature, precursor composition for the deposition of Ge-containing film.
  3. 제 1 항에 있어서,The method of claim 1,
    상기 Ge-함유 막의 증착용 전구체 조성물은 (iPrNCH=CHNiPr)Ge(II) 또는 (tBuNCH=CHNtBu)Ge(II)인 Ge2 +-함유 전구체 화합물을 포함하는 것인, Ge-함유 막의 증착용 전구체 조성물.The precursor composition for deposition of the Ge-containing film, Ge ( I PrNCH = CHN i Pr) Ge (II) or ( t BuNCH = CHN t Bu) Ge (II) that comprises a Ge 2 + -containing precursor compound, -Precursor composition for deposition of the containing film.
  4. 제 3 항에 있어서,The method of claim 3, wherein
    (iPrNCH=CHNiPr)Ge(II)인 Ge2 +-함유 전구체 화합물로 실질적으로 이루어진, Ge-함유 막의 증착용 전구체 조성물. (I PrNCH = CHN i Pr) Ge (II) of Ge 2 + - substantially consists of the precursor-containing compound, Ge- containing film vapor deposition precursor composition.
  5. 제 1 항에 있어서,The method of claim 1,
    상기 Ge2 +-함유 전구체 화합물은 기상 증착에 의하여 Ge-함유 막을 증착하는 데 사용되는 것인, Ge-함유 막의 증착용 전구체 조성물.The Ge 2 + - containing precursor compound is, Ge- containing film vapor deposition precursor composition that is used to deposit Ge- containing film by vapor deposition.
  6. 제 5 항에 있어서,The method of claim 5,
    상기 기상 증착은 ALD 또는 CVD에 의하여 수행되는 것인, Ge-함유 막의 증착용 전구체 조성물.The vapor deposition is performed by ALD or CVD, precursor composition for deposition of Ge-containing film.
  7. 하기 화학식 1로서 표시되는 Ge2 +-함유 전구체 화합물을 포함하는 전구체 조성물을 이용하여 기상 증착하는 것을 포함하는, Ge-함유 막의 형성 방법:To Ge 2 + represented as formula (1) contained by using a precursor composition including a precursor compound, which comprises vapor deposition, Ge- containing film is formed by:
    [화학식 1][Formula 1]
    (R1NCH=CHNR2)Ge(II);(R 1 NCH═CHNR 2 ) Ge (II);
    상기 화학식 1에 있어서, R1과 R2는 각각 독립적으로 탄소수 1 내지 6의 선형 또는 분지형 알킬기 또는 이들의 이성질체인 알킬기를 포함함.In Chemical Formula 1, R 1 and R 2 each independently include a linear or branched alkyl group having 1 to 6 carbon atoms or an alkyl group thereof.
  8. 제 7 항에 있어서,The method of claim 7, wherein
    상기 기상 증착은 ALD 또는 CVD에 의하여 수행되는 것인, Ge-함유 막의 형성 방법.Wherein said vapor deposition is performed by ALD or CVD.
  9. 제 7 항에 있어서,The method of claim 7, wherein
    상기 Ge2 +-함유 전구체 화합물은 (iPrNCH=CHNiPr)Ge(II) 또는 (tBuNCH=CHNtBu)Ge(II)에서 선택되는 것인, Ge-함유 막의 형성 방법.The Ge 2 + - containing precursor compounds are (i PrNCH = CHN i Pr) Ge (II) , or a, Ge- containing film forming method that (t BuNCH = CHN t Bu) Ge (II) is selected from.
  10. 제 7 항에 있어서,The method of claim 7, wherein
    상기 Ge-함유 막은 Ge-Sb-Te(GST) 막을 포함하는 것인, Ge-함유 막의 형성 방법.Wherein said Ge-containing film comprises a Ge-Sb-Te (GST) film.
  11. 제 10 항에 있어서,The method of claim 10,
    상기 Ge-Sb-Te(GST) 막은 GeTe 및 Sb2Te3을 함유하는 고체 용액 혼합물을 포함하는 것인, Ge-함유 막의 형성 방법.And wherein said Ge-Sb-Te (GST) film comprises a solid solution mixture containing GeTe and Sb 2 Te 3 .
  12. 제 10 항에 있어서,The method of claim 10,
    상기 GST 막은 GeTe 및 Sb2Te3의 2:1 고체 용액 혼합물인 Ge2Sb2Te5를 포함하는 것인, Ge-함유 막의 형성 방법.Wherein said GST film comprises Ge 2 Sb 2 Te 5 which is a 2: 1 solid solution mixture of GeTe and Sb 2 Te 3 .
  13. 제 10 항에 있어서,The method of claim 10,
    상기 Ge-함유 막의 형성 방법은, The method of forming the Ge-containing film,
    상기 Ge2 +-함유 전구체 화합물을, 상기 Ge-Sb-Te(GST) 막의 안티모니 성분과 텔루륨 성분 각각을 증착하기 위한 안티모니-함유 전구체 화합물과 텔루륨-함유 전구체 화합물과 함께 동시에 또는 순차적으로 공급하여 GeTe 조성과 Sb2Te3 조성을 포함하는 Ge-Sb-Te 합금의 막을 형성하는 것을 포함하는 것인, Ge-함유 막의 형성 방법.The Ge 2 +-containing precursor compound, the Ge-Sb-Te (GST) film of antimony component and Tel antimony to deposit the tellurium component, respectively containing the precursor compound and the tellurium-simultaneously with the containing precursor compound or sequentially Supplying to form a film of a Ge-Sb-Te alloy comprising a GeTe composition and a Sb 2 Te 3 composition.
PCT/KR2016/008986 2015-08-17 2016-08-16 Ge(ii)-containing precursor composition and method for forming germanium-containing film using precursor composition WO2017030346A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100763916B1 (en) * 2006-06-21 2007-10-05 삼성전자주식회사 Method of manufacturing gesbte thin film and method of manufacturing phase change random access memory using the same
KR20090018629A (en) * 2006-05-12 2009-02-20 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 Low temperature deposition of phase change memory materials
US20120021590A1 (en) * 2008-05-29 2012-01-26 L'air Liquide Societe Anonyme Pour I'etude Et I'exploitation Des Procedes Georges Claude Tellurium Precursors for Film Deposition
EP2444405A1 (en) * 2010-10-07 2012-04-25 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Metal compounds for deposition of chalcogenide films at low temperature
KR20120118060A (en) * 2006-11-02 2012-10-25 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 Antimony and germanium complexes useful for cvd/ald of metal thin films

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090018629A (en) * 2006-05-12 2009-02-20 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 Low temperature deposition of phase change memory materials
KR100763916B1 (en) * 2006-06-21 2007-10-05 삼성전자주식회사 Method of manufacturing gesbte thin film and method of manufacturing phase change random access memory using the same
KR20120118060A (en) * 2006-11-02 2012-10-25 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 Antimony and germanium complexes useful for cvd/ald of metal thin films
US20120021590A1 (en) * 2008-05-29 2012-01-26 L'air Liquide Societe Anonyme Pour I'etude Et I'exploitation Des Procedes Georges Claude Tellurium Precursors for Film Deposition
EP2444405A1 (en) * 2010-10-07 2012-04-25 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Metal compounds for deposition of chalcogenide films at low temperature

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