A-site chiral organic molecule selective regulation perovskite single crystal, flexible detector and preparation method

Abstract

The invention discloses a perovskite single crystal capable of selectively regulating and controlling A-site chiral organic molecules, a flexible detector and a preparation method, and belongs to the technical field of X-ray detection. The method comprises the following steps: after preparing a 0D polar bismuth iodide perovskite single crystal, preparing a perovskite solution from single crystal powder and an organic solvent, filling a flexible high-molecular porous polymer nylon membrane with the perovskite solution, and heating and annealing to slowly crystallize perovskite selectively regulated and controlled by A-site chiral organic molecules in the porous polymer nylon membrane, so as to obtain the porous polymer nylon membrane. The annealed and crystallized perovskite selectively regulated and controlled by the A-site chiral organic molecules is tightly combined with the flexible thick film through heating and pressurizing, the X-ray detector is prepared based on the perovskite flexible thick film selectively regulated and controlled by the A-site chiral organic molecules, and a new thought is provided for application of next-generation wearable electronic equipment. And a new way is opened up for promoting future development of a green, stable, flexible and chiral detector.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of X-ray detection, and particularly relates to a perovskite single crystal with A-site chiral organic molecule selective regulation and a flexible detector and a preparation method. BACKGROUND

[0002] X-ray radiation, also known as Rontgen rays, is a specific electromagnetic radiation with strong penetration to most materials. Due to the strong penetration, X-ray detectors play an indispensable role in medical diagnosis, industrial non-destructive testing and national security. Metal halide perovskite is considered as a new generation of semiconductor material suitable for X-ray detectors due to its excellent optoelectronic properties such as adjustable band gap, high absorption coefficient, high carrier mobility and low cost. Metal halide perovskite X-ray detectors have the advantages of high sensitivity and low detection limit, which help to improve the spatial resolution of imaging.

[0003] Metal halide perovskite has a large carrier diffusion length and solution processability, and its sensitivity is several orders of magnitude higher than that of α-Se, and the detection limit (LoD) is much lower than the medical imaging standard (1.5 nGy air s -1 ~ 5.5 μGy air s -1). This indicates that perovskite is a candidate material for high-performance and low-cost X-ray detectors, and has great prospects. However, perovskite X-ray detectors have high dark current and serious baseline drift, which is a bottleneck for its commercialization. High dark current increases shot noise and saturates the storage capacitor of thin-film transistor (TFT) or complementary metal-oxide-semiconductor (CMOS) pixels, ultimately reducing the signal-to-noise ratio and affecting the dynamic response range. In the long run, baseline drift poses a challenge to reliable signal recording. A key factor leading to high dark current and baseline drift is the high electric field applied to the perovskite X-ray detector. Although the high electric field is used to facilitate the extraction of X-ray generated carriers from thick perovskite, it simultaneously induces carrier injection of the electrode and leads to serious ion migration. In order to solve this problem, self-driven perovskite X-ray detectors are introduced. At the same time, the growth of single crystals with a size sufficient for device integration is very time-consuming, and the brittleness of single crystals makes device integration and manufacturing difficult, which also hinders the use of perovskite as an X-ray detector in commercial applications. The emergence of flexible perovskite X-ray detectors overcomes these shortcomings. The toxicity of lead and the chemical instability of lead-based perovskite are still major drawbacks in the preparation of flexible wearable detectors and commercialization. Further, flexible lead-free perovskite X-ray detectors have been developed, however, due to their high intrinsic resistivity, low charge extraction and inter-grain transport capability, large exciton binding energy and electron trap intolerance, the charge extraction and transport capability in flexible polycrystalline thin films are insufficient. This limits its implementation as an X-ray detector to achieve flexible wearable detectors and commercialization applications. SUMMARY

[0004] The present application aims to overcome the above-mentioned shortcomings of the prior art, and provides an A-site chiral organic molecule selectively regulated perovskite single crystal and flexible detector and preparation method, to solve the high toxicity, low performance, no chiral optical properties, high dark current and serious baseline drift of the existing flexible perovskite X-ray detector, and realize the preparation of a "green", high-sensitivity, low-detection-limit and self-powered large-area flexible A-site chiral organic molecule selectively regulated perovskite detector.

[0005] To achieve the above-mentioned purpose, the following technical solutions are adopted in the present application: An A-site chiral organic molecule selectively regulated perovskite single crystal is a chiral or racemic bismuth calcium iodide perovskite single crystal, and the structural formula is A4Bi2I 10 , the A-site chiral organic molecule selectively regulated perovskite single crystal; the A is Y-XPEA, wherein Y is R , S or Rac , X is fluorine, chlorine or bromine, and PEA is phenethylamine; the Rac is R and Sracemic mixture of equimolar amount; when Y is R or S A4Bi2I 10 is a chiral bismuth iodide perovskite single crystal, when Y is Rac A4Bi2I 10 is a racemic bismuth iodide perovskite single crystal; said chiral or racemic bismuth iodide perovskite single crystal is a zero-dimensional perovskite structure, comprising A-site chiral cations and [Bi2I 10 ] 4 anions, said A-site chiral cations are ( S -F / Cl / BrPEA) + , ( R- F / Cl / BrPEA) + or ( Rac- F / Cl / BrPEA) + , wherein / represents or;said [Bi2I 10 ] 4 anion dimer is formed by two edge-shared [BiI6] 2 octahedra.

[0006] Further improvements of the present application are: Preferably, the structural formula of said chiral or racemic bismuth iodide perovskite single crystal is ( S -FPEA)4Bi2I 10 , ( Rac -FPEA)4Bi2I 10 , ( Rac -ClPEA)4Bi2I 10 or ( Rac -BrPEA)4Bi2I 10 .

[0007] A preparation method of the above-mentioned A-site chiral organic molecule selectively regulated perovskite single crystal, comprising the following steps: respectively dissolving Y-1-(4-X phenyl) ethylamine and bismuth oxide in a mixed solvent of hydriodic acid and hypophosphorous acid according to the molar ratio, continuously stirring after heating, and obtaining chiral or racemic bismuth iodide perovskite single crystal after temperature control and cooling, which is an A-site chiral organic molecule selectively regulated perovskite single crystal.

[0008] Preferably, in the mixed solvent, the cooling speed of said temperature control and cooling is 0.25 ℃ / h ~ 0.3 ℃ / h.

[0009] A preparation method of a flexible detector, comprising the following steps: S1, after grinding the perovskite single crystal selectively regulated by chiral organic molecules at the A site as described in claim 1 or 2 into powder, dissolve it in an organic solvent to obtain a perovskite solution selectively regulated by chiral organic molecules at the A site. S2, fill the flexible polymer porous nylon membrane with a perovskite solution selectively regulated by chiral organic molecules at site A to obtain a flexible polymer porous nylon membrane filled with perovskite solution. S3, after heating and annealing a flexible porous polymer nylon film filled with perovskite solution, a polycrystalline thin film filled with chiral or racemic bismuth iodide perovskite is obtained. S4, the chiral or racemic bismuth iodide perovskite polycrystalline thin film is hot-pressed to obtain a chiral or racemic bismuth iodide perovskite flexible thin film. S5. Prepare a metal electrode on the chiral or racemic bismuth iodide perovskite flexible thin film to obtain a flexible chiral or racemic bismuth iodide perovskite X-ray detector.

[0010] Preferably, in S1, the concentration of the perovskite solution selectively regulated by the chiral organic molecule at the A site is 0.8 mol / L to 1.5 mol / L.

[0011] Preferably, in S2, the organic solvent is a mixed solution of DMF and DMSO.

[0012] Preferably, in step S3, the annealing temperature is 90 ℃~110 ℃, and the annealing time is 2 h~3 h.

[0013] Preferably, in S4, the hot pressing temperature is 100 ℃~150 ℃, the hot pressing pressure is 8 MPa~12 MPa, and the hot pressing time is 2 h~4 h.

[0014] A flexible detector prepared by any one of the above methods uses a flexible porous polymer nylon membrane as a framework, which is filled with chiral or racemic bismuth iodide perovskite with the structural formula A4Bi2I. 10 .

[0015] Compared with the prior art, the present invention has the following beneficial effects: This invention discloses a perovskite single crystal selectively regulated by organic molecules at the A-site, wherein the single crystal is a chiral 0D polar bismuth iodide perovskite single crystal ( S -FPEA)4Bi2I 10 Or racemic 0D polar bismuth iodide perovskite single crystal, ( Rac -F / Cl / BrPEA)4Bi2I 10 All in P21 in chiral space group, such crystals have zero-dimensional (0D) perovskite structure, which is composed of two ionic species: (1) organic cations (A) and (2) [Bi2I S- FPEA + or (1) Rac -F / Cl / BrPEA + Cations and [Bi2I 10 ] 4 Anions. [Bi2I 10 ] 4 Anion dimers are formed by two edge-shared [BiI6] 2 octahedra.

[0016] The application also discloses a preparation method of perovskite single crystals with A-site chiral organic molecules being selectively regulated. R / S / Rac -F / Cl / BrPEA, and Bi2O3 are dissolved in a mixed solvent of hydriodic acid and hypophosphorous acid in a certain proportion, a series of halogen-substituted 0D polar bismuth iodide perovskite single crystals A4Bi2I 10 , i.e. R / S / Rac -F / Cl / BrPEA)4Bi2I 10 , are grown by a cooling crystallization method with the temperature being strictly controlled and the cooling speed being 0.25 ℃ / h-0.3 ℃ / h, realizing the transfer of chirality from organic amine to inorganic perovskite framework, and the experimental method is simple and operable.

[0017] The application further discloses a preparation method of the flexible detector, in the preparation process, the grown crystal is washed, dried, grinded into powder, prepared into a perovskite solution with an organic solvent, filled into a flexible high polymer porous polymer nylon thick film through a simple soaking method, in the whole process, the experimental equipment used is simple and easy to operate.

[0018] The application further discloses a flexible detector, which is prepared by filling chiral or racemic bismuth iodide perovskite into a flexible high polymer porous polymer nylon film as a skeleton. 10Since current research mainly focuses on single chiral molecule systems and lacks systematic structural regulation strategies to understand the intrinsic relationship between chiral optical activity and device performance, this invention proposes an A-site chiral molecule selective regulation strategy. By adjusting the electronegativity difference (F / Cl / Br) of halogen substituents on the benzene ring, the lattice distortion and chiral optical activity of lead-free chiral perovskites are systematically regulated to reveal the synergistic enhancement of chirality and transport. By adjusting the electronegativity difference (F / Cl / Br) of halogen substituents on the benzene ring, the lattice distortion and chiral optical activity of chiral perovskites are systematically regulated, thereby improving detector performance. The flexible X-ray detector of this invention uses two materials: firstly, a chiral or racemic, lead-free, low-toxicity bismuth-based perovskite with chiral optical properties, polarity, and self-powering potential, while also possessing excellent environmentally friendly properties; and secondly, a flexible substrate polymer nylon film. Nylon membrane is a flexible polymer membrane with a porous structure, suitable for supporting lead-free perovskite. The large-scale nylon fibers with a diameter of 10µm provide excellent mechanical flexibility. This polymer also exhibits high temperature resistance, high pressure resistance, and radiation resistance. In the composite membrane, the perovskite and nylon are tightly bonded, resulting in good flexibility and overcoming the drawback of lead-free perovskite peeling off from the flexible substrate due to bending during practical use. It also exhibits good crystallinity, a smooth surface, high quality, good stability, and its size can be controlled according to the substrate size. It is easy to deposit electrodes on its surface to fabricate high-sensitivity flexible X-ray detectors. This detector device has a simple structure; a high-performance flexible X-ray detector can be fabricated by depositing a layer of planar interdigitated gold electrodes on the smooth composite membrane surface. It has great potential for high-performance radiation detection and self-powered radiation detection using environmentally friendly flexible perovskite materials. Attached Figure Description

[0019] Figure 1 shows the chiral bismuth iodide perovskite described in Example 1 of the present invention. R -FPEA)4Bi2I 10 Crystal structure diagram.

[0020] Figure 2 is a flowchart of the preparation process of flexible chiral or racemic bismuth iodide perovskite thick films as described in the example of the present invention.

[0021] Figure 3 shows the flexible chiral bismuth iodide perovskite obtained by the preparation method described in Example 1 of this invention. R -FPEA)4Bi2I 10 A photograph of the thick film before hot pressing.

[0022] Figure 4 shows the flexible chiral bismuth iodide perovskite obtained by the preparation method described in Example 1 of this invention. R -FPEA)4Bi2I 10 Photograph of a thick film.

[0023] Figure 5 is a schematic diagram of a flexible chiral or racemic bismuth iodide perovskite X-ray detector.

[0024] Figure 6 is a graph showing the lattice distortion parameters of a series of flexible chiral or racemic bismuth iodide perovskite crystals obtained by the preparation method of the present application, wherein (a) is a graph of bond length distortion, (b) is a graph of bond length second extension rate, and (c) is a graph of bond angle variance.

[0025] Figure 7 is a graph showing the chiral optical activity of a series of flexible chiral bismuth iodide perovskite crystals obtained by the preparation method of the present application.

[0026] wherein (a) is a circular dichroism (CD) spectrum, and (b) is a g-factor spectrum. Figure 8 is a flexible chiral bismuth iodide perovskite crystal obtained by the preparation method described in Example 8 of the present application. S -BrPEA)4Bi2I 10 Current density-dose rate map of the X-ray detector. DETAILED DESCRIPTION

[0027] The present application will be further described below in conjunction with the accompanying drawings: To enable persons skilled in the art to better understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein have the usual meanings understood by those skilled in the art of the present application, and in the event of a conflict, the definitions in the present specification shall prevail.

[0028] In this document, unless otherwise specified, "comprise", "include", "contain", "have", or similar words encompass the meanings of "consist of" and "consist essentially of", for example, "A comprises a" encompasses the meanings of "A comprises a and other" and "A comprises only a".

[0029] The present application will be further described below in conjunction with the accompanying drawings:

[0030] The following examples use apparatus and equipment that are conventional in the art. The experimental methods in the following examples, unless otherwise specified, are generally conducted in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer. The following examples use various raw materials, unless otherwise specified, and all use conventional commercially available products, which are of conventional specifications in the art. In the specification of the present application and in the following examples, unless otherwise specified, "%" means weight percent, "parts" means weight parts, and the ratio means weight ratio.

[0031] Reference is made to Figure 1 , the first aspect of the present application discloses a chiral organic molecule A-site selective regulation of perovskite single crystal, the single crystal is chiral or racemic bismuth calcium iodide perovskite single crystal, the structural formula is A4Bi2I 10 , the chiral organic molecule A-site selective regulation of perovskite single crystal; A is Y-XPEA, wherein Y is R 、 S or Rac , X is fluorine, chlorine or bromine, PEA is phenethylamine; the Rac is R and S racemic mixture of equimolar amount; the organic amine molecule at A site is combined with perovskite octahedron through hydrogen bond, and Bi 3+ and I - in the octahedron are mainly connected by ionic bond, while Bi and I orbit are hybridized, introducing covalent bond.

[0032] Specifically, by introducing organic cation R / S / Rac -F / Cl / BrPEA, a series of halogen-substituted chiral and racemic 0D polar bismuth iodide perovskite single crystals are grown: R / S / Rac -FPEA)4Bi2I 10 (1 R / 1 S / 1 Rac , R / S / Rac -FPEA= R / S / Rac -1-(4-Fluorophenyl)ethylamine), R / S / Rac -ClPEA)4Bi2I 10 (2 R / 2 S / 2 Rac , R / S / Rac-ClPEA= R / S / Rac -(4-chlorophenyl)ethylamine), ( R / S / Rac -BrPEA)4Bi2I 10 (3 R / 3 S / 3 Rac , R / S / Rac -BrPEA= R / S / Rac (-(4-bromophenyl)ethylamine).

[0033] The structural formula of the single crystal disclosed in this invention is: a chiral 0D polar bismuth iodide perovskite single crystal ( S -FPEA)4Bi2I 10 And racemic 0D polar bismuth iodide perovskite single crystals, ( Rac -F / Cl / BrPEA)4Bi2I 10 .

[0034] The second aspect of this invention discloses a method for preparing perovskite single crystals selectively regulated by chiral organic molecules at the A-site. The specific process of this preparation method is as follows: Each R / S / Rac 1-(4-fluoro / chloro / bromophenyl)ethylamine and bismuth oxide are dissolved in a mixed solvent of hydroiodic acid (55.0~58.0%) and hypophosphorous acid (50.0%) in a molar ratio of 4:1 in a 10:1 ratio. Hypophosphorous acid, as a highly efficient reducing agent, can inhibit the formation of elemental iodine (I₂), thus ensuring the stability of the reaction environment and the quality of the single crystal. The solution is heated to 100 ℃~120 ℃ and continuously stirred to obtain a transparent solution. The solution is then slowly cooled to room temperature to obtain red chiral or racemic bismuth iodide perovskite single crystals. The racemic mixture consists of two chiral substances. S / R An equal mixture of configurations does not possess chiral optical activity.

[0035] in a clear solution, R / S / Rac The molar concentration of 1-(4-fluoro / chloro / bromophenyl)ethylamine is 0.2 mol / L to 0.4 mol / L, and the molar concentration of bismuth oxide is 0.05 mol / L to 0.1 mol / L.

[0036] In the cooling process, the cooling rate of the temperature control cooling is 0.25 ℃ / h ~0.3 ℃ / h.

[0037] A third aspect of the present application discloses a preparation method of a flexible detector, comprising the following steps: Step 1, after washing and drying the crystal, grinding it into powder, dissolving 9 different single crystal powders in a mixed solvent of DMF:DMSO=9:1, stirring to obtain a perovskite solution selectively regulated by A-site chiral organic molecules, with a concentration of 0.8 mol / L~1.5 mol / L.

[0038] Step 2, fill the A-site chiral organic molecule selectively regulated perovskite solution into a flexible high polymer porous polymer nylon film by immersion method.

[0039] Step 3, heat the flexible high polymer filled with A-site chiral organic molecule selectively regulated perovskite solution to 90 ℃~110 ℃ for annealing crystallization for 2 h~3 h. The area of the flexible high polymer porous polymer nylon film is 10 cm 2 ~30 cm 2 , the skeleton diameter is 5 µm ~10 µm, the pore size is 5~10 µm, and the thickness is 80 µm ~120 µm.

[0040] Step 4, heat and press the A-site chiral organic molecule selectively regulated perovskite flexible composite film after heating and annealing crystallization. The hot pressing temperature is 100 ℃~150 ℃, the hot pressing pressure is 8 MPa~12 MPa, and the hot pressing time is 2 h~4 h.

[0041] Step 5, gold electrode high-temperature vacuum evaporation is carried out on the A-site chiral organic molecule selectively regulated perovskite flexible thick film to obtain a flexible A-site chiral organic molecule selectively regulated perovskite X-ray detector. The thickness of the interdigital electrode is 30 nm~150 nm, the finger width is 10 nm~1 mm, the interval is 10 nm~1 mm, the finger length is 10 nm~10 mm, and the photosensitive area is 200nm 2 ~40 mm 2 ; the interdigital electrode is made of gold.

[0042] Step 6, flexible chiral or racemate bismuth iodide perovskite X-ray detector photoelectric conversion signal test: at room temperature, using a current meter of B2912 model, current-time test is carried out under the irradiation condition of X-ray dose rate range, with an applied voltage of 50 V and a delay time of 10~250 ms.

[0043] The fourth aspect of the present application discloses a flexible detector, taking flexible high-molecular porous polymer nylon film as a skeleton, wherein chiral or racemic bismuth calcium titanate monocrystals are filled in the skeleton, and the structural formula is A4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of R -FPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of S -FPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of Rac -FPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of R -ClPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of S -ClPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of Rac -ClPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of R -BrPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of S -BrPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of Rac -BrPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of R -FPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of S -FPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of Rac -FPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of R -ClPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of S -ClPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of Rac -ClPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of R -BrPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of S -BrPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of Rac -BrPEA)4Bi2I 10 The chiral organic molecules at the A position of the flexible detector are selected from the group consisting of R / S / Rac -F / Cl / BrPEA respectively are R / S / Rac -1-(4-fluoro / chloro / bromo phenyl) ethylamine, Bi is bismuth, and I is iodine.

[0044] The present application adopts soaking method to fill, anneal and hot-press to prepare flexible chiral or racemic bismuth iodide perovskite thick film. By introducing chiral organic cations R S Rac -F / Cl / Br PEA, a new type of perovskite material. Among them R S -F / Cl / Br PEA)4Bi2I 10 has chiral polar characteristics, chiral optical properties and potential for self-powered detection. By introducing halogen-substituted chiral organic cations, a series of 0D polar bismuth iodide perovskites are designed and synthesized. The molecular electrostatic force between halogen atoms and adjacent benzene rings and the introduction of F / Cl / Br…I increase the activation energy of ion migration, which can further improve the device performance of flexible chiral or racemic bismuth iodide perovskite X-ray detectors.

[0045] Example 1 1. Growth of chiral bismuth iodide perovskite single crystal: 55.0-58.0% of hydroiodic acid and 50% of hypophosphorous acid are prepared according to the volume ratio of 10:1. 0.233 g of Bi2O3 is weighed, 0.270 mL of ( R ) -1-(4-fluorophenyl) ethylamine is taken with a pipette and dissolved in 5 mL of mixed solvent of hydroiodic acid and hypophosphorous acid. Heat to 120 ℃ on a heating magnetic stirrer while stirring for 24 h to make it completely react, then slowly cool the solution to room temperature at 0.3 ℃ / h, to obtain red chiral bismuth iodide perovskite crystals ( R -F PEA)4Bi2I 10 .

[0046] 2. Place qualitative filter paper in a Buchner funnel, and place the ( R -F PEA)4Bi2I 10 single crystal on the qualitative filter paper and wash it with anhydrous ether. Place the washed single crystal into an oven and dry it at 55 ℃ for 12 h. After drying, grind the single crystal into powder with aagate mortar. Dissolve 1.7976 g of ( R -F PEA)4Bi2I 10 single crystal powder in 1 mL of mixed solvent of DMF:DMSO with a volume ratio of 9:1 to obtain a perovskite solution with a concentration of 0.8 M, stir it on a magnetic stirrer for 12 h to make it react completely, and then filter it with a filter core with a specification of 0.45 µm to obtain a clear chiral bismuth iodide perovskite solution.

[0047] 3. Take a flexible high polymer nylon film and place it in a culture dish, and take 0.5 mL of ( R -F PEA)4Bi2I 10 ​​​The perovskite solution is dropped into the culture dish, so that the chiral bismuth iodide perovskite solution fills the flexible high polymer nylon film.

[0048] 4、Turn on the hot stage, set the temperature to 110 ℃, preheat for 10 min, transfer the chiral bismuth iodide perovskite solution filled nylon film to the hot stage, and perform heating annealing, the annealing time is 2 h, and the obtained flexible film is as shown in Figure 3 .

[0049] 5、The crystallized chiral bismuth iodide perovskite thick film is heated and pressed through a hot press, the temperature is set to 130 ℃, the pressure is 10 MPa, and the time is 3 h. The flexible chiral bismuth iodide perovskite thick film after hot pressing is obtained, and the obtained flexible film is as shown in Figure 4 .

[0050] 6、An interdigital gold electrode with a thickness of 60 nm, a finger width of 50 μm, a spacing of 50 μm, and a finger length of 1 mm is deposited on the surface of the flexible chiral bismuth iodide perovskite thick film, and a flexible chiral bismuth iodide perovskite thick film X-ray detector is obtained, as shown in Figure 5 .

[0051] Example 2 1、Growth of chiral bismuth iodide perovskite single crystal: 55.0-58.0% of hydroiodic acid and 50% of hypophosphorous acid are prepared according to a volume ratio of 10:1. 0.233 g of Bi2O3 is weighed, 0.270 mL of ( S ) -1-(4-fluorophenyl)ethylamine is taken by a pipette, and is dissolved in 5 mL of the mixed solvent of hydroiodic acid and hypophosphorous acid. The solution is heated to 120 ℃ on a heating magnetic stirrer, and is stirred for 24 h to make it completely react. Then the solution is slowly cooled to room temperature to obtain red chiral bismuth iodide perovskite crystals ( S -FPEA)4Bi2I 10 .

[0052] 2、Place the qualitative filter paper in a Buchner funnel, and place the ( S -FPEA)4Bi2I 10 single crystal on the qualitative filter paper, and wash it with anhydrous diethyl ether. The washed single crystal is placed in an oven and dried at 55 ℃ for 12 h. After drying, the single crystal is ground into powder with aagate mortar. 1.7976 g of the single crystal powder of ( S -FPEA)4Bi2I 10 is dissolved in 1 mL of a mixed solvent of DMF and DMSO with a volume ratio of 9:1 to obtain a perovskite solution with a concentration of 0.8 M, which is stirred on a magnetic stirrer for 12 h to make it completely react. After being filtered with a filter core with a specification of 0.45 μm, a clear chiral bismuth iodide perovskite solution is obtained.

[0053] 3. Place a flexible polymer nylon membrane in a petri dish, and use a pipette to take 0.5 mL ( S -FPEA)4Bi2I 10 The perovskite solution was dropped into a petri dish, allowing the chiral bismuth iodide perovskite solution to fill the flexible polymer nylon membrane.

[0054] 4. Turn on the hot plate and set the temperature to 110 ℃ for 10 min. Transfer the nylon film filled with chiral bismuth iodide perovskite solution to the hot plate for heating and annealing for 2 h.

[0055] 5. The crystalline chiral bismuth iodide perovskite thick film was heated and pressurized using a hot press at a temperature of 130 ℃, a pressure of 10 MPa, and a time of 3 h. A flexible chiral bismuth iodide perovskite thick film was obtained after hot pressing.

[0056] 6. A flexible chiral bismuth iodide perovskite thick film X-ray detector was obtained by depositing interdigitated gold electrodes with a thickness of 60 nm, a finger width of 50 μm, a spacing of 50 μm, and a finger length of 1 mm on the surface of the flexible chiral bismuth iodide perovskite thick film.

[0057] Example 3 1. ( R )-1-(4-fluorophenyl)ethylamine and ( S )-1-(4-fluorophenyl)ethylamine was mixed and stirred at a molar ratio of 1:1 to obtain its racemic mixture ( Rac 1-(4-fluorophenyl)ethylamine.

[0058] 2. Growth of racemic bismuth iodide perovskite single crystals: A solution of 55.0-58.0% hydroiodic acid and 50% hypophosphorous acid was prepared at a volume ratio of 10:1. Weigh 0.233 g of Bi₂O₃ and pipette 0.270 mL... Rac 1-(4-fluorophenyl)ethylamine was dissolved in 6 mL of a mixed solvent of hydroiodic acid and hypophosphoric acid. The solution was heated to 120 °C with a magnetic stirrer and stirred for 24 h to allow the reaction to proceed completely. The solution was then slowly cooled to room temperature to obtain red racemic bismuth iodide perovskite crystals. Rac -FPEA)4Bi2I 10 .

[0059] 3. Place the qualitative filter paper in the Buchner funnel, and ( Rac -FPEA)4Bi2I 10 The single crystals were placed on qualitative filter paper and washed with anhydrous ether. The washed single crystals were then placed in an oven and dried at 55 °C for 12 h. After drying, the single crystals were ground into powder using an agate mortar and pestle. 1.7976 g ( Rac-FPEA)4Bi2I 10 The single crystal powder was dissolved in 1 mL of a mixed solvent of DMF and DMSO at a volume ratio of 9:1 to obtain a perovskite solution with a concentration of 0.8 M. The solution was stirred on a magnetic stirrer for 12 h to ensure complete reaction. After filtration through a 0.45 µm filter, a clear racemic bismuth iodide perovskite solution was obtained.

[0060] 4. Place a flexible polymer nylon membrane in a petri dish, and use a pipette to take 0.5 mL ( Rac -FPEA)4Bi2I 10 The perovskite solution was dropped into a petri dish, allowing the racemic bismuth iodide perovskite solution to fill the flexible polymer nylon membrane.

[0061] 5. Turn on the hot stage and preheat at 110 ℃ for 10 min. Transfer the nylon film filled with racemic bismuth iodide perovskite solution to the hot stage for heating and annealing for 2 h.

[0062] 6. The crystalline racemic bismuth iodide perovskite thick film was heated and pressurized using a hot press at a temperature of 130℃ and a pressure of 10 MPa for 3 hours. A flexible racemic bismuth iodide perovskite thick film was obtained after hot pressing.

[0063] 7. A flexible enantiomeric bismuth iodide perovskite thick film X-ray detector was obtained by depositing interdigitated gold electrodes with a thickness of 60 nm, a finger width of 50 μm, a spacing of 50 μm, and a finger length of 1 mm on the surface of a flexible racemic bismuth iodide perovskite thick film.

[0064] Example 4 1. Growth of chiral bismuth iodide perovskite single crystals: A solution of 55.0-58.0% hydroiodic acid and 50% hypophosphorous acid was prepared at a volume ratio of 10:1. Weigh 0.233 g of Bi₂O₃ and pipette 0.280 mL... R 1-(4-chlorophenyl)ethylamine was dissolved in 5 mL of a mixed solvent of hydroiodic acid and hypophosphoric acid. The solution was heated to 120 °C with a magnetic stirrer and stirred for 24 h to allow the reaction to proceed completely. The solution was then slowly cooled to room temperature to obtain red chiral bismuth iodide perovskite crystals. R -ClPEA)4Bi2I 10 .

[0065] 2. Place the qualitative filter paper in the Buchner funnel, and ( R -ClPEA)4Bi2I 10The single crystals were placed on qualitative filter paper and washed with anhydrous diethyl ether. The washed single crystals were then placed in an oven and dried at 55°C for 12 hours. After drying, the single crystals were ground into powder using an agate mortar and pestle. 1.8504 g ( R -ClPEA)4Bi2I 10 The single crystal powder was dissolved in 1 mL of a mixed solvent of DMF and DMSO at a volume ratio of 9:1 to obtain a perovskite solution with a concentration of 0.8 M. The solution was stirred on a magnetic stirrer for 12 h to ensure complete reaction. After filtration through a 0.45 µm filter, a clear chiral bismuth iodide perovskite solution was obtained.

[0066] 3. Place a flexible polymer nylon membrane in a petri dish, and use a pipette to take 0.5 mL ( R -ClPEA)4Bi2I 10 The perovskite solution was dropped into a petri dish, allowing the chiral bismuth iodide perovskite solution to fill the flexible polymer nylon membrane.

[0067] 4. Turn on the hot plate and set the temperature to 110 ℃ for 10 min. Transfer the nylon film filled with chiral bismuth iodide perovskite solution to the hot plate for heating and annealing for 2 h.

[0068] 5. The crystalline chiral bismuth iodide perovskite thick film was heated and pressurized using a hot press at a temperature of 130 ℃, a pressure of 10 MPa, and a time of 3 h. A flexible chiral bismuth iodide perovskite thick film was obtained after hot pressing.

[0069] 6. A flexible chiral bismuth iodide perovskite thick film X-ray detector was obtained by depositing interdigitated gold electrodes with a thickness of 60 nm, a finger width of 50 μm, a spacing of 50 μm, and a finger length of 1 mm on the surface of the flexible chiral bismuth iodide perovskite thick film.

[0070] Example 5 1. Growth of chiral bismuth iodide perovskite single crystals: A solution of 55.0-58.0% hydroiodic acid and 50% hypophosphorous acid was prepared at a volume ratio of 10:1. Weigh 0.233 g of Bi₂O₃ and pipette 0.280 mL... S 1-(4-chlorophenyl)ethylamine was dissolved in 5 mL of a mixed solvent of hydroiodic acid and hypophosphoric acid. The solution was heated to 120 °C with a magnetic stirrer and stirred for 24 h to allow the reaction to proceed completely. The solution was then slowly cooled to room temperature to obtain red chiral bismuth iodide perovskite crystals. S -ClPEA)4Bi2I 10 .

[0071] 2. Place the qualitative filter paper in the Buchner funnel, and ( S -ClPEA)4Bi2I10 The single crystal was placed on qualitative filter paper and washed with anhydrous diethyl ether. The washed single crystal was placed in an oven and dried at 55 °C for 12 h. After drying, the single crystal was ground into powder using a maroon mortar. 1.8504 g of the single crystal powder of (ClPEA)4Bi2I S 10 was dissolved in 1 mL of a mixed solvent of DMF and DMSO with a volume ratio of 9:1 to obtain a perovskite solution with a concentration of 0.8 M. The solution was stirred on a magnetic stirrer for 12 h to make the reaction complete. After filtration using a filter with a specification of 0.45 pm, a clear chiral bismuth iodide perovskite solution was obtained.

[0072] 3. A flexible high polymer nylon film was placed in a culture dish. 0.5 mL of the chiral bismuth iodide perovskite solution was taken using a pipette gun and dropped into the culture dish, so that the chiral bismuth iodide perovskite solution filled the flexible high polymer nylon film. S 10

[0073] 4. The temperature of the hot stage was set to 110 °C and preheated for 10 min. The nylon film filled with the chiral bismuth iodide perovskite solution was transferred to the hot stage for heating and annealing, and the annealing time was 2 h.

[0074] 5. The crystallized chiral bismuth iodide perovskite thick film was heated and pressurized by a hot press, the temperature was set to 130 °C, the pressure was 10 MPa, and the time was 3 h. The flexible chiral bismuth iodide perovskite thick film after hot pressing was obtained.

[0075] 6. Interdigital gold electrodes with a thickness of 60 nm, a finger width of 50 pm, a spacing of 50 pm, and a finger length of 1 mm were deposited on the surface of the flexible chiral bismuth iodide perovskite thick film, and a flexible chiral bismuth iodide perovskite thick film X-ray detector was obtained.

[0076] Example 6 1. (ClPEA)4Bi2I R and (ClPEA)4Bi2I S were mixed and stirred according to a molar ratio of 1:1 to obtain the racemate (ClPEA)4Bi2I Rac

[0077] 2. Growth of the single crystal of the racemate bismuth iodide perovskite: 55.0-58.0% of hydroiodic acid and 50% of hypophosphorous acid were prepared according to a volume ratio of 10:1. 0.233 g of Bi2O3 was weighed, and 0.280 mL of (ClPEA)4Bi2I Rac ​​​​) -1-(4-chlorophenyl)ethylamine, dissolved in 7 mL of a mixed solvent of hydriodic acid and hypophosphorous acid, heated to 120 °C on a heated magnetic stirrer, and allowed to react completely while stirring for 24 h. The solution was then slowly cooled to room temperature to obtain red racemic bismuth iodide perovskite crystals Rac -ClPEA)4Bi2I 10 .

[0078] 3. Place qualitative filter paper in a Buchner funnel, and place the Rac -ClPEA)4Bi2I 10 single crystals on the qualitative filter paper and wash with anhydrous diethyl ether. Place the washed single crystals in an oven and dry at 55 °C for 12 h. After drying, grind the single crystals into a powder using a jade mortar. Dissolve 1.8504 g of the single crystal powder of Rac -ClPEA)4Bi2I 10 in 1 mL of a mixed solvent of DMF and DMSO in a volume ratio of 9:1 to obtain a perovskite solution having a concentration of 0.8 M, and allow it to react completely on a magnetic stirrer for 12 h. After filtering using a filter having a specification of 0.45 µm, obtain a clear racemic bismuth iodide perovskite solution.

[0079] 4. Place a flexible high polymer nylon film in a petri dish, and using a pipette, take 0.5 mL of the Rac -ClPEA)4Bi2I 10 perovskite solution and drop it into the petri dish, so that the racemic bismuth iodide perovskite solution fills the flexible high polymer nylon film.

[0080] 5. Turn on the hot stage, set the temperature to 110 °C, and preheat for 10 min. Transfer the nylon film filled with the racemic bismuth iodide perovskite solution to the hot stage, and perform heating annealing for 2 h.

[0081] 6. Heat and press the crystallized racemic bismuth iodide perovskite thick film using a hot press, set the temperature to 130 °C, the pressure to 10 MPa, and the time to 3 h. Obtain the flexible racemic bismuth iodide perovskite thick film after hot pressing.

[0082] 7. Deposit interdigital gold electrodes having a thickness of 60 nm, a finger width of 50 µm, a spacing of 50 µm, and a finger length of 1 mm on the surface of the flexible racemic bismuth iodide perovskite thick film, and obtain a flexible racemic bismuth iodide perovskite thick film X-ray detector.

[0083] Example 7 1. Growth of chiral bismuth iodide perovskite single crystals: A solution of 55.0-58.0% hydroiodic acid and 50% hypophosphorous acid was prepared at a volume ratio of 10:1. Weigh 0.233 g of Bi₂O₃ and pipette 0.288 mL... R 1-(4-bromophenyl)ethylamine was dissolved in 6 mL of a mixed solvent of hydroiodic acid and hypophosphoric acid. The solution was heated to 120 °C with a magnetic stirrer and stirred for 24 h to allow the reaction to proceed completely. The solution was then slowly cooled to room temperature to obtain red chiral bismuth iodide perovskite crystals. R -BrPEA)4Bi2I 10 .

[0084] 2. Place the qualitative filter paper in the Buchner funnel, and ( R -BrPEA)4Bi2I 10 The single crystals were placed on qualitative filter paper and washed with anhydrous ether. The washed single crystals were then placed in an oven and dried at 55 °C for 12 h. After drying, the single crystals were ground into powder using an agate mortar and pestle. 1.9928 g ( R -BrPEA)4Bi2I 10 The single crystal powder was dissolved in 1 mL of a mixed solvent of DMF and DMSO at a volume ratio of 9:1 to obtain a perovskite solution with a concentration of 0.8 M. The solution was stirred on a magnetic stirrer for 12 h to ensure complete reaction. After filtration through a 0.45 µm filter, a clear chiral bismuth iodide perovskite solution was obtained.

[0085] 3. Place a flexible polymer nylon membrane in a petri dish, and use a pipette to take 0.5 mL ( R -BrPEA)4Bi2I 10 The perovskite solution was dropped into a petri dish, allowing the chiral bismuth iodide perovskite solution to fill the flexible polymer nylon membrane.

[0086] 4. Turn on the hot plate and set the temperature to 110 ℃ for 10 min. Transfer the nylon film filled with chiral bismuth iodide perovskite solution to the hot plate for heating and annealing for 2 h.

[0087] 5. The crystalline chiral bismuth iodide perovskite thick film was heated and pressurized using a hot press at a temperature of 130 ℃, a pressure of 10 MPa, and a time of 3 h. A flexible chiral bismuth iodide perovskite thick film was obtained after hot pressing.

[0088] 6. A flexible chiral bismuth iodide perovskite thick film X-ray detector was obtained by depositing interdigitated gold electrodes with a thickness of 60 nm, a finger width of 50 μm, a spacing of 50 μm, and a finger length of 1 mm on the surface of the flexible chiral bismuth iodide perovskite thick film.

[0089] Example 8 1. Growth of chiral bismuth iodide perovskite single crystals: A solution of 55.0-58.0% hydroiodic acid and 50% hypophosphorous acid was prepared at a volume ratio of 10:1. Weigh 0.233 g of Bi₂O₃ and pipette 0.288 mL... S 1-(4-bromophenyl)ethylamine was dissolved in 6 mL of a mixed solvent of hydroiodic acid and hypophosphoric acid. The solution was heated to 120 °C with a magnetic stirrer and stirred for 24 h to allow the reaction to proceed completely. The solution was then slowly cooled to room temperature to obtain red chiral bismuth iodide perovskite crystals. S -BrPEA)4Bi2I10.

[0090] 2. Place the qualitative filter paper in the Buchner funnel, and ( S -BrPEA)4Bi2I 10 The single crystals were placed on qualitative filter paper and washed with anhydrous diethyl ether. The washed single crystals were then placed in an oven and dried at 55°C for 12 hours. After drying, the single crystals were ground into powder using an agate mortar and pestle. 1.9928 g ( S -BrPEA)4Bi2I 10 The single crystal powder was dissolved in 1 mL of a mixed solvent of DMF and DMSO at a volume ratio of 9:1 to obtain a perovskite solution with a concentration of 0.8 M. The solution was stirred on a magnetic stirrer for 12 h to ensure complete reaction. After filtration through a 0.45 µm filter, a clear chiral bismuth iodide perovskite solution was obtained.

[0091] 3. Place a flexible polymer nylon membrane in a petri dish, and use a pipette to take 0.5 mL ( S -BrPEA)4Bi2I 10 The perovskite solution was dropped into a petri dish, allowing the chiral bismuth iodide perovskite solution to fill the flexible polymer nylon membrane.

[0092] 4. Turn on the hot plate and set the temperature to 110 ℃ for 10 min. Transfer the nylon film filled with chiral bismuth iodide perovskite solution to the hot plate for heating and annealing for 2 h.

[0093] 5. The crystalline chiral bismuth iodide perovskite thick film was heated and pressurized using a hot press at a temperature of 130 ℃, a pressure of 10 MPa, and a time of 3 h. A flexible chiral bismuth iodide perovskite thick film was obtained after hot pressing.

[0094] 6. A flexible chiral bismuth iodide perovskite thick film X-ray detector was obtained by depositing interdigitated gold electrodes with a thickness of 60 nm, a finger width of 50 μm, a spacing of 50 μm, and a finger length of 1 mm on the surface of the flexible chiral bismuth iodide perovskite thick film.

[0095] Example 9 1. Mix ( -1-(4-bromophenyl)ethylamine and ( -1-(4-bromophenyl)ethylamine in a 1:1 molar ratio and stir to obtain its racemate ( -1-(4-bromophenyl)ethylamine. R S Rac

[0096] 2. Growth of racemic bismuth iodide perovskite single crystal: 55.0-58.0% of hydroiodic acid and 50% of hypophosphorous acid are prepared in a 10:1 volume ratio. 0.233 g of Bi2O3 is weighed, 0.288 mL of ( -1-(4-bromophenyl)ethylamine is taken with a pipette, and dissolved in 8 mL of a mixed solvent of hydroiodic acid and hypophosphorous acid to obtain a perovskite solution with a concentration of 0.8 M. Heat to 120°C on a heated magnetic stirrer while stirring for 24 h to allow it to react completely. Then slowly cool the solution to room temperature to obtain red racemic bismuth iodide perovskite crystals ( -BrPEA)4Bi2I Rac Rac 10 .

[0097] 3. Place qualitative filter paper in a Buchner funnel, and place ( -BrPEA)4Bi2I 10 single crystals on the qualitative filter paper, and wash with anhydrous ether. Place the washed single crystals in an oven and dry at 55°C for 12 h. After drying, grind the single crystals into a powder with a jade mortar. Dissolve 1.9928 g of ( -BrPEA)4Bi2I 10 single crystal powder in 1 mL of a mixed solvent of DMF and DMSO in a volume ratio of 9:1, and stir on a magnetic stirrer for 12 h to allow it to react completely. After filtering with a filter cartridge with a specification of 0.45 pm, obtain a clear racemic bismuth iodide perovskite solution. Rac Rac

[0098] 4. Place a flexible high polymer nylon film in a petri dish, and take 0.5 mL of ( -BrPEA)4Bi2I 10 perovskite solution with a pipette and drop it into the petri dish to allow the racemic bismuth iodide perovskite solution to fill into the flexible high polymer nylon film. Rac

[0099] 5. Turn on the hot stage, set the temperature to 110°C and preheat for 10 min, transfer the nylon film filled with racemic bismuth iodide perovskite solution to the hot stage, and perform heating annealing for 2 h.

[0100] ​​​​​​​​6. The crystallized racemic bismuth calcium titanate thick film is heated and pressed by a hot press, the temperature is set to 130°C, the pressure is 10 MPa, and the time is 3h. The flexible racemic bismuth calcium titanate thick film after hot pressing is obtained.

[0101] 7. The interdigital gold electrode with a thickness of 60 nm, a finger width of 50 μm, a spacing of 50 μm, and a finger length of 1 mm is deposited on the surface of the flexible racemic bismuth calcium titanate thick film, and a flexible racemic bismuth calcium titanate thick film X-ray detector is obtained.

[0102] Referring to Figure 6 For the series of flexible chiral or racemic bismuth calcium titanate lattice distortion parameter graphs of Examples 1-9, the smaller the three parameters, the smaller the lattice distortion, and it can be seen from the graph that the Br series of perovskite lattice distortion is the smallest.

[0103] Referring to Figure 7 For the chiral or racemic bismuth calcium titanate chiral optical activity graph of Examples 1-9, the stronger the CD signal, the larger the g factor, and it can be seen from the graph that the Br series of perovskite chiral optical activity is the best.

[0104] Referring to Figure 8 For the flexible chiral bismuth calcium iodide perovskite S -BrPEA)4Bi2I 10 The current density-dose rate graph of the X-ray detector, and it can be seen from the graph that the X-ray detector device exhibits significant light response characteristics, and the current density gradually increases as the X-ray dose rate increases. At the same time, the sensitivity of the X-ray detector gradually improves as the applied bias voltage increases.

[0105] Example 10 In this embodiment, in step 1, the cooling speed of the solution is 0.25°C / h, and a red chiral bismuth calcium iodide perovskite crystal R -FPEA)4Bi2I 10 The rest is not involved in Example 1.

[0106] Example 11 In this embodiment, the concentration of the perovskite solution selectively regulated by the chiral organic molecule at position A is 0.8 mol / L, and the rest is not involved in Example 1.

[0107] Example 12 In this embodiment, the concentration of the perovskite solution selectively regulated by the chiral organic molecule at position A is 1.5 mol / L, and the rest is not involved in Example 1.

[0108] Example 13 In this example, in step 5, the annealing temperature is 90 ℃, the annealing time is 3h, and the rest of the parts not involved are the same as in Example 1.

[0109] Example 14 In this example, in step 5, the annealing temperature is 110 ℃, the annealing time is 2h, and the rest of the parts not involved are the same as in Example 1.

[0110] Example 15 In this example, in step 6, the hot-pressing temperature is 100 ℃, the hot-pressing pressure is 8, the hot-pressing time is 4h, and the rest of the parts not involved are the same as in Example 1.

[0111] Example 16 In this example, in step 6, the hot-pressing temperature is 150 ℃, the hot-pressing pressure is 12, the hot-pressing time is 2h, and the rest of the parts not involved are the same as in Example 1.

[0112] The above description is merely preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A perovskite single crystal selectively modulated by A-site chiral organic molecules, characterized in that, A4Bi2I is a chiral or racemic bismuth iodide perovskite single crystal, and the structural formula is A4Bi2I 10 , A is a chiral organic molecule selectively controlled perovskite single crystal; A is Y-XPEA, wherein Y is R 、 S or Rac , X is fluorine, chlorine or bromine, PEA is phenethylamine; the Rac is R and S racemic mixture of equimolar amount; when Y is R or S, A4Bi2I 10 is a chiral bismuth iodide perovskite single crystal, when Y is Rac, A4Bi2I 10 is a racemic bismuth iodide perovskite single crystal; The chiral or racemic bismuth iodide perovskite single crystal is a zero-dimensional perovskite structure, including A-site chiral cations and [Bi2I 10 ] 4 anions, the A-site chiral cations are ( S -F / Cl / BrPEA) + , ( R-F / Cl / BrPEA) + or ( Rac-F / Cl / BrPEA) + , wherein / represents or; the [Bi2I 10 ] 4 Anion dimers are formed by two edge-shared [BiI6] 2 octahedra. 2.The A-site chiral organic molecule selectively modulated perovskite single crystal according to claim 1, characterized in that, The structural formula of the chiral or racemic bismuth calcium titanate iodide monocrystal is S - FPEA)4Bi2I 10 , ( Rac - FPEA)4Bi2I 10 , ( Rac - ClPEA)4Bi2I 10 or ( Rac - BrPEA)4Bi2I 10 .

3. A method for preparing a perovskite single crystal selectively controlled by an A-site chiral organic molecule according to claim 1 or 2, characterized in that, The method comprises the following steps: dissolving Y-1-(4-X phenyl) ethylamine and bismuth oxide in a mixed solvent of hydriodic acid and hypophosphorous acid according to a molar ratio, and then continuously stirring the reaction after heating, and obtaining chiral or racemic bismuth iodide perovskite single crystals for A-site chiral organic molecule selective regulation after temperature control and cooling.

4. The method for preparing perovskite single crystals according to claim 3, characterized in that, The cooling speed of the temperature control and cooling in the mixed solvent is 0.25 ℃ / h ~0.3 ℃ / h.

5. A method of making a flexible probe, characterized by, The method comprises the following steps: S1, grinding the A-site chiral organic molecule selectively regulated perovskite single crystal in claim 1 or 2 into powder, and then dissolving the powder in an organic solvent to obtain an A-site chiral organic molecule selectively regulated perovskite solution; S2, filling the A-site chiral organic molecule selectively regulated perovskite solution into a flexible high polymer porous polymer nylon film to obtain a flexible high polymer porous polymer nylon film filled with the perovskite solution; S3, heating and annealing the flexible high polymer porous polymer nylon film filled with the perovskite solution to obtain a chiral or racemic bismuth iodide perovskite polycrystalline thin film; S4, hot-pressing the chiral or racemic bismuth iodide perovskite polycrystalline thin film to obtain a chiral or racemic bismuth iodide perovskite flexible thin film; S5, preparing a metal electrode on the chiral or racemic bismuth iodide perovskite flexible thin film to obtain a flexible chiral or racemic bismuth iodide perovskite X-ray detector.

6. The method of claim 5, wherein the flexible probe is prepared by the steps of: In S1, the concentration of the A-site chiral organic molecule selectively regulated perovskite solution is 0.8 mol / L~1.5 mol / L.

7. The method of claim 5, wherein the flexible probe is prepared by the steps of: In S2, the organic solvent is a mixed solution of DMF and DMSO.

8. The method of claim 5, wherein the flexible probe is prepared by the steps of: In S3, the annealing temperature is 90 ℃~110 ℃, and the annealing time is 2 h~3 h.

9. The method of claim 5, wherein the flexible probe is prepared by the steps of: In S4, the hot-pressing temperature is 100 ℃~150 ℃, the hot-pressing pressure is 8 MPa~12 MPa, and the hot-pressing time is 2 h~4 h.

10. A flexible probe produced by the production method according to any one of claims 5 to 9, characterized in that A flexible high polymer porous polymer nylon film is used as a skeleton, and chiral or racemic body iodine bismuth calcium titanate is filled in the skeleton, and the structural formula is A4Bi2I 10 .

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