WO2018099322A1 - 基于Bi基四元卤化物单晶的半导体辐射探测器及制备方法 - Google Patents

基于Bi基四元卤化物单晶的半导体辐射探测器及制备方法 Download PDF

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WO2018099322A1
WO2018099322A1 PCT/CN2017/112762 CN2017112762W WO2018099322A1 WO 2018099322 A1 WO2018099322 A1 WO 2018099322A1 CN 2017112762 W CN2017112762 W CN 2017112762W WO 2018099322 A1 WO2018099322 A1 WO 2018099322A1
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radiation detector
semiconductor radiation
contact layer
selective contact
crystal
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唐江
潘伟程
巫皓迪
罗家俊
牛广达
周英
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
    • H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
    • H10F30/29—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to radiation having very short wavelengths, e.g. X-rays, gamma-rays or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • H10F77/206—Electrodes for devices having potential barriers

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  • the invention belongs to the technical field of radiation imaging detectors prepared by using semiconductor materials, and more particularly to an imaging detector and a preparation method for preparing X-rays and Gama rays by using a Bi-based quaternary halide single crystal.
  • Radiographic technology is a medium that uses radioactive rays (such as X-rays and gamma rays) to obtain structural or functional information of the detected objects in the form of images, and provides various technologies for the industry to diagnose, detect and monitor the observed objects. Means, widely used in industries such as health care, public safety and high-end manufacturing.
  • the detector is an important part of the radiology imaging equipment. Detectors for detecting radioactive rays generally include gas detectors, scintillation detectors, semiconductor detectors, and the like, in which the semiconductor detector can obtain the best energy resolution.
  • the semiconductor detector directly absorbs radioactive rays, and generates electron-hole pairs by photoelectric action, Compton scattering, and electron pair generation. They move in an applied electric field to generate a basic electrical signal of the detector.
  • the light absorbing layer may use a plurality of semiconductor materials such as silicon (Si), amorphous selenium (a-Se), etc. according to different uses, but these materials have a need to increase the bias voltage, the process Complex, low sensitivity and other shortcomings. Therefore, it is very urgent and necessary to find a material having high sensitivity to radioactive rays as an absorption layer of a semiconductor radiation detector.
  • the invention provides a semiconductor radiation detector based on a Bi-based quaternary halide single crystal and a preparation method thereof, aiming at obtaining a high-performance, non-toxic and stable semiconductor radiation detector, which solves the complicated process and low sensitivity of the prior art. , environmental pollution and poor stability, and sensitive Indicators such as degree, work bias, stability, and environmental pollution cannot be balanced.
  • the present invention provides a semiconductor radiation detector based on a wholly inorganic double perovskite single crystal, comprising:
  • Bi-based quaternary halide single crystal as the light absorbing layer of the semiconductor radiation detector to absorb high energy rays to generate electron-hole pairs;
  • Two selective charge contact layers respectively attached to both sides of the light absorbing layer, thereby selectively extracting electron-hole pairs generated by collecting the light absorbing layer;
  • Two electrodes are respectively in direct contact with the two selective charge contact layers to serve as a positive electrode and a negative electrode of the semiconductor radiation detector (the positive electrode is in direct contact with the electron selective contact layer, and the negative electrode is in contact with the hole selective contact layer) .
  • the chemical composition of the Bi-based quaternary halide single crystal is Cs 2 AgBiX 6 and X is Cl or Br.
  • the two selected selective charge contact layers are an electron selective contact layer and a hole selective contact layer, respectively.
  • the electron selective contact layer comprises one or more of carbon sixty (C 60 ), fullerene derivative (PCBM), titanium dioxide (TiO 2 ) or zinc oxide (ZnO).
  • C 60 carbon sixty
  • PCBM fullerene derivative
  • TiO 2 titanium dioxide
  • ZnO zinc oxide
  • the hole selective contact layer comprises nickel oxide (NiO) or none.
  • the two electrodes of the electrode are gold.
  • step (2) on the top and bottom of the crystal An electron selective contact layer and a hole selective contact layer.
  • the invention proposes a Bi-based quaternary halide single crystal as the light absorbing layer of the conductor radiation detector, which has the following advantages:
  • the Bi-based quaternary halide single crystal material has a suitable forbidden band width, high mobility and carrier lifetime, and high stability, and is a novel material for the light absorbing layer of the semiconductor radiation detector. Compared with the traditional cadmium telluride, amorphous selenium, silicon radiation detectors with high sensitivity and low operating bias, Bi-based quaternary halide single crystals are guaranteed compared to the recently proposed methylamine lead bromine. The performance is both non-toxic and highly stable.
  • Figure 1 is a schematic cross-sectional view of a semiconductor radiation detector structure in accordance with the present invention.
  • Figure 2 is a theoretically calculated plot of absorption versus thickness for different materials of 30 KeV energy ray
  • Figure 3 is an explanatory diagram showing the function of a semiconductor radiation detector in accordance with the present invention.
  • Figure 4 is the measured value of ⁇ * ⁇
  • Figure 5 is a graph of the measured IT curve.
  • FIG. 1 is a cross-sectional view showing the structure of a semiconductor radiation detector
  • FIG. 2 is a theoretically calculated absorption coefficient curve of different materials for different energy high energy rays
  • FIG. 3 is in accordance with the present invention.
  • FIG. 3 is an explanatory diagram of the function of the semiconductor radiation detector according to the present invention
  • FIG. 4 is a measured value of ⁇ * ⁇ ( ⁇ is a carrier mobility, ⁇ is Carrier lifetime, the multiplication of the two, indicating that the addition of a small bias, the carrier can be derived, so that the detector has better sensitivity);
  • Figure 5 is the measured IT curve, by IT The graph shows the current change of the detector under high energy ray on and off conditions.
  • the semiconductor radiation detector of the present example includes a Bi-based quaternary halide single crystal as the light absorbing layer 3, and an electron selective contact layer 2 and a hole selective contact layer 4 on the upper and lower sides of the light absorbing layer, On the electron selective contact layer 2 and the hole selective contact layer 4, there are an electrode 1 and an electrode 5, respectively.
  • the electron selective contact layer 2 and the hole selective contact layer 4 may also be absent, and the two electrodes are directly contacted from the upper and lower sides of the Bi-based quaternary halide single crystal.
  • the electron selective contact layer 2 and the hole selective contact layer 4 are for suppressing dark current by utilizing a significant difference in charge transfer between electrons and holes of carriers in a semiconductor.
  • the positive bias is applied to the pressing electrode 1, and in order to suppress the injection of holes, for example, carbon sixty (C 60 ), fullerene derivative (PCBM), titanium oxide (TiO 2 ), zinc oxide (ZnO), or the like is used.
  • C 60 carbon sixty
  • PCBM fullerene derivative
  • TiO 2 titanium oxide
  • ZnO zinc oxide
  • a reverse bias is applied to the electrode 5, and in order to suppress electron injection, nickel oxide (NiO) is used as the hole selective contact layer.
  • the semiconductor radiation detector in this example applies a positive bias to the electrode 1, and the high energy radiation is incident from the electrode 1 through the electron selective contact layer 2 and is absorbed by the Bi-based quaternary halide single crystal light absorbing layer 3, and is in the Bi-based An electron-hole pair is generated in the elementary halogen single crystal light absorbing layer 3, and is respectively moved to the two electrodes to generate a current.
  • a Bi-based quaternary halide single crystal is used as a light absorbing layer of a semiconductor radiation detector, and its absorption coefficient is larger than that of silicon (Si), and cadmium telluride (CdTe), organic-inorganic perovskite (MAPbI3)
  • the material has the advantage of absorption as a light absorbing layer of the semiconductor radiation detector, that is, the efficiency of the Bi-based quaternary halide capable of absorbing high-energy ray is only slightly lower than that of cadmium telluride at the same thickness.
  • CdTe higher than organic inorganic perovskite
  • Si silicon
  • FIG. 5 an IT graph under irradiation of 35 keV of X-rays under a bias voltage of 0.1 V.
  • Figure 5 is a test example showing that the detector has a good light-dark current ratio and good detection performance.
  • This example will describe the preparation of a bismuth silver bismuth bromide (Cs 2 AgBiBr 6 ) crystal and the preparation of a semiconductor radiation detector from the crystal:
  • Silver bromide (AgBr, 0.188 g, 1 mmol), cesium bromide (BiBr 3 , 0.449 g, 1 mmol) and cesium bromide (CsBr, 0.426 g, 2 mmol) were added to 10 ml of hydrobromic acid (HBr) solution.
  • HBr hydrobromic acid
  • the solution was heated to 130 ° C to dissolve the solution sufficiently, and then cooled to 60 ° C at a rate of 1 ° C / h to precipitate crystals, thereby obtaining cerium lanthanum bromide (Cs 2 AgBiBr 6 ) crystals.
  • an 80 nm thick gold electrode was evaporated by thermal evaporation on the upper and lower sides of the crystal.
  • This example will describe the preparation of a bismuth silver bismuth (Cs 2 AgBiBr 6 ) crystal, and a charge selective contact layer on the crystal to prepare a semiconductor radiation detector:
  • Silver bromide (AgBr, 0.188 g, 1 mmol), cesium bromide (BiBr 3 , 0.449 g, 1 mmol) and cesium bromide (CsBr, 0.426 g, 2 mmol) were added to 10 ml of hydrobromic acid (HBr) solution.
  • HBr hydrobromic acid
  • the solution was heated to 130 ° C to dissolve the solution sufficiently, and then cooled to 60 ° C at a rate of 1 ° C / h to precipitate crystals, thereby obtaining cerium lanthanum bromide (Cs 2 AgBiBr 6 ) crystals.
  • Carbon sixty (C 60 ) is vaporized by thermal evaporation on the upper surface of the crystal.
  • an 80 nm thick gold electrode was evaporated by thermal evaporation on the upper and lower sides of the crystal.
  • Silver chloride (AgCl, 0.144 g, 1 mmol), ruthenium chloride (BiBr 3 , 0.317 g, 1 mmol) and cesium chloride (CsCl, 0.382 g, 2 mmol) were added to 10 ml of hydrochloric acid (HCl) solution to dissolve the solution.
  • HCl hydrochloric acid
  • the mixture was heated to 120 ° C to dissolve the solution sufficiently, and then cooled to 60 ° C at a rate of 0.5 ° C / h to precipitate crystals, thereby obtaining cerium silver chloride (Cs 2 AgBiCl 6 ) crystals.
  • an 80 nm thick gold electrode was evaporated by thermal evaporation on the upper and lower sides of the crystal.
  • the examples show that the semiconductor radiation detector prepared by the invention has the advantages of high sensitivity, stability, environmental friendliness and the like.

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  • Measurement Of Radiation (AREA)
  • Light Receiving Elements (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)

Abstract

本发明公开了一种基于Bi基四元卤化物单晶的半导体辐射探测器及其制备方法，涉及半导体材料制备的射线成像探测器技术领域。所述的半导体辐射探测器结构包括以Bi基四元卤化物单晶作为射线吸光层，电子选择性接触选择层，空穴选择性接触层，分别贴合在所述吸光层的两面，两个电极分别与两个选择性电荷接触层接触，作为器件的正极和负极。本发明的半导体辐射探测器具备高灵敏度，环境友好，稳定等优点。

Description

基于Bi基四元卤化物单晶的半导体辐射探测器及制备方法 [技术领域]
本发明属于以半导体材料制备的射线成像探测器技术领域，更具体地，涉及一种利用Bi基四元卤化物单晶制备X射线及Gama射线的成像探测器及制备方法。
[背景技术]
射线成像技术是放射性射线(如X射线和γ射线等)作为媒介，获得以图像形式展现的检测对象的结构或功能信息，为相应行业提供各种对所观察对象进行诊断、检测和监测的技术手段，广泛应用于医疗卫生、公共安全和高端制造业等行业。探测器是射线成像设备的重要组成部分。用于探测放射性射线的探测器一般有气体探测器、闪烁探测器、半导体探测器等类型，其中半导体探测器能得到最好的能量分辨率。
半导体探测器是直接吸收放射性射线，通过光电效应、康普顿散射、电子对产生三种作用方式产生电子-空穴对，它们在外加电场中运动产生探测器的基本电信号。对于这样一种半导体辐射探测器，其吸光层根据不同的用处可以使用多种半导体材料，如硅(Si),非晶硒(a-Se)等，但这些材料具有需要加大偏压，工艺复杂，灵敏度低等缺点。因此寻找一种对于放射性射线具有高灵敏度的材料作为半导体辐射探测器的吸收层是非常迫切和必要的。
[发明内容]
本发明提出一种基于Bi基四元卤化物单晶的半导体辐射探测器及制备方法，目的在于获得高性能、无毒、稳定的半导体辐射探测器，解决现有技术存在的工艺复杂、灵敏度低、环境污染和稳定性差等问题，以及灵敏 度、工作偏压、稳定性和环境污染等指标不能兼顾问题。
特别的，本发明提供了一种基于全无机双钙钛矿单晶的半导体辐射探测器，包括：
以Bi基四元卤化物单晶作为所述半导体辐射探测器的吸光层，以吸收高能射线，产生电子-空穴对；
两个选择性电荷接触层，分别贴合在所述吸光层的两面，从而选择性抽取收集所述吸光层产生的电子-空穴对；和
两个电极，分别与两个所述选择性电荷接触层直接接触，以作为所述半导体辐射探测器的正极和负极(正极与电子选择性接触层直接接触，负极接空穴选择性接触层)。
优选地，Bi基四元卤化物单晶化学组成为Cs2AgBiX6,X为Cl或Br。
优选地，两个所述的选择性电荷接触层分别为电子选择性接触层和空穴选择性接触层。
优选地，所述电子选择性接触层包括碳六十(C60)、富勒烯衍生物(PCBM)、二氧化钛(TiO2)或氧化锌(ZnO)中的一种，多种或无。
优选地，所述的空穴选择性接触层包括氧化镍(NiO)或无。
优选地，所述的电极两个电极为金。
按照本发明的另一方面，还提出所述的半导体辐射探测器的制作方法，包括如下步骤：
(1)按2:1:1的摩尔比称取CsX,AgX,BiX3,其中X为Cl或Br，加入到卤化氢溶液(HX，X＝Br，Cl)中，将溶液加热到130℃-110℃充分溶解后，以小于1℃/h的速度降温，当温度降低到70℃-50℃时，晶体析出,得到Bi基四元卤化物单晶晶体；
(2)将得到的晶体烘干；
(3)在晶体的上下面分别制备金电极。
优选地，在步骤(2)之后，步骤(4)之前，在晶体的上、下面制备 电子选择性接触层和空穴选择性接触层。
本发明提出以Bi基四元卤化物单晶作为导体辐射探测器的吸光层，具有如下优点：
Bi基四元卤化物单晶材料，具有合适的禁带宽度，高的迁移率和载流子寿命，稳定性高，是一种全新的半导体辐射探测器的吸光层材料。相较于传统的碲化镉、非晶硒、硅的辐射探测器具有高的灵敏度和低的工作偏压，相较于最近提出的甲胺铅溴，Bi基四元卤化物单晶在保证性能的同时无毒且具有高的稳定性。
[附图说明]
图1是依照本发明的半导体辐射探测器结构的横段面示意图；
图2是理论计算的不同材料对于30KeV能量射线的吸收与厚度关系的曲线；
图3是依照本发明的半导体辐射探测器功能的解释性示意图；
图4是测量得到的μ*τ值；
图5是测量得到的IT曲线图。
[具体实施方式]
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
下面通过实施例，对本发明作进一步的说明。
图1是显示一种半导体辐射探测器结构的横断面示意图；图2是理论计算的不同材料对于不同能量高能射线的吸收系数曲线；图3是依照本发 明的半导体辐射探测器功能的解释性示意图；图3是依照本发明的半导体辐射探测器功能的解释性示意图；图4是测量得到的μ*τ值(μ是载流子迁移率，τ是载流子寿命，两者相乘大，说明加较小的偏压，就能将载流子导出，从而使得探测器具有较好的灵敏度)；图5是测量得到的IT曲线图，由IT图可看到探测器在高能射线开和关的条件下的电流变化。
如图1所示，本实例中的半导体辐射探测器包括Bi基四元卤化物单晶作为吸光层3，在吸光层的上下侧有电子选择性接触层2和空穴选择性接触层4，在电子选择性接触层2和空穴选择性接触层4上分别有电极1和电极5。电子选择性接触层2和空穴选择性接触层4也可以无，由Bi基四元卤化物单晶上下两侧直接接触两个电极。
电子选择性接触层2和空穴选择性接触层4是为了利用半导体中对载流子的电子和空穴之间的电荷转移作用显著不同而抑制暗电流。其中正偏压施加在施压电极1上，为了抑制空穴的注入，使用如碳六十(C60)、富勒烯衍生物(PCBM)、二氧化钛(TiO2)、氧化锌(ZnO)等作为电子选择性接触层。反向偏压施加于电极5上，为了抑制电子的注入，使用氧化镍(NiO)作为空穴选择性接触层。
在本实例中的半导体辐射探测器向电极1施加正偏压，高能射线从电极1入射穿过电子选择性接触层2被Bi基四元卤化物单晶吸光层3吸收，并在Bi基四元卤化物单晶吸光层3中产生电子空穴对，分别向两个电极移动产生电流。
如图2所示，以Bi基四元卤化物单晶作为半导体辐射探测器的吸光层，其吸收系数比硅(Si)要大，和碲化镉(CdTe),有机无机钙钛矿(MAPbI3)相比差不多，因此该材料作为半导体辐射探测器的吸光层在吸收上具有一定的优势，即在相同厚度的情况下Bi基四元卤化物能够吸收高能射线的效率只略低于碲化镉(CdTe)，高于有机无机钙钛矿(MAPbI3)和硅(Si)。
如图3所示，当施加一个正偏压以便在高能射线入射一侧的电极(即 电压施加电极6)有一个比载流子电极1更高的电位时，由高能射线入射生成的电子移向X射线入射一侧，而空穴移向相反的一侧。在这个过程中产生的电子-空穴对能付达到对应的电极导出由载流子迁移率μ、载流子寿命τ和外加偏压E决定，当μ*τ的值比较大时，导出电子-空穴的外加偏压就会更小，以此材料作为半导体辐射探测器的吸光层，探测器灵敏度就会越高。目前所用的半导体辐射探测器的吸光层μ*τ＝10-5-10-8，所需工作偏压为Kv数量级,而我们提出的Bi基四元卤化物单晶(Cs2AgBiBr6)μ*τ＝10-2,(如图4所示)，只需要1V-10V的工作偏压就能导出载流子，具有高的灵敏度。图4示出在同一高能射线的照射下，改变偏压得到的光电流随电压变化的曲线，通过曲线拟合求得μ*τ＝10-2，远高于半导体辐射探测器吸光层的常用材料μ*τ＝10-5-10-8；表明本发明与其他材料相比，在μ*τ这一关键值相当规模上具有明显优势。
如图5所示，在偏压0.1V条件下，在35keV的X射线的照射下的IT曲线图。图中光电流上升时表示X射线打开，关闭表示X射线关闭。图5是一个测试实例，说明具有探测器具有较好的光暗电流比，探测性能好。
实施案例1：
本实例将介绍铯银铋溴(Cs2AgBiBr6)晶体的制备和以该晶体制备半导体辐射探测器：
取溴化银(AgBr,0.188g，1mmol),溴化铋(BiBr3,0.449g,1mmol)和溴化铯(CsBr,0.426g,2mmol)加入到10ml的氢溴酸(HBr)溶液中，将溶液加热到130℃，使得溶液充分溶解，之后再以1℃/h的速度降温到60℃，析出晶体，从而得到铯银铋溴(Cs2AgBiBr6)晶体。
再在该晶体的上下面用热蒸发蒸上80nm厚的金电极。
实施案例2：
本实例将介绍铯银铋溴(Cs2AgBiBr6)晶体的制备，并在该晶体上加电荷选择性接触层以制备半导体辐射探测器：
取溴化银(AgBr,0.188g，1mmol),溴化铋(BiBr3,0.449g,1mmol)和溴化铯(CsBr,0.426g,2mmol)加入到10ml的氢溴酸(HBr)溶液中，将溶液加热到130℃，使得溶液充分溶解，之后再以1℃/h的速度降温到60℃，析出晶体，从而得到铯银铋溴(Cs2AgBiBr6)晶体。
在晶体的上表面通过热蒸发蒸上碳六十(C60)。
再在该晶体的上下面用热蒸发蒸上80nm厚的金电极。
实施案例3：
本实例将介绍铯银铋氯(Cs2AgBiCl6)晶体的制备和以该晶体制备半导体辐射探测器：
取氯化银(AgCl,0.144g，1mmol),氯化铋(BiBr3,0.317g,1mmol)和氯化铯(CsCl,0.382g,2mmol)加入到10ml的盐酸(HCl)溶液中，将溶液加热到120℃，使得溶液充分溶解，之后再以0.5℃/h的速度降温到60℃，析出晶体，从而得到铯银铋氯(Cs2AgBiCl6)晶体。
再在该晶体的上下面用热蒸发蒸上80nm厚的金电极。
实施例可知，本发明所制备的半导体辐射探测器具有高灵敏度，稳定性，环境友好等优点。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，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、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种基于Bi基四元卤化物单晶的半导体辐射探测器，其特征在于，包括吸光层和两个电极；其中：
    所述吸光层是Bi基四元卤化物单晶晶体制成，用于吸收高能射线，产生电子-空穴对；
    所述两个电极，分别与吸光层直接接触，作为所述半导体辐射探测器的正极和负极。
  2. 根据权利要求1所述的半导体辐射探测器，其特征在于，所述吸光层与电极之间，设有选择性电荷接触层，便于电子、空穴的分离和导出。
  3. 根据权利要求1所述的半导体辐射探测器，其特征在于，所述Bi基四元卤化物为Cs2AgBiX6,其中X为Cl或Br。
  4. 根据权利要求2所述的半导体辐射探测器，其特征在于，所述两个电荷选择性接触层，分别为电子选择性接触层和空穴选择性接触层；所述电子选择性接触层用于导出吸光层产生的电子，空穴选择性接触层用于导出吸光层产生的空穴。
  5. 根据权利要求3或4所述的半导体辐射探测器，其特征在于，所述的电子选择性接触层包括碳六十(C60)、富勒烯衍生物(PCBM)、二氧化钛(TiO2)或氧化锌(ZnO)中的一种。
  6. 根据权利要求3或4所述的半导体辐射探测器，其特征在于，所述的空穴选择性接触层为氧化镍(NiO)。
  7. 根据权利要求1或2所述的半导体辐射探测器，其特征在于，所述的两个电极为金材料制备而成。
  8. 根据权利要求1或2所述的半导体辐射探测器，其特征在于，所述的高能射线包括X射线和Gama射线,能量大于20Kev。
  9. 一种权利要求1所述的半导体辐射探测器的制作方法，其特征在于， 包括如下步骤：
    (1)按2:1:1的摩尔比称取CsX,AgX,BiX3,其中X为Cl或Br，加入到卤化氢溶液(HX，X＝Br，Cl)中，将溶液加热到110℃-130℃充分溶解后，以小于1℃/h的速度降温，当温度降低到70℃-50℃时，晶体析出,得到Bi基四元卤化物单晶晶体；
    (2)将得到的晶体烘干；
    (3)在晶体的上下面分别制备金电极。
  10. 一种权利要求2所述的半导体辐射探测器的制作方法，其特征在于，包括如下步骤：
    (1)按2:1:1的摩尔比称取CsX,AgX,BiX3,其中X为Cl或Br，原料加入到卤化氢(HX，X＝Br，Cl)中，将溶液加热到110℃-130℃充分溶解后，以小于1℃/h的速度降温，当温度降低到70℃-50℃时，晶体析出,得到Bi基四元卤化物单晶晶体；
    (2)将得到的晶体烘干；
    (3)在晶体的上、下面制备电子选择性接触层和空穴选择性接触层；
    (4)在晶体的上、下面分别制作电极。
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