WO2019184979A1 - 超宽禁带MexSn1-xO2合金半导体外延薄膜材料及其制备方法、应用和器件 - Google Patents

超宽禁带MexSn1-xO2合金半导体外延薄膜材料及其制备方法、应用和器件 Download PDF

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WO2019184979A1
WO2019184979A1 PCT/CN2019/080090 CN2019080090W WO2019184979A1 WO 2019184979 A1 WO2019184979 A1 WO 2019184979A1 CN 2019080090 W CN2019080090 W CN 2019080090W WO 2019184979 A1 WO2019184979 A1 WO 2019184979A1
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sno
ultraviolet light
film
semiconductor epitaxial
deep ultraviolet
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PCT/CN2019/080090
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English (en)
French (fr)
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何云斌
黎明锴
程阳
卢寅梅
常钢
张清风
李派
陈俊年
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湖北大学
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Priority claimed from CN201810293770.8A external-priority patent/CN108396288B/zh
Priority claimed from CN201810293211.7A external-priority patent/CN108546918B/zh
Application filed by 湖北大学 filed Critical 湖北大学
Priority to AU2019241284A priority Critical patent/AU2019241284B2/en
Publication of WO2019184979A1 publication Critical patent/WO2019184979A1/zh

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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

Definitions

  • the invention belongs to the technical field of semiconductor optoelectronic materials and devices, and particularly relates to an ultra-wide band gap Me x Sn 1-x O 2 alloy semiconductor epitaxial film material with adjustable band gap, a preparation method thereof and a deep ultraviolet light detector. application.
  • Ultraviolet detection has extremely important applications in many areas, such as high voltage grid monitoring, flame detection, missile plume tracking, sky UV detection and more.
  • problems in the field of ultraviolet detection which are urgently needed to be solved.
  • the most urgent and most interesting issue is the detection of light in the deep ultraviolet band. Since the wavelength of ultraviolet light in this band is less than 280 nm, the traditional detection mainly Photomultiplier tubes and silicon-based detectors are dominant.
  • the photomultiplier tube type detector is bulky and heavy, and needs to be equipped with a high-voltage DC power source, which makes it difficult to miniaturize.
  • the present invention aims to provide a SnO 2 -based ultra-wide bandgap Me x Sn 1-x O 2 alloy semiconductor epitaxial film material with adjustable band gap and a preparation method thereof.
  • the present invention obtains a Me x Sn 1-x O 2 alloy semiconductor epitaxial film having a suitable band gap size by incorporating an appropriate amount of Zr or Hf or Si or two or three elements thereof into the SnO 2 and is used for preparing ultraviolet rays. Photodetector.
  • An ultra-wide bandgap Me x Sn 1-x O 2 alloy semiconductor epitaxial film material comprising: SnO 2 and MeO 2 , wherein: x is greater than 0 and less than 1; Me is Zr or Hf or Si or Any combination of two or three elements.
  • the x is 0.01 to 0.99; more preferably, the x is 0.05 to 0.99; most preferably, the x is 0.05 to 0.30 or x is 0.30 to 0.99.
  • a second object of the present invention is to provide a method for preparing the ultra-wide bandgap Me x Sn 1-x O 2 alloy semiconductor epitaxial film material, comprising the following steps:
  • Step 1 determining a molar ratio of SnO 2 and MeO 2 according to a predetermined semiconductor band gap, and preparing a ceramic target in which MeO 2 and SnO 2 are composited according to the molar ratio;
  • Step 2 Prepare the Me x Sn 1-x O 2 alloy compound semiconductor epitaxial film on a substrate based on the ceramic target in which the MeO 2 and the SnO 2 are composited.
  • the step 1 includes the following steps:
  • step 1b) adding anhydrous ethanol to the preliminary mixed material obtained in step 1a) for ball milling to obtain a uniformly mixed material
  • step 1c) The uniformly mixed material obtained in the step 1b) is subjected to washing and drying to obtain a homogeneous mixture of SnO 2 and MeO 2 ;
  • step 1d grinding a homogeneous mixture of SnO 2 and MeO 2 obtained in step 1c), using anhydrous ethanol as a blocking agent during the grinding process to obtain a ceramic blank;
  • the ceramic green sheet obtained in the step 1e) is sintered to obtain a ceramic target.
  • the ceramic green sheet has a sintering temperature of 1000 to 1200 ° C; and the sintering time is 3 to 4 hours.
  • step 2 includes the following steps:
  • step 2b depositing the ceramic target material obtained in step 1) onto the c-plane sapphire substrate subjected to ultrasonic cleaning and drying by pulsed laser deposition to prepare a grown epitaxial film to obtain a Me x Sn 1-x O 2 alloy semiconductor epitaxial film.
  • a third object of the present invention is to provide the above-mentioned ultra-wide bandgap Me x Sn 1-x O 2 alloy semiconductor epitaxial film material as a matrix layer material for use in a deep ultraviolet light detector.
  • a fourth object of the present invention is to provide a deep ultraviolet light detecting device comprising a substrate layer, a layer of a host material disposed on the substrate layer, and a parallel or interdigitated electrode disposed on the layer of the matrix material,
  • the matrix material layer is formed of an ultra-wide bandgap Me x Sn 1-x O 2 alloy semiconductor epitaxial film material.
  • the detection wavelength of the deep ultraviolet light detector is 300 nm to 220 nm.
  • the matrix material layer has a thickness of 100 to 300 nm, the electrode thickness is 30 to 70 nm, and the electrode spacing is 10 to 100 ⁇ m.
  • the substrate is preferably a c-plane sapphire substrate, and the sapphire substrate has a thickness of 0.35 to 0.45 mm.
  • the electrode material is any one of Pt, Au, Al, or ITO.
  • a fifth object of the present invention is to provide a method for preparing the above-described deep ultraviolet light detecting device by plating a high purity metal (Pt, a Me x Sn 1-x O 2 alloy semiconductor epitaxial film material by vacuum evaporation).
  • the Au, Al) electrode or a transparent conductive ITO electrode is plated by sputtering.
  • the specific method of plating the high-purity metal electrode by the vacuum evaporation method is as follows:
  • the film sample is placed on the mask, and the high-purity metal powder is placed in the evaporation boat, and then placed in the vacuum chamber of the vacuum evaporation instrument, and the mechanical pump and the molecular pump are extracted to obtain a high level of ⁇ 10 -4 Pa.
  • Open the evaporation source in a vacuum environment and then slowly increase the evaporation current. Wait until the end of the evaporation to open the bleed valve.
  • the vacuum chamber is equal to the outside atmospheric pressure, open the vacuum chamber to take out the sample. Finally, vacuum the completed photodetector. Package.
  • the present invention tests the photoelectric properties of the obtained device with an optoelectronic test system, such as a volt-ampere characteristic (current-voltage) curve, a current-time curve, and a spectral response of the sample, thereby judging Me x Sn 1-
  • an optoelectronic test system such as a volt-ampere characteristic (current-voltage) curve, a current-time curve, and a spectral response of the sample.
  • the ultra-wide bandgap Me x Sn 1-x O 2 alloy semiconductor epitaxial film material and the preparation method thereof and the application in the deep ultraviolet light detector have the following beneficial effects:
  • the Me x Sn 1-x O 2 material provided by the present invention is a polyvalent (ternary, quaternary or pentad) alloy compound semiconductor obtained by solid-solubilizing SnO 2 and MeO 2 in a certain molar ratio. Because the wavelength of the day-deep deep ultraviolet light is less than 280 nm, the band gap Eg of the matrix material of the solar blind detector is required to be not less than 4.43 eV, because Me 4+ and Sn 4+ have the same valence, the ionic radius is similar, and the band of MeO 2 The gap reaches 5.5eV, and the lattice type is very close to that of SnO 2 .
  • the ultra-wide band gap Me x Sn 1-x O is successfully prepared by partial replacement of Sn 4+ ions by Me 4+ ions. 2 alloy semiconductor epitaxial film material.
  • the present invention finds that the solid solubility limit of Me 4+ in the alloy is very large by the analysis of the film components, and it is highly likely to form an infinite solid solution replacement solid solution alloy system, which is in a large range. It is possible to freely adjust the band gap size of the alloy, and it is also possible to successfully prepare a photodetector device that responds to the detection of shorter wavelength ultraviolet rays.
  • the Me x Sn 1-x O 2 alloy semiconductor epitaxial film material provided by the present invention may be grown by pulse laser deposition, or may be subjected to various preparation methods such as magnetron sputtering and electron beam evaporation.
  • the preparation and growth, and the equipment and operation are simple and convenient, so the invention has a very positive significance for the deep resolution of the deep ultraviolet light detection, which has long plagued the technical problems in the field of ultraviolet light detection.
  • the present invention can be released Me-doped SnO 2 SnO 2 is forbidden transition, in response to the enhancement of deep ultraviolet light.
  • the Me x Sn 1-x O 2 alloy compound semiconductor epitaxial film material provided by the invention has excellent characteristics of ultra-wide energy gap width and direct photoelectric transition, and provides an ideal device material for deep ultraviolet light detection;
  • the invention can be prepared by using various growth preparation methods, the equipment and the operation process are simple and easy to grasp, suitable for large-scale industrial production, and the raw materials for preparing the device are cheap and easy to obtain, and can be prepared at a lower cost. A complete device, which is extremely important for large-scale production and application.
  • Example 1 is an X-ray diffraction (XRD) theta-2theta scan pattern of different doping ratio Zr x Sn 1-x O 2 epitaxial films prepared in Example 1 and Example 2 of the present invention.
  • XRD X-ray diffraction
  • Example 2 is an X-ray diffraction ⁇ -scan of a Zr 0.3 Sn 0.7 O 2 epitaxial film prepared in Example 2 of the present invention.
  • Example 3 is an X-ray diffraction rocking curve ( ⁇ -scan) spectrum of a Zr 0.3 Sn 0.7 O 2 epitaxial film prepared in Example 2 of the present invention.
  • Example 4 is a transmission spectrum diagram of different doping ratio Zr x Sn 1-x O 2 epitaxial films prepared in Example 1 and Example 2 of the present invention.
  • Example 5 is a current-time graph of a Zr 0.3 Sn 0.7 O 2 epitaxial film-based ultraviolet detector fabricated in Example 2 of the present invention at a voltage of 150 V.
  • Example 6 is a current-time graph of a high zirconium content Zr 0.3 Sn 0.7 O 2 epitaxial film-based ultraviolet detector fabricated in Example 2 of the present invention at a voltage of 100V.
  • FIG. 7 is a current-time graph of a low zirconium content Zr 0.1 Sn 0.9 O 2 epitaxial film-based ultraviolet detector device prepared by the present invention at a voltage of 1 V.
  • Figure 8 is an X-ray diffraction (XRD) theta-2theta scan of different doping ratio Hf x Sn 1-x O 2 epitaxial films prepared by the present invention.
  • XRD X-ray diffraction
  • Figure 10 is a graph showing the current-voltage of the Hf 0.05 Sn 0.95 O 2 epitaxial film-based ultraviolet detector device prepared by the present invention.
  • Figure 11 is a graph showing the current-time of the Hf 0.05 Sn 0.95 O 2 epitaxial film-based ultraviolet detector device prepared by the present invention.
  • Figure 12 is a graph showing the current-voltage of the Hf 0.3 Sn 0.7 O 2 epitaxial film-based ultraviolet detector device prepared by the present invention.
  • Figure 13 is a graph showing the current-time of the Hf 0.3 Sn 0.7 O 2 epitaxial film-based ultraviolet detector device prepared by the present invention.
  • Example 14 is an X-ray diffraction (XRD) theta-2theta scan pattern of different doping ratio Si x Sn 1-x O 2 epitaxial films prepared in Example 11 and Example 12 of the present invention.
  • XRD X-ray diffraction
  • Example 15 is a transmission spectrum diagram of different doping ratio Si x Sn 1-x O 2 epitaxial films prepared in Example 11 and Example 12 of the present invention.
  • Figure 16 is a current-time graph of a Si 0.12 Sn 0.88 O 2 epitaxial film-based ultraviolet detector fabricated in Example 11 of the present invention.
  • Figure 17 is a graph showing the current-time response of a Si 0.12 Sn 0.88 O 2 epitaxial film-based ultraviolet detector fabricated in Example 11 of the present invention.
  • Figure 18 is a graph showing the current-time of a Si 0.88 Sn 0.12 O 2 epitaxial film-based ultraviolet detector fabricated in Example 12 of the present invention.
  • Figure 19 is a graph showing the current-time response of a Si 0.88 Sn 0.12 O 2 epitaxial film-based ultraviolet detector fabricated in Example 12 of the present invention.
  • Drying treatment is carried out, and after the drying is completed, the mixture is transferred to a mortar and anhydrous ethanol is added as a binder to a total mass of about 6% of the powder, and sufficient grinding treatment is performed to uniformly bond the powders together.
  • the billet is formed, and then the billet is pressed into a ceramic blank having a mass of about 10 g and a thickness of about 2-3 mm by an electromagnetic hydraulic press, and then the billet is placed in a tube furnace and sintered at a temperature of 1100 ° C. After 3 hours, a molded ceramic target was finally obtained.
  • the epitaxial film of the present invention is grown by pulse laser deposition on a c-plane sapphire substrate.
  • the substrate substrate is first cleaned, ultrasonically washed with acetone, absolute ethanol and deionized water for 15 minutes, respectively, and then the fired ceramic target and the cleaned sapphire substrate are placed together in a pulsed laser deposition system.
  • vacuum is then extracted by a mechanical pump and a molecular pump to obtain a high vacuum environment of 10 -4 Pa level, and the substrate temperature is set to 700 ° C, the oxygen pressure is set to 3 Pa, and the laser energy is 150-200 mJ/pulse.
  • the laser pulse frequency was 5 Hz and the deposition time was 15 minutes.
  • Film growth was carried out under the conditions and experimental parameters. After the film samples were prepared, they were characterized by X-ray diffractometer and spectrometer, respectively.
  • the X-ray diffraction (XRD) theta-2theta scan and transmission spectra of the film samples were obtained, respectively, as shown in Figures 1 and 4.
  • the prepared film samples were plated with high-purity aluminum parallel electrodes by vacuum evaporation.
  • the film samples were first placed on a mask, and the high-purity aluminum blocks were placed in an evaporation boat, and then placed in a vapor deposition apparatus.
  • the vacuum chamber when the mechanical pump and the molecular pump are extracted to obtain a high vacuum environment of 10 -4 Pa level, the evaporation source is turned on, and then the vapor deposition current is slowly and steadily increased, and after the vapor deposition is completed, the gas release valve is opened, and the vacuum chamber is waited for.
  • the device comprising a substrate layer, disposed on the substrate layer Zr 0.05 Sn 0.95 O 2 and a membrane layer disposed on the Zr 0.05 Sn 0.95 a parallel Al electrode on the O 2 film layer, wherein: the sapphire substrate has a thickness of 0.43 mm, the Zr 0.05 Sn 0.95 O 2 film layer has a thickness of 125 nm, the electrode has a thickness of 50 nm, and the electrode pitch is 10 ⁇ m.
  • the optoelectronic performance of the device was then tested using an optoelectronic test system.
  • the Me is Zr and x is 0.3.
  • the epitaxial film of the present invention is prepared by pulse laser deposition on a c-plane sapphire substrate.
  • the substrate substrate is first cleaned, ultrasonically washed with acetone, absolute ethanol and deionized water for 15 minutes, respectively, and then the fired ceramic target and the cleaned sapphire substrate are placed together in a pulsed laser deposition system.
  • vacuum is then extracted by a mechanical pump and a molecular pump to obtain a high vacuum environment of 10 -4 Pa, and the substrate temperature is set to 700 ° C, the oxygen pressure is set to 3 Pa, and the laser energy is 150-200 mJ/pulse.
  • the pulse frequency was 5 Hz and the deposition time was 15 minutes.
  • Film growth was carried out under the conditions and experimental parameters. After the film samples were prepared, they were characterized by X-ray diffractometer and spectrometer respectively.
  • the XRD theta-2theta scan, XRD ⁇ -scan, XRD rocking curve and transmission spectrum of the film samples were obtained respectively. See Figures 1 and 2, respectively. 3, 4.
  • the prepared film samples were plated with high-purity aluminum parallel electrodes by vacuum evaporation. First, the film samples were placed on a mask, and the high-purity aluminum powder was placed in an evaporation boat, and then placed in a vapor deposition apparatus.
  • the evaporation source is turned on, and then the vapor deposition current is slowly and steadily increased, and after the vapor deposition is completed, the gas release valve is opened, and the vacuum chamber is waited for.
  • the device comprising a substrate layer, disposed on the substrate layer Zr 0.3 Sn 0.7 O 2 thin film layer disposed on the Zr 0.3 Sn 0.7 a parallel Al electrode on the O 2 film layer, wherein: the sapphire substrate has a thickness of 0.43 mm, the Zr 0.3 Sn 0.7 O 2 film layer has a thickness of 125 nm, the electrode has a thickness of 50 nm, and the electrode pitch is 10 ⁇ m.
  • the optoelectronic performance and current-time plots of the device were then tested using an optoelectronic test system (see Figures 5 and 6).
  • ceramic targets having different doping ratios are used as laser ablation targets to prepare Zr x Sn 1-x O 2 alloy semiconductor epitaxial films with different doping ratios.
  • the theta-2theta scan spectrum obtained by XRD characterization of the film sample, as shown in Fig. 1, can be seen, except for the characteristic peak of the film substrate alumina appearing around 41°, which is obvious at 37°-38° and 80°.
  • the diffraction peaks can be determined by the accurate comparison of the PDF cards.
  • the zirconium-doped SnO 2 can release the forbidden transition of SnO 2 and enhance its response to deep ultraviolet light.
  • the Zr 0.3 Sn 0.7 O 2 ternary alloy single crystal film-based ultraviolet detector prepared by the invention has high light response sensitivity, especially high sensitivity in the deep ultraviolet band, reaching 1.99 A/W, and As can be seen from the current-time curve in Fig. 6, the light response time in the current rising phase is 0.25 seconds, and the light response time in the falling phase is 0.5 second.
  • the detector prepared by the invention is more suitable for the deep ultraviolet band light.
  • the zirconium-doped treatment of 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 darkness in the detector.
  • the current level increases the detector's light detection sensitivity and detection rate.
  • Zirconium doping can effectively increase the resistivity of pure SnO 2 for two reasons.
  • the band gap of Zr x Sn 1-x O 2 ternary alloy is larger than that of pure SnO 2 , it will naturally The resistivity of the alloy is larger than that of the pure SnO 2 ; the second is that the defect concentration in the pure SnO 2 can be greatly reduced after the zirconium-doped treatment, for example, the number of defects such as oxygen vacancies and tin gaps is effectively reduced.
  • the background carrier concentration originally present in the pure SnO 2 due to defects makes the resistivity of SnO 2 greatly increased.
  • the zirconium-doped treatment can effectively increase the resistivity while greatly reducing the number of pure SnO 2 defects, and on the other hand, can improve the recombination rate of unbalanced carriers due to illumination.
  • a low zirconium content device (the device comprising a substrate layer, disposed on the substrate layer Zr 0.1 Sn 0.9 O 2 of the thin film layer disposed on the Zr 0.1 Sn 0.9 O 2 parallel Al electrodes on the film layer, wherein: the sapphire substrate has a thickness of 0.43 mm, the Zr 0.1 Sn 0.9 O 2 film layer has a thickness of 125 nm, the electrode has a thickness of 50 nm, and the electrode spacing is 10 ⁇ m)
  • the time response curve (Fig. 7) shows that the larger the zirconium doping concentration, the shorter the current recovery time of the photodetector.
  • An ultra-wide band gap oxide alloy semiconductor epitaxial film material which is an Hf x Sn 1-x O 2 ternary alloy compound semiconductor epitaxial film, comprising: SnO 2 and HfO 2 , wherein x is greater than 0 and less than 1 .
  • the detector material In order to achieve accurate and sensitive detection of deep ultraviolet light, the detector material must be required to have a large forbidden band width. Although the band gap of SnO 2 reaches 3.6 eV, it still cannot meet the requirements for detecting light in the deep ultraviolet band.
  • the equivalent cation substitution doping of pure SnO 2 is an effective way to adjust the band gap size.
  • the equivalent cation substitution requires that the solute ion be a positive tetravalent metal cation, and the ionic radius is not much different from the radius of Sn 4+ , and the band gap of the metal oxide is greater than 4.43 eV, and the oxide lattice type is the same as SnO 2 The lattice type is similar.
  • the final experiment proves that the band gap can be increased by doping the pure SnO 2 .
  • the Hf x Sn 1-x O 2 material provided in this embodiment is a ternary alloy compound semiconductor formed by solid solution of SnO 2 and HfO 2 in a certain molar ratio, because the ultraviolet light wavelength is required to be less than the ultraviolet wavelength. 280nm, so the bandgap Eg of the detector material is required to be not less than 4.43eV, because Hf 4+ and Sn 4+ have the same valence, the ionic radius is similar, and the band gap of HfO 2 reaches 5.5eV, the lattice type and the crystal of SnO 2 The lattice type is also very close, so the replacement type Hf x Sn 1-x O 2 alloy system is prepared by replacing the tin ions with ytterbium ions, which realizes the effective adjustment of the band gap size of the intrinsic SnO 2 , and thus realizes the deep ultraviolet band and Accurate and sensitive detection of light intensity in the day blind zone.
  • a method 100 for preparing an ultra-wide band gap oxide alloy semiconductor epitaxial film material of embodiment 3, comprising the steps of:
  • Step 110 Determine a molar ratio of SnO 2 and HfO 2 according to a predetermined semiconductor band gap, and prepare a ceramic target in which HfO 2 and SnO 2 are combined according to a molar ratio.
  • Step 120 preparing a Hf x Sn 1-x O 2 ternary alloy compound semiconductor epitaxial film on a substrate based on a ceramic target in which HfO 2 and SnO 2 are composited.
  • step 110 is specifically:
  • step 110 includes the following steps:
  • Step 111 According to the molar ratio, different amounts of SnO 2 and HfO 2 powders are respectively weighed and mixed to obtain a first mixture of SnO 2 and HfO 2 .
  • Step 112 adding anhydrous ethanol equivalent to 50% to 70% of its mass to the first mixture, and ball milling for 3 to 10 hours to obtain a second mixture.
  • Step 113 After the second mixture is washed, transferred to an evaporating dish, and the evaporating dish is placed in a drying oven, and the second mixture is dried to obtain a homogeneous mixture of SnO 2 and HfO 2 .
  • step 114 the homogeneous mixture is placed in a mortar, and anhydrous ethanol equivalent to 5% to 7% by mass of the homogeneous mixture is added thereto as a blocking agent, followed by grinding to obtain a ceramic ingot which is uniformly mixed and bonded together.
  • step 115 the ceramic blank is pressed into a ceramic green sheet by an electromagnetic hydraulic machine under a force of 4 to 6 MPa.
  • Step 116 The ceramic green sheet is placed in a tube furnace and sintered at 1000 to 1200 ° C for 3 to 4 hours to prepare a ceramic target in which the HfO 2 and the SnO 2 are composited.
  • step 120 is specifically:
  • Hf x Sn 1-x O 2 ternary alloy compound semiconductor is prepared on the c-plane of sapphire by pulsed laser deposition, magnetron sputtering or electron beam evaporation based on a ceramic target in which HfO 2 and SnO 2 are combined. Epitaxial film.
  • a pulsed laser deposition method is used to prepare a growth film on a c-plane sapphire substrate.
  • the sapphire substrate is first ultrasonically cleaned and dried.
  • the specific operation is: sequentially using acetone, absolute ethanol, deionized water as a cleaning solution.
  • the substrate piece is subjected to sonication for about 10-15 minutes, and then the cleaned substrate piece is blown dry with nitrogen; then the film deposition is performed on the substrate by laser ablation of the ceramic target material by pulsed laser deposition.
  • the parameters are set as follows: film deposition growth temperature is 100-700 ° C, oxygen pressure 0-5 Pa, laser energy 150-400 mJ/pulse.
  • the obtained film samples were characterized by X-ray diffractometers and spectrometers, and the full spectrum was obtained by scanning the film samples of different doping ratios in the range of 20°-85°, and The film samples were subjected to ⁇ scanning to obtain their rocking curve. According to these spectra, the phase composition, doping and film growth quality of the film can be analyzed. The transmission and absorption spectra of the film samples can be obtained by spectrometer characterization. The relationship between the band gap size and the doping ratio is analyzed, and the effect of doping on the band gap size of the intrinsic SnO 2 is judged.
  • the equipment and the operation process are relatively simple and convenient, and the film of the material is easy to grow, the crystal quality is high, and the requirement for the growth environment is low, and is suitable for large-scale production.
  • the film deposition growth temperature is 100 to 700 ° C, and the oxygen pressure is 0 to 5 Pa.
  • the energy is 150-400 mJ/pulse, and the film deposition growth time is 10-15 minutes.
  • Example 8 An application of an ultra-wide band gap oxide alloy semiconductor epitaxial film material prepared in Example 8 for use in a matrix material in an ultraviolet light detector device.
  • An ultraviolet light detector comprises: a substrate, a matrix material layer, a parallel or interdigitated electrode, which are sequentially stacked, and the matrix material layer is made of the above-mentioned ultra-wide band gap oxide alloy semiconductor epitaxial film.
  • the interdigital electrode is an aluminum interdigital electrode.
  • the UV detector using the simplest metal-semiconductor-metal (MSM) structure. That is, a film (here, Hf x Sn 1-x O 2 film) is deposited on the sapphire substrate, and then parallel or interdigitated electrodes are evaporated on the surface of the film. When working, voltage is applied to the two electrodes, and photo-generated current is generated by illumination to detect ultraviolet light.
  • MSM metal-semiconductor-metal
  • the obtained alloy semiconductor epitaxial film sample is plated with a high-purity aluminum parallel or interdigitated electrode by vacuum evaporation.
  • the film sample is placed on a mask, and the high-purity aluminum block is placed in an evaporation boat, and then placed together.
  • the vacuum chamber of the evaporation instrument when the mechanical pump and the molecular pump are extracted to obtain a high vacuum environment of 10 -4 Pa, the evaporation source is turned on, and then the evaporation current is increased slowly and slowly, and the gas release valve is opened after the vapor deposition is finished.
  • the vacuum chamber is equal to the outside atmospheric pressure, the vacuum chamber is opened to take out the sample.
  • the prepared complete photodetector device is then vacuum packaged; and the photoelectric performance of the device, such as current-voltage curve, current-time curve, and spectral response, is measured by an optoelectronic test system.
  • UV detectors can detect the intensity of ultraviolet light is based on the Einstein photoelectric effect.
  • the photon energy is greater than or equal to the band gap Eg of the detector matrix material, it is absorbed, and the electrons in the excitation valence band are transitioned to the conduction band, and the original localized electrons become non-localized electrons, so that the entire crystal material can be Move in and form a photocurrent.
  • a certain wavelength of light illuminates a substance with a specific band gap, it will photoexcitation, which will increase the carrier concentration and enhance the conductivity. The stronger the illumination, the more obvious the conductivity will increase, and the generated photocurrent will be The larger we can use the photoelectric properties of matter to detect light radiation.
  • the band gap of the detector matrix material should not be too small. If the band gap is too small, light in a large wavelength range will be absorbed, so that it cannot be accurately sensitive. The intensity of light waves in a particular band is detected, so the bandgap of the detector matrix material is required to be much smaller than the minimum photon energy of the band of light to be detected. For deep-ultraviolet detectors, the band gap of the matrix material is required to be not less than 4.43 eV, so the intrinsic SnO 2 is doped to increase the forbidden band width Eg, thereby achieving accurate sensitivity to the intensity of the deep ultraviolet light. probe.
  • Hf 0.05 Sn 0.95 O 2 SnO 2 18.6304g and HfO 2 1.3696g are respectively weighed and mixed, and then the mixed mixture is poured into a ball mill tank, and Anhydrous ethanol is added to the total mass of about 60% of the powder, and then ball milled in a ball mill for 8 hours to make it fully uniformly mixed, and then the material which has been sufficiently ball-milled and uniformly mixed is washed and transferred to the evaporating dish. Then, it is placed in a dry box for drying treatment.
  • the mixture is transferred to a mortar, and anhydrous ethanol having a total mass of about 6% of the powder is added as a blocking agent to carry out sufficient Grinding treatment, the powder is evenly bonded together to form a blank, and then the billet is pressed into a ceramic blank of about 10 g and a thickness of about 2 to 3 mm by an electromagnetic hydraulic machine under the force of 4 to 6 MPa, and then the blank is placed.
  • the steel was sintered in a tube furnace at a temperature of 1100 ° C for 3 hours to finally obtain a molded ceramic target.
  • the film was prepared by pulse laser deposition on a c-plane sapphire substrate.
  • the substrate was first cleaned, ultrasonically washed with acetone, absolute ethanol and deionized water for 15 minutes, respectively, and then the fired ceramic target and
  • the cleaned sapphire substrate is placed in the cavity of the pulsed laser deposition system, and then vacuum is extracted by a mechanical pump and a molecular pump to obtain a high vacuum environment of 10 -4 Pa level, and the substrate temperature is 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. Film growth was carried out under the conditions and experimental parameters.
  • the prepared film samples were plated with high-purity aluminum parallel electrodes by vacuum evaporation.
  • the film samples were first placed on a mask, and the high-purity aluminum blocks were placed in an evaporation boat, and then placed in a vapor deposition apparatus.
  • the vacuum chamber when the mechanical pump and the molecular pump are extracted to obtain a high vacuum environment of 10 -4 Pa level, the evaporation source is turned on, and then the vapor deposition current is slowly and steadily increased until the end of the evaporation, and then the deflation valve is opened and the vacuum chamber is waited for.
  • the vacuum chamber is opened to take out the sample, and a complete ultraviolet light detector device is obtained.
  • the device includes a substrate layer, a Hf 0.05 Sn 0.95 O 2 film layer disposed on the substrate layer, and a Hf 0.05.
  • a parallel Al electrode on the Sn 0.95 O 2 film layer wherein: the sapphire substrate has a thickness of 0.43 mm, the Hf 0.05 Sn 0.95 O 2 film layer has a thickness of 125 nm, and the electrode has a thickness of 50 nm, and the electrode spacing is 10 ⁇ m, and then the photoelectric performance of the device was tested with an optoelectronic test system to obtain a current-voltage graph (shown in Figure 10) and a current-time graph (shown in Figure 11).
  • SnO 2 12.5107 g and HfO 2 7.4893 g are respectively weighed and mixed, and then the mixed mixture is poured into a ball mill tank and added thereto.
  • Anhydrous ethanol with a total mass of about 60% of the powder is then ball milled in a ball mill for 8 hours to make it fully uniformly mixed.
  • the material which has been thoroughly ball-milled and uniformly mixed is washed and transferred to an evaporating dish, and then placed. Drying is carried out in a drying oven.
  • the mixture is transferred to a mortar, and anhydrous ethanol, which accounts for about 6% of the total mass of the powder, is added as a blocking agent, and sufficient grinding treatment is performed to make the powder uniform.
  • the ground is bonded together to form a blank, and then the billet is pressed by an electromagnetic hydraulic machine to a ceramic green sheet having a mass of about 10 g and a thickness of about 2 to 3 mm under a force of 4 to 6 MPa, and then the green sheet is placed in a tube furnace. Sintering was carried out for 3 hours at a temperature of 1100 ° C to finally obtain a molded ceramic target.
  • the film was prepared by pulse laser deposition on a c-plane sapphire substrate.
  • the substrate was first cleaned, ultrasonically washed with acetone, absolute ethanol and deionized water for 15 minutes, respectively, and then the fired ceramic target and
  • the cleaned sapphire substrate is placed in the cavity of the pulsed laser deposition system, and then vacuum is extracted by a mechanical pump and a molecular pump to obtain a high vacuum environment of 10 -4 Pa level, and the substrate temperature is 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. Film growth was carried out under the conditions and experimental parameters.
  • the film samples were prepared, they were characterized by X-ray diffractometer and spectrometer, respectively, and the XRD theta-2theta scan map (shown in Figure 8) and the transmission spectrum (shown in Figure 9) of the film samples were obtained.
  • the prepared film samples were plated with high-purity aluminum parallel electrodes by vacuum evaporation.
  • the film samples were first placed on a mask, and the high-purity aluminum blocks were placed in an evaporation boat, and then placed in a vapor deposition apparatus.
  • the vacuum chamber when the mechanical pump and the molecular pump are extracted to obtain a high vacuum environment of 10 -4 Pa level, the evaporation source is turned on, and then the vapor deposition current is slowly and steadily increased, and after the vapor deposition is completed, the gas release valve is opened, and the vacuum chamber is waited for.
  • the device comprising a substrate layer, disposed on the substrate layer Hf 0.3 Sn 0.7 O 2 thin film layer disposed on the Hf 0.3 Sn 0.7 a parallel Al electrode on the O 2 film layer, wherein: the sapphire substrate has a thickness of 0.43 mm, the Hf 0.3 Sn 0.7 O 2 film layer has a thickness of 125 nm, the electrode has a thickness of 50 nm, and the electrode pitch is 10 ⁇ m.
  • the optoelectronic performance of the device was then tested using an optoelectronic test system to obtain a current-voltage graph (shown in Figure 12) and a current-time graph (shown in Figure 13).
  • ceramic targets with different doping ratios are used as laser ablation targets to prepare Hf x Sn 1-x O 2 alloy semiconductor epitaxial films with different doping ratios, which are obtained by XRD characterization of these film samples.
  • the XRD theta-2theta scan pattern can be seen (as shown in Fig. 8).
  • obvious diffraction peaks appear at 37° to 38° and 80°.
  • the two peaks are the diffraction peaks of the (200) and (400) planes of Hf x Sn 1-x O 2 , respectively, and the diffraction peaks of no other impurity phases appear. Therefore, it can be concluded that the doping effect of film samples with different doping ratios is ideal, and Hf 4+ successfully replaces the spatial lattice position of Sn 4+ .
  • the resistivity of Hf 0.3 Sn 0.7 O 2 is much larger than Hf 0.05 Sn 0.95 O 2 , and the ratio is as high as 10 8 .
  • 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.
  • the current-time graph (as shown in Figures 11 and 13), it can be seen that when there is no light irradiation, the current value is small, and when the shutter is quickly opened to allow light to strike the device, the current value suddenly increases, indicating that the device It has a sensitive and fast photoresponse effect and is capable of detecting deep ultraviolet light. That is, it can be seen from the current-time graph (as shown in FIGS. 11 and 13) that the Hf x Sn 1-x O 2 ternary alloy single crystal film-based ultraviolet light detector prepared by the invention has high light response sensitivity. The dark current value is small when there is no light, and the current value suddenly increases when the light hits the detector, and then quickly reaches a constant value.
  • the recovery time of Hf 0.3 Sn 0.7 O 2 is significantly shorter than that of Hf 0.05 Sn 0.95 O 2 time, because for pure SnO 2 doped with hafnium process, significantly reducing the number of defects pure SnO 2 when, on the one hand increases the effective resistivity, on the other hand can increase the recombination rate of non-equilibrium carriers, which Because the number of defects is reduced, the number of deep-level trap centers is significantly reduced, making electrons and holes more recombination. This feature effectively shortens the detector's response time after stopping the illumination, and The greater the doping concentration, the shorter the recovery time.
  • the antimony doping of SnO 2 can release the forbidden transition of SnO 2 and enhance its response to deep ultraviolet light.
  • the erbium-doped treatment of SnO 2 can increase the bandgap Eg on the one hand, making it more suitable for detection in the deep ultraviolet region.
  • it can effectively increase the resistivity of pure SnO 2 and reduce the detector's resistivity.
  • the dark current size increases the photoresponse sensitivity and detection rate of the detector; the third can effectively reduce the defect concentration in pure SnO 2 , especially the number of deep level trap centers, thereby greatly increasing the recombination rate of electrons and holes, shortening
  • the detector's recovery time significantly improves the performance of the detector.
  • the Me is Si and x is 0.12.
  • Drying treatment is carried out, and after the drying is completed, the mixture is transferred to a mortar and anhydrous ethanol is added as a binder to a total mass of about 6% of the powder, and sufficient grinding treatment is performed to uniformly bond the powders together.
  • the billet is formed, and then the billet is pressed into a ceramic blank having a mass of about 10 g and a thickness of about 2-3 mm by an electromagnetic hydraulic press, and then the billet is placed in a tube furnace and sintered at a temperature of 1100 ° C. After 3 hours, a molded ceramic target was finally obtained.
  • the epitaxial film of the present invention is grown by pulse laser deposition on a c-plane sapphire substrate.
  • the substrate substrate is first cleaned, ultrasonically washed with acetone, absolute ethanol and deionized water for 15 minutes, respectively, and then the fired ceramic target and the cleaned sapphire substrate are placed together in a pulsed laser deposition system.
  • vacuum is then extracted by a mechanical pump and a molecular pump to obtain a high vacuum environment of 10 -4 Pa level, and the substrate temperature is set to 650 ° C, the oxygen pressure is set to 2 Pa, and the laser energy is 150-300 mJ/pulse.
  • the laser pulse frequency was 5 Hz
  • the deposition time was 30 minutes
  • film growth was carried out under the conditions and experimental parameters.
  • the film samples were prepared, they were characterized by X-ray diffractometer and spectrometer respectively, and the XRD theta-2theta scan and transmission spectra of the film samples were obtained, respectively, as shown in Figures 14 and 15. Finally, the prepared film samples were plated with high-purity aluminum parallel electrodes by vacuum evaporation. The film samples were first placed on a mask, and the high-purity aluminum blocks were placed in an evaporation boat, and then placed in a vapor deposition apparatus.
  • the evaporation source is turned on, and then the vapor deposition current is slowly and steadily increased, and after the vapor deposition is completed, the gas release valve is opened, and the vacuum chamber is waited for.
  • the device comprising a substrate layer, disposed on the substrate layer Si 0.12 Sn 0.88 O 2 and a thin-film layer provided on the Si 0.12 Sn 0.88 a parallel Al electrode on the O 2 film layer, wherein: the sapphire substrate has a thickness of 0.43 mm, the Si 0.12 Sn 0.88 O 2 film layer has a thickness of 200 nm, the electrode has a thickness of 50 nm, and the electrode pitch is 10 ⁇ m.
  • the optoelectronic performance and current-time plots of the device were then tested using an optoelectronic test system (see Figures 16, 17).
  • the epitaxial film of the present invention is prepared by pulse laser deposition on a c-plane sapphire substrate.
  • the substrate substrate is first cleaned, ultrasonically washed with acetone, absolute ethanol and deionized water for 15 minutes, respectively, and then the fired ceramic target and the cleaned sapphire substrate are placed together in a pulsed laser deposition system.
  • vacuum is then extracted by a mechanical pump and a molecular pump to obtain a high vacuum environment of 10 -4 Pa, and the substrate temperature is set to 650 ° C, the oxygen pressure is set to 2 Pa, the laser energy is 150-300 mJ / pulse, and the laser The pulse frequency was 5 Hz and the deposition time was 30 minutes. Film growth was carried out under the conditions and experimental parameters.
  • the film samples were prepared, they were characterized by X-ray diffractometer and spectrometer respectively, and the XRD theta-2theta scan and transmission spectra of the film samples were obtained, respectively, as shown in Figures 14 and 15. Finally, the prepared film samples were plated with high-purity aluminum parallel electrodes by vacuum evaporation. First, the film samples were placed on a mask, and the high-purity aluminum powder was placed in an evaporation boat, and then placed in a vapor deposition apparatus.
  • the evaporation source is turned on, and then the vapor deposition current is slowly and steadily increased, and after the vapor deposition is completed, the gas release valve is opened, and the vacuum chamber is waited for.
  • the device comprising a substrate layer, disposed on the substrate layer Si 0.88 Sn 0.12 O 2 and a thin-film layer provided on the Si 0.88 Sn 0.12 a parallel Al electrode on the O 2 film layer, wherein: the sapphire substrate has a thickness of 0.43 mm, the Si 0.88 Sn 0.12 O 2 film layer has a thickness of 120 nm, the electrode has a thickness of 50 nm, and the electrode pitch is 10 ⁇ m.
  • the optoelectronic performance and current-time plots of the device were then tested using an optoelectronic test system (see Figures 18, 19).
  • the embodiments of the present invention prepare Si x Sn 1-x O 2 alloy semiconductor epitaxial films with different doping ratios by using ceramic targets of different doping ratios as laser ablation targets, and XRD is performed on these film samples.
  • the diffraction pattern obtained by the characterization that is, Fig. 14 shows that the Si 0.12 Sn 0.88 O 2 film has obvious diffraction peaks at 34° and 72°. It can be confirmed by accurate comparison of PDF cards that these two peaks are SnO 2 respectively.
  • the diffraction peaks of the (101) and (202) planes, except for the diffraction peaks of other heterophases, and the Si 0.88 Sn 0.12 O 2 film has no other diffraction peaks except the substrate peak, so it can be concluded.
  • the film When the x is -0.12, the film is a single crystal film; and when the x content is higher than 0.88, the film is converted into an amorphous film.
  • the increase in concentration is also increasing in the band gap of the Si x Sn 1-x O 2 alloy. From the absorption spectrum, the band gap from Si 0.12 Sn 0.88 O 2 to Si 0.88 Sn 0.12 O 2 was increased from 3.3 eV to 5.2 eV by linear extrapolation.
  • the Sn-doped SnO 2 can release the forbidden transition of SnO 2 and enhance its response to deep ultraviolet light.
  • the amorphous Si 0.88 Sn 0.12 O 2 ternary alloy film-based ultraviolet detector prepared by the invention has a fast photoelectric response speed, and the light response time in the current rising and falling phases can be known from the current-time curve (Fig. 19). Both are less than 0.2 seconds.
  • the detector prepared by the invention is more suitable for the deep ultraviolet band.
  • silicon doping treatment of 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 detector.
  • the dark current size increases the detector's light detection sensitivity and detection rate.
  • silicon doping can effectively increase the resistivity of pure SnO 2 is twofold. First, because the band gap of Si x Sn 1-x O 2 ternary alloy is larger than that of pure SnO 2 , it will naturally The resistivity of the alloy is larger than that of the pure SnO 2 ; the second is that the silicon concentration can greatly reduce the defect concentration in the pure SnO 2 , such as the number of defects such as oxygen vacancies and tin gaps, thereby effectively reducing the number of defects.
  • the background carrier concentration originally present in the pure SnO 2 due to defects makes the resistivity of SnO 2 greatly increased.
  • the silicon doping treatment can effectively increase the resistivity while greatly reducing the number of pure SnO 2 defects, and on the other hand, can improve the recombination rate of unbalanced carriers due to illumination. This is because the number of defects is reduced, so that the number 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 light stops.
  • comparing the high silicon content device (Fig. 19) and the low silicon content device current-time response curve Fig.
  • the amorphous film can effectively promote photo-generated carrier recombination due to the presence of a large number of structural distortion defects as a recombination center, thereby significantly shortening the device recovery time (Fig. 19).
  • the electrode of the ultraviolet detector component provided by the embodiment is an aluminum electrode vapor-deposited by vacuum evaporation, the operation process is simple and easy to grasp, and the raw materials for preparing the whole detector component are inexpensive and easy to obtain, so the implementation The example is very important for the detection of ultraviolet light in deep ultraviolet and solar blind areas.

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Abstract

超宽禁带MexSn1-xO2合金半导体外延薄膜材料，包括SnO2和MeO2，其中：x大于0，且小于1；Me为Zr或Hf或Si或它们中的任意两种或三种元素的组合。还公开了上述薄膜材料的制备方法、应用，以及采用上述薄膜材料作为基质材料层的深紫外光探测器。

Description

超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料及其制备方法、应用和器件 技术领域
本发明属于半导体光电材料与器件技术领域，具体涉及多种带隙可调的超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料及其制备方法和在深紫外光探测器中的应用。
背景技术
紫外探测在许多领域都有着极其重要的应用，如高压电网监测、火焰探测、导弹羽烟追踪、天际紫外探测等等。当然目前紫外探测领域也面临着许多问题急需解决，其中最急迫的也是最引人关注的就是深紫外波段光的探测问题，由于这一波段范围内的紫外光波长都小于280nm，传统探测主要以光电倍增管和硅基探测器为主。光电倍增管型探测器体积大、重量重，需要配高压直流电源，导致其难以小型化。对于硅基探测器，由于硅的带隙只有1.1eV，其响应峰值波长在800nm左右，对深紫外线的响应较低。另外，硅探测器也会对可见光产生响应，所以需要配备昂贵的紫外滤光片。为此开发宽禁带的半导体材料是实现高性能深紫外探测器的微型化、集成化所必须的。
常见的超宽禁带半导体材料有氮化铝(6.2eV)、金刚石(5.5eV)、β-Ga 2O 3(4.8eV)、SnO 2(3.6eV)等。虽然目前对超宽禁带半导体材料的研究已有一些进展，但仍然存在以下一些问题。Al xGa 1-xN体系在高Al组分下容易出现相分离和成分偏析；同时施主和受主能级会变深而难以激发；受持续光电导效应的影响，AlGaN基紫外光电探测器的响应速度难以提高。高质量大面积外延生长金刚石一直很困难，另外也缺乏有效的带隙调节手段。β-Ga 2O 3由于其能带结构的原因，其p型掺杂十分困难。SnO 2带隙达到了3.6eV，但是仍然不能满足深紫外波段光的探测要求，所以要对纯的SnO 2进行掺杂以拓宽其带隙。尽管有研究表明少量Zr掺杂SnO 2能增加带隙，但是未见其实现对深紫外线的探测。
基于上述理由，提出本申请。
发明内容
为了解决当前深紫外光探测的问题，本发明的目的在于提供一种带隙可调的基于SnO 2的超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料及其制备方法和在深紫外光探测器中的应用。本发明通过在SnO 2中掺入适量的Zr或Hf或Si或它们中的两种元素或三种元素得到带隙大小合适的Me xSn 1-xO 2合金半导体外延薄膜，并用于制备紫外光探测器。
本发明上述第一个目的采用如下技术方案实现：
一种超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料，所述材料包括：SnO 2和MeO 2，其中：x大于0，且小于1；Me为Zr或Hf或Si或它们中的任意两种或三种元素的组合。
优选地，上述技术方案，所述x为0.01～0.99；更优选地，所述x为0.05～0.99；最优选地，所述x为0.05～0.30或x为0.30～0.99。
本发明的第二个目的在于提供上述所述超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料的制备方法，包括以下步骤：
步骤1、根据预设半导体带隙，确定SnO 2和MeO 2的摩尔比例，并根据所述摩尔比例，制备 MeO 2与SnO 2复合的陶瓷靶材；
步骤2、基于所述MeO 2与SnO 2复合的陶瓷靶材，在衬底上制备所述Me xSn 1-xO 2合金化合物半导体外延薄膜。
进一步地，上述技术方案，所述步骤1包括以下步骤：
1a)配制SnO 2和MeO 2的初混物料；
1b)向步骤1a)得到的初混物料中加入无水乙醇进行球磨，得到均匀混合的物料；
1c)将步骤1b)得到的均匀混合的物料经过洗料后烘干，得到SnO 2和MeO 2的均匀混合物；
1d)将步骤1c)得到的SnO 2和MeO 2的均匀混合物进行研磨，研磨过程中以无水乙醇作为粘连剂，得到陶瓷坯料；
1e)将步骤1d)得到的陶瓷坯料压制成陶瓷坯片；
1f)将步骤1e)得到的陶瓷坯片进行烧结，得到陶瓷靶材。
更进一步地，上述技术方案，步骤1f)中：所述陶瓷坯片的烧结温度为1000～1200℃；烧结时间为3～4小时。
进一步地，上述技术方案，步骤2包括以下步骤：
2a)对c面蓝宝石衬底进行超声清洗和干燥处理；
2b)采用脉冲激光沉积法将步骤1)得到的陶瓷靶材物质沉积在经过超声清洗和干燥处理的c面蓝宝石衬底上制备生长外延薄膜，得到Me xSn 1-xO 2合金半导体外延薄膜材料，其中：x大于0，且小于1。
更进一步地，步骤2b)中：外延薄膜沉积生长温度为100～700℃；氧压为0～5Pa；脉冲激光的能量为150～400mJ/pulse。
本发明的第三个目的在于提供上述所述超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料作为基质层材料在深紫外光探测器中的应用。
本发明的第四个目的在于提供一种深紫外光探测器件，包括衬底层、设置在所述衬底层上的基质材料层以及设置在所述基质材料层上的平行或叉指电极，所述基质材料层由超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料形成。
进一步地，上述技术方案，所述深紫外光探测器的探测波长为300nm～220nm。
进一步地，上述技术方案，所述基质材料层厚度为100～300nm，所述电极厚度为30～70nm，所述电极间距为10～100μm。
进一步地，上述技术方案，所述衬底优选为c面蓝宝石衬底，所述蓝宝石衬底厚度为0.35～0.45mm。
进一步地，上述技术方案，所述电极材料为Pt、Au、Al或ITO等中的任一种。
本发明的第五个目的在于提供上述所述深紫外光探测器件的制备方法，是将Me xSn 1-xO 2合金半导体外延薄膜材料利用真空蒸镀的方法镀上高纯金属(Pt、Au、Al)电极或利用溅射法镀上透明导电ITO电极。
进一步地，上述技术方案，利用真空蒸镀的方法镀上高纯金属电极具体方法如下：
首先将薄膜样品放到掩模板上，高纯金属粉放到蒸发舟中，然后一并放入真空蒸镀仪的真空室中，待机械泵和分子泵抽取得到≤10 -4Pa级别的高真空环境时打开蒸发源，再平稳缓慢增加蒸镀电流，等到蒸镀结束后打开放气阀门，待到真空室与外界大气压相等时打开真空室取出样品，最后将制备的完整光探测器件进行真空封装。
本发明对得到的器件用光电测试***测试其光电性能，如样品的伏安特性(电流-电压)曲线、电流-时间曲线以及光谱响应等一系列的性能测试，从而判断出Me xSn 1-xO 2合金半导体外延薄膜材料用于制作紫外光探测器件的可行性。
本发明涉及的超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料及其制备方法和在深紫外光探测器中的应用具有如下有益效果：
(1)本发明所提供的Me xSn 1-xO 2材料是通过SnO 2和MeO 2按照一定的摩尔比例固溶而成的多元(三元、四元或五元)合金化合物半导体。因为日盲深紫外光的波长都小于280nm，所以要求日盲探测器基质材料的带隙Eg要不小于4.43eV，因为Me 4+与Sn 4+化合价相同，离子半径相近，且MeO 2的带隙达到5.5eV，晶格类型与SnO 2的晶格类型也十分接近，所以通过Me 4+离子部分取代Sn 4+离子，成功制备出了直接跃迁的超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料。另外，本发明通过对薄膜组分的分析发现，Me 4+在合金中的固溶度极限很大，其极有可能形成无限固溶置换型固溶体合金体系，这一性质为在较大范围内自由调节合金带隙大小提供了可能，也为能够成功制备出响应探测更短波长紫外线的光探测器件提供了可能。
(2)本发明所提供的Me xSn 1-xO 2合金半导体外延薄膜材料除了用脉冲激光沉积法生长外，还可以采用磁控溅射法、电子束蒸发法等多种制备方法进行薄膜的制备生长，且设备和操作简单便捷，所以本发明对深紫外光探测这一长期困扰紫外光探领域的技术难题的成功解决具有十分积极的意义。
(3)本发明通过Me掺杂SnO 2能够解除SnO 2的禁戒跃迁，增强其对深紫外光的响应。
(4)本发明所提供的Me xSn 1-xO 2合金化合物半导体外延薄膜材料具有超宽能隙宽度和直接光电跃迁的优异特性，为深紫外光探测提供了理想的器件材料；且本发明深紫外光探测器制备可以采用多种生长制备方法，采用的设备和操作工艺简单、易于掌握，适宜大规模工业化生产，并且制备器件的原材料价廉且易得，能够以更低的成本制备出完整的器件，这对大规模的生产和应用具有极其重要的意义。
附图说明
图1是本发明实施例1、实施例2制备的不同掺杂比例Zr xSn 1-xO 2外延薄膜的X射线衍射(XRD)theta-2theta扫描图谱。
图2是本发明实施例2制备的Zr 0.3Sn 0.7O 2外延薄膜的X射线衍射φ-扫描图谱。
图3是本发明实施例2制备的Zr 0.3Sn 0.7O 2外延薄膜的X射线衍射摇摆曲线(ω-扫描)图谱。
图4是本发明实施例1、实施例2制备的不同掺杂比例Zr xSn 1-xO 2外延薄膜的透射光谱图。
图5是本发明实施例2制备的Zr 0.3Sn 0.7O 2外延薄膜基紫外探测器件在电压为150V条件下的电流-时间曲线图。
图6是本发明实施例2制备的高锆含量Zr 0.3Sn 0.7O 2外延薄膜基紫外探测器件在电压为100V条件下的电流-时间曲线图。
图7是本发明制备的低锆含量Zr 0.1Sn 0.9O 2外延薄膜基紫外探测器件在电压为1V条件下的电流-时间曲线图。
图8是本发明制备的不同掺杂比例Hf xSn 1-xO 2外延薄膜的X射线衍射(XRD)theta-2theta扫描图谱。
图9是本发明制备的不同掺杂比例Hf xSn 1-xO 2外延薄膜的透射光谱图。
图10是本发明制备的Hf 0.05Sn 0.95O 2外延薄膜基紫外探测器件的电流-电压曲线图。
图11是本发明制备的Hf 0.05Sn 0.95O 2外延薄膜基紫外探测器件的电流-时间曲线图。
图12是本发明制备的Hf 0.3Sn 0.7O 2外延薄膜基紫外探测器件的电流-电压曲线图。
图13是本发明制备的Hf 0.3Sn 0.7O 2外延薄膜基紫外探测器件的电流-时间曲线图。
图14是本发明实施例11、实施例12制备的不同掺杂比例Si xSn 1-xO 2外延薄膜的X射线衍射(XRD)theta-2theta扫描图谱。
图15是本发明实施例11、实施例12制备的不同掺杂比例Si xSn 1-xO 2外延薄膜的透射光谱图。
图16是本发明实施例11制备的Si 0.12Sn 0.88O 2外延薄膜基紫外探测器件的电流-时间曲线图。
图17是本发明实施例11制备的Si 0.12Sn 0.88O 2外延薄膜基紫外探测器件的电流-时间响应曲线图。
图18是本发明实施例12制备的Si 0.88Sn 0.12O 2外延薄膜基紫外探测器件的电流-时间曲线图。
图19是本发明实施例12制备的Si 0.88Sn 0.12O 2外延薄膜基紫外探测器件的电流-时间响应曲线图。
具体实施方式
以下结合实施例和附图对本发明的原理和特征进行描述，所举实施例只用于解释本发明，并非用于限定本发明的范围。
实施例1
本实施例的一种超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料，所述Me为Zr，x为0.05。
按照Zr 0.05Sn 0.95O 2这一掺杂配方分别称取SnO 2 19.1748g、ZrO 2 0.8252g进行配料初混，然后将初混后的混合物料倒入球磨罐中并向其中加入占粉末总质量60％左右的无水乙醇，接着放入球磨机中球磨8小时使其充分地均匀混合，然后将已经充分球磨均匀混合的物料进行洗料处理，并转移到蒸发皿中，随后放到干燥箱中进行烘干处理，烘干结束后再将混合物料转移到研钵中并向其中加入占粉末总质量6％左右的无水乙醇作为粘连剂，进行充分的研磨处理使粉末均匀的粘结在一起形成坯料，然后用电磁液压机把坯料在4-6MPa的压力下压制成质量10g左右，厚度2-3mm左右的陶瓷坯片，紧接着把坯片放到管式炉中在1100℃的温度下烧结3小时，最后得到成型的陶瓷靶材。本发明的外延薄膜利用脉冲激光沉积法在c面蓝宝石衬底上制备生长而成。首先对衬底基片进行清洗，依次分别用 丙酮、无水乙醇、去离子水超声清洗15分钟，然后将烧制好的陶瓷靶材和清洗好的蓝宝石衬底一同放入脉冲激光沉积***的腔体中，然后分别用机械泵和分子泵抽取真空以获得10 -4Pa级别的高真空环境，并且将衬底温度设置为700℃，氧压设置为3Pa，激光能量150-200mJ/pulse，激光脉冲频率为5Hz，沉积时间为15分钟，在此条件和实验参数的设置下进行薄膜生长。薄膜样品制备出来以后分别用X射线衍射仪和光谱仪对其进行表征，分别得到薄膜样品的X射线衍射(XRD)theta-2theta扫描图谱、透射光谱图，分别见附图1、4。最后将制备出的薄膜样品用真空蒸镀的方法镀上高纯铝质平行电极，首先把薄膜样品放到掩模板上，高纯铝块放到蒸发舟中，然后一并放入蒸镀仪的真空室中，待机械泵和分子泵抽取得到10 -4Pa级别的高真空环境时打开蒸发源，然后平稳缓慢增加蒸镀电流，等到蒸镀结束后打开放气阀门，待到真空室与外界大气压相等时打开真空室取出样品，得到完整的紫外光探测器件，所述器件包括衬底层、设置在所述衬底层上的Zr 0.05Sn 0.95O 2薄膜层以及设置在所述Zr 0.05Sn 0.95O 2薄膜层上的平行Al电极，其中：所述蓝宝石衬底厚度为0.43mm，所述Zr 0.05Sn 0.95O 2薄膜层厚度为125nm，所述电极厚度为50nm，所述电极间距为10μm，然后用光电测试***测试该器件的光电性能。
实施例2
本实施例的一种超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料，所述Me为Zr，x为0.3。
按照Zr 0.3Sn 0.7O 2这一掺杂配方分别称取SnO 2 14.8102g、ZrO 2 5.1898g进行配料初混，然后将初混后的混合物料倒入球磨罐中并向其中加入占粉末总质量60％左右的无水乙醇，接着放入球磨机中球磨8小时使其充分地均匀混合，然后将已经充分球磨均匀混合的物料进行洗料处理，并转移到蒸发皿中，随后放到干燥箱中进行烘干处理，烘干结束后再将混合物料转移到研钵中并向其中加入占粉末总质量6％左右的无水乙醇作为粘连剂，进行充分的研磨处理使粉末均匀地粘结在一起形成坯料，然后用电磁液压机把坯料在4-6MPa的压力下压制成质量10g左右，厚度2-3mm左右的陶瓷坯片，紧接着把坯片放到管式炉中在1100℃的温度下烧结3小时，最后得到成型的陶瓷靶材。本发明的外延薄膜利用脉冲激光沉积法在c面蓝宝石衬底上制备而成。首先对衬底基片进行清洗，依次分别用丙酮、无水乙醇、去离子水超声清洗15分钟，然后将烧制好的陶瓷靶材和清洗好的蓝宝石衬底一同放入脉冲激光沉积***的腔体中，然后分别用机械泵和分子泵抽取真空以获得10 -4Pa的高真空环境，并且将衬底温度设置为700℃，氧压设置为3Pa，激光能量150-200mJ/pulse，激光脉冲频率为5Hz，沉积时间为15分钟，在此条件和实验参数的设置下进行薄膜生长。薄膜样品制备出来以后分别用X射线衍射仪和光谱仪对其进行表征，分别得到薄膜样品的XRD theta-2theta扫描图谱、XRDφ-扫描图谱、XRD摇摆曲线图谱和透射光谱，分别见附图1、2、3、4。最后将制备出的薄膜样品用真空蒸镀的方法镀上高纯铝质平行电极，首先把薄膜样品放到掩模板上，高纯铝粉放到蒸发舟中，然后一并放入蒸镀仪的真空室中，待机械泵和分子泵抽取得到10 -4Pa级别的高真空环境时打开蒸发源，然后平稳缓慢增加蒸镀电流，等到蒸镀结束后打开放气阀门，待到真空室与外界大气压相等时打开真空室取出样品，得到完整的紫外光探测器件，所述器件包括衬底层、设置在所述衬底层上的Zr 0.3Sn 0.7O 2薄膜层以及设置在所述Zr 0.3Sn 0.7O 2薄膜层上的平行Al电极，其中：所 述蓝宝石衬底厚度为0.43mm，所述Zr 0.3Sn 0.7O 2薄膜层厚度为125nm，所述电极厚度为50nm，所述电极间距为10μm，然后用光电测试***测试该器件的光电性能、电流-时间曲线图(见附图5、6)。
本发明的上述实施例1、实施例2是以不同掺杂比例的陶瓷靶材作为激光烧蚀靶从而制备出不同掺杂比例的Zr xSn 1-xO 2合金半导体外延薄膜，通过对这些薄膜样品进行的XRD表征得到的theta-2theta扫描图谱，即图1可以看出，除了41°左右出现了薄膜衬底氧化铝的特征峰外，在37°-38°和80°左右出现了明显的衍射峰，通过PDF卡片的精确对比可以确定这两个峰分别是SnO 2的(200)、(400)面的衍射峰，除此之外再无其他杂相的衍射峰出现，故可以得出结论：在x为0.05～0.99范围内不同掺杂比例的薄膜样品的掺杂效果都是较为理想的，Zr 4+成功取代了Sn 4+的空间格点位置。通过XRDφ扫描图谱，即图2，可以明显看出，Zr xSn 1-xO 2薄膜在c面蓝宝石衬底上是外延生长的。通过XRD摇摆曲线图谱，即图3，可明显看出Zr xSn 1-xO 2薄膜具有很高的晶体质量。通过光谱仪对这些薄膜样品进行表征得到的透射光谱，即图4，可以明显看出，随着掺杂浓度的增加，薄膜样品的吸收边向短波方向出现了明显的移动，说明随着Zr掺杂浓度的增加Zr xSn 1-xO 2合金的带隙也是不断增大的。从吸收光谱，利用线性外推法得出从Zr 0.05Sn 0.95O 2到Zr 0.3Sn 0.7O 2带隙从4.25eV增大到5.2eV。最后用光电测试***对制备出的完整探测器件进行了光电性能的测试，从电流-时间曲线图中(见附图5)可以看出，当没有光照射时电流值较小，当快速打开挡板，光线照射到器件上时电流值陡然增加，说明器件具有较灵敏快速的光响应效应，能够进行深紫外光强的探测。
通过锆掺杂SnO 2能够解除SnO 2的禁戒跃迁，增强其对深紫外光的响应。本发明制备的Zr 0.3Sn 0.7O 2三元合金单晶薄膜基紫外探测器具有很高的光响应灵敏度，特别是在深紫外波段具有较高的光响应度，达到1.99A/W，同时从电流-时间曲线图6中可以知道，在电流上升阶段的光响应时间为0.25秒，在下降阶段的光响应时间为0.5秒。相比于纯SnO 2的单晶薄膜基紫外探测器，由于Zr xSn 1-xO 2三元合金具有更大的禁带宽度，所以本发明所制备的探测器更适宜深紫外波段光的探测任务，除此之外，对纯SnO 2进行掺锆处理可以有效地增大其电阻率，这对探测器来说是非常有利的因素，因为增大电阻率可以有效降低探测器中的暗电流大小，提高探测器的光探测灵敏度和探测率。掺锆之所以能够有效增大纯SnO 2的电阻率，有两方面的原因，一是因为Zr xSn 1-xO 2三元合金的带隙要比纯SnO 2的带隙大，自然会导致此种合金的电阻率比纯SnO 2的大；二是因为掺锆处理以后可以大幅减小纯SnO 2中的缺陷浓度，比如说氧空位、锡间隙等缺陷的数量，从而有效地降低了纯SnO 2中原本因为缺陷而存在着的背景载流子浓度，使得SnO 2的电阻率大幅增加。不但如此，掺锆处理在大幅降低纯SnO 2缺陷数量的时候一方面可有效增大电阻率，另一方面可以提高因光照而产生的非平衡载流子的复合率。这是因为缺陷数量减少了，使得一些深能级陷阱中心的数量也随之减少，故使得电子和空穴更易复合，这一特性可以有效缩短探测器在光照停止后的回复时间。并且，对比高锆含量器件(图6)和低锆含量器件(所述器件包括衬底层、设置在所述衬底层上的Zr 0.1Sn 0.9O 2薄膜层以及设置在所述Zr 0.1Sn 0.9O 2薄膜层上的平行Al电极，其中：所述蓝宝石衬底厚度为0.43mm，所述Zr 0.1Sn 0.9O 2薄膜层厚度为125nm，所述电极厚度为50nm，所述电极间距为10μm)电流-时 间响应曲线(图7)可以看出，锆掺杂浓度越大，光探测器的电流回复时间越短。
实施例3
一种超宽禁带氧化物合金半导体外延薄膜材料，该材料为Hf xSn 1-xO 2三元合金化合物半导体外延薄膜，包括：SnO 2和HfO 2，其中，x大于0，且小于1。
要想实现对深紫外光波的精确灵敏探测，必须要求探测器材料具有较大的禁带宽度。虽然SnO 2的带隙达到了3.6eV，但是仍然不能满足对深紫外波段光的探测要求。通过对纯SnO 2进行等价阳离子取代掺杂是调节其带隙大小的有效途径。等价阳离子取代要求溶质离子是正四价金属阳离子，且离子半径与Sn 4+的半径相差不大，并且此种金属氧化物的带隙要大于4.43eV，且氧化物晶格类型要与SnO 2的晶格类型相近。综合考量这些因素，本发明选择用Hf 4+部分取代Sn 4+(r(Hf 4+)＝0.79埃，r(Sn 4+)＝0.71埃，离子半径相差不大；HfO 2的带隙为5.5eV，远大于4.43eV)，形成了Hf xSn 1-xO 2合金体系。最终实验证明，通过对纯的SnO 2掺铪能够实现对其带隙调增的目的。
另外，通过对薄膜组分的分析发现Hf 4+在合金中的固溶度很大，其极有可能形成无限固溶置换型固溶体合金体系，这一性质也为我们能够在较大范围内自由调节合金带隙的大小提供了可能，也为成功制备响应探测更短波长紫外线的光探测器件提供了可能。
本实施例所提供的Hf xSn 1-xO 2材料是通过SnO 2和HfO 2按照一定的摩尔比例固溶而成的三元合金化合物半导体，因为深紫外波段的光探测要求为紫外线波长小于280nm，所以要求探测器材料的带隙Eg要不小于4.43eV，因为Hf 4+与Sn 4+化合价相同，离子半径相近，且HfO 2的带隙达到5.5eV、晶格类型与SnO 2的晶格类型也十分接近，所以通过铪离子取代锡离子制备出了置换型Hf xSn 1-xO 2合金体系，实现了对本征SnO 2带隙大小的有效调节，进而实现了对深紫外波段及日盲区的光波强度的精确灵敏探测。
实施例4
一种实施例3的超宽禁带氧化物合金半导体外延薄膜材料的制备方法100，包括以下步骤：
步骤110、根据预设半导体带隙，确定SnO 2和HfO 2的摩尔比例，并根据摩尔比例，制备HfO 2与SnO 2复合的陶瓷靶材。
步骤120、基于HfO 2与SnO 2复合的陶瓷靶材，在衬底上制备Hf xSn 1-xO 2三元合金化合物半导体外延薄膜。
实施例5
在实施例4的基础上，步骤110具体为：
根据预设半导体带隙，确定SnO 2和HfO 2的摩尔比例，并根据摩尔比例，分别称取不同量的SnO 2、HfO 2粉末并混合，然后经球磨、洗料、烘干、研磨、压片、烧结工序，制得陶瓷靶材，其中，SnO 2和HfO 2的摩尔比例为SnO 2：HfO 2＝99:1-5:95。
实施例6
在实施例4或实施例5的基础上，步骤110包括以下步骤：
步骤111、根据摩尔比例，分别称取不同量的SnO 2、HfO 2粉末并混合，得到SnO 2和HfO 2的第 一混合物料。
步骤112、向第一混合物料中加入相当于其质量50％～70％的无水乙醇，并球磨3～10小时，得到第二混合物料。
步骤113、将第二混合物料经洗料处理后转移到蒸发皿中，并将蒸发皿放在干燥箱中，对第二混合物料进行烘干处理，得到SnO 2和HfO 2的均匀混合物。
步骤114、将均匀混合物放到研钵中，并向其中加入相当于均匀混合物质量5％～7％的无水乙醇，作为粘连剂，然后进行研磨，得到均匀混合粘结在一起的陶瓷坯料。
步骤115、用电磁液压机在4～6MPa的作用力下，将陶瓷坯料压制成陶瓷坯片。
步骤116、将陶瓷坯片放到管式炉中，在1000～1200℃下，烧结3～4小时，制得所述HfO 2与SnO 2复合的陶瓷靶材。
实施例7
在实施例4至实施例6中任一实施例的基础上，步骤120具体为：
基于HfO 2与SnO 2复合的陶瓷靶材，通过脉冲激光沉积法、磁控溅射法或电子束蒸发法，在蓝宝石的c面上，制备Hf xSn 1-xO 2三元合金化合物半导体外延薄膜。
例如，利用脉冲激光沉积法以c面蓝宝石为衬底制备生长薄膜，首先要对蓝宝石衬底进行超声清洗和干燥处理，具体操作为：依次用丙酮、无水乙醇、去离子水作为清洗液对衬底片进行时间约为10-15分钟的超声处理，然后将清洗过的衬底片用氮气吹干；然后利用脉冲激光沉积法通过激光烧蚀陶瓷靶材物质在衬底上进行薄膜沉积，具体实验参数设置为：薄膜沉积生长温度为100-700℃，氧压0-5Pa，激光能量150-400mJ/pulse。
将所得的薄膜样品用X射线衍射仪和光谱仪等设备对其进行表征，通过对不同掺杂比例的薄膜样品进行在20°-85°范围内的theta-2theta扫描得到其全谱，又对这些薄膜样品进行了ω扫描得到了其摇摆曲线图谱，根据这些图谱可以分析薄膜的物相组成、掺杂情况和薄膜生长质量的信息；并且通过光谱仪的表征得到薄膜样品的透射和吸收光谱，从而可以分析带隙大小与掺杂比例之间的关系，判断掺杂对本征SnO 2带隙大小的调节效果。
本实施例，设备和操作工艺都较为简单便捷，且此种材质的薄膜易于生长，结晶质量很高，对生长环境的要求也较低，适合规模化生产。
实施例8
在实施例7的基础上，当通过脉冲激光沉积法制备Hf xSn 1-xO 2三元合金化合物半导体外延薄膜时，薄膜沉积生长温度为100～700℃，氧压为0～5Pa，激光能量为150～400mJ/pulse，薄膜沉积生长时间为10～15分钟。
实施例9
一种实施例8制得的超宽禁带氧化物合金半导体外延薄膜材料的应用，用于紫外光探测器件中的基质材料。
实施例10
一种紫外光探测器，包括：依次层叠的衬底、基质材料层、平行或叉指电极，基质材料层采用上述超宽禁带氧化物合金半导体外延薄膜作为材料制作而成。
优选的，所述叉指电极为铝质叉指电极。
这里是紫外光探测器，采用的是最简单的金属-半导体-金属(MSM)结构。即在蓝宝石衬底上沉积一层薄膜(在这里就是Hf xSn 1-xO 2薄膜)，然后在薄膜表面上蒸镀平行或叉指电极。工作时在两个电极上加上电压，通过光照产生光生电流，从而探测紫外光。
将所得的合金半导体外延薄膜样品利用真空蒸镀的方法镀上高纯铝质平行或叉指电极，首先把薄膜样品放到掩模板上，高纯铝块放到蒸发舟中，然后一并放入蒸镀仪的真空室中，待机械泵和分子泵抽取得到10 -4Pa的高真空环境时打开蒸发源，然后平稳缓慢增加蒸镀电流，等到蒸镀结束后打开放气阀门，待到真空室与外界大气压相等时打开真空室取出样品。然后将制备的完整光探测器件进行真空封装；并用光电测试***测试器件的光电性能，如电流-电压曲线、电流-时间曲线以及光谱响应等等一系列的光电性能。
紫外光探测器之所以能够探测紫外线的强度是基于爱因斯坦光电效应。当光子能量大于等于探测器基质材料的带隙Eg时就会被吸收，激发价带中的电子跃迁到导带，由原来的局域化电子成为非局域化电子，从而可以在整个晶体材料中移动，形成光电流。当某种特定波长的光照射某种具有特定带隙的物质时就会光致激发，使得载流子浓度增加、导电性能增强，并且光照越强导电性能增加就越明显，产生的光生电流就越大，我们可以利用物质的这一光电特性进行光辐射的探测。但是要想实现精确灵敏地对某一波长范围光波的探测，探测器基质材料的带隙不能太小，如果带隙太小的话就会有较大波长范围内的光被吸收，从而不能精确灵敏地探测某一特定波段的光波强度，所以要求探测器基质材料的带隙不能远小于所要探测的光波段的最小光子能量。对于深紫外波段的探测器来说，要求其基质材料带隙不小于4.43eV，故要对本征SnO 2进行掺杂以调大其禁带宽度Eg，从而实现对深紫外波段光波强度的精确灵敏探测。
例如，按照Hf 0.05Sn 0.95O 2这一掺杂比例(摩尔比例)分别称取SnO 2 18.6304g、HfO 2 1.3696g进行配料初混，然后将初混后的混合物料倒入球磨罐中，并向其中加入占粉末总质量60％左右的无水乙醇，接着放入球磨机中球磨8小时，使其充分的均匀混合，然后将已经充分球磨均匀混合的物料进行洗料处理，并转移到蒸发皿中，随后放到干燥箱中进行烘干处理，烘干结束后，再将混合物料转移到研钵中，并向其中加入占粉末总质量6％左右的无水乙醇作为粘连剂，进行充分的研磨处理，使粉末均匀地粘结在一起形成坯料，然后用电磁液压机把坯料在4～6MPa的作用力下压制成质量10g左右、厚度2～3mm左右的陶瓷坯片，紧接着把坯片放到管式炉中在1100℃的温度下烧结3小时，最后得到成型的陶瓷靶材。
利用脉冲激光沉积法在c面蓝宝石衬底上制备薄膜，首先要对衬底进行清洗，依次分别用丙酮、无水乙醇、去离子水超声清洗15分钟，然后将烧制好的陶瓷靶材和清洗好的蓝宝石衬底一同放入脉冲激光沉积***的腔体中，然后分别用机械泵和分子泵抽取真空以获得10 -4Pa级别的高真空环境，并且将衬底温度设置为700℃，氧压设置为3Pa，激光能量150～200mJ/pulse，激光脉冲频率为 5Hz，沉积时间为15分钟，在此条件和实验参数的设置下进行薄膜生长。
薄膜样品制备出来以后，分别用X射线衍射仪(XRD)和光谱仪对其进行表征，分别得到薄膜样品的XRD theta-2theta扫描图谱(如图8所示)以及透射光谱图(如图9所示)。
最后将制备出的薄膜样品用真空蒸镀的方法镀上高纯铝质平行电极，首先把薄膜样品放到掩模板上，高纯铝块放到蒸发舟中，然后一并放入蒸镀仪的真空室中，待机械泵和分子泵抽取得到10 -4Pa级别的高真空环境时打开蒸发源，然后平稳缓慢增加蒸镀电流，等到蒸镀结束，之后打开放气阀门，待到真空室与外界大气压相等时，打开真空室取出样品，得到完整的紫外光探测器件，所述器件包括衬底层、设置在所述衬底层上的Hf 0.05Sn 0.95O 2薄膜层以及设置在所述Hf 0.05Sn 0.95O 2薄膜层上的平行Al电极，其中：所述蓝宝石衬底厚度为0.43mm，所述Hf 0.05Sn 0.95O 2薄膜层厚度为125nm，所述电极厚度为50nm，所述电极间距为10μm，然后用光电测试***测试该器件的光电性能，得到电流-电压曲线图(如图10所示)以及电流-时间曲线图(如图11所示)。
再例如，按照Hf 0.3Sn 0.7O 2这一掺杂比例分别称取SnO 2 12.5107g、HfO 2 7.4893g进行配料初混，然后将初混后的混合物料倒入球磨罐中并向其中加入占粉末总质量60％左右的无水乙醇，接着放入球磨机中球磨8小时，使其充分均匀混合，然后将已经充分球磨均匀混合的物料进行洗料处理，并转移到蒸发皿中，随后放到干燥箱中进行烘干处理，烘干结束后，再将混合物料转移到研钵中，并向其中加入占粉末总质量6％左右的无水乙醇作为粘连剂，进行充分的研磨处理使粉末均匀地粘结在一起形成坯料，然后用电磁液压机把坯料在4～6MPa的作用力下压制成质量10g左右、厚度2～3mm左右的陶瓷坯片，紧接着把坯片放到管式炉中在1100℃的温度下烧结3小时，最后得到成型的陶瓷靶材。
利用脉冲激光沉积法在c面蓝宝石衬底上制备薄膜，首先要对衬底进行清洗，依次分别用丙酮、无水乙醇、去离子水超声清洗15分钟，然后将烧制好的陶瓷靶材和清洗好的蓝宝石衬底一同放入脉冲激光沉积***的腔体中，然后分别用机械泵和分子泵抽取真空以获得10 -4Pa级别的高真空环境，并且将衬底温度设置为700℃，氧压设置为3Pa，激光能量150～200mJ/pulse，激光脉冲频率为5Hz，沉积时间为15分钟，在此条件和实验参数的设置下进行薄膜生长。
薄膜样品制备出来以后分别用X射线衍射仪和光谱仪对其进行表征，分别得到薄膜样品的XRD theta-2theta扫描图谱(如图8所示)以及透射光谱图(如图9所示)。
最后将制备出的薄膜样品用真空蒸镀的方法镀上高纯铝质平行电极，首先把薄膜样品放到掩模板上，高纯铝块放到蒸发舟中，然后一并放入蒸镀仪的真空室中，待机械泵和分子泵抽取得到10 -4Pa级别的高真空环境时打开蒸发源，然后平稳缓慢增加蒸镀电流，等到蒸镀结束后打开放气阀门，待到真空室与外界大气压相等时打开真空室取出样品，得到完整的紫外光探测器件，所述器件包括衬底层、设置在所述衬底层上的Hf 0.3Sn 0.7O 2薄膜层以及设置在所述Hf 0.3Sn 0.7O 2薄膜层上的平行Al电极，其中：所述蓝宝石衬底厚度为0.43mm，所述Hf 0.3Sn 0.7O 2薄膜层厚度为125nm，所述电极厚度为50nm，所述电极间距为10μm，然后用光电测试***测试该器件的光电性能，得到电流-电压曲线图(如图12所示)以及电流-时间曲线图(如图13所示)。
上述例子是以不同掺杂比例的陶瓷靶材作为激光烧蚀靶，从而制备出不同掺杂比例的Hf xSn 1-xO 2合金半导体外延薄膜，通过对这些薄膜样品进行的XRD表征得到的XRD theta-2theta扫描图谱可以看出(如图8所示)，除了41°左右出现了薄膜衬底氧化铝的特征峰外，在37°～38°和80°左右均出现了明显的衍射峰，通过PDF卡片的精确对比，可以确定这两个峰分别是Hf xSn 1-xO 2的(200)、(400)面的衍射峰，除此之外再无其他杂相的衍射峰出现，故可以得出结论：不同掺杂比例的薄膜样品的掺杂效果都是较为理想的，Hf 4+成功取代了Sn 4+的空间格点位置。
通过光谱仪对这些薄膜样品进行表征，从得到的透射和吸收光谱可以明显看出(如图9所示)，随着Hf掺杂浓度的增加，薄膜样品的吸收边向短波方向出现了明显的移动，说明随着Hf掺杂浓度的增加，Hf xSn 1-xO 2合金的带隙也是不断增大的，从吸收光谱利用线性外推法得出的光学带隙结果显示：从Hf 0.05Sn 0.95O 2到Hf 0.3Sn 0.7O 2，合金带隙从4.13eV增大到4.63eV。
最后，用光电测试***对制备出的完整探测器件进行了光电性能测试。
其中，根据Hf 0.05Sn 0.95O 2和Hf 0.3Sn 0.7O 2的电流-电压曲线图(如图10和12所示)可以看出，通过对纯SnO 2进行掺铪处理可以有效地增大其电阻率，且随着掺杂浓度的增大，电阻率也增加得越明显。
如图10和图12所示，Hf 0.3Sn 0.7O 2的电阻率远大于Hf 0.05Sn 0.95O 2，其倍比高达10 8。这一特性对探测器来说是非常有利的因素，因为增大电阻率，可以有效降低探测器中的暗电流大小，提高探测器的光探测灵敏度和探测率。掺铪之所以能够有效增大纯SnO 2的电阻率，有两方面的原因：一是因为Hf xSn 1-xO 2三元合金的带隙要比纯SnO 2的带隙大，自然会导致电阻率比纯SnO 2的大；二是因为掺铪处理以后，可以大幅度减小纯SnO 2中的缺陷浓度，比如氧空位、锡间隙等缺陷的数量，从而有效降低纯SnO 2中原本因为缺陷而存在着的背景载流子浓度，使得SnO 2的电阻率大幅增加。
根据电流-时间曲线图(如图11和13所示)可以看出，当没有光照射时，电流值较小，当快速打开挡板让光线照射到器件上时，电流值陡然增加，说明器件具有较灵敏快速的光响应效应，能够进行深紫外光强的探测。即从电流-时间曲线图(如图11和13所示)可以看出，本发明制备的Hf xSn 1-xO 2三元合金单晶薄膜基紫外光探测器具有较高的光响应灵敏度，当没有光照时暗电流值较小，当光照射到探测器上时电流值猛然增加，然后快速达到恒定值。
对比两种不同铪掺杂比例的探测器，最明显的区别就是光响应时间的长短，特别是在电流下降阶段，Hf 0.3Sn 0.7O 2的回复时间明显短于Hf 0.05Sn 0.95O 2的回复时间，这是因为对纯SnO 2进行掺铪处理，在大幅降低纯SnO 2缺陷数量的时候，一方面可以有效增大电阻率，另一方面又可以提高非平衡载流子的复合率，这是因为缺陷数量减少了的同时也使得一些深能级陷阱中心的数量得到显著减少，从而使电子和空穴更易复合，这一特性有效地缩短了探测器在停止光照后的回复时间，且铪掺杂浓度越大回复时间越短。
综上所述，通过铪掺杂SnO 2能够解除SnO 2的禁戒跃迁，增强其对深紫外光的响应。对SnO 2进行掺铪处理，一方面可以增大其带隙Eg的大小，使得其更适宜在深紫外波段进行探测；二来可以有效地增大纯SnO 2的电阻率，降低探测器中的暗电流大小，提高探测器的光响应灵敏度和探测 率；三可以有效减少纯SnO 2中的缺陷浓度，特别是深能级陷阱中心的数量，从而极大地提高电子和空穴的复合率，缩短探测器的回复时间，显著提高探测器的性能。
实施例11
本实施例的一种超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料，所述Me为Si，x为0.12。
按照Si 0.12Sn 0.88O 2这一掺杂配方分别称取SnO 2 17.524g、SiO 2 1.998g进行配料初混，然后将初混后的混合物料倒入球磨罐中并向其中加入占粉末总质量60％左右的无水乙醇，接着放入球磨机中球磨8小时使其充分地均匀混合，然后将已经充分球磨均匀混合的物料进行洗料处理，并转移到蒸发皿中，随后放到干燥箱中进行烘干处理，烘干结束后再将混合物料转移到研钵中并向其中加入占粉末总质量6％左右的无水乙醇作为粘连剂，进行充分的研磨处理使粉末均匀的粘结在一起形成坯料，然后用电磁液压机把坯料在4-6MPa的压力下压制成质量10g左右，厚度2-3mm左右的陶瓷坯片，紧接着把坯片放到管式炉中在1100℃的温度下烧结3小时，最后得到成型的陶瓷靶材。本发明的外延薄膜利用脉冲激光沉积法在c面蓝宝石衬底上制备生长而成。首先对衬底基片进行清洗，依次分别用丙酮、无水乙醇、去离子水超声清洗15分钟，然后将烧制好的陶瓷靶材和清洗好的蓝宝石衬底一同放入脉冲激光沉积***的腔体中，然后分别用机械泵和分子泵抽取真空以获得10 -4Pa级别的高真空环境，并且将衬底温度设置为650℃，氧压设置为2Pa，激光能量150-300mJ/pulse，激光脉冲频率为5Hz，沉积时间为30分钟，在此条件和实验参数的设置下进行薄膜生长。薄膜样品制备出来以后分别用X射线衍射仪和光谱仪对其进行表征，分别得到薄膜样品的XRD theta-2theta扫描图谱、透射光谱图，分别见附图14、15。最后将制备出的薄膜样品用真空蒸镀的方法镀上高纯铝质平行电极，首先把薄膜样品放到掩模板上，高纯铝块放到蒸发舟中，然后一并放入蒸镀仪的真空室中，待机械泵和分子泵抽取得到10 -4Pa级别的高真空环境时打开蒸发源，然后平稳缓慢增加蒸镀电流，等到蒸镀结束后打开放气阀门，待到真空室与外界大气压相等时打开真空室取出样品，得到完整的紫外光探测器件，所述器件包括衬底层、设置在所述衬底层上的Si 0.12Sn 0.88O 2薄膜层以及设置在所述Si 0.12Sn 0.88O 2薄膜层上的平行Al电极，其中：所述蓝宝石衬底厚度为0.43mm，所述Si 0.12Sn 0.88O 2薄膜层厚度为200nm，所述电极厚度为50nm，所述电极间距为10μm，然后用光电测试***测试器件的光电性能、电流-时间曲线图(见附图16、17)。
实施例12
本实施例的一种超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料，所述Me为Si，x为0.88。
按照Si 0.88Sn 0.12O 2这一掺杂配方分别称取SnO 2 7.726g、SiO 2 12.274g进行配料初混，然后将初混后的混合物料倒入球磨罐中并向其中加入占粉末总质量60％左右的无水乙醇，接着放入球磨机中球磨8小时使其充分地均匀混合，然后将已经充分球磨均匀混合的物料进行洗料处理，并转移到蒸发皿中，随后放到干燥箱中进行烘干处理，烘干结束后再将混合物料转移到研钵中并向其中加入占粉末总质量6％左右的无水乙醇作为粘连剂，进行充分的研磨处理使粉末均匀地粘结在一起形成坯料，然后用电磁液压机把坯料在4-6MPa的压力下压制成质量10g左右，厚度2-3mm左右的陶瓷坯片，紧接着把坯片放到管式炉中在1100℃的温度下烧结3小时，最后得到成型的陶瓷靶材。本 发明的外延薄膜利用脉冲激光沉积法在c面蓝宝石衬底上制备而成。首先对衬底基片进行清洗，依次分别用丙酮、无水乙醇、去离子水超声清洗15分钟，然后将烧制好的陶瓷靶材和清洗好的蓝宝石衬底一同放入脉冲激光沉积***的腔体中，然后分别用机械泵和分子泵抽取真空以获得10 -4Pa的高真空环境，并且将衬底温度设置为650℃，氧压设置为2Pa，激光能量150-300mJ/pulse，激光脉冲频率为5Hz，沉积时间为30分钟，在此条件和实验参数的设置下进行薄膜生长。薄膜样品制备出来以后分别用X射线衍射仪和光谱仪对其进行表征，分别得到薄膜样品的XRD theta-2theta扫描图谱、透射光谱图，分别见附图14、15。最后将制备出的薄膜样品用真空蒸镀的方法镀上高纯铝质平行电极，首先把薄膜样品放到掩模板上，高纯铝粉放到蒸发舟中，然后一并放入蒸镀仪的真空室中，待机械泵和分子泵抽取得到10 -4Pa级别的高真空环境时打开蒸发源，然后平稳缓慢增加蒸镀电流，等到蒸镀结束后打开放气阀门，待到真空室与外界大气压相等时打开真空室取出样品，得到完整的紫外光探测器件，所述器件包括衬底层、设置在所述衬底层上的Si 0.88Sn 0.12O 2薄膜层以及设置在所述Si 0.88Sn 0.12O 2薄膜层上的平行Al电极，其中：所述蓝宝石衬底厚度为0.43mm，所述Si 0.88Sn 0.12O 2薄膜层厚度为120nm，所述电极厚度为50nm，所述电极间距为10μm，然后用光电测试***测试器件的光电性能、电流-时间曲线图(见附图18、19)。
本发明的这些实施例是以不同掺杂比例的陶瓷靶材作为激光烧蚀靶从而制备出不同掺杂比例的Si xSn 1-xO 2合金半导体外延薄膜，通过对这些薄膜样品进行的XRD表征得到的衍射图谱，即图14可以看出，Si 0.12Sn 0.88O 2薄膜在34°和72°左右出现了明显的衍射峰，通过PDF卡片的精确对比可以确定这两个峰分别是SnO 2的(101)、(202)面的衍射峰，除此之外再无其他杂相的衍射峰出现，而Si 0.88Sn 0.12O 2薄膜除了衬底峰外无其他衍射峰，故可以得出结论：在x为～0.12时，薄膜为单晶薄膜；而当x含量较高～0.88，薄膜转变为非晶薄膜。通过光谱仪对这些薄膜样品进行表征得到的透射光谱，即图15，可以明显看出，随着掺杂浓度的增加，薄膜样品的吸收边向短波方向出现了明显的移动，说明随着Si掺杂浓度的增加Si xSn 1-xO 2合金的带隙也是不断增大的。从吸收光谱，利用线性外推法得出从Si 0.12Sn 0.88O 2到Si 0.88Sn 0.12O 2带隙从3.3eV增大到5.2eV。最后用光电测试***对制备出的完整探测器件进行了光电性能的测试，从电流-时间曲线图中(见附图16、17、18、19)可以看出，当没有光照射时电流值较小，当快速打开挡板，光线照射到器件上时电流值陡然增加，说明器件具有较灵敏快速的光响应效应，能够进行深紫外光强的探测。特别是非晶的Si 0.88Sn 0.12O 2探测器，响应速度得到了明显提升。
通过Si掺杂SnO 2能够解除SnO 2的禁戒跃迁，增强其对深紫外光的响应。本发明制备的非晶Si 0.88Sn 0.12O 2三元合金薄膜基紫外探测器具很快的光电响应速度，从电流-时间曲线(图19)中可以知道，在电流上升和下降阶段的光响应时间均小于0.2秒。相比于纯SnO 2的单晶薄膜基紫外光探测器，由于Si xSn 1-xO 2三元合金具有更大的禁带宽度，所以本发明所制备的探测器更适宜深紫外波段的紫外光探测任务，除此之外，对纯SnO 2进行掺硅处理可以有效地增大其电阻率，这对探测器来说是非常有利的因素，因为增大电阻率可以有效降低探测器中的暗电流大小，提高探测器的光探测灵敏度和探测率。掺硅之所以能够有效增大纯SnO 2的电阻率，有两方面的原因，一是因为Si xSn 1-xO 2 三元合金的带隙要比纯SnO 2的带隙大，自然会导致此种合金的电阻率比纯SnO 2的大；二是因为掺硅处理以后可以大幅减小纯SnO 2中的缺陷浓度，比如说氧空位、锡间隙等缺陷的数量，从而有效地降低了纯SnO 2中原本因为缺陷而存在着的背景载流子浓度，使得SnO 2的电阻率大幅增加。不但如此，掺硅处理在大幅降低纯SnO 2缺陷数量的时候一方面可有效增大电阻率，另一方面可以提高因光照而产生的非平衡载流子的复合率。这是因为缺陷数量减少了，使得一些深能级陷阱中心的数量也随之减少，故使得电子和空穴更易复合，这一特性可以有效缩短探测器在光照停止后的回复时间。并且，对比高硅含量器件(图19)和低硅含量器件电流-时间响应曲线(图17)可以看出，硅掺杂浓度越大，光探测器的电流回复时间越短。特别地，非晶薄膜由于存在大量结构畸变缺陷作为复合中心，能有效促进光生载流子复合，从而显著缩短器件回复时间(图19)。
另外，本实施例所提供的紫外光探测器件的电极是采用真空蒸镀法蒸镀的铝质电极，操作工艺简单且易于掌握，同时制备整个探测器件的原材料价廉且易得，所以本实施例对深紫外以及日盲区的紫外光探测具有很重要的意义。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料，其特征在于：所述材料包括：SnO 2和MeO 2，其中：x大于0，且小于1；Me为Zr或Hf或Si或它们中的任意两种或三种元素的组合。
  2. 根据权利要求1所述的超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料，其特征在于：所述x为0.05～0.99。
  3. 权利要求1或2所述的超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料的制备方法，其特征在于：包括以下步骤：
    步骤1、根据预设半导体带隙，确定SnO 2和MeO 2的摩尔比例，并根据所述摩尔比例，制备MeO 2与SnO 2复合的陶瓷靶材；
    步骤2、基于所述MeO 2与SnO 2复合的陶瓷靶材，在衬底上制备所述Me xSn 1-xO 2合金化合物半导体外延薄膜。
  4. 权利要求1或2所述的超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料作为基质层材料在深紫外光探测器中的应用。
  5. 一种深紫外光探测器件，其特征在于：包括衬底层、设置在所述衬底层上的基质材料层以及设置在所述基质材料层上的平行或叉指电极，所述基质材料层由权利要求1或2所述的超宽禁带Me xSn 1-xO 2合金半导体外延薄膜材料形成。
  6. 根据权利要求5所述的深紫外光探测器件，其特征在于：所述深紫外光探测器的探测波长为300nm～220nm。
  7. 根据权利要求5所述的深紫外光探测器件，其特征在于：所述基质材料层厚度为100～300nm，所述电极厚度为30～70nm，所述电极间距为10～100μm。
  8. 根据权利要求5所述的深紫外光探测器件，其特征在于：所述衬底为c面蓝宝石衬底，所述蓝宝石衬底厚度为0.35～0.45mm。
  9. 根据权利要求5所述的深紫外光探测器件，其特征在于：所述电极材料为Pt、Au、Al或ITO中的任一种。
  10. 权利要求5～9任一项所述的深紫外光探测器件的制备方法，其特征在于：将Me xSn 1-xO 2合金半导体外延薄膜材料利用真空蒸镀的方法镀上高纯金属电极或利用溅射法镀上透明导电ITO电极。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1484045A (zh) * 2002-08-07 2004-03-24 Hoya株式会社 制造抗反射涂层基片的方法
US20070049051A1 (en) * 2005-08-29 2007-03-01 Micron Technology, Inc. Atomic layer deposition of Zrx Hfy Sn1-x-y O2 films as high k gate dielectrics
JP2007258468A (ja) * 2006-03-23 2007-10-04 National Institute Of Advanced Industrial & Technology 可視光透過半導体素子およびその製造方法
CN103545397A (zh) * 2013-10-29 2014-01-29 中国科学院化学研究所 薄膜紫外光探测器及其制备方法与应用
CN108396288A (zh) * 2018-03-30 2018-08-14 湖北大学 超宽禁带ZrxSn1-xO2合金半导体外延薄膜材料及其制备方法、应用和器件
CN108546918A (zh) * 2018-03-30 2018-09-18 湖北大学 一种超宽禁带氧化物合金半导体外延薄膜材料及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1484045A (zh) * 2002-08-07 2004-03-24 Hoya株式会社 制造抗反射涂层基片的方法
US20070049051A1 (en) * 2005-08-29 2007-03-01 Micron Technology, Inc. Atomic layer deposition of Zrx Hfy Sn1-x-y O2 films as high k gate dielectrics
JP2007258468A (ja) * 2006-03-23 2007-10-04 National Institute Of Advanced Industrial & Technology 可視光透過半導体素子およびその製造方法
CN103545397A (zh) * 2013-10-29 2014-01-29 中国科学院化学研究所 薄膜紫外光探测器及其制备方法与应用
CN108396288A (zh) * 2018-03-30 2018-08-14 湖北大学 超宽禁带ZrxSn1-xO2合金半导体外延薄膜材料及其制备方法、应用和器件
CN108546918A (zh) * 2018-03-30 2018-09-18 湖北大学 一种超宽禁带氧化物合金半导体外延薄膜材料及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIN, . ZHENGUO: "The Study of Oxide Thin-Film Transistors and Novel Active-Layer Materials", INFORMATION SCIENCE & TECHNOLOGY, 15 July 2018 (2018-07-15), pages 68, ISSN: 1674-022X *
V.S. ANITHA ET AL.: "Bandgap Tuning of Zr02-Sn02 Nanocomposite Thin Films by Sol-gel Dip Coating Technique", MATERIALS TODAY: PROCEEDINGS, vol. 2, no. 3, 31 December 2015 (2015-12-31), pages 1026 - 1030, XP055641435, ISSN: 2214-7853 *

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