WO2006073189A1 - 機能素子及び酸化物材料形成方法 - Google Patents
機能素子及び酸化物材料形成方法 Download PDFInfo
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- WO2006073189A1 WO2006073189A1 PCT/JP2006/300102 JP2006300102W WO2006073189A1 WO 2006073189 A1 WO2006073189 A1 WO 2006073189A1 JP 2006300102 W JP2006300102 W JP 2006300102W WO 2006073189 A1 WO2006073189 A1 WO 2006073189A1
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- Prior art keywords
- substrate
- film
- metal oxide
- oxide material
- oxide
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 31
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims description 101
- 238000004549 pulsed laser deposition Methods 0.000 claims description 20
- 229910052758 niobium Inorganic materials 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052785 arsenic Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 13
- 150000004767 nitrides Chemical class 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract 1
- 239000000696 magnetic material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 121
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 54
- 238000002834 transmittance Methods 0.000 description 28
- 230000003287 optical effect Effects 0.000 description 23
- 239000010936 titanium Substances 0.000 description 23
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 22
- 239000010409 thin film Substances 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 14
- 239000013078 crystal Substances 0.000 description 12
- 238000010586 diagram Methods 0.000 description 12
- 238000005240 physical vapour deposition Methods 0.000 description 12
- 238000006467 substitution reaction Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000002524 electron diffraction data Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000005381 magnetic domain Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001073 sample cooling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
Classifications
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28264—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being a III-V compound
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/09—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on magneto-optical elements, e.g. exhibiting Faraday effect
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/511—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures
- H01L29/513—Insulating materials associated therewith with a compositional variation, e.g. multilayer structures the variation being perpendicular to the channel plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
Definitions
- the present invention relates to an acid oxide material.
- an indium tin oxide film (hereinafter referred to as an ITO film) that also has an indium oxide power with several percent tin doped on the surface of a transparent substrate such as a glass plate that further lowers the resistance value of the transparent conductive thin film.
- an ITO film that also has an indium oxide power with several percent tin doped on the surface of a transparent substrate such as a glass plate that further lowers the resistance value of the transparent conductive thin film.
- titanium dioxide ( ⁇ ) which has both chemical resistance and durability, has attracted attention (example)
- Non-Patent Document 1 TiO film is epitaxially grown on a sapphire substrate, etc.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2004-95240
- Non-patent document 1 Applied physics No. 73-5 (2004) 587-592
- Non-Patent Document 2 Jpn. J. Appl. Phys. Vol. 40 (2001) pp. L 1204 ⁇ L 1206
- Non-Patent Document 3 Nature Materials 3, 221-224 (2004)
- Non-Patent Document 4 APPLIED PHYSICS LETTERS VOLUME 78, NUMBER 18, 2664-2 666 (2001)
- the present invention has been devised in view of the above-described situation, and an object thereof is to provide a functional element having a new characteristic and a method for forming an oxide material.
- the first aspect of the present invention is Al Ga in N (where 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l, 0 ⁇ 1)
- the metal oxide is TiO.
- an oxide material made of a metal oxide is formed on Al Ga in N (where 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l, 0 ⁇ 1). It is a method of forming by a pulse laser deposition method, wherein the metal oxide is TiO.
- the third aspect of the present invention is that Al Ga in N (where 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l, 0 ⁇ z ⁇ l) and a metal formed on the Al Ga In N, An oxide material composed of an oxide and
- the metal oxide is SnO, which is a functional element.
- a fourth aspect of the present invention provides an oxide material made of a metal oxide on Al Ga in N (where 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l, 0 ⁇ 1).
- a high-quality SnO epitaxial film can be formed on a Group 3 nitride having excellent physical and chemical properties, with low contact resistance and low scattering at the interface.
- a film having both chemical resistance and durability with less reflection at the interface is integrally formed on a group III nitride having excellent physical properties.
- FIG. 1 is a diagram showing an oxide material film formed on a substrate.
- FIG. 2 is a diagram showing a RHEED pattern of a substrate before pretreatment and a RHEED pattern of a substrate after pretreatment.
- FIG. 3 is a diagram for explaining the configuration of the PLD apparatus.
- FIG. 4 A diagram showing the crystal structure of GaN (Uruthite (Uluite) Al Ga In N).
- Fig.5 Four levels depending on crystal quality ((A) Levell: Polyphase polycrystalline film, (B) Level2: Single phase polycrystalline film, (C) Level3: Single phase oriented epitaxial film, and (D FIG. 2) shows (Leve4: single crystal epitaxial film).
- FIG. 3 is a diagram showing an electron diffraction pattern (RHEED pattern) with a GaN substrate surface before film formation.
- FIG. 3 is a diagram showing an electron diffraction pattern (RHEED pattern) with a GaN substrate surface before film formation.
- FIG. 9 is a diagram showing the results of measuring the internal transmittance of a metal oxide layer.
- FIG. 10 is a graph showing the temperature dependence of the resistivity of the metal oxide layer.
- FIG. 1 A first figure.
- FIG. 12 A graph showing the wavelength dependence of the Faraday rotation coefficient of Ti Co Nb O at room temperature.
- FIG. 1 A first figure.
- FIG. 1 A first figure.
- FIG. 18 is a diagram showing various measurement results using a film formation temperature gradient film.
- FIG. 19 is a diagram showing the results of X-ray diffraction (XRD) measurement of a SnO film deposited by the PLD method.
- FIG. 20 shows an electron diffraction pattern (RHEED pattern) of a SnO film deposited by the PLD method.
- the oxide material film 12 is formed on the substrate 11.
- the substrate 11 is, for example, a GaN template (TDI (Technolo gies).
- the substrate 11 is made of Al Ga in N (where 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ l, 0 ⁇ z ⁇ 1).
- the oxide material film 12 formed on the substrate 11 is made of a metal oxide TiO.
- the doped M is Nb, Ta, Mo, As, Sb, Al, or W, an improvement in electrical conductivity can be expected while maintaining transparency.
- the doped M is Co, Fe, Cr, Sn, Ni, Mn or V, a magneto-optical effect can be expected.
- the GaN substrate is processed.
- the procedure of this process is as follows, for example. Clean the substrate with gasket, ethanol, etc.
- the substrate is immersed in high-purity hydrochloric acid (EL grade, concentration 36%, manufactured by Kanto Chemical) for 2 minutes.
- the substrate is moved into pure water and rinsed with hydrochloric acid or the like.
- the substrate is moved into fresh pure water, where ultrasonic cleaning is performed for 5 minutes.
- the substrate is taken out from the pure water, and nitrogen gas is blown onto the substrate surface to remove moisture from the substrate surface. These treatments are performed at room temperature, for example.
- oxides, organic substances, and the like are removed from the substrate surface, and Ga ends, not N ends, are exposed on the substrate surface.
- acid such as dynasty and hydrofluoric acid described in the example using hydrochloric acid may be used.
- the treatment may be performed at room temperature or a heated acid may be used.
- the substrate was introduced into the chamber 31 described below, and the state of the sample surface was observed by reflection electron diffraction (RHEED) and heated to 400 ° C. The state was evaluated.
- Fig. 2 shows the RHEED pattern of the substrate before processing and the RHEED pattern of the substrate after processing.
- the flat substrate surface can be obtained from the streak pattern of the RHEED image of the processed substrate.
- Ta TiO is evaporated on the (0001) surface of the substrate 11.
- an oxide material film 12 is deposited on the substrate 11 using a PLD apparatus 30 as shown in FIG.
- This PLD apparatus 30 is configured by disposing a substrate 11 and a target 39 in a chamber 31, and an optical oscillator 32 disposed outside the chamber 31 on the side facing the surface of the target 39, and an optical A reflector 33 for adjusting the position of the pulsed laser light oscillated by the oscillator 32, a lens 34 for controlling the spot diameter of the laser light, and a gas supply for injecting oxygen gas into the chamber 31.
- Part 44 is configured by disposing a substrate 11 and a target 39 in a chamber 31, and an optical oscillator 32 disposed outside the chamber 31 on the side facing the surface of the target 39, and an optical A reflector 33 for adjusting the position of the pulsed laser light oscillated by the oscillator 32, a lens 34 for controlling the spot diameter of the laser light, and a gas supply for injecting oxygen gas into the chamber 31.
- the chamber 31 is provided for producing a high-quality thin film by maintaining an appropriate degree of vacuum and preventing external impurities from being mixed.
- An infrared lamp 36 for heating the substrate is installed in the chamber 31.
- the substrate temperature is monitored by a radiation thermometer 37 installed outside the chamber 31 through the window 31b, and is always controlled to be a constant temperature.
- the chamber is also provided with a valve 45 for adjusting the flow rate of oxygen gas.
- a turbo molecular pump 42 and a pressure valve 43 are connected to the chamber 31.
- the turbo molecular pump 42 has Oil rotary pump 40 and the check valve 41 and is connected, the pressure in the exhaust side of the turbo molecular pump 42 is always kept below 1 X 10- 3 torr.
- the chamber 31 is further provided with a window 31a on the surface facing the target 39, and a pulsed laser beam of 32 optical power is incident through the window 31a.
- the optical oscillator 32 oscillates, for example, a KrF excimer laser having a pulse frequency of 1 to 10 Hz, a laser power of lOOmJ / pulse, and a wavelength of 248 nm as the pulse laser light.
- the oscillated pulsed laser light is spot-adjusted by the reflecting mirror 33 and the lens 34 so that the focal position is in the vicinity of the target 39, and the surface of the target 39 disposed in the chamber 31 through the window 31a Incident at an angle of approximately 45 °.
- the target 39 is made of, for example, a Ta: TiO sintered body.
- the metal to replace here is Ta
- This Ta TiO sintered body has a desired atomic ratio.
- the target 39 is disposed so as to be substantially parallel to the (0001) plane of the substrate 11.
- the target 39 is composed of an Nb: TiO sintered body
- the Nb: Ti02 sintered body is
- Target 39 is Co, Nb: TiO sintered body
- the film forming process based on the PLD method is as follows.
- the pretreated substrate 11 is set in the chamber 31.
- the pulse frequency is set to 2 Hz
- the laser power is set to 100 mJ / pulse
- the oxygen partial pressure is set to 1 ⁇ 10 ”5 torr
- the substrate temperature is set to 400 ° C.
- the substrate is rotated and driven by the motor 35.
- the surface of the target 39 is abruptly raised and ablated by irradiating the pulsed laser light intermittently while the target 39 is rotationally driven through the rotating shaft 38.
- This abrasion plasm Ti, Ta, and 0 atoms contained in the substrate move to the substrate 11 while gradually changing the state while repeating collision reaction with the oxygen gas in the chamber 31 and the like.
- the particles containing Ti, Ta, and O atoms that have reached the substrate 11 are diffused as they are to the (0001) plane on the substrate 11 and are thinned in the most stable state of lattice matching. Then quenched at room temperature until in the substrate in an oxygen partial pressure of 1 X 10- 5 torr. As a result, the oxide material film 12 is produced.
- Non-Special Reference 5 The Blue Laser Diode, S. Nakamura et al., Springer
- Non-patent document 6 Noro Choji: Titanium oxide and glaze ⁇ Ceramic Titanium N0.44P.11-13 (1956)
- Non-patent document 7 Masazo Kataoka: Titanium oxide industrial titanium zirconium vol.12 ⁇ .12 ⁇ .8,9 (1
- Non-Patent Document 8 Shinkosha Website
- the oxide material film 12 can be formed by the PLD method.
- PLD physical vapor deposition
- MBE molecular beam epitaxy
- sputtering method or methods other than PLD method, for example.
- the oxide material film 12 may be formed based on a chemical vapor deposition (CVD) method using the MOCVD method.
- CVD chemical vapor deposition
- Fig. 5 (A) to Fig. 5 (D) in general, when a film is formed by the crystal growth technique, there are four levels depending on the quality of the crystal ((A) Levell: multiphase polycrystalline film) (B) Level2: single-phase polycrystalline film, (C) Level3: single-phase oriented epitaxial film, and (D) Leve4: single-crystal epitaxial film).
- Levell multiphase polycrystalline film
- B Level2: single-phase polycrystalline film
- Level3 single-phase oriented epitaxial film
- Leve4 single-crystal epitaxial film.
- the single-phase film refers to Level 2 or higher
- the epitaxial film refers to Level 3 or higher.
- PVD physical vapor deposition
- MBE molecular beam epitaxy
- CVD chemical vapor deposition
- Fig. 6 shows an electron diffraction pattern (RHEED pattern) of the TiO surface formed by the PVD method on the GaN substrate subjected to the hydrochloric acid treatment and the GaN substrate surface before the film formation. Indicates.
- Figure 7 shows the TiO surface deposited by PVD on a GaN substrate that was not subjected to hydrochloric acid treatment.
- RHEED pattern An electron diffraction pattern (RHEED pattern) between the two surfaces and the GaN substrate surface before film formation is shown.
- Fig. 8 shows the TiO surface film formed by the PVD method on the hydrochloric acid-treated GaN substrate.
- the substrate temperature during film formation is 400 ° C.
- the TiO film is doped with 1% Ta.
- the capsule must not be doped with other elements. The same clear streak pattern is observed even when
- Table 2 shows the properties of Ta: TiO produced on the GaN substrate.
- a tester was used to measure the resistance value at this time.
- the substrate temperature during film formation is preferably set to 320 ° C or more and 550 ° C or less.
- the substrate temperature during film formation is preferably set to 320 ° C. or higher and 450 ° C. or lower.
- 320 ° C or more and 550 ° C is the general growth temperature required for metalorganic vapor phase epitaxy (MOCVD) or molecular beam epitaxy (MBE), which is currently the mainstream for nitride crystal growth. Lower than (over 700 ° C)! Therefore, it is preferable that the substrate temperature is 320 ° C. or more and 550 ° C.
- the film formation at a low temperature can prevent the problem of thermal distortion during the sample cooling process. Furthermore, low-temperature growth with low reactivity is desired even when considering combinations with other materials. Therefore, it is more preferable that the substrate temperature at the time of film formation is 320 ° C. or higher and 400 ° C. or lower. It is highly possible to form a film even between room temperature and 320 degrees.
- Al Ga In N is a light-emitting diode, an optical semiconductor such as a semiconductor laser, a power device, and light emission. It is often used as a semiconductor material for electronic devices such as elements. In order to improve the luminous efficiency without changing these internal structures, it is conceivable to apply the oxide material film 12 of the present invention as a transparent electrode.
- the refractive indexes of GaN, TiO, and ZnO are about 2 respectively.
- GaN and transparent electrode ⁇ is more GaN and transparent electrode
- the oxide material film 12 of the present invention as a transparent electrode of a surface emitting laser.
- the transparent electrode can be arranged in the light emitting region, the area of the electrode can be increased, and there is an advantage from the viewpoint of efficient injection of current into the active layer.
- a transparent electrode is provided on the p-type semiconductor layer. If necessary, the transparent electrode may be in contact with the n-type semiconductor layer.
- Internal transmittance of the oxide material film 12 fabricated as .1, 0.15, 0.2 (The transmittance in the original sense is that the amount of reflection in the oxide material film 12 must be Measured transmittance, which is 100% when subtracted, is hereinafter referred to as internal transmittance.) As shown in Fig. 9, in the visible light region (wavelength 400-800nm), it is a good result of 80% or more. It can be seen that In particular, it has been shown that a sample with Nb substitution force ⁇ 0.06 can achieve an internal transmittance of 95% or more in the visible light region.
- This Nb TiO is made of strontium titanate (100) face finished (
- NbO is considered to exhibit the same basic physical properties (such as resistivity).
- the thickness of the oxide material film 12 is often set to lOOnm or more.
- the internal transmittance is 80% or more with respect to the film thickness.
- an internal transmittance of 95% or more is required for a film thickness of 50 nm.
- the above specifications can be satisfied by limiting the Nb substitution amount to x ⁇ 0.06, so it is also possible to produce transparent conductor thin films that exceed the internal transmittance of conventional ITO thin films. .
- FIG. 10 shows the temperature dependence of the resistivity of the oxide material film 12 manufactured with the above-described substitution amount of Nb.
- the oxide material film 12 with Nb substitution amount X of 0.01 ⁇ x ⁇ 0.2 is 10 _4 Q cm level at room temperature compared to the case where Nb is not substituted. It can be seen that good conduction characteristics are obtained.
- This Nb: TiO also has a (100) surface.
- Ti Co Nb O has the same basic physical properties (resistivity
- the internal transmittance is 95% to 98% (at a film thickness of lOOnm at a film thickness of 50 nm). Up to 80% or more).
- the substitution amount X of Nb in the oxide material film 12 is set to 0.02 ⁇ x ⁇ 0.06, the internal transmittance is further improved and the resistivity is further increased to 5 X at room temperature (280K to 300K). It can be reduced to about 10 " 4 ⁇ cm, and to 1 X 10" 4 ⁇ cm at extremely low temperatures (5K to 20K).
- Nb TiO obtained as a result of substituting the Ti site of anatase (TiO 2) with Nb is an oxide.
- the resistivity of the oxide material film 12 is 2 X 10 4 to 5 X 10 " 4 ⁇ cm at room temperature, or 8 X 10 1 at extremely low temperatures.
- Nb By substituting Nb to be 5 to 2 X 10 " 4 ⁇ cm, it is possible to dramatically expand the applicability to various devices including display panels.
- the oxide material film 12 utilizes the TiO film forming technology that has already been used in photocatalysts.
- this low-resistance oxide material film 12 By applying this low-resistance oxide material film 12 to a display panel, it is possible to reduce the power consumption of these display elements. As a result, the display panel can be increased in size and size. It becomes possible to promote.
- the oxide material film 12 can facilitate the procurement of raw materials, reduce costs associated with the manufacturing process, and greatly reduce the labor involved in manufacturing. It is also possible.
- the oxide material film 12 to which the present invention is applied as an electrode by applying the oxide material film 12 to which the present invention is applied as an electrode, a transparent electrode having a conventional performance can be produced at a lower cost, and the application range can be expanded. It becomes.
- this oxide material film 12 is less likely to be eroded by acids and alkalis, the use of firewood expands the range of application without being controlled by the surrounding environment.
- the transparent metal 1 to which the present invention is applied is not limited to the use as an electrode, but is applied to other parts such as parts, thin films, and devices that are required to be transparent and have high conductivity. Don't do anything wrong! ⁇ .
- Figure 11 shows the Faraday rotation coefficient of Ti Co Nb 0 (thin film thickness: 50 nm) at room temperature.
- This Co Nb O is a (La Sr) (Al Ta) O (LSAT) substrate (substrate thickness: 0.
- the Faraday rotation coefficient was shown near 400 nm in the absence of a magnetic field. Furthermore, in the case of a TiO thin film co-doped with 5% Co and 10% Nb, the Faraday rotation coefficient is about 0.45 X 10 4 degree / cm.
- the film thickness of the film is 5% Co and 10% Nb.
- the Faraday rotation coefficient in the vicinity of 400 is improved by about 2 times.
- Figure 12 shows the Faraday rotation coefficient of Ti Co Nb 0 (thin film thickness: 50 nm) at room temperature.
- This Co Nb O is also prepared on an LSAT substrate (substrate thickness: 0.5 mm).
- Ti Co Nb O is considered to exhibit the same characteristics on other substrates such as GaN substrates.
- FIG. 13 shows the external transmittance at room temperature of a cocoon film co-doped with Co5% and Nbl0%.
- FIG. The horizontal axis indicates the wavelength, and the vertical axis indicates the transmittance.
- a transmittance of 70% or more can be obtained with light of 350 nm or more, and a transmittance of 80% or more can be obtained with light of 500 nm or more.
- this thin film proves that a transmittance of about 70 80% can be secured in the visible light range.
- the magnitude of the Faraday rotation angle can also be controlled by changing the amount of Nb added.
- X of Ti Co Nb 0 is preferably 0 ⁇ x. When 0, ferromagnetism appears
- X is more preferably 0.03 ⁇ x.
- y of Ti Co Nb O is preferably 0.1 ⁇ y ⁇ 0.2. Faraday if 0.1
- the Faraday rotation coefficient is smaller than that of Nb-added. If it is larger, the Faraday rotation coefficient may be reduced again.
- y is more preferably set to 0.1 ⁇ y ⁇ 0.2.
- Fig. 14 (A) shows the composition dependence of the resistivity when a TiO film is formed on the GaN substrate while Fig. 14 (B) is formed on the p-GaN substrate while changing the Nb doping amount.
- FIG. TiO film is formed
- the Nb doping amount is 1% or more and 15% or less, preferably Nb doping amount is 3% or more and 15% in any substrate.
- the Nb doping amount is more preferably 6% to 15%, and further preferably the Nb doping amount is 6% to 10%.
- Fig. 15 (A) is a GaN substrate
- Fig. 15 (B) is a p-GaN substrate.
- TiO film with Nb doping of 6% while changing the substrate temperature during film formation.
- resistivity when the substrate is formed
- Go-between was also 1 X 10- 7 Torr.
- the temperature when the resistance measurement was performed was 300K.
- the substrate temperature during film formation is 350 ° C. or higher and 500 ° C. or lower, preferably 400 ° C., regardless of the substrate. It can be understood that the substrate temperature is preferably 450 ° C. or higher and 500 ° C. or lower, more preferably 450 ° C. or higher and 500 ° C. or lower.
- the substrate temperature 350 ° C or higher 500 ° C, in the case where the oxygen partial pressure and 1 X 10- 6 Torr was if a and 1 X 10- 7 Torr, any substrate the resistivity better when there was an oxygen partial pressure between 1 X 10 "7 Torr even at the time of Teikaka ivy. Further, the substrate temperature was 450 ° C, the oxygen partial pressure and 1 X 10- 7 Torr, G Sheet when a TiO film with a Nb doping amount of 6% is formed on a GaN substrate
- the resistance was 234 ⁇ / mouth.
- Figure 16 (A) shows the wavelength dependence of the transmittance when a Ti 0 film with an Nb doping amount of 6% is formed on a GaN substrate and FIG. 16 (B) shows a p-GaN substrate.
- the oxygen partial pressure was 1 X 10- 6 Torr even when any of the substrate.
- Figure 17 (A) shows the substrate temperature dependence of the transmittance when a 0-film is formed on the GaN substrate
- Figure 17 (B) shows a p-GaN substrate with an Nb doping amount of 6%.
- the oxygen partial pressure when forming the TiO film is 1 X 10 " 6 To for any substrate
- the film formation temperature gradient film is a film formed with a temperature gradient on a single substrate. For example, while the film is formed on a single substrate, film formation on the substrate at a low temperature is performed at one end of the substrate, while film formation on the substrate is performed at a high temperature at the other end of the substrate. . This time, the deposition temperature gradient film was used to investigate the optimum deposition temperature in detail.
- FIG. 18 is a diagram showing various measurement results using the film formation temperature gradient film.
- FIG. 18A shows the relationship between the substrate position and the temperature distribution. As shown in FIG. 18 (A), the deposition temperature is varied along the longitudinal direction of the substrate. Thereby, the position in the longitudinal direction of the substrate and the film forming temperature are associated with each other on a one-to-one basis.
- FIG. 18B is a diagram showing the relationship between the substrate position and the diffraction intensity distribution by X-ray diffraction (XRD).
- XRD X-ray diffraction
- FIG. 18C is a diagram showing the relationship between the substrate position and the resistance value distribution.
- the resistance value is minimized when the substrate temperature force is 50 ° C.
- the resistance may be reduced by 25%. In this measurement, resistance measurement by a two-terminal method was performed.
- Figure 19 shows the X-ray diffraction (XRD) measurement of the SnO film deposited on the p-GaN substrate by the PLD method.
- Figure 20 shows an electron diffraction pattern (RHEED) of a SnO film deposited on a p-GaN substrate by the PLD method.
- SnO can be used only when nothing is doped.
- M SnO (M is P, As, Sb, S
- the doped M is P, As, Sb, S, Se, Te, Al, Ga, or In, an improvement in electrical conductivity can be expected while maintaining transparency.
- the doped M force SCo, Fe, Cr, Mn, V, and Ni the magneto-optical effect can be expected.
- this oxide material can also be used as a magneto-optical device exhibiting a large Faraday rotation coefficient near a wavelength of 400 nm.
- the Faraday rotation coefficient is as large as that of magnetic garnet films currently in practical use is that this oxide material makes it possible to fabricate optical isolators suitable for next-generation short-wavelength band communications. It shows that it becomes.
- the use of the oxide material shown in the present embodiment is not limited to use as an optical isolator. It can also be used for optical circuits, nonreciprocal optical components, nonreciprocal optical elements, semiconductor lasers equipped with isolators, current magnetic field sensors, magnetic domain observation, magneto-optical measurement, and the like.
- the optical isolator for example, a module in which an LD and an isolator are integrated, an optical isolator for fiber insertion, an optical isolator for an optical amplifier, a deflection-dependent optical isolator, a deflection-independent optical isolator, A waveguide type optical isolator may be mentioned.
- Guidance As the waveguide type optical isolator, for example, there are those using a Mach-Zehnder type branching waveguide and those using a rib type waveguide.
- the optical circulator may be a deflection-dependent optical circulator or a deflection-independent circulator.
- the oxide material shown in this embodiment may be used for light receiving elements, high frequency devices such as HEMT (High Electron Mobility Transistor), and electronic devices.
- HEMT High Electron Mobility Transistor
- a SnO film doped with Al, Sb, or the like may be used.
- They may be rutile or anatase. From the viewpoint of lowering the resistivity, the anatase type is preferred, and the rutile type is preferred from the viewpoint of ease of preparation. They can also be amorphous! /.
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Abstract
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US11/794,910 US7968216B2 (en) | 2005-01-08 | 2006-01-06 | Internal gear pump |
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Cited By (6)
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JP2008290028A (ja) * | 2007-05-25 | 2008-12-04 | Toyoda Gosei Co Ltd | 光源一体型光触媒装置 |
JP2008294306A (ja) * | 2007-05-25 | 2008-12-04 | Toyoda Gosei Co Ltd | Iii族窒化物系化合物半導体発光素子 |
WO2009119341A1 (ja) * | 2008-03-24 | 2009-10-01 | ソニー株式会社 | 半導体発光素子及びその製造方法 |
WO2009119273A1 (ja) * | 2008-03-25 | 2009-10-01 | 旭硝子株式会社 | 導電体およびその製造方法 |
JP2010062198A (ja) * | 2008-09-01 | 2010-03-18 | Toyoda Gosei Co Ltd | TiO2からなる導電性透明層の製造方法及び当該導電性透明層の製造方法を利用した半導体発光素子の製造方法。 |
EP2015373B1 (en) * | 2007-07-10 | 2016-11-09 | Toyoda Gosei Co., Ltd. | Light emitting device |
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JPH042167A (ja) * | 1990-04-19 | 1992-01-07 | Fuji Electric Co Ltd | ショットキバリア半導体装置 |
JP2001308383A (ja) * | 2000-04-19 | 2001-11-02 | Sharp Corp | 窒化物系半導体発光素子 |
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Cited By (10)
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JP2008290028A (ja) * | 2007-05-25 | 2008-12-04 | Toyoda Gosei Co Ltd | 光源一体型光触媒装置 |
JP2008294306A (ja) * | 2007-05-25 | 2008-12-04 | Toyoda Gosei Co Ltd | Iii族窒化物系化合物半導体発光素子 |
EP2015373B1 (en) * | 2007-07-10 | 2016-11-09 | Toyoda Gosei Co., Ltd. | Light emitting device |
WO2009119341A1 (ja) * | 2008-03-24 | 2009-10-01 | ソニー株式会社 | 半導体発光素子及びその製造方法 |
JP2009231523A (ja) * | 2008-03-24 | 2009-10-08 | Sony Corp | 半導体発光素子及びその製造方法 |
EP2259343A1 (en) * | 2008-03-24 | 2010-12-08 | Sony Corporation | Semiconductor light emitting element and method for manufacturing the same |
EP2259343A4 (en) * | 2008-03-24 | 2014-08-27 | Sony Corp | Light-emitting semiconductor component and method for its production |
WO2009119273A1 (ja) * | 2008-03-25 | 2009-10-01 | 旭硝子株式会社 | 導電体およびその製造方法 |
JP2009231213A (ja) * | 2008-03-25 | 2009-10-08 | Kanagawa Acad Of Sci & Technol | 導電体およびその製造方法 |
JP2010062198A (ja) * | 2008-09-01 | 2010-03-18 | Toyoda Gosei Co Ltd | TiO2からなる導電性透明層の製造方法及び当該導電性透明層の製造方法を利用した半導体発光素子の製造方法。 |
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CN101099227A (zh) | 2008-01-02 |
KR100964420B1 (ko) | 2010-06-16 |
KR20070099591A (ko) | 2007-10-09 |
JPWO2006073189A1 (ja) | 2008-06-12 |
JP5042636B2 (ja) | 2012-10-03 |
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