Controllable growth method and device for iodine-copper-cesium single crystal with large-size perovskite structure

Abstract

The invention belongs to the technical field of crystal materials, and particularly relates to a controllable growth device and method for a large-size perovskite structure iodine copper cesium single crystal. The designed growth equipment mainly comprises a growth system, a temperature control system and an anti-solvent diffusion system. The method for growing the large-size iodine-copper-cesium single crystal by adopting the temperature-control and speed-control anti-solvent diffusion method comprises the following steps: in the growth process of the iodine-copper-cesium crystal, carrying gas generated by a gas generator carries an anti-solvent into a grower through an anti-solvent device, and controlling the content of the anti-solvent entering a solution by adjusting the flow speed of the carrying gas, and further controlling the supersaturation degree of the growth liquid and carrying out crystal growth. According to the method, the crystal growth can be accurately controlled in the crystal growth process, the problems of small crystal size and poor quality of a volatilization method are solved, the problems of large corrosion, long growth period and the like of an acid solution used in a traditional cooling method are solved, and the problem of crystal cracking caused by large temperature difference and large internal stress after the growth is completed is avoided.

Description

Technical Field

[0001] The present invention belongs to the technical field of crystal materials, and in particular relates to a controllable growth device and method for large-size perovskite structure cesium copper iodide single crystal (Cs3Cu2I5 crystal). Background Art

[0002] As the core technology of nuclear radiation monitoring equipment, nuclear radiation detector technology provides core components and technical support for radiation monitoring equipment through the development and application of new radiation-sensitive materials, special processes, and measurement methods. Due to the high fluorescence quantum efficiency and scintillation luminescence efficiency of halide scintillator crystals, they play an important role in high-energy physics, medical imaging, nuclear test monitoring, and geological exploration. The most commonly used detector for radionuclide identification equipment is NaI:Tl. Although the NaI:Tl detector is relatively cheap, its light yield is low and its energy resolution is poor, which restricts the identification time and accuracy of the equipment. In addition to NaI:Tl, the expensive LaBr3:Ce meets the requirements of high light yield and energy resolution, but is limited by its own radiation background and strong deliquescent properties, which restricts the identification ability and long-term stability of the equipment in low-activity scenes.

[0003] Among many new radiation-sensitive materials, iodine copper cesium is a zero-dimensional metal halide scintillator with outstanding advantages such as wide spectrum emission, no self-absorption, high luminous efficiency, high energy resolution, high irradiation stability, low defect quenching probability, and non-deliquescent, and has attracted much attention in nuclear science research. The light yield of this crystal under X-ray and gamma-ray excitation can reach 30,000ph / MeV, and it has an excellent energy resolution of 3.4%@662keV. This crystal is expected to replace the NaI:Tl and LaBr3:Ce energy spectrum detectors currently in service in our army, and become a new generation of scintillator detectors that support the performance improvement and leap forward of nuclear radiation monitoring equipment.

[0004] Compared with other forms of materials, crystalline materials have the advantages of three-dimensional long-range order, no grain boundaries, good stability, etc. They can maximize the intrinsic properties of the reaction materials and are the preferred carriers of various functional devices. In recent years, the main growth methods for iodine copper cesium single crystals are volatilization method and cooling growth method. However, the crystal growth rate of the volatilization method is uncontrollable, and it is not easy to obtain large-sized and high-quality crystals. The cooling method has the disadvantages of a long growth cycle and the long-term use of acid solution, which is easy to corrode the growth equipment.

[0005] Chinese patent CN118422338A (application number CN202410637712.8) discloses a method for preparing a high-quality large-size Cs3Cu2I5 single crystal scintillator, which mixes CsI, CuI, DMF or DMSO and an acidic additive to obtain a precursor solution. The precursor solution is placed in a water bath at 30-50°C, kept warm and stirred for 5-30 minutes, configured into a nearly saturated solution, filtered and collected, and sealed with a sealing film with 1-8 pores of 1 mm, and placed in a constant temperature box at 30-50°C for evaporation and crystallization. When the liquid level is about to submerge the bottom but not submerged, take out the crystal, wash and dry it to obtain a high-quality large-size Cs3Cu2I5 single crystal. However, this method still belongs to the volatilization method, the crystal growth rate is uncontrollable, and multiple seed crystal nucleation points are easily formed, and the success rate of preparing high-quality large-size Cs3Cu2I5 single crystals is low.

[0006] Therefore, it is necessary to develop a controllable growth device and method for large-size perovskite structure cesium copper iodide single crystal (Cs3Cu2I5 crystal) to overcome the above technical problems. Summary of the invention

[0007] The purpose of the present invention is to provide a controllable growth method and device for large-size perovskite structured copper iodine cesium single crystals in order to obtain high-quality, large-size, and excellent-performance copper iodine cesium single crystals in view of the shortcomings of the current large-size perovskite structured copper iodine cesium crystal preparation technology.

[0008] The present invention adopts a temperature-controlled and speed-controlled anti-solvent diffusion method to grow crystals. The method has low equipment cost, simple operation, short growth cycle, good transparency, no cracking, large size of the grown single crystals, and the device is conducive to the discharge of impurities during the crystal growth process, and adopts low-temperature controllable growth to avoid the cracking of the crystals.

[0009] The large-size perovskite structured copper-cesium iodine single crystal described in the present invention refers to a single crystal having a length and a width both greater than 10 mm.

[0010] The technical solution of the present invention is as follows:

[0011] In the first aspect, the present invention provides a controllable growth method for a large-size perovskite structured copper-cesium iodine single crystal, using a controllable growth device for a copper-cesium iodine single crystal, including a growth system, a temperature control system and an anti-solvent diffusion system; the growth system includes a grower 11, a seed crystal rack 13, a rotating motor 14, and a heating container 17; the temperature control system includes a temperature controller 6, a heating medium 8, a thermocouple 9, and a circulation device 10; the anti-solvent diffusion system includes a gas generator 1 and an anti-solvent device 5;

[0012] The carrier gas delivery pipeline of the gas generator 1 is connected to the inside of the anti-solvent device 5, the anti-solvent is placed in the anti-solvent device 5, and the anti-solvent inlet pipeline 15-1 of the anti-solvent device 5 is connected to the inside of the grower 11; the grower 11 is a sealed container, and a seed crystal rack 13 is provided inside, and a rotating motor 14 is connected to the seed crystal rack 13 to drive the seed crystal rack 13 to rotate; the grower 11 is used to place the growth solution, and the growth solution submerges the seed crystal rack 13; the nozzle of the anti-solvent outlet pipeline 15-2 is located above the nozzle of the anti-solvent inlet pipeline 15-1, and the anti-solvent outlet pipeline 15-2 is connected to the exhaust gas treatment device; the grower 11 is placed in a heating container 17, and the heating container 17 is equipped with a heating medium 8 and a thermocouple 9; the thermocouple 9 is connected to the temperature controller 6;

[0013] The specific steps include:

[0014] S1. Preparation of growth solution: dissolving CsI and CuI compounds in DMF, DMSO or a mixed solvent of any proportion of the two compounds according to a molar ratio of 3:1.8-2.5, adding a reducing agent to obtain an iodine copper cesium growth solution, and placing the solution in a grower 11; placing iodine copper cesium seed crystals on a seed crystal rack 13;

[0015] The reducing agent is one or a mixture of two or more of hypophosphorous acid, ascorbic acid, formic acid and oleic acid in any proportion;

[0016] S2: Anti-solvent vapor is introduced: a carrier gas is generated by a gas generator 1, and the carrier gas passes through an anti-solvent vessel 5 filled with an anti-solvent to form anti-solvent vapor, which is introduced into a growth vessel 11;

[0017] The carrier gas is dry nitrogen, argon, air or a mixture of the above gases in any proportion; the carrier gas flow rate is adjusted according to the solution state and the size of the crystal;

[0018] The anti-solvent is one or a mixed solvent of any proportion of two or more selected from dichloromethane, ethanol, methanol, toluene, acetonitrile, isopropanol, and chlorobenzene;

[0019] S3 Iodine copper cesium crystal growth: During the process, the rotating motor 14 keeps rotating, and the growth temperature is 30-60° C. to obtain a large-sized perovskite structured iodine copper cesium single crystal.

[0020] Preferably, the concentration of the iodine copper cesium solution in the growth solution is 0.1-0.7 mol / L, the mass concentration of the reducing agent is 1-7%; the carrier gas flow rate is 0.1-80 cm 3 / sec; the rotating motor 14 maintains a speed of 15 to 100 r / min

[0021] In a second aspect, the present invention provides a controllable growth device for iodine copper cesium single crystal used in the method of the first aspect, comprising a growth system, a temperature control system and an anti-solvent diffusion system; the growth system comprises a grower 11, a seed crystal rack 13, a rotating motor 14, and a heating container 17; the temperature control system comprises a temperature controller 6, a heating medium 8, and a thermocouple 9; the anti-solvent diffusion system comprises a gas generator 1 and an anti-solvent device 5;

[0022] The carrier gas delivery pipeline of the gas generator 1 is connected to the inside of the anti-solvent device 5, in which the anti-solvent is placed, and the anti-solvent inlet pipeline 15-1 of the anti-solvent device 5 is connected to the inside of the grower 11; the grower 11 is a sealed container, and a seed crystal rack 13 is provided inside, and a rotating motor 14 is connected to the seed crystal rack 13 to drive the seed crystal rack 13 to rotate; the grower 11 is used to place the growth solution, and the growth solution submerges the seed crystal rack 13; the mouth of the anti-solvent outlet pipeline 15-2 is located above the mouth of the anti-solvent inlet pipeline 15-1, and the anti-solvent outlet pipeline 15-2 is connected to the exhaust gas treatment device; the grower 11 is placed in a heating container 17, and the heating container 17 is equipped with a heating medium 8 and a thermocouple 9; the thermocouple 9 is connected to the temperature controller 6.

[0023] Preferably, a heater 4 is provided below the anti-solvent device 5 to control the temperature and adjust the concentration of the anti-solvent; a dryer 2 and a gas flow controller 3 are connected between the gas generator 1 and the anti-solvent device 5;

[0024] Furthermore, the grower 11, the dryer 2 and the anti-solventizer 5 are transparent glass containers or quartz containers, and the container wall thickness is 3 to 8 mm.

[0025] Preferably, a heating resistor 7 is further provided at the bottom of the heating container 17, and the heating resistor 7 is connected to a temperature controller 6, and controls the temperature together with a thermocouple 9. The temperature controller 6 has a temperature accuracy of ≤0.05°C and is connected to a thermocouple.

[0026] Preferably, the heating medium 8 is silicone oil, which is placed in a sealed environment; the circulation device 10 and the heating container 17 form a circulation structure to drive the heating medium 8 to flow.

[0027] Preferably, the growth system is wrapped with a heat-insulating material to prevent the external environment temperature fluctuation from affecting the crystal growth.

[0028] Preferably, a flow monitor 16 is provided between the anti-solvent outlet pipe 15-2 and the exhaust gas treatment device.

[0029] Preferably, the connection between the rotating motor 14 and the grower 11 is sealed by an oil seal 12 .

[0030] The working principle of the present invention is:

[0031] The carrier gas flow rate is controlled by a gas flow meter, and the gas flow rate determines the anti-solvent content. When growing crystals, the carrier gas generated by the gas generator carries the anti-solvent into the grower through the anti-solvent device. By adjusting the carrier gas flow rate, the anti-solvent content entering the solution is controlled, and then the supersaturation of the growth solution is controlled to grow crystals.

[0032] The characteristics and beneficial effects of the present invention are as follows:

[0033] (1) The growth device of the present invention has a simple structure and is easy to operate. It can achieve precise control of crystal growth during the crystal growth process, observe the crystal growth status in real time, and make parameter adjustments in real time.

[0034] (2) The device of the present invention is more likely to obtain high-quality, large-sized crystals, and the crystal growth cycle is short. Generally, large-sized crystal growth can be completed in 7 to 20 days, and the crystal size can reach 40×30×20 mm 3 .

[0035] (3) The growth method of the present invention is a solution method. The raw materials are conventional CsI and CuI compounds, the growth solvent is DMF or DMSO, and the anti-solvent is dichloromethane, ethanol, methanol, toluene, acetonitrile, isopropanol, and chlorobenzene. The raw materials are simple and easy to obtain, and no high-purity raw materials are required. The cost is low, the side reactions are few, and the operating conditions are easy to achieve.

[0036] (4) The method of the present invention effectively solves the problem that large-sized, high-quality crystals cannot be obtained by volatilization of such compounds, and the problem that the traditional cooling method uses acid solution, which causes severe corrosion to the equipment and a long crystal growth cycle.

[0037] (5) The method of the present invention has a low growth temperature and low energy consumption. After the crystal growth is completed, the crystal cracking problem caused by the large temperature difference with the environment can be avoided during the removal process.

[0038] (6) After the crystal growth is completed using the growth method of the present invention, the remaining solution can be used to obtain Cs3Cu2I5 polycrystalline raw material through volatilization and inversion crystallization, which can be used for the next growth solution configuration. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a schematic diagram of the Cs3Cu2I5 crystal growth device in Example 1 of the present invention.

[0040] Figure 2 This is a photograph of the Cs3Cu2I5 crystal grown in Example 2 of the present invention.

[0041] Figure 3 This is a photograph of the crystal growing process in Example 3 of the present invention.

[0042] Figure 4This is a photo of the large-sized Cs3Cu2I5 crystal grown in Example 3 of the present invention.

[0043] Figure 5 It is a high-quality Cs3Cu2I5 single crystal wafer processed by Example 3 of the present invention.

[0044] Figure 6 It is the DSC curve of the Cs3Cu2I5 single crystal grown in Example 2 of the present invention.

[0045] Figure 7 It is the UV-visible absorption spectrum of the Cs3Cu2I5 single crystal grown in Example 2 of the present invention.

[0046] Figure 8 It is the fluorescence spectrum of the Cs3Cu2I5 single crystal grown in Example 2 of the present invention. DETAILED DESCRIPTION

[0047] The present invention will be further described below in conjunction with embodiments and drawings. The present invention may be better understood according to the following embodiments, but the present invention is not limited to the following embodiments.

[0048] Example 1

[0049] like Figure 1 As shown, this embodiment relates to a crystal growth device, and the designed growth equipment mainly includes three parts: a growth system, a temperature control system and an anti-solvent diffusion system.

[0050] The growth system mainly includes a grower 11, an oil seal 12, a seed crystal rack 13, a rotating motor 14, an anti-solvent inlet 15-1, and an anti-solvent outlet 15-2. During the crystal growth process, the inside of the grower is sealed to prevent the volatilization of the organic solvent; the seed crystal rack is connected to the rotating motor to make the seed crystal grow in the solution by rotation, and the mechanical vibration of the rotating motor must be small during operation; the upper part of the grower is provided with an anti-solvent inlet and outlet pipe to ensure the entry of the anti-solvent and the discharge of excess gas, and to maintain the internal air pressure balance of the grower.

[0051] The temperature control system mainly includes a temperature controller 6, a heating resistor 7, a heating medium 8, a thermocouple 9, a circulation device 10, a heating container 17 and external insulation facilities. The temperature controller 6 is mainly used to control the temperature during crystal growth and is connected to the thermocouple 9; the heating medium 8 uses an oily substance to keep it in a sealed environment to reduce the heat loss caused by the temperature increase during crystal growth; the circulation device 10 drives the heating medium to flow, making the heating temperature distribution more uniform and providing a stable temperature for the growth liquid; and the external insulation facilities can reduce the heat loss of the entire growth equipment and can also be used to reduce the temperature fluctuation of the growth liquid caused by changes in the external environment.

[0052] The antisolvent diffusion system mainly includes a gas generator 1, a dryer 2, a gas flow controller 3, a heater 4, an antisolvent device 5, and a gas detector 16. The gas generator 1 mainly generates a carrier gas carrying the antisolvent, and is connected to the gas flow controller 3 and the antisolvent device 5; the gas detector 16 adjusts the amount of the antisolvent entering the growth liquid by adjusting the size of the gas flow meter; the gas detector is connected to the growth liquid outlet pipe to determine the speed of the antisolvent entering the growth liquid; in addition, the antisolvent container 5 is arranged in the heating device 4 to ensure that the temperature of the antisolvent is constant during the crystal growth process.

[0053] The carrier gas delivery pipeline of the gas generator 1 is connected to the inside of the anti-solvent device 5, in which the anti-solvent is placed, and the anti-solvent inlet pipeline 15-1 of the anti-solvent device 5 is connected to the inside of the grower 11; the grower 11 is a sealed container, and a seed crystal rack 13 is provided inside, and a rotating motor 14 is connected to the seed crystal rack 13 to drive the seed crystal rack 13 to rotate; the grower 11 is used to place the growth solution, and the growth solution submerges the seed crystal rack 13; the mouth of the anti-solvent outlet pipeline 15-2 is located above the mouth of the anti-solvent inlet pipeline 15-1, and the anti-solvent outlet pipeline 15-2 is connected to the exhaust gas treatment device; the grower 11 is placed in a heating container 17, and the heating container 17 is equipped with a heating medium 8 and a thermocouple 9; the thermocouple 9 is connected to the temperature controller 6. A heater 4 is provided below the antisolvent 5 to control the temperature and adjust the concentration of the antisolvent; a dryer 2 and a gas flow controller 3 are connected between the gas generator 1 and the antisolvent 5; the grower 11, dryer 2 and antisolvent 5 are transparent glass containers or quartz containers with a wall thickness of 3 to 8 mm. A heating resistor 7 is also provided at the bottom of the heating container 17, which is connected to a temperature controller 6 and controls the temperature together with a thermocouple 9. The temperature accuracy of the temperature controller 6 is ≤0.05°C and is connected to a thermocouple. The heating medium 8 is silicone oil, which is in a sealed environment; the circulation device 10 and the heating container 17 form a circulation structure to drive the heating medium 8 to flow. The growth system is wrapped with insulation material to prevent the external environmental temperature fluctuation from affecting the crystal growth. A flow monitor 16 is provided between the antisolvent outlet pipe 15-2 and the exhaust gas treatment device. The connection between the rotating motor 14 and the grower 11 is sealed by an oil seal 12.

[0054] The crystal growth process is that the gas generator 1 generates gas, which is dried by the dryer 2. The dried gas enters the anti-solvent container 5 after the gas flow rate is adjusted by the gas flow controller 3, and then carries the anti-solvent into the crystal grower 11. Finally, the waste gas is brought into the gas detector 16 for subsequent treatment.

[0055] Example 2

[0056] Seed crystal preparation

[0057] (1) CsI and CuI raw materials were dissolved in 20 ml of DMF at a molar ratio of 3:2 to prepare a Cs3Cu2I5 precursor solution with a concentration of 0.4 mol / L. 0.5 ml of H3PO2 was added thereto. The solution was placed on a heating table and stirred at room temperature until the solution became colorless and transparent.

[0058] (2) Filter the clear solution using 0.1 μm filter paper and transfer the filtered solution into a 100 ml glass beaker.

[0059] (3) The resulting solution was sealed with plastic wrap and sealing film at the same time, three holes were pierced on the top of the beaker with a needle, and the beaker was placed in a 500 ml glass beaker containing dichloromethane anti-solvent, and the glass beaker was sealed with plastic wrap and sealing film at the same time.

[0060] (4) As the antisolvent diffuses into the growth solution, the solution gradually reaches saturation, and crystals begin to nucleate and precipitate to grow. When the liquid level is about to cover the top of the beaker but has not yet covered it, the crystals are taken out.

[0061] (5) Wash the crystal with ethanol and place it in a vacuum drying oven to dry it, thereby obtaining a small-sized Cs3Cu2I5 single crystal.

[0062] Example 3

[0063] A method for growing large-size perovskite-structured copper iodine-cesium crystals, using a controlled antisolvent diffusion method, comprises the following steps:

[0064] (1) CsI and CuI raw materials were dissolved in 300 ml of DMF at a molar ratio of 3:2 to prepare a Cs3Cu2I5 precursor solution with a concentration of 0.5 mol / L. 10 ml of H3PO2 was added to the solution. The solution was placed on a heating table and heated and stirred at 40°C until the solution became colorless and transparent.

[0065] (2) Filter the clear solution using 0.1 μm filter paper and transfer the filtered solution into a growth chamber.

[0066] (3) The grower is placed in the growth device of the invention in Example 1, and the seed crystal obtained in Example 2 is placed in a growth bottle to grow crystals by the temperature-controlled and speed-controlled anti-solvent method. The temperature of the growth device is set to 40°C.

[0067] (4) Slowly introduce dichloromethane vapor into the Cs3Cu2I5 precursor solution, and adjust the antisolvent content and the supersaturation of the solution by controlling the flow rate of the carrier gas to grow crystals. The carrier gas flow rate is continuously adjusted according to the size of the crystals, and the initial carrier gas flow rate is 1 cm 3 / sec.

[0068] (5) After a 20-day growth period, large-sized transparent Cs3Cu2I5 crystals can be obtained.

[0069] The crystal growth process of this experiment is shown in the following figure. Figure 3 shown.

[0070] The crystal size is 40×30×20mm. 3 ,like Figure 4 shown.

[0071] Example 4

[0072] The method for growing large-sized Cs3Cu2I5 single crystals is as described in Example 3, except that the solution concentration is 0.52 mol / L, the seed crystal is fixed on the seed crystal rack, and the seed crystal rack is connected to a rotating motor, the seed crystal rotation speed is 30 rpm / min, and the temperature of the growth device is set to 38°C.

[0073] Test Example 1

[0074] The crystal obtained in Example 3 was processed and polished. Figure 5 As shown, a series of transparent, crack-free, inclusion-free, high-quality single wafers of different sizes were obtained.

[0075] The DSC curve of the crystal obtained in Test Example 3 is as follows: Figure 6 As shown. Figure 6 It can be seen that the melting point of Cs3Cu2I5 single crystal is 391℃, the crystallization point temperature is 327℃, and the eutectic temperature is 352℃, which has good stability.

[0076] The single crystal obtained in Example 3 was subjected to solid ultraviolet-visible absorption spectroscopy. The absorption cutoff edge of the crystal was 340nm and the band gap was 3.65eV. Figure 7 shown.

[0077] The single crystal obtained in Example 3 was subjected to fluorescence spectrum test. Figure 8 As shown, the fluorescence emission peak position of the crystal is at 438 nm, and the excitation peak position is at 335 nm.

[0078] Comparative Example 1

[0079] Cs3Cu2I5 single crystals were grown by temperature- and rate-controlled antisolvent diffusion method. The concentration of the growth solution affected the growth of the crystal.

[0080] The concentration of the iodine copper cesium solution in the growth solution is 0.1-0.7 mol / L, and the carrier gas flow rate is 0.1-80 cm 3 / sec, the lower the concentration of the growth solution, the more carrier gas with anti-solvent needs to be introduced, and the size of the grown single crystal is smaller than that of the crystal grown by the high concentration growth solution, but the quality of the grown crystal remains consistent.

[0081] If the carrier gas flow rate is too high, exceeding 80 cm 3 / sec, the amount of anti-solvent introduced into the crystal growth solution will be too high and the quality of the grown crystals will be poor.

[0082] Comparative Example 2

[0083] There are many types of anti-solvents introduced into the Cs3Cu2I5 crystal growth solution, and a solvent that is volatile and can reduce the solubility of the growth solution is selected.

[0084] Selecting dichloromethane, ethanol, methanol, toluene, acetonitrile, isopropanol, chlorobenzene or a mixed solvent of two or more of the above solvents in any proportion as the anti-solvent can grow suitable crystals.

[0085] If the anti-solvent is not suitable, it will be difficult to grow crystals.

[0086] Comparative Example 3

[0087] When 0.1% to 1% H3PO2 is added to the Cs3Cu2I5 precursor solution, the reducing agent content is too low. - It is easily oxidized to form I2 and polyiodide ions (I 3- ), Cu + Easily oxidized to Cu 2+ , which causes Cs3Cu2I5 to be easily oxidized.

[0088] When 7% to 20% H3PO2 is added to the Cs3Cu2I5 precursor solution, the reducing agent content is too much, the solution viscosity increases, and phosphate is easily generated in the later crystal growth process, which is not conducive to the growth of Cs3Cu2I5 single crystals.

Claims

1. A controllable growth method for large-size perovskite structure copper iodine cesium single crystal, characterized in that: A controllable growth device for iodine copper cesium single crystal is used, comprising a growth system, a temperature control system and an anti-solvent diffusion system; the growth system comprises a grower (11), a seed crystal rack (13), a rotating motor (14), and a heating container (17); the temperature control system comprises a temperature controller (6), a heating medium (8), a thermocouple (9), and a circulation device (10); the anti-solvent diffusion system comprises a gas generator (1) and an anti-solvent device (5); The carrier gas delivery pipeline of the gas generator (1) is connected to the inside of the antisolvent device (5), the antisolvent is placed in the antisolvent device (5), and the antisolvent inlet pipeline (15-1) of the antisolvent device (5) is connected to the inside of the grower (11); the grower (11) is a sealed container, and a seed crystal rack (13) is provided inside, and a rotating motor (14) is connected to the seed crystal rack (13) to drive the seed crystal rack (13) to rotate; the grower (11) is used to place a growth solution, and the growth solution covers the seed crystal rack (13); the pipe mouth of the antisolvent outlet pipeline (15-2) is located above the pipe mouth of the antisolvent inlet pipeline (15-1), and the antisolvent outlet pipeline (15-2) is connected to the exhaust gas treatment device; the grower (11) is placed in a heating container (17), and the heating container (17) is equipped with a heating medium (8) and a thermocouple (9); the thermocouple (9) is connected to the temperature controller (6); The specific steps include: S1 Growth solution preparation: CsI and CuI compounds are dissolved in DMF, DMSO or a mixed solvent of the two in any proportion according to a molar ratio of 3:1.8-2.5, and a reducing agent is added to obtain an iodine copper cesium growth solution, which is placed in a grower (11); iodine copper cesium seed crystals are placed on a seed crystal rack (13); The reducing agent is one or a mixture of two or more of hypophosphorous acid, ascorbic acid, formic acid, and oleic acid in any proportion; S2: Anti-solvent vapor is introduced: a carrier gas is generated by a gas generator (1), and the carrier gas passes through an anti-solvent vessel (5) containing an anti-solvent to form anti-solvent vapor, which is introduced into a growth vessel (11); The carrier gas is dry nitrogen, argon, air or a mixture of the above gases in any proportion; the carrier gas flow rate is adjusted according to the solution state and the size of the crystal; The anti-solvent is one or a mixed solvent of any proportion of two or more selected from dichloromethane, ethanol, methanol, toluene, acetonitrile, isopropanol, and chlorobenzene; S3 Iodine copper cesium crystal growth: During the process, the rotating motor (14) keeps rotating, and the growth temperature is 30-60° C. to obtain a large-sized perovskite structured iodine copper cesium single crystal.

2. The controllable growth method for large-size perovskite structure copper iodine cesium single crystal according to claim 1, characterized in that: The concentration of the iodine copper cesium solution in the growth solution is 0.1-0.7 mol / L, the mass concentration of the reducing agent is 1-7%; the carrier gas flow rate is 0.1-80 cm 3 / sec; the rotating motor (14) maintains a rotation speed of 15-100r / min.

3. A controllable growth device for iodine copper cesium single crystal used in the method of claim 1 or 2, characterized in that: It comprises a growth system, a temperature control system and an anti-solvent diffusion system; the growth system comprises a grower (11), a seed crystal rack (13), a rotating motor (14), and a heating container (17); the temperature control system comprises a temperature controller (6), a heating medium (8), and a thermocouple (9); the anti-solvent diffusion system comprises a gas generator (1) and an anti-solvent device (5); The carrier gas delivery pipeline of the gas generator (1) is connected to the inside of the antisolvent device (5), the antisolvent is placed in the antisolvent device (5), and the antisolvent inlet pipeline (15-1) of the antisolvent device (5) is connected to the inside of the grower (11); the grower (11) is a sealed container, and a seed crystal rack (13) is provided inside, and a rotating motor (14) is connected to the seed crystal rack (13) to drive the seed crystal rack (13) to rotate; the grower (11) is used to place a growth solution, and the growth solution covers the seed crystal rack (13); the pipe mouth of the antisolvent outlet pipeline (15-2) is located above the pipe mouth of the antisolvent inlet pipeline (15-1), and the antisolvent outlet pipeline (15-2) is connected to the exhaust gas treatment device; the grower (11) is placed in a heating container (17), and the heating container (17) is equipped with a heating medium (8) and a thermocouple (9); the thermocouple (9) is connected to a temperature controller (6).

4. The controllable growth device of iodine copper cesium single crystal according to claim 3, characterized in that: A heater (4) is provided below the anti-solvent device (5) for controlling the temperature to adjust the concentration of the anti-solvent; a dryer (2) and a gas flow controller (3) are connected between the gas generator (1) and the anti-solvent device (5).

5. The controllable growth device of iodine copper cesium single crystal according to claim 4, characterized in that: The grower (11), dryer (2) and anti-solvent device (5) are transparent glass containers or quartz containers, and the container wall thickness is 3 to 8 mm.

6. The controllable growth device of iodine copper cesium single crystal according to claim 3, characterized in that: A heating resistor (7) is also provided at the bottom of the heating container (17). The heating resistor (7) is connected to a temperature controller (6) and controls the temperature together with a thermocouple (9).

7. The controllable growth device of iodine copper cesium single crystal according to claim 3, characterized in that: The heating medium (8) is silicone oil, which is placed in a sealed environment; the circulation device (10) and the heating container (17) form a circulation structure to drive the heating medium (8) to flow.

8. The controllable growth device of iodine copper cesium single crystal according to claim 3, characterized in that: The growth system is wrapped with heat-insulating material to prevent the external environment temperature fluctuation from affecting the crystal growth.

9. The controllable growth device of iodine copper cesium single crystal according to claim 3, characterized in that: A flow monitor (16) is provided between the anti-solvent outlet pipeline (15-2) and the waste gas treatment device.

10. The controllable growth device of iodine copper cesium single crystal according to claim 3, characterized in that: The connection between the rotating motor (14) and the grower (11) is sealed by an oil seal (12).

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