CN115124256A - Preparation method of all-inorganic perovskite thin film and narrow-band photoelectric detector - Google Patents
Preparation method of all-inorganic perovskite thin film and narrow-band photoelectric detector Download PDFInfo
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- C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
The invention provides a preparation method of an all-inorganic perovskite thin film and a narrow-band photoelectric detector. According to the invention, a certain amount of lead halide powder and cesium halide powder are respectively dissolved in different solvents to prepare perovskite powder, the perovskite powder is dissolved in DMSO and DMF to obtain a perovskite precursor solution, the ALS spraying process is adopted to obtain the perovskite thin film, the perovskite solubility is improved, the quality of the thin film is optimized, and the finally obtained perovskite thin film has the advantages of good compactness, high quality and high crystallinity, and is beneficial to charge transfer. After the perovskite thin film is obtained, the perovskite thin film is further subjected to high-temperature heating treatment, crystal particles of the thin film subjected to the heating treatment become large and even can span the thickness of the whole thin film, all the perovskite thin films show good continuity and flatness, the crystallization rate of the thin film is increased, the crystallization quality of the thin film is improved, defects in crystal lattices can be reduced, and the flatness of the thin film and the transmission capability of current carriers are optimized.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, relates to a photoelectric conversion technology, and particularly relates to a preparation method of an all-inorganic perovskite thin film and a narrow-band photoelectric detector.
Background
Photodetectors, also known as photosensors, can convert optical signals into electrical signals. When the photoelectric material is irradiated by light, photon energy is equal to or larger than the band gap, photon-generated carriers are generated to form an electric signal. The method has great potential and wide application in the fields of spectrum, optical communication, environmental monitoring, biological detection and the like. The photodetectors may be classified into broadband photodetectors and narrowband photodetectors according to the magnitude of the spectral response width. The broadband photodetector can detect a relatively wide wavelength range, has a flat and high External Quantum Efficiency (EQE) spectrum in the detected wavelength range, and is mainly applied to multicolor photo detection and imaging. In contrast, narrow band photodetectors, which have small full width at half maximum (FWHM) and high EQE values in a specific and relatively narrow wavelength range, are mainly used for light detection at specific wavelengths, such as bio-detection, intelligent monitoring and security systems.
In general, the spectral response of a photodetector depends on the light absorption of the active material and the charge collection characteristics of the device. The regulation and control of the light absorption of the photoelectric detector comprise a coupling optical band-pass filter, a plasma resonance, a coupling optical microcavity and the like; the charge collection characteristics can be formed by increasing the thickness of the photoactive layer or introducing surface charge recombination to form a Charge Collection Narrowing (CCN) effect, etc. The photoactive layer of a photodetector is typically a semiconductor material, and thus the optical and electrical properties of the semiconductor are critical to the performance of the photodetector.
In recent years, organic-inorganic hybrid perovskites have been superior because of their superiorityOptoelectronic properties, e.g. high carrier mobility, high dielectric constant, 10 in the UV-visible region 5 cm -1 The high absorption coefficient, the high defect tolerance and the like of the composite lead to great research interest in the field of photoelectric devices. Although the organic-inorganic hybrid perovskite has relatively excellent properties, it has inevitable disadvantages such as being unstable and easily decomposed by light, and also being easily decomposed by moisture at room temperature. In summary, illumination, oxygen, humidity, temperature, defects all affect the stability of organic-inorganic hybrid perovskites in devices. Oxygen and moisture in the air are important causes of the decomposition of organic-inorganic hybrid perovskites. The effect of oxygen on organic-inorganic hybrid perovskites is also believed to be related to light exposure. Because the ultraviolet rays in the sunlight can form superoxide O with oxygen 2- The superoxide can react with A site cations of the organic-inorganic hybrid perovskite, so that the structure of the perovskite is damaged, and the organic functional groups contained in the superoxide can cause the organic-inorganic hybrid perovskite photoelectric detector to have poor chemical properties and thermal stability, so that the organic-inorganic hybrid perovskite photoelectric detector is limited in the field of photoelectric research.
And inorganic cation Cs is adopted + This disadvantage can be compensated for. All-inorganic perovskite CsPbX 3 (X = Cl, Br, I) has a similar structure compared with organic-inorganic hybrid perovskites, and has the advantages of excellent luminescence property, high fluorescence quantum yield (-90%), better stability, narrow emission peak (full-width at half maximum 12-42 nm), coverage of the whole visible light range of the emission spectrum, and change of crystal phase along with the difference of synthesis temperature and halogen elements contained in the molecular formula. Due to CsPbX 3 Having the above excellent light emitting characteristics, it has attracted attention in the field of light emitting materials. The first all-inorganic perovskite photodetector was the CsPbX reported by Lee et al 3 (X = Cl, Br, I) nanocrystals were prepared by simple, rapid and reproducible ion exchange reaction at room temperature and demonstrated wide band modulation (425-655 nm) and good on-off ratio (10) 5 ). All-inorganic perovskite CsPbBr has also been reported by Zhonghaibo et al 3 Compared with organic-inorganic hybrid perovskite, the material has more excellent stabilityQualitatively, and the photocurrent hardly decays after long-time illumination. At the same time, once Hai et al have reported using flexible materials as substrates followed by construction of CsPbBr 3 The light detector has very good stability and flexibility.
The optical and electrical characteristics of the all-inorganic perovskite photoelectric detector are influenced by the surface morphology, the surface morphology is directly related to the photoelectric characteristics such as light absorption, carrier transport and the like, and the good surface morphology is a prerequisite for realizing high performance of the device. However, the crystal size of the film which can grow is small until now, so that the development and optimization of the perovskite film preparation process is a necessary condition for realizing the successful application of the perovskite material as a photosensitive layer in the photovoltaic field, the luminescence field, the laser field and other photoelectric fields. The existing methods for preparing all-inorganic perovskite thin films and photoelectric detectors mainly comprise the following steps:
1. solution process
The most common solution process for preparing thin films is spin coating, which can be divided into one-step spin coating and two-step spin coating.
(1) The one-step spin coating method is to spin coat the prepared perovskite precursor solution on the prepared substrate material, and anneal the substrate material after the spin coating is finished, so as to finally form the available perovskite thin film. When the perovskite thin film is prepared by adopting the one-step spin-coating method, the selected organic solvent and the annealing process can obviously influence the quality of the finally formed perovskite thin film, and if the organic solvent is not properly selected, the finally prepared perovskite thin film can generate crystal grain clusters, so that the thin film cannot completely cover the substrate, and the hole problem exists.
(2) The two-step spin coating process is also known as a two-step sequential deposition process (with CsPbX) 3 For example), lead halide and cesium halide are respectively dissolved in different solvents, a layer of lead halide thin film is deposited by spin coating, then a cesium halide thin film is deposited, the two layers of thin films react with each other, and finally a perovskite thin film is formed. Finally, the perovskite film is annealed to obtain the desired crystalline phase. Compared with the one-step spin coating method, the perovskite thin film prepared by the two-step spin coating method improves the crystallization quality and the surface coverage rate of the thin film. But because of controlling in the process of preparing the film by the two-step spin coating methodWith more parameters, the prepared film has the problem of poor repeatability. In addition, the two layers of thin film react with each other, and there may be cases where the precursor solution reacts excessively or incompletely, affecting the quality of the finally formed perovskite thin film.
2. Vacuum process
Vacuum thermal evaporation is a mature technology used in the field of film coating, which can realize easy deposition of multiple layers of films on a large area, and the deposited films have good uniformity and flatness. The vacuum thermal evaporation coating can accurately control the thickness of the film, and the repeatability of the film is high. However, the coating technology is complex to operate and has high cost.
3. Chemical Vapor Deposition (CVD) process
For preparing all-inorganic perovskite thin film (CsPbX 3 For example), PbX can be used 2 CsX the powder is used as an evaporation source for CVD reaction, the substrate is placed in a low temperature region downstream, and the perovskite deposition on the substrate can be controlled by adjusting the temperature, pressure and reaction time. At present, the crystal size of the prepared all-inorganic perovskite thin film prepared by CVD is not large, and the all-inorganic perovskite thin film cannot be used for constructing perovskite thin film devices, so that the growing conditions of perovskite thin film crystals with larger sizes need to be explored.
4. Spraying method
The spraying method atomizes the perovskite solution by ultrasonic to form aerosol which is deposited on a preheated conductive substrate. However, the perovskite thin film prepared by the method has large surface roughness and is less used for preparing perovskite photodetectors.
In the preparation process of the all-inorganic perovskite thin film, the method overcomes the problems that the perovskite thin film prepared by the one-step spin coating method is not completely covered and holes in the thin film are not compact. But the method also has the defects of poor repeatability of the prepared film, small grain size of the prepared film, rough surface, poor film quality and the like, and the optical detection performance of the prepared film is generally low. Therefore, it is urgent to develop a simple low-temperature process to prepare high-quality all-inorganic perovskite thin film.
Disclosure of Invention
The invention aims to solve the problems in the preparation of perovskite thin films and detectors in the prior art, and provides a preparation method of an all-inorganic perovskite thin film and an all-inorganic narrow-band photoelectric detector. The perovskite thin film prepared by the method has large grain size and high film forming quality, and the thickness of the thin film can be effectively regulated and controlled by controlling the deposition times, so that the narrow-band photoelectric detector has excellent performance.
In order to solve the above technical problems, the present invention is achieved by the following technical solutions.
The invention provides a preparation method of an all-inorganic perovskite thin film, which comprises the following steps:
(1) mixing PbX 2 Dissolving in aqueous HBr to form a pale yellow solution; the aqueous solution of CsX was then added continuously to give an orange solid; washing and filtering the orange solid to obtain CsPbX 3 Powder, followed by CsPbX 3 Drying the powder;
(2) drying the CsPbX 3 Dissolving the powder in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and uniformly stirring to obtain CsPbX 3 Precursor solution;
(3) carrying out ultrasonic cleaning and drying on the transparent conductive substrate;
(4) CsPbX obtained in step (2) 3 The precursor solution is subjected to ultrasonic atomization treatment and is uniformly sprayed on a transparent conductive substrate in a driving scanning mode to form CsPbX 3 Precursor liquid film and solvent are volatilized to form uniform CsPbX 3 A solid film;
(5) CsPbX obtained in step (4) 3 The solid film is subjected to a heat treatment to promote further growth of the crystals.
Wherein, X is selected from one or more of Cl, Br and I.
Preferably, the drying in step (1) is carried out under vacuum at a temperature of 60 ℃.
Preferably, the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide in the step (2) is 0.5-2:1.
Preferably, the ultrasonic cleaning in the step (3) is specifically: and sequentially carrying out ultrasonic cleaning on the transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol.
Preferably, the transparent conductive substrate in step (3) is selected from one or more of FTO and ITO.
Preferably, the CsPbX in step (4) 3 The ultrasonic atomization treatment of the precursor solution comprises the following specific steps: mixing CsPbX 3 Adding the precursor solution into an atomization container, and adding the CsPbX into the container under the action of an ultrasonic nebulizer 3 And atomizing the precursor solution.
Preferably, the spraying in the step (4) is specifically: placing the transparent conductive substrate on a heating table, introducing inert gas into an atomization container, and atomizing the CsPbX 3 And the precursor solution is uniformly sprayed on the heated substrate through a spray head under the drive of the inert gas.
Preferably, the heating stage temperature is 120-.
Preferably, the flow rate of the inert gas is 1 to 3L/min; most preferably, the inert gas is selected from nitrogen.
Preferably, in the spraying process in the step (4), the height of the spray head from the transparent conductive substrate is 1-10mm, the scanning speed is 0.2-2.5cm/s, and the scanning times are 2-32 times; CsPbX can be controlled by setting the number of driving scans 3 Thickness of the solid film.
Preferably, the heating temperature in the step (5) is 300-.
In a second aspect, the present invention provides an all-inorganic perovskite thin film prepared according to the above method.
The invention provides a third aspect of the invention, which comprises a transparent conductive substrate layer, a hole transport layer and CsPbX in sequence 3 Solid bodyThe electron transport layer comprises a thin film layer, an electron transport layer and an electrode layer, wherein X is selected from one or more of Cl, Br and I.
Preferably, the transparent conductive substrate is selected from one or more of FTO and ITO.
Preferably, the hole transport layer is selected from NiO y 。
Preferably, the electron transport layer is selected from TiO 2 、SnO 2 One or more of fullerene derivative PCBM; more preferably, the electron transport layer is selected from TiO 2 、SnO 2 One or more of; most preferably, the electron transport layer is selected from TiO 2 。
Preferably, the electrode layer is selected from silver.
The fourth aspect of the invention provides a preparation method of an all-inorganic perovskite narrow-band photodetector, which comprises the following steps:
(1) mixing PbX 2 Dissolving in aqueous HBr to form a pale yellow solution; the aqueous solution of CsX was then added continuously to give an orange solid; washing and filtering the orange solid to obtain CsPbX 3 Powder, followed by CsPbX 3 Drying the powder;
(2) drying the CsPbX 3 Dissolving the powder in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and uniformly stirring to obtain CsPbX 3 Precursor solution;
(3) carrying out ultrasonic cleaning and drying on the transparent conductive substrate;
(4) uniformly spraying the hole transport layer solution on a dried substrate in a driving scanning mode after ultrasonic atomization treatment, and volatilizing a solvent to form a hole transport layer film;
(5) CsPbX obtained in step (2) 3 Carrying out ultrasonic atomization treatment on the precursor solution, and uniformly spraying the precursor solution on the hole transport layer film obtained in the step (4) in a driving scanning mode to form CsPbX 3 Precursor liquid film and solvent are volatilized to form uniform CsPbX 3 A solid film;
(6) CsPbX obtained in step (5) 3 Solid bodyThe film is subjected to heating treatment to promote further growth of crystals;
(7) carrying out ultrasonic atomization treatment on the electron transport solution, and uniformly spraying the electron transport solution on the CsPbX subjected to heating treatment in the step (6) in a driving scanning manner 3 Forming an electron transport layer film on the surface of the solid film;
(8) evaporating and plating an electrode layer on the electron transport layer film to obtain the film;
wherein, X is selected from one or more of Cl, Br and I.
Preferably, the drying in step (1) is carried out under vacuum at a temperature of 60 ℃.
Preferably, the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide in the step (2) is 0.5-2:1.
Preferably, the ultrasonic cleaning in the step (3) is specifically: and sequentially carrying out ultrasonic cleaning on the transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol.
Preferably, the transparent conductive substrate in step (3) is selected from one or more of FTO and ITO.
Preferably, the hole transport layer in step (4) is selected from NiO y (ii) a More preferably, the method for preparing the hole transport layer solution comprises the following steps: dissolving nickel acetylacetonate in acetonitrile solution to obtain the final product; most preferably, the NiO y The concentration of the solution is 0.008-0.02 mol/L.
Preferably, the ultrasonic atomization treatment of the hole transport layer solution in the step (4) is specifically as follows: adding the hole transport layer solution into an atomization container, and atomizing the hole transport layer solution under the action of an ultrasonic wave atomizer.
Preferably, the spraying in the step (4) is specifically: heating the transparent conductive substrate, introducing mixed gas into an atomization container, and uniformly spraying the atomized cavity transport layer solution onto the heated substrate through a spray head under the drive of the mixed gas.
Preferably, the temperature at which the transparent substrate is heated is 400-500 ℃.
Preferably, the flow rate of the inert gas is 1 to 3L/min; most preferably, the mixed gas is selected from air.
Preferably, in the spraying process in the step (4), the height of the spray head from the transparent conductive substrate is 1-20mm, the scanning speed is 0.2-2cm/s, and the scanning times are 2-10 times; the thickness of the hole transport layer film can be controlled by setting the number of driving scans.
Further, after the spraying in the step (4) is completed, optionally placing the hole transport layer film on a heating table at 400-500 ℃ for heating for 10-60min, and then naturally cooling to room temperature.
Preferably, the CsPbX in step (5) 3 The ultrasonic atomization treatment of the precursor solution comprises the following specific steps: mixing CsPbX 3 Adding the precursor solution into an atomization container, and adding the CsPbX into the container under the action of an ultrasonic nebulizer 3 And atomizing the precursor solution.
Preferably, the spraying in step (5) is specifically: heating the transparent conductive substrate coated with the hole transport layer film, introducing inert gas into an atomization container, and atomizing to obtain CsPbX 3 And the precursor solution is uniformly sprayed on the heated substrate through a spray head under the drive of the inert gas.
Preferably, the heating temperature of the transparent conductive substrate sprayed with the hole transport layer film is 120-200 ℃.
Preferably, the flow rate of the inert gas is 1 to 3L/min; most preferably, the inert gas is selected from nitrogen.
Preferably, in the spraying process in the step (5), the height of the spray head from the transparent conductive substrate is 1-10mm, the scanning speed is 0.2-2.5cm/s, and the scanning times are 2-32 times; CsPbX can be controlled by setting the number of driving scans 3 Thickness of the solid film.
Preferably, the heating temperature in the step (6) is 300-400 ℃, and the heating time is 1-60 min.
Preferably, the electron transport layer is selected from TiO 2 、SnO 2 One or more of fullerene derivative PCBM; more preferably, the formulaThe electron transport layer is selected from TiO 2 、SnO 2 One or more of; most preferably, the electron transport layer is selected from TiO 2 。
Preferably, the ultrasonic atomization treatment of the electron transport layer solution in the step (7) is specifically as follows: the electron transport layer solution is added into an atomization container and atomized under the action of ultrasonic waves acting as a sprayer.
Preferably, the spraying in step (7) is specifically: spraying CsPbX on the mixture obtained in the step (6) 3 Heating the transparent conductive substrate of the solid film, introducing inert gas into the atomizing container, and uniformly spraying the atomized electron transport layer solution onto the heated substrate through a spray head under the drive of the inert gas.
Preferably, the spray coating is CsPbX 3 The heating temperature of the transparent conductive substrate of the solid film is 200-500 ℃.
Preferably, the flow rate of the inert gas is 1 to 3L/min; most preferably, the inert gas is selected from nitrogen.
Preferably, in the spraying process in the step (7), the height between the spray head and the transparent conductive substrate is 5-20mm, the scanning speed is 0.1-3cm/s, and the scanning times are 1-8 times; the thickness of the electron transport layer film can be controlled by setting the number of driving scans.
Further, after the spraying in the step (7) is completed, optionally placing the electron transport layer film on a heating table at 200-500 ℃ for heating for 30-120min, and then naturally cooling to room temperature.
Preferably, the electrode layer in step (8) is selected from silver.
Preferably, the electrode layer has a thickness of 80 nm.
Compared with the prior art, the invention has the following technical effects:
(1) according to the invention, a certain amount of lead halide powder and cesium halide powder are respectively dissolved in different solvents to prepare perovskite powder, the perovskite powder is dissolved in dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) to obtain perovskite precursor solution, and the ALS spraying process is adopted to obtain the perovskite thin film. The invention improves the perovskite solubility and optimizes the quality of the film, and the finally obtained perovskite film has good compactness, high quality and high crystallinity and is beneficial to charge transmission. In addition, the thickness of the perovskite thin film prepared by the method is controllable, the thickness of the thin film can be accurately regulated and controlled within 0.1-1000 microns, and the narrow-band detection condition is met.
(2) After the perovskite thin film is obtained, the perovskite thin film is further subjected to high-temperature heating treatment, crystal particles of the perovskite thin film subjected to the heating treatment become large and can even span the thickness of the whole thin film, and all the perovskite thin films show good continuity and flatness. While the perovskite thin film which is not subjected to heat treatment has smaller crystal grains and some grains are stacked on other grains in the growth direction of the thin film. Therefore, the film is heated, the crystallization rate of the film is increased, the crystallization quality of the film is improved, the defects in crystal lattices can be reduced, and the flatness of the film and the transmission capability of current carriers are optimized.
(3) The all-inorganic perovskite photoelectric detector prepared by using the high-quality perovskite thin film has obvious narrow-band response under the wavelength of 535nm, the External Quantum Efficiency (EQE) of the all-inorganic perovskite photoelectric detector reaches up to 18 percent, and compared with a device using PCBM as an electron transmission layer, the all-inorganic perovskite photoelectric detector has higher responsivity and detectivity and low noise; in addition, the stability of the all-inorganic perovskite photoelectric detector is better.
Drawings
FIG. 1 is a schematic diagram of a process for forming a perovskite thin film provided by the present invention. Wherein, a is the preparation of CsPbBr 3 A schematic of a powder sample; b is a schematic diagram of the perovskite thin film forming process.
FIG. 2 shows CsPbBr prepared in example 2 3 SEM images and XRD images of the inorganic perovskite thin film, wherein a and c are front view SEM images, b and d are cross-sectional SEM images, and (e) is an XRD image.
FIG. 3 shows CsPbBr deposited in example 2 at different thicknesses and heated for different times 3 SEM pictures of inorganic perovskite thin films, a, c, e, g, iK is a front view SEM image, and b, d, f, h, j, l are cross-sectional SEM images.
FIG. 4 is CsPbBr prepared in comparative example 1 3 SEM image of inorganic perovskite thin film.
FIG. 5 shows CsPbBr prepared in example 2 of the present invention 3 The inorganic perovskite photoelectric detector is structurally schematic.
FIG. 6 shows CsPbBr prepared in example 2 of the present invention 3 Schematic diagram of external quantum efficiency of inorganic perovskite photodetector.
FIG. 7 shows CsPbBr prepared in example 2 of the present invention 3 Inorganic perovskite photoelectric detector responsivity sketch map.
FIG. 8 shows CsPbBr prepared in example 2 of the present invention 3 And (3) the detection rate of the inorganic perovskite photoelectric detector.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
The preparation method of the all-inorganic perovskite thin film comprises the following steps:
(1) 20mmol of PbBr 2 Dissolved in 30ml 48% aqueous HBr to give a pale yellow solution; subsequently, an aqueous CsBr solution (20 mmol CsBr in 10ml water) was added continuously and a bright orange solid precipitated immediately; washing orange solid for multiple times by using absolute ethyl alcohol, and performing suction filtration to obtain CsPbBr 3 Powder, followed by CsPbBr 3 Drying the powder in a vacuum drying oven at 60 ℃;
(2) 2.10g of dried CsPbBr was taken 3 The powder was dissolved in 14.5mL of a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (volume ratio of DMSO to DMF: 2: 1), and stirred uniformly to obtain CsPbBr 3 Precursor solution (the molar concentration is 0.25 mol/L);
(3) sequentially carrying out ultrasonic cleaning on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol, and then putting the FTO transparent conductive substrate into an oven to be dried at 70 ℃ for later use;
(4) the CsPbBr obtained in the step (2) is added 3 Putting the precursor solution into an atomization container for ultrasonic atomization treatment, introducing dry nitrogen into the atomization container at a flow rate of 1.5L/min, uniformly spraying atomized droplets onto a conductive substrate through a nozzle, and volatilizing the solvent at high temperature to form uniform CsPbBr 3 A solid film. During this process, the nozzle is scanned back and forth in the horizontal direction, in the grown CsPbBr 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(5) after the scanning is finished, the obtained CsPbBr is 3 The solid film is placed on a heating table at 400 ℃, different heating time is selected according to different film thicknesses, so that residual solvent in the perovskite solid film is volatilized, crystal grains are promoted to further grow, and the crystallinity of the perovskite film is improved.
The all-inorganic perovskite thin film prepared by the method has higher density, larger grain size and more uniform surface. The forming process of the all-inorganic perovskite thin film is shown in figure 1, wherein figure 1 (a) is used for preparing CsPbBr 3 A schematic of a powder sample; FIG. 1 (b) is a schematic view of a perovskite thin film formation process.
Example 2
CsPbBr 3 The preparation method of the perovskite narrow-band photodetector comprises the following steps:
(1) 20mmol of PbBr 2 Dissolved in 30ml 48% aqueous HBr to give a pale yellow solution; subsequently, an aqueous CsBr solution (20 mmol CsBr in 10ml water) was added continuously and a bright orange solid precipitated immediately; washing orange solid for multiple times by using absolute ethyl alcohol, and performing suction filtration to obtain CsPbBr 3 Powder, followed by CsPbBr 3 Drying the powder in a vacuum drying oven at 60 ℃;
(2) 2.10g of dried CsPbBr was taken 3 The powder was dissolved in 14.5mL of a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (volume ratio of DMSO to DMF: 2: 1), and stirred uniformly to obtain CsPbBr 3 Precursor solution (the molar concentration is 0.25 mol/L);
(3) sequentially carrying out ultrasonic cleaning on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol, and then putting the FTO transparent conductive substrate into an oven to be dried at 70 ℃ for later use;
(4) dissolving nickel acetylacetonate in acetonitrile solution, and uniformly mixing the two solutions according to the proportion of 1:25 to obtain NiO y A solution; placing the transparent conductive substrate on a heating table, heating the heating table to 475 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to be 1cm, and controlling the moving speed of a sprayer to be 1.6 cm/s; NiO is mixed y The solution is atomized to form atomized NiO y A solution; mixed gas is introduced into the atomization device at the flow rate of 2L/min, so that atomized liquid drops are uniformly sprayed on the conductive substrate through the nozzle to form uniform NiO y A film. During the process, the nozzle scans back and forth in the horizontal direction to grow NiO y The film was deposited continuously with 8 scans. After the scanning is finished, the obtained NiO y Placing the film on a heating table at 500 ℃ for 30min, and cooling to room temperature;
(5) will be sprayed with NiO y Placing the conductive substrate of the film on a heating table, raising the temperature of the heating table to 140 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to be 5mm, and controlling the moving speed of a sprayer to be 1.6 cm/s; reacting CsPbBr 3 Atomizing the precursor solution to form atomized CsPbBr 3 Precursor solution; introducing dry nitrogen into the atomization device at a flow rate of 1.5L/min, uniformly spraying atomized liquid drops onto the conductive substrate through a nozzle, and volatilizing the solvent at high temperature to form uniform CsPbBr 3 A solid film. During this process, the nozzle is scanned back and forth in the horizontal direction, in the grown CsPbBr 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(6) after the scanning is finished, the obtained CsPbBr is used 3 Placing the solid film on a heating table at 400 ℃, and selecting different heating time according to different film thicknesses;
(7) dissolving titanium isopropoxide in isopropanol solution, and uniformly mixing the two solutions according to the proportion of 1:20 to obtain TiO 2 A solution; heating the deposited perovskite thin film on a heating table at the temperature of 400 ℃; nozzle is spaced from the upper surface of the conductive substrateThe distance is adjusted to be 2cm, and the moving speed of the spray head is controlled to be 1.7 cm/s; adding TiO into the mixture 2 The solution is atomized to form atomized TiO 2 A solution; dry oxygen is introduced into the atomizing device at the flow rate of 2.4L/min, so that atomized liquid drops are uniformly sprayed on the conductive substrate through the nozzle to form uniform TiO 2 A film. During this process, the nozzle is scanned back and forth in the horizontal direction to grow TiO 2 The film was deposited continuously with 4 scans. After the scanning is finished, the obtained TiO 2 Placing the film on a heating table at 400 ℃ for 120min, and naturally cooling to room temperature;
(8) in TiO 2 The Ag electrode with the thickness of 80nm is vapor-plated on the film layer, and finally CsPbBr is obtained 3 A narrow band photodetector.
Example 3
CsPbCl 3 The preparation method of the perovskite narrow-band photodetector comprises the following steps:
(1) 26mmol of PbCl 2 Dissolved in 20ml 48% aq HBr, to which aqueous CsCl (26 mmol CsCl in 10ml water) was added continuously, and a solid precipitated immediately; washing the solid sample for multiple times by using absolute ethyl alcohol, and performing suction filtration to obtain CsPbCl 3 Powder, followed by CsPbCl 3 Drying the powder sample in a vacuum drying oven at 60 ℃;
(2) 1.62g CsPbCl was taken 3 The powder was dissolved in 18.1ml of a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (volume ratio of DMSO to DMF was (0.5: 1)), and stirred uniformly to obtain CsPbCl 3 Precursor solution (the molar concentration is 0.2 mol/L);
(3) sequentially carrying out ultrasonic cleaning on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol, and then putting the FTO transparent conductive substrate into an oven to be dried at 70 ℃ for later use;
(4) dissolving nickel acetylacetonate in acetonitrile solution, and uniformly mixing the two solutions according to the proportion of 1:25 to obtain NiO y A solution; placing the transparent conductive substrate on a heating table, heating the heating table to 500 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to be 9mm, and controlling the moving speed of a spray head to be 1.8 cm/s; NiO is mixed y Solution atomizationForming atomized NiO y A solution; dry nitrogen is introduced into the atomization device at the flow rate of 3L/min, so that atomized liquid drops are uniformly sprayed on the conductive substrate through the nozzle to form uniform NiO y A film of the solution. During the process, the nozzle scans back and forth in the horizontal direction to grow NiO y The deposition is continued on the solution film, and the scanning times are 8 times. After the scanning is finished, the obtained NiO y Placing the solution film on a heating table at 450 ℃ for 30min, and cooling to room temperature;
(5) will be sprayed with NiO y The conductive substrate of the film is placed on a heating table, the temperature of the heating table is raised to 200 ℃, the distance between a nozzle and the upper surface of the conductive substrate is adjusted to 8mm, and the moving speed of a sprayer is controlled to be 2 cm/s; mixing CsPbCl 3 Atomizing the precursor solution to form atomized CsPbCl 3 Introducing dry nitrogen into the atomization device at a flow rate of 2.5L/min to uniformly spray atomized liquid drops on the conductive substrate through the nozzle, and volatilizing the solvent at high temperature to form uniform CsPbCl 3 A solid film. During this process, the nozzle is scanned back and forth in the horizontal direction, in the grown CsPbCl 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(6) after the scanning is finished, the obtained CsPbCl is used 3 Placing the solid film on a 350 ℃ heating table, and selecting different heating time according to different film thicknesses;
(7) dissolving titanium isopropoxide in isopropanol solution, and uniformly mixing the two according to the proportion of 1:20 to obtain TiO 2 A solution; heating the deposited perovskite thin film on a heating table at the temperature of 400 ℃; the distance between the nozzle and the upper surface of the conductive substrate is adjusted to be 2cm, and the moving speed of the spray head is controlled to be 1.7 cm/s; adding TiO into the mixture 2 The solution is atomized to form atomized TiO 2 A solution; dry nitrogen is introduced into the atomization device at the flow rate of 2.4L/min, so that atomized liquid drops are uniformly sprayed on the conductive substrate through the nozzle to form uniform TiO 2 A film. During this process, the nozzle is scanned back and forth in the horizontal direction to grow TiO 2 The film was deposited continuously with 4 scans. After the scanning is finished, the obtained TiO is treated 2 Placing the film on a heating table at 200 ℃ for 30min, and cooling to room temperature;
(8) subsequently on TiO 2 Ag electrode with the thickness of 80nm is vapor-plated on the film layer, and finally CsPbBr is obtained 3 A narrow band photodetector.
Example 4
CsPbI 3 The preparation method of the perovskite narrow-band photoelectric detector comprises the following steps:
(1) 16mmol of PbI 2 Dissolved in 25ml 48% aq HBr, to which solution CsI aq (16 mmol CsI in 8ml water) was added continuously, and a solid precipitated immediately; washing the sample solid for multiple times by using absolute ethyl alcohol, and performing suction filtration to obtain CsPbI 3 Powder, followed by CsPbI 3 Drying the powder sample in a vacuum drying oven at 60 ℃;
(2) 2.61g CsPbI 3 Dissolving the powder in 12ml of mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (the volume ratio of the DMSO to the DMF is 1: 1), and uniformly stirring to obtain CsPbI 3 Precursor solution (the molar concentration is 0.3 mol/L);
(3) sequentially carrying out ultrasonic cleaning on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol, and then putting the FTO transparent conductive substrate into an oven to be dried at 70 ℃ for later use;
(4) dissolving nickel acetylacetonate in acetonitrile solution, and uniformly mixing the two solutions according to the proportion of 1:25 to obtain NiO y A solution; placing the transparent conductive substrate on a heating table, heating the heating table to 450 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to be 8mm, and controlling the moving speed of a spray head to be 1.6 cm/s; NiO is mixed y The solution is atomized to form atomized NiO y A solution; dry nitrogen is introduced into the atomization device at the flow rate of 2.5L/min, so that atomized liquid drops are uniformly sprayed on the conductive substrate through the nozzle to form uniform NiO y A film. During the process, the nozzle scans back and forth in the horizontal direction to grow NiO y The film was deposited continuously with 8 scans. After the scanning is finished, the obtained NiO y Placing the film on a heating table at 500 ℃ for 10min, and cooling to room temperature;
(5) will be sprayed with NiO y The conductive substrate of the film is placed on a heating table, the temperature of the heating table is raised to 180 ℃, the distance between a nozzle and the upper surface of the conductive substrate is adjusted to be 7mm, and the moving speed of a nozzle is controlled to be 1.8 cm/s; mixing CsPbI 3 Atomizing the precursor solution to form atomized CsPbI 3 Selecting dry nitrogen gas and introducing into the atomizer at a flow rate of 1.8L/min to make atomized liquid drops uniformly sprayed on the conductive substrate through the nozzle, and volatilizing the solvent at high temperature to form uniform CsPbI 3 A solid film. During this process, the nozzle is scanned back and forth in the horizontal direction, in the grown CsPbI 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(6) after the scanning is finished, the obtained CsPbI is used 3 Placing the solid film on a 300 ℃ heating table, and selecting different heating time according to different film thicknesses;
(7) SnO 2 Dissolving the nanoparticles in an aqueous solution to obtain SnO 2 A solution; heating the deposited perovskite thin film on a heating table at the temperature of 350 ℃; the distance between the nozzle and the upper surface of the conductive substrate is adjusted to be 1.5cm, and the moving speed of the spray head is controlled to be 2 cm/s; SnO 2 Atomizing the solution to form atomized SnO 2 A solution; dry nitrogen is introduced into the atomization device at the flow rate of 2.6L/min, atomized liquid drops are uniformly sprayed on the conductive substrate through the nozzle, and uniform SnO is formed 2 A film. During this process, the nozzle is scanned back and forth in the horizontal direction to grow SnO 2 Continuously depositing on the film, wherein the scanning times are 8 times; after the scanning is finished, the obtained SnO 2 Placing the film on a heating table at 500 ℃ for 50min, and cooling to room temperature;
(8) subsequently in SnO 2 Ag electrode with the thickness of 80nm is vapor-plated on the film layer, and finally CsPbBr is obtained 3 A narrow band photodetector.
Example 5
CsPbI 2 The preparation method of the Br perovskite narrow-band photoelectric detector comprises the following steps:
(1) adding 17.2mmol of PbBr 2 17.2mmol CsBr in 30ml 48% aqueous HBr, to which PbI was continuously added 2 And CsI aqueous solution (17.2 mmol of PbI) 2 Dissolving CsPbI in 20ml water), precipitating to obtain solid, washing the solid sample with anhydrous ethanol for several times, and vacuum filtering to obtain CsPbI 2 Br powder, followed by CsPbI 2 Drying Br powder in a vacuum drying oven at 60 ℃;
(2) 2.44g CsPbI was taken 2 Br powder is dissolved in 14.5ml of mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (the volume ratio of the DMSO to the DMF is 2: 1), and the mixture is uniformly stirred to obtain CsPbI 2 Br precursor solution (molar concentration is 0.25 mol/L);
(3) sequentially carrying out ultrasonic cleaning on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol, and then putting the FTO transparent conductive substrate into an oven to be dried at 70 ℃ for later use;
(4) dissolving nickel acetylacetonate in acetonitrile solution, and uniformly mixing the two solutions according to the proportion of 1:25 to obtain NiO y A solution; placing the transparent conductive substrate on a heating table, heating the heating table to 425 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to be 7mm, and controlling the moving speed of a spray head to be 1.6 cm/s; NiO is mixed y The solution is atomized to form atomized NiO y A solution; dry nitrogen is introduced into the atomization device at the flow rate of 1.8L/min, so that atomized liquid drops are uniformly sprayed on the conductive substrate through the nozzle to form uniform NiO y A film. During the process, the nozzle scans back and forth in the horizontal direction to grow NiO y The film was deposited continuously with 8 scans. After the scanning is finished, the obtained NiO y Placing the film on a heating table at 400 ℃ for 30min, and cooling to room temperature;
(5) will be sprayed with NiO y The conductive substrate of the film is placed on a heating table, the temperature of the heating table is raised to 160 ℃, the distance between a nozzle and the upper surface of the conductive substrate is adjusted to 6mm, and the moving speed of a nozzle is controlled to 1.6 cm/s; mixing CsPbI 2 Atomizing Br precursor solution to form atomized CsPbI 2 Introducing dry nitrogen into the atomizer at a flow rate of 1.6L/min to uniformly spray atomized droplets onto the conductive substrate via the nozzle, and volatilizing the solvent at high temperature to form uniform CsPbI 2 A solid film of Br. In the processIn the horizontal direction, the nozzle is scanned back and forth in the grown CsPbI 2 Continuously depositing on the Br solid film, wherein the scanning times are 2-32 times;
(6) after the scanning is finished, the obtained CsPbI is used 2 Placing the Br solid film on a 350 ℃ heating table, and selecting different heating time according to different film thicknesses;
(7) dissolving 1mg of PMMA powder in 1mL of chlorobenzene to obtain a PMMA solution, and dissolving 20mg of PCBM powder in 1mL of chlorobenzene to obtain a PCBM solution; 1mg of amino-functionalized diimine polymer (PPDIN 6) was dissolved in 2, 2, 2-Trifluoroethanol (TFE) to give PPDIN6 solution; taking 30 mu L of PMMA solution in the prepared CsPbI 2 Rotating the Br solid film at 7000rpm for 15s, drying, taking 30 μ L of PCBM solution to rotate at 3000rpm for 30s on the PMMA film layer, and taking 30 μ L of PPDIN6 solution to rotate at 3000rpm for 30s on the PCBM film layer;
(8) ag electrode with the thickness of 80nm is vapor-plated on the PPDIN6 film layer, and finally the CsPbI is obtained 2 A Br narrow band photodetector.
Example 6
CsPbBr 2 The preparation method of the Cl perovskite narrow-band photoelectric detector comprises the following steps:
(1) adding 5mmol of PbBr 2 Dissolved in 40ml 48% aqueous HBr, to which aqueous CsCl (5 mmol CsCl in 15ml water) was added continuously and a solid precipitated immediately; washing the solid sample for multiple times by using absolute ethyl alcohol, and performing suction filtration to obtain CsPbBr 2 Cl powder, followed by CsPbBr 2 Placing Cl powder in a vacuum drying oven at 60 ℃ for drying;
(2) 2.68g CsPbBr 2 Dissolving Cl powder in 14.5ml of mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (the volume ratio of the DMSO to the DMF is 1: 1), and uniformly stirring to obtain CsPbBr 2 Cl precursor solution (the molar concentration is 0.35 mol/L);
(3) sequentially carrying out ultrasonic cleaning on the FTO transparent conductive substrate by using deionized water, acetone, isopropanol and ethanol, and then putting the FTO transparent conductive substrate into an oven to be dried at 70 ℃ for later use;
(4) acetyl is reacted withNickel acetone is dissolved in acetonitrile solution, and the two are uniformly mixed according to the proportion of 1:25 to obtain NiO y A solution; placing the transparent conductive substrate on a heating table, heating the heating table to 400 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to be 6mm, and controlling the moving speed of a spray head to be 1.4 cm/s; NiO is mixed y The solution is atomized to form atomized NiO y A solution; dry nitrogen is introduced into the atomization device at the flow rate of 1.6L/min, so that atomized liquid drops are uniformly sprayed on the conductive substrate through the nozzle to form uniform NiO y A film. During the process, the nozzle scans back and forth in the horizontal direction to grow NiO y The film was deposited continuously with 8 scans. After the scanning is finished, the obtained NiO y Placing the film on a heating table at 450 ℃ for 10min, and cooling to room temperature;
(5) will be sprayed with NiO y The conductive substrate of the film is placed on a heating table, the temperature of the heating table is raised to 120 ℃, the distance between a nozzle and the upper surface of the conductive substrate is adjusted to be 4mm, and the moving speed of a sprayer is controlled to be 1.6 cm/s; mixing CsPbBr 2 Atomizing Cl precursor solution to form atomized CsPbBr 2 Introducing dry nitrogen into the atomization device at a flow rate of 1.4L/min to uniformly spray atomized liquid drops on the conductive substrate through the nozzle, and volatilizing the solvent at high temperature to form uniform CsPbBr 2 Solid film of Cl. During this process, the nozzle is scanned back and forth in the horizontal direction, in the grown CsPbBr 2 Continuously depositing on the Cl solid film, wherein the scanning times are 2-32 times;
(6) after the scanning is finished, the obtained CsPbBr is used 2 Placing the Cl solid film on a heating table at 400 ℃, and selecting different heating time according to different film thicknesses;
(7) dissolving 1mg of PMMA powder in 1mL of chlorobenzene to obtain a PMMA solution, and dissolving 20mg of PCBM powder in 1mL of chlorobenzene to obtain a PCBM solution; 1mg of amino-functionalized diimine polymer (PPDI 6) was dissolved in 2, 2, 2-Trifluoroethanol (TFE) to give a PPDI 6 solution; taking 30 mu L of PMMA solution in the prepared CsPbBr 2 Rotating the Cl solid film at 7000rpm for 15s, after drying, taking 30 μ L of PCBM solution to rotate the PMMA film at 3000rpm for 30s,after drying, 30 μ L of PPDIN6 solution was spun on the PCBM film layer at 3000rpm for 30 s;
(8) an Ag electrode with the thickness of 80nm is vapor-plated on a PPDIN6 film layer, and finally CsPbBr is obtained 2 A Cl narrow band photodetector.
The above experimental examples can also be enumerated, for example, by further changing N 2 The flow rate, scanning speed, distance from the showerhead to the substrate, heat stage temperature, etc. may be any suitable perovskite thin film within the scope of the present invention, but in order to further simplify the process, the parameters of the first and second examples are the most preferred.
Comparative example 1
This comparative example used a direct dissolution method to prepare CsPbBr 3 Inorganic perovskite thin film, and CsPbBr prepared in example one 3 The micro-morphology of the inorganic perovskite thin film is compared and is characterized by SEM.
CsPbBr 3 The preparation method of the inorganic perovskite narrow-band photoelectric detector comprises the following steps:
(1) 1mmol of PbBr 2 1mmol CsBr powder is dissolved in 12.5ml mixed solvent of DMSO and DMF (the volume ratio of DMSO to DMF is 1: 1), and the mixture is stirred uniformly to obtain CsPbBr 3 The precursor solution (molar concentration is 0.08 mol/L);
(2) sequentially carrying out ultrasonic cleaning on a transparent conductive substrate (such as FTO) by using deionized water, acetone, isopropanol and ethanol, and then putting the substrate into an oven to dry at 70 ℃ for later use;
(3) NiO is mixed y The solution and acetonitrile solution are mixed evenly according to the proportion of 1:25 to obtain NiO y A solution; placing the transparent conductive substrate on a heating table, heating the heating table to 475 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to be 5mm, and controlling the moving speed of a sprayer to be 1.6 cm/s; NiO is mixed y The solution is atomized to form atomized NiO y A solution; dry nitrogen is introduced into the atomization device at the flow rate of 1.6L/min, so that atomized liquid drops are uniformly sprayed on the conductive substrate through the nozzle to form uniform NiO y A film. During the process, the nozzle scans back and forth in the horizontal direction to grow NiO y Film(s)The deposition is continued for 8 scans. After the scanning is finished, the obtained NiO y Placing the film on a heating table at 500 ℃ for 30min, and cooling to room temperature;
(4) will be sprayed with NiO y Placing the conductive substrate of the film on a heating table, raising the temperature of the heating table to 140 ℃, adjusting the distance between a nozzle and the upper surface of the conductive substrate to be 5mm, and controlling the moving speed of a sprayer to be 1 cm/s; mixing CsPbBr 3 Atomizing the precursor solution to form atomized CsPbBr 3 Precursor solution; introducing dry nitrogen into the atomization device at a flow rate of 1.5L/min, uniformly spraying atomized liquid drops onto the conductive substrate through a nozzle, and volatilizing the solvent at high temperature to form uniform CsPbBr 3 A solid film. During this process, the nozzle is scanned back and forth in the horizontal direction, in the grown CsPbBr 3 Continuously depositing on the solid film, wherein the scanning times are 2-32 times;
(5) after the scanning is finished, the obtained CsPbBr is used 3 Placing the solid film on a heating table at 220 ℃ for 10 min;
(6) dissolving 1mg of PMMA powder in 1mL of chlorobenzene to obtain a PMMA solution, and dissolving 20mg of PCBM powder in 1mL of chlorobenzene to obtain a PCBM solution; 1mg of amino-functionalized diimine polymer (PPDIN 6) was dissolved in 2, 2, 2-Trifluoroethanol (TFE) to give PPDIN6 solution; taking 30 mu L PMMA solution to prepare the CsPbBr 3 Rotating the solid film at 7000rpm for 15s, drying, taking 30 μ L of PCBM solution to rotate at 3000rpm for 30s, and taking 30 μ L of PPDI 6 solution to rotate at 3000rpm for 30 s;
(7) ag electrode with the thickness of 80nm is vapor-plated on the PPDIN6 film layer, and finally CsPbBr is obtained 3 A narrow band photodetector.
Verification example 1
CsPbBr obtained in example 2 was taken 3 The microstructure of the inorganic perovskite thin film is observed by using a scanning electron microscope and an X-ray diffractometer, and the result is shown in figure 2. Wherein FIGS. 2 a-2 c show CsPbBr deposited at 140 deg.C 3 Heating the perovskite thin film on a heating table for SEM pictures of 0min and 10min respectively, wherein the model of the used instrument is JEOL JSM-7800F; fromAs can be seen from FIGS. 2a (0 min heating) and 2c (10 min heating), CsPbBr was obtained after 10min heating of the perovskite thin film in this example 3 The film surface is uniform and flat, and the grain size is large. Fig. 2b (heating for 0 min) and fig. 2d show that the film thickness can reach several micrometers, in close contact with the substrate.
The crystal structure of the film was characterized by X-ray diffraction pattern with the instrument model Bruker D8 Advance, as shown in FIG. 2e, and the CsPbBr thus prepared 3 Heating the film for 0min to obtain impure CsPbBr 3 Heating the film for 10min to eliminate impurity peak and obtain pure CsPbBr 3 A film. Multiple diffraction peaks appear at 2 theta values corresponding to (100), (110), (200), (210), (211), (202) crystal planes of the CsPbBr3 monoclinic structure, respectively, indicating that the crystal structure of the resulting film is indeed CsPbBr 3 。
Then, the morphology of the film obtained in example 2 by scanning, spraying and heating for different times is detected, and the result is shown in fig. 3. The results show that CsPbBr increased with the number of spray-coats 3 The thickness of the film is increased from 1 micron to 6 microns, the shape of the film is gradually increased in grain size along with the extension of heating time, and the method is shown to be capable of preparing thicker perovskite films with larger grain sizes and has higher quality. CsPbBr prepared by the method 3 The thickness of the inorganic perovskite film is controllable, so that the condition for preparing the narrow-band photoelectric detector is met.
Further, CsPbBr prepared by direct dissolution method in comparative example 1 was taken 3 The microstructure of the inorganic perovskite thin film is detected, and the result is shown in figure 4. As can be seen, CsPbBr obtained by direct dissolution 3 The film is very uneven, and the grain size is far smaller than that of the perovskite film prepared by the method.
Verification example 2
In order to characterize the superiority of the narrow-band photoelectric detector prepared by the method, performance parameters such as apparent quantum efficiency (EQE), responsivity (R), detectivity (D) and the like are tested, wherein the basic figure is shown in figures 5-8CsPbBr prepared in inventive example 2 3 And (3) device structure and performance characterization of the narrow-band photodetector. NiO is shown in FIG. 5 y Being hole-transporting layers, CsPbBr 3 Is a light active layer for absorbing photons; TiO 2 2 As electron transport layer:
the apparent quantum efficiency (EQE) calculation formula for the photodetector is:
whereinJ ph As to the density of the photocurrent,L ligh as to the intensity density of the incident light,his a constant of the number of planck,cin order to be the speed of light,λis a function of the wavelength of the light,qis an electronic charge.
Responsivity (R): defined as the ratio of photocurrent to light intensity, the formula is:
since the responsivity is proportional to the apparent quantum efficiency, the responsivity can also be expressed as:
detectivity (D): the capacity of the reaction device for detecting weak light is related to the responsivity and noise of the detector, and the formula is as follows:
wherein the content of the first and second substances,Ais the active area of the photodetector and,Δfis the bandwidth of the electrons and,i n is a noise current. Noise is mainly derived from three sources: shot noise due to dark current, johnson noise, and "sparkle" noise due to thermal fluctuations. If the detector noise is dominated by shot noise, the detection rate (D) can be expressed as:
wherein the content of the first and second substances,J d the dark current density.
FIG. 6 shows CsPbBr 3 The test results of the apparent quantum efficiency (EQE) of the narrow-band photodetector are shown schematically, fig. 7 shows the responsivity of the detector, and fig. 8 shows the detectivity of the detector.
The above detailed description section specifically describes the analysis method according to the present invention. It should be noted that the above description is only for the purpose of helping those skilled in the art better understand the method and idea of the present invention, and not for the limitation of the related contents. The present invention may be appropriately adjusted or modified by those skilled in the art without departing from the principle of the present invention, and the adjustment and modification also fall within the scope of the present invention.
Claims (10)
1. The preparation method of the all-inorganic perovskite thin film is characterized by comprising the following steps:
(1) mixing PbX 2 Dissolving in aqueous HBr to form a pale yellow solution; the aqueous solution of CsX was then added continuously to give an orange solid; washing and filtering the orange solid to obtain CsPbX 3 Powder, followed by CsPbX 3 Drying the powder;
(2) drying the CsPbX 3 Dissolving the powder in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and uniformly stirring to obtain CsPbX 3 Precursor solution;
(3) carrying out ultrasonic cleaning and drying on the transparent conductive substrate;
(4) the CsPbX obtained in the step (2) is treated 3 The precursor solution is subjected to ultrasonic atomization treatment and is uniformly sprayed on a transparent conductive substrate in a driving scanning mode to form CsPbX 3 Precursor liquid film and solvent are volatilized to form uniform CsPbX 3 A solid film;
(5) will be provided withCsPbX obtained in step (4) 3 Heating the solid film to promote further growth of the crystal;
wherein, X is selected from one or more of Cl, Br and I.
2. The method as claimed in claim 1, wherein the heating temperature in step (5) is 300-400 ℃ and the heating time is 1-60 min.
3. An all-inorganic perovskite thin film produced by the production method according to any one of claims 1 to 2.
4. The all-inorganic perovskite narrow-band photoelectric detector is characterized by sequentially comprising a transparent conductive substrate layer, a hole transport layer and CsPbX 3 The electron transport layer comprises a solid film layer, an electron transport layer and an electrode layer, wherein X is selected from one or more of Cl, Br and I.
5. The all-inorganic perovskite narrow-band photodetector of claim 4, wherein the hole transport layer is selected from NiO y 。
6. An all inorganic perovskite narrow band photodetector as claimed in any one of claims 4, wherein the electron transport layer is selected from TiO 2 、SnO 2 And a fullerene derivative PCBM.
7. A preparation method of an all-inorganic perovskite narrow-band photodetector is characterized by comprising the following steps:
(1) mixing PbX 2 Dissolving in aqueous HBr to form a pale yellow solution; the aqueous solution of CsX was then added continuously to give an orange solid; washing and filtering the orange solid to obtain CsPbX 3 Powder, followed by CsPbX 3 Drying the powder;
(2) drying the CsPbX 3 Dissolving the powder in dimethyl sulfoxide (DMSO) and N, N-dimethyl methylIn a mixed solvent of amide (DMF), evenly stirring to obtain CsPbX 3 Precursor solution;
(3) carrying out ultrasonic cleaning and drying on the transparent conductive substrate;
(4) uniformly spraying the hole transport layer solution on a dried substrate in a driving scanning mode after ultrasonic atomization treatment, and volatilizing a solvent to form a hole transport layer film;
(5) the CsPbX obtained in the step (2) is treated 3 Carrying out ultrasonic atomization treatment on the precursor solution, and uniformly spraying the precursor solution on the hole transport layer film obtained in the step (4) in a driving scanning mode to form CsPbX 3 Precursor liquid film and solvent are volatilized to form uniform CsPbX 3 A solid film;
(6) the CsPbX obtained in the step (5) is treated 3 Heating the solid film to promote further growth of the crystal;
(7) carrying out ultrasonic atomization treatment on the electron transport solution, and uniformly spraying the electron transport solution on the CsPbX subjected to heating treatment in the step (6) in a driving scanning manner 3 Forming an electron transport layer film on the surface of the solid film;
(8) evaporating and plating an electrode layer on the electron transport layer film to obtain the film;
wherein, X is selected from one or more of Cl, Br and I.
8. The method as claimed in claim 7, wherein after the step (4) of spraying, the hole transport layer film is optionally heated on a heating table at 400-500 ℃ for 10-60min and then naturally cooled to room temperature.
9. The method according to claim 7, wherein the heating temperature in step (6) is 300-400 ℃, and the heating time is 1-60 min.
10. The preparation method as claimed in claim 7, wherein after the step (7) of spraying, the electron transport layer film is optionally placed on a heating table at 200-500 ℃ for heating for 30-120min and then naturally cooled to room temperature.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221612A (en) * | 2017-06-15 | 2017-09-29 | 西南大学 | A kind of preparation method of full-inorganic perovskite thin film |
| CN107603614A (en) * | 2017-09-12 | 2018-01-19 | 华中科技大学 | A kind of preparation method of metal halide perovskite quantum dot |
| CN108075020A (en) * | 2017-12-27 | 2018-05-25 | 中国科学院长春光学精密机械与物理研究所 | A kind of caesium lead halogen perovskite thin film material and a kind of light emitting diode and preparation method thereof |
| CN110886017A (en) * | 2019-11-29 | 2020-03-17 | 上海应用技术大学 | Preparation method of all-inorganic cesium-lead halogen perovskite nanocrystalline film |
| US20210230011A1 (en) * | 2018-07-13 | 2021-07-29 | Oxford University Innovation Limited | Tunable blue emitting lead halide perovskites |
| CN113637471A (en) * | 2021-08-31 | 2021-11-12 | 中山大学 | In-situ lead salt coated all-inorganic lead halide perovskite nanocrystalline fluorescent powder and preparation method and application thereof |
| CN113809190A (en) * | 2021-09-14 | 2021-12-17 | 中山大学 | Low-temperature preparation method and application of all-inorganic perovskite thin film |
| CN114235771A (en) * | 2021-12-23 | 2022-03-25 | 重庆大学 | Sensing detection method for heavy metal mercury ion detection |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221612A (en) * | 2017-06-15 | 2017-09-29 | 西南大学 | A kind of preparation method of full-inorganic perovskite thin film |
| CN107603614A (en) * | 2017-09-12 | 2018-01-19 | 华中科技大学 | A kind of preparation method of metal halide perovskite quantum dot |
| CN108075020A (en) * | 2017-12-27 | 2018-05-25 | 中国科学院长春光学精密机械与物理研究所 | A kind of caesium lead halogen perovskite thin film material and a kind of light emitting diode and preparation method thereof |
| US20210230011A1 (en) * | 2018-07-13 | 2021-07-29 | Oxford University Innovation Limited | Tunable blue emitting lead halide perovskites |
| CN110886017A (en) * | 2019-11-29 | 2020-03-17 | 上海应用技术大学 | Preparation method of all-inorganic cesium-lead halogen perovskite nanocrystalline film |
| CN113637471A (en) * | 2021-08-31 | 2021-11-12 | 中山大学 | In-situ lead salt coated all-inorganic lead halide perovskite nanocrystalline fluorescent powder and preparation method and application thereof |
| CN113809190A (en) * | 2021-09-14 | 2021-12-17 | 中山大学 | Low-temperature preparation method and application of all-inorganic perovskite thin film |
| CN114235771A (en) * | 2021-12-23 | 2022-03-25 | 重庆大学 | Sensing detection method for heavy metal mercury ion detection |
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