CN110923666B - Zinc-gallium-oxygen material film and preparation method thereof - Google Patents
Zinc-gallium-oxygen material film and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 28
- 239000011029 spinel Substances 0.000 claims abstract description 9
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 55
- 239000012159 carrier gas Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 150000002259 gallium compounds Chemical class 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 8
- 150000003752 zinc compounds Chemical class 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 6
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 5
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-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
- 238000004519 manufacturing process Methods 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 14
- 230000004044 response Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 229910007486 ZnGa2O4 Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010980 sapphire Substances 0.000 description 4
- 229910052594 sapphire Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 229910003363 ZnMgO Inorganic materials 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- -1 magnesium aluminate Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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- 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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Abstract
The invention provides a zinc-gallium-oxygen material film, wherein the atomic ratio of zinc to gallium in the zinc-gallium-oxygen material film is more than 1:2, and the zinc-gallium-oxygen material film is in a spinel structure. The atomic ratio of zinc and gallium to the conventional 1:2, the proportion of gallium atoms is lower, and when the stoichiometric ratio of Zn and Ga is changed, the ZnGaO material formed in a certain range can still maintain the ZnGa of spinel2O4A crystal structure. The zinc-gallium-oxygen material film effectively shortens the response time of the ZnGaO ultraviolet detector on the premise of not changing other performance parameters. Has potential application prospect in the preparation aspect of photoelectric devices. In addition, the preparation process of the zinc-gallium-oxygen material film provided by the invention is simple, and the reaction process is easy to control.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a zinc-gallium-oxygen material film and a preparation method thereof.
Background
The ultraviolet detection technology can be used for military communication, missile tail flame detection, fire early warning, environmental monitoring, biological effect and the like, and can be widely applied to military affairs and civil use. Ultraviolet rays with wavelengths below 280nm in solar radiation are almost absent on the earth's surface due to the strong absorption of the atmosphere, and this ultraviolet band is figuratively called the solar blind band. The solar blind ultraviolet detector working in the wave band is not interfered by solar radiation, has higher sensitivity and has outstanding advantages in the aspect of weak signal detection.
Currently, commercially available ultraviolet detectors mainly include silicon detectors, photomultiplier tubes, and semiconductor detectors. The silicon-based ultraviolet phototube needs an additional optical filter, the photomultiplier needs to work under high voltage, and the photomultiplier has the advantages of heavy volume, low efficiency, easy damage and higher cost, and has certain limitation on practical application. Compared with silicon detectors and photomultiplier tubes, semiconductor materials are attracting much attention because of their advantages of portability, low cost, high responsivity, etc.
The ZnGaO material is ZnO and Ga2O3Wherein the most common crystal structure is ZnGa2O4The crystal 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 in 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. However, the conventional ZnGa compound2O4The ultraviolet detector prepared from the material has longer photoresponse time, and the performance of the ultraviolet detector is influenced.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a zinc-gallium-oxygen material thin film and a preparation method thereof, wherein the crystal structure of the zinc-gallium-oxygen material thin film provided by the present invention is a spinel structure, and the obtained ultraviolet detector has a short light response time.
The invention provides a zinc-gallium-oxygen material film, wherein the atomic ratio of zinc to gallium in the zinc-gallium-oxygen material film is more than 1:2, and the zinc-gallium-oxygen material film is in a spinel structure.
Preferably, the absorption cut-off edge of the film is located at 250 ± 10 nm.
The invention also provides a preparation method of the zinc-gallium-oxygen material film, which comprises the following steps:
an organic zinc compound is used as a zinc source, an organic gallium compound is used as a gallium source, high-purity oxygen is used as an oxygen source, and a metal organic compound chemical vapor deposition method is utilized to grow a zinc-gallium-oxygen material film on the surface of a substrate.
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 carrier gas, the initial flow rate of the carrier gas is 5-20 mL/min, the flow rate of the carrier gas is gradually increased in the process of growing the zinc-gallium-oxygen material film, and the increasing rate is 0-4.5 mL/30 min; the duration of increasing the flow of the carrier gas is 0-5 hours;
the organic gallium compound takes high-purity nitrogen as carrier gas, the initial flow rate of the carrier gas is 5-40 mL/min, the flow of the carrier gas is gradually reduced in the process of growing the zinc-gallium-oxygen material film, and the reduction rate is 0-4.5 mL/30 min; the duration of reducing the flow of the carrier gas is 0 to 5 hours.
Preferably, the flow rate of the oxygen is 100-1000 mL/min.
Preferably, the growth time is 0.5-5 h, the growth starting temperature is 500-800 ℃, the growth temperature is gradually reduced at a cooling rate of 0.01-5 ℃/min in the process of growing the zinc-gallium-oxygen material film, the cooling time is 0.5-5 h, and the cooling time is less than or equal to the growth time;
the growth was carried out under a vacuum of 2 x 102～1*104Pa。
Preferably, after the growth is finished, the temperature of the substrate is reduced to room temperature, and the cooling rate is 0.1-50 ℃/min.
Compared with the prior art, the invention provides the zinc-gallium-oxygen material film, the atomic ratio of zinc to gallium in the zinc-gallium-oxygen material film is more than 1:2, and the zinc-gallium-oxygen material film is in a spinel structure. The atomic ratio of zinc and gallium to the conventional 1:2, the proportion of gallium atoms is higher than that of gallium atomsLow, when the stoichiometric ratio of Zn and Ga is changed, the ZnGa of spinel can be still maintained by forming ZnGaO material in a certain range2O4A crystal structure. The zinc-gallium-oxygen material film effectively shortens the response time of the ZnGaO ultraviolet detector on the premise of not changing other performance parameters. Has potential application prospect in the preparation aspect of photoelectric devices. In addition, the preparation process of the zinc-gallium-oxygen material film provided by the invention is simple, and the reaction process is easy to control.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of the ZnGaO film of example 1;
FIG. 2 is an electron spectroscopy (EDS) spectrum of the ZnGaO film of example 1;
FIG. 3 is a UV-Vis spectrum of the ZnGaO film of example 1;
FIG. 4 is a graph showing the photoresponse of ZnGaO UV detectors fabricated from films obtained in example 1 and comparative example 1;
FIG. 5 is an IV curve of ZnGaO UV detectors made from films obtained in example 1 and comparative example 1;
fig. 6 is a graph showing the optical switching curves of ZnGaO ultraviolet detectors prepared from the films obtained in example 1 and comparative example 1.
Detailed Description
The invention provides a zinc-gallium-oxygen material film, wherein the atomic ratio of zinc to gallium in the zinc-gallium-oxygen material film is more than 1:2, and the zinc-gallium-oxygen material film is in a spinel structure.
In the invention, the chemical formula of the zinc-gallium-oxygen material film is ZnxGayO4And x: y > 1:2, preferably 1:1.6 ≧ x: y > 1:2
In some embodiments of the invention, the atomic ratio of zinc to gallium is 1: 1.7, 1: 1.92, 1: 1.88, 1: 1.65, 1:1.6, 1: 1.98, 1: 1.9 or 1: 1.62.
the crystalline phase of the zinc-gallium-oxygen film is ZnGa2O4The structure has the light absorption cut-off edge positioned at 250 +/-10 nm and the absorption edge is very steep.
The film with large area can be prepared, and the light absorption property and the crystal structure of the film are very uniform in all ranges, wherein the area of the film is (0.1-6) cm multiplied by (0.1-6).
The invention also provides a preparation method of the zinc-gallium-oxygen material film, which comprises the following steps:
an organic zinc compound is used as a zinc source, an organic gallium compound is used as a gallium source, high-purity oxygen is used as an oxygen source, and a metal organic compound chemical vapor deposition method is utilized to grow a zinc-gallium-oxygen material film on the surface of a substrate.
In the invention, the atomic ratio of zinc to gallium in the zinc-gallium-oxygen material film can be made to be more than 1:2 through three ways.
(1) Gradually reducing the carrier gas flow of the gallium source in the growth process;
(2) gradually increasing the carrier gas flow of the zinc source in the growth process;
(3) the growth temperature was gradually lowered.
In the above three modes, one mode may be adopted alone, or any two or more of the three modes may be combined.
Specifically, before carrying out the metal organic compound chemical vapor deposition, the substrate is cleaned, and the method comprises the following steps:
the substrate was washed sequentially with trichloroethylene, acetone and ethanol and then blown dry with dry nitrogen.
The substrate is sapphire, magnesium oxide, zinc oxide or magnesium aluminate, and is preferably sapphire.
Then, placing the substrate into MOCVD growth equipment, and adjusting the initial growth temperature to be 500-800 ℃, wherein the vacuum degree of a growth chamber in the growth equipment is 2 x 102～1*104Pa, preferably 8X 102～5×103Pa。
The organic zinc compound is diethyl zinc and/or dimethyl zinc; the organic gallium compound is trimethyl gallium and/or triethyl gallium.
The molar concentration ratio of zinc and gallium was adjusted using different ratios of high purity nitrogen carrier gas.
The organic zinc compound takes high-purity nitrogen as carrier gas, the initial flow rate of the carrier gas is 5-20 mL/min, preferably 10-15 mL/min, the flow of the carrier gas is gradually increased in the process of growing the zinc-gallium-oxygen material film, the increasing rate is 0-4.5 mL/30min, preferably 0.5-4 mL/30min, and further preferably 1-3 mL/30 min; the duration time for increasing the flow rate of the carrier gas is 0-5 hours, preferably 1-5 hours, and further preferably 2-4 hours;
the organic gallium compound takes high-purity nitrogen as carrier gas, the initial flow rate of the carrier gas is 5-40 mL/min, preferably 10-35 mL/min, and further preferably 15-30 mL/min, the flow of the carrier gas is gradually reduced in the process of growing the zinc-gallium-oxygen material film, and the reduction rate is 0-4.5 mL/30min, preferably 0.5-4 mL/30min, and further preferably 1-3 mL/30 min; the duration of reducing the flow rate of the carrier gas is 0 to 5 hours, preferably 1 to 5 hours, and more preferably 2 to 4 hours.
The flow rate of the oxygen is 100-1000 mL/min.
When the thin film is grown, the growth time is 0.5-5 h, preferably 1-4 h, and the initial growth temperature is 500-800 ℃, preferably 600-700 ℃.
In the process of growing the zinc-gallium-oxygen material film, gradually reducing the growth temperature at a cooling rate of 0.01-5 ℃/min, preferably at a cooling rate of 0.05-5 ℃/min, and further preferably at a cooling rate of 0.1-3 ℃/min; the cooling time is 0.5-5 h, and the cooling time is not more than the growth time. In the invention, the temperature reduction process can be carried out intermittently or continuously.
And after the growth is finished, reducing the temperature of the substrate to room temperature, wherein the cooling rate is 0.1-50 ℃/min.
The structural characterization method of the ZnGaO film comprises the following steps: the crystal structure was characterized using X-ray diffraction (XRD). Photoelectron spectroscopy (EDS) was used to characterize the elemental proportions of the material. The films were tested for light absorption properties using UV-Vis.
In the present invention, the atomic ratio of zinc and gallium is in proportion to the conventional 1:2, the ratio of gallium atoms is lower, when the stoichiometric ratio of Zn and Ga is changed, the ZnGaO material formed in a certain range can still maintain spinelZnGa2O4A crystal structure. The film prepared by the invention has the characteristics of high crystallization quality, no phase separation, steep absorption cut-off edge and the like. The zinc-gallium-oxygen material film effectively shortens the response time of the ZnGaO ultraviolet detector on the premise of not changing other performance parameters. Has potential application prospect in the preparation aspect of photoelectric devices. In addition, the preparation process of the zinc-gallium-oxygen material film provided by the invention is simple, and the reaction process is easy to control.
For further understanding of the present invention, the following examples are provided to illustrate the zinc-gallium-oxygen material thin film and the preparation method thereof, and the scope of the present invention is not limited by the following examples.
Example 1:
the preparation process of the ZnGaO film is as follows:
1) the sapphire substrate was cleaned with trichloroethylene, acetone, and ethanol, respectively, and then blown dry with dry nitrogen.
2) Placing the sapphire substrate in the step (1) into MOCVD growth equipment, adjusting the growth temperature to 730 ℃, and adjusting the vacuum degree of a growth chamber to be 1.2 x 103Pa, using diethyl zinc as a zinc source, trimethyl gallium as a gallium source, adjusting the molar concentration ratio of zinc and gallium by using different high-purity nitrogen carrier gas ratios, wherein the flow rate of introduced oxygen is 230mL/min, the flow rate of carrier gas of a diethyl zinc pipeline is 10mL/min, and the flow rate of carrier gas of a trimethyl gallium pipeline is 30 mL/min.
3) And 3 hours of growth, turning off the organic source, reducing the temperature at the rate of 5 ℃/min, finally reducing the temperature to the room temperature, and taking out the substrate.
4) During the growth process, the carrier gas flow rate of the zinc source was gradually increased. The rate of rise was 1mL/30 min. The carrier gas flow was increased for a duration of 1 hour.
5) During the growth process, the growth temperature was gradually lowered. The rate of reduction was 3 ℃/min for 1 hour.
FIG. 1 is an X-ray diffraction (XRD) spectrum of ZnGaO thin film, from which it can be seen that the obtained material is ZnGa2O4A crystalline phase structure. The absorption peak of XRD is sharp, which indicates that the crystal quality is high. FIG. 2 shows the photovoltaic effect of the ZnGaO film of example 1Sub-spectrum (EDS) spectrum, from which it can be seen that the ratio of zinc element to gallium element is about 1: 1.7. with standard ZnGa2O4Ratio of zinc and gallium of the film 1:2, the percentage of gallium atoms is lower. FIG. 3 is a UV-Vis spectrum of a ZnGaO film, wherein the film has a steep single light absorption cut-off edge which is about 250 nm.
Example 2
Compared with example 1, a batch of samples was prepared by changing only the rising rate of the carrier gas flow rate of the zinc source without changing other conditions. The rising rate of the flow rate of the zinc source carrier gas of sample numbers 2-1, 2-2, 2-3, 2-4, 2-5 is 0.1mL/30 min; 0.5mL/30 min; 2mL/30 min; 3mL/30 min; 5mL/30 min.
The results are respectively:
2-1, 2-2, 2-3, 2-4 the resulting material was ZnGa2O4The crystal phase structure has a light absorption cut-off edge of about 250 nm.
The material obtained for the samples 2-5 exhibited a small amount of ZnO crystal structure with two absorption cut-off edges.
The ratio of zinc element to gallium element in the sample of 2-1, 2-2, 2-3, 2-4, 2-5 is about 1/1.92,1/1.88,1/1.65,1/1.6,1/1.5
Example 3
Compared with example 1, a batch of samples was prepared by changing only the cooling rate during the production process, without changing other conditions. The cooling rates of the sample numbers of 3-1, 3-2, 3-3, 3-4 and 3-5 are respectively 0.01 ℃/min,1 ℃/min,5 ℃/min,6 ℃/min and 7 ℃/min.
The results are respectively:
the obtained material of the sample of 3-1, 3-2, 3-3 was ZnGa2O4The crystal phase structure has a light absorption cut-off edge of about 250 nm.
The resulting material for the 3-4, 3-5 samples exhibited a small amount of ZnO crystal structure with two absorption cut-off edges.
The ratio of zinc element to gallium element in the samples of 3-1, 3-2, 3-3, 3-4, 3-5 is about 1/1.98,1/1.9,1/1.62,1/1.58,1/1.5
Comparative example 1
Compared with example 1The two processes of step 4 (gradually increasing the carrier gas flow of the zinc source during growth) and step 5 (gradually decreasing the growth temperature during growth) are removed. That is to say, the carrier gas flow rate and the growth temperature of the zinc source are kept unchanged. The obtained sample is ZnGa2O4The crystal phase structure has a light absorption cut-off edge of about 250 nm. The ratio of zinc to gallium is about 1/2.
Example 4
The film samples prepared in example 1 and comparative example 1 were placed in a vacuum coater at a pressure of 1 x 10-3Under Pa, 50mg of Au particles were evaporated onto the sample surface using an evaporation current of 140A.
And photoetching and wet etching the gold on the surface of the obtained sample to obtain an interdigital electrode, and pressing In particles on the interdigital electrode to obtain the ZnGaO ultraviolet detector with the MSM structure. The distance between fingers of the gold interdigital electrode is 2 μm, the number of pairs of fingers is 25, the length of the fingers is 2mm, and the width of the fingers is 2 μm
The ultraviolet detectors prepared from the films obtained in example 1 and comparative example 1 were subjected to performance measurement, and the results are shown in fig. 4 to 6. As can be seen from fig. 4 to 6, as the amount of gallium in the atomic ratio of zinc and gallium decreases, the device responsivity (see fig. 4) and the dark current (see fig. 5) are substantially unchanged. The response time of the device is significantly shortened (see fig. 6).
As shown in FIG. 4, the peak responsivity of the device of example 1 was 9.4A/W, and the peak responsivity of the device provided in comparative example 1 was 9.8A/W.
As shown in fig. 5, the dark current of the device of example 1 at a voltage of 10V was 1.8nA, and the dark current of the device provided in comparative example 1 at a voltage of 10V was 1.8 nA.
As shown in fig. 6, the time required for the current to drop to one-thousandth of the original state after the illumination was turned off in the device of example 1 was about 80 msec, and the time required for the current to drop to one-thousandth of the original state after the illumination was turned off in the device of comparative example 1 was about 500 msec. The device of example 1 is significantly faster than the device of comparative example 1.
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 (6)
1. The preparation method of the zinc-gallium-oxygen material film is characterized by comprising the following steps of:
growing a zinc-gallium-oxygen material film on the surface of a substrate by using an organic zinc compound as a zinc source, an organic gallium compound as a gallium source and high-purity oxygen as an oxygen source and a metal organic compound chemical vapor deposition method;
the organic zinc compound takes high-purity nitrogen as carrier gas, the initial flow rate of the carrier gas is 5-20 mL/min, the flow rate of the carrier gas is gradually increased in the process of growing the zinc-gallium-oxygen material film, and the increasing rate is 0.5-4.5 mL/30 min; the duration of increasing the flow of the carrier gas is 1-5 hours;
the organic gallium compound takes high-purity nitrogen as carrier gas, the initial flow rate of the carrier gas is 5-40 mL/min, the flow of the carrier gas is gradually reduced in the process of growing the zinc-gallium-oxygen material film, and the reduction rate is 0.5-4.5 mL/30 min; the duration of reducing the flow of the carrier gas is 1-5 hours;
the atomic ratio of zinc to gallium in the zinc-gallium-oxygen material film is greater than 1:2, and the zinc-gallium-oxygen material film is of a spinel structure.
2. The method according to claim 1, wherein the absorption cut-off edge of the thin film is located at 250 ± 10 nm.
3. The production method according to claim 1, wherein the organozinc compound is diethyl zinc and/or dimethyl zinc; the organic gallium compound is trimethyl gallium and/or triethyl gallium.
4. The method according to claim 1, wherein the flow rate of the oxygen gas is 100 to 1000 mL/min.
5. The preparation method according to claim 1, wherein the growth time is 0.5-5 h, the growth starting temperature is 500-800 ℃, the growth temperature is gradually reduced at a cooling rate of 0.01-5 ℃/min during the growth of the zinc-gallium-oxygen material film, the cooling time is 0.5-5 h, and the cooling time is less than or equal to the growth time;
the growth was carried out under a vacuum of 2 x 102~1*104Pa。
6. The preparation method according to claim 1, wherein after the growth is finished, the temperature of the substrate is reduced to room temperature, and the cooling rate is 0.1-50 ℃/min.
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| US20150158737A1 (en) * | 2012-06-05 | 2015-06-11 | Korea Institute Of Ceramic Engineering And Technology | Production method for zinc oxide having improved power factor due to increased gallium doping |
| CN107384381A (en) * | 2017-07-26 | 2017-11-24 | 华南理工大学 | A kind of double-colored long after glow luminous material of gallic acid zinc-base and preparation method thereof |
| CN111081798A (en) * | 2019-12-11 | 2020-04-28 | 中国科学院长春光学精密机械与物理研究所 | Zinc-gallium-oxygen material film and preparation method thereof |
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| US20150158737A1 (en) * | 2012-06-05 | 2015-06-11 | Korea Institute Of Ceramic Engineering And Technology | Production method for zinc oxide having improved power factor due to increased gallium doping |
| CN107384381A (en) * | 2017-07-26 | 2017-11-24 | 华南理工大学 | A kind of double-colored long after glow luminous material of gallic acid zinc-base and preparation method thereof |
| CN111081798A (en) * | 2019-12-11 | 2020-04-28 | 中国科学院长春光学精密机械与物理研究所 | Zinc-gallium-oxygen material film and preparation method thereof |
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