WO2022249642A1 - 白金族金属カルコゲナイド薄膜及び該白金族金属カルコゲナイド薄膜を備える半導体材料 - Google Patents
白金族金属カルコゲナイド薄膜及び該白金族金属カルコゲナイド薄膜を備える半導体材料 Download PDFInfo
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- WO2022249642A1 WO2022249642A1 PCT/JP2022/010450 JP2022010450W WO2022249642A1 WO 2022249642 A1 WO2022249642 A1 WO 2022249642A1 JP 2022010450 W JP2022010450 W JP 2022010450W WO 2022249642 A1 WO2022249642 A1 WO 2022249642A1
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- thin film
- platinum group
- group metal
- metal chalcogenide
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- 239000010409 thin film Substances 0.000 title claims abstract description 184
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 120
- 239000002184 metal Substances 0.000 title claims abstract description 120
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 150000004770 chalcogenides Chemical class 0.000 title claims abstract description 86
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000004065 semiconductor Substances 0.000 title claims description 27
- 239000010408 film Substances 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 33
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 21
- 229910052741 iridium Inorganic materials 0.000 abstract description 20
- -1 platinum group metals Chemical class 0.000 abstract description 18
- 238000003775 Density Functional Theory Methods 0.000 abstract description 17
- 238000004364 calculation method Methods 0.000 abstract description 9
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- 238000000231 atomic layer deposition Methods 0.000 description 15
- 238000004544 sputter deposition Methods 0.000 description 15
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- 238000006243 chemical reaction Methods 0.000 description 14
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- 230000015572 biosynthetic process Effects 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
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- 150000004763 sulfides Chemical class 0.000 description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 8
- 229910052798 chalcogen Inorganic materials 0.000 description 8
- 150000001787 chalcogens Chemical class 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
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- 239000002243 precursor Substances 0.000 description 5
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- 230000008901 benefit Effects 0.000 description 4
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- 238000012795 verification Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
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- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
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- AZFHXIBNMPIGOD-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;iridium Chemical compound [Ir].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O AZFHXIBNMPIGOD-LNTINUHCSA-N 0.000 description 1
- 229910004611 CdZnTe Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
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- 230000005283 ground state Effects 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
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Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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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
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02373—Group 14 semiconducting materials
- H01L21/02381—Silicon, silicon germanium, germanium
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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
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02488—Insulating materials
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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
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
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- H—ELECTRICITY
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- 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
- H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
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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
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
Definitions
- the present invention relates to a thin film made of a platinum group metal chalcogenide which is effective as a semiconductor material, particularly as a semiconductor material constituting a light receiving element. More specifically, it relates to a platinum group metal chalcogenide thin film using Ir or Ru as the platinum group metal.
- LIDAR Light Detection and Ranging
- LIDAR is a system that irradiates an object with laser light and senses the reflected light with a light receiving element to detect the distance and angle to the object.
- LIDAR has the advantage of being able to detect the distance and angle to an object with high accuracy, compared to detection systems using cameras and millimeter-wave radar.
- HgCdTe alloy Hg 1-X Cd X Te alloy: MCT alloy
- InGaAs alloy In 1-X Ga XAs alloy
- HgCdTe alloys have a low SN ratio at room temperature and require cooling of the device for normal use.
- Adding a cooling mechanism to the light-receiving element unit is not preferable for drones, smartphones, etc., which must be miniaturized.
- InGaAs alloys also have the problem of poor responsiveness at room temperature, high operating voltage, and structural instability.
- transition metal chalcogenides are attracting attention as semiconductor materials that can be substituted for HgCdTe alloys and the like.
- TMC is a compound of transition metals (group 3 to group 11 metals) and chalcogen elements excluding oxygen.
- TMC exhibits unique electrical characteristics and optical semiconductor characteristics based on the type of central metal M, and is attracting attention as a constituent material for various semiconductor devices such as photoelectric conversion elements in light receiving devices and field effect transistors (FETs). ing.
- TMC is the flexibility of its manufacturing method.
- Various thin film formation processes can be applied to TMC without being limited to a specific method.
- CVD method chemical vapor deposition method
- ALD method atomic layer deposition method
- the base material there are a wide range of options for the base material, and film formation is possible on Si wafers and glass base materials (SiO 2 ).
- MBE Molecular Beam Epitaxy
- the base material is limited to expensive CdZnTe, GaAs, and the like.
- TMC can be used as a low-cost, high-performance semiconductor material due to the flexibility of the manufacturing method and base material.
- Transition metal chalcogenides that have been specifically known so far include sulfides and selenides of transition metals such as Mo, W, Hf, and Zr.
- MoS 2 which is a TMC of Mo, has been reported in many research examples on devices using this.
- the TMC that the applicant of the present application has focused on is a chalcogenide in which a platinum group metal (Pt, Pd, etc.) is used as a transition metal.
- a platinum group metal Pt, Pd, etc.
- TMCs of platinum group metals have more suitable properties than TMCs such as Mo and W described above. For example, it is important to optimize the bandgap of the semiconductor material that constitutes the light-receiving element for application to a light-receiving element that targets the near-infrared region used in the above-described LDAR and the like.
- the bandgap of the semiconductor material be less than about 1.77 eV, given the wavelength range of 700 nm to 1200 nm in this region.
- the TMC of Pt platinum
- the TMC of Pt platinum
- the TMC of Pt is 1.20 eV (single layer) to 0.21 eV (two layers) for PtSe 2 and 2.66 eV (for PtS 2) . It has been confirmed that it exhibits a bandgap of 0.25 eV (single layer) to 0.25 eV (two layers).
- TMC of platinum group metals can exhibit suitable properties as a semiconductor material, TMC of platinum group metals is still an area where there are few research results, and not all of them can form suitable ones. Moreover, even if TMC, which is a platinum group metal, has photoresponse characteristics and photoelectric conversion characteristics in the near-infrared region and the like, it is not suitable for practical use if it lacks stability as a compound. Furthermore, as described above, TMC also has the advantage of a high degree of freedom regarding the manufacturing method. TMC, which can be manufactured only by a limited manufacturing method, loses its superiority.
- the present invention has been made based on the background described above. It is an object of the present invention to provide a platinum group metal chalcogenide thin film having an unstructured structure.
- Platinum group metals include Ag (silver), Au (gold), Pt (platinum), Pd (palladium), Ru (ruthenium), Ir (iridium), Rh (rhodium), Os (osmium), ).
- Ag, Au, Pt, and Pd TMCs have been examined to some extent, and their usefulness has been confirmed.
- PtS 2 , PtSe 2 , PdS 2 , PdSe 2 and the like which are sulfides and selenides (dichalcogenides: TMDC) of Pt and Pd, are known to have a layered structure. TMC with a layered structure can control characteristics such as a bandgap by adjusting the number of layers.
- the current situation is that there is little knowledge about chalcogenides of Ru, Ir, Rh, and Os. If a compound having a suitable bandgap can be found in chalcogenides of these platinum group metals, they may become useful semiconductor materials. Therefore, the present inventors have extensively investigated the chalcogenides of Ru, Ir, Rh, and Os based on both experimental and theoretical verification methods, and as a result, Ir and Ru from the group of platinum group metals described above. and found usefulness for thin films of their sulfides, Ir 2 S 3 , IrS 2 , RuS 2 and RuSe 2 . These TMC thin films are characterized by being capable of exhibiting optical semiconductor properties, being stable and relatively easily produced.
- the present invention provides a thin film containing a platinum group metal chalcogenide formed on a substrate, wherein the platinum group metal chalcogenide is made of either Ir2S3 or IrS2 , RuS2 , or RuSe2 , and
- the thin film is characterized by having a film thickness of 0.5 nm or more and 500 nm or less.
- Ir and Ru are selected as platinum group metals, and the TMC thin film is made of their sulfides.
- the structure of the platinum group metal chalcogenide thin film according to the present invention and the manufacturing method thereof will be described below.
- the present invention is a thin film of platinum group metal chalcogenide to which Ir or Ru is applied as the platinum group metal.
- Chalcogen elements constituting the chalcogenide of Ir include S (sulfur), Se (selenium), and Te (tellurium).
- Ir chalcogenides are limited to sulfides in the present invention is that they are believed to have moderate bandgaps. For example, selenides of Ir (IrSe 2 , Ir 3 Se 8 ) are believed to have too low a bandgap.
- sulfides of Ir include Ir 2 S 3 (diiridium trisulfide), IrS 2 (diiridium disulfide), and Ir 3 S 8 (triiridium octasulfide).
- the present invention is limited from the bandgap point of view to thin films composed of Ir 2 S 3 (diiridium trisulfide) and IrS 2 (diiridium disulfide).
- the chalcogenide of Ru in the present invention is limited to RuS 2 (ruthenium disulfide) which is a sulfide of Ru and RuSe 2 (ruthenium diselenide) which is a selenide of Ru. .
- the appropriate bandgap in the present invention is a bandgap that is dominant in the photoelectric effect in the near-infrared region.
- the wavelength region of the near-infrared region is assumed to be 700 nm or more and 2500 nm or less, and the appropriate bandgap is 0.49 eV or more and 1.77 eV.
- Ir 2 S 3 , IrS 2 , RuS 2 and RuSe 2 are platinum group metal chalcogenides.
- Ir and Ru chalcogenides do not have a layered structure and have a three-dimensional crystal structure.
- characteristics such as a bandgap are inherent to the material, and the bandgap is less likely to change due to the number of layers (thickness). This leads to the advantage that the film thickness can be arbitrarily adjusted according to the design of the applied device.
- the platinum group metal chalcogenide constituting the thin film according to the present invention preferably has a high purity, preferably 99% or more, more preferably 99.9% or more.
- the purity in this case is determined by either the total mass of Ir and S or the total mass of Ru and S based on the mass of the entire thin film.
- inclusion of unavoidable impurities is allowed.
- unavoidable impurities contained in the thin film platinum group elements other than Ir and Ru, Group 4 elements (e.g., Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, etc.).
- the total amount of these unavoidable impurities is preferably 100 ppm or less.
- the platinum group metal chalcogenide thin film of the present invention has a thickness of 0.5 nm or more and 500 nm or less. If it is less than 0.5 nm, it is difficult to form the crystal structure of the platinum group metal chalcogenide, and desired characteristics may not be obtained. Also, TMC thin films with thickness greater than 500 nm can be manufactured, but should be limited due to the large amount of materials used and poor cost-effectiveness.
- the film thickness of the TMC thin film is preferably 0.5 nm or more and 200 nm or less.
- the thin film may be formed entirely on the base material, or may be an island-like thin film partially on the base material. This is because even if the TMC crystals do not form a continuous film over the entire surface, the semiconductor characteristics can be exhibited by the interaction of the TMC crystals scattered like islands.
- An island-shaped thin film is a thin film formed by a growth pattern based on the Volmer-Weber type. This is a state in which three-dimensional islands of platinum group metal chalcogenide are formed on the substrate. That is, it shows a transitional state until the platinum group metal chalcogenide thin film is formed on the entire surface of the substrate.
- the coverage of the platinum group chalcogenide thin film on the substrate is preferably 10% or more.
- the coverage is calculated from the ratio of the surface area of the platinum group metal chalcogenide thin film to the surface area of the surface of the substrate on which the thin film is formed.
- the platinum group chalcogenide thin film (including the island-shaped thin film) of the present invention may have at least one of Ir 2 S 3 , IrS 2 , RuS 2 and RuSe 2 on the surface.
- metal Ir or metal Ru or a compound that is not chalcogenized (sulfurized or selenized) up to Ir 2 S 3 , IrS 2 , RuS 2 and RuSe 2 may exist inside the thin film.
- a metal film reaction method for chalcogenizing a metal film (Ir film, Ru film) can be applied as a method for producing a TMC thin film according to the present invention.
- the chalcogenization of the metal film proceeds from the surface, so that the desired platinum group metal chalcogenide is formed on the surface of the thin film, but the inside of the thin film may not be sufficiently chalcogenized.
- a multi-source sputtering method can also be applied as a method for producing a TMC thin film, but metal portions may exist inside the thin film due to differences in sputtering efficiency.
- the thin film in such a state may be used.
- Ir 2 S 3 , IrS 2 , RuS 2 and RuSe 2 may be present on the surface in contact with an external electrode.
- the entire thin film including the inside may be made of Ir2S3 , IrS2 , RuS2 , or RuSe2 .
- a thin film comprising a platinum group metal chalcogenide according to the present invention is formed on an appropriate substrate.
- a base material is a member for supporting a thin film. Any material can be used for the substrate as long as it can support the platinum group metal chalcogenide thin film. Examples include materials such as glass, quartz, silicon, ceramics, and metals. Moreover, the shape and dimensions of the substrate are not particularly limited.
- the platinum group metal chalcogenide thin film according to the present invention is useful as a semiconductor material for photoelectric conversion, light absorption and light emission.
- This semiconductor material can be used, for example, as a photoelectric conversion element for optical devices such as light receiving devices, optical sensors, and photodetectors.
- the semiconductor material according to the present invention has particularly good sensitivity to light with wavelengths in the near-infrared region. Therefore, specifically, it is suitable for light-receiving elements for LIDAR and SWIR image sensors.
- a platinum group metal chalcogenide thin film according to the present invention is produced by forming a film of a platinum group metal chalcogenide on the substrate described above.
- the film forming method at this time is not particularly limited, and a conventional method for producing a transition metal chalcogenide is applied.
- a thin film of platinum group metal is formed on a substrate, and this is heat-treated in a chalcogen atmosphere (sulfur atmosphere or selenium atmosphere) to form a platinum group metal film.
- chalcogen atmosphere sulfur atmosphere or selenium atmosphere
- Methods for forming platinum group metal thin films include physical vapor deposition methods such as sputtering and vacuum deposition, chemical vapor deposition (CVD), atomic layer deposition (ALD), and the like.
- a known thin film forming process such as the chemical vapor deposition method can be applied.
- the sputtering method and the chemical vapor deposition method can efficiently obtain a platinum group metal thin film having a desired thickness.
- Ir target or a Ru target for forming a platinum group metal thin film by sputtering.
- sputtering conditions normal conditions can be applied.
- the Ir target and the Ru target are preferably high-purity products with a metal content of 99% or more.
- the basic steps of the film formation process by the chemical vapor deposition method are to vaporize the metal compound that is the raw material (precursor) of the thin film, supply the generated raw material gas onto the substrate, and chemically react in the gas phase.
- a reaction decomposition reaction or synthesis reaction is caused to deposit the target substance on the substrate to form a film.
- platinum group metal precursors in chemical vapor deposition include tricarbonyl [(1,2,3- ⁇ )-1,2,3-tris(1,1-dimethylethyl)-2-cyclo Organic iridium such as propen-1-yl]iridium (TICP), tris(acetylacetonato)iridium (Ir(acac) 3 ), (cyclohexadienyl)methylcyclopentadienyliridium ((MeCp)Ir(CHD)) compounds can be used.
- TCP propen-1-yl
- Ir(acac) 3 tris(acetylacetonato)iridium
- (MeCp)Ir(CHD)) compounds can be used.
- Ru is tricarbonyl(trimethylenemethane)ruthenium ([Ru(TMM)(CO) 3 )dicarbonyl-bis(5-methyl-2,4-hexanedionato)ruthenium, hexacarbonyl[methyl-( Organic ruthenium compounds such as 1-methylpropyl)-butene-aminato]ziruthenium and dodecacarbonyl triruthenium (DCR) can be used.
- the chemical vapor deposition method it is common to supply a reaction gas to the substrate surface in order to promote the decomposition of the metal compound in the raw material gas.
- Oxygen, hydrogen, or the like is applied as the reaction gas depending on the type of the precursor (metal compound), and is not particularly limited in the present invention.
- the film formation conditions in the CVD method and the ALD method are the conditions in the normal chemical vapor deposition method.
- the thin film of the platinum group metal (Ir, Ru) is formed so as to have a thickness corresponding to the film thickness of the target platinum group metal chalcogenide. Then, the formed platinum group metal thin film is treated in a chalcogen atmosphere to produce a platinum group metal chalcogenide thin film.
- Hydrogen sulfide ( H2S ) gas or selenium hydride ( H2Se ) can be used to form the chalcogen atmosphere.
- Solid sulfur or selenium can also be used, and can be vaporized by sublimation by heating to form a chalcogen atmosphere.
- Chalcogenization of the platinum group metal thin film is preferably carried out by heating the thin film in a chalcogen atmosphere. The heating temperature is preferably 800° C.
- the formation of Ir 2 S 3 can be preferentially caused by treating at a high temperature within the above temperature range.
- the heating time is preferably 30 minutes or more and 12 hours or less.
- a platinum group metal chalcogenide thin film can also be produced by directly forming a platinum group metal chalcogenide on a substrate.
- a platinum group metal chalcogenide thin film can be produced by reactive sputtering using a platinum group metal target.
- a platinum group metal chalcogenide thin film can also be produced by producing a platinum group metal chalcogenide by a powder metallurgy method or the like and using this as a sputtering target.
- a chalcogen source for example, H 2 S gas or Se vapor
- H 2 S gas or Se vapor can be used as a reactive gas to directly synthesize a platinum group metal chalcogenide thin film on a substrate.
- the platinum group metal chalcogenide thin film can be produced by transferring or coating the platinum group metal chalcogenide synthesized on another container or substrate onto the substrate.
- the present invention relates to a platinum group metal chalcogenide thin film using Ir and Ru as platinum group metals.
- the platinum group metal chalcogenide thin film according to the present invention has an appropriate bandgap as a semiconductor material constituting a light receiving element or the like. In particular, it has sensitivity to light with a wavelength in the near-infrared region, and can be expected to respond to a device equipped with a light-receiving element in that region.
- the platinum group metal chalcogenide thin film according to the present invention has a high degree of freedom in its manufacturing method, can be manufactured by various thin film manufacturing methods, and has good stability.
- FIG. 3 shows the results of XPS analysis of the Ir 2 S 3 thin film and the RuS 2 thin film manufactured in the first embodiment
- FIG. 4 shows evaluation results of photoresponse characteristics (740 nm, 850 nm, 940 nm) of the Ir 2 S 3 thin film and the RuS 2 thin film manufactured in the first embodiment
- FIG. 4 shows the results of XPS analysis of the Ir 2 S 3 thin film and the RuS 2 thin film manufactured in the second embodiment
- FIG. 5 is a graph showing evaluation results of photoresponse characteristics (740 nm, 850 nm, 940 nm) of the Ir 2 S 3 thin film and the RuS 2 thin film manufactured in the second embodiment
- FIG. 2 shows the results of XRD analysis of RuS 2 thin films produced in the first embodiment and the second embodiment
- FIG. 3 is a diagram showing electron density of states in Ir 2 S 3 and RuS 2 obtained by DFT calculation. Photoresponse characteristics of the RuSe2 thin film fabricated in the fourth embodiment
- an embodiment of the present invention will be described below.
- an Ir thin film and a Ru thin film are formed by a sputtering method, and chalcogenized to produce a platinum group metal chalcogenide thin film. Then, these platinum group metal chalcogenide thin films were evaluated for photoresponse characteristics to near-infrared rays.
- Chalcogenization of the thin film was carried out by placing the film-formed base material in a tubular furnace, introducing H 2 S into the furnace, and heating under an air flow of 10 sccm.
- the heating temperature was 900° C. for the Ir film and 800° C. for the Ru film, and both were heat treated for 1 hour.
- the produced platinum group metal chalcogenide thin film was analyzed by X-ray photoelectron spectroscopy (XPS).
- XPS X-ray photoelectron spectroscopy
- the results of this XPS analysis are shown in FIG.
- the difference in the peak position (binding energy) of the Ru3p spectra of metal Ru and RuS2 is as narrow as about 0.2 eV, so the measurement results of the S2p spectrum are also shown. From the results of XPS analysis, it was confirmed that a thin film containing Ir 2 S 3 and a thin film containing RuS 2 were formed in this embodiment.
- the Ir 2 S 3 thin film although the metal Ir partially remains, it can be said that Ir 2 S 3 exists on the surface.
- the thickness of the Ir 2 S 3 thin film was 1.8 nm (1 nm before heat treatment) and 2.5 nm (2 nm before heat treatment).
- the RuS 2 thin film was 1.5 nm (1 nm before heat treatment) and 2.3 nm (2 nm before heat treatment).
- the platinum group metal chalcogenide thin films (Ir 2 S 3 thin film, RuS 2 thin film) produced above were evaluated for photoresponse characteristics as semiconductor characteristics.
- comb-shaped electrodes were formed on the surface of the manufactured thin film to manufacture a light-receiving element, which is a photoelectric conversion element.
- the comb-shaped electrodes were formed by patterning a Ti film (thickness: 5 nm) and an Au film (thickness: 40 nm) in this order into a comb shape on the surface of the platinum group metal chalcogenide thin film.
- the photoresponse to near-infrared rays was measured for the fabricated photodetector.
- each light receiving element was irradiated with near-infrared rays, and the photocurrent was measured at room temperature using a multimeter.
- Three patterns of near-infrared wavelengths of 740 nm, 850 nm, and 940 nm were used to measure the response characteristics at each wavelength.
- the near-infrared irradiation was performed intermittently for 20 seconds with an interval of 30 seconds.
- a bias voltage of 3.0 V was applied from the multimeter.
- FIG. 2 shows the evaluation results of the photoresponse characteristics of the platinum group chalcogenide thin film of this embodiment. From this measurement result, the platinum group metal chalcogenide thin film (Ir 2 S 3 thin film (1.0 nm, 2.0 nm), RuS 2 thin film (1.0 nm, 2.0 nm)) produced in this embodiment has a thickness of 740 nm to 940 nm. It was confirmed that photoresponsivity was demonstrated in the near infrared region of .
- Second Embodiment In this embodiment, a Ru thin film and an Ir thin film were formed by chemical vapor deposition, and the metal thin film was chalcogenized to produce a platinum group metal chalcogenide thin film. Then, the photoresponse characteristics were evaluated in the same manner as in the first embodiment.
- the same base material (Si/SiO 2 base material) as in the first embodiment was prepared, and a Ru thin film and an Ir thin film were formed on this base material by the ALD method.
- the ALD method includes an adsorption step in which a raw material gas is introduced into a reactor to adsorb the raw material on the substrate surface, a purge step in which excess raw material gas is exhausted, a reaction gas is introduced into the reactor, and the raw material is adsorbed on the substrate surface. It is a thin film formation process in which a cycle consisting of each step of a reaction step of reacting a raw material and a reaction gas to deposit a metal and a purge step of exhausting an excess reaction gas is repeated. First, the substrate was set in an ALD apparatus, and the interior of the reactor was purged with nitrogen gas (100 sccm) before film formation.
- the Ru thin film was formed using tricarbonyl(trimethylenemethane)ruthenium ([Ru(TMM)(CO) 3 ), which is a Ru complex, as a precursor.
- a Ru thin film was formed under the following film forming conditions. The film thickness was controlled by adjusting the number of cycles of (1) to (4). In this embodiment, three types of samples were produced by ALD of 42 cycles (film thickness: 4 nm) and 50 cycles (film thickness: 6 nm).
- Adsorption step/raw material heating temperature 10°C ⁇ Carrier gas: Nitrogen/50 sccm ⁇ Introduction time: 10 seconds
- Raw material gas purge step ⁇ Purge with nitrogen gas (100 sccm) ⁇ Introduction time: 10 seconds
- Reaction step ⁇ Reaction gas: pure oxygen/50 sccm ⁇ Introduction time: 10 seconds
- Reaction gas purge step ⁇ Purge with nitrogen gas (100 sccm) ⁇ Introduction time: 10 seconds
- Ir thin films the Ir complex tricarbonyl[(1,2,3- ⁇ )-1,2,3-tris(1,1-dimethylethyl)-2-cyclopropene-1- yl] iridium was used.
- An Ir 2 S 3 thin film was formed under the following film forming conditions. The number of cycles was 384 cycles (film thickness: 4 nm) and 412 cycles (film thickness: 4 nm).
- Raw material gas purge step ⁇ Purge with nitrogen gas (100 sccm) ⁇ Introduction time: 10 seconds
- Reaction step ⁇ Reaction gas: pure oxygen/50 sccm ⁇ Introduction time: 2 seconds
- Reaction gas purge step ⁇ Purge with nitrogen gas (100 sccm) ⁇ Introduction time: 10 seconds
- FIG. 3 shows the results of XPS analysis. It was confirmed that Ir 2 S 3 and RuS 2 were produced in this embodiment.
- AFM measurement was performed to measure the film thickness of the platinum group metal chalcogenide thin film. 4 nm (4 nm before heat treatment) and 8.8 nm (6 nm before heat treatment).
- photodetectors were manufactured in the same manner as in the first embodiment. Then, the photoresponse characteristics in the near-infrared region were evaluated for these photodetectors.
- the measurement method was the same as in the first embodiment, and the wavelength of the near-infrared rays to be irradiated was three patterns of 740 nm, 850 nm, and 940 nm, and the response characteristics at each wavelength were measured.
- FIG. 4 shows the evaluation results of the photoresponse characteristics of the Ir 2 S 3 thin film and the RuS 2 thin film of this embodiment. It was confirmed that the platinum group metal chalcogenide thin film of the embodiment can also exhibit photoresponsivity in the near-infrared region of 740 nm to 940 nm.
- the platinum group metal chalcogenide thin films of the first embodiment and the present embodiment are both manufactured by a metal film reaction method of sulfurizing a metal thin film. It can be said that the difference in the method of manufacturing the metal film (sputtering method, ALD method) does not affect the presence or absence of photoresponse.
- FIG. 5 shows the results of XRD analysis of the RuS 2 thin films produced in the first embodiment and the present embodiment. From FIG. 5, it can be seen that the thin film produced in this embodiment is composed of RuS 2 with high crystallinity. On the other hand, in the thin film manufactured according to the first embodiment, the peak of RuS 2 is difficult to distinguish, and the peak of metal Ru is also observed.
- RuS 2 Although the formation of RuS 2 was confirmed in the results of the XPS analysis of the first embodiment (FIG. 2), it is considered that the metal Ru inside the thin film, which could not be detected by XPS, was confirmed by XRD. Therefore, in order to impart optical semiconductor properties to the thin film, RuS 2 (Ir 2 S 3 ) should be formed at least on the surface, but in order to generate a stronger photocurrent, the inside of the thin film must be sulfurized. is considered preferable.
- This embodiment describes the results of examination of the properties of platinum group metal chalcogenides through theoretical verification in contrast to the experimental verifications of the first and second embodiments.
- a simulation was performed using first-principles calculation based on density functional theory (DFT).
- DFT is a theory that physical properties such as electron distribution and energy in the ground state of an interacting multi-electron system can be calculated using an electron density function.
- the DFT-based first-principles calculation is a calculation method based on the density functional theory. According to first-principles calculation, it becomes possible to quantitatively study the electronic structure of matter without experimental or empirical parameters.
- the electronic state was simulated using VASP, which is a first-principles calculation application (DFT code) based on density functional theory.
- VASP a first-principles calculation application
- atomic structure data in the Materials Project a general-purpose database, was used (Reference: A. Jain et al., “The Materials Project: A materials genome approach to accelerating materials innovation”, APL Materials, 2013, 1(1), 011002).
- the bandgaps (bulk states) of the chalcogenides (sulfides and selenides) of the platinum group metals of Ir, Ru, and Rh were calculated.
- DOS information (electron density of state information) in various platinum group metal chalcogenides can be obtained.
- FIG. 6 shows the calculation results of the DOS of Ir 2 S 3 and RuS 2 . Then, based on the obtained DOS information, the bandgaps of various platinum group metal chalcogenides were calculated. Tables 1 to 3 show bandgaps and absorption wavelengths of various chalcogenides of Ir, Ru, and Rh for the calculation results.
- Rh has a low bandgap and is difficult to exhibit characteristics as a semiconductor material in the subject of the present invention.
- Ir and Ru show different results from Rh and can show suitable bandgaps.
- Ru selenide
- RuS 2 sulfide
- these bandgap values are the results of calculation by semi-DFT, it is necessary to consider that they are underestimated from the actual bandgap. That is, it is considered that RuSe 2 should not be ruled out for practical use in the near-infrared region of 1200 nm or longer. This point will be confirmed in the fourth embodiment.
- Ir sulfide similarly exhibits a suitable value, and especially Ir 2 S 3 and IrS 2 can exhibit a suitable bandgap.
- the result of the theoretical verification by DFT calculation as described above also agrees with the fact that the Ir 2 S 3 thin film and the RuS 2 thin film in the first and second embodiments showed favorable photoresponse characteristics.
- Rh 2 S 3 a chalcogenide thin film (Rh 2 S 3 ) using Rh as a platinum group metal was manufactured.
- Rh chalcogenide thin film Rh 2 S 3
- the Rh thin film was deposited by sputtering.
- the Rh thin film was formed using a Rh target with a purity of 99.99% under the same sputtering apparatus (magnetron sputtering apparatus) and film forming conditions as in the first embodiment (thickness: 2 nm).
- the sulfurization of the Rh thin film was also performed by heating at 900° C. for 1 hour under an H 2 S stream (10 sccm) in the same manner as in the first embodiment.
- Rh 2 S 3 thin film is a conductor. From Table 3 above, it is estimated that Rh 2 S 3 is a conductor with a very small value of 0.192 eV for the bandgap calculated by DFT, which agrees with this measurement result.
- the RuSe 2 thin film which was suggested to have a small bandgap by the DFT calculation, was fabricated and its photoresponsivity at 1550 nm was confirmed.
- a Ru thin film was deposited by chemical vapor deposition, and a metal thin film was selenized to produce a RuSe 2 thin film. Then, the photoresponse characteristics were evaluated in the same manner as in the first and second embodiments.
- the same substrate (Si/SiO 2 substrate) as in the first and second embodiments was prepared, and a Ru thin film was formed on this substrate by the ALD method.
- the ALD method includes an adsorption step in which a raw material gas is introduced into a reactor to adsorb the raw material on the substrate surface, a purge step in which excess raw material gas is exhausted, a reaction gas is introduced into the reactor, and the raw material is adsorbed on the substrate surface. It is a thin film formation process in which a cycle consisting of each step of a reaction step of reacting a raw material and a reaction gas to deposit a metal and a purge step of exhausting an excess reaction gas is repeated. First, the substrate was set in an ALD apparatus, and the interior of the reactor was purged with nitrogen gas (100 sccm) before film formation.
- the Ru thin film was formed using tricarbonyl(trimethylenemethane)ruthenium ([Ru(TMM)(CO) 3 ), which is a Ru complex, as a precursor.
- a Ru thin film was formed under the following film forming conditions. The film thickness was controlled by adjusting the number of cycles of (1) to (4). In this embodiment, a sample was produced by 42 cycles (film thickness: 4 nm).
- Adsorption step/raw material heating temperature 10°C ⁇ Carrier gas: Nitrogen/50 sccm ⁇ Introduction time: 10 seconds
- Raw material gas purge step ⁇ Purge with nitrogen gas (100 sccm) ⁇ Introduction time: 10 seconds
- Reaction step ⁇ Reaction gas: pure oxygen/50 sccm ⁇ Introduction time: 10 seconds
- Reaction gas purge step ⁇ Purge with nitrogen gas (100 sccm) ⁇ Introduction time: 10 seconds
- the base material and selenium powder on which the film was formed were placed in a tubular furnace and heated under an argon gas flow of 10 sccm. At this time, the selenium vapor was transported by the argon gas by placing the selenium powder upstream of the gas stream of the tubular furnace.
- the heating temperature was 800° C. for the film-formed substrate and 220° C. for the selenium powder, and the heat treatment was performed for 1 hour.
- the film thickness of the thin film became 12 nm by the selenization.
- FIG. 7 shows the evaluation results of the photoresponse characteristics of the RuSe 2 thin film of this embodiment. It was confirmed that the RuSe 2 thin film of this embodiment can exhibit photoresponsivity in the near-infrared region of 1550 nm.
- the platinum group metal chalcogenide thin film according to the present invention has an appropriate bandgap as a semiconductor material constituting a light-receiving element and the like, and also has sensitivity to light with a wavelength in the near-infrared region.
- the platinum group metal chalcogenide thin film according to the present invention is relatively easy to manufacture and has a high degree of freedom.
- these platinum group metal chalcogenide thin films have good stability.
- INDUSTRIAL APPLICABILITY As a new semiconductor material, the present invention has applicability to light-receiving elements of optical devices such as LIDAR and SWIR image sensors.
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Abstract
Description
TMCとは、遷移金属(第3族元素~第11族元素の金属)と、酸素を除くカルコゲン元素との化合物である。TMCは、中心金属Mの種類に基づき、特異な電気的特性や光半導体特性を示し、受光デバイスにおける光電変換素子の他、電界効果トランジスタ(FET)等の各種の半導体デバイスの構成材料として着目されている。
(A―1)白金族金属カルコゲナイド薄膜の組成
上記のとおり、本発明は、白金族金属としてIr又はRuを適用する白金族金属カルコゲナイドの薄膜である。ここで、Irのカルコゲナイドを構成するカルコゲン元素としては、S(硫黄)、Se(セレン)、Te(テルル)がある。本発明でIrのカルコゲナイドを硫化物に限定するのは、それらが適度なバンドギャップを有すると考えられるからである。例えば、Irのセレン化物(IrSe2、Ir3Se8)については、バンドギャップが低すぎると考えられる。更に、Irの硫化物としては、Ir2S3(三硫化二イリジウム)、IrS2(二硫化二イリジウム)、Ir3S8(八硫化三イリジウム)がある。本発明は、バンドギャップの観点から、Ir2S3(三硫化二イリジウム)とIrS2(二硫化二イリジウム)で構成される薄膜に限定される。
本発明の白金族金属カルコゲナイド薄膜は、0.5nm以上500nm以下である。0.5nm未満では、白金族金属カルコゲナイドの結晶構造が形成され難く所望の特性が得られない可能性がある。また、膜厚500nmを超えるTMC薄膜は、製造することは可能であるが、使用材料が多くなり対費用効果に乏しくなるので制限すべきである。TMC薄膜の膜厚は、好ましくは、0.5nm以上200nm以下とする。
本発明に係る白金族金属カルコゲナイドからなる薄膜は、適宜の基材上に形成される。基材は、薄膜を支持するための部材である。基材の材質に関しては、白金族金属カルコゲナイド薄膜を支持できるものであれば、どのような材質でも良い。例えば、ガラス、石英、シリコン、セラミックスもしくは金属等の材質が例示される。また、基材の形状及び寸法は、特に限定されない。
本発明に係る白金族金属カルコゲナイド薄膜は、光電変換や光吸収・発光する半導体材料として有用である。この半導体材料は、例えば、受光デバイス、光学センサ、光検出器等の光学デバイス用途の光電変換素子として利用できる。本発明に係る半導体材料は、特に、近赤外線領域の波長の光への感度も良好である。そのため、具体的には、LIDARやSWIRイメージセンサ用途の受光素子に好適である。
次に、本発明に係る白金族金属カルコゲナイド薄膜の製造方法について説明する。本発明に係る白金族金属カルコゲナイド薄膜は、上記した基材に白金族金属カルコゲナイドを成膜することで製造される。このときの成膜方法については、特に限定されることなく、従来の遷移金属カルコゲナイドの製造方法が適用される。本発明の白金族金属カルコゲナイドの製造方法としては、基材上に白金族金属(Ir、Ru)の薄膜を形成し、これをカルコゲン雰囲気(硫黄雰囲気又はセレン雰囲気)で熱処理して白金族金属膜をカルコゲン化(硫化又はセレン化)する金属膜反応法が挙げられる。
Ir薄膜及びRu薄膜の成膜では、ターゲットとして純度99.99%のIrターゲット及びRuターゲットを使用し、スパッタリング装置としてマグネトロンスパッタリング装置にて成膜した。基材は、Si/SiO2基材(表面280nm酸化、寸法:20×20厚さ1.5mm)を使用した。成膜条件は、50W×10秒間のプレスパッタリングでクリーニングを実施した後、50Wでスパッタリングをした。製膜時のチャンバー圧力は0.7Paであった。そして、膜厚1.0nm、2.0nmのIr薄膜及びRu薄膜を成膜した。
上記製造した白金族金属カルコゲナイド薄膜(Ir2S3薄膜、RuS2薄膜)について、半導体特性として光応答特性を評価した。本実施形態では、製造した薄膜表面にくし形電極を形成して光電変換素子である受光素子を製造した。くし形電極は、白金族金属カルコゲナイド薄膜の表面に対して、Ti膜(膜厚5nm)、Au膜(膜厚40nm)の順にくし形へパターニングして形成した。
第1実施形態と同じ基材(Si/SiO2基材)を用意し、この基材にALD法によりRu薄膜及びIr薄膜を成膜した。ALD法は、反応器内に原料ガスを導入して基材表面に原料を吸着させる吸着工程、余剰な原料ガスを排気するパージ工程、反応器内に反応ガスを導入し、基材表面に吸着した原料と反応ガスとを反応させて金属を析出させる反応工程、余剰な反応ガスを排気するパージ工程、の各工程からなるサイクルを繰り返す薄膜形成プロセスである。まず、基材をALD装置にセットし、成膜前に反応器内を窒素ガス(100sccm)でパージした。
(1)吸着工程
・原料加熱温度:10℃
・キャリアガス:窒素/50sccm
・導入時間:10秒
(2)原料ガスパージ工程
・窒素ガス(100sccm)でパージ
・導入時間:10秒
(3)反応工程
・反応ガス:純酸素/50sccm
・導入時間:10秒
(4)反応ガスパージ工程
・窒素ガス(100sccm)でパージ
・導入時間:10秒
・原料加熱温度:55℃
・キャリアガス:窒素/100sccm
・導入時間:7秒
(2)原料ガスパージ工程
・窒素ガス(100sccm)でパージ
・導入時間:10秒
(3)反応工程
・反応ガス:純酸素/50sccm
・導入時間:2秒
(4)反応ガスパージ工程
・窒素ガス(100sccm)でパージ
・導入時間:10秒
製造した白金族金属カルコゲナイド薄膜(Ir2S3薄膜及びRuS2薄膜)をもとに、第1実施形態と同様にして受光素子を製造した。そして、これらの受光素子について近赤外領域における光応答特性を評価した。測定方法は、第1実施形態と同様とし、照射する近赤外線の波長は、740nm、850nm、940nmの3パターンで行い、各波長における応答特性を測定した。
genome approach to accelerating materials innovation”,APL
Materials, 2013, 1(1), 011002)。そして、本実施形態では、Ir、Ru、Rhの各白金族金属のカルコゲナイド(硫化物、セレン化物)のバンドギャップ(バルク状態)を計算した。
第1実施形態および第2実施形態と同じ基材(Si/SiO2基材)を用意し、この基材にALD法によりRu薄膜を成膜した。ALD法は、反応器内に原料ガスを導入して基材表面に原料を吸着させる吸着工程、余剰な原料ガスを排気するパージ工程、反応器内に反応ガスを導入し、基材表面に吸着した原料と反応ガスとを反応させて金属を析出させる反応工程、余剰な反応ガスを排気するパージ工程、の各工程からなるサイクルを繰り返す薄膜形成プロセスである。まず、基材をALD装置にセットし、成膜前に反応器内を窒素ガス(100sccm)でパージした。
(1)吸着工程
・原料加熱温度:10℃
・キャリアガス:窒素/50sccm
・導入時間:10秒
(2)原料ガスパージ工程
・窒素ガス(100sccm)でパージ
・導入時間:10秒
(3)反応工程
・反応ガス:純酸素/50sccm
・導入時間:10秒
(4)反応ガスパージ工程
・窒素ガス(100sccm)でパージ
・導入時間:10秒
製造したRuSe2をもとに、第1実施形態および第2実施形態と同様にして受光素子を製造した。そして、これらの受光素子について近赤外領域における光応答特性を評価した。測定方法は、第1実施形態と同様とし、照射する近赤外線の波長は、1550nmで行い、応答特性を測定した。
Claims (5)
- 基材上に形成され、白金族金属カルコゲナイドを含む薄膜において、
前記白金族金属カルコゲナイドは、Ir2S3、IrS2、RuS2、RuSe2のいずれかよりなり、
前記薄膜の膜厚は0.5nm以上500nm以下であることを特徴とする薄膜。 - 前記薄膜の膜厚は0.5nm以上200nm以下である請求項1記載の薄膜。
- 基材上にアイランド状に形成された請求項1記載の薄膜。
- 基材と請求項1~請求項3のいずれかに記載の薄膜が形成されてなる半導体材料。
- 請求項4記載の半導体材料を含む受光素子。
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