CN111525035A - Inorganic perovskite battery modified by single-particle nano heterojunction interface and preparation method - Google Patents

Inorganic perovskite battery modified by single-particle nano heterojunction interface and preparation method Download PDF

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CN111525035A
CN111525035A CN202010395603.1A CN202010395603A CN111525035A CN 111525035 A CN111525035 A CN 111525035A CN 202010395603 A CN202010395603 A CN 202010395603A CN 111525035 A CN111525035 A CN 111525035A
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inorganic perovskite
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CN111525035B (en
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杨英
王惟嘉
朱从潭
刘圣
林飞宇
马书鹏
罗媛
郭学益
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Central South University
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Abstract

An inorganic perovskite battery modified by a single-particle nano heterojunction interface and a preparation method thereof. The inorganic perovskite solar cell of the invention is a single-particle binary nano heterojunction (ZnS-Cu)2S or MnS-Cu2S or CdS-Cu2S) inserting the electronic transmission material and the perovskite thin film as a modification layer, and passivating the oxygen vacancy of the metal oxide and the perovskite defect through interfacial chemical bonding so as to improve the electronic state and stability; secondly, the formation of crystals is influenced through the interaction of the interface functional groups and the perovskite material; and thirdly, the interface composition between the metal oxide and the perovskite layer is adjusted to promote the charge extraction and improve the device performance. The inventionThe preparation method has simple process and easy operation.

Description

Inorganic perovskite battery modified by single-particle nano heterojunction interface and preparation method
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a single-particle nano heterojunction interface modified inorganic perovskite cell and a preparation method thereof.
Background
Perovskite solar cells consist mainly of an electron transport layer (ETL, such as SnO)2、TiO2) Perovskite light absorbing material (ABX)3（A=CH3NH3(MA) or Cs, etc., B = Pb, Sn, etc., X = I, Br, Cl)), a hole transport layer (HTL, such as spiro-OMeTAD), and a metal electrode. The method has become a research focus in the field of photoelectric devices due to high efficiency, low cost, simple process and environmental friendliness. In 2019, the conversion efficiency of the solar cell reaches 25.2%, and the solar cell has extremely high development and application potential. Although being a new type of photovoltaic device, perovskite solar cells have achieved photoelectric conversion efficiencies far exceeding those of other types of solar cells; but with organic-inorganic hybrid perovskite CH3NH3BX3Devices which are light absorption materials are extremely sensitive to photo-thermal, water oxygen and the like and are easy to decompose, so that the stability of the devices is poor, and the practicability of the perovskite solar cell is limited.
Researchers have formed CsPbX using stable inorganic cations instead of traditional inorganic-organic perovskites3(X = I, Br) an inorganic perovskite light absorbing material. Inorganic perovskite solar cells have attracted more and more attention in recent years due to their superior thermal stability and photoelectric properties. However, in planar structural perovskite cells, the interfacial area between the perovskite and the transport layer is very limited. The most studied positive perovskite solar cells have shown TiO in them2Material, especially porous TiO2The defect states are excessive and the charge transfer speed is very slow.
The perovskite solar cell is provided with two charge transport layers above and below a perovskite layer, and the charge transport layers determine the extraction and transmission of charges; an interface is inevitably formed between the charge transport layer and the perovskite layer, and if the charge transport layer and the perovskite layer cannot be brought into close contact, the interface becomes a non-radiative recombination center, which results in serious energy loss of the device and reduces the efficiency and stability of the device. Interface engineering is considered to be an effective method to improve the charge transport at the electron transport layer/perovskite interface.
CN110911566A discloses a carbon-based perovskite solar cell based on a multifunctional interface modification layer. The structure of the transparent conductive substrate comprises a transparent conductive substrate, an electron transport layer, a perovskite layer and a carbon electrode. The alkali metal hydroxide is modified between the electron transport layer and the perovskite layer, mainly by coating. The modification layer improves the film forming quality of the perovskite layer by reducing the interfacial tension and work function of the electron transport layer, so that the carrier transport between interfaces is promoted and the non-radiative recombination in the film is weakened. The photoelectric conversion efficiency is improved, and the stability and the hysteresis effect are improved.
CN110459680A discloses a perovskite solar cell. The perovskite solar cell sequentially comprises from bottom to top: the device comprises a substrate, a transparent electrode, an electron transport layer, an interface modification layer, a perovskite light absorption layer, a hole transport layer and a top electrode; the electron transmission layer is a nano titanium dioxide film; the interface modification layer is a polymer film, and the invention also provides a preparation method of the perovskite solar cell. This perovskite solar cell through the interface modification layer that has set up polymer film on electron transport layer, has improved interface quality, improves the crystalline phase quality of perovskite through the reduction of surface energy, and then optimizes the interface, improves the quality of perovskite light absorption layer, has effectively improved the open circuit voltage and the fill factor of device to make solar cell's energy conversion efficiency show the improvement.
The technical scheme disclosed above respectively adopts alkali metal hydroxide and a polymer film as interface modification layers, which all improve the photoelectric conversion efficiency and stability of the solar cell, but still need to be further improved for accelerating the application of the solar cell.
Disclosure of Invention
The invention aims to overcome the defects and provide a single-particle nano heterojunction interface modified inorganic perovskite battery and a preparation method thereof. The inorganic perovskite battery has excellent photoelectric conversion performance and good stability. The preparation method has simple process and easy operation.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the inorganic perovskite battery with the single-particle nano heterojunction interface modification sequentially comprises an electron transmission layer, an inorganic perovskite thin film, a hole transmission layer and a metal electrode layer, wherein an interface modification layer is arranged between the electron transmission layer and the inorganic perovskite thin film, and the interface modification layer is made of single-particle binary nano heterojunction ZnS-Cu2S、MnS-Cu2S or CdS-Cu2S。
Preferably, the material of the inorganic perovskite thin film is CsPbI3、CsPbBrI2、CsPbBr2I or CsPbBr3。
The preparation method of the inorganic perovskite battery modified by the single-particle nano heterojunction interface comprises the following steps:
(1) cleaning transparent FTO conductive glass to obtain a transparent conductive substrate;
(2) sequentially preparing compact TiO on the transparent conductive substrate obtained in the step (1)2Layer and mesoporous TiO2Obtaining an FTO/electron transport layer;
(3) dripping dispersion liquid of single-particle binary nano heterojunction on the electronic transmission layer obtained in the step (2) in an inert atmosphere, spin-coating to form a film, and performing heat treatment to obtain an FTO/electronic transmission layer/interface modification layer;
(4) under inert atmosphere, adding CsPbI into inorganic perovskite3、CsPbBrI2、CsPbBr2I or CsPbBr3Dropwise adding the precursor solution on the FTO/electron transport layer/interface modification layer obtained in the step (3), spin-coating to form a film, and carrying out heat treatment to obtain the final productFTO/electron transport layer/interface modification layer/inorganic perovskite thin film;
(5) preparing a spiro-OMeTAD hole transport layer on the FTO/electron transport layer/interface modification layer/inorganic perovskite thin film obtained in the step (4) in an inert atmosphere to obtain an FTO/electron transport layer/single-particle binary nano heterojunction/inorganic perovskite thin film/hole transport layer;
(6) and (3) depositing a counter electrode on the FTO/electron transport layer/single-particle binary nano heterojunction/inorganic perovskite composite film/hole transport layer obtained in the step (5) by an evaporation coating method to obtain the inorganic perovskite solar cell.
Preferably, in the step (1), the cleaning method is as follows: and cleaning the transparent FTO conductive glass by respectively adopting deionized water, absolute ethyl alcohol and isopropanol through ultrasonic oscillation, and oxidizing organic groups on the surface of the transparent FTO conductive glass by adopting ozone after the oscillation is finished.
Preferably, in the step (2), the specific process for preparing the titanium dioxide electron transport layer is as follows: spin-coating tetraisopropyl titanate on a transparent conductive substrate at the rotating speed of 2000-3000 rpm for 30-50 s, uniformly forming a film, and roasting at the temperature of 450-500 ℃ for 30-60 min to obtain compact TiO2Layer, washing compact TiO with absolute ethanol2Drying the surface of the layer at 100-120 ℃; then rotating at 3000-5000 rpm to compact TiO2Spin-coating 18NRT slurry on the layer for 25-40 s, uniformly forming a film, and roasting at 450-500 ℃ for 30-60 min to obtain mesoporous TiO2Layer, then washing the mesoporous TiO with absolute ethyl alcohol2And (3) drying the surface of the layer at 100-120 ℃ for 10-20 min to form the FTO/electron transmission layer.
Preferably, the specific process of step (3) is: under inert atmosphere, adding 0.5-1 mg of single-particle binary nano heterojunction into each milliliter of isopropanol, dispersing the single-particle binary nano heterojunction into the isopropanol to obtain dispersion liquid of the single-particle binary nano heterojunction, then dropwise adding the dispersion liquid of the single-particle binary nano heterojunction onto the FTO/electronic transmission layer, spin-coating for 30-50 s at the rotating speed of 2000-3000 rpm, uniformly forming a film, and carrying out heat treatment at 80-120 ℃ for 10-15 min to obtain the FTO/electronic transmission layer/interface modification layer.
Preference is given toIn the step (4), the method for preparing the precursor solution comprises: weighing CsI, CsBr and PbI according to proportion2And PbBr2Dissolving in an organic solvent, stirring for 3-9 h at 60-90 ℃, and filtering to obtain a clear solution, namely the inorganic perovskite CsPbI3、CsPbBrI2、CsPbBr2I or CsPbBr3The precursor solution of (1).
Selectively weighing one or two of CsI and CsBr and PbI according to the required prepared target inorganic perovskite precursor solution2And PbBr2One or two of them, for preparing CsPbI3、CsPbBrI2、CsPbBr2I and CsPbBr3Any one of (1).
Preferably, the organic solvent in the method for preparing the inorganic perovskite precursor solution is dimethylformamide/dimethyl sulfoxide with the mass ratio of 20-50: 50-80.
Preferably, in the step (4), the rotation speed of the precursor solution in the spin coating is 2500-4000 rpm, and the spin coating time is 30-60 s.
Preferably, in the step (4), the heat treatment temperature is 220-320 ℃, and the heat treatment time is 5-20 min.
Preferably, in step (5), the specific process for preparing the Spiro-OMeTAD hole transport layer is as follows: and (4) dropwise adding Sprio-OMeTAD precursor solution on the electron transport layer/single-particle binary nano heterojunction/inorganic perovskite composite film obtained in the step (4), spin-coating to form a film, and performing heat treatment to obtain the electron transport layer/single-particle binary nano heterojunction/inorganic perovskite composite film/hole transport layer. Preferably, the rotation speed of the spin coating is 1500-3500 rpm, and the spin coating time is 20-40 s. Preferably, the temperature of the heat treatment is 25-35 ℃, and the time is 1-3 h.
Preferably, in the step (6), the evaporation coating speed in the evaporation coating method is 0.1-0.7 nm/s, and the coating thickness is 80-100 nm. Preferably, the counter electrode is a gold counter electrode or a silver counter electrode.
The preparation process of the inorganic perovskite thin film and the hole electron transport layer in the inorganic perovskite cell is carried out in a nitrogen atmosphere, the obtained thin film is difficult to stably exist in air containing moisture without packaging or modification, and the stability of the solar cell assembled by the thin film is extremely poor.
The invention provides a nano heterojunction (such as ZnS-Cu) with quantum size effect and ultraviolet-visible light-near infrared light absorption characteristics2S，MnS-Cu2S、CdS-Cu2S) is applied to an electron transmission layer/perovskite thin film interface in an inorganic perovskite battery, the absorption spectrum range of a light absorption material is expanded, the interface charge separation is increased, the inorganic perovskite crystallization is induced, the material stability is optimized, and finally the photoelectric conversion performance and the long-term stability of a device are improved.
The inorganic perovskite solar cell of the invention is a single-particle binary nano heterojunction (ZnS-Cu)2S or MnS-Cu2S or CdS-Cu2S) inserting the titanium dioxide into the space between the electron transmission material and the perovskite thin film to serve as a modification layer, and passivating the oxygen vacancy and the perovskite defect of the titanium dioxide through interface chemical bonding, so that the electron transmission performance of the titanium dioxide and the inorganic perovskite light absorption material is improved; by the interaction of the interface functional group and the perovskite material, a nucleation site is provided for the growth of the inorganic perovskite crystal, and the formation of the crystal is further influenced; by adjusting the interface composition between the metal oxide and the perovskite layer, the charge extraction is promoted, and the device performance is improved. Therefore, the photoelectric conversion performance and stability of the inorganic perovskite battery are improved. The inorganic perovskite solar cell (not packaged) can still keep the photoelectric efficiency above 80% after a stability test is carried out for 1000h in the air with the humidity of about 30%.
Detailed Description
The present invention will be further described with reference to the following examples.
Single particle binary nano-heterojunction ZnS-Cu in the following examples2S、MnS-Cu2S or CdS-Cu2S; single-particle binary nano heterojunction ZnS-Cu2The specific preparation process of S comprises the following steps: with Cu2-xS nano-particles are used as parent nano-crystals, and Cu with independent phases can be synthesized by adopting a cation exchange method2-xS-ZnS single-particle binary nano particleTexture structure; cu can be realized in the spectral range of 300-3000 nm by controlling the content of ZnS phase2-xAdjustable absorption spectrum of S-ZnS single-particle binary nano heterostructure[1]。MnS-Cu2S and CdS-Cu2Preparation of S single-particle binary nano heterojunction and Cu2-xThe preparation of the S-ZnS single-particle binary nano heterojunction is similar, and the only difference is that Zn in the cation exchange process is adopted2+By Mn2+、 Cd2+[2]。
The references for the preparation of single particle binary nano-heterojunctions are as follows:
[1] Ha D-H.; Caldwell AH.; Ward M. J.; Honrao S.; Mathew K.; Hovden R.; Koker M. K. A.; Muller D. A.; Hennig R. G.; Robinson R. D. Solid-solid phase transformations induced through cation exchange and strain in 2D heterostructured copper sulfide nanocrystals. Nano Lett., 2014,14, 7090.
[2]FentonJ. L.; Steimle B. C.; Schaak R. E. Tunable intraparticleframeworks for creating complex heterostructured nanoparticle libraries.Science, 2018, 360, 513.
example 1
The embodiment comprises the following steps:
(1) preparing a transparent conductive substrate: respectively adopting deionized water, absolute ethyl alcohol and isopropanol to ultrasonically vibrate and clean transparent FTO conductive etched glass, after vibrating for 30min, adopting a blast drying oven to dry a surface organic solvent at 120 ℃, and then adopting ozone to oxidize organic groups on the surface of the transparent FTO conductive glass to obtain a clean transparent conductive substrate;
(2) preparing and cleaning a titanium dioxide electron transport layer on the transparent conductive substrate obtained in the step (1): under the atmosphere of nitrogen, spin-coating 100 μ L of tetraisopropyl titanate on a transparent conductive substrate by a spin-coating method at 2000rpm for 30 s to form a uniform film, placing the film in a muffle furnace, and roasting at 500 ℃ for 30min to form compact TiO2Layer, washing compact TiO with absolute ethanol2Drying the surface of the layer at 120 ℃; then 100. mu.L of 18NRT slurry was spin coated onto the dense TiO at 5000 rpm for 30 s2Uniformly forming a film on the surface of the layer, placing the layer in a muffle furnace, and roasting at the high temperature of 500 ℃ for 30min to obtain the mesoporous TiO2Layer, then washing the mesoporous TiO with absolute ethyl alcohol2And (3) washing impurities on the surface of the layer, placing the layer in a forced air drying oven, and drying for 10min at 120 ℃ to obtain the FTO/electron transport layer, wherein the electron transport layer is the photo-anode.
(3) Preparing a single-particle binary nano heterojunction interface modification layer on the FTO/electron transmission layer obtained in the step (2): 0.5mg of single-particle binary nano heterojunction ZnS-Cu2S is dispersed in 1mL of isopropanol to obtain a dispersion liquid of a single-particle binary nano heterojunction, and the dispersion liquid is dispersed in N2In the atmosphere, 100 mu L of single-particle binary nano heterojunction dispersion liquid is dripped on the FTO/electronic transmission layer, then the single-particle binary nano heterojunction dispersion liquid is spin-coated for 50s at the rotating speed of 2000rpm to form a film uniformly and flatly, and then the film is baked for 10min in a heating table at the temperature of 80 ℃ to obtain the FTO/electronic transmission layer/interface modification layer.
(4) Preparing CsPbI on the FTO/electron transport layer/interface modification layer obtained in the step (3)2Br inorganic perovskite thin film:
（4-I）CsPbI2preparing a Br inorganic perovskite precursor solution: CsI and PbI are added according to the molar ratio of 2:1:12、PbBr2Dissolving in a dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare a precursor solution with a concentration of 1.0M, and stirring at 65 ℃ for 3h to obtain uniform CsPbI2Br inorganic perovskite precursor solution;
(4-II) CsPbI obtained in the step (4-I) was added under nitrogen2Dripping and spin-coating Br inorganic perovskite precursor on the FTO/electron transport layer/interface modification layer obtained in the step (3), wherein the spin-coating operation is as follows: spin-coating at 3000rpm for 30 s to form a film, performing heat treatment at 240 deg.C for 5min, and drying to form a film, to obtain FTO/electron transport layer/interface modification layer/inorganic perovskite thin film;
(5) preparing a hole transport layer on the FTO/electron transport layer/interface modification layer/inorganic perovskite thin film obtained in the step (4-II) in the atmosphere of the step (4-II): spin-coating 100 mu L of Sprio-OMeTAD precursor solution on the obtained FTO/electron transport layer/interface modification layer/inorganic perovskite thin film by a spin coating method at 1500 rpm for 20 s to uniformly form a film, placing the film in a drying box, and oxidizing for 1.5h at 25 ℃ to form a Sprio-OMeTAD hole transport layer, thereby obtaining an FTO/electron transport layer/single-particle binary nano heterojunction/inorganic perovskite thin film/hole transport layer;
(6) and (4) depositing a gold counter electrode on the obtained product in the step (5) by an evaporation coating method to obtain the single-particle binary nano heterojunction interface modified inorganic perovskite solar cell, wherein the evaporation coating speed is 0.3nm/s, and the coating thickness is 90 nm.
The performance of the inorganic perovskite solar cell (not packaged) modified by the single-particle binary nano heterojunction interface obtained in the embodiment was tested: simulating sunlight at 23 deg.c with xenon lamp in light intensity of 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of (2) was 16.8%, and the photoelectric efficiency was reduced to 88% of the initial value in a stability test conducted in air having a relative humidity of 32% for 1000 hours.
Example 2
The difference between this embodiment and embodiment 1 is that in step (4), CsPbI is added2Replacing Br inorganic perovskite precursor solution with CsPbI3Inorganic perovskite precursor solution, namely CsI and PbI are added according to the molar ratio of 1:12Dissolving in a dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare a precursor solution with a concentration of 0.8M, and stirring at 75 ℃ for 6 hours to obtain uniform CsPbI3An inorganic perovskite precursor solution;
the performance of the inorganic perovskite solar cell (not packaged) modified by the binary nano heterojunction interface obtained in the embodiment is tested: in a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of the sensor is 17.9%, and the photoelectric efficiency is reduced to 78% of the initial value after the stability test is carried out for 1000 hours.
Example 3
The difference between this embodiment and embodiment 1 is that in step (4), CsPbI is added2Br inorganic perovskite precursor solutionChange to CsPbIBr2Inorganic perovskite precursor solution, namely CsI and PbBr are added according to the molar ratio of 1:12Dissolving in a dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare a precursor solution with a concentration of 0.8M, and stirring at 90 ℃ for 3 hours to obtain uniform CsPbIBr2An inorganic perovskite precursor solution;
the performance of the inorganic perovskite solar cell based on single-particle binary nano heterojunction interface modification obtained in the embodiment is tested: in a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of the light source is 11.5%, and the photoelectric efficiency is reduced to 90% of the initial value after the stability test is carried out for 1000 hours.
Example 4
The difference between this embodiment and embodiment 1 is that in step (4), CsPbI is added2Replacing Br inorganic perovskite precursor solution with CsPbBr3Inorganic perovskite precursor solution, namely CsBr and PbBr are added according to the molar ratio of 1:12Dissolving in dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare precursor solution with a concentration of 1.0M, and stirring at 90 ℃ for 6h to obtain uniform CsPbBr3An inorganic perovskite precursor solution;
the performance of the inorganic perovskite solar cell based on single-particle binary nano heterojunction interface modification obtained in the embodiment is tested: in a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of the sensor is 9.1%, and the photoelectric efficiency is reduced to 98% of the initial value after the stability test is carried out for 1000 hours.
The performance of the inorganic perovskite cell prepared in comparative examples 1-4 shows that for different inorganic perovskite thin films, the addition of a single-particle binary nano heterojunction interface modification layer has the effects of improving the photoelectric conversion efficiency and the stability of the solar cell.
Example 5
The interface modification layer in this embodiment is made of: MnS-Cu2S; the inorganic perovskite precursor liquid is as follows: CsPbI2Br; the embodiment comprisesThe method comprises the following steps:
(1) preparing a transparent conductive substrate: respectively adopting deionized water, absolute ethyl alcohol and isopropanol to ultrasonically vibrate and clean transparent FTO conductive etched glass, after vibrating for 30min, adopting a blast drying oven to dry a surface organic solvent at 120 ℃, and then adopting ozone to oxidize organic groups on the surface of the transparent FTO conductive glass to obtain a clean transparent conductive substrate;
(2) preparing and cleaning a titanium dioxide electron transport layer on the transparent conductive substrate obtained in the step (1): under the atmosphere of nitrogen, spin-coating 100 μ L of tetraisopropyl titanate on a transparent conductive substrate by a spin-coating method at 2500 rpm for 30 s to form a uniform film, placing the film in a muffle furnace, and roasting at 500 ℃ for 30min to form compact TiO2Layer, washing compact TiO with absolute ethanol2Drying the surface of the layer at 120 ℃; then 100. mu.L of 18NRT slurry was spin coated onto the dense TiO at 4500 rpm for 30 s2Uniformly forming a film on the surface of the layer, placing the layer in a muffle furnace, and roasting at the high temperature of 500 ℃ for 30min to obtain the mesoporous TiO2Layer, then washing the mesoporous TiO with absolute ethyl alcohol2And (3) washing impurities on the surface of the layer, placing the layer in a forced air drying oven, and drying for 10min at 120 ℃ to obtain the FTO/electron transport layer.
(3) Preparing a single-particle binary nano heterojunction interface modification layer on the FTO/electron transmission layer obtained in the step (2): 0.7mg of single-particle binary nano heterojunction MnS-Cu2S is dispersed in 1mL of isopropanol to obtain a dispersion liquid of a single-particle binary nano heterojunction, and the dispersion liquid is dispersed in N2In the atmosphere, 100 mu L of single-particle binary nano heterojunction dispersion liquid is dripped on the FTO/electronic transmission layer, then the single-particle binary nano heterojunction dispersion liquid is spin-coated for 50s at the rotating speed of 3000rpm, the single-particle binary nano heterojunction dispersion liquid is uniformly and flatly formed into a film, and the film is placed on a heating table at 100 ℃ and is baked for 15min, so that the FTO/electronic transmission layer/interface modification layer is obtained.
(4) Preparing CsPbI on the FTO/electron transport layer/interface modification layer obtained in the step (3)2Br inorganic perovskite thin film:
（4-I）CsPbI2preparing a Br inorganic perovskite precursor solution: CsI and PbI are added according to the molar ratio of 2:1:12、PbBr2DissolutionPreparing 0.8M precursor solution in a dimethyl sulfoxide/N, N-dimethylformamide mixed solution with the mass ratio of 80:20, and stirring for 3 hours at 90 ℃ to obtain uniform CsPbI2Br inorganic perovskite precursor solution;
(4-II) CsPbI obtained in the step (4-I) was added under nitrogen2Dripping and spin-coating Br inorganic perovskite precursor on the FTO/electron transport layer/interface modification layer obtained in the step (3), wherein the spin-coating operation is as follows: spin-coating at 4000rpm for 40s to form a film, carrying out heat treatment at 240 ℃ for 5min, and drying to form the film, thereby obtaining the FTO/electron transport layer/interface modification layer/inorganic perovskite film;
(5) preparing a hole transport layer on the FTO/electron transport layer/interface modification layer/inorganic perovskite thin film obtained in the step (4-II) in the atmosphere of the step (4-II): spin-coating 100 mu L of Sprio-OMeTAD precursor solution on the FTO/electron transport layer/interface modification layer/inorganic perovskite thin film by a spin coating method at 3000rpm for 15 s to uniformly form a film, placing the film in a drying box, and oxidizing for 1.5h at 25 ℃ to form a Sprio-OMeTAD hole transport layer, thereby obtaining an FTO/electron transport layer/single-particle binary nano heterojunction/inorganic perovskite composite thin film/hole transport layer;
(6) and (3) depositing a gold counter electrode on the FTO/electron transport layer/single-particle binary nano heterojunction/inorganic perovskite thin film/hole transport layer obtained in the step (5) by an evaporation coating method to obtain the single-particle binary nano heterojunction interface modified inorganic perovskite solar cell, wherein the evaporation coating speed is 0.4nm/s, and the coating thickness is 90 nm.
The performance of the inorganic perovskite solar cell (not packaged) modified by the single-particle binary nano heterojunction interface obtained in the embodiment was tested: simulating sunlight at 23 deg.c with xenon lamp in light intensity of 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of (2) was 16.8%, and the photoelectric efficiency was reduced to 86% of the initial value in a stability test conducted in air having a relative humidity of 32% for 1000 hours.
Example 6
This embodiment is different from embodiment 5 in that, in step (4), CsPbI is added2Replacing Br inorganic perovskite precursor solution with CsPbI3Inorganic perovskite precursor solution, namely CsI and PbI are added according to the molar ratio of 1:12Dissolving in a dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare a precursor solution with a concentration of 0.8M, and stirring at 75 ℃ for 9 hours to obtain uniform CsPbI3An inorganic perovskite precursor solution;
the performance of the inorganic perovskite solar cell modified by the single-particle binary nano heterojunction interface obtained in the embodiment is tested: in a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of the light source is 17.6%, and the photoelectric efficiency is reduced to 75% of the initial value after the stability test is carried out for 1000 hours.
Example 7
This embodiment is different from embodiment 5 in that, in step (4), CsPbI is added2Replacement of Br inorganic perovskite precursor solution by CsPbIBr2Inorganic perovskite precursor solution, namely CsI and PbBr are added according to the molar ratio of 1:12Dissolving in a dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare a precursor solution with a concentration of 0.8M, and stirring at 90 ℃ for 6 hours to obtain uniform CsPbIBr2An inorganic perovskite precursor solution;
the performance of the inorganic perovskite solar cell modified by the single-particle binary nano heterojunction interface obtained in the embodiment is tested: in a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of (2) is 11.9%, and the photoelectric efficiency is reduced to 89% of the initial value after a stability test for 1000 hours.
Example 8
This embodiment is different from embodiment 5 in that, in step (4), CsPbI is added2Replacing Br inorganic perovskite precursor solution with CsPbBr3Inorganic perovskite precursor solution, namely CsBr and PbBr are added according to the molar ratio of 1:12Dissolving in dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare precursor solution with a concentration of 1.0M, and stirring at 65 ℃ for 9 hours to obtain uniform CsPbBr3An inorganic perovskite precursor solution;
the performance of the inorganic perovskite solar cell modified by the single-particle binary nano heterojunction interface obtained in the embodiment is tested: in a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of the sensor is 9.1%, and the photoelectric efficiency is reduced to 98% of the initial value after the stability test is carried out for 1000 hours.
Example 9
The interface modification layer in this embodiment is made of: CdS-Cu2S; the inorganic perovskite precursor liquid is as follows: CsPbI2Br; the embodiment comprises the following steps:
(1) preparing a transparent conductive substrate: respectively adopting deionized water, absolute ethyl alcohol and isopropanol to ultrasonically vibrate and clean transparent FTO conductive etched glass, after vibrating for 30min, adopting a blast drying oven to dry a surface organic solvent at 120 ℃, and then adopting ozone to oxidize organic groups on the surface of the transparent FTO conductive glass to obtain a clean transparent conductive substrate;
(2) preparing and cleaning a titanium dioxide electron transport layer on the transparent conductive substrate obtained in the step (1): under the atmosphere of nitrogen, coating 100 mu L of tetraisopropyl titanate on a transparent conductive substrate in a spin coating method at 3500rpm for 30 s to form a uniform film, placing the film in a muffle furnace, and roasting at the high temperature of 500 ℃ for 30min to form compact TiO2Layer, washing compact TiO with absolute ethanol2Drying the surface of the layer at 120 ℃; then 100. mu.L of 18NRT slurry was spin coated onto the dense TiO at 4000rpm for 30 s2Uniformly forming a film on the surface of the layer, placing the layer in a muffle furnace, and roasting at the high temperature of 500 ℃ for 30min to obtain the mesoporous TiO2Layer, then washing the mesoporous TiO with absolute ethyl alcohol2And (3) washing impurities on the surface of the layer, placing the layer in a forced air drying oven, and drying for 10min at 120 ℃ to obtain the FTO/electron transport layer.
(3) Preparing a single-particle binary nano heterojunction interface modification layer on the FTO/electron transmission layer obtained in the step (2): 0.9mg of single-particle binary nano heterojunction CdS-Cu2S is dispersed in 1mL of isopropanol to obtain a dispersion liquid of a single-particle binary nano heterojunctionN2In the atmosphere, 100 mu L of single-particle binary nano heterojunction dispersion liquid is dripped on the FTO/electronic transmission layer, then the single-particle binary nano heterojunction dispersion liquid is spin-coated for 50s at the rotating speed of 4000rpm to form a film uniformly and flatly, and then the film is baked for 10min in a heating table at 120 ℃ to obtain the FTO/electronic transmission layer/interface modification layer.
(4) Preparing CsPbI on the FTO/electron transport layer/interface modification layer obtained in the step (3)2Br inorganic perovskite thin film:
（4-I）CsPbI2preparing a Br inorganic perovskite precursor solution: CsI and PbI are added according to the molar ratio of 2:1:12、PbBr2Dissolving in dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare precursor solution with a concentration of 1.0M, and stirring at 90 ℃ for 3h to obtain uniform CsPbI2Br inorganic perovskite precursor solution;
(4-II) CsPbI obtained in the step (4-I) was added under a nitrogen atmosphere2Dripping and spin-coating Br inorganic perovskite precursor on the FTO/electron transport layer/interface modification layer obtained in the step (3), wherein the spin-coating operation is as follows: spin-coating at 4000rpm for 40s to form a film, carrying out heat treatment at 220 ℃ for 15min, and drying to form the film, thereby obtaining the FTO/electron transport layer/interface modification layer/inorganic perovskite film;
(5) preparing a hole transport layer on the FTO/electron transport layer/interface modification layer/inorganic perovskite thin film obtained in the step (4-II) in the atmosphere of the step (4-II): spin-coating 100 mu L of Sprio-OMeTAD precursor solution on the FTO/electron transport layer/interface modification layer/inorganic perovskite thin film by a spin coating method at 3000rpm for 15 s to uniformly form a film, placing the film in a drying box, and oxidizing for 1.5h at 25 ℃ to form a Sprio-OMeTAD hole transport layer, thereby obtaining an FTO/electron transport layer/single-particle binary nano heterojunction/inorganic perovskite composite thin film/hole transport layer;
(6) and (3) depositing a gold counter electrode on the FTO/electron transport layer/single-particle binary nano heterojunction/inorganic perovskite thin film/hole transport layer obtained in the step (5) by an evaporation coating method to obtain the single-particle binary nano heterojunction interface modified inorganic perovskite solar cell, wherein the evaporation coating speed is 0.4nm/s, and the coating thickness is 90 nm.
The performance of the inorganic perovskite solar cell (not packaged) modified by the single-particle binary nano heterojunction interface obtained in the embodiment was tested: simulating sunlight at 23 deg.c with xenon lamp in light intensity of 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of (2) was 16.8%, and the photoelectric efficiency was reduced to 87% of the initial value in a stability test conducted in air having a relative humidity of 32% for 1000 hours.
Example 10
This embodiment is different from embodiment 9 in that, in step (4), CsPbI is added2Replacing Br inorganic perovskite precursor solution with CsPbI3Inorganic perovskite precursor solution, namely CsI and PbI are added according to the molar ratio of 1:12Dissolving in a dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare a precursor solution with a concentration of 0.8M, and stirring at 75 ℃ for 9 hours to obtain uniform CsPbI3An inorganic perovskite precursor solution;
the performance of the inorganic perovskite solar cell modified by the single-particle binary nano heterojunction interface obtained in the embodiment is tested: in a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of (2) is 17.4%, and the photoelectric efficiency drops to 77% of the initial value after 1000 hours of stability test.
Example 11
This embodiment is different from embodiment 9 in that, in step (4), CsPbI is added2Replacement of Br inorganic perovskite precursor solution by CsPbIBr2Inorganic perovskite precursor solution, namely CsI and PbBr are added according to the molar ratio of 1:12Dissolving in a dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare a precursor solution with a concentration of 0.8M, and stirring at 65 ℃ for 9 hours to obtain uniform CsPbIBr2An inorganic perovskite precursor solution;
the performance of the inorganic perovskite solar cell modified by the single-particle binary nano heterojunction interface obtained in the embodiment is tested: in the room temperature environment, a xenon lamp is used for simulating sunlight and lightThe strength is 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of the sensor is 11.3%, and the photoelectric efficiency is reduced to 91% of the initial value after the stability test is carried out for 1000 hours.
Example 12
This embodiment is different from embodiment 9 in that, in step (4), CsPbI is added2Replacing Br inorganic perovskite precursor solution with CsPbBr3Inorganic perovskite precursor solution, namely CsBr and PbBr are added according to the molar ratio of 1:12Dissolving in dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare 0.8M precursor solution, and stirring at 65 ℃ for 6h to obtain uniform CsPbBr3An inorganic perovskite precursor solution;
the performance of the inorganic perovskite solar cell modified by the single-particle binary nano heterojunction interface obtained in the embodiment is tested: in a room temperature environment, a xenon lamp is used for simulating sunlight, and the light intensity is 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of the photoelectric conversion element is 8.7%, and the photoelectric efficiency is reduced to 99% of the initial value after the stability test is carried out for 1000 hours.
Comparative example 1
Preparation of an inorganic perovskite solar cell, comprising the steps of:
(1) preparing a transparent conductive substrate: respectively adopting deionized water, absolute ethyl alcohol and isopropanol to ultrasonically vibrate and clean transparent FTO conductive etched glass, after vibrating for 30min, adopting a blast drying oven to dry a surface organic solvent at 120 ℃, and then adopting ozone to oxidize organic groups on the surface of the transparent FTO conductive glass to obtain a clean transparent conductive substrate;
(2) preparing and cleaning a titanium dioxide electron transport layer on the transparent conductive substrate obtained in the step (1): under the atmosphere of nitrogen, spin-coating 100 μ L of tetraisopropyl titanate on a transparent conductive substrate by a spin-coating method at 2000rpm for 30 s to form a uniform film, placing the film in a muffle furnace, and roasting at 500 ℃ for 30min to form compact TiO2Layer, washing compact TiO with absolute ethanol2Drying the surface of the layer at 120 ℃; then 100. mu.L of 18NRT slurry was spin coated onto the dense TiO at 5000 rpm for 30 s2The surface of the layer is provided with a plurality of grooves,uniformly forming a film, placing the film in a muffle furnace, and roasting at the high temperature of 500 ℃ for 30min to obtain the mesoporous TiO2Layer, then washing the mesoporous TiO with absolute ethyl alcohol2And (3) washing impurities on the surface of the layer, placing the layer in a forced air drying oven, and drying for 10min at 120 ℃ to obtain the FTO/electron transport layer, wherein the electron transport layer is the photo-anode.
(3) Preparing CsPbI on the FTO/electron transport layer obtained in the step (2)2Br inorganic perovskite thin film:
（3-I）CsPbI2preparing a Br inorganic perovskite precursor solution: CsI and PbI are added according to the molar ratio of 2:1:12、PbBr2Dissolving in a dimethyl sulfoxide/N, N-dimethylformamide mixed solution with a mass ratio of 80:20 to prepare a precursor solution with a concentration of 1.0M, and stirring at 65 ℃ for 3h to obtain uniform CsPbI2Br inorganic perovskite precursor solution;
(3-II) CsPbI obtained in the step (3-I) was added under nitrogen2Dripping and spin-coating Br inorganic perovskite precursor on the FTO/electron transport layer obtained in the step (2), wherein the spin-coating operation is as follows: spin-coating at 3000rpm for 30 s to form a film, performing heat treatment at 240 deg.C for 5min, and drying to obtain FTO/electron transport layer/inorganic perovskite film;
(4) preparing a hole transport layer on the FTO/electron transport layer/inorganic perovskite thin film obtained in the step (3-II) in the atmosphere of the step (3-II): spin-coating 100 mu L of Sprio-OMeTAD precursor solution on the obtained FTO/electron transport layer/inorganic perovskite thin film by a spin coating method at 1500 rpm for 20 s to form a uniform film, placing the film in a drying box, and oxidizing for 1.5h at 25 ℃ to form a Sprio-OMeTAD hole transport layer, thereby obtaining the FTO/electron transport layer/inorganic perovskite thin film/hole transport layer;
(5) and (4) depositing a gold counter electrode on the obtained material in the step (4) by an evaporation coating method to obtain the single-particle binary nano heterojunction interface modified inorganic perovskite solar cell, wherein the evaporation coating speed is 0.3nm/s, and the coating thickness is 90 nm.
The performance of the inorganic perovskite solar cell (not encapsulated) obtained in this example was tested: using xenon at 23 deg.CThe lamp simulates sunlight and has light intensity of 100 mW/cm2The effective illumination area is 0.17cm2The photoelectric conversion efficiency of (2) was 15.4%, and the photoelectric efficiency was reduced to 58% of the initial value in a stability test conducted in air having a relative humidity of 33% for 1000 hours.

Claims (10)

1. The inorganic perovskite battery modified by the single-particle nano heterojunction interface sequentially comprises an electron transmission layer, an inorganic perovskite thin film, a hole transmission layer and a metal electrode layer, and is characterized in that an interface modification layer is arranged between the electron transmission layer and the inorganic perovskite thin film, and the interface modification layer is made of a single-particle binary nano heterojunction ZnS-Cu material2S、MnS-Cu2S or CdS-Cu2S。
2. The single-particle nano-heterojunction interface-modified inorganic perovskite battery as claimed in claim 1, wherein the material of the inorganic perovskite thin film is CsPbI3、CsPbBrI2、CsPbBr2I or CsPbBr3。
3. A method of preparing a single-particle nano-heterojunction interface-modified inorganic perovskite battery as claimed in claim 1 or 2, comprising the steps of:
(1) cleaning transparent FTO conductive glass to obtain a transparent conductive substrate;
(2) sequentially preparing compact TiO on the transparent conductive substrate obtained in the step (1)2Layer and mesoporous TiO2Obtaining an FTO/electron transport layer;
(3) dripping dispersion liquid of single-particle binary nano heterojunction on the electronic transmission layer obtained in the step (2) in an inert atmosphere, spin-coating to form a film, and performing heat treatment to obtain an FTO/electronic transmission layer/interface modification layer;
(4) under inert atmosphere, adding CsPbI into inorganic perovskite3、CsPbBrI2、CsPbBr2I or CsPbBr3Dropwise adding the precursor solution on the FTO/electronic transmission layer/interface modification layer obtained in the step (3), spin-coating to form a film, and carrying out heat treatment to obtain the FTO/electronic transmission layer/interfaceA finishing layer/inorganic perovskite thin film;
(5) preparing a spiro-OMeTAD hole transport layer on the FTO/electron transport layer/interface modification layer/inorganic perovskite thin film obtained in the step (4) in an inert atmosphere to obtain an FTO/electron transport layer/single-particle binary nano heterojunction/inorganic perovskite thin film/hole transport layer;
(6) and (3) depositing a counter electrode on the FTO/electron transport layer/single-particle binary nano heterojunction/inorganic perovskite composite film/hole transport layer obtained in the step (5) by an evaporation coating method to obtain the inorganic perovskite solar cell.
4. The method for preparing the single-particle nano heterojunction interface modified inorganic perovskite battery as claimed in claim 3, wherein the specific process of the step (3) is as follows: under inert atmosphere, adding 0.5-1 mg of single-particle binary nano heterojunction into each milliliter of isopropanol, dispersing the single-particle binary nano heterojunction into the isopropanol to obtain dispersion liquid of the single-particle binary nano heterojunction, then dropwise adding the dispersion liquid of the single-particle binary nano heterojunction onto the FTO/electronic transmission layer, spin-coating for 30-50 s at the rotating speed of 2000-3000 rpm, uniformly forming a film, and carrying out heat treatment at 80-120 ℃ for 10-15 min to obtain the FTO/electronic transmission layer/interface modification layer.
5. The method for preparing the single-particle nano heterojunction interface modified inorganic perovskite battery as claimed in claim 3 or 4, wherein in the step (1), the cleaning method comprises the following steps: and cleaning the transparent FTO conductive glass by respectively adopting deionized water, absolute ethyl alcohol and isopropanol through ultrasonic oscillation, and oxidizing organic groups on the surface of the transparent FTO conductive glass by adopting ozone after the oscillation is finished.
6. The method for preparing the inorganic perovskite battery with the single-particle nano heterojunction interface modified according to any one of claims 3 to 5, wherein in the step (2), the specific process for preparing the titanium dioxide electron transport layer is as follows: spin-coating tetraisopropyl titanate on a transparent conductive substrate at a rotating speed of 2000-3000 rpm for 30-50 s, uniformly forming a film, and then performing spin coating at 450-5Roasting at 00 ℃ for 30-60 min to obtain compact TiO2Layer, washing compact TiO with absolute ethanol2Drying the surface of the layer at 100-120 ℃; then rotating at 3000-5000 rpm to compact TiO2Spin-coating 18NRT slurry on the layer for 25-40 s, uniformly forming a film, and roasting at 450-500 ℃ for 30-60 min to obtain mesoporous TiO2Layer, then washing the mesoporous TiO with absolute ethyl alcohol2And (3) drying the surface of the layer at 100-120 ℃ for 10-20 min to form the FTO/electron transmission layer.
7. The method for preparing a single-particle nano heterojunction interface modified inorganic perovskite battery as claimed in any one of claims 3 to 6, wherein in the step (4), the method for preparing the precursor solution comprises the following steps: weighing CsI, CsBr and PbI according to proportion2And PbBr2Dissolving in an organic solvent, stirring for 3-9 h at 60-90 ℃, and filtering to obtain a clear solution, namely the inorganic perovskite CsPbI3、CsPbBrI2、CsPbBr2I or CsPbBr3The precursor solution of (1); preferably, the organic solvent in the method for preparing the inorganic perovskite precursor solution is dimethylformamide/dimethyl sulfoxide with the mass ratio of 20-50: 50-80.
8. The preparation method of the single-particle nano heterojunction interface modified inorganic perovskite battery as claimed in any one of claims 3 to 7, wherein in the step (4), the rotation speed of the spin coating of the precursor solution is 2500-4000 rpm, and the time of the spin coating is 30-60 s; preferably, the heat treatment temperature is 220-320 ℃, and the heat treatment time is 5-20 min.
9. The method for preparing the single-particle nano heterojunction interface modified inorganic perovskite battery as claimed in any one of claims 3 to 8, wherein in the step (5), the specific process for preparing the Spiro-OMeTAD hole transport layer is as follows: dripping Sprio-OMeTAD precursor solution on the electron transport layer/single-particle binary nano heterojunction/inorganic perovskite composite film obtained in the step (4), spin-coating to form a film, and performing heat treatment to obtain the electron transport layer/single-particle binary nano heterojunction/inorganic perovskite composite film/hole transport layer; preferably, the rotation speed of the spin coating is 1500-3500 rpm, and the spin coating time is 20-40 s; preferably, the temperature of the heat treatment is 25-35 ℃, and the time is 1-3 h.
10. The method for preparing a single-particle nano heterojunction interface-modified inorganic perovskite battery as claimed in any one of claims 3 to 9, wherein in the step (6), the evaporation coating speed in the evaporation coating method is 0.1 to 0.7 nm/s, and the coating thickness is 80 to 100 nm; preferably, the counter electrode is a gold counter electrode or a silver counter electrode.
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