Halogen perovskite heterojunction photodetector and preparation method thereof and information communication device
By fabricating a MAPbBr3/MAPbCl3 perovskite heterojunction photodetector, the problems of high cost and instability of existing photodetector materials were solved, and high-sensitivity photodetection and dual-channel optical communication at room temperature were realized.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- FIRST RARE MATERIALS CO LTD
- Filing Date
- 2022-10-14
- Publication Date
- 2026-06-26
AI Technical Summary
Existing photodetector materials suffer from high synthesis costs, complex processes, difficulty in use at room temperature, and poor stability. In particular, halide perovskite thin film detectors exhibit operational instability and low repeatability due to ion migration.
Centimeter-scale MAPbBr3 and MAPbCl3 perovskite single crystals were prepared by inverted temperature crystallization. The surface of the bulk single crystals was then treated with pressure-assisted and precursor solution to form MAPbBr3/MAPbCl3 perovskite heterojunctions, which reduced defect density and suppressed ion migration. Electrodes were then prepared by Au metal evaporation.
It achieves high-sensitivity detection of visible to ultraviolet light at room temperature, with good stability, simple and low-cost fabrication process, and is capable of dual-channel optical communication.
Smart Images
Figure CN115581109B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the fields of organic semiconductor materials and ultraviolet detectors, specifically to a halide perovskite heterojunction photodetector, its preparation method, and an information communication device. Background Technology
[0002] Photodetectors are crucial components in imaging and optical communication applications, and are key parts of many electronic products, such as digital cameras, smartphones, and medical diagnostic instruments. Currently, most commercially available photodetectors are based on traditional inorganic crystalline semiconductors, such as silicon, indium gallium arsenide, amorphous selenium, and carbon nanotubes. However, these semiconductor materials have some inherent defects or long-standing unresolved problems, such as high synthesis costs, complex processes, and difficulty in using them at room temperature. Therefore, the search for novel semiconductor materials with excellent detection performance, simple fabrication processes, and low cost has attracted close attention from researchers.
[0003] In recent years, perovskite materials have shown many excellent properties in the field of photoelectric detection, such as simple synthesis methods, low cost, high carrier mobility, long carrier lifetime, long diffusion length and tunable band gap. Perovskite single crystals have become the most promising photoelectric detection materials due to their outstanding optical and charge transport properties.
[0004] Researchers have designed a series of fast and sensitive visible-to-ultraviolet light detectors based on direct detection methods, taking advantage of the excellent properties exhibited by materials such as MAPbCl3 perovskite thin films and MAPbBr3 perovskite thin films. However, most of the absorbing materials in these detectors suffer from problems such as instability due to ion migration, low repeatability, and low accuracy. Summary of the Invention
[0005] In view of the problems existing in the prior art, the purpose of this disclosure is to provide a halide perovskite heterojunction photodetector, a method for preparing the same, and an information communication device.
[0006] To achieve the above objectives, this disclosure provides a method for fabricating a halide perovskite heterojunction photodetector, comprising the following steps: Step 1, weighing MABr and PbBr2, adding N,N-dimethylformamide (DMF) solution and stirring until the solution becomes clear and transparent, thus obtaining a perovskite (MAPbBr3) precursor solution; Step 2, heating the MAPbBr3 precursor solution, with a programmed temperature increase until reaching 120°C and maintaining this temperature until a single crystal grows, placing the grown single crystal into a new precursor solution until a MAPbBr3 perovskite bulk single crystal is obtained; Step 3, replacing PbBr2 in Step 1 with PbCl2, and repeating the steps. In steps one and two, the solvent is replaced with a 1:1 mixture of DMF and DMSO to prepare MAPbCl3 perovskite bulk single crystals; in step four, a heterojunction is prepared by dropping MAPbBr3 precursor solution into the surface of the (100) plane of MAPbCl3 and MAPbBr3 perovskite bulk single crystals, so that the (100) planes of MAPbCl3 and MAPbBr3 perovskite bulk single crystals are bonded together, a certain pressure is applied to the single crystal heterojunction, and then the single crystal heterojunction is heated; in step five, electrodes are prepared on the prepared perovskite heterojunction to make a photodetector based on MAPbBr3 / MAPbCl3 perovskite heterojunction.
[0007] In some embodiments, in step one, the weight of the MABr is 1.1g-2.3g, and the purity is ≥99.5%.
[0008] In some embodiments, in step one, the weight of the PbBr2 is 3.6g-7.3g, and the purity is ≥99.5%.
[0009] In some embodiments, in step one, the volume of the N,N-dimethylformamide (DMF) solution is 9 ml to 21 ml.
[0010] In some embodiments, the temperature rise in step two is as follows: the initial temperature is set to 60°C, and then increased by 10°C every 30 minutes until the temperature reaches 90°C, and so on until it reaches 120°C.
[0011] In some embodiments, in step four, the concentration of the MAPbBr3 solution is 1M.
[0012] In some embodiments, in step four, the heating condition is to maintain a temperature of 50°C for 24 hours.
[0013] In some embodiments, step five specifically involves: first, placing an electrode mask on the prepared MAPbBr3 / MAPbCl3 perovskite heterojunction; then, using a vapor deposition method, evaporating and depositing Au metal onto the perovskite heterojunction under a vacuum atmosphere, finally obtaining a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction.
[0014] In some embodiments, this application also provides a halide perovskite heterojunction photodetector, which is prepared according to the aforementioned method for preparing a halide perovskite heterojunction photodetector. The detector can rapidly detect light in the 450nm-325nm range at room temperature.
[0015] In some embodiments, the detector can perform dual-channel optical communication tasks.
[0016] In some embodiments, this application also discloses an information communication device, which includes the aforementioned halide perovskite heterojunction photodetector.
[0017] The beneficial effects of this disclosure are as follows:
[0018] The method disclosed herein can prepare centimeter-scale MAPbBr3 / MAPbCl3 perovskite bulk heterojunctions, and can directly grow single crystals on substrates, effectively solving problems such as integrated large-scale production, high compatibility and stability, and long service life. In particular, the prepared visible to ultraviolet light detector has the characteristic of low ion migration. The prepared perovskite photodetector is combined with a laser communication module to realize dual-channel optical communication. Attached Figure Description
[0019] Figure 1 The image shows the XRD phase diagrams of the MAPbBr3 and MAPbCl3 perovskite single crystals from Example 1.
[0020] Figure 2 This is an IV diagram of the perovskite detector in Example 1.
[0021] Figure 3 This is an IT diagram of the perovskite detector in Example 1.
[0022] Figure 4 This is the light response diagram of the perovskite detector in Example 1.
[0023] Figure 5 The response speed diagram of the information communication device prepared in Example 1.
[0024] Figure 6 Oscilloscope waveform of the dual-channel optical communication device prepared in Example 1.
[0025] Figure 7This is a schematic diagram of the optical communication process and modules.
[0026] Figure 8 This is Figure IV of the perovskite detector in Example 3. Detailed Implementation
[0027] [Fabrication method of halide perovskite heterojunction photodetector]
[0028] The following details the fabrication method of the halide perovskite heterojunction photodetector of this application.
[0029] This application discloses a method for fabricating a halide perovskite heterojunction photodetector, comprising the following steps: Step 1, weighing MABr and PbBr2, adding N,N-dimethylformamide (DMF) solution and stirring until the solution becomes clear and transparent, thus obtaining a perovskite (MAPbBr3) precursor solution; Step 2, heating the MAPbBr3 precursor solution, with a programmed temperature increase until reaching 120°C and maintaining it until a single crystal grows, growing for 2 hours, then placing the grown single crystal into a new precursor solution until a MAPbBr3 perovskite bulk single crystal is obtained; Step 3, replacing PbBr2 in Step 1 with PbCl2, and repeating Step 1 and Step 4. Step 2: Replace the solvent with a 1:1 mixture of DMF and DMSO to prepare a MAPbCl3 perovskite bulk single crystal; Step 4: Prepare a heterojunction by dropping a MAPbBr3 precursor solution onto the surface of the (100) plane of the MAPbCl3 and MAPbBr3 perovskite bulk single crystal, so that the (100) planes of the MAPbCl3 and MAPbBr3 perovskite bulk single crystal are bonded together, apply a certain pressure to the single crystal heterojunction, and then heat the single crystal heterojunction; Step 5: Prepare an electrode on the prepared perovskite heterojunction to make a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction.
[0030] This application prepares centimeter-scale MAPbBr3 and MAPbCl3 perovskite single crystals by reverse temperature crystallization. Then, the surface of the bulk single crystals is treated with pressure-assisted and precursor solution treatment to stack the two bulk perovskites together to form a perovskite heterojunction structure, which reduces defect density and suppresses ion migration.
[0031] In some embodiments, in step one, the weight of the MABr is 1.1g-2.3g, and the purity is ≥99.5%.
[0032] In some embodiments, in step one, the weight of the PbBr2 is 3.6g-7.3g, and the purity is ≥99.5%.
[0033] In some embodiments, in step one, the volume of the N,N-dimethylformamide (DMF) solution is 9 ml to 21 ml.
[0034] In some embodiments, the temperature rise in step two is as follows: the initial temperature is set to 60°C, and then increased by 10°C every 30 minutes until the temperature reaches 90°C, and so on until it reaches 120°C.
[0035] In some embodiments, in step four, the concentration of the MAPbBr3 solution is 1M.
[0036] In some embodiments, in step four, the heating condition is to maintain a temperature of 50°C for 24 hours.
[0037] In some embodiments, step five specifically involves: first, placing an electrode mask on the prepared MAPbBr3 / MAPbCl3 perovskite heterojunction; then, using a vapor deposition method, evaporating and depositing Au metal onto the perovskite heterojunction under a vacuum atmosphere, finally obtaining a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction.
[0038] [Halo-based perovskite heterojunction photodetector]
[0039] In some embodiments, a halide perovskite heterojunction photodetector is prepared by the above-described method for preparing a halide perovskite heterojunction photodetector.
[0040] In some embodiments, the detector can rapidly detect light in the 450nm-325nm range at room temperature. The detector is used for rapid detection of light in the 450nm-325nm range at room temperature. Under different light intensities, the detector current value varies significantly, exhibiting high sensitivity, stable operation, and the ability to perform detection directly at room temperature. The fabrication process is simple, low-cost, and pollution-free.
[0041] In some embodiments, the detector can perform dual-channel optical communication tasks.
[0042] [Laser Communication Device]
[0043] A laser communication device is a means of information communication, comprising a laser emitting module for information encoding, generating and emitting laser light, and a laser receiving module for receiving laser light and decoding information. It is a single laser communication module that can be freely placed in any laser communication environment to achieve laser communication, unaffected by wireless shielding or electromagnetic interference, and possesses high security and anti-interference capabilities. It solves the problems of large device size, unstable signal transmission, and inconvenient disassembly and installation due to fixed application scenarios in laser communication devices. (See the schematic diagram of the optical communication process and module proposed in this application.) Figure 7 )
[0044] The laser emitting circuit includes encoding the information received by the microcontroller, encoding the current command sent by the host computer to the microcontroller to form an encoded pulse to drive the laser head, and generating laser under the drive of the encoded pulse.
[0045] The laser receiving circuit includes a perovskite photodetector that receives light information and generates a voltage, which is then transformed and sent to a signal amplification circuit. The received voltage signal is amplified and sent to a modulation and demodulation circuit module. The amplified signal is then decoded to remove interfering noise and obtain an accurate signal.
[0046] The encoding protocol of the laser emitting module includes a handshake protocol and a verification protocol, which can ensure the accuracy of transmitted information.
[0047] In some embodiments, the laser communication device includes the halide perovskite heterojunction photodetector described above in this application.
[0048] [test]
[0049] Example 1
[0050] Step 1: Weigh 1.12g MABr and 3.69g PbBr2 and put them into a glass bottle. Add 10ml of N,N-dimethylformamide (DMF) solution and stir until the solution is clear and transparent. This gives you the precursor solution of perovskite (MAPbBr3).
[0051] Step 2: Heat the MAPbBr3 precursor solution and program the temperature increase. The initial temperature is set to 60℃, and then the temperature is increased by 10℃ every 60 minutes until it reaches 90℃, and then up to 120℃ and held until the single crystal grows. After growing for 2 hours, the grown single crystal is placed in a new precursor solution until a MAPbBr3 perovskite block single crystal is obtained.
[0052] Step 3: Replace PbBr2 in Step 1 with PbCl2, weigh out a certain amount of 337.6 mg of MACl and 1390 mg of PbCl2, repeat Step 1 and Step 2, replace the solvent with a 1:1 mixture of DMF and DMSO, and then prepare MAPbCl3 perovskite block single crystal.
[0053] Step 4: Prepare a heterojunction by dropping a 1M concentration MAPbBr3 precursor solution onto the surface of the (100) plane of the MAPbCl3 and MAPbBr3 perovskite bulk single crystal, so that the (100) plane of the MAPbCl3 and MAPbBr3 perovskite bulk single crystal is bonded together. Then, place the heterojunction on a glass slide and apply a certain pressure to the heterostructure by winding a sub-film. After that, place the device on a heating plate and maintain a temperature of 50°C for 24 hours.
[0054] Step 5: Fabricate electrodes on the prepared perovskite heterojunction to create a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction. The steps are as follows: First, place the electrode mask on the prepared MAPbBr3 / MAPbCl3 perovskite heterojunction. Then, using a vapor deposition method, evaporate and deposit Au metal onto the perovskite heterojunction in a vacuum atmosphere to finally obtain a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction.
[0055] XRD phase diagrams of MAPbBr3 and MAPbCl3 perovskite single crystals are shown below. Figure 1 ;
[0056] IV diagram of the perovskite detector is shown below. Figure 2 ;
[0057] The IT diagram of the perovskite detector is shown below. Figure 3 ;
[0058] The light response diagram of the perovskite detector is shown below. Figure 4 ;
[0059] The response speed of the prepared information communication device is shown in the figure. Figure 5 ;
[0060] The oscilloscope waveform of the dual-channel optical communication device used in the fabricated information communication system is shown below. Figure 6 .
[0061] Example 2
[0062] Step 1: Weigh 1.12g MABr and 3.69g PbBr2 and put them into a glass bottle. Add 10ml of N,N-dimethylformamide (DMF) solution and stir until the solution is clear and transparent. This gives you the precursor solution of perovskite (MAPbBr3).
[0063] Step 2: Heat the MAPbBr3 precursor solution and program the temperature increase. The initial temperature is set to 80℃, and then the temperature is increased by 10℃ every 60 minutes until it reaches 120℃ and is maintained until the single crystal grows. After growing for 2 hours, the grown single crystal is placed in a new precursor solution until a MAPbBr3 perovskite block single crystal is obtained.
[0064] Step 3: Replace PbBr2 in Step 1 with PbCl2, repeat Step 1 and Step 2, weigh out a certain amount of 337.6 mg of MACl and 1390 mg of PbCl2, replace the solvent with a 1:1 mixture of DMF and DMSO, and then prepare MAPbCl3 perovskite block single crystal.
[0065] Step 4: Prepare a heterojunction by dropping a 1M concentration MAPbBr3 precursor solution onto the surface of the (100) plane of the MAPbCl3 and MAPbBr3 perovskite bulk single crystal, so that the (100) plane of the MAPbCl3 and MAPbBr3 perovskite bulk single crystal is bonded together. Then, place the heterojunction on a glass slide and apply a certain pressure to the heterostructure by winding a sub-film. After that, place the device on a heating plate and maintain a temperature of 50°C for 24 hours.
[0066] Step 5: Fabricate electrodes on the prepared perovskite heterojunction to create a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction. The steps are as follows: First, place the electrode mask on the prepared MAPbBr3 / MAPbCl3 perovskite heterojunction. Then, using a vapor deposition method, evaporate and deposit Au metal onto the perovskite heterojunction in a vacuum atmosphere to finally obtain a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction.
[0067] Example 3
[0068] Step 1: Weigh 1.12g MABr and 3.69g PbBr2 and put them into a glass bottle. Add 10ml of N,N-dimethylformamide (DMF) solution and stir until the solution is clear and transparent. This gives you the precursor solution of perovskite (MAPbBr3).
[0069] Step 2: Heat the MAPbBr3 precursor solution and program the temperature increase. The initial temperature is set to 90℃, and then the temperature is increased by 10℃ every 60 minutes until it reaches 120℃ and is maintained until the single crystal grows. After growing for 2 hours, the grown single crystal is placed in a new precursor solution until a MAPbBr3 perovskite block single crystal is obtained.
[0070] Step 3: Replace PbBr2 in Step 1 with PbCl2, repeat Step 1 and Step 2, weigh out a certain amount of 337.6 mg of MACl and 1390 mg of PbCl2, replace the solvent with a 1:1 mixture of DMF and DMSO, and then prepare MAPbCl3 perovskite block single crystal.
[0071] Step 4: Prepare a heterojunction by dropping a 1M concentration MAPbCl3 precursor solution onto the surface of the (100) plane of the MAPbCl3 and MAPbBr3 perovskite bulk single crystals, so that the (100) planes of the MAPbCl3 and MAPbBr3 perovskite bulk single crystals are bonded together. Then, place the heterojunction on a glass slide and apply a certain pressure to the heterostructure by winding a sub-film. After that, place the device on a heating plate and maintain a temperature of 50°C for 24 hours.
[0072] Step 5: Fabricate electrodes on the prepared perovskite heterojunction to create a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction. The steps are as follows: First, place the electrode mask on the prepared MAPbBr3 / MAPbCl3 perovskite heterojunction. Then, using a vapor deposition method, evaporate and deposit Au metal onto the perovskite heterojunction in a vacuum atmosphere to finally obtain a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction.
[0073] In this application, such as Figure 1 The XRD phase diagrams of MAPbBr3 and MAPbCl3 perovskite single crystals are shown. Diffraction peaks are present in the diffraction patterns of all samples. The absence of diffraction peaks for other substances indicates that MAPbBr3 exhibits good crystallinity and high purity, making it a high-quality single crystal. Figure 8 The electrical performance tests of the photodetectors fabricated in the three embodiments showed that, in Example 3, the detector synthesized by dissolving two single-crystal surfaces with a MAPbCl3 precursor solution to form a heterojunction did not exhibit reverse current, while this phenomenon did occur when using a MAPbBr3 precursor solution. Furthermore, the three embodiments revealed that in Example 1, the grown crystal was regular and transparent; therefore, gradually increasing the precursor temperature improved the crystal quality. Higher crystal quality results in a lower defect density in the single crystal. This paper also examines the photoelectric characteristics of the devices using lasers of different powers (450nm and 355nm).
[0074] like Figure 2 As shown, the detector proposed in this paper exhibits bidirectional current, and the voltage increases with increasing voltage.
[0075] like Figure 4 As shown, the detector proposed in this paper can achieve a detectivity of 2.4*10⁻⁶. 10 Jones, with a response rate of up to 1.6 mA / W.
[0076] Figure 3 The image shows the IT diagram of the perovskite detector in Example 1. As the laser is switched on and off at a certain frequency, the current of the device also shows a rectangular change. The baseline of the device does not drift, which also proves the stability of the device.
[0077] Figure 5 The above describes the response speed of the device prepared in Experimental Example 1. When irradiated with a 450nm laser, the rise time of the device is 647μs and the fall time is 683μm; when irradiated with a 355nm laser, the rise time of the device is 584μs and the fall time is 1270μm.
[0078] Figure 6The oscilloscope waveforms of the dual-channel optical communication device prepared in Experiment Example 1 are shown. We simultaneously irradiated the device with light of 450nm and 355nm, respectively, and applied a sinusoidal voltage of -10V to 10V with a frequency of 1Hz across the device. By controlling the laser switch, the information to be transmitted was encoded and decoded, and finally the information "UM" and "SCNU" were obtained.
[0079] Figure 7 This is a schematic diagram of the optical communication process and modules proposed in this paper, which includes a laser emitting module, a laser receiving module, a signal processing and analysis module, and a display module. Different results are displayed on the screen multiple times, demonstrating the repeatability of the device and the feasibility of the optical communication system.
[0080] The above detailed description of this application is intended to enable those skilled in the art to understand and implement its contents, but it should not be construed as limiting the scope of protection of this application. All equivalent changes or modifications made in accordance with the spirit and essence of this application should be included within the scope of this application.
Claims
1. A method for fabricating a halide perovskite heterojunction photodetector, comprising the following steps: Step 1: Weigh MABr and PbBr2, add N,N-dimethylformamide (DMF) solution and stir until the solution is clear and transparent to obtain the perovskite (MAPbBr3) precursor solution; Step 2: Heat the MAPbBr3 precursor solution, program the temperature up to 120°C and hold until a single crystal grows. Place the grown single crystal into a new precursor solution until a MAPbBr3 perovskite bulk single crystal is obtained. Step 3: Replace PbBr2 in Step 1 with PbCl2, repeat Step 1 and Step 2, and replace the solvent with a 1:1 mixture of DMF and DMSO to prepare MAPbCl3 perovskite bulk single crystals. Step 4: Prepare a heterojunction by dropping in a MAPbBr3 precursor solution to dissolve the surface of the (100) plane of the MAPbCl3 and MAPbBr3 perovskite bulk single crystal, so that the (100) plane of the MAPbCl3 and MAPbBr3 perovskite bulk single crystal is bonded together. Apply a certain pressure to the single crystal heterojunction and then heat it. Step 5: Fabricate electrodes on the prepared perovskite heterojunction to create a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction.
2. The method for fabricating a halide perovskite heterojunction photodetector according to claim 1, characterized in that, In step one, the weight of the MABr is 1.1g-2.3g, and the purity is ≥99.5%; In step one, the weight of the PbBr2 is 3.6g-7.3g, and the purity is ≥99.5%. In step one, the volume of the N,N-dimethylformamide (DMF) solution is 9 ml to 21 ml.
3. The method for fabricating a halide perovskite heterojunction photodetector according to claim 1, characterized in that, The temperature rise program in step two is as follows: the initial temperature is set to 60°C, and then increased by 10°C every 30 minutes until the temperature reaches 90°C, and then up to 120°C.
4. The method for fabricating a halide perovskite heterojunction photodetector according to claim 1, characterized in that, In step four, the concentration of the MAPbBr3 solution is 1M.
5. The method for fabricating a halide perovskite heterojunction photodetector according to claim 1, characterized in that, In step four, the heating condition is to maintain a temperature of 50°C for 24 hours.
6. The method for fabricating a halide perovskite heterojunction photodetector according to claim 1, characterized in that, Step 5 involves the following steps: First, an electrode mask is placed on the prepared MAPbBr3 / MAPbCl3 perovskite heterojunction. Then, Au metal is evaporated and deposited on the perovskite heterojunction under a vacuum atmosphere using a vapor deposition method. Finally, a photodetector based on the MAPbBr3 / MAPbCl3 perovskite heterojunction is obtained.
7. A halide perovskite heterojunction photodetector, prepared according to the method of any one of claims 1-6, characterized in that, The detector can quickly detect light in the 450nm-325nm range at room temperature.
8. The halide perovskite heterojunction photodetector according to claim 7, characterized in that, The detector is capable of performing dual-channel optical communication tasks.
9. An information communication device comprising the halide perovskite heterojunction photodetector according to any one of claims 7-8.