WO2023213030A1 - Quasi-two-dimensional perovskite single crystal, preparation method therefor, and x-ray detector - Google Patents

Quasi-two-dimensional perovskite single crystal, preparation method therefor, and x-ray detector Download PDF

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WO2023213030A1
WO2023213030A1 PCT/CN2022/114602 CN2022114602W WO2023213030A1 WO 2023213030 A1 WO2023213030 A1 WO 2023213030A1 CN 2022114602 W CN2022114602 W CN 2022114602W WO 2023213030 A1 WO2023213030 A1 WO 2023213030A1
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single crystal
quasi
perovskite single
dimensional perovskite
ray detector
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郑熠
王芳
吴少凡
黄鑫
王帅华
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闽都创新实验室
中国科学院福建物质结构研究所
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    • 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
    • C30B29/54—Organic compounds
    • 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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
    • 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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Definitions

  • the present application relates to a quasi-two-dimensional perovskite single crystal and a preparation method thereof and an X-ray detector, belonging to the technical field of X-ray detection.
  • Radiation detection materials are a class of materials that can convert high-energy photons into low-energy photons (X-ray imaging) or charges (X-ray detectors). They have become widely used in medical diagnostic technology, computerized tomography, quality inspection, and safety. key. Metal halide perovskite-type direct conversion detectors are promising candidates for such applications because they contain heavy atoms (such as Pb 2+ , BI 3+ , I ⁇ ) and have high X-ray absorption cross sections. Furthermore, these materials are solution processable at low temperatures, possess tunable band gaps, near-unity photoluminescence quantum yields, low trap densities, high carrier mobility, and fast photoresponses. However, traditional three-dimensional perovskites have limited their further commercial development due to problems such as poor stability.
  • this application introduces long-chain cations containing hydrophobic groups into three-dimensional perovskite to form a layered perovskite structure to improve its stability, and prepare a perovskite with both excellent performance and good stability. mineral crystals.
  • a quasi-two-dimensional perovskite single crystal is provided.
  • the general structural formula of the quasi-two-dimensional perovskite single crystal is (BDA)(MA) 2 Pb 3 Br 10 .
  • the crystal structure characteristics of the quasi-two-dimensional perovskite single crystal are: a bromine-lead octahedral corner-sharing three-layer film is sandwiched between large organic cations butanediamine, and the methylamine ions are restricted by the adjacent corners.
  • the inorganic perovskite three-layer film extends infinitely along the [001] plane.
  • the quasi-two-dimensional perovskite single crystal has a layered structure.
  • Another aspect of the present application provides a method for preparing the above-mentioned quasi-two-dimensional perovskite single crystal, including the following steps:
  • a precursor solution containing 1,4-butanediamine hydrobromide, methylamine hydrobromide, lead bromide, and a solvent is cooled and crystallized according to the cooling crystallization method to obtain the quasi-two-dimensional perovskite single crystal;
  • the molar ratio of 1,4-butanediamine hydrobromide, methylamine hydrobromide and lead bromide is 1:1-4:1-4.
  • the molar ratios of 1,4-butanediamine hydrobromide, methylamine hydrobromide and lead bromide are independently selected from 1:1:1, 1:4:1, and 1:1 :4, any value among 1:4:4 or any value between any two points above.
  • the concentration of lead bromide in the precursor solution is 0.32 mol/L to 0.54 mol/L.
  • the concentration of lead bromide is independently selected from any value among 0.32mol/L, 0.36mol/L, 0.40mol/L, 0.44mol/L, 0.48mol/L, 0.54mol/L or the above Any value between any two points.
  • the solvent is selected from at least one of hydrobromic acid, isopropyl alcohol, and N,N-dimethylformamide.
  • the temperature of the precursor solution is 70°C to 100°C;
  • the cooling rate is 0.5°C/h to 3°C/h.
  • the temperature of the precursor solution is independently selected from any value among 70°C, 80°C, 90°C, 100°C or any value between any two points mentioned above.
  • the cooling rate is independently selected from any value among 0.5°C/h, 1°C/h, 1.5°C/h, 2°C/h, 2.5°C/h, 3°C/h, or any two of the above. Any value between points.
  • the preparation method of the quasi-two-dimensional perovskite single crystal is as follows:
  • the molar ratio of BDADBr, MABr, and PbBr in the precursor described in step (a1) is 1:4:4;
  • the concentration of lead bromide in the precursor solution described in step (a1) is 0.32M
  • the slow cooling rate described in step (a2) is 1°C/h.
  • an X-ray detector which includes two metal electrode layers and a quasi-two-dimensional perovskite single crystal layer located between the two electrode layers;
  • the quasi-two-dimensional perovskite single crystal layer includes the above-mentioned quasi-two-dimensional perovskite single crystal or the quasi-two-dimensional perovskite single crystal obtained according to the above-mentioned preparation method.
  • the electrode material of the electrode layer is selected from one or more of gold, silver, and aluminum.
  • the sensitivity of the X-ray detector reaches 1661.15 ⁇ C Gy air s -1 cm -2 ;
  • the detection limit of the X-ray detector is 21.87n Gy air s -1 .
  • the preparation method of the X-ray detector is:
  • Electrode layers are plated on both surfaces of the quasi-two-dimensional perovskite single crystal layer.
  • the new (BDA)(MA) 2 Pb 3 Br 10 perovskite single crystal of the present invention has good crystal quality and high crystallinity.
  • the X-ray detector based on the perovskite has higher sensitivity and lower detection limit.
  • Figure 1 is a schematic structural diagram of the X-ray detector obtained in Embodiment 2 of the present application.
  • Figure 2 is the crystal structure of the layered (BDA)(MA) 2 Pb 3 Br 10 perovskite obtained in Example 1 of the present application;
  • Figure 3 is the XRD pattern of the layered (BDA)(MA) 2 Pb 3 Br 10 perovskite obtained in Example 1 of the present application;
  • Figure 4 is a diagram showing the relationship between photocurrent and voltage under X-ray detector radiation obtained in Embodiment 2 of the present application;
  • Figure 5 is a fitting curve diagram of the relationship between photocurrent and voltage under X-ray detector radiation obtained in Embodiment 2 of the present application;
  • Figure 6 is a diagram showing the relationship between dose rate and current density of the X-ray detector obtained in Embodiment 2 of the present application under bias voltages of 10V, 20V, 80V, 100V, 150V, and 200V;
  • Figure 7 is the signal-to-noise ratio curve of the X-ray detector under different bias voltages obtained in Embodiment 2 of the present application.
  • I is the device response current
  • I 0 is the saturation photocurrent
  • L is the device thickness
  • s is the surface recombination rate
  • V is the bias voltage
  • ⁇ is the carrier mobility
  • ⁇ is the carrier lifetime.
  • I signal is the effective device signal current
  • I noise is the effective device noise current
  • is the average device current under X-ray irradiation represents the average dark current
  • N is the number of parallel experiments under each bias.
  • SC-XRD Single crystal X-ray diffraction
  • the 1030Miniflex600 was used to conduct XRD detection on the obtained new quasi-two-dimensional perovskite single crystal (BDA) (MA) 2 Pb 3 Br 10.
  • BDA quasi-two-dimensional perovskite single crystal
  • MA multi-dimensional perovskite single crystal
  • the detection pattern is shown in Figure 3.
  • the measured XRD pattern of the perovskite single crystal grown in this application is consistent with
  • the simulation diagrams are in good agreement, with sharp diffraction peaks and high crystallinity.
  • FIG. 1 The schematic diagram of the obtained X-ray detector structure is shown in Figure 1, which includes a quasi-two-dimensional perovskite (BDA) (MA) 2 Pb 3 Br 10 single crystal layer and two metal electrode layers.
  • BDA quasi-two-dimensional perovskite
  • MA multi-dimensional perovskite
  • the obtained X-ray detector was tested using a Keithley 2450 high-voltage source meter. The test results are shown in Figures 4 to 7.
  • Figure 4 is a diagram showing the relationship between photocurrent and voltage under radiation of the X-ray detector prepared in Example 2. As shown in the figure, the device has a good response to X-rays.
  • Figure 5 is a fitting curve diagram of the relationship between photocurrent and voltage under the X-ray detector prepared in Example 2. Using the obtained photocurrent data without bias voltage and fitting it with the Hecht equation, the carrier mobility-carrier lifetime deposition ( ⁇ ) of the single crystal can be obtained, as shown in Figure 5, X-ray detector ⁇ can reach 1.65x10 -5 cm 2 V -1 .
  • Figure 6 is a diagram showing the relationship between dose rate and current density of the X-ray detector prepared in Example 2 under bias voltages of 10V, 20V, 80V, 100V, 150V, and 200V.
  • the sensitivity of the detector can be obtained by fitting the curve.
  • the sensitivity of the X-ray detector is 249.92 ⁇ C Gyair s -1 cm -2 under 10V bias, 441 ⁇ C Gyair s -1 cm -2 under 20V bias, and 1100.2 ⁇ C under 80V bias.
  • the sensitivity under 100V bias is 1221.74 ⁇ C Gyair s -1 cm -2
  • the sensitivity under 150V bias is 1465.8 ⁇ C Gyair s -1 cm -2
  • the sensitivity of the device changes with the applied bias
  • the sensitivity of the device reaches its maximum under 200V, and the sensitivity can reach 1661.15 ⁇ C Gyair s -1 cm -2 under 200V bias.
  • Figure 7 is a signal-to-noise ratio curve of the X-ray detector of Embodiment 2 under different bias voltages. According to the standards of the International Union of Pure and Applied Chemistry, resolvable signals should remain at an SNR value above 3. As shown in Figure 7, the lowest detectable dose of this X-ray detector is 21.87n Gyair s -1 .
  • Example 1 The difference from Example 1 lies in the preparation of the precursor in step (1): in a glove box environment, accurately weigh 0.1200g BDADBr, 0.2096g MABr, and 0.2000g PbBr 2 , and dissolve these raw materials in 6 mL, 48% In hydrobromic acid; in this example, colorless BDAPbBr 4 crystals were obtained, but (BDA)(MA) 2 Pb 3 Br 10 crystals were not obtained.
  • Example 1 The difference from Example 1 lies in the preparation of the precursor in step (1): in a glove box environment, accurately weigh 0.1200g BDADBr, 0.2096g MABr, and 1.2000g PbBr 2 , and dissolve these raw materials in 6 mL, 48% In hydrobromic acid; in this example, light yellow (BDA)(MA) 2 Pb 3 Br 10 crystals were obtained.
  • BDA light yellow
  • the concentration of lead bromide in the precursor solution will affect the growth of quasi-two-dimensional perovskite.

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Abstract

A quasi-two-dimensional perovskite single crystal, a preparation method therefor, and an X-ray detector. The structural general formula of the quasi-two-dimensional perovskite single crystal is (BDA)(MA)2Pb3Br10. The preparation method comprises the following steps: (1) preparing a perovskite precursor solution: dissolving 1,4-butanediamine hydrobromide, methylamine hydrobromide and lead bromide in hydrobromic acid to prepare a precursor solution; (2) stirring the solution at a high temperature until the solution is clarified, and then slowly cooling the solution to obtain a perovskite single crystal; and (3) coating the perovskite single crystal with a metal electrode. The perovskite single crystal has high crystallinity, and the X-ray detector based on the perovskite has high sensitivity and low detection limit.

Description

一种准二维钙钛矿单晶及其制备方法和一种X射线探测器A quasi-two-dimensional perovskite single crystal and its preparation method and an X-ray detector 技术领域Technical field
本申请涉及一种准二维钙钛矿单晶及其制备方法和一种X射线探测器，属于X射线探测技术领域。The present application relates to a quasi-two-dimensional perovskite single crystal and a preparation method thereof and an X-ray detector, belonging to the technical field of X-ray detection.
背景技术Background technique
辐射探测材料是一类能将高能光子转换成低能光子(X射线成像)或电荷(X射线探测器)的一类材料，已成为医疗诊断技术、计算机层析成像、质量检测和安全等广泛应用的关键。金属卤化物钙钛矿型直接转换探测器是此类应用的有前景的候选材料，因为它们含有重原子(如Pb 2+、BI 3+、I -)，具有高的X射线吸收截面。此外，这些材料在低温下是可溶液处理的，具有可调的带隙、接近单位的光致发光量子产率、低陷阱密度、高载流子迁移率和快速的光响应。然而传统的三维钙钛矿因其稳定性差等问题限制了其进一步的商业化发展。 Radiation detection materials are a class of materials that can convert high-energy photons into low-energy photons (X-ray imaging) or charges (X-ray detectors). They have become widely used in medical diagnostic technology, computerized tomography, quality inspection, and safety. key. Metal halide perovskite-type direct conversion detectors are promising candidates for such applications because they contain heavy atoms (such as Pb 2+ , BI 3+ , I − ) and have high X-ray absorption cross sections. Furthermore, these materials are solution processable at low temperatures, possess tunable band gaps, near-unity photoluminescence quantum yields, low trap densities, high carrier mobility, and fast photoresponses. However, traditional three-dimensional perovskites have limited their further commercial development due to problems such as poor stability.
发明内容Contents of the invention
为解决上述问题，本申请在三维钙钛矿中引入含疏水基团的长链阳离子形成层状钙钛矿结构来改善其稳定性，制备出既具有优异性能、又具有良好稳定性的钙钛矿晶体。In order to solve the above problems, this application introduces long-chain cations containing hydrophobic groups into three-dimensional perovskite to form a layered perovskite structure to improve its stability, and prepare a perovskite with both excellent performance and good stability. mineral crystals.
本申请的一个方面，提供了一种准二维钙钛矿单晶，所述准二维钙钛矿单晶的结构通式为(BDA)(MA) 2Pb 3Br 10。 In one aspect of the present application, a quasi-two-dimensional perovskite single crystal is provided. The general structural formula of the quasi-two-dimensional perovskite single crystal is (BDA)(MA) 2 Pb 3 Br 10 .
可选地，所述准二维钙钛矿单晶的晶体结构特征为：溴铅八面体共角三层膜夹在大的有机阳离子丁二胺之间，甲胺离子被限制在由邻角共用的溴铅八面体构成的空穴中，无机钙钛矿三层膜沿[001]面无限延伸。Optionally, the crystal structure characteristics of the quasi-two-dimensional perovskite single crystal are: a bromine-lead octahedral corner-sharing three-layer film is sandwiched between large organic cations butanediamine, and the methylamine ions are restricted by the adjacent corners. In the holes composed of shared bromine-lead octahedra, the inorganic perovskite three-layer film extends infinitely along the [001] plane.
可选地，所述准二维钙钛矿单晶具有层状结构。Optionally, the quasi-two-dimensional perovskite single crystal has a layered structure.
本申请的另一个方面，提供一种上述的准二维钙钛矿单晶的制备方法，包括以下步骤：Another aspect of the present application provides a method for preparing the above-mentioned quasi-two-dimensional perovskite single crystal, including the following steps:
含有1,4-丁二胺氢溴酸盐、甲胺氢溴酸盐、溴化铅、溶剂的前驱体溶液，按照降温结晶法降温析晶，获得所述准二维钙钛矿单晶；A precursor solution containing 1,4-butanediamine hydrobromide, methylamine hydrobromide, lead bromide, and a solvent is cooled and crystallized according to the cooling crystallization method to obtain the quasi-two-dimensional perovskite single crystal;
其中，所述前驱体溶液中，1,4-丁二胺氢溴酸盐、甲胺氢溴酸盐、溴化铅的摩尔比为1：1～4：1～4。Wherein, in the precursor solution, the molar ratio of 1,4-butanediamine hydrobromide, methylamine hydrobromide and lead bromide is 1:1-4:1-4.
可选地，所述1,4-丁二胺氢溴酸盐、甲胺氢溴酸盐、溴化铅的摩尔比独立的选自1：1：1、1：4：1、1：1：4、1：4：4中的任意值或上述任意两点间的任意值。Alternatively, the molar ratios of 1,4-butanediamine hydrobromide, methylamine hydrobromide and lead bromide are independently selected from 1:1:1, 1:4:1, and 1:1 :4, any value among 1:4:4 or any value between any two points above.
可选地，所述前驱体溶液中，溴化铅的浓度为0.32mol/L～0.54mol/L。Optionally, the concentration of lead bromide in the precursor solution is 0.32 mol/L to 0.54 mol/L.
可选地，所述溴化铅的浓度独立的选自0.32mol/L、0.36mol/L、0.40mol/L、0.44mol/L、0.48mol/L、0.54mol/L中的任意值或上述任意两点间的任意值。Alternatively, the concentration of lead bromide is independently selected from any value among 0.32mol/L, 0.36mol/L, 0.40mol/L, 0.44mol/L, 0.48mol/L, 0.54mol/L or the above Any value between any two points.
可选地，所述溶剂选自氢溴酸、异丙醇、N,N-二甲基甲酰胺中的至少一种。Optionally, the solvent is selected from at least one of hydrobromic acid, isopropyl alcohol, and N,N-dimethylformamide.
可选地，所述前驱体溶液的温度为70℃～100℃；Optionally, the temperature of the precursor solution is 70°C to 100°C;
所述降温的速率为0.5℃/h～3℃/h。The cooling rate is 0.5°C/h to 3°C/h.
可选地，所述前驱体溶液的温度独立的选自70℃、80℃、90℃、100℃中的任意值或上述任意两点间的任意值。Optionally, the temperature of the precursor solution is independently selected from any value among 70°C, 80°C, 90°C, 100°C or any value between any two points mentioned above.
可选地，所述降温的速率独立的选自0.5℃/h、1℃/h、1.5℃/h、2℃/h、2.5℃/h、3℃/h中的任意值或上述任意两点间的任意值。Optionally, the cooling rate is independently selected from any value among 0.5°C/h, 1°C/h, 1.5°C/h, 2°C/h, 2.5°C/h, 3°C/h, or any two of the above. Any value between points.
作为一种具体实施方法，所述准二维钙钛矿单晶的制备方法如下：As a specific implementation method, the preparation method of the quasi-two-dimensional perovskite single crystal is as follows:
(a1)制备钙钛矿前驱液：将1,4-丁二胺氢酸盐(BDADBr)、甲胺氢溴酸盐(MABr)、溴化铅(PbBr 2)溶于氢溴酸中制备前驱液； (a1) Preparation of perovskite precursor solution: Dissolve 1,4-butanediamine hydrobromide (BDADBr), methylamine hydrobromide (MABr), and lead bromide (PbBr 2 ) in hydrobromic acid to prepare the precursor liquid;
(a2)在70℃下搅拌前驱液至澄清后缓慢降温得(BDA)(MA) 2Pb 3Br 10单晶； (a2) Stir the precursor solution at 70°C until it becomes clear and then slowly cool down to obtain (BDA)(MA) 2 Pb 3 Br 10 single crystal;
步骤(a1)中所述的前驱体中的BDADBr、MABr、PbBr 2摩尔比为1：4：4； The molar ratio of BDADBr, MABr, and PbBr in the precursor described in step (a1) is 1:4:4;
步骤(a1)中所述的前驱液溴化铅的浓度为0.32M；The concentration of lead bromide in the precursor solution described in step (a1) is 0.32M;
步骤(a2)中所述的缓慢降温速率为1℃/h。The slow cooling rate described in step (a2) is 1°C/h.
本申请的再一个方面，提供一种X射线探测器，所述X射线探测器包括两个金属电极层和位于两个电极层中间的准二维钙钛矿单晶层；In yet another aspect of the present application, an X-ray detector is provided, which includes two metal electrode layers and a quasi-two-dimensional perovskite single crystal layer located between the two electrode layers;
其中所述准二维钙钛矿单晶层包括上述准二维钙钛矿单晶或根据上述的制备方法获得的准二维钙钛矿单晶。The quasi-two-dimensional perovskite single crystal layer includes the above-mentioned quasi-two-dimensional perovskite single crystal or the quasi-two-dimensional perovskite single crystal obtained according to the above-mentioned preparation method.
可选地，所述电极层的电极材质选自金、银、铝中的一种或多种。Optionally, the electrode material of the electrode layer is selected from one or more of gold, silver, and aluminum.
可选地，所述X射线探测器的灵敏度达到1661.15μC Gy air s -1cm -2； Optionally, the sensitivity of the X-ray detector reaches 1661.15μC Gy air s -1 cm -2 ;
所述X射线探测器的探测极限为21.87n Gy air s -1。 The detection limit of the X-ray detector is 21.87n Gy air s -1 .
所述X射线探测器的制备方法为：The preparation method of the X-ray detector is:
在所述准二维钙钛矿单晶层的两个表面镀上电极层。Electrode layers are plated on both surfaces of the quasi-two-dimensional perovskite single crystal layer.
本申请能产生的有益效果包括：The beneficial effects this application can produce include:
本发明的新型(BDA)(MA) 2Pb 3Br 10钙钛矿单晶有着良好的晶体品质，具有高的结晶度，基于该钙钛矿的X射线探测器有较高的灵敏度以及较低的探测极限。 The new (BDA)(MA) 2 Pb 3 Br 10 perovskite single crystal of the present invention has good crystal quality and high crystallinity. The X-ray detector based on the perovskite has higher sensitivity and lower detection limit.
附图说明Description of the drawings
图1为本申请实施例2获得的X射线探测器的结构示意图；Figure 1 is a schematic structural diagram of the X-ray detector obtained in Embodiment 2 of the present application;
图2为本申请实施例1获得的层状(BDA)(MA) 2Pb 3Br 10钙钛矿的晶体结构； Figure 2 is the crystal structure of the layered (BDA)(MA) 2 Pb 3 Br 10 perovskite obtained in Example 1 of the present application;
图3为本申请实施例1获得的层状(BDA)(MA) 2Pb 3Br 10钙钛矿的XRD图谱； Figure 3 is the XRD pattern of the layered (BDA)(MA) 2 Pb 3 Br 10 perovskite obtained in Example 1 of the present application;
图4为本申请实施例2获得的X射线探测器射线下光电流与电压的关系图；Figure 4 is a diagram showing the relationship between photocurrent and voltage under X-ray detector radiation obtained in Embodiment 2 of the present application;
图5为本申请实施例2获得的X射线探测器射线下光电流与电压的关系拟合曲线图；Figure 5 is a fitting curve diagram of the relationship between photocurrent and voltage under X-ray detector radiation obtained in Embodiment 2 of the present application;
图6为本申请实施例2获得的X射线探测器在10V、20V、80V、100V、150V、200V偏压下剂量率与电流密度关系图；Figure 6 is a diagram showing the relationship between dose rate and current density of the X-ray detector obtained in Embodiment 2 of the present application under bias voltages of 10V, 20V, 80V, 100V, 150V, and 200V;
图7为本申请实施例2获得的X射线探测器在不同偏压下的信噪比曲线。Figure 7 is the signal-to-noise ratio curve of the X-ray detector under different bias voltages obtained in Embodiment 2 of the present application.
具体实施方式Detailed ways
下面结合实施例详述本申请，但本申请并不局限于这些实施例。The present application will be described in detail below with reference to examples, but the present application is not limited to these examples.
如无特别说明，本申请的实施例中的原料均通过商业途径购买。Unless otherwise specified, the raw materials in the examples of this application were all purchased through commercial channels.
本申请的实施例中，涉及的计算公式如下：In the embodiment of this application, the calculation formula involved is as follows:
(1)Hecht方程：(1)Hecht equation:
Figure PCTCN2022114602-appb-000001
Figure PCTCN2022114602-appb-000001
其中，I是器件响应电流，I 0是饱和光电流，L是器件厚度，s是表面复合速率，V是偏压，μ是载流子迁移率，τ是载流子寿命。 Among them, I is the device response current, I 0 is the saturation photocurrent, L is the device thickness, s is the surface recombination rate, V is the bias voltage, μ is the carrier mobility, and τ is the carrier lifetime.
(2)SNR值是用下列公式计算(2)The SNR value is calculated using the following formula
Figure PCTCN2022114602-appb-000002
Figure PCTCN2022114602-appb-000002
Figure PCTCN2022114602-appb-000003
Figure PCTCN2022114602-appb-000003
Figure PCTCN2022114602-appb-000004
Figure PCTCN2022114602-appb-000004
其中，I signal是有效器件信号电流，I noise是有效器件噪声电流，
Figure PCTCN2022114602-appb-000005
是X射线照射下的平均器件电流，
Figure PCTCN2022114602-appb-000006
表示平均暗电流，N是在每个偏置下的平行实验次数。 Among them, I signal is the effective device signal current, I noise is the effective device noise current,
Figure PCTCN2022114602-appb-000005
is the average device current under X-ray irradiation,
Figure PCTCN2022114602-appb-000006
represents the average dark current, and N is the number of parallel experiments under each bias.
实施例1Example 1
一种准二维钙钛矿单晶的制备方法，具体步骤如下：A method for preparing quasi-two-dimensional perovskite single crystal. The specific steps are as follows:
(1)钙钛矿前驱液的制备：在手套箱中环境中，准确称取0.12g BDADBr、0.2096g MABr、0.7046g PbBr 2，这些原料共同溶于6mL、48％氢溴酸中； (1) Preparation of perovskite precursor solution: In a glove box environment, accurately weigh 0.12g BDADBr, 0.2096g MABr, and 0.7046g PbBr 2 , and dissolve these raw materials in 6 mL, 48% hydrobromic acid;
(2)新型准二维钙钛矿单晶的制备：将步骤(1)的前驱液在70℃下搅拌2h，将前驱液迅速转移至烘箱中，以1℃/h的速率降至 室温；获得新型准二维钙钛矿单晶(BDA)(MA) 2Pb 3Br 10。 (2) Preparation of new quasi-two-dimensional perovskite single crystal: Stir the precursor solution in step (1) at 70°C for 2 hours, quickly transfer the precursor solution to an oven, and lower to room temperature at a rate of 1°C/h; A new type of quasi-two-dimensional perovskite single crystal (BDA)(MA) 2 Pb 3 Br 10 was obtained.
单晶X射线衍射(SC-XRD)数据是在Super Nova衍射仪上使用Co Ka辐射在100K获得的。使用olex软件，通过直接方法求解晶体结构。所得晶体结构如图2所示。Single crystal X-ray diffraction (SC-XRD) data were obtained on a Super Nova diffractometer using Co Ka radiation at 100 K. Solve the crystal structure by direct method using Olex software. The resulting crystal structure is shown in Figure 2.
采用1030Miniflex600对获得的新型准二维钙钛矿单晶(BDA)(MA) 2Pb 3Br 10进行XRD检测，检测图谱如图3所示，本申请生长的钙钛矿单晶实测XRD图与模拟图吻合良好，衍射峰尖锐，晶体结晶度高。 The 1030Miniflex600 was used to conduct XRD detection on the obtained new quasi-two-dimensional perovskite single crystal (BDA) (MA) 2 Pb 3 Br 10. The detection pattern is shown in Figure 3. The measured XRD pattern of the perovskite single crystal grown in this application is consistent with The simulation diagrams are in good agreement, with sharp diffraction peaks and high crystallinity.
实施例2Example 2
一种X射线探测器的制备方法，具体步骤如下：A method for preparing an X-ray detector. The specific steps are as follows:
(1)取出实施例1所获得的新型准二维钙钛矿单晶(BDA)(MA) 2Pb 3Br 10，放在真空干燥箱中干燥12h； (1) Take out the new quasi-two-dimensional perovskite single crystal (BDA)(MA) 2 Pb 3 Br 10 obtained in Example 1, and place it in a vacuum drying oven to dry for 12 hours;
(2)在单晶两侧镀上银电极，得到X射线探测器。(2) Coat silver electrodes on both sides of the single crystal to obtain an X-ray detector.
获得的X射线探测器结构示意图见图1，包括了准二维钙钛矿(BDA)(MA) 2Pb 3Br 10单晶层、两层金属电极层。 The schematic diagram of the obtained X-ray detector structure is shown in Figure 1, which includes a quasi-two-dimensional perovskite (BDA) (MA) 2 Pb 3 Br 10 single crystal layer and two metal electrode layers.
使用吉时利2450高压源表对获得的X射线探测器进行了测试，测试结果见图4～图7。The obtained X-ray detector was tested using a Keithley 2450 high-voltage source meter. The test results are shown in Figures 4 to 7.
图4为实施例2制备的X射线探测器射线下光电流与电压的关系图，如图所示，器件对X射线有着较好的响应。Figure 4 is a diagram showing the relationship between photocurrent and voltage under radiation of the X-ray detector prepared in Example 2. As shown in the figure, the device has a good response to X-rays.
图5为实施例2制备的X射线探测器射线下光电流与电压的关系拟合曲线图。利用得到的不用偏压下的光电流数据，用Hecht方程进行拟合，则可以得到单晶的载流子迁移率-载流子寿命沉积(μτ)，如图5所示，X射线探测器μτ可以达1.65x10 -5cm 2V -1。 Figure 5 is a fitting curve diagram of the relationship between photocurrent and voltage under the X-ray detector prepared in Example 2. Using the obtained photocurrent data without bias voltage and fitting it with the Hecht equation, the carrier mobility-carrier lifetime deposition (μτ) of the single crystal can be obtained, as shown in Figure 5, X-ray detector μτ can reach 1.65x10 -5 cm 2 V -1 .
图6为实施例2制备的X射线探测器在10V、20V、80V、100V、150V、200V偏压下剂量率与电流密度关系图，拟合曲线可得探测器的灵敏度。如图6所示，X射线探测器在10V偏压下灵敏度为249.92μC Gyair s -1cm -2，20V偏压下灵敏度为441μC Gyair s -1cm -2，80V偏压下灵敏度为1100.2μC Gyair s -1cm -2，100V偏压下灵敏度为1221.74μC Gyair s -1cm -2，150V偏压下灵敏度为1465.8μC Gyair s -1cm -2，可以看 到器件的灵敏度随施加偏压的增大而增大，在200V下器件的灵敏度达到最大，200V偏压下灵敏度可达到1661.15μC Gyair s -1cm -2。 Figure 6 is a diagram showing the relationship between dose rate and current density of the X-ray detector prepared in Example 2 under bias voltages of 10V, 20V, 80V, 100V, 150V, and 200V. The sensitivity of the detector can be obtained by fitting the curve. As shown in Figure 6, the sensitivity of the X-ray detector is 249.92μC Gyair s -1 cm -2 under 10V bias, 441μC Gyair s -1 cm -2 under 20V bias, and 1100.2μC under 80V bias. Gyair s -1 cm -2 , the sensitivity under 100V bias is 1221.74μC Gyair s -1 cm -2 , the sensitivity under 150V bias is 1465.8μC Gyair s -1 cm -2 , it can be seen that the sensitivity of the device changes with the applied bias The sensitivity of the device reaches its maximum under 200V, and the sensitivity can reach 1661.15μC Gyair s -1 cm -2 under 200V bias.
图7是实施例2的X射线探测器在不同偏压下的信噪比曲线。根据国际纯化学和应用化学联合会的标准，可分辨的信号应保持在3以上的SNR值。如图7所示，该X射线探测器的最低可探测剂量为21.87n Gyair s -1。 Figure 7 is a signal-to-noise ratio curve of the X-ray detector of Embodiment 2 under different bias voltages. According to the standards of the International Union of Pure and Applied Chemistry, resolvable signals should remain at an SNR value above 3. As shown in Figure 7, the lowest detectable dose of this X-ray detector is 21.87n Gyair s -1 .
对比例1Comparative example 1
与实施例1的区别在于步骤(1)中，前驱体的制备：在手套箱中环境中，准确称取0.1200g BDADBr、0.2096g MABr、0.2000g PbBr 2，这些原料共同溶于6mL、48％氢溴酸中；该实施例得到无色BDAPbBr 4晶体，未得到(BDA)(MA) 2Pb 3Br 10晶体。 The difference from Example 1 lies in the preparation of the precursor in step (1): in a glove box environment, accurately weigh 0.1200g BDADBr, 0.2096g MABr, and 0.2000g PbBr 2 , and dissolve these raw materials in 6 mL, 48% In hydrobromic acid; in this example, colorless BDAPbBr 4 crystals were obtained, but (BDA)(MA) 2 Pb 3 Br 10 crystals were not obtained.
对比例2Comparative example 2
与实施例1的区别在于步骤(1)中，前驱体的制备：在手套箱中环境中，准确称取0.1200g BDADBr、0.2096g MABr、1.2000g PbBr 2，这些原料共同溶于6mL、48％氢溴酸中；该实施例得到淡黄色(BDA)(MA) 2Pb 3Br 10晶体。前驱液中溴化铅浓度将影响准二维钙钛矿的生长。 The difference from Example 1 lies in the preparation of the precursor in step (1): in a glove box environment, accurately weigh 0.1200g BDADBr, 0.2096g MABr, and 1.2000g PbBr 2 , and dissolve these raw materials in 6 mL, 48% In hydrobromic acid; in this example, light yellow (BDA)(MA) 2 Pb 3 Br 10 crystals were obtained. The concentration of lead bromide in the precursor solution will affect the growth of quasi-two-dimensional perovskite.
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above are only a few embodiments of the present application, and are not intended to limit the present application in any way. Although the present application is disclosed as above with preferred embodiments, they are not intended to limit the present application. Any skilled person familiar with this field, Without departing from the scope of the technical solution of this application, slight changes or modifications made using the technical content disclosed above are equivalent to equivalent implementation examples and fall within the scope of the technical solution.

Claims (11)

  1. 一种准二维钙钛矿单晶，其特征在于，所述准二维钙钛矿单晶的结构通式为(BDA)(MA) 2Pb 3Br 10。 A quasi-two-dimensional perovskite single crystal, characterized in that the general structural formula of the quasi-two-dimensional perovskite single crystal is (BDA)(MA) 2 Pb 3 Br 10 .
  2. 根据权利要求1所述的准二维钙钛矿单晶，其特征在于，所述准二维钙钛矿单晶的晶体结构特征为：溴铅八面体共角三层膜夹在大的有机阳离子丁二胺之间，甲胺离子被限制在由邻角共用的溴铅八面体构成的空穴中，无机钙钛矿三层膜沿[001]面无限延伸。The quasi-two-dimensional perovskite single crystal according to claim 1, characterized in that the crystal structure of the quasi-two-dimensional perovskite single crystal is: bromine-lead octahedral three-layer films sandwiched between large organic Between the cationic butanediamine, the methylamine ions are confined in holes composed of bromine-lead octahedrons sharing adjacent corners, and the inorganic perovskite three-layer film extends infinitely along the [001] plane.
  3. 根据权利要求1所述的准二维钙钛矿单晶，其特征在于，所述准二维钙钛矿单晶具有层状结构。The quasi-two-dimensional perovskite single crystal according to claim 1, wherein the quasi-two-dimensional perovskite single crystal has a layered structure.
  4. 一种权利要求1～3任一项所述的准二维钙钛矿单晶的制备方法，其特征在于，包括以下步骤：A method for preparing a quasi-two-dimensional perovskite single crystal according to any one of claims 1 to 3, characterized by comprising the following steps:
    含有1,4-丁二胺氢溴酸盐、甲胺氢溴酸盐、溴化铅、溶剂的前驱体溶液，降温析晶，获得所述准二维钙钛矿单晶；A precursor solution containing 1,4-butanediamine hydrobromide, methylamine hydrobromide, lead bromide, and a solvent is cooled and crystallized to obtain the quasi-two-dimensional perovskite single crystal;
    其中，所述前驱体溶液中，溴化铅的浓度为0.32mol/L～0.54mol/L。Wherein, the concentration of lead bromide in the precursor solution is 0.32 mol/L to 0.54 mol/L.
  5. 根据权利要求4所述的制备方法，其特征在于，所述前驱体溶液中，1,4-丁二胺氢溴酸盐、甲胺氢溴酸盐、溴化铅的摩尔比为1：1～4：1～4。The preparation method according to claim 4, characterized in that in the precursor solution, the molar ratio of 1,4-butanediamine hydrobromide, methylamine hydrobromide and lead bromide is 1:1 ~4:1~4.
  6. 根据权利要求4所述的制备方法，其特征在于，所述溶剂选自氢溴酸、异丙醇、N,N-二甲基甲酰胺中的至少一种。The preparation method according to claim 4, characterized in that the solvent is selected from at least one of hydrobromic acid, isopropyl alcohol, and N,N-dimethylformamide.
  7. 根据权利要求4所述的制备方法，其特征在于，所述前驱体溶液的温度为70℃～100℃。The preparation method according to claim 4, characterized in that the temperature of the precursor solution is 70°C to 100°C.
  8. 根据权利要求4所述的制备方法，其特征在于，所述降温的速率为0.5℃/h～3℃/h。The preparation method according to claim 4, characterized in that the cooling rate is 0.5°C/h˜3°C/h.
  9. 一种X射线探测器，其特征在于，所述X射线探测器包括两个金属电极层和位于两个电极层中间的准二维钙钛矿单晶层；An X-ray detector, characterized in that the X-ray detector includes two metal electrode layers and a quasi-two-dimensional perovskite single crystal layer located between the two electrode layers;
    其中所述准二维钙钛矿单晶层包括权利要求1～3任一项所述准二维钙钛矿单晶或根据权利要求4～8任一项所述的制备方法获得的准二维钙钛矿单晶。Wherein the quasi-two-dimensional perovskite single crystal layer includes the quasi-two-dimensional perovskite single crystal according to any one of claims 1 to 3 or the quasi-two-dimensional perovskite single crystal obtained according to the preparation method according to any one of claims 4 to 8. dimensional perovskite single crystal.
  10. 根据权利要求9所述的X射线探测器，其特征在于，所述电极层的电极材质选自金、银、铝中的一种或多种。The X-ray detector according to claim 9, wherein the electrode material of the electrode layer is selected from one or more of gold, silver, and aluminum.
  11. 根据权利要求9所述的X射线探测器，其特征在于，所述X射线探测器的灵敏度≤1662μC Gy airs -1cm -2；所述X射线探测器的探测极限≥22n Gy airs -1。 The X-ray detector according to claim 9, characterized in that the sensitivity of the X-ray detector is ≤1662 μC Gy air s -1 cm -2 ; the detection limit of the X-ray detector is ≥22n Gy air s - 1 .
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