CN110335914A - A kind of MSM type (GaMe)2O3Ternary alloy three-partalloy solar blind UV detector and preparation method thereof - Google Patents
A kind of MSM type (GaMe)2O3Ternary alloy three-partalloy solar blind UV detector and preparation method thereof Download PDFInfo
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- CN110335914A CN110335914A CN201910344454.3A CN201910344454A CN110335914A CN 110335914 A CN110335914 A CN 110335914A CN 201910344454 A CN201910344454 A CN 201910344454A CN 110335914 A CN110335914 A CN 110335914A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 title description 8
- 239000000956 alloy Substances 0.000 title description 8
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 229910002058 ternary alloy Inorganic materials 0.000 claims abstract description 53
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 34
- 239000010980 sapphire Substances 0.000 claims abstract description 34
- 239000010408 film Substances 0.000 claims description 84
- 239000000919 ceramic Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 238000000151 deposition Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 239000011812 mixed powder Substances 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 238000004549 pulsed laser deposition Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001259 photo etching Methods 0.000 claims description 4
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 abstract description 46
- 229910052751 metal Inorganic materials 0.000 abstract description 43
- 239000002184 metal Substances 0.000 abstract description 43
- 230000004044 response Effects 0.000 abstract description 28
- 150000002500 ions Chemical class 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 description 40
- 230000008020 evaporation Effects 0.000 description 40
- 239000010931 gold Substances 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 238000010792 warming Methods 0.000 description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229960000935 dehydrated alcohol Drugs 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 238000005137 deposition process Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000608 laser ablation Methods 0.000 description 10
- 238000007747 plating Methods 0.000 description 10
- 238000010257 thawing Methods 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- 238000007738 vacuum evaporation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 241001504664 Crossocheilus latius Species 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 229910003443 lutetium oxide Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 4
- 229910001195 gallium oxide Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910002704 AlGaN Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910014032 c-Al2O3 Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier
- H01L31/108—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier the potential barrier being of the Schottky type
- H01L31/1085—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier the potential barrier being of the Schottky type the devices being of the Metal-Semiconductor-Metal [MSM] Schottky barrier type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of MSM types (GaMe)2O3Ternary alloy three-partalloy solar blind UV detector and preparation method thereof.The detector sequentially consists of c surface sapphire substrate, active layer, parallel metal electrode, in which: active layer is (GaMe)2O3Ternary alloy film.The present invention utilizes Me2O3Band gap (5.5eV) be greater than Ga2O3Band gap (4.9eV), use Me3+Ionic portions replace Ga3+Ion obtains (GaMe)2O3Ternary alloy three-partalloy improves Ga2O3Band gap be effectively reduced the dark current of device, and be blue shifted to cutoff wavelength within 280nm, improve device to the detectivity of deep ultraviolet light.And the solar blind UV panel detector structure and manufacture craft of MSM structure of the invention are simple, and dark current is less than 0.2pA, device relaxation response time τd2It can be down to 0.190s, fast response time, performance stabilization.
Description
Technical field
The invention belongs to semiconductor detector technical fields, and in particular to a kind of solar blind UV spy with MSM structure
Device is surveyed, it is more particularly related to a kind of MSM type (GaMe)2O3Ternary alloy three-partalloy solar blind UV detector and its preparation side
Method.
Background technique
Since the dark purple outer portion (200~280nm) in sunlight can be inhaled strongly before reaching earth surface by ozone layer
It receives, the features such as solar blind UV electric explorer is worked at the earth's surface with strong antijamming capability, high sensitivity.It is pre- in guided missile
Alert, ultraviolet communication, fire prevention and control, environmental monitoring etc. is military and there is highly important application in people's livelihood field.Traditional vacuum is purple
Outer photomultiplier tube detectors power consumption is high and at high price, the solar blind UV electric explorer based on semiconductor material with wide forbidden band by
In having the characteristics that small in size, gain is big, low energy consumption, become the focus of countries in the world research and competition.Wherein research is main
Concentrate on MgZnO, AlGaN and Ga2O3On equal semiconductor material with wide forbidden band.But to realize the detection of solar blind UV, active layer
The band gap of semiconductor material must be greater than 4.4eV, and MgZnO and AlGaN is improved by the way that Mg and Al content is respectively increased
Band gap can make crystal quality be remarkably decreased while reaching 4.4eV, can greatly reduce the performance and stability of device.Ga2O3It is
A kind of semiconductor material with 4.9eV direct band gap, and exciton bind energy is higher, has good physics and chemical stabilization
Property, it is a kind of ideal solar blind UV detection material.
Although the peak response wavelength of pure zirconia gallium base solar blind UV electric explorer, near 255nm, it cuts
Only wavelength is greater than 280nm, namely still has obvious response to the ultraviolet light (280~315nm) of UVB wave band, and due to depth
Ultraviolet light is fainter, and influence of the noise to signal detection can be effectively reduced in the dark current for reducing device.Based on the above reasons, I
Use Me3+Ion (Me3+Ion is Lu3+Ion or Sc3+Ion) part substitution Ga2O3In Ga3+Ion obtains (GaMe)2O3Ternary alloy three-partalloy improves Ga2O3Band gap, so as to be effectively reduced the dark current of device, and be blue shifted to cutoff wavelength
Within 280nm, device is improved to the detectivity of deep ultraviolet light.
Metal-semiconductor-metal (MSM) feature detector is particularly conducive to surface light absorption simultaneously, simple with structure,
It is high-efficient and convenient for it is integrated the advantages that, can be regulated and controled as parameters such as control metal types, channel widths obtained by detector property
Energy.So we select to prepare a kind of MSM type (GaMe)2O3Ternary alloy three-partalloy solar blind UV detector.
Summary of the invention
The purpose of the present invention is to provide a kind of MSM types (GaMe)2O3Ternary alloy three-partalloy solar blind UV detector and its preparation
Method.The present invention is by utilizing Me3+Ion (Me3+Ion is Lu3+Ion or Sc3+Ion) doping improve gallium oxide film
Band gap so that the dark current of gallium oxide solar blind UV detector reduces, cutoff wavelength blue shift is improved to deep ultraviolet light
Detectivity.
In order to realize above-mentioned first purpose of the invention, the present invention adopts the following technical scheme:
A kind of MSM type (GaMe)2O3Ternary alloy three-partalloy solar blind UV detector, the detector successively include c from bottom to up
Surface sapphire substrate, active layer, a pair of of parallel pole, in which: the active layer is (GaMe)2O3Ternary alloy film；The Me
For any one of Lu or Sc.
Further, above-mentioned technical proposal, the active layer with a thickness of 150~300nm.
Further, above-mentioned technical proposal, the parallel pole with a thickness of 30~70nm.
Further, above-mentioned technical proposal, the spacing of the parallel pole are 10~100 μm.
Further, above-mentioned technical proposal, the parallel pole material can any one of for Pt, Au, Al or ITO,
Preferably Au.
Another object of the present invention is to provide MSM types (GaMe) described above2O3Ternary alloy three-partalloy solar blind UV detector
Preparation method, the described method comprises the following steps:
(1) substrate grown using c surface sapphire as film is used after being cleaned by ultrasonic using cleaning solution to the substrate
It is dried with nitrogen, is immediately placed in vacuum chamber；
(2) (GaMe) is used2O3Ceramic target, using pulsed laser ablation deposition, magnetron sputtering or electron beam evaporation method
(GaMe) to form (- 201) orientation is deposited in step (1) pretreated c surface sapphire substrate surface2O3Ternary alloy film；
(3) vapour deposition method, photoetching process or sputtering method are utilized, at (GaMe)2O3The parallel electricity of ternary alloy film surface preparation
Pole obtains MSM type (GaMe) of the present invention2O3Ternary alloy three-partalloy solar blind UV detector.
Further, above-mentioned technical proposal, cleaning solution described in step (1) include acetone, ethyl alcohol, deionized water, described
Each cleaning solution ultrasonic cleaning time is preferably 15min.
Further, above-mentioned technical proposal, (GaMe) of (- 201) orientation in step (2)2O3Ternary alloy film is specifically
It is made using pulsed laser ablation deposition method, the specific process is as follows:
It utilizes (GaMe)2O3Ceramics be used as target, control underlayer temperature be 300~800 DEG C, pulsed laser energy be 200~
600mJ/Pulse, oxygen pressure are 1~8Pa, deposit to form (- 201) and take in step (1) pretreated c surface sapphire substrate surface
To (GaMe)2O3Ternary alloy film.
Preferably, above-mentioned technical proposal, the sedimentation time are 10~60min.
Further, above-mentioned technical proposal, described in step (2) (GaMe)2O3Ceramic target is using solid-phase sintering legal system
, the specific method is as follows:
(a) Ga is weighed for the ratio of 95:5~70:30 in molar ratio2O3、Me2O3Powder is placed in ball grinder by powder,
Ball milling is carried out after ultrapure water is added, be uniformly mixed powder；
(b) step (a) the mixed-powder solution is screened out into zirconium ball postposition in a vacuum drying oven, is cooled to room after dry
Then temperature is pulverized, disk is pressed into；
(c) in air atmosphere, disk obtained by step (b) is placed in vacuum tube furnace, in 1000~1400 DEG C of conditions
1~4h of lower firing, obtains (GaMe) of the present invention2O3Ceramics.
Further, above-mentioned technical proposal, step (b) the vacuum oven temperature is 100~120 DEG C, when dry
Between be 10~12h.
The principle of the present invention is as follows:
The present invention utilizes Me2O3(wherein Me2O3For Lu2O3Or Sc2O3) band gap (5.5eV) be greater than Ga2O3Band gap
(4.9eV), uses Me3+Ionic portions replace Ga2O3In Ga3+Ion obtains (GaMe)2O3Ternary alloy three-partalloy improves Ga2O3's
Band gap so as to be effectively reduced the dark current of device, and is blue shifted to cutoff wavelength within 280nm, improves device to depth
The detectivity of ultraviolet light.
The invention has the benefit that
1, the present invention passes through Me3+Ionic portions replace Ga2O3In Ga3+Ion obtains (GaMe)2O3Ternary alloy three-partalloy can be with
Significantly improve Ga2O3Band gap.
2, band gap of the present invention is higher (GaMe)2O3Carrier concentration is lower in film, blind so as to be effectively reduced its day
The dark current of UV photodetector, and cutoff wavelength blue shift can be made, improve the detectivity to deep ultraviolet light.
3, (GaMe) of the invention2O3Conventional pulsed laser ablation deposition can be used in ternary alloy three-partalloy semiconductor material, magnetic control splashes
Penetrate, a variety of methods such as electron beam evaporation are grown, electrode material can be using metallic aluminium, gold, platinum etc. or transparent electrode
ITO, electrode shape and channel width freely can adjust and optimize.Electrode of the present invention can be both deposited using vapour deposition method,
It can also be made using photoetching process or using sputtering method.Vapour deposition method simple process, facilitates large scale preparation；Photoetching process is highly beneficial
In high-precision, the development of microsized device.
4, the solar blind UV electric explorer structure of MSM structure produced by the present invention and manufacture craft are simple, in addition this hair
Bright detector obtained has good detectivity to deep ultraviolet light, and dark current is minimum, fast response time, and performance is stablized.
Detailed description of the invention
Fig. 1 is the embodiment of the present invention 1 based on (GaLu)2O3The structure of the solar blind UV detector of ternary alloy film
Schematic diagram；
Fig. 2 is (GaLu) in the embodiment of the present invention 12O3Pure Ga in film and comparative example 12O3The X-ray diffraction of film
(XRD) comparison diagram；
Fig. 3 is (GaLu) in the embodiment of the present invention 12O3Pure Ga in ternary alloy film and comparative example 12O3The transmission of film
Spectrogram；
Fig. 4 is (GaLu) in the embodiment of the present invention 12O3Pure Ga in ternary alloy film and comparative example 12O3(the α hv) of film2
∝(hv-Eg) relational graph；
Fig. 5 is (GaLu) in the embodiment of the present invention 12O3The time t- electric current I response curve of base solar blind UV electric explorer
Figure；
Fig. 6 is (GaLu) in the embodiment of the present invention 22O3The time t- electric current I response curve of base solar blind UV electric explorer
Figure；
Fig. 7 is pure Ga in comparative example 1 of the present invention2O3The time t- electric current I response curve of base solar blind UV electric explorer
Figure；
Fig. 8 is (GaLu) in the embodiment of the present invention 12O3With Ga pure in comparative example 12O3Base solar blind UV electric explorer
Spectral responsivity test result comparison diagram；
Fig. 9 is in the embodiment of the present invention 5 based on (GaSc)2O3The structure of the solar blind UV detector of ternary alloy film
Schematic diagram；
Figure 10 is that the embodiment of the present invention 5 prepares (GaSc)2O3Pure Ga prepared by film and comparative example 22O3The X of film is penetrated
Line diffraction (XRD) figure；
Figure 11 is (GaSc) in the embodiment of the present invention 52O3The I-V curve of base solar blind UV electric explorer；
Figure 12 is (GaSc) in the embodiment of the present invention 52O3Time t- electric current I of base solar blind UV electric explorer responds bent
Line chart；
Figure 13 is (GaSc) in the embodiment of the present invention 62O3The I-V curve of base solar blind UV electric explorer；
Figure 14 is (GaSc) in the embodiment of the present invention 62O3Time t- electric current I of base solar blind UV electric explorer responds bent
Line chart；
Figure 15 is pure Ga in comparative example 2 of the present invention2O3The I-V curve of base solar blind UV electric explorer；
Figure 16 is pure Ga in comparative example 2 of the present invention2O3The time t- electric current I response curve of base solar blind UV electric explorer
Figure；
Figure 17 is (GaSc) in the embodiment of the present invention 52O3With Ga pure in comparative example 22O3Base solar blind UV electric explorer
Spectral responsivity test result.
Specific embodiment
It elaborates with reference to the accompanying drawing to case study on implementation of the invention.The implementation case is in technical solution of the present invention
Under the premise of implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to
Following case study on implementation.
The information for including according to the application, to those skilled in the art can be easily to essence of the invention
Really description carries out various changes, without departing from spirit and scope of the appended claims.It should be understood that the scope of the present invention is not
Process, property defined by being confined to or component, because these embodiments and other descriptions are just for the sake of schematic
Illustrate certain aspects of the present disclosure.In fact, this field or those skilled in the relevant art obviously can be to embodiment party of the present invention
The various changes that formula is made all cover within the scope of the appended claims.
It is not intended to limit the scope of the invention for a better understanding of the present invention, expression dosage used in this application,
All numbers of percentage and other numerical value, are understood to be modified with word " about " in all cases.Therefore,
Unless stated otherwise, otherwise digital parameters listed in specification and appended book are all approximations, may
It can be changed according to the difference for the desirable properties for attempting to obtain.Each digital parameters at least should be considered as according to being reported
Effective digital and obtained by the conventional method of rounding up.
The following each Sapphire Substrates used in the examples of the present invention, main component is aluminium oxide (Al2O3), c-Al2O3
Indicate c surface sapphire.The thickness of Sapphire Substrate is preferably 0.35~0.45mm in the present invention.
Embodiment 1
As shown in Figure 1, one kind of the present embodiment is based on (GaLu)2O3The solar blind UV detector of ternary alloy film, institute
State detector successively includes c surface sapphire substrate, active layer, a pair of of parallel metal Au electrode from bottom to up, in which: described active
Layer is (GaLu) of (- 201) orientation2O3Ternary alloy film.The substrate with a thickness of 0.43mm, the thickness of the active layer
For 150nm, the Au electrode with a thickness of 50nm, the spacing of the parallel pole is 10 μm.
The present embodiment is above-mentioned based on (GaLu)2O3The solar blind UV detector of ternary alloy film is with the following method
It is prepared, includes the following steps:
Step 1: (GaLu) is prepared using solid sintering technology firing2O3Ternary ceramics target
1.1 Ga in molar ratio2O3: Lu2O3=70:30 weighs 5.236g Ga2O3Powder and 4.763g Lu2O3Powder mixes
After conjunction, 15g deionized water is added, the ball grinder being subsequently placed in planetary ball mill (ball-milling medium is zirconia ceramics ball)
In, ball milling 4h obtains mixed-powder；
The mixed-powder solution is weeded out zirconium ball postposition in a vacuum drying oven by 1.2, is dried in vacuo under the conditions of 110 DEG C
1g deionized water is added in 12h, cooled to room temperature after taking-up, using tablet press machine in 8MPa after being fully ground uniformly with stone roller alms bowl
Pressure depresses to the round blank of diameter 27.5mm, thickness 2mm；
1.3 are placed in the blank in the crucible in vacuum tube furnace, and the identical powder of ingredient is put around it
(15.000g).Tube furnace is warming up to 1300 DEG C and keeps the temperature 3h, subsequent cooled to room temperature obtains of the present invention
(GaLu)2O3Ternary ceramics target.
Step 2 utilizes (GaLu)2O3Ternary ceramics target prepares solar blind UV detector
2.1 with (GaLu) made from step 12O3Ternary ceramics are as laser ablation target, with process acetone, dehydrated alcohol
The Sapphire Substrate for being cleaned by ultrasonic 15min respectively with deionized water etc. is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 700 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 4Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 300mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- metal Au 0.15g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after metal Au thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Made from the present embodiment (GaLu)2O3The XRD of ternary alloy film is composed as shown in Figure 2 entirely.It can be seen that in addition to c
Outside (0003) of surface sapphire substrate, (0006) and (0009) three diffraction maximum, has and only there are three diffraction maximums, be located at
Near 18.9 °, 38.3 ° and 59.1 °, Ga is compared2O3Standard x RD spectrogram (JCPDS File No.41-1103) it is found that this three
A diffraction maximum respectively represents Ga2O3(- 201), (- 402) and (- 603) crystal face illustrates that (- 201) have successfully been made in the present embodiment
(GaLu) of orientation2O3Ternary film.
Fig. 3 is (GaLu)2O3With pure Ga2O3Transmitted light spectrogram.As shown, (GaLu)2O3With pure Ga2O3Infrared and
The transmitance of visible light region is 90% or more.(GaLu)2O3The ABSORPTION EDGE of film is near 235nm, relative to pure Ga2O3
Blue shift obviously occurs for the ABSORPTION EDGE (~255nm) of film.Because gallium oxide is direct band-gap semicondictor, it is possible to pass through (α
hv)2∝(hv-Eg) relational expression obtain the band gap of film, wherein hv represents incident photon energy, α represents absorption coefficient.(α
hv)2Figure relative to hv obtains (GaLu) as shown in figure 4, by the method for linear extrapolation2O3The band gap of film is 5.2eV, and
Pure Ga2O3Band gap be 4.9eV.It can be seen that the band gap of gallium oxide can be significantly improved by the doping of Lu.This is because Lu2O3's
Band gap (5.5eV) is greater than Ga2O3Band gap (4.9eV).
Further, apply the voltage of 10V between the MSM type device electrode made from the present embodiment and use monochromatic light exposure
Sample surfaces carry out photoelectric properties test.Fig. 5 and Fig. 8 is respectively the when m- electric current and wavelength-responsiveness curve of the device.Knot
Fruit shows that the device has apparent detectivity to solar blind UV, compared to pure Ga2O3Solar blind UV electric explorer has
Lower dark current (Idark< 0.2pA) and faster response speed, device relaxation response τd2For 0.190s, and peak response
Blue shift occurs for wavelength and cutoff wavelength, shows the detectivity more sensitive to solar blind UV.This has benefited from (GaLu)2O3It is thin
Film is relative to pure Ga2O3With broader band gap and less Lacking oxygen, broader band gap causes the dark current of device significantly to drop
Low, blue shift occurs for peak response wavelength and cutoff wavelength, and in film the reduction of Lacking oxygen so that the concentration of Trapping Centers reduces,
It is substantially reduced so as to cause the device relaxation time.
In conclusion (GaLu)2O3Base detector is relative to pure Ga2O3Base detector has lower dark current, faster
Response speed and shorter cutoff wavelength are shown to the more sensitive and quick detectivity of solar blind UV.
Embodiment 2
One kind of the present embodiment is based on (GaLu)2O3The solar blind UV detector of ternary alloy three-partalloy, the detector from down toward
On successively include c surface sapphire substrate, active layer, a pair of of parallel metal Au electrode, in which: the active layer is (GaLu)2O3Three
First alloy firm, the substrate with a thickness of 0.43mm, the active layer with a thickness of 150nm, the electrode with a thickness of
55nm, the spacing of the parallel pole are 10 μm.
The present embodiment is above-mentioned based on (GaLu)2O3The solar blind UV detector of film is prepared with the following method,
Include the following steps:
Step 1: (GaLu) is prepared using solid sintering technology firing2O3Ternary ceramics target
1.1 Ga in molar ratio2O3: Lu2O3=95:5 weighs 8.995g Ga2O3Powder and 1.005g Lu2O3Powder, mixing
Afterwards, 15g deionized water is added, is subsequently placed in the ball grinder in planetary ball mill (ball-milling medium is zirconia ceramics ball),
Ball milling 4h, obtains mixed-powder；
The mixed-powder solution is weeded out zirconium ball postposition in a vacuum drying oven by 1.2, is dried in vacuo under the conditions of 110 DEG C
1g deionized water is added in 12h, cooled to room temperature after taking-up, using tablet press machine in 8MPa after being fully ground uniformly with stone roller alms bowl
Pressure depresses to the round blank of diameter 27.5mm, thickness 2mm；
1.3 are placed in the blank in the crucible in vacuum tube furnace, and the identical powder of ingredient is put around it
(15.000g).Tube furnace is warming up to 1300 DEG C and keeps the temperature 3h, subsequent cooled to room temperature obtains of the present invention
(GaLu)2O3Ternary ceramics target.
Step 2 utilizes (GaLu)2O3Ternary ceramics target prepares solar blind UV detector
2.1 with (GaLu) made from step 12O3Ternary ceramics are as laser ablation target, with process acetone, dehydrated alcohol
The Sapphire Substrate for being cleaned by ultrasonic 15min respectively with deionized water etc. is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 700 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 4Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 300mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- metal Au 0.15g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after metal Au thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Apply the voltage of 10V between the device electrode made from the present embodiment and carries out light with monochromatic light exposure sample surfaces
Electric performance test.The result shows that the very low (I of the device dark currentdark< 0.2pA), response speed is very fast, the device relaxation response time
τd2For 0.228s, show to the preferable detectivity of solar blind UV.Test result is shown in Fig. 6.
Embodiment 3
One kind of the present embodiment is based on (GaLu)2O3The solar blind UV detector of ternary alloy three-partalloy, the detector from down toward
On successively include c surface sapphire substrate, active layer, a pair of of parallel metal Au electrode, in which: the active layer is (GaLu)2O3Three
First alloy firm, the substrate with a thickness of 0.43mm, the active layer with a thickness of 300nm, the electrode with a thickness of
30nm, the spacing of the parallel pole are 50 μm.
The present embodiment is above-mentioned based on (GaLu)2O3The solar blind UV detector of film is prepared with the following method,
Include the following steps:
Step 1: (GaLu) is prepared using solid sintering technology same as Example 12O3Ternary ceramics target；
Step 2: utilizing (GaLu)2O3Ternary ceramics target prepares solar blind UV detector
2.1 with (GaLu) made from step 12O3Ternary ceramics are as laser ablation target, with process acetone, dehydrated alcohol
The Sapphire Substrate for being cleaned by ultrasonic 15min respectively with deionized water etc. is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 500 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 1Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 500mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- metal Au 0.10g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after metal Au thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Embodiment 4
One kind of the present embodiment is based on (GaLu)2O3The solar blind UV detector of ternary alloy three-partalloy, the detector from down toward
On successively include c surface sapphire substrate, active layer, a pair of of parallel metal Au electrode, in which: the active layer is (GaLu)2O3Three
First alloy firm, the substrate with a thickness of 0.43mm, the active layer with a thickness of 200nm, the electrode with a thickness of
70nm, the spacing of the parallel pole are 100 μm.
The present embodiment is above-mentioned based on (GaLu)2O3The solar blind UV detector of film is prepared with the following method,
Include the following steps:
Step 1: (GaLu) is prepared using solid sintering technology same as Example 12O3Ternary ceramics target；
Step 2: utilizing (GaLu)2O3Ternary ceramics target prepares solar blind UV detector
2.1 with (GaLu) made from step 12O3Ternary ceramics are as laser ablation target, with process acetone, dehydrated alcohol
The Sapphire Substrate for being cleaned by ultrasonic 15min respectively with deionized water etc. is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 300 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 8Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 600mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- metal Au 0.25g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after metal Au thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Comparative example 1
One kind of this comparative example is based on Ga2O3The solar blind UV detector of film, the detector successively wrap from bottom to up
Include c surface sapphire substrate, active layer, a pair of of parallel metal Au electrode, in which: the active layer is Ga2O3Film, the substrate
With a thickness of 0.43mm, the active layer with a thickness of 150nm, the electrode with a thickness of 55nm, between the parallel pole
Away from being 10 μm.
This comparative example is above-mentioned based on Ga2O3The solar blind UV detector of film is prepared with the following method, including
Following steps:
Step 1: preparation Ga is fired using solid sintering technology2O3Ceramic target
1.1 weigh 10g Ga2O315g deionized water, the ball grinder (ball being subsequently placed in planetary ball mill is added in powder
Grinding media is zirconia ceramics ball) in, ball milling 4h obtains finely dispersed powder；
The mixed-powder solution is weeded out zirconium ball postposition in a vacuum drying oven by 1.2, is dried in vacuo under the conditions of 110 DEG C
1g deionized water is added in 12h, cooled to room temperature after taking-up, using tablet press machine in 8MPa after being fully ground uniformly with stone roller alms bowl
Pressure depresses to the round blank of diameter 27.5mm, thickness 2mm；
1.3 are placed in the blank in the crucible in vacuum tube furnace, and the identical powder of ingredient is put around it
(15.000g).Tube furnace is warming up to 1300 DEG C and keeps the temperature 3h, subsequent cooled to room temperature obtains of the present invention
Ga2O3Ceramic target.
Step 2 utilizes Ga2O3Ceramic target prepares solar blind UV detector
2.1 with Ga made from step 12O3Ceramics are used as laser ablation target, with process acetone, dehydrated alcohol and deionization
The Sapphire Substrate that water etc. is cleaned by ultrasonic 15min respectively is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 700 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 4Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 300mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- metal Au 0.15g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after metal Au thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Apply the voltage of 10V between the device electrode made from this comparative example and carries out light with monochromatic light exposure sample surfaces
Electric performance test.The result shows that device dark current Idark=10.6pA, relaxation response time τd2For 0.661s.It can be seen that the device
Dark current be substantially higher in above-mentioned (GaLu)2O3The detector of base, and response speed is slower.(GaLu) is embodied2O3Base is visited
Survey the more excellent solar blind UV detectivity of device.Test result is shown in Fig. 7.
Embodiment 5
As shown in figure 9, one kind of the present embodiment is based on (GaSc)2O3The solar blind UV detector of ternary alloy film, institute
State detector successively includes c surface sapphire substrate, active layer, a pair of of parallel metal Au electrode from bottom to up, in which: described active
Layer is (GaSc) of (- 201) orientation2O3Ternary alloy film.The substrate with a thickness of 0.43mm, the thickness of the active layer
For 150nm, the Au electrode with a thickness of 50nm, the spacing of the parallel pole is 10 μm.
The present embodiment is above-mentioned based on (GaSc)2O3The solar blind UV detector of ternary alloy film is with the following method
It is prepared, includes the following steps:
Step 1: (GaSc) is prepared using solid sintering technology firing2O3Ternary ceramics target
1.1 Ga in molar ratio2O3: Sc2O3=95:5 weighs 9.627g Ga2O3Powder and 0.373g Sc2O3Powder, mixing
Afterwards, 15g deionized water is added, is subsequently placed in the ball grinder in planetary ball mill (ball-milling medium is zirconia ceramics ball),
Ball milling 4h, obtains mixed-powder；
The mixed-powder solution is weeded out zirconium ball postposition in a vacuum drying oven by 1.2, is dried in vacuo under the conditions of 110 DEG C
1g deionized water is added in 12h, cooled to room temperature after taking-up, using tablet press machine in 8MPa after being fully ground uniformly with stone roller alms bowl
Pressure depresses to the round blank of diameter 27.5mm, thickness 2mm；
1.3 are placed in the blank in the crucible in vacuum tube furnace, and the identical powder of ingredient is put around it
(15.000g).Tube furnace is warming up to 1300 DEG C and keeps the temperature 3h, subsequent cooled to room temperature obtains of the present invention
(GaSc)2O3Ternary ceramics target.
Step 2 utilizes (GaSc)2O3Ternary ceramics target prepares solar blind UV detector
2.1 with (GaSc) made from step 12O3Ternary ceramics are as laser ablation target, with process acetone, dehydrated alcohol
The Sapphire Substrate for being cleaned by ultrasonic 15min respectively with deionized water etc. is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 700 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 4Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 300mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- metal Au 0.15g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after metal Au thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Made from the present embodiment (GaSc)2O3The XRD of ternary alloy film is composed as shown in Figure 10 entirely.It can be seen that in addition to
Outside the diffraction maximum of c surface sapphire substrate, has and only there are three diffraction maximums, be located near 18.9 °, 38.3 ° and 59.1 °, it is right
Compare Ga2O3Standard x RD spectrogram (JCPDS File No.41-1103) it is found that these three diffraction maximums correspond respectively to Ga2O3's
(- 201), (- 402) and (- 603) crystal face illustrate that (GaSc) of (- 201) orientation has successfully been made in the present embodiment2O3Ternary alloy three-partalloy
Film.
Figure 11 is made from the present embodiment (GaSc)2O3The I-V curve of solar blind UV electric explorer, it can be clearly seen that
I-V curve under light illumination be it is nonlinear, illustrate Au and (GaSc)2O3Schottky contacts are formd between film.Figure 12 is should
When m- current-responsive curve of the device under 10V operating voltage.As shown in Figure 12, under 10V bias, the dark current of the device
Very small (< 0.2pA) is much smaller than pure Ga2O3The dark current (~10.6pA) of base detector.This is because Sc2O3Band gap
(5.9eV) is greater than Ga2O3Band gap (4.9eV), Sc3+The incorporation of ion can significantly improve Ga2O3Band gap so that having
(GaSc) of more broad-band gap2O3The dark current of base detector significantly reduces.Meanwhile we use two fingers number relaxation equation I=I0+
Ae-t/τ1+Be-t/τ2Curve is fitted, device relaxation response time τ is obtainedr2And τd2Respectively 0.202s and 0.228s, it is bright
It is powerful and influential to be faster than pure Ga2O3Relaxation response time (the τ of base detectorr2=0.579s τd2=0.661s).This is because Sc3+Ion with
O2-Combination between ion can compare Ga3+Ion and O2-Combination between ion can be stronger, so that (GaSc)2O3Ternary alloy three-partalloy
Film is relative to pure Ga2O3Film has more hypoxemia vacancy concentration, and lower oxygen vacancy concentration causes in film in less trap
The heart, so that the relaxation response speed of device be promoted obviously to accelerate.Figure 17 is (GaSc)2O3With pure Ga2O3The wavelength of base detector is rung
Response curve has benefited from (GaSc)2O3Relatively broader band gap, (GaSc)2O3The peak response wavelength and cut-off wave of base detector
Length is relative to pure Ga2O3Blue shift obviously occurs for base detector, shows that it is more sensitive to solar blind UV.In conclusion
(GaSc)2O3Base detector is relative to pure Ga2O3Base detector has lower dark current, faster response speed and shorter
Cutoff wavelength, show to the more sensitive and quick detectivity of solar blind UV.
Embodiment 6
One kind of the present embodiment is based on (GaSc)2O3The solar blind UV detector of ternary alloy three-partalloy, the detector from down toward
On successively include c surface sapphire substrate, active layer, a pair of of parallel metal Au electrode, in which: the active layer is (GaSc)2O3Three
First alloy firm, the substrate with a thickness of 0.43mm, the active layer with a thickness of 150nm, the electrode with a thickness of
55nm, the spacing of the parallel pole are 10 μm.
The present embodiment is above-mentioned based on (GaSc)2O3The solar blind UV detector of film is prepared with the following method,
Include the following steps:
Step 1: (GaSc) is prepared using solid sintering technology firing2O3Ternary ceramics target
1.1 Ga in molar ratio2O3: Sc2O3=70:30 weighs 7.603g Ga2O3Powder and 2.397g Sc2O3Powder mixes
After conjunction, 15g deionized water is added, the ball grinder being subsequently placed in planetary ball mill (ball-milling medium is zirconia ceramics ball)
In, ball milling 4h obtains mixed-powder；
The mixed-powder solution is weeded out zirconium ball postposition in a vacuum drying oven by 1.2, is dried in vacuo under the conditions of 110 DEG C
1g deionized water is added in 12h, cooled to room temperature after taking-up, using tablet press machine in 8MPa after being fully ground uniformly with stone roller alms bowl
Pressure depresses to the round blank of diameter 27.5mm, thickness 2mm；
1.3 are placed in the blank in the crucible in vacuum tube furnace, and the identical powder of ingredient is put around it
(15.000g).Tube furnace is warming up to 1300 DEG C and keeps the temperature 3h, subsequent cooled to room temperature obtains of the present invention
(GaSc)2O3Ternary ceramics target.
Step 2 utilizes (GaSc)2O3Ternary ceramics target prepares solar blind UV detector
2.1 with (GaSc) made from step 12O3Ternary ceramics are as laser ablation target, with process acetone, dehydrated alcohol
The Sapphire Substrate for being cleaned by ultrasonic 15min respectively with deionized water etc. is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 700 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 4Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 300mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- metal Au 0.15g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after metal Au thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Apply the voltage of 10V between the device electrode made from the present embodiment and carries out light with monochromatic light exposure sample surfaces
Electric performance test.The result shows that the very low (I of the device dark currentdark< 0.2pA), response speed is very fast, the device relaxation response time
τr2And τd2Respectively 0.171s and 0.197s is shown to the preferable detectivity of solar blind UV.Test result is shown in figure respectively
13, Figure 14.
Embodiment 7
One kind of the present embodiment is based on (GaSc)2O3The solar blind UV detector of ternary alloy three-partalloy, the detector from down toward
On successively include c surface sapphire substrate, active layer, a pair of of parallel metal Al electrode, in which: the active layer is (GaSc)2O3Three
First alloy firm, the substrate with a thickness of 0.43mm, the active layer with a thickness of 300nm, the electrode with a thickness of
30nm, the spacing of the parallel pole are 50 μm.
The present embodiment is above-mentioned based on (GaSc)2O3The solar blind UV detector of film is prepared with the following method,
Include the following steps:
Step 1: (GaSc) is prepared using solid sintering technology same as Example 12O3Ternary ceramics target.
Step 2: utilizing (GaSc)2O3Ternary ceramics target prepares solar blind UV detector
2.1 with (GaSc) made from step 12O3Ternary ceramics are as laser ablation target, with process acetone, dehydrated alcohol
The Sapphire Substrate for being cleaned by ultrasonic 15min respectively with deionized water etc. is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 500 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 1Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 500mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- metal Al 0.10g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after metal Al thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Embodiment 8
One kind of the present embodiment is based on (GaSc)2O3The solar blind UV detector of ternary alloy three-partalloy, the detector from down toward
On successively include c surface sapphire substrate, active layer, a pair of of parallel metal Pt electrode, in which: the active layer is (GaSc)2O3Three
First alloy firm, the substrate with a thickness of 0.43mm, the active layer with a thickness of 200nm, the electrode with a thickness of
70nm, the spacing of the parallel pole are 100 μm.
The present embodiment is above-mentioned based on (GaSc)2O3The solar blind UV detector of film is prepared with the following method,
Include the following steps:
Step 1: (GaSc) is prepared using solid sintering technology same as Example 12O3Ternary ceramics target.
Step 2: utilizing (GaSc)2O3Ternary ceramics target prepares solar blind UV detector
2.1 with (GaSc) made from step 12O3Ternary ceramics are as laser ablation target, with process acetone, dehydrated alcohol
The Sapphire Substrate for being cleaned by ultrasonic 15min respectively with deionized water etc. is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 300 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 8Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 600mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- Pt metal 0.25g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after Pt metal thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Comparative example 2
One kind of this comparative example is based on Ga2O3The solar blind UV detector of film, the detector successively wrap from bottom to up
Include c surface sapphire substrate, active layer, a pair of of parallel metal Au electrode, in which: the active layer is Ga2O3Film, the substrate
With a thickness of 0.43mm, the active layer with a thickness of 150nm, the electrode with a thickness of 55nm, between the parallel pole
Away from being 10 μm.
This comparative example is above-mentioned based on Ga2O3The solar blind UV detector of film is prepared with the following method, including
Following steps:
Step 1: preparation Ga is fired using solid sintering technology2O3Ceramic target
1.1 weigh 10g Ga2O315g deionized water, the ball grinder (ball being subsequently placed in planetary ball mill is added in powder
Grinding media is zirconia ceramics ball) in, ball milling 4h obtains finely dispersed powder；
The mixed-powder solution is weeded out zirconium ball postposition in a vacuum drying oven by 1.2, is dried in vacuo under the conditions of 110 DEG C
1g deionized water is added in 12h, cooled to room temperature after taking-up, using tablet press machine in 8MPa after being fully ground uniformly with stone roller alms bowl
Pressure depresses to the round blank of diameter 27.5mm, thickness 2mm；
1.3 are placed in the blank in the crucible in vacuum tube furnace, and the identical powder of ingredient is put around it
(15.0000g).Tube furnace is warming up to 1300 DEG C and keeps the temperature 3h, subsequent cooled to room temperature obtains of the present invention
Ga2O3Ceramic target.
Step 2 utilizes Ga2O3Ceramic target prepares solar blind UV detector
2.1 with Ga made from step 12O3Ceramics are used as laser ablation target, with process acetone, dehydrated alcohol and deionization
The Sapphire Substrate that water etc. is cleaned by ultrasonic 15min respectively is packed into vacuum chamber together, and is evacuated to 10-4Pa；
2.2 after underlayer temperature is warming up to 700 DEG C, are passed through oxygen, so that air pressure is tieed up in entire film deposition process
It holds in 4Pa；It is then turned on substrate and target platform rotation, sets laser output energy as 300mJ/pulse, pulse recurrence frequency is
5Hz is then turned on laser and starts deposition film.Oxygen and heating are closed after depositing 30min, it is finally that sample is naturally cold in a vacuum
But to taking out after room temperature；
2.3 are placed in obtained film in the vacuum chamber on mask plate and being installed to vacuum evaporation plating machine, are subsequently mounted tungsten boat
And it is put into evaporation source --- metal Au 0.15g closes vacuum chamber, opens mechanical pump, preceding step valve, molecular pump, vacuum degree is evacuated to
10-4Pa slowly improves electric current hereinafter, be then turned on evaporation power supply, keeps electric current constant after metal Au thawing, opens
Baffle starts to be deposited.Electric current is slowly reduced after evaporation of metal, closes evaporation source, closes molecular pump, preceding step valve, mechanical pump,
And air valve is opened, finally obtain target MSM solar blind UV electric explorer.
Apply the voltage of 10V between the device electrode made from this comparative example and carries out light with monochromatic light exposure sample surfaces
Electric performance test.The result shows that device dark current Idark=10.6pA, relaxation response time τr2And τd2Respectively 0.579s and
0.661s, test result are shown in Figure 15, Figure 16 respectively.It can be seen that the dark current of device made from this comparative example is substantially higher in above-mentioned
(GaSc)2O3The detector of base, and response speed is slower.The comparative example is compared, (GaSc) of the invention has been embodied2O3Base detection
The more excellent solar blind UV detectivity of device.
Claims (9)
1. a kind of MSM type (GaMe)2O3Ternary alloy three-partalloy solar blind UV detector, it is characterised in that: the detector is from bottom to up
It successively include c surface sapphire substrate, active layer, a pair of of parallel pole, in which: the active layer is (GaMe)2O3Ternary alloy three-partalloy is thin
Film；The Me is any one of Lu or Sc.
2. MSM type (GaMe) according to claim 12O3Ternary alloy three-partalloy solar blind UV detector, it is characterised in that: institute
State active layer with a thickness of 150~300nm.
3. MSM type (GaMe) according to claim 12O3Ternary alloy three-partalloy solar blind UV detector, it is characterised in that: institute
State parallel pole with a thickness of 30~70nm.
4. MSM type (GaMe) according to claim 12O3Ternary alloy three-partalloy solar blind UV detector, it is characterised in that: institute
The spacing for stating parallel pole is 10~100 μm.
5. MSM type (GaMe) according to claim 12O3Ternary alloy three-partalloy solar blind UV detector, it is characterised in that: institute
Stating parallel pole material is any one of Pt, Au, Al or ITO.
6. the described in any item MSM types (GaMe) of Claims 1 to 52O3The preparation side of ternary alloy three-partalloy solar blind UV detector
Method, it is characterised in that: the described method comprises the following steps:
(1) substrate grown using c surface sapphire as film uses nitrogen after being cleaned by ultrasonic using cleaning solution to the substrate
Drying, is immediately placed in vacuum chamber；
(2) (GaMe) is used2O3Ceramic target, using pulsed laser ablation deposition, magnetron sputtering or electron beam evaporation method in step
Suddenly (1) pretreated c surface sapphire substrate surface deposits (GaMe) to form (- 201) orientation2O3Ternary alloy film；
(3) vapour deposition method, photoetching process or sputtering method are utilized, at (GaMe)2O3Ternary alloy film surface prepares parallel pole,
Obtain the MSM type (GaMe)2O3Ternary alloy three-partalloy solar blind UV detector.
7. MSM type (GaMe) according to claim 62O3The preparation method of ternary alloy three-partalloy solar blind UV detector, it is special
Sign is: (GaMe) that (- 201) are orientated in step (2)2O3Ternary alloy film is specifically to use pulsed laser ablation deposition side
Method is made, the specific process is as follows:
It utilizes (GaMe)2O3Ceramics be used as target, control underlayer temperature be 300~800 DEG C, pulsed laser energy be 200~
600mJ/Pulse, oxygen pressure are 1~8Pa, deposit to form (- 201) and take in step (1) pretreated c surface sapphire substrate surface
To (GaMe)2O3Ternary alloy film.
8. MSM type (GaMe) according to claim 72O3The preparation method of ternary alloy three-partalloy solar blind UV detector, it is special
Sign is: the sedimentation time is 10~60min.
9. MSM type (GaMe) according to claim 62O3The preparation method of ternary alloy three-partalloy solar blind UV detector, it is special
Sign is: described in step (2) (GaMe)2O3Ceramic target is made using solid sintering technology, and the specific method is as follows:
(a) Ga is weighed for the ratio of 95:5~70:30 in molar ratio2O3、Me2O3Powder is placed in ball grinder by powder, is added super
Ball milling is carried out after pure water, be uniformly mixed powder；
(b) step (a) the mixed-powder solution is screened out into zirconium ball postposition in a vacuum drying oven, is cooled to room temperature after dry,
Then it pulverizes, is pressed into disk；
(c) in air atmosphere, disk obtained by step (b) is placed in vacuum tube furnace, is burnt under the conditions of 1000~1400 DEG C
1~4h is made, (GaMe) of the present invention is obtained2O3Ceramics.
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| CN111276573A (en) * | 2020-02-18 | 2020-06-12 | 湖北大学 | Based on amorphous (GaLu)2O3Solar blind ultraviolet detector of film |
| CN113921627A (en) * | 2021-09-18 | 2022-01-11 | 厦门大学 | (In)xGa1-x）2O3Solar blind ultraviolet photoelectric detector and preparation method thereof |
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| CN106409963A (en) * | 2016-09-21 | 2017-02-15 | 浙江理工大学 | Zn: Ga2O3 film-based MSM structure solar-blind ultraviolet photoelectric detector and preparation method thereof |
| CN107507876A (en) * | 2017-08-28 | 2017-12-22 | 北京邮电大学 | A kind of β Ga2O3Base solar blind UV electric explorer array and preparation method thereof |
| CN109585593A (en) * | 2018-12-06 | 2019-04-05 | 湖北大学 | A kind of spontaneous polarization field enhanced ultraviolet optical detector and preparation method thereof based on BeZnOS quaternary alloy |
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| US20140284598A1 (en) * | 2013-03-22 | 2014-09-25 | University Of Central Florida Research Foundation, Inc. | Uv photodetectors having semiconductor metal oxide layer |
| CN106409963A (en) * | 2016-09-21 | 2017-02-15 | 浙江理工大学 | Zn: Ga2O3 film-based MSM structure solar-blind ultraviolet photoelectric detector and preparation method thereof |
| CN107507876A (en) * | 2017-08-28 | 2017-12-22 | 北京邮电大学 | A kind of β Ga2O3Base solar blind UV electric explorer array and preparation method thereof |
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| CN111276573B (en) * | 2020-02-18 | 2021-03-23 | 湖北大学 | Based on amorphous (GaLu)2O3Solar blind ultraviolet detector of film |
| CN113921627A (en) * | 2021-09-18 | 2022-01-11 | 厦门大学 | (In)xGa1-x）2O3Solar blind ultraviolet photoelectric detector and preparation method thereof |
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