CN114678486A - Near-infrared low-lead halogen perovskite photoelectric material, and preparation method and application thereof - Google Patents

Near-infrared low-lead halogen perovskite photoelectric material, and preparation method and application thereof Download PDF

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CN114678486A
CN114678486A CN202210425821.4A CN202210425821A CN114678486A CN 114678486 A CN114678486 A CN 114678486A CN 202210425821 A CN202210425821 A CN 202210425821A CN 114678486 A CN114678486 A CN 114678486A
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perovskite
ito glass
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朱毅辉
杨得鑫
霍德璇
洪嘉伟
饶敏
张宇航
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Hangzhou Dianzi University
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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Abstract

The invention discloses a near-infrared low-lead halogen perovskite photoelectric material, a preparation method and application thereof, wherein the near-infrared low-lead halogen perovskite photoelectric material comprises an electrode, a hole transport layer, an electron transport layer and a luminescent layer; the method is characterized in that: the structure of the luminescent layer material is ABX3A is one of Cs, EA, FA and MA orMultiple types, wherein B is one or more of Pb, Sn, Ge, Mn, Zn, Cd, Co, Cu and Ni, and X is one or more of Cl, Br and I; the invention spin-coats an electron transport layer ZnO/PEIE, a perovskite luminescent layer and a hole transport layer TFB on ITO glass by a spin coating method and then uses a thermal evaporation method to evaporate an electrode MoO3and/Au. The method has the advantages that the electroluminescent efficiency is guaranteed, the difficulty of experimental preparation of the perovskite luminescent device is reduced, and the content of heavy metal lead in the whole device is also reduced.

Description

Near-infrared low-lead halogen perovskite photoelectric material, and preparation method and application thereof
Technical Field
The invention belongs to the field of photoelectronic devices and material science, and particularly relates to a synthesis method and application of a perovskite photoelectric material with low lead and low toxicity, and a device preparation method, wherein the perovskite photoelectric material can be applied to medical equipment, medical detection, medical physiotherapy, spectral analysis, military and civil detection, a new-generation solar cell, detection, signal receiving and emission and the like.
Background
Metal Halide Perovskites (MHPs) have the same or similar crystal structure as the natural mineral calcium titanate, and are suitable for the next generation of high-efficiency and low-cost photoelectric devices including Light Emitting Diodes (LEDs), solar cells, photodetectors and the like. Perovskite light emitting diodes (PeLEDs) have superior properties over conventional inorganic LEDs, such as low fabrication temperature, solution-processable, and tunable bandgap. Compared with organic leds (oleds), PeLED has potential advantages of superior spectral purity and lower cost. These characteristics are advantageous for low cost and large area photovoltaic applications. Since the first discovery in 2014 of perovskite LEDs that can emit light at room temperature, the electroluminescent External Quantum Efficiency (EQE) of perovskite LEDs has increased by more than 20% from 0.76% over only about 4 years. In the aspect of perovskite solar cells, many subject groups at home and abroad aim to realize the aspects of low open-circuit voltage, room-temperature blade coating, large area, high efficiency and the like, and the current Photoelectric Conversion Efficiency (PCE) can be comparable to the traditional silicon-based solar devices. In the field of detectors, the light irradiation condition of the light detector based on the perovskite quantum dot/PDVY-10 planar heterojunction structure is up to 1.64 multiplied by 10 under 450nm light irradiation condition4A W-1The photoelectric response rate of the optical fiber reaches 3.17 multiplied by 1012Jones, photosensitivity up to 5.33X 106And the excellent performances are further improved, and the high-performance composite material has excellent civil and military values.
However, at present, halogen perovskite ABX commonly used in the fields of PelLEDs, solar cells and detectors, etc3The heavy metal element lead (Pb) at the B site of the luminescent layer material has serious environmental and safety hidden dangers. Both the former synthesis and preparation and the latter commercial production, use and recovery have adverse effects on the environment and biological health, thus severely limiting the commercial application. Therefore, it is a hot issue of research in the perovskite field to explore how to reduce the amount of Pb used as much as possible while ensuring the excellent performance of perovskite optoelectronic devices. The most common research idea at present is to use tin ions (Sn) with low toxicity2+) The partial or complete replacement of lead element, the highest photoelectric conversion efficiency of the tin-based perovskite solar cell is 14.6%, while the highest electroluminescent external quantum efficiency of the tin-based perovskite light-emitting diode is only 5.4%, which causes the great difference because of Sn2+Is very easily oxidized into Sn4+Thereby reducing the stability and photoelectric characteristics of the low-toxicity halogen perovskite photoelectric material. Therefore, it is imperative to find better solutions to reduce lead content and maintain high performance perovskite photovoltaic devices.
In order to reduce a plurality of problems caused by lead element and ensure and even improve the performance of perovskite photoelectric devices, the patent mainly aims at the FAPBI (near infrared perovskite material) which is generally researched in the fields of solar devices, perovskite LED (light emitting diode) devices and optical detection3The environmental-friendly element germanium Ge is used for partially replacing Pb, and meanwhile, an amino acid additive is introduced into the perovskite precursor solution, and finally, the perovskite surface defects are effectively passivated and the non-radiative recombination is reduced through a reasonable preparation process. More importantly, the use of Pb element is reduced, the toxicity is reduced, and the electroluminescent efficiency of the near-infrared perovskite LED device is improved. Provides a feasible solution for the research of the current perovskite photoelectric material with low lead and low toxicityAnd good technical foundation is laid for the commercial application of near-infrared perovskite LED devices and related photoelectric devices in the future.
Disclosure of Invention
The invention provides a near-infrared low-lead halogen perovskite photoelectric material, a preparation method and application aiming at the defects of the prior art.
The near-infrared low-lead halogen perovskite photoelectric material comprises an electrode, a hole transport layer, an electron transport layer and a light emitting layer; the method is characterized in that: the structure of the luminescent layer material is ABX3A is one or more of Cs, Ethylammonium, Formamidinium and methylimmonium, wherein B is one or more of Pb, Sn, Ge, Mn, Zn, Cd, Co, Cu and Ni, and X is one or more of Cl, Br and I; wherein Ethyllammonium is abbreviated as EA, Formaminium is abbreviated as FA, and Methalammonium is abbreviated as MA.
Preferably, the material of the light-emitting layer is: FAPBI3。
Preferably, the material of the light-emitting layer is: FAPb1-xGexI3Wherein x is ∈ [0.01,0.2 ]]。
Preferably, the preparation method adopts thermal evaporation, magnetron sputtering, MOCVD, ALD, spraying, printing, solution spin coating and vacuum calcination.
The preparation method of the near-infrared low-lead halogen perovskite photoelectric material specifically comprises the following steps:
step (1), weighing the four materials according to a molar ratio of 2-2.4: 1-x: x: 0.5-0.7, wherein x belongs to [0.01,0.2 ]]And putting the weighed materials into a sample bottle, wherein the first material is as follows: one or more of CsX, EAX, FAX or MAX, and PbX as material II2、SnX2、MnX2、ZnX2、CdX2、CoX2、CuX2、NiX2GeZ as material III2The material IV is 5-amino over ACID, X is Cl, Br or I; z ═ Br or I;
step (2), adding the weighed powder into DMF solvent to ensure that the concentration of the DMF solvent is 0.06-0.13mmol/mL, and obtaining ABX3Precursor bodyA solution;
step (3), adding a stirrer into ABX3Putting the precursor solution into a magnetic stirrer to stir for 2 hours;
filtering the solution to obtain a clear perovskite precursor solution for later use; the aperture of the filtration is 0.22 μm;
drying the ITO glass cleaned by acetone and isopropanol by using high-purity nitrogen;
step (6), putting the ITO glass into a high-power ozone generator, and treating for 30 minutes in a high-concentration ozone environment;
step (7) setting the acceleration of the spin coater to be 5000 r/s2Placing the cleaned ITO glass which is beaten with ozone on a tray of a spin coater at the rotating speed of 5000 r/s for 45-60 s;
step (8), taking ZnO nano solution with the concentration of 5-10 mg/mL, paving the ZnO nano solution on the surface of the ITO glass, and then starting to spin-coat the ZnO nano solution for 45-60s to obtain a zinc oxide film with the thickness of 10-20 nm;
step (9), placing the ITO/zinc oxide film subjected to suspension coating on a baking glue hot table at the temperature of 100-150 ℃ for annealing for 10 minutes to obtain a compact ZnO film;
step (10), after the ITO glass with the zinc oxide film is completely cooled, placing the ITO glass with the zinc oxide film on the well-arranged suspension coater in the step (7), dropwise adding a PEIE solution, and after the solution is completely spread, spin-coating the PEIE solution for 45-60s to obtain the PEIE film with the thickness of 10 nm;
step (11), placing the ITO/zinc oxide/PEIE film subjected to suspension coating on a glue baking hot table at 120 ℃ for annealing for 10 minutes to obtain a compact ITO/zinc oxide/PEIE film;
step (12), after the ITO glass is completely cooled, placing the ITO glass on the suspension coater which is arranged in the step (7), dropwise adding the perovskite precursor solution in the step (4), and after the perovskite precursor solution is completely spread, starting to spin-coat the perovskite precursor solution for 45-60s to obtain a perovskite thin film with the thickness of 50-80 nm;
step (13), placing the ITO glass which is spin-coated with the perovskite thin film on a glue baking hot table at the temperature of 90-110 ℃ for annealing for 16 min;
step (14), after the ITO glass with the perovskite thin film is completely cooled, placing the ITO glass with the perovskite thin film on a suspension coater which is arranged in the step (7), dropwise adding TFB solution with the concentration of 8mg-12mg/mL, and after the TFB solution is completely spread, starting to spin-coat the TFB solution for 45-60s to obtain the TFB thin film with the thickness of 30-50 nm;
step (15), putting the TFB film into an evaporation instrument after the TFB film is completely dried; taking the intermediate transition layer MoO3Placing the powder and Au particles on evaporation boat of evaporation plating apparatus, and using MoO3The particle size of the powder is less than 10 mu m, and 10-30nm MoO is evaporated3Then, evaporating Au with the thickness of 50-100 nm; and finally, packaging the evaporated device.
Preferably, the annealing temperature of the ITO/zinc oxide film subjected to suspension coating placed on a glue baking hot table is 150 ℃; and placing the ITO glass spin-coated with the perovskite thin film on a glue baking hot table for annealing at 100 ℃.
Preferably, the MoO is3The thickness of the evaporation was 15nm, and the thickness of the Au evaporation was 80 nm.
Preferably, the concentration of the TFB solution is 12 mg/mL.
The near-infrared low-lead halogen perovskite photoelectric material is applied to medical equipment, medical detection and chemical spectrum analysis, and can be applied to various photoelectric devices including solar cells, light-emitting diodes, detectors, fluorescent films, fluorescent powder, semiconductor transistors and lasers.
The invention has the beneficial effects that: the invention uses the spin coating method to spin coat the electron transmission layer ZnO/PEIE, the perovskite luminescent layer and the hole transmission layer TFB on the ITO glass, and then uses the thermal evaporation method to evaporate the electrode MoO3and/Au. The method has the advantages that the electroluminescent efficiency is guaranteed, the difficulty in experimental preparation of the perovskite luminescent device is reduced, and the content of heavy metal lead in the whole device is also reduced.
Drawings
FIG. 1 structural characterization of low-lead, low-toxicity near-infrared perovskite thin films using TOPAS-V6 software for different Ge contentsAnd (3) carrying out Rietveld method structure refinement on the perovskite sample to obtain an XRD (X-ray diffraction) spectrum and corresponding unit cell parameters. Fig. a-f correspond to FAPb1-xGexI3Wherein x is 0, 0.01, 0.02, 0.03, 0.05 and 0.1.
FIG. 2 is an Atomic Force Microscope (AFM) profile of a low lead, low toxicity near infrared perovskite thin film, graphs a-f corresponding to FApB1-xGexI3Wherein x is 0, 0.01, 0.02, 0.03, 0.05 and 0.1.
FIG. 3 is a current density-voltage-radiance (J-V-R) profile of a perovskite LED device with 5% Ge substitution.
FIG. 4. FApB with different Ge (0 mol%, 2 mol%, 3 mol%, 5 mol% and 10 mol%) contents1-xGexI3The functional relation (a) and the variation trend (b) between the device luminous efficiency (EQE) and the current density of the perovskite thin film are shown in the figure.
Detailed Description
The FAPB is prepared by adopting a simple and low-cost solution spin-coating method1-xGexI3(x ═ 0, 0.01, 0.02, 0.03, 0.05 and 0.1) perovskite luminescent thin films, and the luminescent properties of the halogen perovskite thin films were further improved by adding a certain amount of 5-aminovaleric acid additive (5 AVA). Then a simple device model is designed, and the lead-less perovskite photoelectric device is manufactured by a mode of combining spin coating and evaporation coating. The crystal structure information of the material was obtained using X-ray diffraction (XRD). The surface morphology of the halogen perovskite thin film was obtained using an Atomic Force Microscope (AFM) and a Scanning Electron Microscope (SEM). Measurement of electroluminescence efficiency (EQE) A Keithley2400 source table and an Everfine OLED-200 commercial OLED Performance analysis System were used.
Example 1:
step (1) mixing FAI and PbI2And 5AVA as per 2: 1: weighing 0.7 mol ratio, and placing into a sample bottle;
step (2), adding the weighed powder into a 1mL DMF solvent, wherein the concentration of the powder is 0.13 mmol/mL;
step (3), adding a stirrer into FApB1-xGexI3Adding the precursor solution into a magnetic stirrer for addingThermally stirring for 2 hours;
filtering the solution by using a disposable needle tube and a filter head which is made of Jinteng, is made of PTFE and has a pore diameter of 0.22 mu m to obtain a clear perovskite precursor solution;
step (5), putting the ITO glass into a high-power ozone generator, and treating for 30 minutes in a high-concentration ozone environment;
step (6) setting the acceleration of the spin coater to be 5000 r/s2Placing the cleaned ITO glass after ozone spraying on a tray of a glue homogenizing machine at the rotating speed of 5000 r/s for 60 s;
step (7), taking 30 mu L of ZnO nano solution with the concentration of 10mg/mL, paving the solution on the surface of the ITO glass, and then starting spin coating for about 60 s;
step (8), placing the ITO/zinc oxide film subjected to suspension coating on a glue baking hot table at 150 ℃ for annealing for 10 minutes to obtain a compact ZnO film;
step (9), after the ITO glass with the zinc oxide film is completely cooled, placing the ITO glass with the zinc oxide film on the suspension coater which is arranged in the step (6), dripping 30 mu L PEIE solution, and after the solution is completely spread, starting spin coating for about 60s to obtain a PEIE film with the thickness of 10 nm;
placing the ITO/zinc oxide/PEIE film subjected to suspension coating on a glue baking hot table at 120 ℃ for annealing for 10 minutes to obtain a compact ITO/zinc oxide/PEIE film;
step (11), after the ITO glass is completely cooled, placing the ITO glass on the suspension coater which is arranged in the step (6), dripping 30 mu L of the perovskite precursor solution in the step (4), and after the solution is completely spread, starting spin coating for about 60 s; obtaining a perovskite thin film with the thickness of 50 nm;
step (12), placing the ITO glass which is spin-coated with the perovskite thin film on a glue baking hot table at 110 ℃ for annealing for 16 min;
step (13), after the ITO glass with the perovskite thin film is completely cooled, placing the ITO glass with the perovskite thin film on a suspension coater which is arranged in the step (7), dripping 30 mu L of TFB solution with the concentration of 8mg/mL, and after the solution is completely spread, starting spin coating for about 60s to obtain the TFB thin film with the thickness of 30 nm;
step (14), putting the TFB film into an evaporation plating instrument after the TFB film is completely dried; taking the intermediate transition layer MoO3Putting the powder (with particle diameter less than 10 μm) and electrode Au particles on a corresponding evaporation boat of an evaporation plating instrument, and evaporating 15nmMoO3Then evaporating 80nm Au; and finally, packaging the evaporated device, and testing the electroluminescent efficiency, current density-voltage-radiance and other photoelectric properties of the device.
Shown in fig. 1 as FAPb1-xGexI3(x ═ 0, 0.01, 0.02, 0.03, 0.05, and 0.1) fine maps of XRD structures and corresponding unit cell parameters of the films, the positions of diffraction peaks corresponding to the maps were substantially identical to those of undoped when Ge element was doped. From the unit cell parameters of the respective formulations, the doping with Ge element still maintains the same cubic system as the undoped one, but for the side length a, the doping is reduced, which is reflected in the reduction of the unit cell after doping. FIG. 2 is a perovskite FApB1-xGexI3(x ═ 0, 0.01, 0.02, 0.03, 0.05, and 0.1) by Atomic Force Microscopy (AFM). Through comparison, the following results are found: the replacement of Ge element can improve the film quality to some extent. FIG. 3 is a current density-voltage-radiance (J-V-R) profile of a perovskite LED device with 5% Ge substitution, which was found to have a maximum radiance of about 420W/m2. FIG. 4 is a functional relationship between device luminous efficiency (EQE) and current density of perovskite thin films with different Ge (0 mol%, 2 mol%, 3 mol%, 5 mol% and 10 mol%) contents, wherein when the replacement amount of Ge is 5%, the efficiency value EQE of the device reaches the highest value (17.3%), which indicates that partial replacement of Ge not only reduces the amount of Pb, but also improves the photoelectric performance of the device.
Example 2:
step (1) mixing FAI and PbI2And 5AVA as per 2: 1: weighing 0.5 mol ratio, and placing into a sample bottle;
step (2), adding the weighed powder into a 1mL DMF solvent, wherein the concentration of the powder is 0.13 mmol/mL;
step (3), adding a stirring piece into FApB1-xGexI3Adding the precursor solution into a magnetic stirrer, heating and stirringStirring for 2 h;
filtering the solution by using a disposable needle tube and a filter head with a Jinteng brand, PTFE material and 0.22 mu m of pore diameter to obtain a clear perovskite precursor solution;
step (5), putting the ITO glass into a high-power ozone generator, and treating for 30 minutes in a high-concentration ozone environment;
step (6) setting the acceleration of the spin coater to be 5000 r/s2Placing the cleaned ITO glass which is beaten with ozone on a tray of a spin coater at the rotating speed of 5000 r/s for 60 s;
step (7), taking 30 mu L of ZnO nano solution with the concentration of 10mg/mL, paving the solution on the surface of ITO glass, and then starting spin coating for about 60s to obtain a zinc oxide film with the thickness of 17 nm;
step (8), placing the ITO/zinc oxide film subjected to suspension coating on a baking glue hot table at 100 ℃ for annealing for 10 minutes to obtain a compact ZnO film;
step (9), after the ITO glass with the zinc oxide film is completely cooled, placing the ITO glass with the zinc oxide film on the suspension coater which is arranged in the step (6), taking a 30 mu LPEIE solution to drop in, and after the solution is completely spread, starting spin coating for about 60 s; obtaining a PEIE film with the thickness of 10 nm;
placing the ITO/zinc oxide/PEIE film subjected to suspension coating on a glue baking hot table at 120 ℃ for annealing for 10 minutes to obtain a compact ITO/zinc oxide/PEIE film;
step (11), after the ITO glass is completely cooled, placing the ITO glass on the suspension coater which is arranged in the step (6), dripping 40 mu L of the perovskite precursor solution in the step (4), and after the solution is completely spread, starting spin coating for about 60 s; obtaining a perovskite thin film with the thickness of 80 nm;
step (12), placing the ITO glass which is coated with the perovskite thin film in a spin coating manner on a glue baking hot table at 90 ℃ for annealing for 16 min;
step (13), after the ITO glass with the perovskite thin film is completely cooled, placing the ITO glass with the perovskite thin film on a suspension coater which is arranged in the step (7), dripping 30 mu L of TFB solution with the concentration of 12mg/mL, and after the solution is completely spread, starting spin coating for about 60s to obtain the TFB thin film with the thickness of 50 nm;
step (14), putting the TFB film into an evaporation instrument after the TFB film is completely dried; taking the intermediate transition layer MoO3Putting the powder (with particle diameter less than 10 μm) and electrode Au particles on a corresponding evaporation boat of an evaporation plating instrument, and evaporating 15nmMoO3Then, evaporating 80nm Au; and finally, packaging the evaporated device, and testing the electroluminescent efficiency, current density-voltage-radiance and other photoelectric properties of the device.
Example 3:
step (1) mixing FAI and PbI2And 5AVA as per 2.4: 1: weighing 0.7 mol ratio, and placing into a sample bottle;
step (2), adding the weighed powder into a 1mL DMF solvent, wherein the concentration of the powder is 0.06 mmol/mL;
step (3), adding a stirring piece into FApB1-xGexI3Putting the precursor solution into a magnetic stirrer, heating and stirring for 2 hours;
filtering the solution by using a disposable needle tube and a filter head with a Jinteng brand, PTFE material and 0.22 mu m of pore diameter to obtain a clear perovskite precursor solution;
step (5), putting the ITO glass into a high-power ozone generator, and treating for 30 minutes in a high-concentration ozone environment;
step (6) setting the acceleration of the spin coater to be 5000 r/s2Placing the cleaned ITO glass which is beaten with ozone on a tray of a spin coater at the rotating speed of 5000 r/s for 60 s;
step (7), taking 30 mu L of ZnO nano solution with the concentration of 6mg/mL, paving the solution on the surface of the ITO glass, and then starting spin coating for about 60 s; obtaining a zinc oxide film with the thickness of 12 nm;
step (8), placing the ITO/zinc oxide film subjected to suspension coating on a glue baking hot table at the temperature of 150 ℃ for annealing for 10 minutes to obtain a compact ZnO film;
step (9), after the ITO glass with the zinc oxide film is completely cooled, placing the ITO glass with the zinc oxide film on the suspension coater which is arranged in the step (6), dripping 30 mu L PEIE solution, and after the solution is completely spread, starting spin coating for about 60s to obtain a PEIE film with the thickness of 10 nm;
placing the ITO/zinc oxide/PEIE film subjected to suspension coating on a glue baking hot table at 120 ℃ for annealing for 10 minutes to obtain a compact ITO/zinc oxide/PEIE film;
step (11), after the ITO glass is completely cooled, placing the ITO glass on the suspension coater which is arranged in the step (6), dripping 30 mu L of the perovskite precursor solution in the step (4), and after the solution is completely spread, starting spin coating for about 60s to obtain a perovskite thin film with the thickness of 60 nm;
step (12), placing the ITO glass which is spin-coated with the perovskite thin film on a glue baking hot table at 110 ℃ for annealing for 16 min;
step (13), after the ITO glass with the perovskite thin film is completely cooled, placing the ITO glass with the perovskite thin film on the well-arranged suspension coater in the step (7), dropwise adding 30 mu L of TFB solution with the concentration of 10mg/mL, and after the solution is completely spread, starting to spin-coat for about 60s to obtain the TFB thin film with the thickness of 36 nm;
step (14), putting the TFB film into an evaporation plating instrument after the film is completely dried; taking the intermediate transition layer MoO3Putting the powder (with particle diameter less than 10 μm) and electrode Au particles on a corresponding evaporation boat of an evaporation plating instrument, and evaporating 20nm MoO3Then, evaporating 100nm Au; and finally, packaging the evaporated device, and testing the photoelectric properties of the evaporated device, such as electroluminescent efficiency, current density-voltage-radiance and the like.
Example 4:
step (1) mixing FAI and PbI2And 5AVA as per 2: 1: 1, and putting the mixture into a sample bottle;
step (2), adding the weighed powder into a 1mL DMF solvent, wherein the concentration of the powder is 0.13 mmol/mL;
step (3), adding a stirrer into FApB1-xGexI3Putting the precursor solution into a magnetic stirrer, heating and stirring for 2 hours;
filtering the solution by using a disposable needle tube and a filter head which is made of Jinteng, is made of PTFE and has a pore diameter of 0.22 mu m to obtain a clear perovskite precursor solution;
step (5), putting the ITO glass into a high-power ozone generator, and treating for 30 minutes in a high-concentration ozone environment;
step (6) setting the acceleration of the spin coater to be 5000 r/s2Placing the cleaned ITO glass after ozone spraying on a tray of a glue homogenizing machine at the rotating speed of 5000 r/s for 60 s;
step (7), taking 30 mu L of ZnO nano solution with the concentration of 8mg/mL, paving the solution on the surface of the ITO glass, and then starting spin coating for about 60s to obtain a zinc oxide film with the thickness of 15 nm;
step (8), placing the ITO/zinc oxide film subjected to suspension coating on a baking glue hot table at 120 ℃ for annealing for 10 minutes to obtain a compact ZnO film;
step (9), after the ITO glass with the zinc oxide film is completely cooled, placing the ITO glass with the zinc oxide film on the suspension coater which is arranged in the step (6), dripping 30 mu L PEIE solution, and after the solution is completely spread, starting spin coating for about 60s to obtain a PEIE film with the thickness of 10 nm;
placing the ITO/zinc oxide/PEIE film subjected to suspension coating on a glue baking hot table at 120 ℃ for annealing for 10 minutes to obtain a compact ITO/zinc oxide/PEIE film;
step (11), after the ITO glass is completely cooled, placing the ITO glass on the suspension coater which is arranged in the step (6), dripping 35 mu L of the perovskite precursor solution in the step (4), and after the solution is completely spread, starting spin coating for about 60s to obtain a perovskite thin film with the thickness of 60 nm;
step (12), placing the ITO glass which is coated with the perovskite thin film in a spin coating manner on a baking glue hot table at 100 ℃ for annealing for 16 min;
step (13), after the ITO glass with the perovskite thin film is completely cooled, placing the ITO glass with the perovskite thin film on a suspension coater which is arranged in the step (7), dripping 30 mu L of TFB solution with the concentration of 10mg/mL, and after the solution is completely spread, starting spin coating for about 60s to obtain the TFB thin film with the thickness of 38 nm;
step (14), putting the TFB film into an evaporation plating instrument after the film is completely dried; taking the intermediate transition layer MoO3Powder (grain diameter less than 10 μm) and electrode Au particles are put into corresponding of evaporation plating instrumentOn the evaporation boat, 10nmMoO is evaporated3Then, evaporating Au of 50 nm; and finally, packaging the evaporated device, and testing the photoelectric properties of the evaporated device, such as electroluminescent efficiency, current density-voltage-radiance and the like.
Example 5:
step (1) mixing FAI and PbI2And 5AVA as per 2.4: 1: weighing 0.5 mol ratio, and placing into a sample bottle;
step (2), adding the weighed powder into a 1mL DMF solvent, wherein the concentration of the powder is 0.13 mmol/mL;
step (3), adding a stirrer into FApB1-xGexI3Putting the precursor solution into a magnetic stirrer, heating and stirring for 2 hours;
filtering the solution by using a disposable needle tube and a filter head which is made of Jinteng, is made of PTFE and has a pore diameter of 0.22 mu m to obtain a clear perovskite precursor solution;
step (5), putting the ITO glass into a high-power ozone generator, and treating for 30 minutes in a high-concentration ozone environment;
step (6) setting the acceleration of the spin coater to be 5000 r/s2Placing the cleaned ITO glass which is beaten with ozone on a tray of a spin coater at the rotating speed of 5000 r/s for 60 s;
step (7), taking 30 mu L ZnO nano solution with the concentration of 9mg/mL, paving the solution on the surface of the ITO glass, and then starting spin coating for about 60 s; obtaining a zinc oxide film with the thickness of 14 nm;
step (8), placing the ITO/zinc oxide film subjected to suspension coating on a glue baking hot table at the temperature of 150 ℃ for annealing for 10 minutes to obtain a compact ZnO film;
step (9), after the ITO glass with the zinc oxide film is completely cooled, placing the ITO glass with the zinc oxide film on the suspension coater which is arranged in the step (6), taking a 30 mu LPEIE solution to drop in, and after the solution is completely spread, starting spin coating for about 60 s; obtaining a PEIE film with the thickness of 10 nm;
placing the ITO/zinc oxide/PEIE film subjected to suspension coating on a glue baking hot table at 120 ℃ for annealing for 10 minutes to obtain a compact ITO/zinc oxide/PEIE film;
step (11), after the ITO glass is completely cooled, placing the ITO glass on the suspension coater which is arranged in the step (6), dripping 30 mu L of the perovskite precursor solution in the step (4), and after the solution is completely spread, starting spin coating for about 60 s; obtaining a perovskite thin film with the thickness of 60 nm;
step (12), placing the ITO glass which is spin-coated with the perovskite thin film on a glue baking hot table at 110 ℃ for annealing for 16 min;
step (13), after the ITO glass with the perovskite thin film is completely cooled, placing the ITO glass with the perovskite thin film on the well-arranged suspension coater in the step (7), dropwise adding 30 mu L of TFB solution with the concentration of 12mg/mL, and after the solution is completely spread, starting spin coating for about 60 s; obtaining a TFB film with the thickness of 40 nm;
step (14), putting the TFB film into an evaporation plating instrument after the film is completely dried; taking the intermediate transition layer MoO3Putting the powder (with particle diameter less than 10 μm) and electrode Au particles on a corresponding evaporation boat of an evaporation plating instrument, and evaporating 15nmMoO3Then, evaporating 100nm Au; and finally, packaging the evaporated device, and testing the electroluminescent efficiency, current density-voltage-radiance and other photoelectric properties of the device.
Example 6:
step (1) mixing FAI and PbI2And 5AVA as per 2.4: 1: weighing 0.7 mol ratio, and placing into a sample bottle;
step (2), adding the weighed powder into a 1mL DMF solvent, wherein the concentration of the powder is 0.13 mmol/mL;
step (3), adding a stirrer into FApB1-xGexI3Putting the precursor solution into a magnetic stirrer, heating and stirring for 2 hours;
filtering the solution by using a disposable needle tube and a filter head with a Jinteng brand, PTFE material and 0.22 mu m of pore diameter to obtain a clear perovskite precursor solution;
step (5), putting the ITO glass into a high-power ozone generator, and treating for 30 minutes in a high-concentration ozone environment;
step (6), setting the acceleration of the spin coater to 4000 revolutions per second2Rotational speed of4000 revolutions per second for 45 seconds, and putting the cleaned ITO glass which is beaten with ozone on a tray of a spin coater;
step (7), taking 30 mu L of ZnO nano solution with the concentration of 7mg/mL, paving the solution on the surface of the ITO glass, and then starting spin coating for about 45s to obtain a zinc oxide film with the thickness of 11 nm;
step (8), placing the ITO/zinc oxide film subjected to suspension coating on a glue baking hot table at the temperature of 150 ℃ for annealing for 10 minutes to obtain a compact ZnO film;
step (9), after the ITO glass with the zinc oxide film is completely cooled, placing the ITO glass with the zinc oxide film on the suspension coater which is arranged in the step (6), dripping 30 mu L PEIE solution, and after the solution is completely spread, starting to spin-coat for about 45s to obtain a PEIE film with the thickness of 10 nm;
placing the ITO/zinc oxide/PEIE film subjected to suspension coating on a glue baking hot table at 120 ℃ for annealing for 10 minutes to obtain a compact ITO/zinc oxide/PEIE film;
step (11), after the ITO glass is completely cooled, placing the ITO glass on the suspension coater which is arranged in the step (6), dripping 30 mu L of the perovskite precursor solution in the step (4), and after the solution is completely spread, starting spin coating for about 45 s; obtaining a perovskite thin film with the thickness of 50 nm;
step (12), placing the ITO glass which is spin-coated with the perovskite thin film on a baking glue hot table at 100 ℃ for annealing for 16 min;
step (13), after the ITO glass with the perovskite thin film is completely cooled, placing the ITO glass with the perovskite thin film on a suspension coater which is arranged in the step (7), dripping 30 mu L of TFB solution with the concentration of 12mg/mL, and after the solution is completely spread, starting spin coating for about 45s to obtain the TFB thin film with the thickness of 35 nm;
step (14), putting the TFB film into an evaporation plating instrument after the film is completely dried; taking the intermediate transition layer MoO3Putting the powder (with particle diameter less than 10 μm) and electrode Au particles on a corresponding evaporation boat of an evaporation plating instrument, and evaporating 15nmMoO3Then, 70nm Au is evaporated; and finally, packaging the evaporated device, and testing the electroluminescent efficiency, current density-voltage-radiance and other photoelectric properties of the device.

Claims (9)

1. The near-infrared low-lead halogen perovskite photoelectric material comprises an electrode, a hole transport layer, an electron transport layer and a light emitting layer; the method is characterized in that: the structure of the luminescent layer material is ABX3A is one or more of Cs, ethyllamonium, Formamidinium and methylilamonium, wherein B is one or more of Pb, Sn, Ge, Mn, Zn, Cd, Co, Cu and Ni, and X is one or more of Cl, Br and I; wherein Ethyllamonium is abbreviated as EA, Formaminium is abbreviated as FA, and Methalamonium is abbreviated as MA.
2. The near-infrared low-lead-halogen perovskite photoelectric material according to claim 1, characterized in that: the luminescent layer material is: FAPbI3。
3. The near-infrared low-lead-halogen perovskite photoelectric material according to claim 1, characterized in that: the luminescent layer material is: FAPb1-xGexI3Wherein x is ∈ [0.01,0.2 ]]。
4. The method for preparing a near-infrared low-lead-halogen perovskite photoelectric material according to claim 1, characterized by comprising: the preparation method adopts thermal evaporation, magnetron sputtering, MOCVD, ALD, spraying, printing, solution spin-coating and vacuum calcination methods.
5. The method for preparing a near-infrared low-lead-halogen perovskite photoelectric material according to claim 1, characterized by comprising: the method specifically comprises the following steps:
step (1), weighing the four materials according to a molar ratio of 2-2.4: 1-x: x: 0.5-0.7, wherein x belongs to [0.01,0.2 ]]And putting the weighed materials into a sample bottle, wherein the first material is as follows: one or more of CsX, EAX, FAX or MAX, and the second material is PbX2、SnX2、MnX2、ZnX2、CdX2、CoX2、CuX2、NiX2One or more of (a) and (b), material IIIIs GeZ2The material IV is 5-amino over ACID, X is Cl, Br or I; z ═ Br or I;
step (2), adding the weighed powder into a DMF solvent to ensure that the concentration of the DMF solvent is 0.06-0.13mmol/mL to obtain ABX3Precursor solution;
step (3), adding a stirrer into ABX3Putting the precursor solution into a magnetic stirrer to stir for 2 hours;
filtering the solution to obtain a clear perovskite precursor solution for later use; the aperture of the filtration is 0.22 μm;
drying the ITO glass cleaned by acetone and isopropanol by using high-purity nitrogen;
step (6), putting the ITO glass into a high-power ozone generator, and treating for 30 minutes in a high-concentration ozone environment;
step (7) setting the acceleration of the spin coater to be 5000 r/s2Placing the cleaned ITO glass which is beaten with ozone on a tray of a spin coater at the rotating speed of 5000 r/s for 45-60 s;
step (8), taking ZnO nano solution with the concentration of 5-10 mg/mL, paving the ZnO nano solution on the surface of the ITO glass, and then starting to spin-coat the ZnO nano solution for 45-60s to obtain a zinc oxide film with the thickness of 10-20 nm;
step (9), placing the ITO/zinc oxide film subjected to suspension coating on a baking glue hot table at the temperature of 100-150 ℃ for annealing for 10 minutes to obtain a compact ZnO film;
step (10), after the ITO glass with the zinc oxide film is completely cooled, placing the ITO glass with the zinc oxide film on the suspension coater which is arranged in the step (7), taking the PEIE solution to be dripped, and after the solution is completely spread, spin-coating the PEIE solution for 45-60s to obtain the PEIE film with the thickness of 10 nm;
step (11), placing the ITO/zinc oxide/PEIE film subjected to suspension coating on a glue baking hot table at 120 ℃ for annealing for 10 minutes to obtain a compact ITO/zinc oxide/PEIE film;
step (12), after the ITO glass is completely cooled, placing the ITO glass on the suspension coater which is arranged in the step (7), dropwise adding the perovskite precursor solution in the step (4), and after the perovskite precursor solution is completely spread, starting to spin-coat the perovskite precursor solution for 45-60s to obtain a perovskite thin film with the thickness of 50-80 nm;
step (13), placing the ITO glass which is spin-coated with the perovskite thin film on a glue baking hot table at the temperature of 90-110 ℃ for annealing for 16 min;
step (14), after the ITO glass with the perovskite thin film is completely cooled, placing the ITO glass with the perovskite thin film on a suspension coater which is arranged in the step (7), dropwise adding TFB solution with the concentration of 8mg-12mg/mL, and after the TFB solution is completely spread, starting to spin-coat the TFB solution for 45-60s to obtain the TFB thin film with the thickness of 30-50 nm;
step (15), putting the TFB film into an evaporation instrument after the TFB film is completely dried; taking the intermediate transition layer MoO3Putting the powder and electrode Au particles on a corresponding evaporation boat of an evaporation plating instrument, and firstly evaporating 10-30nm MoO3Then, evaporating Au with the thickness of 50-100 nm; and finally, packaging the evaporated device.
6. The method for preparing a near-infrared low-lead-halogen perovskite photoelectric material according to claim 5, wherein the method comprises the following steps: the annealing temperature of the ITO/zinc oxide film subjected to suspension coating and placed on a glue baking hot table is 150 ℃; and placing the ITO glass spin-coated with the perovskite thin film on a glue baking hot table for annealing at 100 ℃.
7. The method for preparing a near-infrared low-lead-halogen perovskite photoelectric material according to claim 5, wherein the method comprises the following steps: the MoO3The thickness of the evaporation was 15nm, and the thickness of the Au evaporation was 80 nm.
8. The method for preparing a near-infrared low-lead-halogen perovskite photoelectric material according to claim 5, wherein the method comprises the following steps: the concentration of the TFB solution is 12 mg/mL.
9. The application of the near-infrared low-lead halogen perovskite photoelectric material is characterized in that: the near-infrared low-lead halogen perovskite photoelectric material is applied to medical equipment, medical detection and chemical spectrum analysis, and can be applied to various photoelectric devices including solar cells, light-emitting diodes, detectors, fluorescent films, fluorescent powder, semiconductor transistors and lasers.
CN202210425821.4A 2022-04-21 2022-04-21 Near-infrared low-lead halogen perovskite photoelectric material, and preparation method and application thereof Pending CN114678486A (en)

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