AU2019241284B2 - Ultra-wide band gap MexSn1-xO2 alloy semiconductor epitaxial thin film material and preparation method therefor, application thereof and device thereof - Google Patents
Ultra-wide band gap MexSn1-xO2 alloy semiconductor epitaxial thin film material and preparation method therefor, application thereof and device thereof Download PDFInfo
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
Abstract
An ultra-wide band gap Me
Description
ULTRA-WIDE BAND GAP MExSN1x02 ALLOY SEMICONDUCTOR SINGLE CRYSTAL EPITAXIAL THIN FILM MATERIAL AND PREPARATION METHOD THEREFOR, APPLICATION THEREOF AND DEVICE THEREOF
TECHNICAL FIELD The present invention relates to the technical field of semiconductor optoelectronic materials and devices, and particularly relates to several ultra-wide bandgap MexSn1.x0 2 alloy semiconductor epitaxial film materials having an adjustable bandgap, preparation methods thereof and applications thereof in deep ultraviolet detector.
BACKGROUND Ultraviolet detection has extremely important applications in many areas, such as high voltage grid monitoring, flame detection, missile plume tracking, and sky UV detection. Of course, there are still many problems to be solved urgently in the field of ultraviolet detection, among which the most urgent and most noteworthy is the detection of light in the deep ultraviolet band. Since the wavelength ofultraviolet light in this band is less than 280 nm, photomultiplier tubes and silicon-based detectors are dominant in the conventional detection. The photomultiplier tube type detector is bulky and heavy, and must be equipped with a high-voltage DC power source, which makes it difficult to miniaturize. As for the silicon-based detector, since the bandgap of silicon is only 1.1 eV, its response peak wavelength is around 800 nm, and the response to deep ultraviolet rays is low. In addition, silicon detectors also respond to visible light, so expensive UV filters must be equipped. Therefore, wide-bandgap semiconductor materials must be developed in order to achieve miniaturization and integration of high-performance deep-UV detectors. Typical ultra-wide bandgap semiconductor materials include aluminum nitride (6.2 eV), diamond (5.5 eV), P-Ga 203 (4.8 eV), Sn02 (3.6 eV), and the like. Although advances have been made in the study of ultra-wide bandgap semiconductor materials, the following problems still exist. The AlxGa1.xN system is prone to phase separation and element segregation at high Al content; at the same time, the donor and acceptor levels become deep and difficult to excite; due to the persistent photoconductivity effect, the response speed of AlGaN-based UV photodetectors is difficult to improve. High-quality large-area epitaxial growth of diamonds has always been difficult, and there is not an effective way to adjust the bandgap, either. Due to its band structure, p-type doping of P-Ga2 03 is very difficult. The bandgap of Sn02 reaches 3.6 eV, but still cannot meet the requirement of deep ultraviolet light detection, so pure Sn0 2 needs to be doped to broaden its bandgap. Although studies have shown that doping Sn02 with a small amount of Zr can increase the bandgap, it has not been reported to achieve detection of deep ultraviolet rays. In view of the above reasons, the present application has been made.
SUMMARY OF THE PRESENT INVENTION In order to solve the problems in conventional deep ultraviolet light detection, the present invention seeks to provide a SnO 2-based ultra-wide bandgap MexSn1.x02 alloy semiconductor epitaxial film material having an adjustable bandgap, a preparation method thereof, and an application thereof in a deep ultraviolet detector. The present invention obtains a MexSn1.x02 alloy semiconductor epitaxial film having a suitable bandgap by doping SnO2 with an appropriate amount of Zr, or Hf, or Si, or a combination of any two or three elements thereof, for fabricating an ultraviolet photodetector. The first aspect of the present invention is to provide: An ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film material, comprising: a homogenous mixture of SnO2 and MeO 2 , where x is greater than 0 and less than 1, and Me is Zr, or Hf, or Si, or a combination of any two or three elements thereof, wherein the film material is in the form of a single layer. In the above technical solution, preferably, x is between 0.01 and 0.99; more preferably, x is between 0.05 and 0.99; most preferably, x is between 0.05 and 0.30 or x is between 0.30 and 0.99. A second aspect of the present invention is to provide a method for preparing the ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film material, comprising the following steps: Step 1: determining a molar ratio of SnO 2 and MeO 2 according to a predetermined semiconductor bandgap, and preparing a ceramic target compounded with MeO2 and SnO2 according to the molar ratio; and Step 2: preparing the MexSn1.x02 alloy compound semiconductor epitaxial film on a substrate based on the ceramic target compounded with MeO2 and SnO 2 .
Further, in the above technical solution, Step 1 comprises the following steps: la). preparing a mixed material of SnO 2 and MeO 2 ; lb). adding anhydrous ethanol to the mixed material obtained in the step la) and ball milling to obtain a homogeneous mixed material; ic). washing the homogeneous mixed material obtained in the step lb) and drying to obtain a homogeneous mixture of SnO 2 and MeO 2 ; Id). grinding the homogeneous mixture of SnO 2 and MeO2 obtained in the step 1c) with anhydrous ethanol used as a binder during grinding to obtain bound powders; le). pressing the bound powders obtained in the step Id) into a disc; and If). sintering the pressed disc obtained in the step le) to obtain a ceramic target. Further, in the above technical solution, in the step If), the sintering temperature of the pressed disc is 1000 to 1200 °C; and the sintering time is 3 to 4 hours. Further, in the above technical solution, Step 2 comprises the following steps: 2a). ultrasonically cleaning and drying a c-plane sapphire substrate; 2b). depositing the ceramic target material obtained in Step 1) onto the c-plane sapphire substrate subjected to ultrasonically cleaning and drying by pulsed laser deposition to prepare an epitaxially grown film, so as to obtain the MexSn1.x02 alloy semiconductor single crystal epitaxial film material, where x is greater than 0 and less than 1. Further, in the step 2b), the epitaxial film deposition temperature is 100 to 700 °C, the oxygen pressure is 0 to 5 Pa, and the pulsed laser energy is 150 to 400mJ/pulse. A third aspect of the present invention is to provide an application of the above-mentioned ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film material as a functional layer material in a deep ultraviolet detector. A fourth aspect of the present invention is to provide a deep ultraviolet detector comprising: a substrate, a functional layer deposited on the substrate, and a parallel or interdigital electrode deposited on the functional layer. The functional layer is formed by the ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film material. Further, in the above technical solution, the detection wavelength of the deep ultraviolet detector is 300 nm to 220 nm. Further, in the above technical solution, the functional layer has a thickness of 100 to 300 nm, the electrode has a thickness of 30 to 70 nm, and the electrode spacing is 10 to 100 [m. Further, in the above technical solution, the substrate is preferably a c-plane sapphire substrate, and the sapphire substrate has a thickness of 0.35 to 0.45 mm. Further, in the above technical solution, the electrode is made of any one of Pt, Au, Al and ITO.
A fifth aspect of the present invention is to provide a method for fabricating the above-mentioned deep ultraviolet detector, wherein the MexSn1.x0 2 alloy semiconductor single crystal epitaxial film material is plated with a high-purity metal (Pt, Au, Al) electrode by vacuum evaporation, or is plated with a transparent conductive ITO electrode by sputtering. Further, in the above technical solution, the method of plating the high-purity metal electrode by vacuum evaporation is specifically as follows: First, the film sample was placed on a mask, and high-purity metal powders were placed in an evaporation boat, and then they were placed in a vacuum chamber of a vacuum evaporator. When a high vacuum environment on the order of no higher than 10-4 Pa was obtained by evacuating with a mechanical pump and a molecular pump, the evaporation source was turned on, and then the evaporation current was increased smoothly and slowly. After the evaporation was completed, the relief valve was opened, and when the pressure of the vacuum chamber was equal to the outside atmospheric pressure, the vacuum chamber was opened to take out the sample. Finally, the completed photodetector fabricated was vacuum packaged. The device obtained according to the present invention is measured using an optoelectronic test system for photoelectric properties, such as a volt-ampere characteristic (current-voltage) curve, a current-time curve, and a spectral response of the sample, thereby judging the feasibility of using the MexSn1.x0 2 alloy semiconductor epitaxial film materials in fabricating ultraviolet detectors. The ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film material, the preparation method thereof and the application thereof in the deep ultraviolet detector according to the present invention have the following beneficial effects: (1) The MexSni.02 material provided by the present invention is a multi-element (ternary, quaternary or quinary) alloy compound semiconductor obtained by solid -solution of SnO2 and MeO2 in a certain molar ratio. Because the wavelength of the solar blind - deep ultraviolet region is less than 280 nm, the bandgap Eg of the matrix material of the solar blind detector is required to be no less than 4.43 eV. Me*4and 4 Sn*have the same valence, their ionic radii are close, MeO2 has a bandgap of up to 5.5eV, and its lattice type is very close to that of SnO 2 , thus the ultra-wide bandgap MexSn1.x02 alloy semiconductor epitaxial film material with direct transition is successfully obtained by partially substituting Sn4* ions with Me*ions. In addition, it is found through the analysis of the film compositions that Mee xhibits a big solid solubility limit in the alloy, and it is very likely to form a substitutional solid solution alloy system of complete solubility. This property provides the possibility of freely adjusting the bandgap of the alloy in a larger range as well as the possibility of successfully fabricating photodetectors that can respond to and detect ultraviolet light of an even shorter wavelength. (2) Besides the pulsed laser deposition method, the MexSn1.x0 2 alloy semiconductor single crystal epitaxial film material provided by the present invention can also be prepared or grown by various methods such as magnetron sputtering and electron beam evaporation, and the equipment and operation are simple and convenient, so the present invention has a very positive effect on successfully solving the technical problem of deep ultraviolet light detection, with which the field of ultraviolet light detection has long been plagued. (3) According to the present invention, Me doping in Sn02 can release the forbidden transition of Sn02 and enhance its response to deep ultraviolet light. (4) The MexSni.02 alloy compound semiconductor single crystal epitaxial film material provided by the present invention has excellent characteristics of ultra-wide energy gap and direct photoelectric transition, and provides an ideal device material for deep ultraviolet light detection. Moreover, the deep ultraviolet detector of the present invention can be fabricated by a variety of growth or preparation methods, the equipment and operation process are simple and easy to learn, and suitable for large scale industrial production; the raw materials for fabricating the device are cheap and easy to obtain, so the complete device can be fabricated at a lower cost, which is extremely important to large scale production and applications.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is X-ray diffraction (XRD) 0-20 scan spectra of ZrxSn1.x02 epitaxial films with different doping ratios prepared according to Examples 1 and 2 of the present invention; Figure 2 is an X-ray diffraction (p-scan spectrum of a Zro.3 Sno.702 epitaxial film prepared according to Example 2 of the present invention; Figure 3 is an X-ray diffraction rocking curve (o-scan) spectrum of a Zro.3 Sno.702 epitaxial film prepared according to Example 2 of the present invention; Figure 4 is transmission spectra of ZrxSn1.x02 epitaxial films with different doping ratio prepared according to Examples 1 and 2 of the present invention; Figure 5 is a current-time curve of an ultraviolet detector based on a Zro.3Sno.70 2 epitaxial film prepared according to Example 2 of the present invention at a voltage of 150V; Figure 6 is a current-time curve of an ultraviolet detector based on a Zro.3Sno.70 2 epitaxial film with a high zirconium content prepared according to Example 2 of the present invention at a voltage of 1OV; Figure 7 is a current-time curve of an ultraviolet detector based on a Zro.1 Sno. 90 2 epitaxial film with a low zirconium content prepared according to the present invention at a voltage of1V; Figure 8 is XRD 0-20 scan spectra of HfxSn1x02 epitaxial films with different doping ratios prepared according to the present invention; Figure 9 is transmission spectra of HfxSn1x02 epitaxial films with different doping ratios prepared according to the present invention; Figure 10 is a current-voltage curve of an ultraviolet detector based on a Hfo. 0 5Sno. 9 5 0 2 epitaxial film prepared according to the present invention; Figure 11 is a current-time of an ultraviolet detector based on a Hfo.Sno.9 5 0 2 epitaxial film prepared according to the present invention; Figure 12 is a current-voltage curve of an ultraviolet detector based on a Hfo.3 Sno. 7 0 2 epitaxial film prepared according to the present invention; Figure 13 is a current-time of an ultraviolet detector based on a Hfo.3 Sno. 7 0 2 epitaxial film prepared according to the present invention; Figure 14 is XRD 0-20 scan spectra of SixSn1.02 epitaxial films with different doping ratios prepared according to Examples 11 and 12 of the present invention; Figure 15 is transmission spectra of SixSn.02 epitaxial films with different doping ratios prepared according to Examples 11 and 12 of the present invention; Figure 16 is a current-time curve of an ultraviolet detector based on a SiO. 12Sn. 8 8 0 2epitaxial flm prepared according to Example 11 of the present invention; Figure 17 is a current-time response curve of an ultraviolet detector based on a SiO. 12Sn. 8 8 0 2epitaxial flm prepared according to Example 11 of the present invention; Figure 18 is a current-time curve of an ultraviolet detector based on a Si 0. 8 8Sn .0120 2 epitaxial film prepared according to Example 12 of the present invention; Figure 19 is a current-time response curve of an ultraviolet detector based on a Si 0. 8 Sn 8 .0120 2 epitaxial film prepared according to Example 12 of the present invention.
The principles and features of the present invention are described in conjunction with the embodiments and accompanying drawings. The embodiments are intended to illustrate the present invention rather than limit the scope of the present invention. Example 1 This example provides an ultra-wide bandgap MexSn-x02 alloy semiconductor epitaxial film material, where the Me is Zr, and x is 0.05. According to the doping formula of Zro.Sno.950 2 , 19.1748g of SnO 2 and 0.8252g of ZrO2 were weighed respectively and mixed. The mixed material was poured into a ball mill tank, added with anhydrous ethanol accounting for about 60% of the total mass of the powder, and ball milled in a ball mill for 8 hours so as to be fully and uniformly mixed. The ball milled mixed material was washed and transferred to an evaporating dish, and dried in a drying oven. After the drying was completed, the dried mixed material was transferred to a mortar, added with anhydrous ethanol accounting for about 6% of the total mass of the powder as a binder, and fully ground such that the powders were uniformly bound together to form bound powders. The bound powders were pressed at a pressure of 4 to 6 MPa by an electromagnetic hydraulic press into a disc having a mass of about 10 g and a thickness of about 2 to 3 mm. Subsequently, the pressed disc was sintered in a tube furnace at a temperature of 1100°C for 3 hours. A shaped ceramic target was finally obtained. The epitaxial film of the present invention was grown by pulsed laser deposition on a c-plane sapphire substrate. First the substrate was cleaned, namely, ultrasonically cleaned sequentially with acetone, anhydrous ethanol and deionized water for 15 minutes, respectively. Then the sintered ceramic target and the cleaned sapphire substrate were placed in a chamber of a pulsed laser deposition system. The chamber was evacuated with a mechanical pump and a molecular pump to obtain a high vacuum environment on the order of 10-4 Pa, and the substrate temperature was set to 700 °C, the oxygen pressure was set to 3 Pa, the laser energy was 150 to 200 mJ/pulse, the laser pulse frequency was 5 Hz, the deposition time was 15 minutes, and the film was grown under these conditions and experimental parameters. After the film sample was prepared, it was characterized by X-ray diffractometer and spectrometer, respectively. The XRD 0-20 scan spectrum and transmission spectrum of the film sample were obtained, respectively, as shown in Figures 1 and 4. Finally, the prepared film sample was plated with high-purity aluminum parallel electrodes by vacuum evaporation. First, the film sample was placed on a mask, and a high-purity aluminum mass was placed in an evaporation boat, and then they were placed in the vacuum chamber of an evaporator. When a high vacuum environment on the order of 10-4 Pa was obtained by evacuating with a mechanical pump and a molecular pump, the evaporation source was turned on, and then the evaporation current was increased smoothly and slowly. After the evaporation was completed, the relief valve was opened, and when the pressure of the vacuum chamber was equal to the outside atmospheric pressure, the vacuum chamber was opened to take out the sample, and a complete ultraviolet detector was obtained. The device comprises a substrate layer, a Zro.0 5Sno. 9 50 2 film layer deposited on the substrate layer, and a parallel Al electrode deposited on the Zro.0 5 Sno. 9 5 0 2 film layer, in which the sapphire substrate has a thickness of 0.43 mm, the Zro.0 5 Sno. 9 5 0 2 film layer has a thickness of 125 nm, the electrode has a thickness of 50 nm, and the electrode spacing is 10 m. Then the photoelectric properties of the device were measured using an optoelectronic test system. Example 2 This example provides an ultra-wide bandgap MexSn-x02 alloy semiconductor epitaxial film material, where Me is Zr and x is 0.3. According to the doping formula of Zro.3 Sno.70 2 , 14.8102 g of SnO 2 and 5.1898 g of ZrO 2 were weighed respectively and mixed. The mixed material was poured into a ball mill tank, added with anhydrous ethanol accounting for about 60% of the total mass of the powder, and ball milled in a ball milled for 8 hours so as to be fully and uniformly mixed. The ball milled mixed material was washed and transferred to an evaporating dish, and dried in a drying oven. After the drying was completed, the dried mixed material was transferred to a mortar, added with anhydrous ethanol accounting for about 6% of the total mass of the powder as a binder, and fully ground such that the powders were uniformly bound together to form bound powders. Then, the bound powders were pressed at a pressure of 4 to 6 MPa by an electromagnetic hydraulic press into a disc having a mass of about 10 g and a thickness of about 2 to 3 mm. Subsequently, the pressed disc was sintered in a tube furnace at a temperature of 1100 °C for 3 hours. A shaped ceramic target was finally obtained. The epitaxial film of the present invention was grown by pulsed laser deposition on a c-plane sapphire substrate. The substrate was cleanedfirst, namely, ultrasonically cleaned sequentially with acetone, anhydrous ethanol and deionized water for 15 minutes, respectively. Then the sintered ceramic target and the cleaned sapphire substrate were placed in a chamber of a pulsed laser deposition system. The chamber was evacuated with a mechanical pump and a molecular pump to obtain a high vacuum environment on the order of 10-4 Pa, and the substrate temperature was set to 700 °C, the oxygen pressure was set to 3 Pa, the laser energy was 150 to 200mJ/pulse, the laser pulse frequency was 5 Hz, the deposition time was 15 minutes, and the film was grown under these conditions and experimental parameters. After the film sample was prepared, it was characterized by X-ray diffractometer and spectrometer, respectively. The XRD 0-20 scan spectrum, XRD p-scan spectrum, XRD rocking curve spectrum and transmission spectrum of the film sample were obtained respectively, as shown in Figures 1, 2, 3 and 4. Finally, the prepared film sample was plated with high-purity aluminum parallel electrodes by vacuum evaporation. First, the film sample was placed on a mask, and high-purity aluminum powders were placed in an evaporation boat, and then they were placed in the vacuum chamber of an evaporator. When a high vacuum environment on the order of 10-4 Pa was obtained by evacuating with a mechanical pump and a molecular pump, the evaporation source was turned on, and then the evaporation current was increased smoothly and slowly. After the evaporation was completed, the relief valve was opened, and when the pressure of the vacuum chamber was equal to the outside atmospheric pressure, the vacuum chamber was opened to take out the sample, and a complete ultraviolet detector was obtained. The device comprises a substrate layer, a ZrO. 3 SnO. 7 0 2 film layer deposited on the substrate layer, and a parallel Al electrode deposited on the ZrO. 3 SnO.702 film layer, in which the sapphire substrate has a thickness of 0.43 mm, the Zro.0 5 Sno. 9 5 0 2 film layer has a thickness of 125 nm, the electrode has a thickness of 50 nm, and the electrode spacing is 10 m. Then the photoelectric properties and current-time curve of the device were measured using an optoelectronic test system (as shown in Figures 5 and 6). In Examples 1 and 2 of the present invention, ZrxSn-x02 alloy semiconductor epitaxial films with different doping ratios were prepared by using ceramic targets with different doping ratios as laser ablation targets. It can be seen from the 0-20 scan spectra obtained by XRD characterizing of these film samples (i.e., Fig. 1), except the characteristic peak of the alumina film substrate appearing at about 41°, obvious diffraction peaks appear at about 370 to 380 and about 80°. By exact comparison with the PDF cards it can be determined that the two peaks are the diffraction peaks of the (200) and (400) planes of SnO 2 , respectively, and there are no other peaks of impurity phases, so it can be concluded that when x is in the range of 0.05 to 0.99, the doping effects of film samples with different doping ratios are all relatively desirable, and
Zr* +has successfully substituted the spatial lattice position of Sn**. It is apparent from the XRD (p scan spectrum (i.e., Fig. 2) that the ZrxSn1.x02 film was epitaxially grown on the c-plane sapphire substrate. It is apparent from the XRD rocking curve (i.e., Figure 3) that the ZrxSn1.x02 film has a high crystal quality. It is apparent from the transmission spectra (i.e., Fig. 4) obtained by characterizing of these film samples by a spectrometer that, as the doping concentration increases, the absorption edge of the film sample shows a significant shift in the direction of shorter waves, indicating that the bandgap of the ZrxSn1.x02 alloy also increases as the Zr doping concentration increases. It can be determined from the absorption spectrum by linear extrapolation that the bandgap was increased from 4.25 eV of Zro. 0 5 Sno. 9 5 0 2 to 5.2eV of Zro. 3 Sno. 7 0 2
. Finally, the photoelectric properties of the completed photoelectric detector fabricated were measured using a photoelectric test system. It can be seen from the current-time curve (as shown in Figure 5) that when there is no illumination, the current value is small, but when the shielding plate is opened quickly and the light hits the device, the current value increases sharply, indicating that the device has a sensitive and fast photoresponse and can detect deep ultraviolet light. Zirconium doping in SnO2 can release the forbidden transition of SnO 2 and enhance its response to deep ultraviolet light. The ultraviolet detector based on the Zro.3 Sno.702 ternary alloy single crystal film prepared according to the present invention has high photoresponse sensitivity, especially in the deep ultraviolet band, reaching 1.99 A/W; moreover, the current-time curve in Fig. 6 shows that the photoresponse time in the current rising phase is 0.25 seconds, and the photoresponse time in the falling phase is 0.5 second. Compared with the ultraviolet detector based on the pure SnO 2 single crystal film, the ZrxSn1.x02 ternary alloy has a larger forbidden band width, so the detector fabricated according to the present invention is more suitable for the task of detecting deep ultraviolet band light; moreover, zirconium doping in pure SnO 2 can effectively increase its resistivity, which is a very favorable factor for the detector, because increasing the resistivity can effectively reduce the dark current in the detector and improve the light detection sensitivity and detection rate of the detector. Zirconium doping can effectively increase the resistivity of pure SnO 2 for two reasons: first, because the bandgap of ZrxSn1.x02 ternary alloy is larger than that of pure SnO 2 , it will naturally lead to the larger resistivity of this alloy than pure SnO 2 ; second, zirconium doping can greatly reduce the concentration of defects in pure SnO2 , such as the quantity of oxygen vacancies and tin interstices, thereby effectively reducing the background carrier concentration caused by the existence of defects in pure SnO 2, and making the resistivity of SnO 2 increase significantly. In addition, when zirconium doping greatly reduces the quantity of defects in pure SnO 2 , it cannot only effectively increase the resistivity but also improve the recombination rate of unbalanced carriers due to illumination. This is because as the quantity of defects is reduced, the quantity of deep-level trap centers is also reduced, so that electrons and holes are more easily recombined. This feature can effectively shorten the detector's recovery time after the illumination stops. Furthermore, it can be seen by comparing the current-time response curves of a high zirconium content device (Fig. 6) and a low zirconium content device (Fig. 7) that the larger the zirconium doping concentration, the shorter the current recovery time of the photodetector. The low zirconium content device comprises a substrate layer, a Zro.1 Sno. 90 2 film layer deposited on the substrate layer, and a parallel Al electrode deposited on the Zro.1 Sno. 90 2 film layer, in which the sapphire substrate has a thickness of 0.43 mm, the Zro.1 Sno. 9 0 2 film layer has a thickness of 125 nm, the electrode has a thickness of 50 nm, and the electrode spacing is 10 m. Example 3 This example provides an ultra-wide bandgap oxide alloy semiconductor epitaxial film material, which is a HfxSn1x02 ternary alloy compound semiconductor epitaxial film comprising SnO2 and Hf 2,where x is greater than 0 and less than 1. In order to achieve accurate and sensitive detection of deep ultraviolet light, the detector material must have a large forbidden band width. Although the bandgap of SnO2 reaches 3.6 eV, it still cannot meet the requirement for detecting light in the deep ultraviolet band. Doping pure SnO 2 through equivalent cation substitution is an effective way to adjust its bandgap size. The equivalent cation substitution requires that the solute ion is a positive tetravalent metal cation, its ionic radius is close to the radius of Sn*, the bandgap of such a metal oxide is greater than 4.43 eV, and the lattice type of the oxide is close to the lattice type of SnO 2. After considering these factors comprehensively, the present invention chooses Hf+ to partially substitute Sn 4 , forming a HfxSn1x02 alloy system. r(Hf) is 0.79 angstroms, r(Sn4*) is 0.71 angstroms, their ionic radii are close, and HfO 2 has a bandgap of 5.5 eV, much larger than 4.43 eV. The experiments eventually prove that doping pure SnO 2 with hafnium can increase its bandgap. In addition, it is found through the analysis of the film compositions that Hfe exhibits a big solid solubility in the alloy, and it is very likely to form a substitutional solid solution alloy system of complete solubility. This property also provides the possibility of freely adjusting the bandgap of the alloy in a larger range as well as the possibility of successfully fabricating photodetectors that can respond to and detect ultraviolet light of an even shorter wavelength. The HfxSn1x02 material provided in the example is a ternary alloy compound semiconductor formed by solid-solution of SnO2 and HfO2 in a certain molar ratio. Since the light detection in the deep ultraviolet band requires the ultraviolet wavelength to be less than 280 nm, the bandgap Eg of the detector material must be no less than 4.43 eV. As Hf" and Sn have the same valence, their ionic radii are close, and HfO 2 has a bandgap of 5.5 eV, and its lattice type is very close to that of SnO2 , the substitutional HfxSn1x02 alloy system was prepared by substituting the tin ions with hafnium ions, which realized the effective adjustment of the bandgap of the intrinsic SnO2 , and further realized the accurate and sensitive detection of the light wave intensity in the deep ultraviolet band and the sun blind region. Example 4 This example provides a method 100 for preparing an ultra-wide bandgap oxide alloy semiconductor epitaxial film material of Example 3, which comprises the following steps: Step 110: determining a molar ratio of Sn0 2 and HfO 2 according to a predetermined semiconductor bandgap, and preparing a ceramic target compounded with HfI2 and Sn02 according to the molar ratio; and Step 120: preparing a HfxSn1x02 ternary alloy compound semiconductor epitaxial film on a substrate based on the ceramic target compounded with HfO 2 and Sn0 2 .
Example 5 On the basis of Example 4, step 110 is specifically: determining a molar ratio of Sn02 and Hf2 according to a predetermined semiconductor bandgap, weighing different amounts of Sn02 and Hf2 powders respectively according to the molar ratio and mixing them, and then performing the steps of ball milling, washing, drying, grinding, pressing and sintering, such that the ceramic target is obtained, in which the molar ratio of Sn02 to HfI2 is Sn02 : Hf 2 99 : I to 5 : 95. Example 6 On the basis of Example 4 or Example 5, step110 comprises the following steps: Step 111: weighing different amounts of Sn02 and Hf 2 powders respectively according to the molar ratio and mixing them to obtain a first mixed material of SnO 2 and HfO 2 ; Step 112: adding anhydrous ethanol into the first mixed material, and ball milling for 3 to 10 hours to obtain a second mixed material, the mass of the anhydrous ethanol added is about 50% to 70% of the mass of the first mixed material; Step 113: transferring the second mixed material after washing it to an evaporating dish, placing the evaporating dish in a drying oven, and drying the second mixed material to obtain a homogeneous mixture of SnO 2 and HfO 2 ; Step 114: placing the homogeneous mixture in a mortar, adding anhydrous ethanol thereto as a binder, and grinding them to obtain a bound powders which is uniformly mixed and bound together, the mass of the anhydrous ethanol added is about 5% to 7% of the homogeneous mixture; Step 115: pressing the bound powders into a disc by an electromagnetic hydraulic press under a pressure of 4 to 6 MPa; and Step 116: placing the pressed disc in a tube furnace and sintering at 1000 to 1200 °C for 3 to 4 hours to prepare the ceramic target compounded with HfO2 and SnO 2 .
Example 7 On the basis of any of Example 4 to Example 6, the step 120 is specifically: based on the ceramic target compounded with Hf2 and SnO 2 , preparing the HfxSn-x02 ternary alloy compound semiconductor epitaxial flm on the c-plane of sapphire by pulsed laser deposition, magnetron sputtering or electron beam evaporation. For example, the pulsed laser deposition method may be used to prepare or grow a film on a c-plane sapphire substrate. First the sapphire substrate is ultrasonically cleaned and dried. Specifically, the substrate is ultrasonically cleaned for about 10 to 15 minutes sequentially with acetone, anhydrous ethanol and deionized water as the cleaning solution, and then the cleaned substrate is blown dried with nitrogen. Subsequently, the flm is deposited on the substrate by laser ablation of the ceramic target material using the pulsed laser deposition method. The experiment parameters are set as follows: the film deposition growth temperature is 100 to 700 °C, the oxygen pressure is 0 to 5 Pa, and the laser energy is 150 to 400mJ/pulse. The obtained film samples were characterized by X-ray diffractometers and spectrometers. The full spectra were obtained by 0-20 scanning the film samples with different doping ratios in the range of 20° to 85°, and their rocking curve were obtained by o scanning the film samples. The phase composition, doping and film growth quality of the films can be analyzed based on these spectra. The transmission and absorption spectra of the film samples can be obtained by characterizing using a spectrometer, so that the relationship between the size of the bandgap and the doping ratio can be analyzed, and the adjusting effect of doping on the bandgap size of the intrinsic SnO 2 can be judged. In the present embodiment, the equipment and the operation process are relatively simple and convenient, and the film of such materials is easy to grow, the crystal quality is high, the requirements for the growth environment are low, and it is suitable for large-scale production. Example 8 On the basis of Example 7, when the HfSn-x02 ternary alloy compound semiconductor epitaxial film was prepared by the pulsed laser deposition method, the film deposition growth temperature was 100 to 700 °C, the oxygen pressure was 0 to 5 Pa, the laser energy was 150 to 400 mJ/pulse, and thefilm deposition growth time was 10 to 15 minutes. Example 9 This example provides an application of the ultra-wide bandgap oxide alloy semiconductor epitaxial film material prepared according to Example 8 as a matrix material in an ultraviolet detector. Example 10 This Example provides an ultraviolet detector comprising: a substrate, a functional layer and a parallel or interdigital electrode, which are sequentially stacked, and the functional layer is made of the above-mentioned ultra-wide bandgap oxide alloy semiconductor epitaxial film. Preferably, the interdigital electrode is an aluminum interdigital electrode. Herein the UV detector is of the simplest metal-semiconductor-metal (MSM) structure. Namely, a film (here, HfxSnx02 film) is deposited on the sapphire substrate, and then a parallel or interdigital electrode is evaporated on the surface of the film. When the UV detector works, voltage is applied to the two electrodes, and photo-generated current is generated by illumination, so that ultraviolet light can be detected. The obtained alloy semiconductor epitaxial flm sample was plated with a high-purity aluminum parallel or interdigital electrode by vacuum evaporation. First, the film sample was placed on a mask, and a high-purity aluminum mass was placed in an evaporation boat, and then they are placed in the vacuum chamber of an evaporator. When a high vacuum environment on the order of 10-4 Pa is obtained by evacuating with a mechanical pump and a molecular pump, the evaporation source is turned on, and then the evaporation current is increased smoothly and slowly. After the evaporation is completed, the relief valve is opened, and when the pressure of the vacuum chamber is equal to the outside atmospheric pressure, the vacuum chamber is opened to take out the sample. The complete photodetector device fabricated is then vacuum packaged, and its photoelectric properties, such as current-voltage curve, current-time curve, and spectral response, are measured by an optoelectronic test system. The reason why UV detectors can detect the intensity ofultraviolet light is based on the Einstein photoelectric effect. When the photon energy is greater than or equal to the bandgap Eg of the matrix material of the detector, it will be absorbed and excite the transition of electrons in the valence band to the conduction band, and the original localized electrons become non-localized electrons and can move in the entire crystal material, so that a photocurrent is formed. When light of a specific wavelength illuminates a substance with a specific bandgap, photoexcitation occurs, which will increase the carrier concentration and enhance the electrical conductivity. The stronger the illumination is, the more the conductivity will increase, and the larger the generated photocurrent will be. Such a photoelectric property of matter can be used to detect light radiation. However, in order to accurately and sensitively detect light waves in a certain wavelength range, the bandgap of the matrix material of the detector cannot be too small. If the bandgap is too small, light in a large wavelength range will be absorbed, and thus the intensity of light waves in a particular band cannot be detected accurately and sensitively. Therefore, the bandgap of the matrix material of the detector cannot be much smaller than the minimum photon energy of the band to be detected. For deep-ultraviolet detectors, the bandgap of its matrix material is required to be no less than 4.43 eV. Therefore, the intrinsic SnO 2 should be doped to increase its forbidden band width Eg, so as to achieve accurate and sensitive detection of the intensity of light in the deep ultraviolet band. For example, according to the doping ratio (molar ratio) of Hf.5 Sna. 95 0 2 ,
18.6304g of SnO 2 and 1.3696g of HfO 2 were weighed respectively and mixed. The mixed material was poured into a ball mill tank, added with anhydrous ethanol accounting for about 60% of the total mass of the powder, and ball milled in a ball mill for 8 hours so as to be fully and uniformly mixed. The ball milled mixed material was washed and transferred to an evaporating dish, and dried in a drying oven. After the drying was completed, the dried mixed material was transferred to a mortar, added with anhydrous ethanol accounting for about 6% of the total mass of the powder as a binder, and fully ground such that the powders were uniformly bound together to form bound powders. Then, the bound powders were pressed at a pressure of 4 to 6 MPa by an electromagnetic hydraulic press into a disc having a mass of about 10 g and a thickness of about 2 to 3 mm. Subsequently, the pressed disc was sintered in a tube furnace at a temperature of 1100 °C for 3 hours. A shaped ceramic target was finally obtained. The film was prepared by pulsed laser deposition on a c-plane sapphire substrate. First the substrate was cleaned, namely, ultrasonically cleaned sequentially with acetone, anhydrous ethanol and deionized water for 15 minutes, respectively. Then the sintered ceramic target and the cleaned sapphire substrate were placed in a chamber of a pulsed laser deposition system. The chamber was evacuated with a mechanical pump and a molecular pump to obtain a high vacuum environment on the order of 10-4
Pa, and the substrate temperature was set to 700 °C, the oxygen pressure was set to 3 Pa, the laser energy was 150 to 200 mJ/pulse, the laser pulse frequency was 5 Hz, the deposition time was 15 minutes, and the film was grown under these conditions and experimental parameters. After the film sample was prepared, it was characterized by X-ray diffractometer (XRD) and spectrometer, respectively, to obtain an XRD 0-20 scan spectrum (as shown in Figure 8) and a transmission spectrum (as shown in Fig. 9). Finally, the prepared film sample was plated with high-purity aluminum parallel electrodes by vacuum evaporation. First, the film sample was placed on a mask, and a high-purity aluminum mass was placed in an evaporation boat, and then they were placed in the vacuum chamber of an evaporator. When a high vacuum environment on the order of 10-4 Pa was obtained by evacuating with a mechanical pump and a molecular pump, the evaporation source was turned on, and then the evaporation current was increased smoothly and slowly. After the evaporation was completed, the relief valve was opened, and when the pressure of the vacuum chamber was equal to the outside atmospheric pressure, the vacuum chamber was opened to take out the sample, and a complete ultraviolet detector was obtained. The device comprises a substrate layer, a Hfa. 0 5Sna. 9 5 0 2 flm layer deposited on the substrate layer, and a parallel Al electrode deposited on the Hfa.0 5 Sna. 9 5 0 2 film layer, in which the sapphire substrate has a thickness of 0.43 mm, the Hfa.0 5 Sna. 9 5 0 2 film layer has a thickness of
125 nm, the electrode has a thickness of 50 nm, and the electrode spacing is 10 m. Then, the photoelectric properties of the device were measured using an optoelectronic test system, and a current-voltage curve (as shown in FIG. 10) and a current-time curve (as shown in FIG. 11) were obtained. For another example, according to the doping ratio of Hfo.3 Sno.70 2 , 12.5107 g of SnO2 and 7.4893 g of HfO 2 were weighed respectively and mixed. The mixed material was poured into a ball mill tank, added with anhydrous ethanol accounting for about 60% of the total mass of the powder, and ball milled in a ball mill for 8 hours so as to be fully and uniformly mixed. The ball milled mixed material was washed and transferred to an evaporating dish, and dried in a drying oven. After the drying was completed, the dried mixed material was transferred to a mortar, added with anhydrous ethanol accounting for about 6% of the total mass of the powder as a binder, and fully ground such that the powders were uniformly bound together to form bound powders. Then, the bound powders were pressed at a pressure of 4 to 6 MPa by an electromagnetic hydraulic press into a disc having a mass of about 10 g and a thickness of about 2 to 3 mm. Subsequently, the pressed disc was sintered in a tube furnace at a temperature of 1100 °C for 3 hours. A shaped ceramic target was finally obtained. The film was prepared by pulsed laser deposition on a c-plane sapphire substrate. First the substrate was cleaned, namely, ultrasonically cleaned sequentially with acetone, anhydrous ethanol and deionized water for 15 minutes, respectively. Then the sintered ceramic target and the cleaned sapphire substrate were placed in a chamber of a pulsed laser deposition system. The chamber was evacuated with a mechanical pump and a molecular pump to obtain a high vacuum environment on the order of 10-4 Pa, and the substrate temperature was set to 700 °C, the oxygen pressure was set to 3 Pa, the laser energy was 150 to 200 mJ/pulse, the laser pulse frequency was 5 Hz, the deposition time was 15 minutes, and the film was grown under these conditions and experimental parameters. After the film sample was prepared, it was characterized by X-ray diffractometer and spectrometer, respectively, to obtain an XRD 0-20 scan spectrum (as shown in Figure 8) and a transmission spectrum (as shown in Fig. 9). Finally, the prepared film sample was plated with high-purity aluminum parallel electrodes by vacuum evaporation. First, the film sample was placed on a mask, and a high-purity aluminum mass was placed in an evaporation boat, and then they were placed in the vacuum chamber of an evaporator. When a high vacuum environment on the order of 10-4 Pa was obtained by evacuating with a mechanical pump and a molecular pump, the evaporation source was turned on, and then the evaporation current was increased smoothly and slowly. After the evaporation was completed, the relief valve was opened, and when the pressure of the vacuum chamber was equal to the outside atmospheric pressure, the vacuum chamber was opened to take out the sample, and a complete ultraviolet detector was obtained. The device comprises a substrate layer, a Hfo. 3 Sno. 7 0 2 flm layer deposited on the substrate layer, and a parallel Al electrode deposited on the Hfo.3 Sno. 7 0 2 film layer, in which the sapphire substrate has a thickness of 0.43 mm, the Hfo. 3 Sno. 7 0 2 film layer has a thickness of 125 nm, the electrode has a thickness of 50 nm, and the electrode spacing is 10 m. Then, the photoelectric properties of the device were measured using an optoelectronic test system, and a current-voltage curve (as shown in FIG. 12) and a current-time curve (as shown in FIG. 13) were obtained. In the above examples, HfxSn1x02 alloy semiconductor epitaxial films with different doping ratios were prepared by using ceramic targets with different doping ratios as laser ablation targets. It can be seen from the 0-20 scan spectra (as shown in Fig. 8) obtained by XRD characterizing of these film samples, except the characteristic peak of the alumina film substrate appearing at about 41, obvious diffraction peaks appear at about 37-38° and about 80°. By exact comparison with the PDF cards it can be determined that the two peaks are the diffraction peaks of the (200) and (400) planes of HfxSn1x0 2 , respectively, and there are no other peaks of impurity phases, so it can be concluded that the doping effects offilm samples with different doping ratios are all relatively desirable, and Hf4 has successfully substituted the spatial lattice position of Sn It is apparent from the transmission and absorption spectra (as shown in Fig. 9) obtained by characterizing these film samples by a spectrometer that, as the Hf doping concentration increases, the absorption edge of the film sample shows a significant shift in the direction of shorter waves, indicating that the bandgap of the HfxSn1x02 alloy also increases as the Hf doping concentration increases. It can be determined from the absorption spectrum by linear extrapolation that the bandgap was increased from 4.13 eV of Hfo.0 5 Sno.9 5 0 2 to 4.63 eV of Hfa. 3 Sno.702. Finally, the photoelectric properties of the completed photoelectric detector fabricated were measured using a photoelectric test system. Among them, it can be seen from the current-voltage curves of Hfo. 0 5 Sno. 95 0 2 and
Hfo.3 Sno. 7 0 2 (as shown in Figures 10 and 12) that, hafnium doping in pure SnO 2 can effectively increase its resistivity, and as the doping concentration increases, the resistivity increases more significantly. As shown in Figures 10 and 12, the resistivity of Hfo.3 Sno.702 is much larger than that of Hfa. 0 5Sno. 9 5 0 2 , and the multiple ratio is as high as 108. This feature is a very favorable factor for the detector, because increasing the resistivity can effectively reduce the dark current in the detector and improve the light detection sensitivity and detection rate of the detector. Hafnium doping can effectively increase the resistivity of pure SnO 2 for two reasons: first, because the bandgap of HfxSn-x02 ternary alloy is larger than that of pure SnO 2 , it will naturally lead to the larger resistivity of this alloy than pure SnO 2 ; second, hafnium doping can greatly reduce the concentration of defects in pure SnO 2
, such as the quantity of oxygen vacancies and tin interstices, thereby effectively reducing the background carrier concentration caused by the existence of defects in pure SnO 2, and making the resistivity of SnO 2 increase significantly. It can be seen from the current-time curve (as shown in Figures 11 and 13) that when there is no illumination, the current value is small, but when the shielding plate is opened quickly and the light hits the device, the current value increases sharply, indicating that the device has a sensitive and fast photoresponse and can detect deep ultraviolet light. In other words, it can be seen from the current-time curve (as shown in Figures 11 and 13) that the ultraviolet detector based on HfxSn-x02 ternary alloy single crystal film prepared according to the present invention has high photoresponse sensitivity, when there is no illumination the dark current value is small, and when the light hits the detector the current value increases sharply and then quickly reaches a constant value. If the detectors with two different hafnium doping ratios are compared, the most noticeable difference is the length of the photo response time, especially in the current falling phase, the recovery time of Hfo.3 Sno. 7 0 2 is significantly shorter than the recovery time of Hfa.0 5 Sno. 9 5 0 2 . This is because when the hafnium doping in pure SnO2 greatly reduces the quantity of defects in pure SnO 2 , it cannot only effectively increase the resistivity but also improve the recombination rate of unbalanced carriers due to illumination. This is because as the quantity of defects is reduced, the quantity of deep-level trap centers is also reduced, so that electrons and holes are more easily recombined. This feature can effectively shorten the detector's recovery time after the illumination stops, and the more the hafnium doping concentration, the shorter the response time.
In sum, the hafnium doping in Sn02 can release the forbidden transition of Sn0 2 and enhance its response to deep ultraviolet light. The hafnium doping in Sn02 can achieve the following effects: first, it can increase the bandgap Eg, such that it is more suitable for detection in the deep ultraviolet band; second, it can effectively increase the resistivity of pure Sn0 2 , reduce the dark current in the detector, and improve the photoresponse sensitivity and detection rate of the detector; third, it can effectively reduce the concentration of defects in pure Sn0 2, especially the quantity of deep level trap centers, thereby greatly increasing the recombination rate of electrons and holes, shortening the detector's recovery time, and significantly improving the properties of the detector. Example 11 This example provides an ultra-wide bandgap MexSn-x02 alloy semiconductor epitaxial film material, where the Me is Si and x is 0.12. According to the doping formula of Sio. 12 Sno. 8 8 0 2 , 17.524 g of SnO 2 and 1.998 g of SiO 2 were weighed respectively and mixed. The mixed material was poured into a ball mill tank, added with anhydrous ethanol accounting for about 60% of the total mass of the powder, and ball milled in a ball milled for 8 hours so as to be fully and uniformly mixed. The ball milled mixed material was washed and transferred to an evaporating dish, and dried in a drying oven. After the drying was completed, the dried mixed material was transferred to a mortar, added with anhydrous ethanol accounting for about 6% of the total mass of the powder as a binder, and fully ground such that the powders were uniformly bound together to form bound powders. Then, the bound powders were pressed at a pressure of 4 to 6 MPa by an electromagnetic hydraulic press into a disc having a mass of about 10 g and a thickness of about 2 to 3 mm. Subsequently, the pressed disc was sintered in a tube furnace at a temperature of 1100 °C for 3 hours. A shaped ceramic target was finally obtained. The epitaxial film of the present invention was grown by pulsed laser deposition on a c-plane sapphire substrate. First the substrate was cleaned, namely, ultrasonically cleaned sequentially with acetone, anhydrous ethanol and deionized water for 15 minutes, respectively. Then the sintered ceramic target and the cleaned sapphire substrate were placed in a chamber of a pulsed laser deposition system. The chamber was evacuated with a mechanical pump and a molecular pump to obtain a high vacuum environment on the order of 10-4 Pa, and the substrate temperature was set to 650 °C, the oxygen pressure was set to 2 Pa, the laser energy was 150-300 mJ/pulse, the laser pulse frequency was 5 Hz, the deposition time was 30 minutes, and the film was grown under these conditions and experimental parameters. After the film sample was prepared, it was characterized by X-ray diffractometer and spectrometer, respectively. The XRD 0-20 scan spectrum and transmission spectrum of the film sample were obtained, respectively, as shown in Figures 14 and 15. Finally, the prepared film sample was plated with high-purity aluminum parallel electrodes by vacuum evaporation. First, the film sample was placed on a mask, and a high-purity aluminum mass was placed in an evaporation boat, and then they were placed in the vacuum chamber of an evaporator. When a high vacuum environment on the order of 10-4 Pa was obtained by evacuating with a mechanical pump and a molecular pump, the evaporation source was turned on, and then the evaporation current was increased smoothly and slowly. After the evaporation was completed, the relief valve was opened, and when the pressure of the vacuum chamber was equal to the outside atmospheric pressure, the vacuum chamber was opened to take out the sample, and a complete ultraviolet detector was obtained. The device comprises a substrate layer, a Sio. 1 2 Sno. 88 02 film layer deposited on the substrate layer, and a parallel Al electrode deposited on the Si. 12 Sno. 8 8 02 film layer, in which the sapphire substrate has a thickness of 0.43 mm, the Sio. 12 Sno.8 8 02 film layer has a thickness of 200 nm, the electrode has a thickness of 50 nm, and the electrode spacing is 10 m. Then the photoelectric properties and current-time curve of the device were measured using an optoelectronic test system (as shown in Figures 16 and 17). Example 12 This example provides an ultra-wide bandgap MexSn1.x02 alloy semiconductor epitaxial film material, where the Me is Si and x is 0.88. According to the doping formula of Sio.ssSno. 120 2, 7.726g of SnO 2 and 12.274g of SiO 2 were weighed respectively and mixed. The mixed material was poured into a ball mill tank, added with anhydrous ethanol accounting for about 60% of the total mass of the powder, and ball milled in a ball milled for 8 hours so as to be fully and uniformly mixed. The ball milled mixed material was washed and transferred to an evaporating dish, and dried in a drying oven. After the drying was completed, the mixed material was transferred to a mortar, added with anhydrous ethanol accounting for about 6% of the total mass of the powder as a binder, and fully ground such that the powders were uniformly bound together to form bound powders. Then, the bound powders were pressed at a pressure of 4 to 6 MPa by an electromagnetic hydraulic press into a disc having a mass of about 10 g and a thickness of about 2 to 3 mm.
Subsequently, the pressed disc was sintered in a tube furnace at a temperature of 1100 °C for 3 hours. A shaped ceramic target was finally obtained. The epitaxial film of the present invention was grown by pulsed laser deposition on a c-plane sapphire substrate. First the substrate was cleaned, namely, ultrasonically cleaned sequentially with acetone, anhydrous ethanol and deionized water for 15 minutes, respectively. Then the sintered ceramic target and the cleaned sapphire substrate were placed in a chamber of a pulsed laser deposition system. The chamber was evacuated with a mechanical pump and a molecular pump to obtain a high vacuum environment on the order of 10-4 Pa, and the substrate temperature was set to 650 °C, the oxygen pressure was set to 2 Pa, the laser energy was 150-300 mJ/pulse, the laser pulse frequency was 5 Hz, the deposition time was 30 minutes, and the film was grown under these conditions and experimental parameters. After the film sample was prepared, it was characterized by X-ray diffractometer and spectrometer, respectively. The XRD 0-20 scan spectrum and transmission spectrum of the film sample were obtained, respectively, as shown in Figures 14 and 15. Finally, the prepared film sample was plated with high-purity aluminum parallel electrodes by vacuum evaporation. First, the film sample was placed on a mask, and a high-purity aluminum mass was placed in an evaporation boat, and then they were placed in the vacuum chamber of an evaporator. When a high vacuum environment on the order of 10-4 Pa was obtained by evacuating with a mechanical pump and a molecular pump, the evaporation source was turned on, and then the evaporation current was increased smoothly and slowly. After the evaporation was completed, the relief valve was opened, and when the pressure of the vacuum chamber was equal to the outside atmospheric pressure, the vacuum chamber was opened to take out the sample, and a complete ultraviolet detector was obtained. The device comprises a substrate layer, a Sio.ssSno. 12 02 flm layer deposited on the substrate layer, and a parallel Al electrode deposited on the Sio.ssSno. 120 2 film layer, in which the sapphire substrate has a thickness of 0.43 mm, the Sio.ssSno. 120 2 film layer has a thickness of 120 nm, the electrode has a thickness of 50 nm, and the electrode spacing is 10 m. Then the photoelectric properties and current-time curve of the device were measured using an optoelectronic test system (as shown in Figures 18 and 19). In these examples of the present invention, SiSn1x02 alloy semiconductor epitaxial films with different doping ratios were prepared by using ceramic targets with different doping ratios as laser ablation targets. It can be seen from the diffraction spectrum (i.e., Fig. 14) obtained by XRD characterizing of these film samples, the Si 0 . 12 Sno. 8 8 02 film has obvious diffraction peaks at about 34 and about 72, and by exact comparison with the PDF cards it can be determined that the two peaks are the diffraction peaks of the (101) and (202) planes of SnO 2, respectively, and there are no other peaks of impurity phases; the Sio.ssSno. 1202 film has no other diffraction peaks except the peak of the substrate. So it can be concluded that when x is around 0.12, the film is a single crystal film; when the x content is high and around 0.88, the film is transitioned into an amorphous film. It is apparent from the transmission spectra (i.e., Fig. 15) obtained by characterizing these film samples by a spectrometer that, as the doping concentration increases, the absorption edge of the film sample shows a significant shift in the direction of shorter waves, indicating that the bandgap of the SiSn1x02 alloy also increases as the Si doping concentration increases. It can be determined from the absorption spectrum by linear extrapolation that the bandgap was increased from 3.3 eVof Si. 12 Sno.8 8 02 to 5.2 eV of Sio.ssSno. 12 0 2
. Finally, the photoelectric properties of the completed photoelectric detector fabricated were measured using a photoelectric test system. It can be seen from the current-time curves (as shown in Figures 16, 17, 18 and 19) that when there is no illumination, the current value is small, but when the shielding plate is opened quickly and the light hits the device, the current value increases sharply, indicating that the device has a sensitive and fast photoresponse and can detect deep ultraviolet light. Si doping in Sn02 can release the forbidden transition of Sn02 and enhance its response to deep ultraviolet light. Compared with the ultraviolet detector based on the pure Sn02 single crystal film, the SixSn1.x02 ternary alloy has a larger forbidden band width, so the detector fabricated according to the present invention is more suitable for the task of detecting deep ultraviolet band light; moreover, silicon doping in pure Sn02 can effectively increase its resistivity, which is a very favorable factor for the detector, because increasing the resistivity can effectively reduce the dark current in the detector and improve the light detection sensitivity and detection rate of the detector. Silicon doping can effectively increase the resistivity of pure Sn02 for two reasons. First, because the bandgap of SixSn1.x02 ternary alloy is larger than that of pure Sn0 2 , it will naturally lead to the larger resistivity of this alloy than pure Sn0 2 .
Second, silicon doping can greatly reduce the concentration of defects in pure Sn0 2 ,
such as the quantity of oxygen vacancies and tin interstices, thereby effectively reducing the background carrier concentration caused by the existence of defects in pure SnO 2 , and making the resistivity of SnO 2 increase significantly. In addition, when silicon doping greatly reduces the quantity of defects in pure SnO 2 , it cannot only effectively increase the resistivity but also improve the recombination rate of unbalanced carriers due to illumination. This is because as the quantity of defects is reduced, the quantity of deep-level trap centers is also reduced, so that electrons and holes are more easily recombined. This feature can effectively shorten the detector's recovery time after the illumination stops. Furthermore, it can be seen by comparing the current-time response curves of a high silicon content device (Fig. 19) and a low silicon content device (Fig. 17) that the larger the silicon doping concentration, the shorter the current recovery time of the photodetector. In addition, the electrode of the ultraviolet detector according to the present embodiment is an aluminum electrode deposited by vacuum evaporation, the operation process is simple and easy to learn, and the raw materials for fabricating the whole detector are inexpensive and easy to obtain, so the present embodiment is very important for the detection of ultraviolet light in deep ultraviolet and solar blind regions. The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalents and improvements made within the spirit and scope of the present invention should fall within the protection scope of the present invention. Throughout the specification and the claims that follow, unless the context requires otherwise, the words "comprise" and "include" and variations such as "comprising" and "including" will be understood to imply the inclusion of a stated integer or group of integers, but not the exclusion of any other integer or group of integers. The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that such prior art forms part of the common general knowledge.
Claims (17)
- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. An ultra-wide bandgap MexSni.x0 2 alloy semiconductor single crystal epitaxial film material, comprising: a homogeneous mixture of SnO 2 and MeO 2, where x is greater than 0 and less than 1, and Me is selected from the group consisting of Zr, Hf and Si, wherein the film material is in the form of a single layer.
- 2. The ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film material according to claim 1, wherein the x is between 0.05 and 0.99.
- 3. The ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film material according to any one of claims 1 to 2, wherein the x is between 0.05 and 0.30.
- 4. The ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film material according to any one of claims 1 to 2, wherein the x is between 0.30 and 0.99.
- 5. The ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film according to any one of claims 1 to 4, wherein the bandgap Eg of the alloy semiconductor single crystal epitaxial film material is no less than 4.43 eV.
- 6. A method for preparing the ultra-wide bandgap MexSn1.x0 2 alloy semiconductor single crystal epitaxial film material according to any one of claims 1 to 5, comprising the following steps: Step 1: determining a molar ratio of Sn0 2 and MeO 2 according to a predetermined semiconductor bandgap, and preparing a ceramic target compounded with MeO2 and Sn02 according to the molar ratio; and Step 2: preparing the MexSn1.x02 alloy compound semiconductor epitaxial film on a substrate based on the ceramic target compounded with MeO2 and Sn0 2 .
- 7. The method according to claim 6, wherein Step 1 includes the following steps: la). preparing a mixed material of Sn02 and Me2 in accordance with the molar ratio; lb). adding anhydrous ethanol to the mixed material obtained in the step la) and ball milling to obtain a homogeneous mixed material; 1c). washing the homogeneous mixed material obtained in the step lb) and drying to obtain a homogeneous mixture of SnO2 and Me 2 ; ld). grinding the homogeneous mixture of SnO2 and MeG2 obtained in the step 1c) with anhydrous ethanol used as a binder during grinding to obtain bound powders;1e). pressing the bound powders obtained in the step Id) into a disc; and If). sintering the pressed disc obtained in the step le) to obtain the ceramic target compounded with MeO 2 and SnO 2.
- 8. The method according to claim 7, wherein in the step If), the pressed disc is sintered at 1000 to 1200 °C for 3 to 4 hours.
- 9. The method according to any one of claims 6 to 8, wherein Step 2 includes the following steps: 2a). ultrasonically cleaning and drying a c-plane sapphire substrate; 2b). depositing the ceramic target compounded with MeO2 and SnO 2 obtained in Step 1) onto the c-plane sapphire substrate that has been subject to ultrasonically cleaning and drying by pulsed laser deposition to prepare an epitaxially grown film, so as to obtain the MexSn1.x02 alloy semiconductor single crystal epitaxial film material, where x is greater than 0 and less than 1.
- 10. The method according to claim 9, wherein the deposition to prepare the epitaxially grown film is operated at the following conditions: a temperature of 100 to 700 °C, an oxygen pressure of 0 to 5 Pa, and a pulsed laser energy of 150 to 400 mJ/pulse.
- 11. Use of the ultra-wide bandgap MexSni.02 alloy semiconductor single crystal epitaxial film material according to any one of claims 1 to 5 as a functional layer material in a deep ultraviolet detector.
- 12. A deep ultraviolet detector, comprising: a substrate, a functional layer deposited on the substrate, and a parallel or interdigital electrode deposited on the functional layer, wherein the functional layer is formed by the ultra-wide bandgap MexSn1.x02 alloy semiconductor single crystal epitaxial film material according to any one of claims I to 5.
- 13. The deep ultraviolet detector according to claim 12, wherein the deep ultraviolet detector has a detection wavelength of 300 nm to 220 nm.
- 14. The deep ultraviolet detector according to any one of claims 12 to 13, wherein the functional layer has a thickness of 100 to 300 nm, the electrode has a thickness of 30 to 70 nm, and the electrode spacing is 10 to 100 [m.
- 15. The deep ultraviolet detector according to any one of claims 12 to 14, wherein the substrate is a c-plane sapphire substrate, and the sapphire substrate has a thickness of 0.35 to 0.45 mm.
- 16. The deep ultraviolet detector according to any one of claims 12 to 15, wherein the electrode is made of any one of Pt, Au, Al and ITO.
- 17. A method for fabricating the deep ultraviolet detector according to any one of claims 12 to 16, wherein the MexSn-x02 alloy semiconductor single crystal epitaxial film material is plated with a high-purity metal electrode by vacuum evaporation, or is plated with a transparent conductive ITO electrode by sputtering.diffraction intensity (a.u.) diffraction intensity (a.u.)2θ/º 1/10FIG. 2 FIG. 1 transmission (%) diffraction intensity (a.u.) 2/10FIG. 4 FIG. 3wavelength (nm)
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| CN201810293211.7A CN108546918B (en) | 2018-03-30 | 2018-03-30 | Ultra-wide bandgap oxide alloy semiconductor epitaxial thin film material and preparation method and application thereof |
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| PCT/CN2019/080090 WO2019184979A1 (en) | 2018-03-30 | 2019-03-28 | Ultra-wide band gap mexsn1-xo2 alloy semiconductor epitaxial thin film material and preparation method therefor, application thereof and device thereof |
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