Metal halide perovskite material capable of absorbing ultraviolet light to visible light to near-infrared light and preparation method and application of metal halide perovskite material

Abstract

The invention discloses a metal halide perovskite material capable of absorbing ultraviolet light, visible light and near-infrared light as well as a preparation method and application of the metal halide perovskite material. The preparation method of the metal halide perovskite material comprises the following steps: adding supramolecules into a solution of a precursor material of metal halide perovskite, and forming a supramolecular hybrid crystal through solution deposition and annealing crystallization induced growth, and further obtaining the metal halide perovskite material with a biphase structure in which the supramolecular hybrid crystal and the perovskite phase coexist. The supramolecules are selected from at least one of crown ether molecules, cyclodextrin, calixarene, calixpyrrole, calixarbazole, cucurbituril and pillararene. The metal halide perovskite material provided by the invention has continuous and wide-spectrum-range light absorption capability from visible light to infrared light, and the prepared photoelectric detector has visible light to infrared light detection performance.

Description

Technical Field

[0001] The invention relates to a metal halide perovskite material with ultraviolet, visible and near-infrared light absorption, a preparation method and application thereof, and belongs to the field of perovskite materials and photoelectric detectors. Background Art

[0002] Since the first report of metal halide perovskites in the device structure of solar cells in 2009, new semiconductor materials such as metal halide perovskites have attracted great attention from the scientific research and industry. This new type of perovskite material has the advantages of adjustable band gap, high defect tolerance, long carrier diffusion length and mobility, strong light absorption ability, and solution-based processability, which has led to in-depth and extensive research on metal halide perovskites and photovoltaic, optoelectronic and other semiconductor devices based on them. However, due to the limitation of the band gap of the perovskite material itself, perovskite photodetectors that take into account the range from ultraviolet light to visible light to near-infrared light have always been a huge challenge for metal halide perovskite photodetectors.

[0003] In recent years, metal halide perovskite photodetectors have made great progress. Researchers have developed perovskite visible light detectors, perovskite X-ray detectors, perovskite α light detectors, and perovskite γ light detectors. Although the band gap of perovskite materials is very suitable for the absorption and detection of visible light, it is still a huge difficulty and challenge to realize a fully compatible photodetector from ultraviolet light to visible light to near-infrared light. Therefore, the realization of perovskite photodetectors that take into account the range from ultraviolet light to visible light to near-infrared light is of great significance and practical value in exploring and using perovskite materials for detection, sensing, imaging and other applications. Summary of the invention

[0004] The purpose of the present invention is to provide a metal halide perovskite material with ultraviolet to visible to near-infrared light absorption and a metal halide perovskite photodetector, which can realize ultraviolet to visible to near-infrared light absorption and light detection.

[0005] The method for preparing the metal halide perovskite material having ultraviolet, visible and near-infrared light absorption provided by the present invention comprises the following steps:

[0006] Adding supramolecular molecules to a solution of a precursor material of a metal halide perovskite, forming supramolecular hybrid crystals by solution deposition and annealing crystallization induction growth, and then obtaining a metal halide perovskite material having a dual-phase structure in which supramolecular hybrid crystals and perovskite phases coexist;

[0007] The supramolecule is selected from at least one of crown ether molecules, cyclodextrin, calixarene, calixpyrrole, calixcarbazole, cucurbituril and pillararene.

[0008] Wherein, the crown ether molecule is selected from one or more of the following compounds:

[0009] 12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6, benzo-18-crown-6, dibenzo-18-crown-6, dibenzo-21-crown-7, dibenzo-24-crown-8, dibenzo-30-crown-10, thiacrown ethers, azacrown ethers, phosphacrown ethers, seleniacrown ethers, spherical ethers and cryptands.

[0010] In the precursor solution, the concentration of the supramolecule is 10-1000 mmol / L, preferably 50-500 mmol / L.

[0011] In the present invention, the metal halide perovskite is an ABX3 compound with a three-dimensional crystal structure; wherein A is an alkali metal ion or a mixture thereof; B is lead, tin, germanium, copper or a mixture thereof; and X is a halide ion, thiocyanate or a mixture thereof.

[0012] Preferably, the metal halide perovskite is selected from one or more of the following materials:

[0013] CsPbI3, CsPbBr3, CsPbCl3, CsPb(I n Br 1-n )3(0 <n<1)、Cs x R 1-x PbI3(0 <x<1)、Cs x R 1- x PbBr3

[0014] (0≤x<1), Cs x R 1-x PbCl3(0≤x<1), Cs x R 1-x Pb(I n Br 1-n )3(0≤x,n≤1).

[0015] The present invention is prepared by any one of the following methods 1)-3):

[0016] 1) Preparing perovskite thin films by spin coating, blade coating, slit coating, spray coating, printing or screen printing;

[0017] 2) Preparation of perovskite single crystals by solution growth method;

[0018] 3) The perovskite powder is prepared by solution volatilization, sintering and reaction.

[0019] Based on the metal halide perovskite material, the present invention further provides a photodetector;

[0020] The photodetector is selected from one or more of the following devices: a photoconductor type photodetector, a photodiode type photodetector, and a phototransistor type photodetector.

[0021] Preferably, the structure of the photodetector is as follows:

[0022] It includes a transparent conductive electrode / substrate, a charge carrier transport layer, a perovskite light absorption layer, a charge carrier transport layer, and an electrode arranged in sequence;

[0023] The perovskite light absorbing layer is made of the metal halide perovskite material;

[0024] The thickness of the perovskite light absorbing layer is 100-10000 nanometers, preferably 200-2000 nanometers.

[0025] The metal halide perovskite material and photodetector with ultraviolet, visible and near-infrared light absorption provided by the present invention have the following advantages compared with the metal halide perovskite material and photodetector without the introduction of supramolecular crown ether (the traditional and mainstream metal halide perovskite with reduced band gap brought about by mixing and doping with tin element):

[0026] 1. Innovation in implementation methods: For metal halide perovskite semiconductor materials, if you want to achieve near-infrared light absorption and light detection, you usually use a large amount of tin mixing or substitution doping to reduce the band gap of the material, expand the light absorption range, and then achieve a certain degree of near-infrared light absorption. For light detection, it is all based on the effective light absorption of the material. For example, the band gap of perovskite FASnI3 is 1.42eV, and its absorption spectrum range can reach 873nm; the narrowest band gap perovskite Cs x MA y FA z Pb m Sn n The band gap of I3 (x+y+z=1, m+n=1) is 1.2 eV, and its absorption spectrum ranges to 1000 nm (not more than 1100 nm at most). The method of the present invention is to introduce a molecule into the metal halide perovskite precursor solution, and through crystallization induction, the formation of new supramolecular hybrid crystals and the polaron effect in the condensed material can achieve visible to infrared light absorption and corresponding light detection performance in the wide-bandgap metal halide perovskite.

[0027] 2. Wider spectral absorption and detection range: The spectral absorption range of conventional lead-tin mixed extremely narrow bandgap metal halide perovskite is about 300-1000nm; the method of the present invention can achieve 300-1600nm light absorption and corresponding light detection capabilities. The wider light absorption and light detection range gives the material greater application potential and more applicable scenarios.

[0028] 3. Higher chemical stability: The narrow-bandgap lead-tin mixed perovskite introduces a large amount of divalent tin, which is chemically extremely unstable and can be easily oxidized to tetravalent tin, which in turn leads to the destruction of the crystal structure and the failure of the photoelectric performance of the material. The method of the present invention does not introduce divalent tin, so it avoids and eliminates the chemical stability problem of narrow-bandgap metal halide perovskite that is easily oxidized.

[0029] 4. Higher humidity stability: Conventional perovskite materials are ionic crystals, and narrow-bandgap lead-tin mixed perovskites are very sensitive to humidity. They are very likely to undergo phase transitions in a humid environment, transforming into yellow-phase materials that do not have visible to near-infrared light absorption activity. The method of the present invention can enable the perovskite material and its photodetector to maintain effective ultraviolet to visible to near-infrared light absorption and light detection capabilities in a humid environment.

[0030] 5. The method is simple and direct, efficient and low-cost: by introducing a low-dose and extremely low-cost molecule into the metal halide perovskite precursor solution, the formation of new supramolecular hybrid crystals is directly induced by thin film crystallization, thereby enabling the metal halide perovskite material and its photodetector to obtain a wider spectrum of light absorption and light detection performance. In the preparation process of the perovskite thin film material of the present invention, no additional complex personnel operation and high equipment investment are required. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a device structure diagram and optical photograph of a photoconductor-type perovskite photodetector;

[0032] Figure 2 The perovskite (CsPbI 1.8 Br 1.2 ) Absorption spectrum of the film;

[0033] Figure 3 The current-time photoelectric response characteristic curve of the photoconductor type photodetector of the perovskite before and after the introduction of 150 mmol / L 15-crown ether-5 under 350-663 nanometer wavelength light;

[0034] Figure 4The current-time photoelectric response characteristic curve of the photoconductor type photodetector of the perovskite before and after the introduction of 150 mmol / L 15-crown ether-5 under the illumination of 700-1087 nanometer wavelength;

[0035] Figure 5 The perovskite (CsPbI) before and after the introduction of 100 mmol / L dibenzo-21-crown ether-7 1.8 Br 1.2 ) Absorption spectrum of the film;

[0036] Figure 6 The current-time photoelectric response characteristic curve of the photoconductor type photodetector of the perovskite before and after the introduction of 100 mmol / L dibenzo-21-crown ether-7 under 350-663 nanometer wavelength light;

[0037] Figure 7 The current-time photoelectric response characteristic curve of the perovskite photoconductor type photodetector under 700-1087 nanometer wavelength light before and after the introduction of 100 mmol / L dibenzo-21-crown ether-7. DETAILED DESCRIPTION

[0038] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0039] Embodiment 1,

[0040] The present invention prepares a typical metal halide perovskite film and a photoelectric detector thereof at laboratory level.

[0041] Preparation of perovskite precursor solution: Select metal halide perovskite CsPbI 1.8 Br 1.2 The precursor components of cesium iodide (CsI), lead iodide (PbI2), and lead bromide (PbBr2) are weighed according to the corresponding stoichiometric ratio. The solvent is DMSO:DMF with a volume ratio of 1:3. The molar concentration of the perovskite precursor solution (calculated as lead element) is 0.8 mol / L. Weigh, stir, dissolve, filter, and set aside. The preparation method of the perovskite solution introducing 15-crown ether-5 is: weigh or measure the required amount of 15-crown ether-5 and add it to the prepared perovskite solution to obtain the required concentration, stir it fully, and dissolve it evenly.

[0042] Cleaning of the substrate: For the perovskite photodetector, the substrate is interdigitated ITO / glass. Ultrasonic clean the substrate with detergent / water, deionized water, and isopropyl alcohol for about 15 minutes respectively, then dry it in a drying oven or blow it dry with nitrogen gas for standby use.

[0043] Pretreatment of substrate: The clean substrate is pretreated with UV-ozone or oxygen plasma for about 15 minutes.

[0044] Preparation of perovskite film: In a glove box, take an appropriate amount of prepared perovskite precursor solution and a perovskite solution introduced with 150 mmol / L 15-crown ether-5 and spin-coat them on a clean substrate (for perovskite photodetectors, the substrate is ITO / glass). 10-15 seconds before the end of spin coating, the spinning solution film is treated with anti-solvent using chlorobenzene. Finally, the spin-coated substrate is placed on a hot plate at 270°C for annealing for about 3-5 minutes to complete the preparation of the perovskite film layer. The thickness is about 350 nanometers.

[0045] Edge cleaning: Remove unnecessary perovskite film areas to expose the electrode area. Finally, the preparation of the photoconductor type perovskite photodetector is completed.

[0046] Figure 1 It is a device structure diagram and optical photograph of the photoconductor type perovskite photodetector of the present invention.

[0047] Device testing: The current-time photoelectric response of the perovskite photodetector was tested under light of different wavelengths.

[0048] like Figure 2 As shown in the figure, the perovskite (CsPbI 1.8 Br 1.2 ) film, it can be seen that compared with the film without the introduction of 15-crown ether-5, the perovskite film after the introduction of 15-crown ether-5 has a strong light absorption in the range of 630-1600 nanometers, which will expand the absorption range of the perovskite film from the visible light region to the near-infrared region.

[0049] The perovskite film and the photodetector thereof before and after the introduction of 150 mmol / L 15-crown ether-5 in this embodiment have the following characteristics:

[0050] (1) Compared with the perovskite film without the introduction of supramolecular crown ether, the perovskite (CsPbI 1.8 Br 1.2 The light absorption characteristics of the film have been expanded from the original 300-630 nanometers to 300-1600 nanometers, achieving an ultra-wide light absorption range covering the ultraviolet, visible and near-infrared regions. Figure 2 shown.

[0051] (2) Compared with the perovskite photodetector without the introduction of supramolecular crown ether, the perovskite (CsPbI 1.8 Br 1.2) photodetector produces a photoelectric response of 700-1087 nanometers outside the optical absorption edge determined by the band gap, achieving ultra-wide photoelectric detection covering the ultraviolet to visible to near-infrared light region. Figure 3 and 4 shown.

[0052] Embodiment 2,

[0053] This embodiment prepares a typical metal halide perovskite film and its photodetector at laboratory level.

[0054] Preparation of perovskite precursor solution: Select metal halide perovskite CsPbI 1.8 Br 1.2 The precursor components of cesium iodide (CsI), lead iodide (PbI2), and lead bromide (PbBr2) are weighed according to the corresponding stoichiometric ratio. The solvent is DMSO:DMF with a volume ratio of 1:3. The molar concentration of the perovskite precursor solution (calculated as lead element) is 0.8 mol / L. Weigh, stir, dissolve, filter, and set aside. The preparation method of the perovskite solution introducing the crown ether (dibenzo-21-crown ether-7) is as follows: weigh or measure the required amount of dibenzo-21-crown ether-7 and add it to the prepared perovskite solution to obtain the required concentration, stir fully, and dissolve evenly.

[0055] Cleaning of the substrate: For the perovskite photodetector, the substrate is interdigitated ITO / glass. Ultrasonic clean the substrate with detergent / water, deionized water, and isopropyl alcohol for about 15 minutes respectively, then dry it in a drying oven or blow it dry with nitrogen gas for standby use.

[0056] Pretreatment of substrate: The clean substrate is pretreated with UV-ozone or oxygen plasma for about 15 minutes.

[0057] Preparation of perovskite film: In a glove box, take an appropriate amount of the prepared perovskite precursor solution and the perovskite solution introduced with the preferred 100 mmol / L dibenzo-21-crown ether-7 and spin-coat them on a clean substrate (for perovskite photodetectors, the substrate is ITO / glass). 10-15 seconds before the end of spin coating, the rotating solution film is treated with chlorobenzene as an anti-solvent. Finally, the spin-coated substrate is placed on a hot plate at 270°C for annealing for about 3-5 minutes to complete the preparation of the perovskite film layer. The thickness is about 350 nanometers.

[0058] Edge cleaning: Remove unnecessary perovskite film areas to expose the electrode area. Finally, the preparation of the photoconductor type perovskite photodetector is completed.

[0059] Device testing: The current-time photoelectric response of the perovskite photodetector was tested under light of different wavelengths.

[0060] Figure 5 The perovskite (CsPbI 1.8 Br 1.2 ) film absorption spectrum, it can be seen that compared with the film without the introduction of dibenzo-21-crown ether-7, the perovskite film after the introduction of dibenzo-21-crown ether-7 showed strong light absorption in the range of 630-1600 nanometers, which will expand the absorption range of the perovskite film from the visible light region to the near-infrared light region.

[0061] The perovskite film and the photodetector thereof before and after the introduction of 100 mmol / L dibenzo-21-crown ether-7 in this embodiment have the following characteristics:

[0062] (1) Compared with the perovskite film without the introduction of supramolecular crown ether, the perovskite film (CsPbI 1.8 Br 1.2 The light absorption characteristics of the film have been expanded from the original 300-630 nanometers to 300-1600 nanometers, achieving an ultra-wide light absorption range covering the ultraviolet, visible and near-infrared regions. Figure 5 shown.

[0063] (2) Compared with the perovskite photodetector without the introduction of supramolecular crown ether, the perovskite (CsPbI 1.8 Br 1.2 ) photodetector produces a photoelectric response of 700-1087 nanometers outside the optical absorption edge determined by the band gap, achieving ultra-wide photoelectric detection covering the ultraviolet to visible to near-infrared light region. Figure 6 and 7 shown.

Claims

1. A method for preparing a metal halide perovskite material having ultraviolet to visible to near-infrared light absorption, comprising the following steps: Adding supramolecular molecules to a solution of a precursor material of a metal halide perovskite, forming supramolecular hybrid crystals by solution deposition and annealing crystallization induction growth, and then obtaining a metal halide perovskite material having a dual-phase structure in which supramolecular hybrid crystals and perovskite phases coexist; The supramolecule is selected from at least one of crown ether molecules, cyclodextrin, calixarene, calixpyrrole, calixcarbazole, cucurbituril and pillararene.

2. The preparation method according to claim 1, characterized in that: The crown ether molecules are selected from one or more of the following compounds: 12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6, benzo-18-crown-6, dibenzo-18-crown-6, dibenzo-21-crown-7, dibenzo-24-crown-8, dibenzo-30-crown-10, thiacrown ethers, azacrown ethers, phosphacrown ethers, seleniacrown ethers, spherical ethers and cryptands.

3. The preparation method according to claim 1 or 2, characterized in that: In the precursor solution, the concentration of the supramolecule is 10-1000 mmol / L.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The metal halide perovskite is an ABX3 compound with a three-dimensional crystal structure; wherein A is an alkali metal ion or a mixture thereof; B is lead, tin, germanium, copper or a mixture thereof; and X is a halogen ion, thiocyanate or a mixture thereof.

5. The preparation method according to claim 4, characterized in that: The metal halide perovskite is selected from one or more of the following materials: CsPbI3、CsPbBr3、CsPbCl3、CsPb(I n Br 1-n )3(0<n<1)、Cs x Rb 1-x PbI3(0<x<1)、Cs x Rb 1-x PbBr3 (0≤x<1)、Cs x Rb 1-x PbCl3(0≤x<1)、Cs x Rb 1-x Pb(I n Br 1-n )3(0≤x,n≤1)。 6. The preparation method according to any one of claims 1 to 5, characterized in that: Prepared by any of the following methods 1)-3): 1) Preparing perovskite thin films by spin coating, blade coating, slit coating, spray coating, printing or screen printing; 2) Preparation of perovskite single crystals by solution growth method; 3) The perovskite powder is prepared by solution volatilization, sintering and reaction.

7. The metal halide perovskite material prepared by the method according to any one of claims 1 to 6.

8. A photodetector based on the metal halide perovskite material according to claim 7.

9. The photoelectric detector according to claim 8, characterized in that: The photodetector is selected from one or more of the following devices: a photoconductor photodetector, a photodiode photodetector, and a phototransistor photodetector; The photodetector comprises a transparent conductive electrode / substrate, a charge carrier transport layer, a perovskite light absorption layer, a charge carrier transport layer, and an electrode arranged in sequence; The perovskite light-absorbing layer is made of the metal halide perovskite material according to claim 7.

10. The photoelectric detector according to claim 9, characterized in that: The thickness of the perovskite light-absorbing layer is 100-10000 nanometers.

Images