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WO2012161265A1 - Procédé et appareil de production d'un cristal en couche mince semi-conductrice - Google Patents

Procédé et appareil de production d'un cristal en couche mince semi-conductrice Download PDF

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WO2012161265A1
WO2012161265A1 PCT/JP2012/063352 JP2012063352W WO2012161265A1 WO 2012161265 A1 WO2012161265 A1 WO 2012161265A1 JP 2012063352 W JP2012063352 W JP 2012063352W WO 2012161265 A1 WO2012161265 A1 WO 2012161265A1
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thin film
substrate
gas
germanium
film
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PCT/JP2012/063352
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Japanese (ja)
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武彦 永井
近藤　道雄
宏 野毛
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独立行政法人産業技術総合研究所
コーニングホールディングジャパン合同会社
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/16—Controlling or regulating
    • C30B25/165—Controlling or regulating the flow of the reactive gases
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/12—Production of homogeneous polycrystalline material with defined structure directly from the gas state
    • C30B28/14—Production of homogeneous polycrystalline material with defined structure directly from the gas state by chemical reaction of reactive gases
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/08—Germanium
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H10F71/1212—The active layers comprising only Group IV materials consisting of germanium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/121—The active layers comprising only Group IV materials
    • H10F71/1215—The active layers comprising only Group IV materials comprising at least two Group IV elements, e.g. SiGe
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a method and apparatus for manufacturing a semiconductor thin film crystal that can be used for a semiconductor integrated circuit, a solar cell, or the like.
  • silicon germanium (SiGe) and germanium (Ge) crystals have a smaller band gap than silicon crystals, which are already widely used semiconductors, high-efficiency solar cells and infrared light especially in the infrared region Application as a detection element is expected.
  • thermal CVD chemical vapor deposition
  • SiH 4 monosilane
  • GeH 4 monogermane
  • the substrate temperature is as high as 650 ° C. or more in the case of SiGe and 500 ° C. or more in the case of Ge, and it is difficult to use an inexpensive glass-based substrate. Due to the difference in thermal expansion from the substrate, it was difficult to grow a high-quality crystal film having a thickness of 1 ⁇ m or more particularly suitable for solar cells.
  • a method of depositing a thin film of SiGe or Ge at a low temperature of about 300 ° C. is known (for example, see Patent Document 1 below).
  • a gas source material linear silane compound, linear germane compound, etc.
  • a gaseous halogen oxidant fluorine etc.
  • a plurality of precursors including an excited state precursor are introduced into the reaction chamber space and brought into chemical contact with each other, and at least one of the precursors is supplied to a deposition film component source.
  • a deposited film forming method a deposited film is formed on a substrate in a deposition space.
  • monosilane (SiH 4 ) which is a linear silane compound is 20 sccm
  • monogermane (GeH 4 ) which is a linear germane compound is 5 sccm
  • F 2 which is a gaseous halogen oxidant is 5 sccm
  • He is used as a dilution gas.
  • an amorphous silicon germanium (SiGe) film containing hydrogen and fluorine having a thickness of about 2 ⁇ m can be deposited on a quartz substrate at a substrate temperature of 300 ° C. in 2 hours.
  • sccm is an abbreviation for standard cc / min and represents a flow rate in a standard state.
  • monogermane GaH 4
  • F 2 at 4 sccm
  • He at 40 sccm
  • the thickness of the substrate was about 1.5 ⁇ m on a quartz substrate at 300 ° C. for 2 hours.
  • An amorphous Ge film containing hydrogen and fluorine can be deposited.
  • a thin film of SiGe or Ge can be deposited at a low temperature of about 300 ° C.
  • the film to be formed is an amorphous film, has a short minority carrier lifetime, and low carrier mobility, so that it is not necessarily suitable for applications such as high-efficiency solar cells and high-speed integrated circuits. was there.
  • germanium fluoride (GeF 4 ) For example, if the volume flow rate of germanium fluoride (GeF 4 ) is changed in the range of 0.9 to 2.7 sccm with respect to a disilane (Si 2 H 6 ) flow rate of 20 sccm at a pressure of 133 Pa or less, about 1.5 nm / sec.
  • SiGe silicon germanium
  • germanium fluoride gas having a chemical etching property in the range of 200 to 500 ° C. with respect to silicon (Si), a silane-based source gas, and a carrier gas for increasing the dilution rate of the silane-based source gas
  • germanium fluoride gas promotes relaxation and crystallization of the Si network structure by thermally activating the silane-based source gas with a heated substrate in the presence of polycrystalline SiGe on the substrate.
  • a method of manufacturing a semiconductor substrate for forming a film wherein a volume flow ratio (germanium fluoride gas / silane-based source gas) of the germanium fluoride gas and the silane-based source gas is in a range of 0.07 to 0.15
  • the temperature of the heated substrate is a constant temperature within the range of 350 to 450 ° C.
  • the formation of the polycrystalline SiGe film Disclosed is a method for manufacturing a semiconductor substrate in which the pressure of the Si is a constant pressure within a range of 1.33 to 2.67 kPa and the Si composition of the polycrystalline SiGe film is 80 atomic% or more (for example, the following patents) Reference 3).
  • a SiGe polycrystalline film having a GeF 4 / Si 2 H 6 volume flow rate ratio of 0.02 to 0.5 and a Ge composition of 73 to 99 atomic% is obtained.
  • the maximum film formation rate is about 2.8 nm / sec.
  • a SiGe polycrystalline thin film having a relatively high carrier mobility and a long minority carrier lifetime can be deposited at a low temperature of 450 ° C. or lower.
  • the present invention relates to a semiconductor thin film crystal manufacturing method and manufacturing apparatus for forming a SiGe or Ge crystal thin film having a wide composition freedom, a high carrier mobility, and a long minority carrier lifetime on a crystal substrate at a high film forming speed. Is to provide.
  • the present invention has the following features in order to solve the above problems.
  • the method for producing a semiconductor thin film crystal according to the present invention uses monosilane (SiH 4 ), monogermane (GeH 4 ), fluorine (F 2 ), and an inert gas for diluting them as a supply gas,
  • the flow rate ratio is 0.005 to 1 in volume flow ratio
  • the flow rate ratio of fluorine is 0.5 to 4 in volume flow ratio
  • the substrate temperature is 350 ° C. to 650 ° C.
  • the pressure is 13.3 Pa to 1.
  • the pressure is 33 kPa or less
  • a single crystal or polycrystalline thin film of SiGe or Ge is formed on the substrate.
  • the substrate for forming the silicon germanium single crystal thin film or the germanium single crystal thin film is preferably a bulk single crystal substrate of silicon, silicon germanium or germanium.
  • a substrate in which a single crystal thin film of silicon, silicon germanium, or germanium is bonded to a glass plate is preferable.
  • the substrate for forming the silicon germanium polycrystalline thin film or the germanium polycrystalline thin film is preferably glass or metal.
  • a substrate in which a polycrystalline thin film of silicon, silicon germanium or germanium is formed on a glass plate or a metal plate is preferable.
  • the semiconductor thin film crystal manufacturing apparatus is a semiconductor thin film crystal manufacturing apparatus for forming a semiconductor thin film by supplying a gas onto a substrate, and the thin film is formed on the substrate by supplying a raw material gas.
  • a film blowing chamber for supplying monosilane, monogermane and fluorine as the source gas and an inert gas for diluting them, and the substrate at 350 ° C. to 650 ° C.
  • a substrate heater for heating, and adjusting the flow rate ratio of monogermane to monosilane of the raw material gas to 0.005 to 1 in volume flow ratio and the flow rate ratio of fluorine to 0.5 to 4 in volume flow ratio.
  • a mass flow controller for supplying the source gas into the film formation chamber, and a vacuum pump for adjusting the pressure in the film formation chamber to 13.3 Pa or more and 1.33 kPa or less,
  • the semiconductor thin film crystal manufacturing apparatus is characterized in that a branch for supplying fluorine gas is provided in the monosilane gas and monogermane gas flow paths.
  • monosilane (SiH 4 ), monogermane (GeH 4 ), fluorine (F 2 ), and argon (Ar) or helium (He) for diluting them are used as supply gas.
  • the flow rate ratio of monogermane to the flow rate of monosilane is 0.005 to 1.0 by volume flow rate ratio
  • the flow rate ratio of fluorine is 0.5 to 4 by volume flow rate ratio
  • the substrate temperature is 350 to 650 ° C.
  • a Ge composition having a wide range of compositional freedom, high carrier mobility, and long minority carrier lifetime on the crystal substrate is set to a molar ratio of 0.
  • a 1 to 1.0 SiGe or Ge crystal thin film can be formed at a high film formation rate in accordance with the supply gas flow rate.
  • fluorine is necessary for decomposing monosilane and monogermane to remove hydrogen.
  • the film forming chamber is also cleaned.
  • a substrate for growing a SiGe or Ge single crystal thin film a bulk single crystal substrate of silicon (Si), germanium (Ge) or silicon germanium (SiGe) is used. And having good crystallinity equivalent to the above.
  • an inexpensive glass can be mainly used by using a substrate in which a single crystal thin film of Si, Ge, or SiGe is bonded on a glass plate.
  • the substrate for growing the SiGe or Ge polycrystalline thin film glass or metal is preferably used, and the cost can be lowered particularly when a glass substrate is used.
  • a substrate on which a polycrystalline thin film of Si, Ge or SiGe having a large crystal grain size and high orientation is formed on a glass plate or a metal plate high-quality SiGe reflecting the crystal grain size and orientation of the base
  • a thick polycrystalline film of Ge can be grown.
  • the apparatus for producing a semiconductor thin film crystal according to the present invention includes monosilane (SiH 4 ), monogermane (GeH 4 ) and fluorine (F 2 ) as supply gases, and argon (Ar) or helium (He) for diluting them as necessary.
  • SiH 4 monosilane
  • GeH 4 monogermane
  • F 2 fluorine
  • Ar argon
  • He helium
  • the substrate temperature is 350.
  • the pressure in the range of ⁇ 650 ° C. and the pressure in the range of 13.3 Pa to 1.33 kPa the Ge composition having a wide range of compositional freedom and high carrier mobility and a long minority carrier lifetime is 0.1 to 1.
  • a zero-SiGe or Ge crystal thin film can be deposited at a high deposition rate in accordance with the supply gas flow rate.
  • the semiconductor thin film crystal manufacturing apparatus is provided with a branch capable of supplying fluorine (F 2 ) gas to the monosilane (SiH 4 ) and monogermane (GeH 4 ) gas flow paths.
  • F 2 fluorine
  • SiH 4 monosilane
  • GeH 4 monogermane
  • FIG. 1 is an X-ray diffraction spectrum diagram of a single crystal SiGe thin film according to the present invention. It is a diagram illustrating a SiH 4 flow rate dependency of the single-crystal SiGe film growth rate according to the present invention. Is a diagram illustrating a GeH 4 / SiH 4 flow ratio presence of Ge composition of the single crystal SiGe thin film according to the present invention. It is a Raman spectrum spectrum figure of the single crystal Ge thin film concerning the present invention.
  • a semiconductor thin film manufacturing apparatus 1 includes a film forming chamber 2 for forming a thin film, and a preparation chamber 3 that allows the substrate 11 to be taken in and out normally without exposing the film forming chamber 2 to the atmosphere. Become.
  • SiH 4 , GeH 4, and F 2 gases are decompressed from the respective gas cylinders 4 to an appropriate pressure by a pressure reducing valve 5 and then supplied into the film forming chamber 2 at a predetermined flow rate by a mass flow controller (also referred to as a mass flow meter) 6. Is done. For safety, these gases may be diluted with an inert gas such as Ar or He.
  • the gas outlet 7 may be an independent tube for each raw material gas, or SiH 4 and GeH 4 may be mixed and supplied as a single tube.
  • each gas may be discharged from a multi-cylindrical outlet, or SiH 4 , GeH 4, and F 2 are alternately released from adjacent holes from the outlet having a number of holes in a shower head shape. May be.
  • a branch that allows the F 2 gas used for film formation to flow separately for etching is provided in the middle of the F 2 gas piping in the middle of the SiH 4 and GeH 4 piping, so that the SiH 4 and GeH after the film formation is completed.
  • F 2 instead of 4 fine particles of Si, Ge, and SiGe adhering to the periphery of the gas outlet 7 are removed by etching, and generation of defects due to incorporation of these fine particles into the film can be suppressed.
  • SiH 4 and GeH 4 and F 2 flow between the pipes at the same time so that they do not react in the pipes, and between the SiH 4 and GeH 4 supply valves and the F 2 gas branch valve. It is desirable to provide an interlock 8 on the door.
  • Ar gas is also supplied from the gas cylinder 9 into the film forming chamber 2 through the pressure reducing valve 5 and the mass flow controller 6 in order to facilitate adjustment of temperature and pressure and improve safety.
  • an inert gas such as He may be used instead of Ar.
  • the substrate 11 is fixed to the substrate holder 12 and introduced from the preparation chamber 3, evacuated by a turbo molecular pump or the like as the vacuum pump 20, and then transferred to the film formation chamber 2 by opening and closing the gate valve 13.
  • the substrate 11 is heated to a predetermined temperature while the temperature is monitored by the substrate heater 14 on the back of the substrate holder 12 and the thermocouple 15 installed in or near the substrate holder 12.
  • a reflection high energy electron diffraction (RHEED) apparatus having an RHEED gun and an RHEED screen 16 installed in the film forming chamber 2 may be used.
  • the state of the reaction can be confirmed by observing the emission color from the window 18 of the film forming chamber 2.
  • the pressure in the film forming chamber 2 is adjusted by a balance with the flow rates of the source gas and the inert gas for dilution by evacuating with a vacuum pump 20 such as a mechanical booster pump or a turbo molecular pump through a pressure adjusting valve 19. To do.
  • a material having corrosion resistance against highly reactive F 2 gas As a member inside the film forming chamber 2, it is desirable to use a material having corrosion resistance against highly reactive F 2 gas.
  • materials such as the substrate holder 12, the shutter 17, the gas outlet 7, the heat shield 21, the substrate heater 14, and the insulator 22 that become high temperature are relatively resistant to corrosion, such as monel, molybdenum, silicon carbide, and alumina. It is desirable to use etc. Further, it is desirable to use glass coated with a fluoride such as sapphire or magnesium fluoride as the window material. Further, before and after the film formation chamber 2 is opened to the atmosphere, it is desirable to perform sufficient baking in order to remove F 2 and moisture.
  • a single-crystal Si substrate on glass (see US Pat. No. 7,176,528, etc.) made by Corning, Inc., in which a thin Si single-crystal film of about 300 nm is bonded to glass, is immersed in a diluted hydrofluoric acid aqueous solution to remove the natural oxide film. After that, it is fixed to the substrate holder 12 and introduced into the preparation chamber 3 of the semiconductor thin film manufacturing apparatus 1 in a short time.
  • the substrate holder 12 is transferred to the film formation chamber 2 and heated to about 600 ° C. and left for about 30 minutes to remove the oxide film by the RHEED pattern obtained by the RHEED screen 16. Make sure that it is.
  • SiH 4 is diluted with the mass flow controller 6 at 15 sccm, GeH 4 diluted with Ar gas to a volume flow rate ratio of 10% is 11.6 sccm, F 2 is 10 sccm, and Ar for dilution is added. 170 sccm is supplied into the film forming chamber 2, and the pressure is adjusted to about 107 Pa by the pressure adjusting valve 19.
  • the shutter 17 is opened and the film formation of SiGe is started. After 30 minutes, the shutter 17 is closed, and supply of each gas and substrate heating are stopped.
  • a (100) -oriented SiGe single crystal having a thickness of 3.9 ⁇ m and a Ge composition of 0.44 in molar ratio could be epitaxially grown on a (100) -oriented Si single crystal substrate on glass.
  • the substrate temperature In the general thermal CVD method using only SiH 4 and GeH 4 , it is usually necessary to set the substrate temperature to 650 ° C. or more for the film formation of single crystal SiGe, but in the embodiment according to the present invention, glass is mainly used. Even with the substrate 11, a single crystal film could be formed at a low temperature of 550 ° C. without any alteration.
  • the substrate 11 is a Si-on-glass substrate with a small amount of Si material used, which is expected to reduce the cost.
  • SiGe film to be deposited etc.
  • a SiGe single crystal substrate on glass and a more general Si or Ge bulk single crystal substrate may be used.
  • the volume flow ratio of GeH 4 and F 2 to SiH 4 is fixed at 12: 1: 12, and the flow rate of Ar to be diluted and the pressure adjustment valve 19 are adjusted, so that the pressure in the film forming chamber 2 is about 107 Pa. While maintaining this, the flow rate of SiH 4 was changed from 9 sccm to 20 sccm, and a SiGe single crystal thin film was grown.
  • the Ge composition is approximately 0.5 in molar ratio.
  • the growth rate increased as the raw material gas flow rate increased, and a maximum of 13.8 ⁇ m / h (3.8 ⁇ m / sec) and conventional Si 2 H 6 and GeF 4 were used. It was possible to obtain a deposition rate higher than that of the deposition method.
  • the volume flow rate of GeH 4 with respect to SiH 4 was formed by changing the ratio from 0.007 to 0.32.
  • the substrate temperature was changed from 350 ° C. to 600 ° C. depending on the volume flow rate ratio.
  • the Ge composition is 0 in molar ratio according to the volume flow ratio of GeH 4 / SiH 4. It was possible to change within a wide range of 1 to 1.0.
  • GeH 4 / SiH 4 volume flow ratio, the substrate temperature, and the pressure for growing the SiGe and Ge single crystal thin films are not limited to the above conditions.
  • the volumetric flow ratio of GeH 4 / SiH 4 may be varied in the range of 0.005 to 1.0 depending on the composition of the growing SiGe thin film.
  • the substrate temperature is too low, the film becomes amorphous or polycrystallized, and if it is too high, the variation in composition increases due to the diffusion and segregation of Ge atoms, or etching by F 2 becomes significant.
  • the temperature is preferably in the range of 350 to 650 ° C.
  • the pressure is preferably in the range of 13.3 Pa to 1.33 kPa.
  • a Ge bulk single crystal substrate is sequentially immersed in a diluted hydrofluoric acid solution and a hydrogen peroxide solution to form an oxide film on the surface, and then fixed to the substrate holder 12, and in a short time the preparation chamber 3 of the semiconductor thin film manufacturing apparatus 1 To introduce.
  • the substrate holder 12 is transferred to the film formation chamber 2 and heated to about 450 ° C. and left for about 30 minutes to remove the oxide film with the RHEED pattern obtained by the RHEED screen 16. Make sure that it is.
  • a (100) -oriented Ge single crystal thin film having a thickness of 1.6 ⁇ m could be epitaxially grown on a (100) -oriented Ge bulk single crystal substrate.
  • the grown Ge epitaxial film has good crystallinity equivalent to that of the bulk Ge single crystal.
  • each film thickness of the Ge epitaxial film 0 .6 ⁇ m and 0.5 ⁇ m, which were smaller than those when SiH 4 and GeH 4 and F 2 were all used simultaneously as in the present invention.
  • a p-type Ge single crystal thin film is grown.
  • a pn junction having a uniform doping density can be formed, and can be applied to solar cells for the infrared light region.
  • a Ge bulk single crystal lattice-matched with a Ge single crystal thin film is used as the substrate 11.
  • an Si bulk single crystal substrate or a single crystal thin film of Si or SiGe or Ge on a glass plate is used. It may be a bonded substrate.
  • a SiGe polycrystalline substrate on glass in which a SiGe polycrystalline thin film is formed on a glass plate is prepared by a method called an aluminum induced layer exchange growth (AIC) method.
  • AIC aluminum induced layer exchange growth
  • Al aluminum
  • Al aluminum
  • the SiGe is polycrystallized by heat treatment at a temperature of 20 ° C. for 20 to 200 hours, and Al deposited on the surface is etched with dilute hydrochloric acid or the like.
  • a SiGe polycrystalline substrate on glass having a Ge composition in a molar ratio of 0.5 and a film thickness of 200 nm is prepared by an AIC method, and the surface is immersed in a diluted hydrofluoric acid aqueous solution and a hydrogen peroxide solution sequentially. After the oxide film is formed, the substrate is fixed to the substrate holder 12 and introduced into the preparation chamber 3 of the semiconductor thin film manufacturing apparatus 1 in a short time.
  • the substrate holder 12 is transferred to the film formation chamber 2 and heated to about 550 ° C. and left for about 30 minutes to remove the oxide film with the RHEED pattern obtained by the RHEED screen 16. Make sure that it is.
  • SiH 4 is supplied at 15 sccm by the mass flow controller 6
  • GeH 4 diluted to 10% by volume with Ar gas is supplied at 11.6 sccm
  • F 2 is supplied at 10 sccm
  • Ar for dilution is supplied at 170 sccm into the film forming chamber 2.
  • the pressure is adjusted to a pressure of about 107 Pa by the pressure adjusting valve 19.
  • the shutter 17 is opened and the film formation of SiGe is started. After 30 minutes, the shutter 17 is closed, and supply of each gas and substrate heating are stopped.
  • a SiGe polycrystalline thin film having a large grain size which was oriented in the same manner as a base substrate having a thickness of 1.5 ⁇ m and a Ge composition of 0.5, could be grown on a SiGe polycrystalline substrate on glass.
  • the thermal expansion coefficient of the glass substrate polycrystalline glass coincide with the thermal expansion coefficient of the growing SiGe, it is possible to suppress the occurrence of defects due to thermal strain and warpage of the substrate 11.
  • a SiGe polycrystalline substrate on glass having a large grain size and no lattice mismatch was used as the substrate 11, but a polycrystalline Si substrate on glass, a polycrystalline Ge substrate on glass, and an inexpensive glass substrate or metal substrate. May be used.
  • the GeH 4 / SiH 4 volume flow ratio, the substrate temperature, and the pressure for growing the SiGe and Ge polycrystalline thin films are not limited to the above conditions.
  • the volumetric flow ratio of GeH 4 / SiH 4 may be varied in the range of 0.005 to 1.0 depending on the composition of the growing SiGe thin film.
  • the substrate temperature is too low, the film becomes amorphous, and if it is too high, the dispersion of the composition increases due to the diffusion and segregation of Ge atoms, and the etching by F 2 becomes remarkable. It is preferable to be in the range.
  • the pressure is too low, the film forming rate is lowered, and if it is too high, it becomes difficult to control. Therefore, the pressure is preferably in the range of 13.3 Pa to 1.33 kPa.
  • a Ge polycrystal having a thickness of 1.2 ⁇ m and oriented mainly in the (111) direction could be grown on the glass substrate.
  • the present invention when SiH 4 and GeH 4 and F 2 were used at the same time, a Ge deposition rate comparable to 450 ° C. was obtained even at a substrate temperature of 300 ° C. By reducing the substrate temperature, it is possible to further reduce the warpage and defects of the substrate 11 due to thermal strain.
  • an inexpensive glass substrate is used as the substrate 11, but a metal substrate may be used, or a substrate in which a polycrystalline thin film of Si, SiGe or Ge is formed on a glass plate or a metal plate. It may be.
  • the thermal expansion coefficient of the glass plate or metal plate with the thermal expansion coefficient of the germanium (Ge) or silicon germanium (SiGe) crystal to be grown, the difference in thermal expansion between the grown crystal thin film and glass or metal It is possible to suppress occurrence of defects and warping of the substrate 11.

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Abstract

La présente invention concerne un procédé de production d'un cristal en couche mince semi-conductrice qui permet de former une couche mince semi-conductrice en délivrant un gaz sur un substrat. Le procédé est caractérisé par une étape consistant à déposer un monocristal de SiGe ou de Ge ou un polycristal sur le substrat en utilisant, à titre de gaz d'apport, du gaz de monosilane (SiH4), du gaz de germane (GeH4), du gaz de fluor (F2) et un gaz inerte qui les dilue. Le rapport de débit volumique du germane par rapport au monosilane se situe entre 0,005 et 1. Le rapport de débit du fluor se situe entre 0,5 et 4 dans un rapport de débit volumique. La température du substrat se situe entre 350 et 650 °C et la pression entre 13,3 Pa et 1,33 kPa.
PCT/JP2012/063352 2011-05-24 2012-05-24 Procédé et appareil de production d'un cristal en couche mince semi-conductrice WO2012161265A1 (fr)

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JP2011-115630 2011-05-24
JP2011115630A JP2014144875A (ja) 2011-05-24 2011-05-24 半導体薄膜結晶の製造方法および装置

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JP7232499B2 (ja) * 2018-09-03 2023-03-03 国立大学法人 筑波大学 半導体装置とその製造方法および光電変換装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62151573A (ja) * 1985-12-25 1987-07-06 Canon Inc 堆積膜形成法
JPS62158875A (ja) * 1985-12-28 1987-07-14 Canon Inc 堆積膜形成法
JPH08203847A (ja) * 1995-01-25 1996-08-09 Nec Corp 半導体装置の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62151573A (ja) * 1985-12-25 1987-07-06 Canon Inc 堆積膜形成法
JPS62158875A (ja) * 1985-12-28 1987-07-14 Canon Inc 堆積膜形成法
JPH08203847A (ja) * 1995-01-25 1996-08-09 Nec Corp 半導体装置の製造方法

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