CN110323303B - Ga2O3-CuSCN core-shell heterojunction solar blind ultraviolet detector and preparation method thereof - Google Patents
Ga2O3-CuSCN core-shell heterojunction solar blind ultraviolet detector and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
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Abstract
The invention provides Ga2O3-CuSCN core-shell heterojunction solar-blind UV detector comprising Ga as n-type core material2O3The thin film transistor comprises a single crystal, a CuSCN thin film used as a p-type shell layer material, a first electrode in ohmic contact with an n-type core material and a second electrode in ohmic contact with the p-type shell layer material. The invention also discloses Ga2O3A preparation method of a CuSCN core-shell heterojunction solar blind ultraviolet detector. The core-shell structured solar blind ultraviolet detector has the advantages of simple preparation process and excellent device performance, can detect ultra-weak solar blind ultraviolet signals, can realize self-powered work, and is suitable for a high-sensitivity and high-precision ultraviolet detection system.
Description
Technical Field
The invention relates to a solar blind ultraviolet detector and a preparation method thereof, in particular to a solar blind ultraviolet detector based on Ga2O3A solar blind ultraviolet detector of a CuSCN core-shell heterojunction and a preparation method thereof, belonging to the field of semiconductor optoelectronic devices.
Background
Photoelectric detection is the basis of imaging technology, deep ultraviolet astronomy, environmental monitoring, safety communication, biochemical analysis, national defense early warning, fire detection and other fields, and has received significant attention and stable development in recent decades because of its wide application. The working principle of the optical detector is to convert the captured optical signal into an electrical signal, thereby realizing detection. The optical detector can be divided into an ultraviolet detector, a visible light detector, an infrared detector and the like according to the wave band of the optical signal responded by the optical detector. The ultraviolet detector can be subdivided into detectors corresponding to UVA (315-400 nm), UVB (280-315 nm), UVC (200-280 nm) and EUV (10-200 nm) wave bands. The UVC wave band is called a solar blind wave band, and the reason is that ultraviolet light with a wave band of 200-280 nm hardly exists on the earth surface due to the absorption of an ozone layer. The absence of the background light on the earth is avoided, so that the solar blind ultraviolet detector has extremely high optical signal detection sensitivity and extremely high accuracy, and becomes a high-end technology in the fields of safety communication, military guidance and the like.
The photo-detected optical signal response is based on the forbidden bandwidth of the semiconductor material. Ga2O3The material has a forbidden band width of 4.2-5.3 eV, can almost realize the full coverage of a solar blind waveband, and is an excellent core material of a solar blind detector. But based on Ga alone2O3The detection device with the metal-semiconductor-metal (MSM) structure has the defects of low sensitivity, slow response speed and the like, and generally can work under the condition of external power supply. In recent years, a novel heterojunction device has attracted extensive attention because a built-in electric field existing at an interface of the novel heterojunction device can realize effective separation of electron-hole pairs and high-efficiency transmission of carriers, and contributes remarkably to improvement of performance of a detection device. Therefore, the development was based on Ga2O3The heterojunction solar blind detector necessarily gives Ga2O3The application of materials brings new growth poles.
Disclosure of Invention
Against the existing Ga2O3The technical defects of the performance of the detector, the invention aims to provide Ga2O3CuSCN core-shell heterojunction solar-blind UV detector by using Ga2O3The single crystal wire is wrapped with the CuSCN film, so that the photoelectric performance of the detector is effectively improved, and the detection of ultra-weak ultraviolet signals and the self-powered operation of devices are realized.
Another object of the present invention is to provide a Ga compound2O3A preparation method of a CuSCN core-shell heterojunction solar blind ultraviolet detector.
The technical scheme for realizing the above purpose of the invention is as follows:
ga2O3-CuSCN core-shell heterojunction solar-blind UV detector comprising Ga as n-type core material2O3The thin film transistor comprises a single crystal, a CuSCN thin film used as a p-type shell layer material, a first electrode in ohmic contact with an n-type core material and a second electrode in ohmic contact with the p-type shell layer material.
Wherein Ga as n-type core material2O3The thickness of the single crystal is 5 nm-50 μmThe width is 50 nm-500 μm, and the length is 3 mm-5 cm.
Preferably, Ga as the n-type core material2O3The thickness of the single crystal is 100 nm-10 μm, the width is 200 nm-200 μm, and the length is 5 mm-2 cm.
Wherein the thickness of the CuSCN film used as the p-type shell layer material is 5 nm-5 μm.
Preferably, the thickness of the CuSCN film used as the p-type shell layer material is 10-500 nm.
Wherein the first electrode in ohmic contact with the n-type core material is one or a combination of more of aluminum, copper, silver, platinum, titanium, gallium, indium, and gold.
Wherein the thickness of the first electrode is 10-200 nm.
Preferably, the first electrode in ohmic contact with the n-type core material is indium.
Preferably, the first electrode in ohmic contact with the n-type core material is a combination of titanium and gold.
Preferably, the first electrode in ohmic contact with the n-type core material is an indium gallium alloy.
Wherein the second electrode in ohmic contact with the p-type shell material is one or more of aluminum, copper, silver, platinum, titanium, gallium, indium and gold.
Wherein the thickness of the second electrode is 10-200 nm.
Preferably, the second electrode in ohmic contact with the p-type shell material is indium.
Preferably, the second electrode in ohmic contact with the p-type shell material is a titanium-gold combination.
Preferably, the second electrode in ohmic contact with the p-type shell material is an indium gallium alloy.
A second aspect of the present invention provides Ga2O3The preparation method of the-CuSCN core-shell heterojunction solar blind ultraviolet detector comprises the following steps: in Ga2O3Growing a CuSCN film on the surface of the single crystal to form Ga2O3The single crystal and the CuSCN film form a heterojunction; respectively in Ga2O3And forming electrodes on the single crystal and the CuSCN film.
Preferably in Ga2O3The step of generating the CuSCN film on the surface of the single crystal comprises the following steps: in Ga2O3Attaching a CuSCN solution to the surface of the single crystal; ga to which CuSCN solution is adhered2O3Baking the single crystal to form Ga2O3And generating a CuSCN film on the surface of the single crystal.
Preferably, the Ga is2O3The single crystal being linear, i.e. Ga2O3A single crystal line; in Ga2O3When a CuSCN solution is attached to the surface of a single-crystal wire, the CuSCN solution is attached to the Ga2O3Part of the length of the single crystal line.
Preferably, the Ga is2O3The single crystal line being from doped or undoped Ga2O3Single crystal wires stripped on a single crystal, or doped or undoped Ga synthesized by chemical means2O3A single crystal line.
Preferably, the solute of the CuSCN solution is CuSCN, and the solvent is dipropyl sulfide or diethyl sulfide.
Preferably, the preparation method comprises the following steps:
(1) preparation of Ga2O3A single crystal line;
(2) preparing a solution of CuSCN;
(3) ga is mixed with2O3Immersing a part of the single crystal wire (the immersed part is 1/5 with the length being larger than the whole length of the single crystal wire and 4/5 with the length being smaller than the whole length of the single crystal wire) into a CuSCN solution for 5-30 s;
(4) washing the single crystal wire soaked with the CuSCN for 5-30 s by using clear water;
(5) ga with CuSCN attached after cleaning2O3Heating and drying the single crystal wire at the heating temperature of 100-250 ℃ for 5-40 min;
(6) preparing a first electrode in ohmic contact with the n-type core material;
(7) preparing a second electrode in ohmic contact with the p-type shell material;
(8) and annealing the device with the prepared electrode to form good ohmic contact.
Wherein the content of the first and second substances,said Ga being2O3Single crystal wires, doped or undoped single crystal wires chemically synthesized, or from doped or undoped Ga2O3A single crystal wire stripped on the single crystal.
Preferably, the Ga is2O3The single crystal line being from doped or undoped Ga2O3A single crystal wire stripped on the single crystal.
Wherein the solute of the CuSCN solution is CuSCN, the solvent is dipropyl sulfide or diethyl sulfide, and the concentration of the solution is 5-100 mg/ml.
Preferably, the solvent is diethyl sulfide.
Preferably, the concentration of the solution of CuSCN in diethyl sulfide is 5-30 mg/ml.
Wherein, the Ga is2O3One half of the single crystal wire is immersed in the CuSCN solution, and the holding time is preferably 5-10 s.
Wherein the Ga to which CuSCN is attached after cleaning2O3And heating and drying the single crystal line, preferably, the heating temperature is 150-200 ℃, and the heating time is 10-20 min.
The preparation method of the first electrode in ohmic contact with the n-type core material and the second electrode in ohmic contact with the p-type shell material is one or a combination of thermal evaporation, magnetron sputtering and hot melting.
Preferably, the preparation method of the first electrode and the second electrode is thermal evaporation.
The invention has the beneficial effects that:
(1) provides a Ga2O3A CuSCN core-shell heterojunction solar blind ultraviolet detector, wherein the core material of the device is n-type Ga2O3The shell layer material of the single crystal and the device is a p-type CuSCN film, the formed core-shell structure is a pn junction, and the p-type CuSCN film is formed in Ga2O3A built-in electric field is formed at the interface of the CuSCN and can effectively separate and transmit electron hole pairs generated under light irradiation, thereby effectively improving Ga2O3Sensitivity and response speed of-CuSCN core-shell heterojunction solar blind ultraviolet detector, and ultra-weak ultraviolet is realizedDetection of optical signals and self-powered operation of the device.
(2) The solution infiltration method used in the invention has the advantages of simple operation, no need of high vacuum and high temperature equipment, low cost and suitability for industrial production and scientific research exploration.
Drawings
FIG. 1 is Ga prepared by the process of the present invention2O3A schematic structural diagram of a CuSCN core-shell heterojunction solar blind ultraviolet detector, wherein 01 is a core material Ga2O302 is a shell material CuSCN, 03 is a sapphire substrate material, 04 is a first electrode in ohmic contact with a core material, and 05 is a second electrode in ohmic contact with the shell material;
FIG. 2 is Ga2O3-a spectral selection curve of a CuSCN core-shell heterojunction solar blind ultraviolet detector;
FIG. 3 is Ga2O3Time-current curve of infinitesimal ultraviolet light irradiation of CuSCN core-shell heterojunction solar blind ultraviolet detector, the test conditions are as follows: the external bias voltage is 1V, and the light intensity is 1.5/2.5/3.5/4.5/5.5 muW/cm2Ultra-weak 254nm ultraviolet radiation.
FIG. 4 is Ga2O3The time-current curve of the CuSCN core-shell heterojunction solar blind ultraviolet detector under the bias voltage of 0V is as follows: the external bias voltage is 0V, and the light intensity is 200/400/600/800/1000 mu W/cm2Irradiation with 254nm ultraviolet light.
FIG. 5 shows Ga2O3The time-current curve of the CuSCN core-shell heterojunction solar blind ultraviolet detector is as follows: external bias voltage of 1V and light intensity of 1mW/cm2While a response time fitting calculation was performed based on the measured response curve.
FIG. 6 shows the use of simple Ga2O3The time-current curve of the MSM prepared by the single crystal line and the metal indium is compared with that of the device 1, and the test conditions are as follows: under the external bias voltage of 1V, the light intensity of 1mW/cm2 is irradiated by 254nm ultraviolet light, and meanwhile, the fitting calculation of the response time is carried out according to the measured response curve.
FIG. 7 is a time-current curve of a MSM comparative device 2 prepared with a simple CuSCN thin film and indium metalThe test conditions were: external bias voltage of 1V and light intensity of 1mW/cm2While a response time fitting calculation was performed based on the measured response curve.
Detailed Description
In order to solve the problems of the prior art, the invention provides Ga2O3-CuSCN core-shell heterojunction solar-blind UV detector comprising Ga as n-type core material2O3Single crystal, CuSCN film as p-type shell layer material. In addition, a first electrode in ohmic contact with the n-type core material and a second electrode in ohmic contact with the p-type shell material are included. The core material of the device is n-type Ga2O3The shell layer material of the single crystal and the device is a p-type CuSCN film, the formed core-shell structure is a pn junction, and the p-type CuSCN film is formed in Ga2O3A built-in electric field is formed at the interface of the CuSCN and can effectively separate and transmit electron hole pairs generated under light irradiation, thereby effectively improving Ga2O3The sensitivity and the response speed of the CuSCN core-shell heterojunction solar blind ultraviolet detector are high, and the detection of ultra-weak ultraviolet signals and the self-powered operation of devices are realized.
To prepare the above Ga2O3The invention also provides a preparation method of the solar blind ultraviolet detector, which comprises the following steps: in Ga2O3Growing a CuSCN film on the surface of the single crystal to form Ga2O3The single crystal and the CuSCN film form a heterojunction; then, respectively in Ga2O3And forming electrodes on the single crystal and the CuSCN film.
In a preferred embodiment, the present invention is applied to Ga2O3When a CuSCN thin film is formed on the surface of a single crystal, Ga is first added2O3Attaching a CuSCN solution to the surface of the single crystal; then the Ga with the CuSCN solution is attached2O3And (5) drying the single crystal.
Proved by experiments, the Ga is more preferable2O3The single crystal being linear, i.e. Ga2O3A single crystal line; in Ga2O3When the surface of the single crystal line is attached with the CuSCN solution, the CuSCN solution is attachedIs attached to the Ga2O3Part of the length of the single crystal line, so that part of Ga is obtained2O3Single crystal line bare, part of Ga2O3The surface of the single crystal wire is wrapped with a layer of CuSCN film, so that the exposed Ga can be respectively coated2O3The single crystal wire part forms a first electrode, and a second electrode is formed on the wrapping layer CuSCN film part.
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
From undoped beta-Ga by mechanical stripping methods2O3Obtaining beta-Ga on a single crystal wafer2O3 Single crystal wire 01, beta-Ga2O3The single crystal line had a thickness of 2 μm, a width of 100 μm and a length of 1.2 cm.
Preparing a dipropyl sulfide solution of CuSCN, wherein the concentration of the solution is 10mg/ml, the solution needs to be stirred and dissolved for 24 hours on a magnetic stirring platform, and the solution is kept still for 12 hours.
Reacting beta-Ga2O3Cleaning single crystal line, drying to obtain beta-Ga2O3And immersing one half of the single crystal line into the dipropyl sulfide liquid drop of CuSCN, keeping the liquid drop for 5s, taking out the single crystal line, standing the single crystal line for 5min, cleaning the single crystal line in deionized water, and drying the single crystal line on a heating platform at the heating temperature of 150 ℃ for 10min to obtain the shell CuSCN film 02.
Ga which will form good contact2O3-CuSCN heterojunction microwire onto a sapphire substrate 03, in the core material Ga2O3Pressing a metal indium electrode on the end of the single crystal wire 01 as a first electrode 04, pressing a metal indium electrode on the end of the shell material CuSCN film 02 as a second electrode 05, and heating for 3min at 130 ℃ on a thermal platform to ensure that the electrodes are in full contact. Ga prepared2O3The structural schematic diagram of the-CuSCN core-shell heterojunction solar blind ultraviolet detector is shown in figure 1.
Ga prepared2O3The spectrum selection curve of the-CuSCN core-shell heterojunction solar blind ultraviolet detector is shown in figure 2, the spectrum selection curve is measured by a monochromator provided with a xenon lamp and a semiconductor analyzer, and different wave bands are measuredIs normalized. Ga prepared from the spectral curve2O3The main response wave band of the CuSCN core-shell heterojunction detector is 200-275 nm, the CuSCN core-shell heterojunction detector is a solar blind wave band, and the prepared detector is a solar blind ultraviolet detector.
Ga prepared2O3The CuSCN core-shell heterojunction solar blind ultraviolet detector can detect extremely weak ultraviolet signals, as shown in figure 3, even under the light intensity of 1.5 muW/cm2Can also stably respond to 1 mu W/cm under the irradiation of 254nm light2The light intensity fluctuation can also be sensitively reflected, and the ultra-sensitive detection capability is shown.
Ga prepared2O3The working curve of the CuSCN core-shell heterojunction solar-blind ultraviolet detector under the bias voltage of 0V is shown in fig. 4, namely under the condition of no external voltage, the prepared detector can also respond to light with different light intensities, and the operation is stable, which shows that the prepared detector can work in a self-powered mode.
Ga prepared2O3-CuSCN core-shell heterojunction solar blind ultraviolet detector under 1V bias voltage and 1mW/cm2The time-current curve measured under 254nm ultraviolet irradiation of light intensity is shown in fig. 5, the steady current under irradiation is about 2nA, the fitting calculation of response time is performed according to the measured response curve, the obtained rise response time is 0.19s, and the fall response time is 0.16 s.
In other embodiments, Ga is2O3A portion of the single crystal wire is immersed in the CuSCN solution and the length of the immersed portion may be greater than 1/5 and less than 4/5 of the total length of the single crystal wire.
In other embodiments, Ga2O3The single crystal wire can be kept for 5 to 30 seconds after being immersed in the CuSCN solution.
In other embodiments, the single crystal wire immersed with CuSCN can be rinsed with clean water for 5-30 s.
In other embodiments, the Ga to which CuSCN is attached after cleaning2O3And heating and drying the single crystal line, wherein the heating temperature can be 100-250 ℃, and the heating time can be 5-40 min.
In order to exhibit the advantageous effects of the present invention, the following comparative examples were conducted.
Comparative example 1
From undoped beta-Ga by mechanical stripping methods2O3Obtaining beta-Ga on a single crystal wafer2O3Single crystal wire, beta-Ga2O3The single crystal line had a thickness of 2 μm, a width of 100 μm and a length of 1.2 cm.
Reacting beta-Ga2O3Cleaning and drying the single crystal wire, pressing metal indium electrodes at two ends respectively, and heating for 3min at 130 ℃ on a thermal platform to make the electrodes fully contacted.
Prepared In-Ga2O3In (MSM structure) photodetector at 1V bias, 1mW/cm2The time-current curve measured under 254nm ultraviolet irradiation of light intensity is shown in fig. 6, the steady current under irradiation is about 8pA, the fitting calculation of response time is performed according to the measured response curve, the obtained rise response time is 2.42s, and the fall response time is 2.20 s.
Comparative example 2
Preparing a dipropyl sulfide solution of CuSCN, wherein the concentration of the solution is 10mg/ml, the solution needs to be dissolved for 24 hours on a magnetic stirring platform, and the solution is kept still for 12 hours.
The prepared dipropyl sulfide solution of CuSCN is spin-coated on a sapphire substrate, the rotation speed is 2500 rpm, the spin-coating time is 50s, and then the sapphire substrate is heated and dried on a thermal platform, the heating temperature is 150 ℃, and the heating time is 10 min.
Pressing two metal indium electrodes on the surface of the CuSCN film, and heating for 3min at 130 ℃ on a thermal platform to ensure that the electrodes are in full contact.
The prepared In-CuSCN-In (MSM structure) photoelectric detector is biased at 1V and has a concentration of 1mW/cm2The time-current curve measured under 254nm ultraviolet irradiation of light intensity is shown in fig. 7, the steady current under irradiation is about 12pA, the fitting calculation of response time is performed according to the measured response curve, the obtained rise response time is 2.96s, and the fall response time is 17.97 s.
Exemplary embodiments of the present invention are specifically illustrated and described above. It is to be understood that the invention is not limited to the precise construction and methodology described herein; on the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
In addition, the structures, proportions, sizes, and the like shown in the drawings are only used for matching with the disclosure of the present disclosure, so as to be understood and read by those skilled in the art, and are not used for limiting the limit conditions of the present disclosure, so that the present disclosure has no technical essence, and any structural modification, proportion relationship change, or size adjustment should still fall within the scope of the technical contents of the present disclosure without affecting the technical effects and the achievable objectives of the present disclosure.
In addition, the terms "above", "first", "second" and "a" as used in the present specification are for the sake of clarity only, and are not intended to limit the scope of the present disclosure, and changes or modifications of the relative relationship may be made without substantial technical changes and modifications.
Claims (8)
1. Ga2O3-CuSCN core-shell heterojunction solar-blind UV detector, characterized in that it comprises Ga as n-type core material2O3Single crystal, CuSCN thin film as p-type shell layer material, and n-type coreA first electrode in ohmic contact with the core material and a second electrode in ohmic contact with the p-type shell material; wherein Ga as n-type core material2O3The thickness of the single crystal is 5 nm-50 μm, the width is 50 nm-500 μm, and the length is 3 mm-5 cm; the thickness of the CuSCN film used as the p-type shell layer material is 5 nm-5 mu m.
2. Ga according to claim 12O3-CuSCN core-shell heterojunction solar-blind uv detector, characterized in that the first electrode in ohmic contact with the n-type core material is one or a combination of more of aluminum, copper, silver, platinum, titanium, gallium, indium and gold.
3. Ga according to claim 12O3-CuSCN core-shell heterojunction solar-blind uv detector, characterized in that the second electrode in ohmic contact with the p-type shell material is one or a combination of more of aluminum, copper, silver, platinum, titanium, gallium, indium and gold.
4. Ga2O3The preparation method of the CuSCN core-shell heterojunction solar blind ultraviolet detector is characterized by comprising the following steps of:
in Ga2O3Growing a CuSCN film on the surface of the single crystal to form Ga2O3The single crystal and the CuSCN film form a heterojunction, the Ga2O3The thickness of the single crystal is 5 nm-50 μm, the width is 50 nm-500 μm, and the length is 3 mm-5 cm; the thickness of the CuSCN film is 5 nm-5 mu m;
respectively in Ga2O3And forming electrodes on the single crystal and the CuSCN film.
5. Ga according to claim 42O3The preparation method of the-CuSCN core-shell heterojunction solar blind ultraviolet detector is characterized in that the method is carried out on Ga2O3The step of generating the CuSCN film on the surface of the single crystal comprises the following steps:
in Ga2O3Attaching a CuSCN solution to the surface of the single crystal;
ga to which CuSCN solution is adhered2O3Baking the single crystal to form Ga2O3And generating a CuSCN film on the surface of the single crystal.
6. Ga according to claim 52O3The preparation method of the-CuSCN core-shell heterojunction solar blind ultraviolet detector is characterized in that the Ga2O3The single crystal being linear, i.e. Ga2O3A single crystal line; in Ga2O3When a CuSCN solution is attached to the surface of a single-crystal wire, the CuSCN solution is attached to the Ga2O3Part of the length of the single crystal line.
7. Ga according to claim 62O3The preparation method of the-CuSCN core-shell heterojunction solar blind ultraviolet detector is characterized in that the Ga2O3The single crystal line being from doped or undoped Ga2O3Single crystal wires stripped on a single crystal, or doped or undoped Ga synthesized by chemical means2O3A single crystal line.
8. Ga according to claim 52O3The preparation method of the-CuSCN core-shell heterojunction solar blind ultraviolet detector is characterized in that a solute of a CuSCN solution is CuSCN, and a solvent is dipropyl sulfide or diethyl sulfide.
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