CN101099227A - Functional device and method for forming oxide material - Google Patents

Functional device and method for forming oxide material Download PDF

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Publication number
CN101099227A
CN101099227A CNA2006800018193A CN200680001819A CN101099227A CN 101099227 A CN101099227 A CN 101099227A CN A2006800018193 A CNA2006800018193 A CN A2006800018193A CN 200680001819 A CN200680001819 A CN 200680001819A CN 101099227 A CN101099227 A CN 101099227A
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film
substrate
metal oxide
oxide material
tio
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CN100530552C (en
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一杉太郎
古林宽
长谷川哲也
广濑靖
笠井淳平
守山实希
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Toyoda Gosei Co Ltd
Kanagawa Institute of Industrial Science and Technology
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Kanagawa Academy of Science and Technology
Toyoda Gosei Co Ltd
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    • 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
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    • 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
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—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
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    • 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
    • H—ELECTRICITY
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    • 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
    • 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

Abstract

There have been demands on transparent electrode materials and magnetic materials having a wide range of applications. Disclosed are a novel functional device and a method for forming an oxide material for meeting such demands. Specifically disclosed is a functional device comprising an AlxGayInzN base (wherein 0 = x = 1, 0 = y = 1, 0 = z = 1) and an oxide material composed of a metal oxide which is formed on the AlxGayInzN base. This functional device is characterized in that the metal oxide is TiO2 or the like. In this functional device, a film which hardly reflects at the interface and has both chemical resistance and durability is integrally formed on a group III nitride having excellent physical and chemical properties.

Description

Function element and oxide material formation method
Technical field
The present invention relates to oxide material.
Background technology
In recent years, display screen is improving constantly to the demand of maximization, miniature portableization.In order to realize this demand, need the low power consumption of display element, using luminous ray transmissivity height, transparency electrode that resistance value is low to become must be indispensable.
Therefore, in order further to reduce the resistance value of transparent conducting film, proposed on transparent base surfaces such as glass plate, to be provided with the scheme (for example, with reference to patent documentation 1) of the indium oxide tin film (hereinafter referred to as the ITO film) of the indium oxide that contains several % tin that mixed.
But, though this IT0 film transparency is excellent, having high conductivity, the earth's crust containing ratio with In is low to reach 50ppb, follows resource exhaustion and shortcoming that the cost of raw material is risen.
In addition, particularly in recent years, added zinc oxide based material has been proposed as plasma-resistance height and cheap material.
But not acid and alkali resistance of added zinc oxide based material is even also can slowly be corroded in carbon dioxide atmosphere.In addition, in order to improve described chemical-resistant, thereby also considered to tackle, but must increase by 1 painting process, the problem that also exists manufacturing cost to increase by zinc oxide surface being coated with processing.
That is, in order to enlarge the scope of application of transparent conductive body, need it be constituted, need simultaneously it to be constituted with the raw material that have chemical-resistant, durability concurrently with raw material that can stable supplying.
Therefore, have the titanium dioxide (TiO of chemical-resistant, durability concurrently 2) receive publicity (for example, with reference to non-patent literature 1), TiO 2Film epitaxial growth (for example, with reference to non-patent literature 2,3 and 4) on sapphire substrate etc.
But if use sapphire substrate, the function that then can not utilize the combination (heterogeneous joint) of the foreign material between baseplate material and thin-film material to produce is difficult to make sapphire substrate to become non-simple structural material and brings into play function.
Patent documentation 1: the spy opens the 2004-95240 communique
Non-patent literature 1: (2004) 587～592 of No. the 5th, Applied Physics the 73rd volumes
Non-patent literature 2:Jpn.J.Appl.Phys.Vol.40 (2001) pp.L1204～L1206
Non-patent literature 3:Nature Materials 3,221-224 (2004)
Non-patent literature 4:APPLIED PHYSICS LETTERS VOLUME 78, NUMBER 18,2664～2666 (2001)
Summary of the invention
Therefore, the present invention proposes in view of above-mentioned condition, and purpose is to provide function element and the oxide material formation method with new features.
According to the present invention, to achieve these goals, adopted as the described formation of the claimed scope of the present invention.Below the present invention is described in detail.
The 1st side of the present invention relates to function element, it is characterized in that: have Al xGa yIn zN (wherein, 0≤x≤1,0≤y≤1,0≤z≤1) and at above-mentioned Al xGa yIn zForm, contain the oxide material of metal oxide on the N, above-mentioned metal oxide is TiO 2
According to this formation, obtain on 3 group-III nitrides integrally formed reflection at the interface with excellent physicochemical properties less, have the TiO of chemical-resistant and durability concurrently 2Film and the function element that constitutes.
The 2nd side of the present invention relates to oxide material formation method, is to adopt pulsed laser deposition at Al xGa yIn zForm, contain the method for the oxide material of metal oxide on the N (wherein, 0≤x≤1,0≤y≤1,0≤z≤1), wherein, above-mentioned metal oxide is TiO 2
According to this formation, can on 3 group-III nitrides, form with excellent physicochemical properties contact resistance little, at the good TiO of the little quality of the scattering at interface 2Epitaxial film.
The 3rd side of the present invention relates to function element, it is characterized in that: have Al xGa yIn zN (wherein, 0≤x≤1,0≤y≤1,0≤z≤1) and at above-mentioned Al xGa yIn zForm, contain the oxide material of metal oxide on the N, above-mentioned metal oxide is SnO 2
According to this formation, the reflection that obtains integrally formed interface on 3 group-III nitrides with excellent physicochemical properties less, have the SnO of chemical-resistant and durability concurrently 2Film and the function element that constitutes.
The 4th side of the present invention relates to oxide material formation method, is to adopt pulsed laser deposition at Al xGa yIn zForm, contain the method for the oxide material of metal oxide on the N (wherein, 0≤x≤1,0≤y≤1,0≤z≤1), wherein, above-mentioned metal oxide is SnO 2
According to this formation, can on 3 group-III nitrides, form with excellent physicochemical properties contact resistance little, at the good SnO of the little quality of the scattering at interface 2Epitaxial film.
Moreover, said Al in the claimed scope of this specification and the present invention xGa yIn zN (wherein, 0≤x≤1,0≤y≤1,0≤z≤1) also comprises: the situation of x+y+z=1, and without any the situation of mixing, the situation of mixed transition metal, Si, Mg, Zn etc. and for the situation of p N-type semiconductor N and n N-type semiconductor N etc.
According to the present invention, the reflection that obtains integrally formed interface on 3 group-III nitrides with excellent physicochemical properties less, have the film of chemical-resistant and durability concurrently and the function element that constitutes.
Other purposes of the present invention, feature or advantage are by becoming clear based on embodiments of the present invention described later, detailed description that accompanying drawing carried out.
Description of drawings
Fig. 1 is the figure of the oxide material films that forms on the substrate of expression.
Fig. 2 is the figure of the RHEED pattern of the RHEED pattern of the substrate of expression before the pre-treatment and the substrate after the pre-treatment.
Fig. 3 is used for the figure that the formation to the PLD device describes.
Fig. 4 is expression GaN (buergerite (wurtzite-type) Al xGa yIn zThe figure of crystalline texture N).
Fig. 5 is 4 grades ((A) grade 1: heterogeneous polycrystalline film, (B) grade 2: single-phase polycrystalline film, (C) grade 3: single-phase oriented epitaxial growth film and (D) class 4: the figure single crystal epitaxial growing film) of the quality of expression crystallization.
Fig. 6 is illustrated in the TiO that adopts above-mentioned PVD method film forming on the GaN substrate of having implemented the salt acid treatment 2The figure of the electron beam diffraction picture (RHEED pattern) of the GaN substrate surface before surface and the film forming.
Fig. 7 is illustrated in the TiO that adopts PVD method film forming on the GaN substrate that does not carry out the salt acid treatment 2The figure of the electron beam diffraction picture (RHEED pattern) of the GaN substrate surface before surface and the film forming.
Fig. 8 is illustrated in the TiO that adopts PVD method film forming on the GaN substrate of having implemented the salt acid treatment 2The surface atomic force microscope (AFM) as figure.
Fig. 9 is the result's of the expression internal transmission rate of measuring metal oxide layer figure.
Figure 10 is the temperature dependent figure of the resistivity of expression metal oxide layer.
Figure 11 is expression Ti 1-x-yCo xNb yO 2The dependent figure of externally-applied magnetic field of faraday's coefficient of rotary at room temperature.
Figure 12 is expression Ti 1-x-yCo xNb yO 2The figure of the wavelength dependency of faraday's coefficient of rotary at room temperature.
Figure 13 is the TiO that represents to have added simultaneously Co5% and Nb10% 2The figure of film outside transmissivity at room temperature.
Figure 14 is that expression has formed TiO while the Nb doping is changed 2The figure of the compositing dependence of the resistivity during film.
Figure 15 is that the substrate temperature variation of expression when on one side making film forming formed that to make the Nb doping be 6% TiO 2The dependent figure of the substrate temperature of the resistivity during film.
Figure 16 is that expression has formed that to make the Nb doping be 6% TiO 2The figure of the wavelength dependency of the transmissivity during film.
Figure 17 is that expression has formed that to make the Nb doping be 6% TiO 2The substrate temperature dependence of the transmissivity during film and the dependent figure of partial pressure of oxygen.
Figure 18 is the figure that the various measurement results of film-forming temperature gradient film have been used in expression.
Figure 19 is the SnO that expression has carried out adopting PLD method film forming 2The result's that the X-ray diffraction of film (XRD) is measured figure.
Figure 20 is the SnO that PLD method film forming is adopted in expression 2The figure of the electron beam diffraction picture of film (RHEED pattern).
Symbol description
11 substrates, 12 oxide material films, 30 PLD devices, Room 31,32 optical generators, 33 speculums, 34 lens, 36 infrared lamps, 39 targets, 40 oil rotary pumps, 41 valve for preventing reverse-flow, 42 turbomolecular pumps, 43 pressure valve, 45 oxygen flow adjuster valves
Embodiment
Followingly embodiments of the present invention are elaborated with reference to accompanying drawing.
As shown in Figure 1, on substrate 11, form oxide material films 12.
Substrate 11 is GaN template (TDI society (Technologies and Devices International, Inc.) the system Si Doped n-type GaN) formation of (0001) face by for example substrate surface 11a.
Moreover substrate 11 can be by Al xGa yIn zN (wherein, 0≤x≤1,0≤y≤1,0≤z≤1) constitutes.
The oxide material films 12 that forms on this substrate 11 is by metal oxide TiO 2Constitute.
Moreover, TiO 2Not only can be any situation that does not have doping, also can be by M:TiO 2(M is any or their combination among Nb, Ta, Mo, As, Sb, Al, W, Co, Fe, Cr, Sn, Ni, Mn or the V) constitutes.As described later, the M of doping is if Nb, Ta, Mo, As, Sb, Al or W can keep the raising of expecting conductivity under the situation of transparency.On the other hand, the M of doping is if Co, Fe, Cr, Sn, Ni, Mn or V can expect the magnetooptics effect.
Secondly the manufacture method to this oxide material films 12 describes.
At first, carry out the processing of GaN substrate.The step of this processing is for example as described below.With acetone, ethanol etc. substrate is washed.Then, substrate was flooded 2 minutes in high-purity hydrochloric acid (EL level, concentration 36%, Northeast chemistry system).Then, substrate is transferred in the pure water flushing hydrochloric acid etc.Then, substrate is transferred in the new pure water, carried out 5 minutes ultrasonic washings here.Then, substrate is taken out from pure water, moisture is removed from substrate surface thereby spray nitrogen to substrate surface.These processing are for example at room temperature carried out.
By these processing, think that oxide, organic substance etc. remove from substrate surface, not that N end but Ga end expose at substrate surface.Though here the example that has used hydrochloric acid is illustrated, can uses acid such as chloroazotic acid, hydrofluoric acid.In addition, this processing can at room temperature also can be used the acid of heating.
Moreover, after these are handled, substrate being imported in the chamber 31 of following explanation, the state of sample surfaces adopts reflection-type electron beam diffraction method (RHEED) to observe, and estimates being heated under 400 ℃ the state.For relatively, the RHEED pattern of the substrate before handling and the RHEED pattern of the substrate after the processing are shown in Fig. 2.Candy strip by the RHEED picture of handling metacoxal plate has obtained smooth substrate surface as can be known.
Following according to physical vapor evaporation (PVD) method, evaporation Ta:TiO for example on (0001) of substrate 11 face 2In the following embodiments, the situation of implementing this evaporation according to pulsed laser deposition (Pulsed LaserDeposition:PLD method) is described.
In this PLD method, use PLD device 30 for example shown in Figure 3, deposition oxide material membrane 12 on substrate 11.This PLD device 30 constitutes by placement substrate 11 in chamber 31 and target 39, the outside of this external this chamber 31 has and is configured in the optical generator 32 of above-mentioned target 39 surperficial opposite sides, is used to regulate by the speculum 33 of the position of the pulse laser of optical generator 32 vibrations and is used to control the lens 34 in the some footpath of laser, also has to be used for the gas supply parts 44 in the oxygen flood chamber 31 are constituted.
The setting of chamber 31 is for by keeping appropriate vacuum, thereby preventing simultaneously that impurity from sneaking into from the outside makes high-quality film.In chamber 31, be provided with the infrared lamp 36 that is used for heated substrates.By window 31b, utilization is arranged on 37 pairs of substrate temperatures of radiation thermometer of 31 outsides, chamber and monitors, and controls to make it remain on uniform temperature frequently.In addition, at the indoor valve 45 that is used to control oxygen flow that is equipped with.System film under realizing reducing pressure is connected with turbomolecular pump 42 and pressure valve 43 on chamber 31.Use oxygen flow adjuster valve 45 and pressure valve 43, the pressure of chamber 31 for example is controlled in oxygen atmosphere, is 1 * 10 -7Holder～1 * 10 -4Holder.Moreover, oil rotary pump 40 and valve for preventing reverse-flow 41 are connected on the turbomolecular pump 42, the pressure of the exhaust side of turbomolecular pump 42 is remained on 1 * 10 frequently -3Below the holder.
In this chamber 31, in the face relative, also set fenestrate 31a, by the pulse laser of window 31a incident from optical generator 32 with target 39.Vibrate pulse frequency for example of optical generator 32 is that 1～10Hz, laser energy are that 100mJ/ pulse, wavelength are that the KrF excimer laser of 248nm is as above-mentioned pulse laser.Pulse laser by speculum 33 and 34 pairs of these vibrations of lens carries out an adjusting so that the focal position is near above-mentioned target 39, by window 31a with it with respect to being provided in target 39 surfaces in the chamber 31 into about 45 ° angle incident.
Target 39 is by for example Ta:TiO 2Sintered body constitutes.Though the metal of displacement here is example with Ta, also can use any of Nb, Mo, As, Sb, W, perhaps also can and use multiple metal.This Ta:TiO 2Sintered body is by will be with the TiO of the mode weighing of the atomic ratio that reaches hope 2And Ta 2O 5Each powder mixes, and then the powder hot briquetting that will mix and making.With (0001) the face almost parallel in this target 39 and the substrate 11 set.
Moreover target 39 is by Nb:TiO 2When sintered body constitutes, Nb:TiO 2Sintered body is by will be with the TiO of the mode weighing of the atomic ratio that reaches hope 2And Nb 2O 5Each powder mixes, and then the powder hot briquetting that will mix and making.Target 39 is by Co, Nb:TiO 2When sintered body constitutes, Co, Nb:TiO 2Sintered body is by will be with the TiO of the mode weighing of the atomic ratio that reaches hope 2And Nb 2O 5Mix with each powder of CoO, and then the powder hot briquetting that will mix and making.
In addition, as described below based on the film-forming process of this PLD method.
At first, the substrate 11 with pre-treatment is arranged in the chamber 31.
Secondly, for example respectively pulse frequency is set in 2Hz, laser energy is set at the 100mJ/ pulse, partial pressure of oxygen is set at 1 * 10 -5Holder is set at 400 ℃ with substrate temperature, carries out 40 minutes system films while utilize motor 35 that the substrate rotation is driven.And then, by rotating shaft 38 target 39 rotations are driven, shine above-mentioned pulse laser intermittently simultaneously, thereby the temperature on target 39 surfaces is risen sharp, produce the ablation plasma.Ti, the Ta that contains in this ablation plasma, each atom of O, and meanwhile carry out repeatedly with chamber 31 in oxygen crash response etc. state is changed, move to substrate 11.Then, arrived substrate 11 contain Ti, Ta, the O atomic particle directly is diffused into (0001) face on the substrate 11, filming under the stable status of lattice match.Then, in partial pressure of oxygen 1 * 10 -5Holder is quenched to room temperature with substrate down.Its result makes oxide material films 12.
Usually known in heteroepitaxial growth, the lattice between film and substrate does not match and produces big influence to generating crystal defect in the film.The lattice unmatch list is shown:
Lattice do not match=(afilm-asub)/and asub
(afilm: the lattice constant of film, asub: the lattice constant of substrate crystallization).This value is big more, and then lattice does not match greatly more, and heteroepitaxial growth is difficult more.In addition, as table 1 and shown in Figure 4, the crystalline texture of GaN and TiO 2Crystalline texture different fully.
[table 1]
GaN * Anatase Rutile
Crystalline texture Buergerite (hexagonal crystal) Anatase (regular crystal) Rutile
Lattice constant a-axle (nm) 03189 0.3784 0.4594
C-axle (nm) 0517 0 9515 0.2958
Thermal coefficient of expansion (* 10 5/K) 559 (a-axles) 10.2 ** 7.14 **(a-axle)
(for *, non-patent literature 5)
(for * *, non-patent literature 6,7 and 8)
Non-patent literature 5:The Blue Laser Diode, S.Nakamura et al., Springer
Non-patent literature 6: long time of Noguchi: titanium oxide and glaze-ware titanium No.44P.11-13 (1956)
Non-patent literature 7: sheet ridge positive three: titanium oxide commercial titanium zirconium vol.12 No.12P.8,9 (1964)
Non-patent literature 8: letter light society's homepage (home page)
Therefore, prediction is made TiO on the GaN substrate 2The film difficulty.But, this time attempt on the GaN substrate, making TiO 2The result of film growth is opposite with anticipation, distinguishes TiO 2Film epitaxial growth on the GaN substrate.
As mentioned above, distinguish that employing PLD method can form oxide material films 12.But, be not limited to above-mentioned PLD method, according to for example molecular ray epitaxial growth (MBE) method, sputtering method etc., the method beyond other physical vapor evaporation (PVD) methods or the PLD method has for example utilized chemical vapor coating (CVD) method of mocvd method also can form oxide material films 12.
Shown in Fig. 5 (A)-Fig. 5 (D), usually when adopting crystalline growth fabrication techniques film, but think that quality rough classification according to crystallization is 4 grades ((A) grades 1: heterogeneous polycrystalline film, (B) grade 2: single-phase polycrystalline film, (C) grade 3: single-phase oriented epitaxial growth film and (D) class 4: the single crystal epitaxial growing film).Should illustrate that so-called single phase film is meant grade more than 2 in the claimed scope of this specification and the present invention, so-called epitaxial film is meant that grade is more than 3.
For for example molecular ray epitaxial growth (MBE) method, sputtering method etc., the method beyond other physical vapor evaporation (PVD) methods or the PLD method has for example been utilized chemical vapor coating (CVD) method of mocvd method, thinks to form the film of grade more than 2.
At this, Fig. 6 is illustrated in the TiO that adopts above-mentioned PVD method film forming on the above-mentioned GaN substrate of implementing the salt acid treatment 2The electron beam diffraction picture (RHEED pattern) of the GaN substrate surface before surface and the film forming.In addition, Fig. 7 is illustrated in the TiO that adopts PVD method film forming on the GaN substrate that does not carry out the salt acid treatment 2The electron beam diffraction picture (RHEEED pattern) of the GaN substrate surface before surface and the film forming.
At TiO 2The surface observes tangible candy strip, has carried out epitaxial growth as can be known.By with this result and X-ray diffraction (XRD) and usefulness, can confirm to adopt the PLD method to form the film of grade more than 3.
In addition, when having carried out the GaN processing substrate, obtained the TiO of smooth and good crystallinity as can be known by the candy strip of RHEED picture 2Film.
And then Fig. 8 is illustrated in the TiO that adopts PVD method film forming on the GaN substrate of having implemented the salt acid treatment 2The surface atomic force microscope (AFM) as.The mean value of surface roughness is 0.2nm.By these as can be known, obtained the high TiO of flatness 2Film.
Moreover Fig. 6, Fig. 7 and any situation shown in Figure 8 all are that the film forming time substrate temperature is 400 ℃, TiO 21% Ta has mixed in the film.In addition, even at TiO 2Other elements that do not mix in the film have also observed equally clearly candy strip.
Below M:TiO to adopting said method to make 2Characteristic describe.
Table 2 is illustrated in the Ta:TiO that makes on the GaN substrate 2Characteristic.
[table 2]
Target Substrate Substrate temperature Partial pressure of oxygen Color resistance
Ta1％ TiO 2 GaN (0001) 550℃ 1×10 -5Holder Transparent 10K Ω
Ta1％ TiO 2 GaN (0001) 400℃ 1×10 -5Holder Transparent a few K Ω
Ta1％ TiO 2 GaN (0001) 320℃ 1×10 -5Holder Transparent R＜1K Ω
Ta1％ TiO 2 GaN (0001) 450℃ 1×10 -5Holder Transparent R=1K Ω
Should illustrate that the resistance value of this moment is measured and used universal instrument.
By this table as can be known, in order to reduce resistance value, the substrate temperature during preferably with film forming is set at more than 320 ℃ below 550 ℃.In addition, in order further to reduce resistance value, the substrate temperature during preferably with film forming is set at more than 320 ℃ below 450 ℃.So-called more than 320 ℃ below 550 ℃, liken low for the required common growth temperature (more than 700 ℃) of the organic metal vapor growth method (mocvd method) of main flow or molecular ray epitaxial growth method (MBE method) now into the crystalline growth method of nitride to.Therefore, from the aspect little to the influence of substrate, also preferably making substrate temperature is more than 320 ℃ below 550 ℃.In addition, film forming can also prevent the problem of the thermal deformation of sample in cooling procedure at low temperatures.Further, even the combination of consideration and other materials, the also low low-temperature epitaxy of preferred reactive.Therefore, from these viewpoints, the substrate temperature during film forming is more preferably more than 320 ℃ below 400 ℃.Moreover, even possibility height that also can film forming between room temperature and 320 degree.
Al xGa yIn zN is many, and semi-conducting material as electronic devices such as photosemiconductors such as light-emitting diode, semiconductor laser, power device, light-emitting components uses.Under the situation of the internal structure that does not change these,, think suitable oxide material films 12 of the present invention is used as transparency electrode in order to improve luminous efficiency.At this, GaN, TiO 2, ZnO refractive index be respectively about 2.5, about 2.5, about 2.0, GaN and transparency electrode TiO 2Combination compare with the combination of transparency electrode ZnO with GaN, the reflection at interface is few.Therefore, in order to improve luminous efficiency, use by TiO as can be known 2The transparency electrode that constitutes is favourable.Moreover, in order to reduce refringence, also can be with other elements to TiO 2In doping regulate.
In addition, think that oxide material films 12 of the present invention suits as the transparency electrodes of surface-emitting laser.In this case,, therefore can get big electrode area even also can dispose transparency electrode at light emitting region, also favourable from electric current to the efficient viewpoint of injecting of active layer.
Moreover, for light-emitting component etc., it has been generally acknowledged that transparency electrode is set on the p type semiconductor layer, but transparency electrode and n type semiconductor layer are joined.
Below to Nb:TiO 2(chemical formula Ti 1-xNb xO 2) internal transmission rate etc. describe.
To making Nb:TiO 2(chemical formula Ti 1-xNb xO 2) in the replacement amount x of Nb be the internal transmission rate (transmissivity on the meaning originally of x=0,0.01,0.02,0.03,0.06,0.1,0.15,0.2 oxide material films 12 of making, owing to volume reflection must be considered as loss, become 100% transmissivity during the therefore following volume reflection that will deduct in the oxide material films 12 and be called the internal transmission rate) measure, as shown in Figure 9, (in the wavelength 400～800nm), obtained the good result more than 80% as can be known at visible-range.Be the sample of x≤0.06 particularly, demonstrate at visible-range and can realize internal transmission rate more than 95% for the Nb replacement amount.Along with the replacement amount that makes Nb improves, the internal transmission rate reduces, and as its reason, thinks because Ti 3+Amount together increases with the Nb replacement amount, has the t of absorption edge at visible-range 2g-e gThe migration probability cause of increased of interband.Should illustrate, though this Nb:TiO 2Be the strontium titanates (SrTiO that makes for the mode of (100) face with the surface 3) make on the substrate, but think on other substrates such as GaN substrate Ti 1-x-yCo xNb yO 2Also show equal basic rerum natura (resistivity etc.).
But many thickness with this oxide material films 12 are set at more than the 100nm when using in the device of reality, desired specification among the particularly present ITO, and requiring the internal transmission rate for the thickness more than the 100nm is more than 80%.In order to satisfy this specification,, need the internal transmission rate more than 95% for thickness 50nm.Therefore as shown in Figure 9,, can satisfy above-mentioned specification, also can make the transparent conductive film that the internal transmission rate with in the past ito thin film improves by the Nb replacement amount is controlled at x≤0.06.
In addition, Figure 10 represents the temperature dependency of the resistivity of the oxide material films 12 made from above-mentioned Nb replacement amount.As shown in Figure 10, the oxide material films 12 that the replacement amount x of Nb is set at 0.01≤x≤0.2 is compared when not replacing Nb, and having obtained at room temperature as can be known is 10 -4Good transport properties about Ω cm.This Nb:TiO should be described 2Also be the strontium titanates (SrTiO that makes for the mode of (100) face with the surface 3) make on the substrate, but think on other substrates such as GaN substrate Ti 1-x-yCo xNb yO 2Also show equal basic rerum natura (resistivity etc.).
Be not only replacement amount x with Nb in this oxide material films 12 and be set at 0.01≤x≤0.2 o'clock, be set at 0.001≤x≤0.2, also can obtain 10 by replacement amount x with this Nb -4Resistivity about Ω cm.
In addition, in this oxide material films 12 the replacement amount x of Nb is set at 0.01≤x≤0.06 o'clock, can makes during for 50nm the internal transmission rate bring up to 95%～98% when thickness is counted 100nm (even also reach more than 80%) at thickness.
In addition, in this oxide material films 12, the replacement amount x of Nb is set at 0.02≤x≤0.06 o'clock, when further improving the internal transmission rate, can also makes resistivity (be reduced to 5 * 10 under the 280K～300K) in room temperature -4About Ω cm, and (be reduced to 1 * 10 under the 5K～20K) at utmost point low temperature -4Ω cm.
That is, by replacing anatase (TiO with Nb 2) the Nb:TiO that obtains of the result of Ti position 2As oxide material films 12, transparency is improved, but also can access the low-resistivity (10 that compares favourably with ITO -4Conductivity about Ω cm).
In addition, by replacing Nb so that the resistivity of oxide material films 12 at room temperature is 2 * 10 -4～5 * 10 -4Ω cm perhaps is 8 * 10 under utmost point low temperature -5～2 * 10 -4Ω cm will use possibility to expand to the various devices of display screen as representative as can leaping.
In addition, oxide material films 12 is by utilizing the TiO of utilization in photochemical catalyst etc. 2Masking technique, can realize large tracts of landization, a large amount of production.Be applied to display screen by the oxide material films 12 that this is had low-resistivity, can realize the low consumption electrification of these display elements, and then can promote the maximization or the miniature portableization of display screen.In addition, oxide material films 12 because above-mentioned reason, can realize the raw material modulation facilitation, simplify cost together with manufacturing process and reduce, in addition, can also reduce significantly and make labour together.
That is, by being suitable for oxide material films 12 of the present invention as electrode, more qurer production has the transparency electrode of performance in the past, therefore can widen range of application.In addition, as this oxide material films 12, corrode few M:TiO if use by acid, alkali 2, under the situation that is not subjected to the surrounding environment domination, also can enlarge range of application.
Further, be suitable for transparent metal 1 of the present invention and be not limited to purposes,, certainly be used for transparent and require the parts, film, device etc. of high conductance as other purposes as electrode.
Below Ti to adopting said method to make 1-x-yCo xNb yO 2The magnetooptics characteristic describe.
Figure 11 is expression Ti 1-x-yCo xNb yO 2(the thickness of film: 50nm) the dependent figure of externally-applied magnetic field of faraday's coefficient of rotary at room temperature.Transverse axis is represented externally-applied magnetic field, and the longitudinal axis is represented faraday's coefficient of rotary.Moreover, though this Ti 1-x-yCo xNb yO 2At (La xSr 1-x) (Al xTa 1-x) O 3(LSAT) substrate (thickness of substrate: make 0.5mm), even but on other substrates such as GaN substrate, think Ti 1-x-yCo xNb yO 2Also show equal characteristic.
Added the TiO of Co 5% and Nb 20% at the same time 2Under the situation of film, added the TiO of Co 5% and Nb 10% simultaneously 2Under the situation of film and the TiO that has added Co 5% 2Under the situation of film, satisfy 0.1 * 10 of enough realistic scales 4The value that degree/cm is above.
Under no magnetic field, near 400nm, show faraday's coefficient of rotary.Further, added the TiO of Co 5% and Nb 10% at the same time 2Under the situation of film, faraday's coefficient of rotary demonstrates about 0.45 * 10 4The value of degree/cm.Compare with the film that does not add Nb as can be known, added the TiO of Co 5% and Nb 10% simultaneously 2During film, near the faraday's coefficient of rotary the 400nm has improved about 2 times.
Figure 12 is expression Ti 1-x-yCo xNb yO 2(the thickness of film: the 50nm) figure of the wavelength dependency of faraday's coefficient of rotary at room temperature.Transverse axis is represented wavelength, and the longitudinal axis is represented faraday's coefficient of rotary.Moreover, though this Ti 1-x-yCo xNb yO 2Also at the LSAT substrate (thickness of substrate: make 0.5mm), even but on other substrates such as GaN substrate, think Ti 1-x-yCo xNb yO 2Also show equal characteristic.
Added the TiO of Co 5% and Nb 20% at the same time 2Under the situation of film, added the TiO of Co 5% and Nb 10% simultaneously 2Under the situation of film and the TiO that has added Co 5% 2Under the situation of film, demonstrate and below 600nm, satisfy 0.1 * 10 of enough realistic scales 4Faraday's coefficient of rotary of the above value of degree/cm.Further, added the TiO of Co 5% and Nb 10% at the same time 2Under the situation of film, especially improve at the following faraday's coefficient of rotary of 600nm as can be known.
Figure 13 is the TiO that has represented to add simultaneously Co 5% and Nb 10% 2The figure of film outside transmissivity at room temperature.Transverse axis is represented wavelength, and the longitudinal axis is represented transmissivity.
Hence one can see that so long as the light of the above wavelength of 260nm just can see through this film.In addition, as can be known so long as the above light of 350nm just can access the transmissivity more than 70%, further, so long as the above light of 500nm just can access the transmissivity more than 80%.That is,, just can guarantee about 70～80% transmissivity at visible-range as can be known so long as this film.
As mentioned above, adopt the oxide material shown in the present embodiment, can access at the useful magnetooptic material of short wavelength range.
In addition, also can the size of faraday's anglec of rotation be controlled by changing the addition of Nb.
Moreover, Ti 1-x-yCo xNb yO 2X be preferably 0≤x.This is because x is 0 o'clock, might exist and can't embody ferromagnetic rough sledding.In order to obtain bigger spontaneous magnetization, x is 0.03≤x more preferably.
Ti 1-x-yCo xNb yO 2Y be preferably 0.1≤y≤0.2.This be because y less than 0.1 o'clock, the rough sledding that exists faraday's coefficient of rotary to diminish, when bigger than 0.2, the rough sledding that exists faraday's coefficient of rotary to diminish once more.
Ti 1-x-yCo xNb yO 2(x=0.05) y is preferably 0≤y≤0.2.This is because do not compare the rough sledding that exists faraday's coefficient of rotary little when not containing Nb when adding Nb, greater than the rough sledding that existed faraday's coefficient of rotary to diminish once more at 0.2 o'clock.In order to obtain big faraday's coefficient of rotary, more preferably making y is the value of 0.1≤y≤0.2.
Below to forming Ti on the i-GaN substrate or on the p-GaN substrate 1-xNb xO 2Various rerum naturas during film describe.
Figure 14 (A) be illustrated on the i-GaN substrate, Figure 14 (B) is illustrated on the p-GaN substrate, formed TiO while the Nb doping is changed 2The figure of the compositing dependence of the resistivity during film.Form TiO 2Partial pressure of oxygen during film all is 1 * 10 under any substrate -6Holder.
Be understood that from reducing the viewpoint of resistivity by these figure, can make the Nb doping under the situation of any substrate is more than 1% below 15%, preferably making the Nb doping is more than 3% below 15%, more preferably making the Nb doping is more than 6% below 15%, and further preferably making the Nb doping is more than 6% below 10%.
Figure 15 (A) be illustrated on the i-GaN substrate, Figure 15 (B) is for being illustrated on the p-GaN substrate, while the substrate temperature when making film forming changes and formed that to make the Nb doping be 6% TiO 2The dependent figure of the substrate temperature of the resistivity during film.Form TiO 2Partial pressure of oxygen during film all is 1 * 10 under any substrate -7Holder.Moreover the temperature when carrying out resistance measurement is 300K.
Be understood that from reducing the viewpoint of resistivity by these figure, substrate temperature in the time of can making film forming under the situation of any substrate is more than 350 ℃ below 500 ℃, preferably making substrate temperature is more than 400 ℃ below 500 ℃, and more preferably making substrate temperature is more than 450 ℃ below 500 ℃.
Moreover, be more than 350 ℃ under the condition below 500 ℃ at substrate temperature, be 1 * 10 making partial pressure of oxygen -6During holder and be 1 * 10 -7During holder, be 1 * 10 making partial pressure of oxygen for any substrate -7Resistivity is all low during holder.In addition, making substrate temperature is 450 ℃, and making partial pressure of oxygen is 1 * 10 -7Holder, having formed on the i-GaN substrate and having made the Nb doping is 6% TiO 2Face resistance during film is 234 Ω/.
Figure 16 (A) be illustrated on the i-GaN substrate, Figure 16 (B) is illustrated on the p-GaN substrate, having formed and having made the Nb doping is 6% TiO 2The figure of the wavelength dependency of the resistivity during film.Formed TiO 2Partial pressure of oxygen during film all is 1 * 10 under any substrate -6Holder.
By these figure as can be known, transmissivity depends on the kind of film-forming temperature and substrate hardly, and can both guarantee that in wide wave-length coverage transmissivity is more than 90%.
Figure 17 (A) for be illustrated on the i-GaN substrate, Figure 17 (B) is for being illustrated on the p-GaN substrate, having formed and having made the Nb doping is 6% TiO 2The substrate temperature dependence of the transmissivity during film and the dependent figure of partial pressure of oxygen.Formed TiO 2Partial pressure of oxygen during film all is 1 * 10 under any substrate -6Holder or 1 * 10 -7Holder.
By these figure as can be known, under the situation of any substrate, partial pressure of oxygen is 1 * 10 -6Guarantee transmissivity during holder more than 93%, partial pressure of oxygen is 1 * 10 -7During holder, can guarantee transmissivity 75%～80%.
Below the mensuration that adopts film-forming temperature gradient film to carry out is described.
So-called film-forming temperature gradient film is to make temperature produce gradient on 1 piece of substrate and film that film forming obtains.For example, 1 end that on 1 piece of substrate, can be implemented in substrate simultaneously carry out at low temperatures on the substrate film forming, at high temperature carry out film forming on the substrate at the other end of substrate.This time use film-forming temperature gradient film for the best film-forming temperature of concrete research.
Figure 18 is the figure that the various measurement results of film-forming temperature gradient film have been used in expression.
Figure 18 (A) is the figure of the relation of expression substrate position and Temperature Distribution.Shown in Figure 18 (A), film-forming temperature is changed along the length direction of substrate.Make 1 pair 1 ground in position and film-forming temperature of length direction of substrate corresponding like this.
Figure 18 (B) is the figure of the relation of expression substrate position and the diffracted intensity distribution of adopting X-ray diffraction (XRD).The position-finding of this XRD is represented the relation of substrate position and 2 θ relation.According to Figure 18 (A) and Figure 18 (B), the position that diffracted intensity is high is near 450 ℃ of the film-forming temperatures.That is when, crystallinity is preferably near film-forming temperature is 450 ℃ as can be known.
Figure 18 (C) is the figure of relation of the distribution of expression substrate position and resistance value.According to Figure 18 (A) and Figure 18 (C), it is when substrate temperature is 450 ℃ that resistance value reaches minimum.If particularly compare,, might make resistance value reduce 25% 450 ℃ of following film forming with 500 ℃.Moreover, adopted 2 terminal methods to carry out resistance measurement during this mensuration.
Below SnO to adopting the PLD method to form 2Film describes.
Figure 19 is the SnO that has carried out adopting PLD method film forming on the p-GaN substrate 2The result's that the X-ray diffraction of film (XRD) is measured figure.According to this XRD wave spectrum, can confirm on the p-GaN substrate, stably to have generated SnO 2
Figure 20 is illustrated in the SnO that adopts PLD method film forming on the p-GaN substrate 2The figure of the electron beam diffraction picture of film (RHEED pattern).At SnO 2The surface observes clearly candy strip, has carried out epitaxial growth as can be known.In addition, obtained the SnO of good crystallinity as can be known by the candy strip of RHEED picture 2Film.
Form these SnO 2Partial pressure of oxygen during film is 1 * 10 -5Holder, thickness is 50nm, resistivity is 5 * 10 -2Ω cm -1
Moreover, SnO 2Not only can be without any the situation of mixing, also can be by M:SnO 2(M is any or their combination among P, As, Sb, S, Se, Te, Al, Ga, In, Co, Fe, Cr, Mn, V and the Ni) constitutes.The M that mixes can be in the raising that keep expectation conductivity under the situation of transparency if P, As, Sb, S, Se, Te, Al, Ga, In.On the other hand, if the M of doping is Co, Fe, Cr, Mn, V, Ni, can expect the magnetooptics effect.
In the near future, the light wavelength used in optical communication of prediction will be moved to short wavelength band such as blueness or ultraviolet lights.In this situation, near the photomagnetic device as also show big faraday's coefficient of rotary wavelength 400nm also can use this oxide material.Particularly the magnetic garnet of practicability (garnet) film and big faraday's coefficient of rotary till now, use this oxide material if demonstrate, can make the optical isolator that is suitable for short wavelength band communication of future generation.
The purposes of the oxide material shown in the present embodiment, be not limited to use, also can be used for light circulator, variable optical attenuator, optic communication device equimagnetic optics, photomagnetic device, optical circuit, non-opposite optics, non-opposite optical element, semiconductor laser, current field transducer, magnetic region observation, magnetooptics mensuration etc. with isolator as optical isolator.
In addition, as optical isolator, can enumerate for example LD and the incorporate assembly of isolator, insert optical isolator, the image intensifer that optical fiber uses and rely on light type optical isolator, the no dependent form optical isolator of deflection, guided wave road type optical isolator with optical isolator, deflection.As guided wave road type optical isolator, have the branch guided wave road of for example having used the mach-zehnder type optical isolator, used the optical isolator on ridge guided wave road.
As light circulator, can be deflection dependent form light circulator, the no dependent form light circulator of deflection.
If use the TiO of the Co that in the luminescent device that constitutes by GaN compounds semiconductor, mixed etc. 2, can realize the optical isolator that short wavelength band such as blueness or ultraviolet light are also adapted to.If pass through at TiO 2Further make the optical isolator epitaxial growth on the film and realize TiO 2Film is not only brought into play function as the resilient coating of crystalline growth, and integrally obtains function element.That is, not only can develop high efficiency light-emitting element, low price and large-area display, and can develop whole function element, for example can realize the fusion of fusion, luminescent device and the photomagnetic device of transparency electrode and optical device.In addition, can in photo detector, HEMT high frequency device, electronic devices such as (High Electron Mobility Transistor), use the oxide material shown in the present embodiment.
For above-mentioned item, can use the SnO of mixed Al, Sb etc. 2Film.
More than to various TiO 2Film, various SnO 2Oxide materials such as film are illustrated, and they can be rutile-types, also can be anatase titanium dioxides.From the viewpoint of reduction resistivity, preferred anatase titanium dioxide, from the easy degree aspect that makes, preferred rutile-type.In addition, they can be amorphous.
The specific execution mode of above reference describes the present invention.But apparent, in the scope that does not break away from purport of the present invention, those skilled in the art can revise or replace this execution mode.That is, disclosing the present invention with illustrative execution mode, is not that the record content of this specification is carried out explaining limitedly.In order to judge purport of the present invention, should be with reference to the claimed scope of the present invention hurdle of title record.
In addition, the present invention illustrates that the execution mode of usefulness realized above-mentioned purpose as can be known, but also can understand those skilled in the art can change or other embodiment in a large number.Can or be used in combination the element of each execution mode of the claimed scope of the present invention, specification, accompanying drawing and explanation usefulness or component and other 1.The purpose of the claimed scope of the present invention is these changes, other execution modes are also contained in the scope, and these are included in technological thought of the present invention and the technical scope.
Possess the metal oxide of excellent specific property by formation, can be applied to various function element.

Claims (22)

1. a function element is characterized in that: have Al xGa yIn zN and at described Al xGa yIn zForm, contain the oxide material of metal oxide on the N, wherein, 0≤x≤1,0≤y≤1,0≤z≤1; Described metal oxide is TiO 2
2. the described function element of claim 1 is characterized in that: in described metal oxide, mix be selected among Nb, Ta, Mo, As, Sb, Al and the W more than a kind or 2 kinds.
3. claim 1 or 2 described function element is characterized in that: in described metal oxide, mix be selected among Co, Fe, Cr, Sn, Ni, Mn and the V more than a kind or 2 kinds.
4. the described function element of claim 1, it is characterized in that: described oxide material is a single phase film.
5. the described function element of claim 1, it is characterized in that: described oxide material is an epitaxial film.
6. claim 1 or 2 described function element is characterized in that: be transparency electrode.
7. the described function element of claim 1 is characterized in that: be light-emitting component.
8. the described function element of claim 1 is characterized in that: be high-frequency element.
9. the described function element of claim 3 is characterized in that: as photomagnetic device performance function.
10. the described function element of claim 3 is characterized in that: as isolator performance function.
11. an oxide material formation method is to adopt pulsed laser deposition at Al xGa yIn zThe last method that forms the oxide material that contains metal oxide of N, wherein, 0≤x≤1,0≤y≤1,0≤z≤1; Described metal oxide is TiO 2
12. the described oxide material of claim 11 formation method is characterized in that: the Ta that mixes in described metal oxide, the substrate temperature during deposition are set at more than 320 ℃ below 550 ℃.
13. the described oxide material of claim 11 formation method is characterized in that: the Ta that mixes in described metal oxide, the substrate temperature during deposition are set at more than 320 ℃ below 450 ℃.
14. the described oxide material of claim 11 formation method is characterized in that: the Ta that mixes in described metal oxide, the substrate temperature during deposition are set at more than 320 ℃ below 400 ℃.
15. the described oxide material of claim 11 formation method is characterized in that: also having advances in deposition exercises the operation of the processing that the Ga end exposes at substrate surface.
16. the described oxide material of claim 11 formation method is characterized in that: also have the operation that the acid used is handled substrate surface before deposition.
17. the described oxide material of claim 11 formation method is characterized in that: the Nb that mixes in described metal oxide, the substrate temperature during deposition are set at more than 350 ℃ below 500 ℃.
18. a function element is characterized in that: have Al xGa yIn zN and at described Al xGa yIn zForm, contain the oxide material of metal oxide on the N, wherein, 0≤x≤1,0≤y≤1,0≤z≤1; Described metal oxide is Ti 1-αNb αO 2Wherein, 0.01≤α≤0.15.
19. a function element is characterized in that: have Al xGa yIn zN and at described Al xGa yIn zForm, contain the oxide material of metal oxide on the N, wherein, 0≤x≤1,0≤y≤1,0≤z≤1; Described metal oxide is SnO 2
20. the described function element of claim 19 is characterized in that: in described metal oxide, mix be selected among P, As, Sb, S, Se, Te, Al, Ga and the In more than a kind or 2 kinds.
21. the described function element of claim 19 is characterized in that: in described metal oxide, mix be selected among Co, Fe, Cr, Mn, V and the Ni more than a kind or 2 kinds.
22. an oxide material formation method is to adopt pulsed laser deposition at Al xGa yIn zThe last method that forms the oxide material that contains metal oxide of N, wherein, 0≤x≤1,0≤y≤1,0≤z≤1; Described metal oxide is SnO 2
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Patentee before: Toyoda Gosei Co., Ltd.