WO2018018676A1 - 一种高电阻率单晶氧化锌及其制备方法和应用 - Google Patents

一种高电阻率单晶氧化锌及其制备方法和应用 Download PDF

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WO2018018676A1
WO2018018676A1 PCT/CN2016/095816 CN2016095816W WO2018018676A1 WO 2018018676 A1 WO2018018676 A1 WO 2018018676A1 CN 2016095816 W CN2016095816 W CN 2016095816W WO 2018018676 A1 WO2018018676 A1 WO 2018018676A1
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single crystal
preparation
zno
zinc oxide
wafer
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黄丰
季旭
董美
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Sun Yat Sen University
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
    • C30B31/04—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion materials in the liquid state
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
    • C30B31/04—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion materials in the liquid state
    • C30B31/045—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion materials in the liquid state by electrolysis
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • C30B33/02—Heat treatment

Definitions

  • the invention belongs to the technical field of radiation detectors. More specifically, it relates to a high resistivity single crystal zinc oxide and a preparation method and application thereof.
  • the technical problem to be solved by the present invention is to overcome the defects and technical deficiencies in the prior art that it is difficult to obtain high-resistivity single crystal ZnO, and to provide a method for preparing a high-resistivity single crystal ZnO of a radiation or photodetector.
  • the method adopts electrochemical method combined with annealing treatment to obtain a single-crystal ZnO wafer with ultra-high resistivity, and has novel preparation method, simple operation, low cost and high repeatability.
  • Another object of the present invention is to provide a high resistivity single crystal zinc oxide prepared by the method.
  • a preparation method of high resistivity single crystal zinc oxide comprising the following steps:
  • the single crystal ZnO wafer is placed in a metal lithium electrochemical device, and subjected to constant current discharge treatment to realize lithium implantation in the ZnO single crystal;
  • the ZnO single crystal treated in the step S1 is annealed in an oxygen atmosphere furnace at 600 to 1000 ° C and 5 to 30 atm for 10 to 28 hours to remove lithium metal, thereby obtaining a high-resistivity ZnO single wafer.
  • step S1 and step S2 must be strictly controlled, and step S1 is performed first, and then step S2 is performed.
  • step S1 a controllable discharge process is adopted to utilize the difference in the natural chemical potential of lithium and ZnO to achieve efficient injection of lithium in ZnO.
  • the single crystal ZnO wafer described in step S1 is a low resistance high quality single crystal ZnO wafer.
  • the electrolyte in the metal lithium electrochemical device of step S1 is 0.5-1.5 M LiPF 6 solution dispersed in ethylene carbonate, ethyl methyl carbonate and a volume ratio of 2 to 5:2 to 4:2 to 4
  • a mixed solution of diethyl carbonate was used as an electronic separator using a Celgard 2400 polyethylene microporous membrane.
  • the electrolyte in the metal lithium electrochemical device of step S1 is a 1 M LiPF 6 solution dispersed in a mixed solution of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 4:3:3.
  • the metal lithium electrochemical device of step S1 is a lithium battery case.
  • the ZnO wafer was placed in a commercial lithium battery structure for constant current discharge treatment.
  • the method for placing the single crystal ZnO wafer in the lithium metal electrochemical device in step S1 is specifically assembling the single crystal ZnO wafer into the lithium battery case in the following order: positive shell, single crystal ZnO wafer, polyethylene
  • the microporous film, the metal lithium plate, the flash electrode, the spring electrode, the negative electrode case, and the outer ring are insulating sleeve layers.
  • the constant current discharge treatment in step S1 is a constant current discharge treatment of 1 to 4 uA for 10 to 25 hours.
  • the constant current discharge treatment in step S1 is a 3uA constant current discharge treatment for 15 hours.
  • the size of the single crystal ZnO wafer described in the step S1 is 10 cm square.
  • the single crystal ZnO wafer described in step S1 has a thickness of 0.2 to 0.5 mm.
  • a 3 uA constant current discharge treatment is performed for 10 hours; when the thickness of the single crystal ZnO wafer is 0.3 mm, a 3 uA constant current discharge treatment is performed for 15 hours; At a thickness of 0.5 mm, a 3 uA constant current discharge treatment was carried out for 25 hours.
  • step S2 is to place the ZnO single crystal processed in step S1 at 800 to 900 ° C and 15 to 25 atm. Annealing in an oxygen atmosphere furnace for 22 to 26 hours.
  • step S2 the ZnO single crystal treated in step S1 is annealed in a high pressure oxygen atmosphere furnace at 800 ° C for 20 hours in an atmosphere of 800 ° C for 24 hours.
  • the high resistivity single crystal zinc oxide prepared by the above method and the use of the high resistivity single crystal zinc oxide in the preparation of the radiation detector member or the photodetector device are also within the scope of the present invention.
  • the invention provides a preparation method of a high-resistivity single crystal ZnO of a radiation or photodetector element.
  • the method adopts an electrochemical method combined with annealing treatment, and only requires two simple steps to obtain an ultrahigh resistivity single crystal ZnO.
  • the resulting ZnO wafer has a resistivity as high as 10 11 ⁇ cm.
  • the preparation method of the invention is novel, simple in operation, low in cost, high in repeatability, and has good application prospects.
  • FIG. 1 is a sequence diagram of an electrochemical cell configuration in which a low-resistance zinc oxide crystal lattice is placed in a metal lithium battery can when a high-resistivity single crystal ZnO is prepared.
  • Figure 2 is a diagram of the apparatus used in the annealing of a high temperature and high pressure oxygen atmosphere.
  • a 10 cm square high-quality low-resistance zinc oxide wafer was assembled into a commercial CR 2032 battery case in the order shown in Fig. 1 at room temperature in an argon-filled glove box, wherein the electrolyte used was 1 M LiPF6.
  • the solution was dispersed in a mixed solution of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 4:3:3, and a Celgard 2400 polyethylene microporous membrane was used as an electronic separator.
  • the LAND BT2013A multi-channel battery test system performs constant current discharge treatment at room temperature to realize the injection of lithium into the ZnO single crystal.
  • the high-quality low-resistance zinc oxide wafer used in this embodiment has a thickness of 0.3 mm, and the constant current discharge current is set to 3 microamps, the discharge time was set to 15 hours.
  • the lithium removing device used in this embodiment can withstand a high temperature and high pressure oxygen atmosphere.
  • the oxygen pressure is set to 20 standard atmospheric pressure
  • the temperature is set to 800 degrees Celsius
  • the annealing time is set to 24 hours.
  • the method was the same as in Example 1, except that the thickness of the ZnO wafer in the step (1) was 0.2 mm, the constant current discharge current was set to 3 ⁇ A, and the discharge time was set to 10 hours.
  • the present embodiment shortens the discharge time due to the decrease in the thickness of the wafer, thereby obtaining the same processing result.
  • the method was the same as in Example 1, except that the thickness of the ZnO wafer in the step (1) was 0.5 mm, the constant current discharge current was set to 3 ⁇ A, and the discharge time was set to 25 hours.
  • the present embodiment has a longer discharge time due to an increase in the thickness of the wafer, thereby obtaining the same processing result.
  • a high-quality low-resistance zinc oxide wafer having a thickness of 0.2 mm and a thickness of 10 cm was assembled into a commercial CR 2032 battery case in the order shown in Fig. 1 at room temperature in an argon-filled glove box.
  • the electrolyte was a 1 M LiPF6 solution dispersed in a mixed solution of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 1:1:1, and a Celgard 2400 polyethylene microporous membrane was used as an electronic separator.
  • Constant current discharge treatment at room temperature by LAND BT2013A multi-channel battery test system The implantation of lithium in ZnO single crystals.
  • the high-quality low-resistance zinc oxide wafer used in this example had a thickness of 0.2 mm, a constant current discharge current of 4 ⁇ A, and a discharge time of 8 hours.
  • the lithium removing device used in this embodiment can withstand a high temperature and high pressure oxygen atmosphere.
  • the oxygen pressure is set to 25 standard atmospheric pressure
  • the temperature is set to 900 degrees Celsius
  • the annealing time is set to 22 hours.
  • a high-quality low-resistance zinc oxide wafer having a thickness of 0.2 mm and a thickness of 10 cm was assembled into a commercial CR 2032 battery case in the order shown in Fig. 1 at room temperature in an argon-filled glove box.
  • the electrolyte was a 1 M LiPF6 solution dispersed in a mixed solution of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 5:4:4, and a Celgard 2400 polyethylene microporous membrane was used as an electronic separator.
  • the LAND BT2013A multi-channel battery test system performs constant current discharge treatment at room temperature to realize the injection of lithium into the ZnO single crystal.
  • the high-quality low-resistance zinc oxide wafer used in this example had a thickness of 0.5 mm, a constant current discharge current of 3 ⁇ A, and a discharge time of 25 hours.
  • the lithium removal device used in this embodiment can withstand a high temperature and high pressure oxygen atmosphere.
  • the oxygen pressure is set to 15 standard atmospheric pressure
  • the temperature is set to 900 degrees Celsius
  • the annealing time is set to 26 hours.

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

本发明公开了一种高电阻率单晶氧化锌及其制备方法和应用。该方法是将单晶ZnO晶片置于金属锂电化学装置中恒流放电处理后，放于800～1000℃、10～30atm的高压氧气气氛中退火处理20～28小时，得到所述高电阻率单晶氧化锌。该方法采用电化学方法结合退火处理，只需要简单的两个步骤即可获得超高电阻率的单晶ZnO晶片，得到的ZnO晶片电阻率高达1011ohm cm。而且，本发明的制备方法新颖、操作简单，成本低，可重复性高，具有很好的推广应用前景。

Description

一种高电阻率单晶氧化锌及其制备方法和应用 技术领域
本发明属于辐射探测器技术领域。更具体地，涉及一种高电阻率单晶氧化锌及其制备方法和应用。
背景技术
半导体核辐射探测器的研究已经经历了半个多世纪的时间。其在核科学、天文学、宇宙物理、核能利用、工业自动化、核电站、核医学成像、反恐防恐和环保监测等众多领域得到了广泛的应用。
目前，由于器件工艺的成熟，基于硅、锗为代表的第一代半导体材料已经发展了较为成熟的探测器件制备技术。但是，无论硅还是锗都因其较窄的带隙而对环境温度敏感、抗辐射能力弱，因而将其装备到强辐照环境下工作的系统中受到较大的限制。另一方面，对于化合物半导体，如III-V族化合物GaAs、InGaAs、GaN，II-VI族化合物CdTe、CdZnTe，VII-B族二元卤族化合物HgI2、PbI2、TlBr以及它们的三元化合物HgCdTe等，这些材料大多数都存在熔点低、易分解、抗辐照能力弱的缺点，基于其所搭建器件性能的稳定性及可靠性难以保证，这些问题大大限制了相关辐射探测器件的广泛应用。
比之相比，具有更强抗辐照能力、更宽带隙、更高的击穿电场强度等优异特性的ZnO宽禁带半导体材料逐渐受到关注，但是，如何获得高电阻率从而强烈抑制暗电流噪声以便获得高信噪比的高电阻率单晶ZnO，一直是阻碍其在辐射探测领域应用的重要阻碍。
发明内容
本发明要解决的技术问题是克服现有技术中难以获得高电阻率单晶ZnO的缺陷和技术不足，提供一种辐射或光电探测器件级高电阻率单晶ZnO的制备方法。该方法采用电化学方法结合退火处理即可获得超高电阻率的单晶ZnO晶片，制备方法新颖、操作简单，成本低，可重复性高。
本发明的目的是提供一种高电阻率单晶氧化锌的制备方法。
本发明另一目的是提供所述方法制备得到的高电阻率单晶氧化锌。
本发明的再一目的是提供所述高电阻率单晶氧化锌的应用。
本发明上述目的通过以下技术方案实现：
一种高电阻率单晶氧化锌的制备方法，包括如下步骤：
S1.将单晶ZnO晶片置于金属锂电化学装置中，恒流放电处理，实现锂在ZnO单晶中的注入；
S2.将步骤S1处理过的ZnO单晶放于600～1000℃、5～30atm的氧气气氛炉中退火处理10～28小时，进行锂金属的去除处理，即可得到高电阻率ZnO单晶片。
其中，步骤S1和步骤S2的操作顺序必须严格控制，先进行步骤S1，再进行步骤S2。
步骤S1中，利用锂与ZnO天然化学位能的差异，采取可控的放电过程，实现锂在ZnO中的高效注入。
步骤S1所述的单晶ZnO晶片为低阻高质量单晶ZnO晶片。
优选地，步骤S1所述金属锂电化学装置内的电解液为0.5～1.5M LiPF6溶液分散于体积比为2～5：2～4：2～4的碳酸亚乙酯、碳酸甲乙酯和碳酸二乙酯混合溶液，采用Celgard 2400聚乙烯多微孔膜做为电子隔膜。
更优选地，步骤S1所述金属锂电化学装置内的电解液为1M LiPF6溶液分散于体积比为4：3：3的碳酸亚乙酯、碳酸甲乙酯和碳酸二乙酯混合溶液。
作为一种优选的可实施方案，步骤S1所述金属锂电化学装置为锂电池壳。使用时，将ZnO晶片放于商用的锂电池结构中恒流放电处理。
优选地，步骤S1所述将单晶ZnO晶片置于金属锂电化学装置中的方法具体是按照如下顺序将单晶ZnO晶片装配到锂电池壳中：正级壳、单晶ZnO晶片、聚乙烯多微孔膜、金属锂片、闪电极、弹簧电极、负极壳，外圈是绝缘套层。
优选地，步骤S1所述恒流放电处理是1～4uA恒流放电处理10～25小时。
优选地，步骤S1所述恒流放电处理是3uA恒流放电处理15小时。
另外，优选地，步骤S1所述的单晶ZnO晶片的大小为10厘米见方。
优选地，步骤S1所述的单晶ZnO晶片的厚度为0.2～0.5毫米。
更优选地，是当单晶ZnO晶片的厚度为0.2毫米时，3uA恒流放电处理10小时；当单晶ZnO晶片的厚度为0.3毫米时，3uA恒流放电处理15小时；单晶ZnO晶片的厚度为0.5毫米时，3uA恒流放电处理25小时。
优选地，步骤S2是将步骤S1处理过的ZnO单晶放于800～900℃、15～25atm 的氧气气氛炉中退火处理22～26小时。
更优选地，步骤S2是将步骤S1处理过的ZnO单晶放于800℃、20atm的高压氧气气氛炉中退火处理24小时。
另外，由上述方法制备得到的高电阻率单晶氧化锌，以及所述高电阻率单晶氧化锌在制备辐射探测器件或光电探测器件方面的应用，也都在本发明的保护范围之内。
本发明具有以下有益效果：
本发明提供了一种辐射或光电探测器件级高电阻率单晶ZnO的制备方法，该方法采用电化学方法结合退火处理，只需要简单的两个步骤即可获得超高电阻率的单晶ZnO晶片，得到的ZnO晶片电阻率高达1011Ωcm。
而且，本发明的制备方法新颖、操作简单，成本低，可重复性高，具有很好的推广应用前景。
附图说明
图1为制备高电阻率单晶ZnO时低阻氧化锌晶格置于金属锂电池壳的电化学池配置顺序图。
图2为高温高压氧气气氛退火所使用的装置图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明，本发明所用试剂和材料均为市购。
实施例1
1、制备高电阻率单晶ZnO
(1)室温下在氩气填充的手套箱中，将10厘米见方的高质量低阻氧化锌晶片按图1所示顺序装配到商用CR 2032电池壳中，其中所用到的电解液为1M LiPF6溶液分散于体积比为4：3：3的碳酸亚乙酯、碳酸甲乙酯和碳酸二乙酯混合溶液中，采用Celgard 2400聚乙烯多微孔膜做为电子隔膜。
通过LAND BT2013A多通道电池测试系统在室温下进行恒流放电处理，实现锂在ZnO单晶中的注入。
本实施例所用高质量低阻氧化锌晶片的厚度0.3毫米，恒流放电电流设定为 3微安，放电时间设定为15小时。
(2)将上述步骤(1)处理过的进锂氧化锌晶片放置于图2所示的高温高压退火炉中，进行晶格中锂的去除，得到高电阻率ZnO单晶片。
本实施例所用的锂去除装置，其可承受高温高压氧气气氛，按实验需求，氧压设为20标准大气压，温度设为800摄氏度，退火时间设为24小时。
2、上述制备得到的高电阻率ZnO单晶片的电阻率为1011Ωcm，比处理之前提高了1011。
实施例2
1、制备高电阻率单晶ZnO
方法同实施例1，不同之处在于，步骤(1)中的ZnO晶片的厚度0.2毫米，恒流放电电流设定为3微安，放电时间设定为10小时。
本实施例与实施例1相比，由于晶片厚度的降低，而缩短了放电时间，从而获得相同的处理结果。
2、本实施例制备得到的高电阻率ZnO单晶片的电阻率为1011Ωcm，比处理之前提高了1011。
实施例3
1、制备高电阻率单晶ZnO
方法同实施例1，不同之处在于，步骤(1)中的ZnO晶片的厚度0.5毫米，恒流放电电流设定为3微安，放电时间设定为25小时。
本实施例与实施例1相比，由于晶片厚度的增加，而延长了放电时间，从而获得相同的处理结果。
2、本实施例制备得到的高电阻率ZnO单晶片的电阻率为1011Ωcm，比处理之前提高了1011。
实施例4
1、制备高电阻率单晶ZnO
(1)室温下在氩气填充的手套箱中，将厚度为0.2毫米、10厘米见方的高质量低阻氧化锌晶片按图1所示顺序装配到商用CR 2032电池壳中，其中所用到的电解液为1M LiPF6溶液分散于体积比为1：1：1的碳酸亚乙酯、碳酸甲乙酯和碳酸二乙酯混合溶液中，采用Celgard 2400聚乙烯多微孔膜做为电子隔膜。
通过LAND BT2013A多通道电池测试系统在室温下进行恒流放电处理，实 现锂在ZnO单晶中的注入。
本实施例所用高质量低阻氧化锌晶片的厚度0.2毫米，恒流放电电流设定为4微安，放电时间设定为8小时。
(2)将上述步骤(1)处理过的进锂氧化锌晶片放置于图2所示的高温高压退火炉中，进行晶格中锂的去除，得到高电阻率ZnO单晶片。
本实施例所用的锂去除装置，其可承受高温高压氧气气氛，按实验需求，氧压设为25标准大气压，温度设为900摄氏度，退火时间设为22小时。
2、上述制备得到的高电阻率ZnO单晶片的电阻率为1011Ωcm，比处理之前提高了1011。
实施例5
1、制备高电阻率单晶ZnO
(1)室温下在氩气填充的手套箱中，将厚度为0.2毫米、10厘米见方的高质量低阻氧化锌晶片按图1所示顺序装配到商用CR 2032电池壳中，其中所用到的电解液为1M LiPF6溶液分散于体积比为5：4：4的碳酸亚乙酯、碳酸甲乙酯和碳酸二乙酯混合溶液中，采用Celgard 2400聚乙烯多微孔膜做为电子隔膜。
通过LAND BT2013A多通道电池测试系统在室温下进行恒流放电处理，实现锂在ZnO单晶中的注入。
本实施例所用高质量低阻氧化锌晶片的厚度0.5毫米，恒流放电电流设定为3微安，放电时间设定为25小时。
(2)将上述步骤(1)处理过的进锂氧化锌晶片放置于图2所示的高温高压退火炉中，进行晶格中锂的去除，得到高电阻率ZnO单晶片。
本实施例所用的锂去除装置，其可承受高温高压氧气气氛，按实验需求，氧压设为15标准大气压，温度设为900摄氏度，退火时间设为26小时。
2、上述制备得到的高电阻率ZnO单晶片的电阻率为1011Ωcm，比处理之前提高了1011。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受所述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种高电阻率单晶氧化锌的制备方法，其特征在于，包括如下步骤：
    S1.将单晶ZnO晶片置于金属锂电化学装置中，恒流放电处理；
    S2.将步骤S1处理过的ZnO单晶放于600～1000℃、5～30atm的氧气气氛中退火处理10～28小时，即可得到高电阻率ZnO单晶片。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤S1所述金属锂电化学装置内的电解液为0.5～1.5M LiPF6溶液分散于体积比为2～5：2～4：2～4的碳酸亚乙酯、碳酸甲乙酯和碳酸二乙酯混合溶液中，采用聚乙烯多微孔膜做为电子隔膜。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤S1所述金属锂电化学装置为锂电池壳。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤S1所述将单晶ZnO晶片置于金属锂电化学装置中的方法具体是按照如下顺序将单晶ZnO晶片装配到锂电池壳中：正级壳、单晶ZnO晶片、聚乙烯多微孔膜、金属锂片、闪电极、弹簧电极、负极壳。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤S1所述恒流放电处理是1～4uA恒流放电处理10～25小时。
  6. 根据权利要求5所述的制备方法，其特征在于，步骤S1所述恒流放电处理是3uA恒流放电处理15小时。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤S2是将步骤S1处理过的ZnO单晶放于800～900℃、15～25atm的氧气气氛炉中退火处理22～26小时。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤S2是将步骤S1处理过的ZnO单晶放于800℃、20atm的高压氧气气氛中退火处理24小时。
  9. 根据权利要求1～8任一所述方法制备得到的高电阻率单晶氧化锌。
  10. 权利要求9所述高电阻率单晶氧化锌在制备辐射探测器件或光电探测器件方面的应用。
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