CN111081799A - Zinc-gallium-oxygen ultraviolet detector and preparation method thereof - Google Patents
Zinc-gallium-oxygen ultraviolet detector and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title description 7
- 239000010408 film Substances 0.000 claims abstract description 58
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 229910007486 ZnGa2O4 Inorganic materials 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 239000010409 thin film Substances 0.000 claims abstract description 20
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 16
- 150000002259 gallium compounds Chemical class 0.000 claims abstract description 16
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 16
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 7
- 239000012159 carrier gas Substances 0.000 claims description 22
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 10
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 9
- 229920002120 photoresistant polymer Polymers 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 229910052594 sapphire Inorganic materials 0.000 claims description 9
- 239000010980 sapphire Substances 0.000 claims description 9
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052596 spinel Inorganic materials 0.000 claims description 5
- 239000011029 spinel Substances 0.000 claims description 5
- 238000001259 photo etching Methods 0.000 claims description 4
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 230000004298 light response Effects 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- -1 magnesium aluminate Chemical class 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 230000007547 defect Effects 0.000 abstract description 4
- 238000005191 phase separation Methods 0.000 abstract description 3
- 238000007747 plating Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000001459 lithography Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910003363 ZnMgO Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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Abstract
The invention provides ZnGa2O4An ultraviolet detector comprises a substrate and ZnGa sequentially compounded2O4A thin film and a metal interdigital electrode; the ZnGa compound2O4The film is obtained by taking an organic zinc compound as a zinc source, taking an organic gallium compound as a gallium source and taking high-purity oxygen as an oxygen source and depositing on the surface of a substrate by utilizing a metal organic compound chemical vapor deposition method. The invention uses the metal organic compound chemical vapor deposition method to prepare ZnGa2O4The film is used for reducing oxygen defects by increasing oxygen flow, increasing oxygen partial pressure and leading the prepared ZnGa to be2O4The thin film layer has high crystalline quality, no phase separation, and absorption interceptionSteep edge, and the like, thereby further containing ZnGa2O4The ultraviolet detector of the thin film layer has low dark current and high responsivity.
Description
Technical Field
The invention belongs to the technical field of ultraviolet detectors, and particularly relates to ZnGa2O4An ultraviolet detector and a preparation method thereof.
Background
The ultraviolet detection technology has wide application prospect in military and civil fields such as missile tail flame detection, flame sensing, air and water purification, air-to-air communication and the like. Ultraviolet radiation having a wavelength of less than 280nm is known as solar blind ultraviolet radiation, which hardly propagates to the earth's surface due to the blockage of the ozone layer in the air above the earth. The solar blind ultraviolet detector working in the solar blind waveband is not interfered by solar radiation, has higher sensitivity, and can be used for missile early warning and the like. In recent years, wide bandgap semiconductor ultraviolet detectors are considered to be third generation ultraviolet detectors that can replace vacuum photomultipliers and Si photomultipliers due to their advantages of small size, light weight, no need for filters during operation, no need for refrigeration, etc.
ZnGa2O4Is ZnO and Ga2O3The composite oxide has a spinel structure, belongs to a direct band gap semiconductor, has a forbidden band width of 4.4-5.0eV, and can be applied to the fields of ultraviolet photoelectric devices and the like within the range of 248-280nm in principle. ZnGa2O4Compared with ZnMgO, the structure phase splitting problem can be avoided; ZnGa2O4And Ga2O3Compared with the prior art, the method can realize electrical characteristic regulation and control and improve conductivity. And due to ZnGa2O4The method has the advantages of good stability and radiation resistance, high electron saturation drift velocity and the like. Thus, ZnGa2O4Is a candidate material for preparing solar blind ultraviolet detectors.
ZnGa is prepared by adopting pulse laser deposition and radio frequency magnetron sputtering2O4A film. ZnGa prepared by the two methods2O4The prepared ultraviolet detector has higher dark current, lower light responsivity and poorer device performance due to lower quality of film crystals and more defect states.
Disclosure of Invention
In view ofThe technical problem to be solved by the invention is to provide ZnGa2O4The ultraviolet detector provided by the invention has low dark current and high light responsivity.
The invention provides ZnGa2O4An ultraviolet detector comprises a substrate and ZnGa sequentially compounded2O4A thin film and a metal interdigital electrode;
the ZnGa compound2O4The film is obtained by taking an organic zinc compound as a zinc source, taking an organic gallium compound as a gallium source and taking high-purity oxygen as an oxygen source and depositing on the surface of a substrate by utilizing a metal organic compound chemical vapor deposition method.
Preferably, the ZnGa is2O4The film is of a spinel structure, grows along the (111), (222) and (333) orientations and is in a single orientation;
the ZnGa compound2O4The thickness of the film is 100-600 nm;
the ZnGa compound2O4The absorption cut-off edge of the film is 240-280 nm;
the ZnGa compound2O4The light response cut-off edge of the ultraviolet detector is 250-280 nm.
Preferably, the organic zinc compound is diethyl zinc and/or dimethyl zinc; the organic gallium compound is trimethyl gallium and/or triethyl gallium.
Preferably, the organic zinc compound takes high-purity nitrogen as a carrier gas, and the flow rate of the carrier gas is 5-20 sccm; the organic gallium compound takes high-purity nitrogen as carrier gas, and the flow rate of the carrier gas is 10-40 sccm; the flow rate of the oxygen is 100-400 sccm.
Preferably, the substrate is selected from a sapphire substrate, magnesium oxide or magnesium aluminate.
Preferably, the deposition temperature is 400-1100 ℃; the deposition time is 1-3 h; the degree of vacuum for deposition was 2X 102～1×104Pa。
Preferably, after the growth is finished, the temperature of the substrate is reduced to room temperature to obtain ZnGa2O4A film; said temperature reductionThe rate is 0.2-0.8 ℃/s.
Preferably, the metal interdigital electrode is a gold interdigital electrode, and the thickness of the metal interdigital electrode is 20-40 nm.
Preferably, indium particles are compounded on the surface of the interdigital electrode.
The invention also provides a preparation method of the ultraviolet detector, which comprises the following steps:
A) organic zinc compound is used as zinc source, organic gallium compound is used as gallium source, high-purity oxygen is used as oxygen source, and ZnGa is deposited on the surface of a substrate by utilizing a metal organic compound chemical vapor deposition method2O4A film;
B) in ZnGa2O4Forming an interdigital electrode mask on the thin film material by using negative photoresist photoetching, and removing the colloid mask after sputtering metal gold to obtain a metal interdigital electrode;
C) pressing In particles on the interdigital electrode to obtain ZnGa with an MSM structure2O4An ultraviolet detector.
Compared with the prior art, the invention provides ZnGa2O4An ultraviolet detector comprises a substrate and ZnGa sequentially compounded2O4A thin film and a metal interdigital electrode; the ZnGa compound2O4The film is obtained by taking an organic zinc compound as a zinc source, taking an organic gallium compound as a gallium source and taking high-purity oxygen as an oxygen source and depositing on the surface of a substrate by utilizing a metal organic compound chemical vapor deposition method. The invention uses the metal organic compound chemical vapor deposition method to prepare ZnGa2O4The film is used for reducing oxygen defects by increasing oxygen flow, increasing oxygen partial pressure and leading the prepared ZnGa to be2O4The thin film layer has the characteristics of high crystallization quality, no phase separation, steep absorption cut-off edge and the like, so that the ZnGa is contained2O4The ultraviolet detector of the thin film layer has low dark current and high responsivity.
Drawings
FIG. 1 shows ZnGa obtained in example 1 of the present invention2O4The structure schematic diagram of the ultraviolet detector;
FIG. 2 shows the present inventionZnGa obtained in example 12O4A powder X-ray diffraction pattern of the film;
FIG. 3 shows ZnGa obtained in example 1 of the present invention2O4A UV-VIS absorption spectrum of the film;
FIG. 4 shows ZnGa obtained in example 1 of the present invention2O4Scanning electron microscope pictures of the thin film;
FIG. 5 shows ZnGa obtained in example 1 of the present invention2O4A current-voltage characteristic curve of the ultraviolet detector;
FIG. 6 shows ZnGa obtained in inventive example 12O4A spectral response characteristic curve of the ultraviolet detector;
FIG. 7 shows ZnGa obtained in comparative example 12O4Powder X-ray diffraction pattern of the film.
Detailed Description
The invention provides ZnGa2O4An ultraviolet detector comprises a substrate and ZnGa sequentially compounded2O4A thin film and a metal interdigital electrode;
the ZnGa compound2O4The film is obtained by taking an organic zinc compound as a zinc source, taking an organic gallium compound as a gallium source and taking high-purity oxygen as an oxygen source and depositing on the surface of a substrate by utilizing a metal organic compound chemical vapor deposition method.
The ultraviolet detector provided by the present invention includes a substrate, which is well known to those skilled in the art, and is not particularly limited, and a sapphire substrate, magnesium oxide or magnesium aluminate is preferred in the present invention.
The ultraviolet detector also comprises ZnGa compounded on the substrate2O4A film.
Wherein the ZnGa is2O4The film is obtained by taking an organic zinc compound as a zinc source, taking an organic gallium compound as a gallium source and taking high-purity oxygen as an oxygen source and depositing on the surface of a substrate by utilizing a metal organic compound chemical vapor deposition method.
The invention takes an organic zinc compound as a zinc source, wherein the organic zinc compound is diethyl zinc and/or dimethyl zinc, and diethyl zinc is preferred. The organic zinc compound takes high-purity nitrogen as a carrier gas, and the flow rate of the carrier gas is 5-20 sccm, preferably 10-15 sccm.
The invention takes an organic gallium compound as a gallium source, wherein the organic gallium compound is trimethyl gallium and/or triethyl gallium, and is preferably trimethyl gallium. The organic gallium compound takes high-purity nitrogen as a carrier gas, and the flow rate of the carrier gas is 10-40 sccm, preferably 20-30 sccm.
The invention takes high-purity oxygen as an oxygen source, and the flow rate of the oxygen is 100-400 sccm, preferably 200-300 sccm.
The invention adopts the metal organic compound chemical vapor deposition method to carry out single orientation ZnGa2O4Preparation of a film, wherein the monoriented ZnGa2O4The preparation of the film is carried out in a metal organic compound chemical vapor deposition device.
Firstly, putting a substrate into a cavity of metal organic compound chemical vapor deposition equipment, wherein the substrate is preferably placed in a growth chamber of MOCVD equipment after being cleaned and dried. The distance between the base and the gas spray gun is adjusted within the range of 10-40 cm by moving the height of the base of the substrate.
And after the substrate is placed in the cavity, vacuumizing the cavity. Then heating the substrate to the temperature of deposition reaction, namely depositing ZnGa on the surface of the substrate2O4A film.
The deposition temperature is 400-1100 ℃, and preferably 800-900 ℃; the deposition time is 1-3 h, preferably 1.5-2.5 h; the degree of vacuum for deposition was 2X 102～1×104Pa, preferably 8X 102～8×103Pa。
After the deposition growth is finished, the temperature of the substrate is reduced to room temperature to obtain ZnGa2O4A film; the cooling rate is 0.2-0.8 ℃/s, preferably 0.4-0.6 ℃/s. In the present invention, the room temperature is defined as 25. + -. 5 ℃.
The ZnGa compound2O4The film is spinel structure, and is arranged along (111), (222), (333)And (4) performing oriented growth, namely performing single orientation. The ZnGa compound2O4The absorption cut-off edge of the film is 240-280 nm. The ZnGa compound2O4The thickness of the film is 100 to 600nm, preferably 200 to 500nm, and more preferably 300 to 400 nm.
The ultraviolet detector also comprises a ZnGa compound2O4Metal interdigital electrodes of the film. The metal interdigital electrode is a gold interdigital electrode, and the thickness of the metal interdigital electrode is 20-40 nm, preferably 25-35 nm.
In the invention, indium particles are compounded on the surface of the interdigital electrode.
The ZnGa compound2O4The light response cut-off edge of the ultraviolet detector is 250-280 nm.
The invention also provides a preparation method of the ultraviolet detector, which comprises the following steps:
A) organic zinc compound is used as zinc source, organic gallium compound is used as gallium source, high-purity oxygen is used as oxygen source, and ZnGa is deposited on the surface of a substrate by utilizing a metal organic compound chemical vapor deposition method2O4A film;
B) in ZnGa2O4Forming an interdigital electrode mask on the thin film material by using negative photoresist photoetching, and removing the colloid mask after sputtering metal gold to obtain a metal interdigital electrode;
C) pressing In particles on the interdigital electrode to obtain ZnGa with an MSM structure2O4An ultraviolet detector.
Firstly, the method utilizes the metal organic compound chemical vapor deposition method to deposit ZnGa on the surface of a substrate2O4A film. The specific method is as described above, and is not described herein again.
Obtaining ZnGa2O4After the film, in ZnGa2O4And forming an interdigital electrode mask on the film material by using negative photoresist photoetching, and removing the colloid mask after sputtering metal gold to obtain the metal interdigital electrode.
The method for sputtering the metallic gold is not particularly limited, and a film plating machine can be adopted to prepare the metallic gold electrode film, wherein the sputtering current of the film plating machine is 5-8 mA, and preferably 6-7 mA.
And then removing the colloid mask through ultrasound to obtain the metal interdigital electrode. The ultrasonic time is preferably 3-5 min.
Finally, pressing In particles on the metal interdigital electrode to obtain ZnGa with the MSM structure2O4An ultraviolet detector.
The invention uses the metal organic compound chemical vapor deposition method to prepare ZnGa2O4The film is used for reducing oxygen defects by increasing oxygen flow, increasing oxygen partial pressure and leading the prepared ZnGa to be2O4The thin film layer has the characteristics of high crystallization quality, no phase separation, steep absorption cut-off edge and the like, so that the ZnGa is contained2O4The ultraviolet detector of the thin film layer has low dark current and high responsivity.
For further understanding of the present invention, the ZnGa provided by the present invention is described below in conjunction with examples2O4The ultraviolet detector and the method for manufacturing the same are illustrated, and the scope of the present invention is not limited by the following examples.
Example 1
Putting the cleaned sapphire substrate into an MOCVD growth chamber, adjusting the growth temperature to 850 ℃ and the pressure to be 1 multiplied by 103Pa. Diethyl zinc was used as the zinc source, trimethyl gallium as the gallium source, and the carrier gas flow rate for the zinc source was 5sccm and the carrier gas flow rate for the gallium source was 10 sccm. The flow rate of oxygen was 300sccm, which is much greater than the flow rates of the zinc source and the gallium source. Growing for 2h, closing the organic source and oxygen, reducing the substrate temperature to room temperature at 0.6 ℃/s to obtain ZnGa with the thickness of about 300nm2O4A film.
In ZnGa2O4A50-pair interdigital electrode mask having a pitch of 10 μm and a length of 500 μm was formed on the thin film material using negative resist lithography. And putting the obtained sample into a small-sized film plating machine, and sputtering metal gold under the condition that the pressure is 8Pa and the current is 6 mA. The colloid mask is then removed by ultrasound. Pressing In particles on the interdigital electrode to obtain ZnGa with MSM structure2O4An ultraviolet detector. The device structure is shown in fig. 1.
To the embodimentsZnGa obtained in 12O4The film was subjected to powder X-ray diffraction (XRD) measurement, and the spectrum thereof was found to be as shown in FIG. 2. As can be seen from the figure, ZnGa is prepared on a sapphire substrate2O4The film is of a spinel structure. The crystal grows along the (111) and (333) orientations, is in a single orientation, and has a relatively sharp XRD absorption peak, which indicates that the crystal quality is high.
For ZnGa obtained in example 12O4The film is subjected to ultraviolet-visible light absorption spectrum test, and the obtained spectrum is shown in figure 3, from which it can be seen that the ZnGa prepared2O4The film has a steep single light absorption cut-off edge, which is around 250 nm.
For ZnGa obtained in example 12O4The film was subjected to Scanning Electron Microscope (SEM) testing, and its surface pattern was as shown in fig. 4. As can be seen from the figure, ZnGa is produced2O4The surface of the film is smooth, and the crystal quality is good.
For ZnGa obtained in example 12O4The ultraviolet detector is used for testing current-voltage characteristic curves under dark state and 254nm illumination, and the obtained spectrum is shown as 5. As can be seen from the figure, ZnGa is produced2O4The dark current of the ultraviolet detector under 10V is 2.38nA, the photocurrent is 0.94mA, and the light-dark suppression ratio is 4x106Description of the ZnGa prepared2O4The ultraviolet detector has a low dark current.
For ZnGa obtained in example 12O4The ultraviolet detector performs a photoresponse characteristic test to obtain a spectrum shown as 6. As can be seen from the figure, ZnGa is produced2O4The light responsivity of the ultraviolet detector under 10V is 155A/W, the cut-off edge of-3 dB is 254nm, which shows that the prepared ZnGa2O4The ultraviolet detector has high light responsivity.
Example 2
Putting the cleaned sapphire substrate into an MOCVD growth chamber, adjusting the growth temperature to 900 ℃, and adjusting the pressure to 1 × 103Pa. Using diethylzinc as the zinc source, trimethylgallium as the gallium source, zincThe source carrier gas flow rate was 5sccm and the gallium source carrier gas flow rate was 10 sccm. The flow rate of oxygen was 300sccm, which is much greater than the flow rates of the zinc source and the gallium source. Growing for 2h, closing the organic source and oxygen, reducing the substrate temperature to room temperature at 0.6 ℃/s to obtain ZnGa with the thickness of about 300nm2O4A film.
In ZnGa2O4A50-pair interdigital electrode mask having a pitch of 10 μm and a length of 500 μm was formed on the thin film material using negative resist lithography. And putting the obtained sample into a small-sized film plating machine, and sputtering metal gold under the condition that the pressure is 8Pa and the current is 6 mA. The colloid mask is then removed by ultrasound. Pressing In particles on the interdigital electrode to obtain ZnGa with MSM structure2O4An ultraviolet detector.
For ZnGa obtained in example 22O4The ultraviolet detector is tested to obtain that the light responsivity of the ultraviolet detector is 120A/W under 10V, and the cut-off edge of the ultraviolet detector is 256nm at minus 3 dB.
Example 3
Putting the cleaned sapphire substrate into an MOCVD growth chamber, adjusting the growth temperature to 850 ℃, and adjusting the pressure to 1 × 103Pa. Diethyl zinc was used as the zinc source, trimethyl gallium as the gallium source, and the carrier gas flow rate for the zinc source was 5sccm and the carrier gas flow rate for the gallium source was 10 sccm. The flow rate of oxygen was 400sccm, which is much greater than the flow rates of the zinc source and the gallium source. Growing for 1h, closing the organic source and oxygen, and reducing the substrate temperature to room temperature at 0.6 ℃/s to obtain ZnGa with the thickness of about 300nm2O4A film.
In ZnGa2O430 pairs of interdigital electrode masks with a pitch of 10 μm and a length of 500 μm are formed on the thin film material using negative photoresist lithography. And putting the obtained sample into a small-sized film plating machine, and sputtering metal gold under the condition that the pressure is 8Pa and the current is 4 mA. The colloid mask is then removed by ultrasound. Pressing In particles on the interdigital electrode to obtain ZnGa with MSM structure2O4An ultraviolet detector.
For ZnGa obtained in example 32O4And testing by an ultraviolet detector to obtain that the light responsivity of the ultraviolet detector is 99A/W under 10V, and the cut-off edge of-3 dB is 261 nm.
Comparative example 1
Putting the cleaned sapphire substrate into an MOCVD growth chamber, adjusting the growth temperature to 850 ℃ and the pressure to be 1 multiplied by 103Pa. Diethyl zinc was used as the zinc source, trimethyl gallium as the gallium source, and the carrier gas flow rate for the zinc source was 5sccm and the carrier gas flow rate for the gallium source was 10 sccm. The flow rate of oxygen was 30 sccm. Growing for 2h, closing the organic source and oxygen, reducing the substrate temperature to room temperature at 0.6 ℃/s to obtain ZnGa with the thickness of about 300nm2O4A film. ZnGa obtained in comparative example 12O4The film was subjected to powder X-ray diffraction (XRD) measurement, and its spectrum was as shown in FIG. 7. As can be seen, in addition to the 111,222,333 peak, there are 220 and 440 peaks, which are non-mono-oriented films, as shown.
In ZnGa2O4A50-pair interdigital electrode mask having a pitch of 10 μm and a length of 500 μm was formed on the thin film material using negative resist lithography. And putting the obtained sample into a small-sized film plating machine, and sputtering metal gold under the condition that the pressure is 8Pa and the current is 6 mA. The colloid mask is then removed by ultrasound. Pressing In particles on the interdigital electrode to obtain ZnGa with MSM structure2O4An ultraviolet detector.
ZnGa obtained in comparative example 12O4The ultraviolet detector is tested to obtain that the light responsivity of the ZnGa material under 10V is 0.1A/W and the cut-off edge of-3 dB is 256nm, which proves that the ZnGa material obtained by the method2O4The ultraviolet detector has low responsivity and poor performance.
Comparative example 2
Putting the cleaned sapphire substrate into an MOCVD growth chamber, adjusting the growth temperature to 350 ℃, and adjusting the pressure to 1 × 103Pa. Diethyl zinc was used as the zinc source, trimethyl gallium as the gallium source, and the carrier gas flow rate for the zinc source was 5sccm and the carrier gas flow rate for the gallium source was 10 sccm. The flow rate of oxygen was 300 sccm. Growing for 3h, closing the organic source and oxygen, reducing the substrate temperature to room temperature at 0.6 ℃/s to obtain ZnGa with the thickness of about 300nm2O4A film.
In ZnGa2O450 is formed on the thin film material using negative photoresist lithographyThe interdigital electrode was masked with a pitch of 10 μm and a length of 500. mu.m. And putting the obtained sample into a small-sized film plating machine, and sputtering metal gold under the condition that the pressure is 8Pa and the current is 6 mA. The colloid mask is then removed by ultrasound. Pressing In particles on the interdigital electrode to obtain ZnGa with MSM structure2O4An ultraviolet detector.
ZnGa obtained in comparative example 22O4The ultraviolet detector is tested to obtain that the light responsivity of the ZnGa material under 10V is 0.07A/W and the cut-off edge of-3 dB is 253nm, which proves that the ZnGa material obtained by the method2O4The ultraviolet detector has low responsivity and poor performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. ZnGa2O4The ultraviolet detector is characterized by comprising a substrate and ZnGa which are compounded in sequence2O4A thin film and a metal interdigital electrode;
the ZnGa compound2O4The film is obtained by taking an organic zinc compound as a zinc source, taking an organic gallium compound as a gallium source and taking high-purity oxygen as an oxygen source and depositing on the surface of a substrate by utilizing a metal organic compound chemical vapor deposition method.
2. Ultraviolet detector according to claim 1, characterized in that the ZnGa2O4The film is of a spinel structure, grows along the (111), (222) and (333) orientations and is in a single orientation;
the ZnGa compound2O4The thickness of the film is 100-600 nm;
the ZnGa compound2O4The absorption cut-off edge of the film is 240-280 nm;
the ZnGa compound2O4The light response cut-off edge of the ultraviolet detector is 250-280 nm.
3. The uv detector according to claim 1, characterized in that the organozinc compound is diethylzinc and/or dimethylzinc; the organic gallium compound is trimethyl gallium and/or triethyl gallium.
4. The ultraviolet detector according to claim 1, wherein the organozinc compound uses high-purity nitrogen as a carrier gas, and the flow rate of the carrier gas is 5-20 sccm; the organic gallium compound takes high-purity nitrogen as carrier gas, and the flow rate of the carrier gas is 10-40 sccm; the flow rate of the oxygen is 100-400 sccm.
5. The uv detector of claim 1, wherein the substrate is selected from a sapphire substrate, magnesium oxide or magnesium aluminate.
6. The ultraviolet detector according to claim 1, wherein the deposition temperature is 400-1100 ℃; the deposition time is 1-3 h; the degree of vacuum for deposition was 2X 102～1×104Pa。
7. The UV detector of claim 1, wherein after the growth is completed, the substrate temperature is reduced to room temperature to obtain ZnGa2O4A film; the cooling rate is 0.2-0.8 ℃/s.
8. The ultraviolet detector according to claim 1, wherein the metal interdigital electrode is a gold interdigital electrode, and the thickness of the metal interdigital electrode is 20-40 nm.
9. The ultraviolet detector according to claim 1, characterized in that indium particles are compounded on the surface of the interdigital electrode.
10. A method for preparing an ultraviolet detector according to any one of claims 1 to 9, comprising the steps of:
A) organic zinc compound is used as zinc source, organic gallium compound is used as gallium source, high-purity oxygen is used as oxygen source, and ZnGa is deposited on the surface of a substrate by utilizing a metal organic compound chemical vapor deposition method2O4A film;
B) in ZnGa2O4Forming an interdigital electrode mask on the thin film material by using negative photoresist photoetching, and removing the colloid mask after sputtering metal gold to obtain a metal interdigital electrode;
C) pressing In particles on the interdigital electrode to obtain ZnGa with an MSM structure2O4An ultraviolet detector.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111628019A (en) * | 2020-06-28 | 2020-09-04 | 中国科学院长春光学精密机械与物理研究所 | Gallium sesquioxide solar blind ultraviolet detector and preparation method thereof |
| CN111816715A (en) * | 2020-08-24 | 2020-10-23 | 中国科学院长春光学精密机械与物理研究所 | Zinc oxide nanowire array ultraviolet detector and preparation method thereof |
| CN113192992A (en) * | 2021-04-29 | 2021-07-30 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of semiconductor thin film composite structural member |
| CN114657637A (en) * | 2022-03-10 | 2022-06-24 | 中国科学院长春光学精密机械与物理研究所 | Zinc gallate thin film and preparation method thereof, ultraviolet detector and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107758726A (en) * | 2017-09-30 | 2018-03-06 | 南京理工大学 | One kind can be used for deep ultraviolet pole weak light detection high-purity nm structure ZnGa2O4Preparation method |
| TWI643320B (en) * | 2017-09-12 | 2018-12-01 | 鼎元光電科技股份有限公司 | Solar-blind detecting device with wide bandgap oxide |
-
2019
- 2019-12-11 CN CN201911267465.2A patent/CN111081799A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| TWI643320B (en) * | 2017-09-12 | 2018-12-01 | 鼎元光電科技股份有限公司 | Solar-blind detecting device with wide bandgap oxide |
| US20190081192A1 (en) * | 2017-09-12 | 2019-03-14 | Tyntek Corporation | Solar-blind detecting device with wide-bandgap oxide |
| CN107758726A (en) * | 2017-09-30 | 2018-03-06 | 南京理工大学 | One kind can be used for deep ultraviolet pole weak light detection high-purity nm structure ZnGa2O4Preparation method |
Non-Patent Citations (1)
| Title |
|---|
| RAY-HUA HORNG ET AL.: ""Epitaxial growth of ZnGa2O4:A new, deep ultraviolet semiconductor candidate"", 《CRYSTAL GROWTH & DESIGN》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111628019A (en) * | 2020-06-28 | 2020-09-04 | 中国科学院长春光学精密机械与物理研究所 | Gallium sesquioxide solar blind ultraviolet detector and preparation method thereof |
| CN111816715A (en) * | 2020-08-24 | 2020-10-23 | 中国科学院长春光学精密机械与物理研究所 | Zinc oxide nanowire array ultraviolet detector and preparation method thereof |
| CN111816715B (en) * | 2020-08-24 | 2024-03-08 | 中国科学院长春光学精密机械与物理研究所 | Zinc oxide nanowire array ultraviolet detector and preparation method thereof |
| CN113192992A (en) * | 2021-04-29 | 2021-07-30 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of semiconductor thin film composite structural member |
| CN113192992B (en) * | 2021-04-29 | 2023-03-24 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of semiconductor thin film composite structural member |
| CN114657637A (en) * | 2022-03-10 | 2022-06-24 | 中国科学院长春光学精密机械与物理研究所 | Zinc gallate thin film and preparation method thereof, ultraviolet detector and preparation method thereof |
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