CN109962124B - Semiconductor photoelectric detector based on three-layer structure and preparation method thereof - Google Patents

Semiconductor photoelectric detector based on three-layer structure and preparation method thereof Download PDF

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CN109962124B
CN109962124B CN201910249215.XA CN201910249215A CN109962124B CN 109962124 B CN109962124 B CN 109962124B CN 201910249215 A CN201910249215 A CN 201910249215A CN 109962124 B CN109962124 B CN 109962124B
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钱凌轩
侯爽
邢志阳
张万里
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University of Electronic Science and Technology of China
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Abstract

The invention provides a semiconductor photoelectric detector based on a three-layer structure and a preparation method thereof, wherein the semiconductor photoelectric detector comprises a substrate at the bottom and a three-layer material structure above the substrate, wherein the three-layer material structure is as follows from bottom to top: the photoelectric detector comprises an intrinsic semiconductor, a doped or alloyed semiconductor and a spacing layer, wherein the upper part of the spacing layer is connected with an electrode layer, the electrode layer comprises a first electrode and a second electrode, and the photoelectric detector based on the intrinsic semiconductor-doped or alloyed semiconductor-spacing layer three-layer structure is formed; the invention optimizes the light and dark current of the semiconductor photoelectric detector, and improves the responsivity and specific detectivity, thereby providing a better solution for preparing the high-sensitivity photoelectric detector.

Description

Semiconductor photoelectric detector based on three-layer structure and preparation method thereof
Technical Field
The invention belongs to the field of electronic information materials and components, and particularly relates to a semiconductor photoelectric detector and a preparation method thereof, which can be used in the field of photoelectric detection.
Background
In recent years, the photoelectric detection technology is rapidly developed, mainly comprises infrared detection, ultraviolet detection, laser detection, photoelectric comprehensive detection and the like, and is widely applied to the military and civil fields.
The semiconductor photoelectric detector has small volume, low power consumption, higher energy resolution, wider energy response linear range and shorter response time, and gradually develops into a mainstream technology in the field of photoelectric detection. Among them, a metal-semiconductor-metal (MSM) type detector is a more commonly used type of detector. Compared with other types of photoelectric detectors, the MSM type detector has the advantages of simple process, only one conductive active layer, easiness in integration with peripheral circuits, low parasitic capacitance and the like.
In practical application, the MSM type photodetector based on a single-layer semiconductor material generally has the problems of small photocurrent and low responsivity, and further influences the detection sensitivity of the device. Taking gallium oxide commonly used for solar blind ultraviolet detection as an example, the intrinsic state of gallium oxide has n-type conductivity due to the existence of oxygen vacancy defects. However, the mobility of gallium oxide is low, and the contact resistance with a metal electrode is high, which affects the performance of a solar blind ultraviolet detector prepared by the gallium oxide. Doping and alloying are commonly used to alter the carrier concentration and mobility of semiconductor materials. Research shows that the carrier concentration and mobility of the gallium oxide material can be improved by doping or alloying elements such as In and Sn, which is beneficial to improving the photocurrent and responsivity of the detector and provides possibility for obtaining high sensitivity. In addition, impurity defects introduced by doping or alloying can also improve the internal gain of the MSM type detector, namely the photoconductive gain, and also has the effect of improving the responsivity. For oxide semiconductors, increasing oxygen vacancies is also a special "doping" approach that can increase the carrier concentration of the material, while increasing oxygen vacancy defects also increases the internal gain of the detector, thereby achieving high responsivity, similar to the doping or alloying effects described above. However, doping or alloying can lead to an increase in the conductivity of the material, which can result in excessive dark current in the device, which can be detrimental to the improvement in specific detection rate and sensitivity.
Therefore, the spacer layer is additionally introduced on the doped or alloyed semiconductor layer to regulate and control the contact characteristic between metal and semiconductor and inhibit the increase of dark current, so that the detection sensitivity of the device is optimized. On the other hand, doping or alloying may cause deterioration of the crystalline quality of the semiconductor material, which is not favorable for improvement of the performance of the detector. Therefore, the present invention grows the intrinsic semiconductor layer at a high temperature before epitaxially growing the doped or alloyed semiconductor layer as a buffer layer to improve the crystalline quality of the doped or alloyed semiconductor layer.
Disclosure of Invention
The invention provides a semiconductor photoelectric detector based on a three-layer structure and a preparation method thereof, aiming at solving the problems of small photocurrent and low responsivity of the traditional photoelectric detector based on a single-layer semiconductor and further optimizing the detection sensitivity of the traditional photoelectric detector.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a semiconductor photoelectric detector based on a three-layer structure and a preparation method thereof are disclosed, wherein the semiconductor photoelectric detector comprises a substrate 1 at the bottom and a three-layer material structure above the substrate 1, and the three-layer material structure is respectively as follows from bottom to top: the photoelectric detector comprises an intrinsic semiconductor 2, a doped or alloyed semiconductor 3 and a spacing layer 4, wherein the upper part of the spacing layer is connected with an electrode layer 5, the electrode layer 5 comprises a first electrode 6 and a second electrode 7, and the photoelectric detector based on the intrinsic semiconductor-doped or alloyed semiconductor-spacing layer three-layer structure is formed.
Preferably, the material of the spacer layer 4 is a semiconductor or an insulating medium.
Preferably, the intrinsic semiconductor 2 and the doped or alloyed semiconductor 3 are both oxides.
Preferably, the element introduced by doping or alloying the semiconductor 3 comprises one of Si, Ti, Sn, In, Zn, Mn, Ga, Cu, Ge, Ta and Nb.
Preferably, the doped semiconductor 3 is doped using vacancy doping, such as oxygen vacancies.
Preferably, the doping or alloying process of the doped or alloyed semiconductor 3 is one of plasma treatment, ion implantation, spray pyrolysis, sol-gel method, and epitaxial growth.
Preferably, the substrate 1 is one of sapphire, silicon, glass, polyimide, silicon carbide, gallium oxide, gallium nitride, lithium gallate, lithium aluminate, indium nitride, gallium arsenide, magnesium oxide, and magnesium aluminate spinel.
Preferably, the material form of the doped or alloyed semiconductor 3 is one of a thin film, a single crystal bulk, a nanobelt, a nanowire, and a quantum dot.
Preferably, the intrinsic semiconductor 2 material is Ga2O3、ZnO、SnO2、In2O3、InGaZnO、MgZnO、Al2O3One of them.
Preferably, the electrode layer 5 is a patterned electrode.
Preferably, the electrode layer 5 is made of a single-layer or multi-layer conductive material selected from Ti, Ni, Al, Ag, Au, Cu, Pt, graphene, and conductive oxide thin film materials.
In order to achieve the above object, the present invention further provides a method for manufacturing a semiconductor photodetector with a three-layer structure, including the following steps:
step 1, surface treatment of a substrate;
step 2, preparation of an intrinsic semiconductor: epitaxially growing an intrinsic semiconductor on the substrate cleaned in the step 1;
step 3, preparation of doped or alloyed semiconductors: epitaxially growing a doped or alloyed semiconductor on the intrinsic semiconductor of step 2;
step 4, preparing a spacing layer: growing an intrinsic semiconductor or insulating medium on the doped or alloyed semiconductor of step 3;
step 5, photoetching;
step 6, depositing a metal electrode;
and 7, annealing.
The first layer of material of the three-layer structure is an intrinsic semiconductor and is mainly used as a high-temperature buffer layer for improving the crystallization quality of the upper epitaxial material; the second layer is made of a doped or alloyed semiconductor and is used for improving the carrier concentration and the mobility of the material or introducing an internal gain mechanism so as to improve the photocurrent and the responsivity of the detector; the third layer of material is a spacing layer, can be a semiconductor or an insulating medium, and is used for regulating and controlling the contact characteristic between metal and the semiconductor and inhibiting the increase of dark current, so that the specific detection rate of the detector is optimized, and the sensitivity is improved.
The invention has the beneficial effects that: compared with the traditional MSM type photoelectric detector based on a single-layer semiconductor material, the photoelectric current and the responsivity of the device are improved through doping or alloying; the intrinsic semiconductor at the lower part is beneficial to improving the crystallization quality of the doped or alloyed semiconductor, and the performance of the device is further improved; the upper spacer layer helps to suppress dark current, further optimizes specific detectivity, and finally provides a better solution for manufacturing a high-sensitivity photoelectric detector.
Drawings
FIG. 1 is a schematic perspective view of a semiconductor photodetector based on a three-layer structure according to the present invention;
FIG. 2 is a cross-sectional view of a semiconductor photodetector based on a three-layer structure in accordance with the present invention;
fig. 3 is a flow chart of a process for manufacturing a semiconductor photodetector based on a three-layer structure according to embodiment 3 of the present invention; a is the growth process of a doped or alloyed semiconductor, b is the growth process of a spacing layer, and c is the preparation process of a graphical electrode;
FIG. 4 shows the results of X-ray diffraction (XRD) measurements of the epitaxial thin film of example 3 of the present invention, wherein (a) is step 3 at β -Ga2O3Epitaxially grown (In) on thin filmsxGa1-x)2 O 32 theta scan of the film; (b) epitaxially growing beta-Ga on a substrate for step 22 O 32 theta scan of the film.
FIG. 5 shows epitaxially grown beta-Ga on a substrate in example 3 of the present invention2O3Film and (In) grown thereon by epitaxial growthxGa1-x)2O3XRD testing of films
Figure BDA0002011918460000031
ω scan of crystal plane.
Fig. 6 is a current-voltage characteristic of a semiconductor photodetector based on a three-layer structure according to embodiment 3 of the present invention, wherein (a) is a current-voltage curve under no illumination; (b) the current-voltage curve is under 254nm ultraviolet illumination.
Wherein 1 is a substrate, 2 is an intrinsic semiconductor, 3 is a doped or alloyed semiconductor, 4 is a spacer layer, 5 is an electrode layer, 6 is a first electrode, and 7 is a second electrode.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
A semiconductor photoelectric detector based on a three-layer structure comprises a substrate 1 at the bottom and a three-layer material structure above the substrate 1, wherein the three-layer material structure is respectively as follows from bottom to top: the photoelectric detector comprises an intrinsic semiconductor 2, a doped or alloyed semiconductor 3 and a spacing layer 4, wherein the upper part of the spacing layer 4 is connected with an electrode layer 5, the electrode layer 5 comprises a first electrode 6 and a second electrode 7, and the photoelectric detector is made of a metal-semiconductor-metal photoelectric detector based on an intrinsic semiconductor-doped or alloyed semiconductor-spacing layer three-layer structure.
Specifically, the material of the spacer layer 4 may be a semiconductor, or may be an insulating medium.
In particular, the intrinsic semiconductor 2 and the doped or alloyed semiconductor 3 are both oxides
Specifically, the element introduced by the doped or alloyed semiconductor 3 includes one of Si, Ti, Sn, In, Zn, Mn, Ga, Cu, Ge, Ta, and Nb.
Specifically, the doped semiconductor 3 employs vacancy doping, such as oxygen vacancy.
Specifically, the doping or alloying method of the doped or alloyed semiconductor 3 is one of plasma treatment, ion implantation, spray pyrolysis, sol-gel method, and epitaxial growth.
Specifically, the substrate 1 is one of sapphire, silicon, glass, polyimide, silicon carbide, gallium oxide, gallium nitride, lithium gallate, lithium aluminate, indium nitride, gallium arsenide, magnesium oxide, and magnesium aluminate spinel.
Specifically, the material form of the doped or alloyed semiconductor 3 is one of a thin film, a single crystal bulk, a nanobelt, a nanowire, and a quantum dot.
In particular, the intrinsic semiconductor 2 material is Ga2O3、ZnO、SnO2、In2O3、InGaZnO、MgZnO、Al2O3One of them.
Specifically, the electrode layer 5 is a patterned electrode.
Specifically, the electrode layer 5 is made of a single-layer or multi-layer conductive material selected from Ti, Ni, Al, Ag, Au, Cu, Pt, graphene, a conductive oxide thin film, and the like.
Example 2
The method for manufacturing a semiconductor photodetector based on a three-layer structure in embodiment 1 includes the steps of:
step 1, surface treatment of a substrate;
step 2, preparation of an intrinsic semiconductor: epitaxially growing an intrinsic semiconductor on the substrate cleaned in the step 1;
step 3, preparation of doped or alloyed semiconductors: epitaxially growing a doped or alloyed semiconductor on the intrinsic semiconductor of step 2;
step 4, preparing a spacing layer: growing an intrinsic semiconductor or insulating medium on the doped or alloyed semiconductor of step 3;
step 5, photoetching;
step 6, depositing a metal electrode;
and 7, annealing.
Example 3
The method for manufacturing a semiconductor photodetector based on a three-layer structure in embodiment 1 includes the steps of:
step 1, surface treatment of a substrate: ultrasonically cleaning a sapphire substrate with the size of 5mm multiplied by 10mm and the thickness of 0.5mm in acetone, absolute ethyl alcohol and deionized water for 1min, drying the sapphire substrate by using nitrogen, and baking the sapphire substrate for 5min at the temperature of 80 ℃ by using a hot plate to remove adsorbates on the surface of the sapphire substrate, so as to ensure that the surface of the sapphire substrate is clean and dry;
step 2, slowStrike layer beta-Ga2O3Preparing a film: epitaxially growing beta-Ga with the thickness of about 20nm on the cleaned sapphire substrate in the step 1 by adopting a molecular beam epitaxy method2O3The film is grown under the following conditions: vacuum degree of the back bottom is 1.5 multiplied by 10-5The temperature of a substrate is 760 ℃, the temperature of a Ga source is 920 ℃, the input power of a radio frequency power supply is 300W, the reflected power of the radio frequency power supply is 6W, and the flow of introduced oxygen is 1 sccm;
step 3, doping or alloying (In)xGa1-x)2O3Preparing a film: the temperature of the substrate is reduced to 560 ℃, and epitaxial growth (In) is carried outxGa1-x)2O3The growth time is 2 hours, and the film thickness is 50 nm. The growth conditions were: vacuum degree of the back bottom is 1.5 multiplied by 10- 5The temperature of a Ga source is 920 ℃, the temperature of an In source is 500 ℃, the input power of a radio frequency power supply is 300W, the reflected power of the radio frequency power supply is 6W, and the flow of introduced oxygen is 1 sccm;
step 4, spacing layer beta-Ga2O3Preparing a film: grown In step 3 (In)xGa1-x)2O3Continuing to epitaxially grow beta-Ga with the thickness of 5nm on the film2O3The film is grown under the following conditions: vacuum degree of the back bottom is 1.5 multiplied by 10-5Torr, the temperature of the substrate is 560 ℃, the temperature of the Ga source is 920 ℃, the input power of the radio frequency power supply is 300W, the reflected power of the radio frequency power supply is 6W, and the flow of the introduced oxygen is 1 sccm;
step 5, photoetching process: (1) coating glue, namely uniformly coating AZ5214 reverse photoresist on the film in the step 4 at the rotating speed of 3000 r/min; (2) prebaking, baking the coated photoresist at 100 ℃ for 60 s; (3) first exposure, covering the designed photoetching plate on the photoresist, wherein the exposure time is 0.3-2.0 s; (4) post-baking, baking the exposed photoresist at 120 ℃ for 90 s; (5) flood exposure is carried out, no photoetching plate is used, and the exposure time is 45 s; (6) developing, namely putting the flood-exposed sample into a developing solution for 30 s; (7) checking whether the width and the distance of the interdigital meet the set size;
and 6, depositing a metal electrode: evaporating metal Ti with thickness of 10nm by electron beam evaporation; the evaporation rate was kept at 0.1 nm/s; and then evaporating metal Al on the Ti layer, wherein the thickness is 100nm, the evaporation rate is kept at 2nm/s, after the metal is deposited, sequentially putting the sample into acetone, absolute ethyl alcohol and deionized water, and removing the photoresist, the redundant Ti and the Al to obtain the patterned electrode layer.
Step 7, rapid annealing: heating the sample obtained in the step 6 from room temperature to 400 ℃ at the heating rate of 50 ℃/s in the nitrogen atmosphere, annealing for 5min, improving the contact between the metal and the semiconductor, and finally obtaining the beta-Ga-based alloy2O3-(InxGa1-x)2O3-β-Ga2O3MSM type photoelectric detector of three-layer structure.
In beta-Ga2O3Grown on the buffer layer (In)xGa1-x)2O3Film is referred to as beta-Ga for short2O3-(InxGa1-x)2O3A film. As shown in FIG. 4, beta-Ga2O3-(InxGa1-x)2O3Thin film and beta-Ga2O3The characteristic peaks of the film in X-ray diffraction are all beta-Ga2O3Is/are as follows
Figure BDA0002011918460000051
Figure BDA0002011918460000061
Series of peaks indicating the utilization of beta-Ga2O3The film being grown as a buffer layerxGa1-x)2O3The film has no phenomenon of crystal phase separation and has better crystallization quality. As can be seen from FIG. 5, β -Ga2O3Thin film and beta-Ga2O3-(InxGa1-x)2O3The full widths at half maximum of the omega scan of the film were 1.630 deg. and 1.865 deg., respectively, further confirming that beta-Ga2O3The high-temperature buffer layer well avoids epitaxial growth (In) thereonxGa1-x)2O3Deterioration of the crystalline quality of the thin film.
This exampleThe MSM type photoelectric detector adopts a 'voltage-current measurement' working mode, and the current-voltage characteristic is tested. As shown in FIG. 6, based on β -Ga in the absence of light2O3-(InxGa1-x)2O3-β-Ga2O3Three-layer structure detector and single-layer beta-Ga-based detector2O3The dark current of the film detector is close to that of the detector adopting beta-Ga2O3-(InxGa1-x)2O3The case of a two-layer structure. Thus, it can be seen that beta-Ga2O3The existence of the spacer layer effectively regulates and controls the contact characteristic between the metal and the semiconductor, and inhibits the increase of dark current. At 254nm, 42. mu.W/cm2Based on beta-Ga under ultraviolet irradiation2O3-(InxGa1-x)2O3Two layers and beta-Ga2O3-(InxGa1-x)2O3-β-Ga2O3Three-layer structure of the detector, compared with the detector adopting single layer of beta-Ga2O3Thin film detectors, all with higher photocurrent due to increased mobility of the thin film after doping, reduced contact resistance between metal and semiconductor, and enhanced internal gain mechanism: in2O3Compared with beta-Ga2O3Has higher carrier mobility, and the In doping can improve beta-Ga2O3The mobility of the film can obtain higher photocurrent at the same voltage; in addition to mobility, In doping also increases the carrier concentration of the material, improving the contact characteristics between the metal and the semiconductor, which also helps to obtain higher photocurrent; in doping leads to the introduction of impurity defects In the thin film, and the impurity defects can restrict holes, so that the internal gain, namely the photoconductive gain, of the device is improved, and the photocurrent of the device is further improved.
Benefit from the increase of photocurrent and under the working bias of 20V, based on beta-Ga2O3-(InxGa1-x)2O3Two layers and beta-Ga2O3-(InxGa1-x)2O3-β-Ga2O3The responsivity of the detector with the three-layer structure is 165.32A/W and 323.80A/W respectively, which is much higher than that of a detector adopting single-layer beta-Ga2O3Film prepared detector (8.16A/W). Furthermore, the specific detectivity (D) is another commonly used detection indicator, which is not only related to responsivity, but also takes into account background noise caused by dark current:
Figure BDA0002011918460000062
wherein R represents the responsivity of the detector, q represents the electron charge amount, S represents the effective light receiving area of the detector, and IdarkRepresenting the dark current of the detector. Based on a single layer of beta-Ga2O3Thin film and beta-Ga2O3-(InxGa1-x)2O3Specific detectivity D of a two-layer detector*Are respectively 7.14 multiplied by 1012And 7.01X 1012cm·Hz1/2W, based on beta-Ga2O3-(InxGa1-x)2O3-β-Ga2O3The specific detection rate of the detector with the three-layer structure reaches 1.13 multiplied by 1014cm·Hz1/2and/W, the improvement is nearly two orders of magnitude. The comprehensive optimization of light and dark current proves that the three-layer material structure provided by the invention can effectively improve the sensitivity of the semiconductor photoelectric detector.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (5)

1. A semiconductor photoelectric detector based on a three-layer structure is characterized in that: comprises a substrate (1) at the bottom, a three-layer material structure above the substrate (1), threeThe layer material structure is as follows from bottom to top: buffer layer beta-Ga2O3Thin film, doped or alloyed (In)xGa1-x)2O3Thin film, spacer layer beta-Ga2O3Film of said spacer layer beta-Ga2O3The upper part of the thin film is connected with an electrode layer (5), wherein the electrode layer (5) comprises a first electrode (6) and a second electrode (7) to form a photoelectric detector based on an intrinsic semiconductor-doped or alloyed semiconductor-spacing layer three-layer structure; doping or alloying (In)xGa1-x)2O3The thin film is used for improving the mobility of the material or introducing an internal gain mechanism; the three layers of materials are films which are grown by continuous epitaxy;
buffer layer beta-Ga2O3The preparation method of the film comprises the following steps: epitaxially growing beta-Ga with the thickness of about 20nm on the cleaned sapphire substrate in the step 1 by adopting a molecular beam epitaxy method2O3The film is grown under the following conditions: vacuum degree of the back bottom is 1.5 multiplied by 10-5The temperature of a substrate is 760 ℃, the temperature of a Ga source is 920 ℃, the input power of a radio frequency power supply is 300W, the reflected power of the radio frequency power supply is 6W, and the flow of introduced oxygen is 1 sccm;
doping or alloying (In)xGa1-x)2O3The preparation method of the film comprises the following steps: the temperature of the substrate is reduced to 560 ℃, and epitaxial growth (In) is carried outxGa1-x)2O3The growth time is 2 hours, and the thickness of the film is 50 nm; the growth conditions were: vacuum degree of the back bottom is 1.5 multiplied by 10-5The temperature of a Ga source is 920 ℃, the temperature of an In source is 500 ℃, the input power of a radio frequency power supply is 300W, the reflected power of the radio frequency power supply is 6W, and the flow of introduced oxygen is 1 sccm;
spacer layer beta-Ga2O3The preparation method of the film comprises the following steps: grown In step 3 (In)xGa1-x)2O3Continuing to epitaxially grow beta-Ga with the thickness of 5nm on the film2O3The film is grown under the following conditions: vacuum degree of the back bottom is 1.5 multiplied by 10-5Torr, the substrate temperature is 560 ℃, the Ga source temperature is 920 ℃, the input power of the radio frequency power supply is 300W, and the reflected power of the radio frequency power supply is 6WThe flow rate of the introduced oxygen was 1 sccm.
2. The semiconductor photodetector based on a three-layer structure as claimed in claim 1, wherein: the substrate (1) is one of sapphire, silicon, glass, polyimide, silicon carbide, gallium oxide, gallium nitride, lithium gallate, lithium aluminate, indium nitride, gallium arsenide, magnesium oxide and magnesium aluminate spinel.
3. The semiconductor photodetector based on a three-layer structure as claimed in claim 1, wherein: the electrode layer (5) is a patterned electrode.
4. The semiconductor photodetector based on a three-layer structure as claimed in claim 1, wherein: the electrode layer (5) is made of a single-layer or multi-layer conductive material, and the material is selected from Ti, Ni, Al, Ag, Au, Cu, Pt, graphene and conductive oxide thin film materials.
5. The method for producing a semiconductor photodetector based on a three-layer structure as claimed in any one of claims 1 to 4, characterized by comprising the steps of:
step 1, surface treatment of a substrate;
step 2, preparation of an intrinsic semiconductor: epitaxially growing a buffer layer beta-Ga on the cleaned substrate in the step 12O3A film;
step 3, preparation of doped or alloyed semiconductors: buffer layer beta-Ga in step 22O3Epitaxial growth of doped or alloyed (In) on thin filmsxGa1-x)2O3A film;
step 4, preparing a spacing layer: doping or alloying In step 3 (In)xGa1-x)2O3Epitaxial growth of spacer layer beta-Ga on thin films2O3A film;
step 5, photoetching;
step 6, depositing a metal electrode;
and 7, annealing.
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