Preparation method of double-layer composite material and application thereof

Abstract

The application discloses a preparation method of a double-layer composite material and application thereof, and the preparation method of the double-layer composite material comprises the following steps: dissolving formamidinium hydriodide, methylammonium iodide, lead iodide, stannous iodide and an additive in a mixed solution of dimethylformamide and dimethyl sulfoxide to prepare a perovskite precursor solution; coating the perovskite precursor solution on a substrate in a spin coating mode; treating the precursor solution with an anti-solvent during the spin coating process to obtain an intermediate phase thin film; and performing annealing treatment on the intermediate phase thin film to obtain a fully crystallized double-layer perovskite thin film. By using the method, the problems that the existing perovskite battery has poor absorption to near-infrared light, the photoelectric conversion efficiency is reduced, the utilization rate of light is not high, the device temperature is increased, and the application field is limited, and the existing double-layer perovskite thin film is prepared in layers, the preparation process is increased, and the production efficiency of the battery is reduced and the like can be solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photovoltaic cells, in particular to a preparation method of a double-layer composite material and application thereof. BACKGROUND

[0002] Perovskite thin film materials have attracted much attention in the field of photovoltaics due to their high efficiency and low cost advantages. However, there are also some challenges and limitations with general perovskite thin films. The existing perovskite thin films have poor near-infrared light absorption ability, which not only limits their application in certain fields (such as photoelectric conversion, photo-thermal conversion, optoelectronic devices, etc.), but also may cause a series of technical and performance challenges.

[0003] The poor near-infrared light absorption ability of perovskite thin films will directly lead to low photoelectric conversion efficiency in applications such as solar cells. Since the solar spectrum contains a large amount of near-infrared light components, if they cannot be effectively utilized, the energy conversion efficiency of the entire system will be severely affected. The unabsorbed near-infrared light is converted to heat energy inside the perovskite thin film, causing the device temperature to rise. High temperature not only further reduces the photoelectric performance of perovskite, but also may cause problems such as material aging and decreased stability. Due to the limitations of perovskite thin films in near-infrared light absorption, their application fields will also be limited, especially in applications that require efficient use of near-infrared light (such as infrared imaging, infrared communication, etc.), which will affect the sensitivity and accuracy of the device.

[0004] The preparation method of double-layer perovskite thin films now mostly adopts a layered preparation method, that is, first preparing perovskite thin films on two substrates, then attaching the two perovskite thin films towards each other to form a double-layer perovskite thin film; or first preparing one layer of perovskite thin film, then preparing another layer of perovskite thin film on the layer of perovskite thin film to obtain a double-layer perovskite thin film. The layered preparation method of double-layer perovskite thin films increases the preparation process of perovskite cells, thereby reducing the production efficiency of perovskite cells, which is not conducive to industrial development. SUMMARY

[0005] The purpose of the present application is to provide a preparation method of a double-layer composite material and application thereof, which can effectively solve the problems of poor near-infrared light absorption of existing perovskite cells, leading to low photoelectric conversion efficiency, low light utilization rate, high device temperature, and limited application fields, and also solve the problems of existing double-layer perovskite thin film preparation methods, such as multiple preparation processes and low production efficiency of perovskite cells.

[0006] The purpose of the present application is achieved by the following technical solutions:

[0007] A preparation method of a double-layer composite material, comprising the following steps:

[0008] S1. Dissolving formamidinium iodide (FAI), methylammonium iodide (MAI), lead iodide (PbI2), stannous iodide (SnI2) and an additive in a mixed solvent to obtain a perovskite precursor solution; the mixed solvent comprises dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The additive is a divalent tin halide, which is used to inhibit the oxidation of divalent tin ions in the perovskite precursor solution.

[0009] Since the divalent tin cations in the perovskite precursor solution are easy to be oxidized to tetravalent tin ions, the overall stability of the solution is reduced, which makes the perovskite precursor solution more prone to decomposition or deterioration, and the film quality of the prepared perovskite film is also reduced. Moreover, the oxidation reaction of divalent tin ions in the perovskite precursor solution also produces some harmful by-products, such as oxides and hydroxides, which can cause harm to the environment and human health. Therefore, when preparing the perovskite precursor solution, the additive is added, and the additive is selected from divalent tin halides. The divalent tin halides can inhibit the oxidation of divalent tin cations in the perovskite precursor solution, and divalent tin ions generally have better stability in the perovskite precursor solution, avoiding decomposition and deterioration of the perovskite precursor solution, improving the film quality of the perovskite film, reducing the generation of harmful by-products, and reducing the harm to the environment and human health.

[0010] S2. The perovskite precursor solution is coated on a substrate by spin coating, and an antisolvent is used to treat the perovskite precursor solution during the coating (spin coating) process to obtain an intermediate phase film. The intermediate phase film is annealed to obtain a fully crystallized double-layer perovskite film. The antisolvent can promote the rapid film formation and crystallization of the perovskite film. The double-layer perovskite film comprises a first perovskite layer and a second perovskite layer. The first perovskite layer has a composition of FASnI3 and is used to absorb near-infrared light and visible light. The second perovskite layer has a composition of FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 and is used for secondary absorption of the visible light and the near-infrared light.

[0011] The single-layer perovskite thin film currently used has poor near-infrared light absorption capacity, which reduces the photoelectric conversion efficiency of the perovskite battery. Since the solar spectrum contains a large amount of near-infrared light component, if it cannot be effectively utilized, the unabsorbed near-infrared light will be converted into heat energy inside the perovskite thin film, causing the device temperature to rise. High temperature not only further reduces the photoelectric performance of the perovskite, but also causes problems such as material aging and stability decline. The double-layer perovskite thin film has a first perovskite layer in addition to the single-layer perovskite thin film, the first perovskite layer has a component of FASnI3 and a band gap of about 1.4 eV, so the first perovskite layer can absorb infrared light and visible light, the second perovskite layer has a component of FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 and a band gap of about 1.25 eV, which can perform secondary absorption on the visible light and the near-infrared light, improve the utilization rate of the double-layer perovskite thin film to sunlight, and also reduce the conversion of near-infrared light into heat energy inside the double-layer perovskite thin film, thereby avoiding the high temperature generated inside the device to avoid reducing the photoelectric conversion performance of the perovskite battery.

[0012] By adding the additive to the perovskite precursor solution, controlling the content of divalent tin ions, and then using common spin coating method and annealing treatment, the double-layer perovskite layer (i.e. double-layer perovskite thin film) can be obtained, the whole preparation process is simple, reduces the production cost, and improves the production efficiency.

[0013] Further, in step S1 of the preparation method of the double-layer composite material, the divalent tin halide is stannous fluoride (SnF2), stannous chloride (SnCl2) or stannous bromide (SnBr2).

[0014] Further, in step S1 of the preparation method of the double-layer composite material, the anti-solvent is chlorobenzene or ethyl acetate. In step S2 of the preparation method of the double-layer composite material, the annealing treatment adopts two-step annealing, including first annealing treatment and second annealing treatment, the temperature of the first annealing treatment is 50-100 DEG C and the annealing time is 1-10 min, the temperature of the second annealing treatment is 100-150 DEG C and the annealing time is 1-10 min. Preferably, the temperature of the first annealing treatment is 70 DEG C and the annealing time is 2 min, the temperature of the second annealing treatment is 100 DEG C and the annealing time is 7 min.

[0015] Meanwhile, the application also provides a perovskite battery with a double-layer perovskite thin film, which comprises a substrate, a hole transport layer, a double-layer perovskite thin film, an electron transport layer and a metal electrode, wherein the double-layer perovskite thin film is prepared by the above-mentioned preparation method of the double-layer composite material.

[0016] The perovskite cell with the double-layer perovskite thin film can optimize the energy band structure and charge transport characteristics of the material, thereby improving the stability of the perovskite thin film. The double-layer perovskite thin film can further absorb near-infrared light through the double-layer structure, so as to realize sufficient absorption and efficient conversion of sunlight. This can not only improve the photoelectric conversion efficiency of the solar cell, but also expand the application field thereof.

[0017] Further, the perovskite cell is a form perovskite cell or an inverse perovskite cell.

[0018] Further, in the perovskite cell with the double-layer perovskite thin film, the hole transport layer comprises one of nickel oxide (NiO x ), 3-hexylthiophene (P3HT), cuprous thiocyanate (CuSCN), [2-(9h-carbazol-9-yl)ethyl] phosphonic acid (2PACZ), [2-(3,6-dimethoxy-9H-carbazol-9-yl) ethyl] phosphonic acid (MeO-2PACZ), [4-(3,6-dimethyl-9H-carbazol-9-yl) butyl] phosphonic acid (Me-4PACZ), and [4-(3,6-dimethoxy-9H-carbazol-9-yl) butyl] phosphonic acid (MeO-4PACZ); the annealing temperature of the hole transport layer is 50-350℃, and the thickness of the hole transport layer is 10-70nm; the electron transport layer is fullerene (C 60 ) or [6,6]-phenyl-C71-butyric acid methyl ester (PC 71 BM), and the thickness of the electron transport layer is 10-70nm.

[0019] Further, when the perovskite cell adopts an inverse structure, it further comprises a hole blocking layer, the hole blocking layer is arranged between the electron transport layer and the metal electrode, the material of the hole blocking layer is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), and the thickness of the hole blocking layer is 1-10nm.

[0020] Further, in the perovskite cell with the double-layer perovskite thin film, the substrate is indium tin oxide (ITO) glass, fluorine-doped tin oxide (FTO) glass, or aluminum-doped zinc oxide (AZO) glass.

[0021] Further, the application also provides a photoelectric detection system, comprising a bias adjusting device, a light power meter, an output device and at least one photoelectric detector; the photoelectric detector is the perovskite cell with the double-layer perovskite film; the photoelectric detector and the light power meter are both connected to the output device; the bias adjusting device is connected to the photoelectric detector, for applying a positive bias or a negative bias to the photoelectric detector; the light power meter is used for measuring and outputting a light power signal of the light to be detected, for reading a photocurrent signal of the light to be detected under the corresponding bias; and the output device is used for receiving the light power signal and the photocurrent signal and outputting spectral information of the light to be detected.

[0022] The photoelectric detection system can improve the detection capability of visible light and near-infrared light, and compared with the traditional photoelectric detection system, does not need additional optical filters or light splitting devices, simplifies the structure of the system and reduces the requirements for the environment and equipment during use.

[0023] Further, in the photoelectric detection system, a plurality of photoelectric detectors are distributed in a rectangular array to form a photoelectric detector array, a plurality of photoelectric detectors share a top electrode, a plurality of photoelectric detectors in each row of the photoelectric detector array share a row bottom electrode, and a plurality of photoelectric detectors in each column of the photoelectric detector array share a column bottom electrode; the bias device is connected to the photoelectric detector array, for applying a bias to each photoelectric detector; the photoelectric detector array is also connected to the output device; and the photoelectric detector array can output a photoelectric signal of each photoelectric detector.

[0024] Further, the photoelectric detection system further comprises a control circuit connected to the photoelectric detector array, for controlling the readout logic of the photoelectric detector array.

[0025] In summary, due to the adoption of the above technical solutions, the application has the following advantages:

[0026] (1) The preparation method of the double-layer composite material can inhibit the oxidation of divalent tin ions in the perovskite precursor solution by adding divalent tin halide to the perovskite precursor solution during the preparation of the perovskite precursor solution. Compared with the single-layer perovskite film, the double-layer perovskite film can absorb further infrared light and visible light, improve the utilization rate of sunlight by the double-layer perovskite film, and reduce the conversion of sunlight into heat energy inside the double-layer perovskite film, so as to avoid reducing the photoelectric conversion performance of the perovskite cell. By adding the additive to the perovskite precursor solution and using the common spin coating method and annealing treatment, the double-layer perovskite layer can be obtained, the whole preparation process is simple, the production cost is reduced, and the production efficiency is improved.

[0027] (2) The perovskite battery with the double-layer perovskite film has the double-layer structure, the double-layer perovskite film can further absorb visible light and near-infrared light, and high-efficiency conversion of sunlight can be realized. Therefore, the photoelectric conversion efficiency of the solar cell can be improved, and the application field of the solar cell can be widened.

[0028] (3) The photoelectric detection system adopts the perovskite battery with the double-layer perovskite film as a photoelectric detector, and the detector has high light responsivity to light in a visible to near-infrared waveband range. Compared with a traditional photoelectric detection system, the photoelectric detection system does not need an additional optical filter or a light splitting device, the structure of the system is simplified, and the requirements for the environment and equipment during use are reduced. BRIEF DESCRIPTION OF DRAWINGS

[0029] The application will be described in further detail below with reference to the drawings.

[0030] Figure 1 The preparation flow chart of the preparation method of the double-layer composite material described in Embodiment 1 of the application.

[0031] Figure 2 The structure diagram of the transverse perovskite battery of the perovskite battery with the double-layer perovskite film described in Embodiment 2 of the application.

[0032] Figure 3 The connection diagram of the photoelectric detection system described in Embodiment 3 of the application.

[0033] Figure 4 The I-V characteristic curve diagram of the detector prepared in Embodiment 3 of the application under detection of light with different wavelengths.

[0034] Figure 5 The connection diagram of the photoelectric detector array distribution of the photoelectric detection system described in Embodiment 4 of the application.

[0035] As shown in the figure: 1 - substrate; 2 - hole transport layer; 3 - double-layer perovskite film; 31 - first perovskite layer; 32 - second perovskite layer; 4 - electron transport layer; 5 - hole blocking layer; 6 - metal electrode. DETAILED DESCRIPTION

[0036] The embodiments of the application will be described in detail below with reference to specific embodiments. Those skilled in the art can easily understand other advantages and effects of the application from the content disclosed in the specification. The described embodiments are only a part of the embodiments of the application, not all. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0037] It should be understood that the structures, proportions, sizes, etc., depicted in the accompanying drawings of this specification are merely for illustrative purposes to aid those skilled in the art in understanding and reading the content disclosed herein, and are not intended to limit the conditions under which the invention can be implemented. Therefore, they have no substantial technical significance. Any modifications to the structure, changes in proportions, or adjustments to the size, without affecting the effects and objectives achieved by the invention, should still fall within the scope of the technical content disclosed herein. Furthermore, the terms such as "upper," "lower," "left," "right," and "middle" used in this specification are merely for clarity and are not intended to limit the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention's implementation.

[0038] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "connected" and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances. Example 1

[0039] like Figure 1 As shown, this embodiment provides a method for preparing a bilayer composite material, including the following steps:

[0040] S1. Preparation of perovskite precursor solution:

[0041] S11. Weigh out specific amounts of formamidinium hydroiodate (FAI), methylammonium iodide (MAI), lead iodide (PbI2), stannous iodide (SnI2), and additives for later use; mix dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) to obtain a mixed solvent for later use. The additive is a divalent tin halide, used to inhibit the oxidation of divalent tin ions in the perovskite precursor solution. The divalent tin halide is any one of stannous fluoride (SnF2), stannous chloride (SnCl2), and stannous bromide (SnBr2).

[0042] S12. Weigh out formamidin hydroiodide (FAI), methylammonium iodide (MAI), lead iodide (PbI2), stannous iodide (SnI2) and additives and dissolve them in a mixed solvent to prepare a perovskite precursor solution.

[0043] S2. Preparation of bilayer perovskite thin film 3:

[0044] S21. The perovskite precursor solution obtained in step S12 is coated onto the substrate by spin coating to form a wet precursor film.

[0045] S22. Vacuum-assisted crystallization treatment is performed on the wet film of the precursor using a counter solvent chlorobenzene or ethyl acetate in a spin coating process to obtain an intermediate phase thin film. The counter solvent can promote rapid film formation and crystallization of the perovskite thin film.

[0046] S23. The intermediate phase thin film obtained in step S22 is subjected to annealing treatment, and the annealing treatment adopts two-step annealing, the first step annealing temperature is 70°C, the annealing time is 2 min, the second step annealing temperature is 100°C, the annealing time is 7 min, and after the annealing treatment is completed, a double-layer perovskite thin film 3 with a thickness of 500 nm and sufficient crystallization is prepared.

[0047] The double-layer perovskite thin film 3 comprises a first perovskite layer 31 and a second perovskite layer 32.

[0048] The first perovskite layer 31 is composed of FASnI3, which is used to absorb near-infrared light and visible light.

[0049] The second perovskite layer 32 is composed of FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3, which is used for secondary absorption of the visible light and the near-infrared light.

[0050] Compared with a single-layer perovskite thin film, the double-layer perovskite thin film 3 can absorb further infrared light and visible light, improve the utilization rate of sunlight by the double-layer perovskite thin film 3, and reduce the conversion of sunlight into heat energy inside the double-layer perovskite thin film 3, thereby avoiding the reduction of the photoelectric conversion performance of the perovskite battery. The double-layer perovskite layer can be obtained by adding an additive to the perovskite precursor solution and using a common spin coating method and annealing treatment, which is simple in preparation process, reduces production cost, and improves production efficiency. Example 2

[0051] Based on the double-layer perovskite thin film prepared in the example, as shown in the figure, the present embodiment provides a perovskite battery with a double-layer perovskite thin film, which comprises a substrate 1, a hole transport layer 2, a double-layer perovskite thin film 3, an electron transport layer 4, and a metal electrode 6. Figure 2

[0052] The substrate 1 is indium tin oxide (ITO) glass, fluorine-doped tin oxide (FTO) glass, or aluminum-doped zinc oxide (AZO) glass.

[0053] The hole transport layer 2 is nickel oxide (NiO x ​The hole transport layer 2 is selected from the following: 3-hexylthiophene (P3HT), cuprous thiocyanate (CuSCN), [2-(9h-carbazole-9-yl)ethyl]phosphonic acid (2PACZ), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACZ), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACZ), and [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid (MeO-4PACZ); the annealing temperature of the hole transport layer 2 is 50-350℃, and the thickness of the hole transport layer 2 is 10-70nm.

[0054] The bilayer perovskite film 3 was prepared by the method for preparing bilayer composite materials in Example 1.

[0055] The electron transport layer 4 is a fullerene (C 60 ) or [6,6]-phenyl-C71-butyrate methyl ester (PC) 71 The thickness of the electron transport layer 4 is 10-70 nm.

[0056] The metal electrode 6 is made of silver and has a thickness of about 200 nm.

[0057] The use of a perovskite solar cell with a double-layer perovskite thin film 3 optimizes the band structure and charge transport characteristics of the material, thereby improving the stability of the perovskite thin film. The double-layer perovskite thin film 3 can further absorb near-infrared light through its double-layer structure, achieving full absorption and efficient conversion of sunlight. This not only improves the photoelectric conversion efficiency of solar cells but also broadens their application areas.

[0058] The following example uses an inverted perovskite solar cell, such as... Figure 2 The diagram shows an inverted perovskite solar cell, comprising, from bottom to top, a substrate 1, a hole transport layer 2, a bilayer perovskite thin film 3, an electron transport layer 4, a hole blocking layer 5, and a metal electrode 6, stacked sequentially. The bilayer perovskite thin film includes a first perovskite layer 31 and a second perovskite layer 32. The hole blocking layer 5 is made of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), and its thickness is 1-10 nm.

[0059] The fabrication process of the inverted perovskite solar cell is as follows:

[0060] A. Preparation of the substrate 1: The substrate 1 was ultrasonically cleaned with anhydrous ethanol, thoroughly dried, and then subjected to ultraviolet-ozone treatment for 20 minutes.

[0061] B. Preparation of the hole transport layer 2: In this embodiment, the hole transport layer 2 (NiO) is prepared by sputtering. x), the substrate 1 is transferred to the base of the sputtering device, and NiO x The target material is fixed at the target position of the sputtering gun or sputtering chamber. The relevant parameters of the sputtering device are set, and the gas is set as argon. Vacuum is pumped to reach a vacuum degree of 10 -6 Sputtering is started after T, and the deposition rate is controlled at 2 nm / min. After 40 nm is deposited, the sample is taken out for post-processing.

[0062] C. Preparing the double-layer perovskite film 3: a perovskite precursor solution is prepared, and in this embodiment, a certain amount of FAI, PbI2, MAI, SnI2 and the additive are dissolved in a mixed solvent of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) to prepare the perovskite precursor solution. The perovskite precursor solution is coated on the top surface of the hole transport layer 2 by spin coating. 200 μL of anti-solvent chlorobenzene is added 20 s before the spin coating is completed. The double-layer perovskite film 3 is annealed in two steps, the first step is annealed at 70℃ for 2 min, and the second step is annealed at 100℃ for 7 min. A double-layer perovskite film 3 with a thickness of 500 nm is prepared. The prepared double-layer perovskite film 3 includes a first perovskite layer 31 and a second perovskite layer 32.

[0063] D. Preparing the electron transport layer 4 and the hole blocking layer 5: the thickness of the electron transport layer 4 is 30 nm; the material of the hole blocking layer 5 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), and the thickness of the hole blocking layer is 6 nm.

[0064] E. Preparing the metal electrode 6: the material of the metal electrode 6 in this embodiment is silver, and the thickness of the metal electrode 6 is 200 nm. Embodiment 3

[0065] This embodiment further provides a photoelectric detection system based on the embodiment 2, which includes a photoelectric detector, a bias voltage adjusting device, a light power meter and an output device. At least one perovskite cell with a double-layer perovskite film as described in embodiment 2 is used as the photoelectric detector in the photoelectric detection system.

[0066] The photoelectric detector and the light power meter are both connected to the output device.

[0067] The bias voltage adjusting device is connected to the photoelectric detector, and is used to apply a positive bias voltage or a negative bias voltage to the photoelectric detector.

[0068] The light power meter is used to measure and output the light power signal of the light to be measured, and is used to read the photocurrent signal of the light to be measured under the corresponding bias voltage.

[0069] The output device is used to receive optical power signals and photocurrent signals and output the spectral information of the light to be measured.

[0070] The method for identifying the output device is as follows:

[0071] (1) Calibration of the test system:

[0072] The test system for the output device is calibrated using a known single-wavelength light source. Let the known single wavelength be λ. n One light source after another is incident on the photoelectric detection system, and the optical power P(λ) is obtained by the optical power meter. n The photodetector receives the photocurrent I(λ) under the corresponding bias voltage. n Then, the photocurrent for each wavelength is normalized according to the optical power, i.e., I'(λ). n ,V)=I(λ n ,V) / P(λ n The data for each wavelength is labeled λ. n .

[0073] (2) Function fitting:

[0074] The obtained data is fed into a neural network for training, which can fit a function of the IV characteristic curve and wavelength of the incident light.

[0075] (3) Measurement of actual spectra:

[0076] After obtaining the IV characteristic curve of the unknown light, the spectral information of the unknown light can be obtained by solving the function.

[0077] like Figure 4 The graphs show the IV characteristics of the fabricated detector under different wavelengths of light, covering the red, green, and blue visible light, as well as near-infrared light. Its dark current was also measured. Figure 4 As shown, the detector's detection range extends from visible light to near-infrared. The photocurrent for red light reaches 10. -3 A, the photocurrent of near-infrared light also reached 10. -4 A. Therefore, this detector can be applied to fields such as infrared night vision. Furthermore, the photoelectric response curves for different wavelengths exhibit high distinguishability, providing a good foundation for spectral identification. Example 4

[0078] like Figure 5 As shown, this embodiment further provides a photoelectric detection system based on embodiment 3. In addition to the structure described in embodiment 3, the photoelectric detection system also includes a control circuit.

[0079] The photoelectric detection system, a plurality of photoelectric detectors are distributed in a rectangular array to form a photoelectric detector array, a plurality of photoelectric detectors share a top electrode, each row of photoelectric detectors in the photoelectric detector array shares a row bottom electrode, and each column of photoelectric detectors in the photoelectric detector array shares a column bottom electrode. The photoelectric detector array top electrode adopts an ITO electrode, and the row bottom electrode and the column bottom electrode both adopt a copper electrode.

[0080] The bias device is connected with the photoelectric detector array, and is used to apply a bias voltage to each photoelectric detector of the photoelectric detector array.

[0081] The photoelectric detector array is also connected with an output device, and the photoelectric detector array can output a photoelectric signal of each photoelectric detector.

[0082] The control circuit is connected with the photoelectric detector array, and is used to control the readout logic of the photoelectric detector array. The control circuit first selects a specific row through the row bottom electrode, and then selects a specific photoelectric detector through the column bottom electrode controlled by the control circuit, and reads out and transmits the photoelectric current signal under the bias voltage to the output device. In the case that the bias voltage is unchanged, the control circuit controls different row bottom electrodes and column bottom electrodes to repeat the above steps, so as to obtain the photoelectric current signal of the photoelectric detector array under a specific bias voltage. The bias device changes the applied bias voltage, and the whole photoelectric detector array is read repeatedly for multiple times. Thus, the output device obtains the I-V curve of each photoelectric detector, and obtains the spectrum of the light signal received by each photoelectric detector in the array through function recovery, and the obtained spectrum information can be used to realize color imaging of the photoelectric detector array. Since the detection wavelength can reach the near-infrared range, the photoelectric detector array can be used in the fields of all-weather imaging security and the like.

[0083] Other details of the present application are well known to those skilled in the art.

[0084] It should be noted that the terms "comprising", "including", or any other variant thereof are intended to cover non-exclusive inclusion, so that processes, methods, articles or devices including a series of elements not only include those elements, but also include other elements not explicitly listed, or inherent to such processes, methods, articles or devices.

[0085] The protection scope of the present application is not limited to the technical solutions disclosed in the specific embodiments, and any modification, equivalent replacement, improvement, etc. made to the above embodiments according to the technical essence of the present application all fall within the protection scope of the present application.

Claims

1. A method for producing a double-layered composite material, characterized by, The method comprises the following steps: S1. Dissolving formamidinium iodide (FAI), methylammonium iodide (MAI), lead iodide (PbI2), stannous iodide (SnI2) and an additive in a mixed solvent to obtain a perovskite precursor solution; the mixed solvent comprises dimethylformamide (DMF) and dimethyl sulfoxide (DMSO); the additive is a divalent tin halide, which is used to inhibit the oxidation of divalent tin ions in the perovskite precursor solution; S2. Coating the perovskite precursor solution on a substrate; During the coating process, the perovskite precursor solution is treated by using an anti-solvent to obtain an intermediate phase thin film; the intermediate phase thin film is subjected to annealing treatment to obtain a fully crystallized double-layer perovskite thin film; The double-layer perovskite film comprises a first perovskite layer and a second perovskite layer; the component of the first perovskite layer is FASnI3, for absorbing near-infrared light and visible light; the component of the second perovskite layer is FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3, for secondary absorption of the visible light and the near-infrared light.

2. The method of claim 1, wherein: The divalent tin halide is stannous fluoride (SnF2), stannous chloride (SnCl2) or stannous bromide (SnBr2).

3. The method of claim 1, wherein: The anti-solvent is chlorobenzene or ethyl acetate; the annealing treatment comprises a first annealing treatment and a second annealing treatment; the temperature of the first annealing treatment is 50-100°C and the annealing time is 1-10 min; the temperature of the second annealing treatment is 100-150°C and the annealing time is 1-10 min.

4. A perovskite cell having a double layer perovskite thin film, characterized by: The perovskite battery comprises a substrate, a hole transport layer, a double-layer perovskite thin film, an electron transport layer and a metal electrode, wherein the double-layer perovskite thin film is obtained by the method for preparing the double-layer composite material according to any one of claims 1-3.

5. The perovskite cell having a double-layer perovskite thin film according to claim 4, characterized by: The perovskite battery is a cis perovskite battery or a trans perovskite battery.

6. The perovskite battery with a double-layer perovskite thin film according to claim 4, wherein: The hole transport layer comprises one of nickel oxide (NiO x ), poly-3-hexylthiophene (P3HT), cuprous thiocyanate (CuSCN), [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACZ), [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACZ), [4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid (Me-4PACZ), and [4-(3,6-dimethoxy-9H-carbazol-9-yl)butyl]phosphonic acid (MeO-4PACZ); the annealing temperature of the hole transport layer is 50-350℃, the thickness of the hole transport layer is 10-70nm; the electron transport layer is fullerene (C 60 ) or [6,6]-phenyl-C71-butyric acid methyl ester (PC 71 BM), and the thickness of the electron transport layer is 10-70nm.

7. The perovskite cell having a double layer perovskite thin film according to claim 5, characterized by: When the perovskite battery adopts a trans structure, it further comprises a hole blocking layer, which is arranged between the electron transport layer and the metal electrode; the material of the hole blocking layer is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), and the thickness of the hole blocking layer is 1-10 nm.

8. A photodetection system, characterized by: The bias adjusting device, the optical power meter, the output device and at least one photodetector; the photodetector is the perovskite battery with a double-layer perovskite thin film according to any one of claims 4-7; the photodetector and the optical power meter are both connected to the output device; the bias adjusting device is connected to the photodetector, which is used to apply a positive bias or a negative bias to the photodetector; the optical power meter is used to measure and output the optical power signal of the light to be measured, which is used to read the photocurrent signal of the light to be measured under the corresponding bias; the output device is used to receive the optical power signal and the photocurrent signal and output the spectral information of the light to be measured.

9. The photodetection system of claim 8, wherein: A plurality of photodetectors are distributed in a rectangular array to form a photodetector array, a plurality of photodetectors share a top electrode, a plurality of photodetectors in each row of the photodetector array share a row bottom electrode, and a plurality of photodetectors in each column of the photodetector array share a column bottom electrode; the bias adjusting device is connected to the photodetector array, which is used to apply a bias to each photodetector. The photoelectric detector array is also connected with an output device; the photoelectric detector array can output photoelectric signals of each photoelectric detector.

10. The photodetection system of claim 9, wherein: A control circuit is also included, which is connected with the photoelectric detector array and used for controlling the readout logic of the photoelectric detector array.

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