CN110335914B - MSM type (GaMe)2O3Ternary alloy solar blind ultraviolet detector and preparation method thereof - Google Patents
MSM type (GaMe)2O3Ternary alloy solar blind ultraviolet detector and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an MSM type (GaMe)2O3A ternary alloy solar blind ultraviolet detector and a preparation method thereof. The detector is from supreme c face sapphire substrate, active layer, parallel metal electrode of being in proper order down, wherein: the active layer is (GaMe)2O3A ternary alloy thin film. The invention makes use of Me2O3Has a band gap (5.5eV) larger than Ga2O3Band gap (4.9eV) of (2), Me was used3+Partial substitution of Ga by ions3+Ion to obtain (GaMe)2O3Ternary alloys to increase Ga2O3The band gap effectively reduces the dark current of the device, enables the cut-off wavelength to be within 280nm in blue, and improves the detection capability of the device on deep ultraviolet light. The solar blind ultraviolet detector with the MSM structure has simple structure and manufacturing process, dark current less than 0.2pA, and relaxation response time tau of the deviced2Can be as low as 0.190s, and has high response speed and stable performance.
Description
Technical Field
The invention belongs to the technical field of semiconductor detectors, particularly relates to a solar blind ultraviolet detector with an MSM structure, and more particularly relates to an MSM (GaMe) type2O3A ternary alloy solar blind ultraviolet detector and a preparation method thereof.
Background
Because the deep ultraviolet part (200-280 nm) in sunlight can be strongly absorbed by an ozone layer before reaching the surface of the earth, the solar blind ultraviolet photoelectric detector has the characteristics of strong anti-interference capability, high sensitivity and the like when working on the surface of the earth. The method has very important application in military and civil fields of missile early warning, ultraviolet communication, fire prevention and control, environmental monitoring and the like. The traditional vacuum ultraviolet photomultiplier detector has high power consumption and high price, and the solar blind ultraviolet photoelectric detector based on the wide-bandgap semiconductor material has the characteristics of small volume, large gain, low energy consumption and the like, so that the solar blind ultraviolet photoelectric detector becomes the focus of research and competition of all countries in the world. Wherein the research is mainly focused on MgZnO, AlGaN and Ga2O3The semiconductor material with the same width forbidden band. However, to realize the detection of solar blind ultraviolet light, the band gap of the semiconductor material of the active layer must be larger than 4.4eV, and the crystal quality is obviously reduced and the performance and the stability of the device are greatly reduced when the band gap of the MgZnO and the AlGaN is increased to 4.4eV by respectively increasing the content of Mg and Al. Ga2O3The material is a semiconductor material with a direct band gap of 4.9eV, has high exciton confinement energy and good physical and chemical stability, and is an ideal solar blind ultraviolet detection material.
Although the peak value response wavelength of the pure gallium oxide-based solar blind ultraviolet photoelectric detector is about 255nm, the cut-off wavelength of the pure gallium oxide-based solar blind ultraviolet photoelectric detector is larger than 280nm, namely, the pure gallium oxide-based solar blind ultraviolet photoelectric detector still has obvious response to ultraviolet light (280-315 nm) of a UVB wave band, and because the deep ultraviolet light is weak, the dark current of the device is reduced, and the influence of noise on signal detection can be effectively reduced. For the above reasons, we use Me3+Ion (Me)3+The ion is Lu3+Ions or Sc3+Ionic) partial substitution of Ga2O3Ga (1) in3+Ion to obtain (GaMe)2O3Ternary elementAlloy to increase Ga2O3The band gap can effectively reduce the dark current of the device, enables the cut-off wavelength to be within 280nm in blue, and improves the detection capability of the device on deep ultraviolet light.
Meanwhile, the metal-semiconductor-metal (MSM) structure detector is particularly beneficial to surface light absorption, has the advantages of simple structure, high efficiency, convenience in integration and the like, and can regulate and control the performance of the obtained detector by controlling parameters such as metal types, channel widths and the like. We therefore chose to prepare an MSM type (GaMe)2O3A solar blind ternary alloy ultraviolet detector.
Disclosure of Invention
The object of the present invention is to provide a MSM type (GaMe)2O3A ternary alloy solar blind ultraviolet detector and a preparation method thereof. The invention is realized by utilizing Me3+Ion (Me)3+The ion is Lu3+Ions or Sc3+Ions) to improve the band gap of the gallium oxide film, thereby reducing the dark current of the gallium oxide solar blind ultraviolet detector, cutting off the blue shift of the wavelength and improving the detection capability of deep ultraviolet.
In order to achieve the first object of the present invention, the present invention adopts the following technical solutions:
MSM type (GaMe)2O3The blind ultraviolet light detector of ternary alloy day, the detector includes c face sapphire substrate, active layer, a pair of parallel electrode from supreme down in proper order, wherein: the active layer is (GaMe)2O3A ternary alloy film; the Me is any one of Lu or Sc.
Further, according to the technical scheme, the thickness of the active layer is 150-300 nm.
Further, according to the technical scheme, the thickness of the parallel electrodes is 30-70 nm.
Further, according to the technical scheme, the distance between the parallel electrodes is 10-100 mu m.
Further, in the above technical solution, the parallel electrode material may be any one of Pt, Au, Al, or ITO, and is preferably Au.
In addition to the inventionOne purpose is to provide the MSM type (GaMe) described above2O3The preparation method of the ternary alloy solar blind ultraviolet detector comprises the following steps:
(1) taking c-plane sapphire as a substrate for film growth, ultrasonically cleaning the substrate by using cleaning solution, drying the substrate by using nitrogen, and immediately placing the substrate in a vacuum chamber;
(2) use (GaMe)2O3Depositing the ceramic target on the surface of the c-surface sapphire substrate pretreated in the step (1) by adopting a pulse laser ablation deposition, magnetron sputtering or electron beam evaporation method to form (-201) oriented (GaMe)2O3A ternary alloy film;
(3) by evaporation, photolithography or sputtering, in the presence of (GaMe)2O3Preparing parallel electrodes on the surface of the ternary alloy film to obtain the MSM (GaMe) type2O3A solar blind ternary alloy ultraviolet detector.
Further, in the above technical scheme, the cleaning solution in step (1) includes acetone, ethanol, and deionized water, and the ultrasonic cleaning time of each cleaning solution is preferably 15 min.
Further, in the above technical solution, the (GaMe) oriented in the (-201) step (2)2O3The ternary alloy film is prepared by a pulse laser ablation deposition method, and the specific process comprises the following steps:
utilization (GaMe)2O3Ceramic is used as a target material, the temperature of the substrate is controlled to be 300-800 ℃, the Pulse laser energy is 200-600 mJ/Pulse, the oxygen pressure is 1-8 Pa, and the ceramic is deposited on the surface of the c-plane sapphire substrate pretreated in the step (1) to form (-201) oriented (GaMe)2O3A ternary alloy thin film.
Preferably, in the technical scheme, the deposition time is 10-60 min.
Further, the above technical solution, step (2) said (GaMe)2O3The ceramic target is prepared by adopting a solid-phase sintering method, and the specific method comprises the following steps:
(a) the molar ratio of the components is 95: 5-70: 30 proportion Ga2O3、Me2O3Powder, namely placing the powder in a ball milling tank, adding ultrapure water, and then carrying out ball milling to obtain uniformly mixed powder;
(b) screening zirconium balls out of the mixed powder solution in the step (a), placing the mixed powder solution in a vacuum drying box, drying, cooling to room temperature, grinding, and pressing into a wafer;
(c) in the air atmosphere, putting the wafer obtained in the step (b) into a vacuum tube furnace, and firing at 1000-1400 ℃ for 1-4 h to obtain the (GaMe)2O3A ceramic.
Furthermore, in the technical scheme, the temperature of the vacuum drying oven in the step (b) is 100-120 ℃, and the drying time is 10-12 hours.
The principle of the invention is as follows:
the invention makes use of Me2O3(wherein Me2O3Is Lu2O3Or Sc2O3) Has a band gap (5.5eV) larger than Ga2O3Band gap (4.9eV) of (2), Me was used3+Partial substitution of Ga by ions2O3Ga (1) in3+Ion to obtain (GaMe)2O3Ternary alloys to increase Ga2O3The band gap can effectively reduce the dark current of the device, enables the cut-off wavelength to be within 280nm in blue, and improves the detection capability of the device on deep ultraviolet light.
The invention has the beneficial effects that:
1. the invention is based on Me3+Partial substitution of Ga by ions2O3Ga (1) in3+Ion to obtain (GaMe)2O3The ternary alloy can obviously improve Ga2O3The band gap of (a).
2. The invention has higher band gap (GaMe)2O3The carrier concentration in the film is lower, so that the dark current of the solar blind ultraviolet photoelectric detector can be effectively reduced, the blue shift of cut-off wavelength can be realized, and the detection capability of deep ultraviolet light is improved.
3. Of the invention (GaMe)2O3The ternary alloy semiconductor material can be prepared by conventional pulsed laser ablation deposition, magnetron sputtering,The growth is carried out by various methods such as electron beam evaporation and the like, the electrode material can adopt metal aluminum, gold, platinum and the like or transparent electrode ITO, and the shape of the electrode and the width of a channel can be freely adjusted and optimized. The electrode of the invention can be prepared by vapor deposition, photolithography or sputtering. The evaporation method has simple process and is convenient for large-scale preparation; photolithography is very useful for the development of high-precision, micro-scale devices.
4. The solar blind ultraviolet photoelectric detector with the MSM structure has simple structure and manufacturing process, and the detector manufactured by the invention has good detection capability on deep ultraviolet light, and has extremely small dark current, high response speed and stable performance.
Drawings
FIG. 1 is a graph based on (GaLu) of example 1 of the present invention2O3The structural schematic diagram of a solar blind ultraviolet detector of the ternary alloy film;
FIG. 2 shows the results of example 1 of the present invention (GaLu)2O3Films and pure Ga from comparative example 12O3X-ray diffraction (XRD) contrast patterns of the films;
FIG. 3 shows the results of example 1 of the present invention (GaLu)2O3Ternary alloy thin film and pure Ga in comparative example 12O3A transmitted light spectrum of the film;
FIG. 4 shows the results of example 1 of the present invention (GaLu)2O3Ternary alloy thin film and pure Ga in comparative example 12O3Of film (α hv)2∝(hv-Eg) A relationship graph;
FIG. 5 shows the results of example 1 of the present invention (GaLu)2O3A time t-current I response curve graph of the solar-based blind ultraviolet photoelectric detector;
FIG. 6 shows the results of example 2 of the present invention (GaLu)2O3A time t-current I response curve graph of the solar-based blind ultraviolet photoelectric detector;
FIG. 7 shows pure Ga in comparative example 1 of the present invention2O3A time t-current I response curve graph of the solar-based blind ultraviolet photoelectric detector;
FIG. 8 shows the results of example 1 of the present invention (GaLu)2O3And comparisonPure Ga in example 12O3A comparison graph of the spectral responsivity test result of the basic solar blind ultraviolet photoelectric detector;
FIG. 9 shows a graph based on (GaSc) in example 5 of the present invention2O3The structural schematic diagram of a solar blind ultraviolet detector of the ternary alloy film;
FIG. 10 is (GaSc) prepared in example 5 of the present invention2O3Films and pure Ga prepared in comparative example 22O3X-ray diffraction (XRD) pattern of the film;
FIG. 11 shows GaSc in example 5 of the present invention2O3An I-V curve of the solar-based blind ultraviolet photoelectric detector;
FIG. 12 shows GaSc in example 5 of the present invention2O3A time t-current I response curve graph of the solar-based blind ultraviolet photoelectric detector;
FIG. 13 shows GaSc in example 6 of the present invention2O3An I-V curve of the solar-based blind ultraviolet photoelectric detector;
FIG. 14 shows GaSc in example 6 of the present invention2O3A time t-current I response curve graph of the solar-based blind ultraviolet photoelectric detector;
FIG. 15 shows pure Ga in comparative example 2 of the present invention2O3An I-V curve of the solar-based blind ultraviolet photoelectric detector;
FIG. 16 shows pure Ga in comparative example 2 of the present invention2O3A time t-current I response curve graph of the solar-based blind ultraviolet photoelectric detector;
FIG. 17 shows GaSc in example 5 of the present invention2O3And pure Ga in comparative example 22O3And (5) testing the spectral responsivity of the basic solar blind ultraviolet photoelectric detector.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and a specific operation process are given, but the protection scope of the invention is not limited to the following embodiment.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The sapphire substrate used in each of the following examples of the present invention was one whose main component was alumina (Al)2O3)，c-Al2O3C-plane sapphire is shown. The thickness of the sapphire substrate is preferably 0.35-0.45 mm.
Example 1
As shown in FIG. 1, a base of this embodiment (GaLu)2O3Solar blind ultraviolet detector of ternary alloy film, the detector includes c face sapphire substrate, active layer, a pair of parallel metal Au electrode from supreme down in proper order, wherein: the active layer is (-201) oriented (GaLu)2O3A ternary alloy thin film. The thickness of the substrate is 0.43mm, the thickness of the active layer is 150nm, the thickness of the Au electrode is 50nm, and the distance between the parallel electrodes is 10 mu m.
The embodiment is based on (GaLu)2O3The solar blind ultraviolet detector of the ternary alloy film is prepared by the following method, and comprises the following steps:
step 1: miningPreparation by firing by solid-phase sintering (GaLu)2O3Ternary ceramic target material
1.1 in molar ratio Ga2O3：Lu2O370: 30, weighing 5.236g Ga2O3Powder and 4.763g Lu2O3Mixing the powder, adding 15g of deionized water, then placing the mixture into a ball milling tank (zirconia ceramic balls are used as a ball milling medium) in a planetary ball mill, and carrying out ball milling for 4 hours to obtain mixed powder;
1.2, screening zirconium balls out of the mixed powder solution, placing the mixed powder solution in a vacuum drying oven, carrying out vacuum drying for 12 hours at the temperature of 110 ℃, taking out the mixed powder solution, naturally cooling to room temperature, adding 1g of deionized water, fully and uniformly grinding the mixed powder solution by using a grinding bowl, and pressing the mixed powder solution into round blank sheets with the diameter of 27.5mm and the thickness of 2mm by using a tablet press under the pressure of 8 MPa;
1.3 the slab was placed in a crucible in a vacuum tube furnace and powder of the same composition (15.000g) was placed around it. Heating the tube furnace to 1300 ℃ and preserving the temperature for 3h, and then naturally cooling to room temperature to obtain the (GaLu)2O3A ternary ceramic target material.
2.1 preparation of (GaLu) in step 12O3The ternary ceramic is used as a laser ablation target material, and is loaded into a vacuum chamber together with a sapphire substrate which is respectively subjected to ultrasonic cleaning for 15min by acetone, absolute ethyl alcohol, deionized water and the like, and is vacuumized to 10 DEG-4Pa；
2.2 after the temperature of the substrate is raised to 700 ℃, introducing oxygen to ensure that the air pressure is maintained at 4Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 300mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporator, then installing a tungsten boat and placing an evaporation source, namely 0.15g of metal Au, closing the vacuum cavity, and opening the vacuum cavityA mechanical pump, a front valve and a molecular pump for pumping the vacuum degree to 10-4And below Pa, starting an evaporation power supply, slowly increasing the current until the metal Au melts and then keeping the current constant, and opening a baffle to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
Prepared in this example (GaLu)2O3The XRD full spectrum of the ternary alloy film is shown in figure 2. It can be seen that, in addition to the three diffraction peaks (0003), (0006) and (0009) of the c-plane sapphire substrate, there are only three diffraction peaks located in the vicinity of 18.9 °, 38.3 ° and 59.1 °, respectively, comparing Ga2O3As can be seen from the standard XRD spectrum (JCPDS File No.41-1103), these three diffraction peaks represent Ga respectively2O3(-201), (-402) and (-603) planes, indicating that this example successfully produced (GaLu) oriented (-201)2O3A ternary film.
FIG. 3 is (GaLu)2O3And pure Ga2O3A transmission spectrum of (a). As shown in the figure, (GaLu)2O3And pure Ga2O3The transmittance in the infrared and visible light regions is 90% or more. (GaLu)2O3The absorption edge of the film is near 235nm relative to pure Ga2O3The absorption edge of the film (255 nm) is clearly blue-shifted because gallium oxide is a direct bandgap semiconductor and can pass through (α hv)2∝(hv-Eg) Wherein hv represents the incident photon energy and α represents the absorption coefficient (α hv)2The graph against hv is shown in FIG. 4, and obtained by linear extrapolation (GaLu)2O3The band gap of the film is 5.2eV, while the pure Ga2O3The band gap of (A) is 4.9 eV. It can be seen that the band gap of gallium oxide can be obviously improved by doping with Lu. This is because Lu2O3Having a band gap (5.5eV) greater than Ga2O3Bandgap (4.9 eV).
Further, 10V was applied between electrodes of the MSM type device manufactured in this exampleAnd pressing and irradiating the surface of the sample with monochromatic light to perform photoelectric property test. Fig. 5 and 8 are time-current and wavelength-responsivity curves for the device, respectively. The result shows that the device has obvious detection capability on solar blind ultraviolet light compared with pure Ga2O3Solar blind ultraviolet photoelectric detector with lower dark current (I)dark<0.2pA) and faster response speed, device relaxation response taud20.190s and a blue shift of the peak response wavelength and the cut-off wavelength, showing a more sensitive detection capability to solar blind uv light. This benefits from (GaLu)2O3Film vs. pure Ga2O3Has a wider band gap and fewer oxygen vacancies, the wider band gap causes the dark current of the device to be significantly reduced, the peak response wavelength and the cut-off wavelength to be blue-shifted, and the reduction of oxygen vacancies in the thin film causes the concentration of trap centers to be reduced, thereby causing the relaxation time of the device to be significantly reduced.
In conclusion, (GaLu)2O3Base detector vs. pure Ga2O3The base detector has lower dark current, faster response speed and shorter cut-off wavelength, and shows more sensitive and rapid detection capability to solar blind ultraviolet light.
Example 2
One of the embodiments is based on (GaLu)2O3Solar blind ultraviolet detector of ternary alloy, the detector includes c face sapphire substrate, active layer, a pair of parallel metal Au electrode from supreme down in proper order, wherein: the active layer is (GaLu)2O3The thickness of the substrate is 0.43mm, the thickness of the active layer is 150nm, the thickness of the electrode is 55nm, and the distance between the parallel electrodes is 10 microns.
The embodiment is based on (GaLu)2O3The solar blind ultraviolet detector of the film is prepared by the following method, comprising the following steps:
step 1: prepared by adopting a solid-phase sintering method (GaLu)2O3Ternary ceramic target material
1.1 in molar ratio Ga2O3：Lu2O395: 5, weighing 8.995g Ga2O3Powder and 1.005g Lu2O3Mixing the powder, adding 15g of deionized water, then placing the mixture into a ball milling tank (zirconia ceramic balls are used as a ball milling medium) in a planetary ball mill, and carrying out ball milling for 4 hours to obtain mixed powder;
1.2, screening zirconium balls out of the mixed powder solution, placing the mixed powder solution in a vacuum drying oven, carrying out vacuum drying for 12 hours at the temperature of 110 ℃, taking out the mixed powder solution, naturally cooling to room temperature, adding 1g of deionized water, fully and uniformly grinding the mixed powder solution by using a grinding bowl, and pressing the mixed powder solution into round blank sheets with the diameter of 27.5mm and the thickness of 2mm by using a tablet press under the pressure of 8 MPa;
1.3 the slab was placed in a crucible in a vacuum tube furnace and powder of the same composition (15.000g) was placed around it. Heating the tube furnace to 1300 ℃ and preserving the temperature for 3h, and then naturally cooling to room temperature to obtain the (GaLu)2O3A ternary ceramic target material.
2.1 preparation of (GaLu) in step 12O3The ternary ceramic is used as a laser ablation target material, and is loaded into a vacuum chamber together with a sapphire substrate which is respectively subjected to ultrasonic cleaning for 15min by acetone, absolute ethyl alcohol, deionized water and the like, and is vacuumized to 10 DEG-4Pa；
2.2 after the temperature of the substrate is raised to 700 ℃, introducing oxygen to ensure that the air pressure is maintained at 4Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 300mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporator, then installing a tungsten boat and placing an evaporation source, namely 0.15g of metal Au, closing the vacuum cavity, starting a mechanical pump, a front valve and a molecular pump, and pumping the vacuum degree to 10-4Pa below, then starting an evaporation power supply, slowly increasing the current until the metal Au melts and then keeping the current constant,the shutter is opened to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
A voltage of 10V was applied between the electrodes of the device fabricated in this example and the surface of the sample was irradiated with monochromatic light for photoelectric property test. The results show that the dark current of the device is very low (I)dark<0.2pA), high response speed and high relaxation response time tau of the deviced20.228s, showing better detection ability for solar blind ultraviolet light. The test results are shown in FIG. 6.
Example 3
One of the embodiments is based on (GaLu)2O3Solar blind ultraviolet detector of ternary alloy, the detector includes c face sapphire substrate, active layer, a pair of parallel metal Au electrode from supreme down in proper order, wherein: the active layer is (GaLu)2O3The thickness of the substrate is 0.43mm, the thickness of the active layer is 300nm, the thickness of the electrode is 30nm, and the distance between the parallel electrodes is 50 microns.
The embodiment is based on (GaLu)2O3The solar blind ultraviolet detector of the film is prepared by the following method, comprising the following steps:
step 1: prepared by the same solid-phase sintering method as in example 1 (GaLu)2O3A ternary ceramic target material;
step 2: utilization (GaLu)2O3Solar blind ultraviolet detector prepared from ternary ceramic target material
2.1 preparation of (GaLu) in step 12O3The ternary ceramic is used as a laser ablation target material, and is loaded into a vacuum chamber together with a sapphire substrate which is respectively subjected to ultrasonic cleaning for 15min by acetone, absolute ethyl alcohol, deionized water and the like, and is vacuumized to 10 DEG-4Pa；
2.2 after the temperature of the substrate is raised to 500 ℃, introducing oxygen to ensure that the air pressure is maintained at 1Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 500mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporator, then installing a tungsten boat and placing an evaporation source, namely 0.10g of metal Au, closing the vacuum cavity, starting a mechanical pump, a front-stage valve and a molecular pump, and pumping the vacuum degree to 10-4And below Pa, starting an evaporation power supply, slowly increasing the current until the metal Au melts and then keeping the current constant, and opening a baffle to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
Example 4
One of the embodiments is based on (GaLu)2O3Solar blind ultraviolet detector of ternary alloy, the detector includes c face sapphire substrate, active layer, a pair of parallel metal Au electrode from supreme down in proper order, wherein: the active layer is (GaLu)2O3The thickness of the substrate is 0.43mm, the thickness of the active layer is 200nm, the thickness of the electrode is 70nm, and the distance between the parallel electrodes is 100 mu m.
The embodiment is based on (GaLu)2O3The solar blind ultraviolet detector of the film is prepared by the following method, comprising the following steps:
step 1: prepared by the same solid-phase sintering method as in example 1 (GaLu)2O3A ternary ceramic target material;
step 2: utilization (GaLu)2O3Solar blind ultraviolet detector prepared from ternary ceramic target material
2.1 preparation of (GaLu) in step 12O3The ternary ceramic is used as a laser ablation target material, and is loaded into a vacuum chamber together with a sapphire substrate which is respectively subjected to ultrasonic cleaning for 15min by acetone, absolute ethyl alcohol, deionized water and the like, and is vacuumized to 10 DEG-4Pa；
2.2 after the temperature of the substrate is raised to 300 ℃, introducing oxygen to ensure that the air pressure is maintained at 8Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 600mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporator, then installing a tungsten boat and placing an evaporation source, namely 0.25g of metal Au, closing the vacuum cavity, starting a mechanical pump, a front-stage valve and a molecular pump, and pumping the vacuum degree to 10-4And below Pa, starting an evaporation power supply, slowly increasing the current until the metal Au melts and then keeping the current constant, and opening a baffle to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
Comparative example 1
One of the present comparative examples is based on Ga2O3The solar blind ultraviolet light detector of film, the detector includes c face sapphire substrate, active layer, a pair of parallel metal Au electrode from supreme down in proper order, wherein: the active layer is Ga2O3The thickness of the substrate is 0.43mm, the thickness of the active layer is 150nm, the thickness of the electrode is 55nm, and the distance between the parallel electrodes is 10 microns.
Comparative example Ga-based as described above2O3The solar blind ultraviolet detector of the film is prepared by the following method, comprising the following steps:
step 1: preparation of Ga by solid-phase sintering2O3Ceramic target material
1.1 weighing 10g Ga2O3Adding 15g of deionized water into the powder, then placing the powder into a ball milling tank (zirconia ceramic balls are used as a ball milling medium) in a planetary ball mill, and carrying out ball milling for 4 hours to obtain uniformly dispersed powder;
1.2, screening zirconium balls out of the mixed powder solution, placing the mixed powder solution in a vacuum drying oven, carrying out vacuum drying for 12 hours at the temperature of 110 ℃, taking out the mixed powder solution, naturally cooling to room temperature, adding 1g of deionized water, fully and uniformly grinding the mixed powder solution by using a grinding bowl, and pressing the mixed powder solution into round blank sheets with the diameter of 27.5mm and the thickness of 2mm by using a tablet press under the pressure of 8 MPa;
1.3 the slab was placed in a crucible in a vacuum tube furnace and powder of the same composition (15.000g) was placed around it. Heating the tube furnace to 1300 ℃ and preserving heat for 3h, and then naturally cooling to room temperature to obtain the Ga of the invention2O3A ceramic target material.
2.1 Ga prepared in step 12O3Ceramic as laser ablation target material, loading into vacuum chamber together with sapphire substrate respectively ultrasonically cleaned with acetone, anhydrous alcohol and deionized water for 15min, and vacuumizing to 10%-4Pa；
2.2 after the temperature of the substrate is raised to 700 ℃, introducing oxygen to ensure that the air pressure is maintained at 4Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 300mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporator, then installing a tungsten boat and placing an evaporation source, namely 0.15g of metal Au, closing the vacuum cavity, starting a mechanical pump, a front valve and a molecular pump, and pumping the vacuum degree to 10-4And below Pa, starting an evaporation power supply, slowly increasing the current until the metal Au melts and then keeping the current constant, and opening a baffle to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
A voltage of 10V was applied between the electrodes of the device manufactured in this comparative example and the surface of the sample was irradiated with monochromatic light for photoelectric property test. The result shows that the device has dark current Idark10.6pA, relaxation response time τd2Is 0.661s. It can be seen that the dark current of the device is significantly higher than that (GaLu)2O3A basic detector and a slower response speed. Embody (GaLu)2O3The base detector has more excellent solar blind ultraviolet detection capability. The test results are shown in FIG. 7.
Example 5
As shown in FIG. 9, a base of the present embodiment (GaSc)2O3Solar blind ultraviolet detector of ternary alloy film, the detector includes c face sapphire substrate, active layer, a pair of parallel metal Au electrode from supreme down in proper order, wherein: the active layer is (GaSc) oriented in the (-201)2O3A ternary alloy thin film. The thickness of the substrate is 0.43mm, the thickness of the active layer is 150nm, the thickness of the Au electrode is 50nm, and the distance between the parallel electrodes is 10 mu m.
The embodiment is based on (GaSc)2O3The solar blind ultraviolet detector of the ternary alloy film is prepared by the following method, and comprises the following steps:
step 1: prepared by firing by a solid-phase sintering method (GaSc)2O3Ternary ceramic target material
1.1 in molar ratio Ga2O3：Sc2O395: 9.627g Ga were weighed2O3Powder and 0.373g Sc2O3Mixing the powder, adding 15g of deionized water, then placing the mixture into a ball milling tank (zirconia ceramic balls are used as a ball milling medium) in a planetary ball mill, and carrying out ball milling for 4 hours to obtain mixed powder;
1.2, screening zirconium balls out of the mixed powder solution, placing the mixed powder solution in a vacuum drying oven, carrying out vacuum drying for 12 hours at the temperature of 110 ℃, taking out the mixed powder solution, naturally cooling to room temperature, adding 1g of deionized water, fully and uniformly grinding the mixed powder solution by using a grinding bowl, and pressing the mixed powder solution into round blank sheets with the diameter of 27.5mm and the thickness of 2mm by using a tablet press under the pressure of 8 MPa;
1.3 the slab was placed in a crucible in a vacuum tube furnace and powder of the same composition (15.000g) was placed around it. Heating the tube furnace to 1300 ℃ and preserving the temperature for 3h, and then naturally cooling to room temperature to obtain the (GaSc)2O3A ternary ceramic target material.
2.1 preparation of (GaSc) in step 12O3The ternary ceramic is used as a laser ablation target material, and is loaded into a vacuum chamber together with a sapphire substrate which is respectively subjected to ultrasonic cleaning for 15min by acetone, absolute ethyl alcohol, deionized water and the like, and is vacuumized to 10 DEG-4Pa；
2.2 after the temperature of the substrate is raised to 700 ℃, introducing oxygen to ensure that the air pressure is maintained at 4Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 300mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporator, then installing a tungsten boat and placing an evaporation source, namely 0.15g of metal Au, closing the vacuum cavity, starting a mechanical pump, a front valve and a molecular pump, and pumping the vacuum degree to 10-4And below Pa, starting an evaporation power supply, slowly increasing the current until the metal Au melts and then keeping the current constant, and opening a baffle to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
Prepared in this example (GaSc)2O3The XRD full spectrum of the ternary alloy film is shown in FIG. 10. It can be seen that, in addition to the diffraction peaks of the c-plane sapphire substrate, there are only three diffraction peaks, respectively located in the vicinity of 18.9 °, 38.3 ° and 59.1 °, comparing Ga2O3The standard XRD spectrum (JCPDS File No.41-1103) shows that the three diffraction peaks correspond to Ga respectively2O3(-201), (-402) and (-603) crystal planes, indicating that this example successfully produced (GaSc) oriented with (-201)2O3A ternary alloy thin film.
FIG. 11 shows (GaSc) obtained in this example2O3The I-V curve of the solar blind ultraviolet photoelectric detector can be obviously seen to be nonlinear under the illumination, which indicates Au and (GaSc)2O3Schottky contacts are formed between the films. Fig. 12 is a time-current response curve of the device at 10V operating voltage. As can be seen from FIG. 12, the dark current of the device is very small under 10V bias voltage (<0.2pA), much smaller than pure Ga2O3Dark current (-10.6 pA) of the base detector. This is because of Sc2O3Has a band gap (5.9eV) larger than Ga2O3Band gap (4.9eV), Sc3+The ion doping can obviously improve Ga2O3Thereby enabling a wider band gap (GaSc)2O3The dark current of the base detector is significantly reduced. At the same time, we use the bi-exponential relaxation equation I ═ I0+Ae-t/τ1+Be-t/τ2Fitting the curve to obtain the relaxation response time tau of the devicer2And τd20.202s and 0.228s, respectively, significantly faster than pure Ga2O3Relaxation response time (τ) of base detectorr2＝0.579sτd20.661 s). This is because of Sc3+Ions with O2-Binding energy ratio between ions Ga3+Ions with O2-The binding energy between ions is stronger, so that (GaSc)2O3Ternary alloy films vs. pure Ga2O3The film has a lower concentration of oxygen vacancies, which results in fewer trap centers in the film, thereby promoting a significantly faster relaxation response speed of the device. FIG. 17 is (GaSc)2O3And pure Ga2O3Wavelength responsivity curve of base detector benefiting from (GaSc)2O3Relatively wider band gap, (GaSc)2O3Peak response and cut-off wavelengths of the base detector relative to pure Ga2O3The base detector clearly undergoes a blue shift, indicating that it is more sensitive to solar blind uv light. In conclusion, (GaSc)2O3Base detector vs. pure Ga2O3The base detector has lower dark current, faster response speed and shorter cut-off wavelength, and shows better sunlight blind ultraviolet lightSensitive and fast detection capability.
Example 6
One of the embodiments is based on (GaSc)2O3Solar blind ultraviolet detector of ternary alloy, the detector includes c face sapphire substrate, active layer, a pair of parallel metal Au electrode from supreme down in proper order, wherein: the active layer is (GaSc)2O3The thickness of the substrate is 0.43mm, the thickness of the active layer is 150nm, the thickness of the electrode is 55nm, and the distance between the parallel electrodes is 10 microns.
The embodiment is based on (GaSc)2O3The solar blind ultraviolet detector of the film is prepared by the following method, comprising the following steps:
step 1: prepared by firing by a solid-phase sintering method (GaSc)2O3Ternary ceramic target material
1.1 in molar ratio Ga2O3：Sc2O370: 30, weighing 7.603g Ga2O3Powder and 2.397g Sc2O3Mixing the powder, adding 15g of deionized water, then placing the mixture into a ball milling tank (zirconia ceramic balls are used as a ball milling medium) in a planetary ball mill, and carrying out ball milling for 4 hours to obtain mixed powder;
1.2, screening zirconium balls out of the mixed powder solution, placing the mixed powder solution in a vacuum drying oven, carrying out vacuum drying for 12 hours at the temperature of 110 ℃, taking out the mixed powder solution, naturally cooling to room temperature, adding 1g of deionized water, fully and uniformly grinding the mixed powder solution by using a grinding bowl, and pressing the mixed powder solution into round blank sheets with the diameter of 27.5mm and the thickness of 2mm by using a tablet press under the pressure of 8 MPa;
1.3 the slab was placed in a crucible in a vacuum tube furnace and powder of the same composition (15.000g) was placed around it. Heating the tube furnace to 1300 ℃ and preserving the temperature for 3h, and then naturally cooling to room temperature to obtain the (GaSc)2O3A ternary ceramic target material.
2.1 preparation of (GaSc) in step 12O3Ternary ceramicsFor laser ablation of target material, the target material and sapphire substrate respectively cleaned by ultrasonic for 15min by acetone, absolute ethyl alcohol and deionized water are put into a vacuum chamber and vacuumized to 10 deg.C-4Pa；
2.2 after the temperature of the substrate is raised to 700 ℃, introducing oxygen to ensure that the air pressure is maintained at 4Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 300mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporator, then installing a tungsten boat and placing an evaporation source, namely 0.15g of metal Au, closing the vacuum cavity, starting a mechanical pump, a front valve and a molecular pump, and pumping the vacuum degree to 10-4And below Pa, starting an evaporation power supply, slowly increasing the current until the metal Au melts and then keeping the current constant, and opening a baffle to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
A voltage of 10V was applied between the electrodes of the device fabricated in this example and the surface of the sample was irradiated with monochromatic light for photoelectric property test. The results show that the dark current of the device is very low (I)dark<0.2pA), high response speed and high relaxation response time tau of the devicer2And τd20.171s and 0.197s, respectively, showed better detection of solar-blind uv light. The test results are shown in fig. 13 and 14, respectively.
Example 7
One of the embodiments is based on (GaSc)2O3Solar blind ultraviolet detector of ternary alloy, the detector includes c face sapphire substrate, active layer, a pair of parallel metal Al electrode from supreme down in proper order, wherein: the active layer is (GaSc)2O3The thickness of the substrate is 0.43mm, the thickness of the active layer is 300nm, the thickness of the electrode is 30nm, and the distance between the parallel electrodes is equal to that of the active layerIs 50 μm.
The embodiment is based on (GaSc)2O3The solar blind ultraviolet detector of the film is prepared by the following method, comprising the following steps:
step 1: prepared by the same solid-phase sintering method as in example 1 (GaSc)2O3A ternary ceramic target material.
Step 2: utilizing (GaSc)2O3Solar blind ultraviolet detector prepared from ternary ceramic target material
2.1 preparation of (GaSc) in step 12O3The ternary ceramic is used as a laser ablation target material, and is loaded into a vacuum chamber together with a sapphire substrate which is respectively subjected to ultrasonic cleaning for 15min by acetone, absolute ethyl alcohol, deionized water and the like, and is vacuumized to 10 DEG-4Pa；
2.2 after the temperature of the substrate is raised to 500 ℃, introducing oxygen to ensure that the air pressure is maintained at 1Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 500mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporator, then installing a tungsten boat and placing an evaporation source, namely 0.10g of metal Al, closing the vacuum cavity, starting a mechanical pump, a front valve and a molecular pump, and pumping the vacuum degree to 10-4And (4) below Pa, starting an evaporation power supply, slowly increasing the current until the current is kept constant after the metal Al is melted, and opening a baffle to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
Example 8
One of the embodiments is based on (GaSc)2O3Solar blind ultraviolet detector of ternary alloy, the detector includes c face sapphire substrate, active layer, a pair of parallel metal Pt electrode from supreme down in proper order, wherein: the active layer is (GaSc)2O3The thickness of the substrate is 0.43mm, the thickness of the active layer is 200nm, the thickness of the electrode is 70nm, and the distance between the parallel electrodes is 100 mu m.
The embodiment is based on (GaSc)2O3The solar blind ultraviolet detector of the film is prepared by the following method, comprising the following steps:
step 1: prepared by the same solid-phase sintering method as in example 1 (GaSc)2O3A ternary ceramic target material.
Step 2: utilizing (GaSc)2O3Solar blind ultraviolet detector prepared from ternary ceramic target material
2.1 preparation of (GaSc) in step 12O3The ternary ceramic is used as a laser ablation target material, and is loaded into a vacuum chamber together with a sapphire substrate which is respectively subjected to ultrasonic cleaning for 15min by acetone, absolute ethyl alcohol, deionized water and the like, and is vacuumized to 10 DEG-4Pa；
2.2 after the temperature of the substrate is raised to 300 ℃, introducing oxygen to ensure that the air pressure is maintained at 8Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 600mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporation machine, then installing a tungsten boat and placing an evaporation source, namely 0.25g of metal Pt, closing the vacuum cavity, starting a mechanical pump, a front-stage valve and a molecular pump, and pumping the vacuum degree to 10-4And (4) below Pa, starting an evaporation power supply, slowly increasing the current until the current is kept constant after the metal Pt is melted, and opening a baffle to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
Comparative example 2
One of the present comparative examples is based on Ga2O3Solar blind ultraviolet detector of filmThe detector comprises a c-plane sapphire substrate, an active layer and a pair of parallel metal Au electrodes from bottom to top in sequence, wherein: the active layer is Ga2O3The thickness of the substrate is 0.43mm, the thickness of the active layer is 150nm, the thickness of the electrode is 55nm, and the distance between the parallel electrodes is 10 microns.
Comparative example Ga-based as described above2O3The solar blind ultraviolet detector of the film is prepared by the following method, comprising the following steps:
step 1: preparation of Ga by solid-phase sintering2O3Ceramic target material
1.1 weighing 10g Ga2O3Adding 15g of deionized water into the powder, then placing the powder into a ball milling tank (zirconia ceramic balls are used as a ball milling medium) in a planetary ball mill, and carrying out ball milling for 4 hours to obtain uniformly dispersed powder;
1.2, screening zirconium balls out of the mixed powder solution, placing the mixed powder solution in a vacuum drying oven, carrying out vacuum drying for 12 hours at the temperature of 110 ℃, taking out the mixed powder solution, naturally cooling to room temperature, adding 1g of deionized water, fully and uniformly grinding the mixed powder solution by using a grinding bowl, and pressing the mixed powder solution into round blank sheets with the diameter of 27.5mm and the thickness of 2mm by using a tablet press under the pressure of 8 MPa;
1.3 the slab was placed in a crucible in a vacuum tube furnace and powder of the same composition (15.0000g) was placed around it. Heating the tube furnace to 1300 ℃ and preserving heat for 3h, and then naturally cooling to room temperature to obtain the Ga of the invention2O3A ceramic target material.
2.1 Ga prepared in step 12O3Ceramic as laser ablation target material, loading into vacuum chamber together with sapphire substrate respectively ultrasonically cleaned with acetone, anhydrous alcohol and deionized water for 15min, and vacuumizing to 10%-4Pa；
2.2 after the temperature of the substrate is raised to 700 ℃, introducing oxygen to ensure that the air pressure is maintained at 4Pa in the whole film deposition process; then starting the substrate and the target table to rotate, setting the output energy of the laser to be 300mJ/pulse and the pulse repetition frequency to be 5Hz, and starting the laser to deposit the film. After deposition for 30min, closing oxygen and heating, and finally, naturally cooling the sample to room temperature in vacuum and taking out;
2.3 placing the obtained film on a mask plate and installing the film into a vacuum cavity of a vacuum evaporator, then installing a tungsten boat and placing an evaporation source, namely 0.15g of metal Au, closing the vacuum cavity, starting a mechanical pump, a front valve and a molecular pump, and pumping the vacuum degree to 10-4And below Pa, starting an evaporation power supply, slowly increasing the current until the metal Au melts and then keeping the current constant, and opening a baffle to start evaporation. And slowly reducing the current after the metal evaporation is finished, closing the evaporation source, closing the molecular pump, the front-stage valve and the mechanical pump, and opening the air valve to finally obtain the target MSM solar blind ultraviolet photoelectric detector.
A voltage of 10V was applied between the electrodes of the device manufactured in this comparative example and the surface of the sample was irradiated with monochromatic light for photoelectric property test. The result shows that the device has dark current Idark10.6pA, relaxation response time τr2And τd20.579 s and 0.661s, respectively, the test results are shown in fig. 15 and fig. 16, respectively. It can be seen that the dark current of the device made by this comparative example is significantly higher than that of the above (GaSc)2O3A basic detector and a slower response speed. Comparison of this comparative example shows the invention (GaSc)2O3The base detector has more excellent solar blind ultraviolet detection capability.
Claims (9)
1. MSM type (GaMe)2O3The solar blind ternary alloy ultraviolet detector is characterized in that: the detector includes c face sapphire substrate, active layer, a pair of parallel electrode from supreme down in proper order, wherein: the active layer is (GaMe)2O3A ternary alloy film; the Me is any one of Lu or Sc.
2. The MSM type (GaMe) of claim 12O3The solar blind ternary alloy ultraviolet detector is characterized in that: the thickness of the active layer is 150-300 nm.
3. The MSM type (GaMe) of claim 12O3The solar blind ternary alloy ultraviolet detector is characterized in that: the thickness of the parallel electrode is 30-70 nm.
4. The MSM type (GaMe) of claim 12O3The solar blind ternary alloy ultraviolet detector is characterized in that: the distance between the parallel electrodes is 10-100 mu m.
5. The MSM type (GaMe) of claim 12O3The solar blind ternary alloy ultraviolet detector is characterized in that: the parallel electrode material is any one of Pt, Au, Al or ITO.
6. The MSM type (GaMe) according to any one of claims 1 to 52O3The preparation method of the ternary alloy solar blind ultraviolet detector is characterized by comprising the following steps of: the method comprises the following steps:
(1) taking c-plane sapphire as a substrate for film growth, ultrasonically cleaning the substrate by using cleaning solution, drying the substrate by using nitrogen, and immediately placing the substrate in a vacuum chamber;
(2) use (GaMe)2O3Depositing the ceramic target on the surface of the c-surface sapphire substrate pretreated in the step (1) by adopting a pulse laser ablation deposition, magnetron sputtering or electron beam evaporation method to form (-201) oriented (GaMe)2O3A ternary alloy film;
(3) by evaporation, photolithography or sputtering, in the presence of (GaMe)2O3Preparing parallel electrodes on the surface of the ternary alloy film to obtain the MSM (GaMe)2O3A solar blind ternary alloy ultraviolet detector.
7. The MSM type (GaMe) according to claim 62O3The preparation method of the ternary alloy solar blind ultraviolet detector is characterized by comprising the following steps of: step (2) with (-201) orientation (GaMe)2O3The ternary alloy film is prepared by pulse laser sinteringThe etching deposition method is prepared by the following specific processes:
utilization (GaMe)2O3Ceramic is used as a target material, the temperature of the substrate is controlled to be 300-800 ℃, the Pulse laser energy is 200-600 mJ/Pulse, the oxygen pressure is 1-8 Pa, and the ceramic is deposited on the surface of the c-plane sapphire substrate pretreated in the step (1) to form (-201) oriented (GaMe)2O3A ternary alloy thin film.
8. MSM type (GaMe) according to claim 72O3The preparation method of the ternary alloy solar blind ultraviolet detector is characterized by comprising the following steps of: the deposition time is 10-60 min.
9. The MSM type (GaMe) according to claim 62O3The preparation method of the ternary alloy solar blind ultraviolet detector is characterized by comprising the following steps of: (GaMe) described in step (2)2O3The ceramic target is prepared by adopting a solid-phase sintering method, and the specific method comprises the following steps:
(a) the molar ratio of the components is 95: 5-70: 30 proportion Ga2O3、Me2O3Powder, namely placing the powder in a ball milling tank, adding ultrapure water, and then carrying out ball milling to obtain uniformly mixed powder;
(b) screening zirconium balls out of the mixed powder solution in the step (a), placing the mixed powder solution in a vacuum drying box, drying, cooling to room temperature, grinding, and pressing into a wafer;
(c) in an air atmosphere, placing the wafer obtained in the step (b) into a vacuum tube furnace, and firing at 1000-1400 ℃ for 1-4 h to obtain the (GaMe)2O3A ceramic target material.
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