CN113394347A - Preparation method of all-inorganic perovskite solar cell - Google Patents
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Abstract
A preparation method of an all-inorganic perovskite solar cell comprises the steps of pretreating conductive glass FTO; spin coating TiO on the surface of conductive glass2An electron transport layer; spin coating CsPbI on the surface of the prepared electron transport layer3Coating the perovskite precursor solution with chlorobenzene solution of tris (2-hydroxyethyl) isocyanuric acid (THEICA), and annealing at 210 deg.C for 5min to obtain CsPbI after interface treatment3A film; in CsPbI3Spin-coating and depositing a hole transport layer on the surface of the film; and depositing an Ag metal electrode on the surface of the hole transport layer. The invention modifies CsPbI through THECTA3The film has good appearance, high crystallinity, low defect density, excellent humidity and temperature stability, and the prepared solar cell has high circuit voltage (V)oc) 1.05V, short-circuit current density（Jsc) Reaches 19.26mA/cm2The Fill Factor (FF) reached 78.2%, and the photoelectric conversion efficiency of the prepared solar cell was improved from the first 14.59% to 15.96%.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a preparation method of an all-inorganic perovskite solar cell.
Background
All-inorganic cesium-lead haloperovskite (CsPbX 3, X ═ I, Br) thin films have a high absorption coefficient, and excellent thermal stability and charge mobility are receiving much attention. CsPbI in black phase3The perovskite serving as an all-inorganic perovskite has excellent thermal stability and a band gap of about 1.7eV, is considered as one of candidate materials of high-efficiency solar cells (PSCs), and has potential application value in the field of photovoltaics. The process for preparing the all-inorganic perovskite thin film is roughly divided into an evaporation method and a solution method (one-step spin coating method, two-step dipping method and spraying/blade coating method), wherein the one-step spin coating method is prepared by preparing a precursor solution and carrying out spin coating and heating annealing, the preparation method is simple, but is very sensitive to conditions, the solution concentration, the solvent selection, the precursor solution composition and the annealing temperature can influence the thin film, and the solution and the components are volatilized due to annealing, so that crystal grains are aggregated and shrunk, and the defects of gaps, holes and the like are formed3The perovskite can rapidly generate phase change at room temperature to generate yellow delta phase CsPbI without photovoltaic effect3The Power Conversion Efficiency (PCE) and stability of solar cells (PSCs) are affected.
At present, a series of strategies for stabilizing perovskite through quantum dots, component engineering, interface engineering and the like are available, and various ideas are provided for preparing high-stability all-inorganic perovskite thin films and devices thereof. In the prior art, inorganic perovskite thin films are often modified by small organic molecules to improve the stability of the thin films, but when the modification of the small organic molecules reduces the surface defects of the thin films, the crystallinity of the thin films is reduced, and when the crystallinity is ensured to be stable, the crystal grains of the thin films are reduced, so that the defect density of the thin films cannot be reduced, the crystallinity and the crystal grain structure of the thin films cannot be influenced, and the performance improvement effect of the thin films is not obvious, therefore, in PSCs, the excellent photoelectric performance depends on the manufacturing process of perovskite materials, and the perovskite thin films with good appearance, high crystallinity and low defect density are prepared to have important significance.
Disclosure of Invention
The invention aims to provide a preparation method of an all-inorganic perovskite solar cell. The prepared inorganic perovskite thin film has good appearance, high crystallinity and low defect density, thereby improving the performance of the solar cell.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an all-inorganic perovskite solar cell is characterized by comprising the following steps:
(1) pretreating the conductive glass FTO;
(2) spin coating TiO on the surface of conductive glass2An electron transport layer;
(3) spin coating CsPbI on the surface of the electron transport layer prepared in the step (2)3Coating the perovskite precursor solution with chlorobenzene solution of tris (2-hydroxyethyl) isocyanuric acid (THEICA), and annealing at 210 deg.C for 5min to obtain CsPbI after interface treatment3A film;
(4) CsPbI prepared in step (3)3Spin-coating and depositing a hole transport layer on the surface of the film;
(5) depositing an Ag metal electrode on the surface of the hole transport layer prepared in the step (4);
further, CsPbI described in step (3)3The precursor solution is DMAPbI3And CsI are dissolved in DMF, and the mixture is stirred for 10 to 12 hours at the temperature of 60 ℃ to form CsPbI3Precursor solution of DMAPbI3And the molar volume ratio of the CsI to the DMF is 1mol:1mol: 1.25-1.5 mL.
Further, the spin coating in the step (3) is performed for 5s at 450-500 rpm, and then for 30s at 2800-3000 rpm.
Further, in the chlorobenzene solution of the THECTA in the step (3), the mass-volume ratio of the THECTA to the chlorobenzene is 1-5mg/mL, and the coating is carried out by spin coating at 3000-3200 rpm for 30 s.
During the research, the THECTA is found to generate a crosslinking phenomenon at the temperature of more than 190 ℃, and CsPbI3The optimal annealing temperature is about 210 ℃, chlorobenzene is used as an organic solvent for dissolving THEICA in the invention, and CsPbI is spin-coated3After the precursor solution is coated with THEICA chlorobenzene solution on the surface, the chlorobenzene is coated in CsPbI3Surface, CsPbI enhancement during temperature rise3The interaction of Pb in the crystal and C-O, C-N and other groups in THECTA leads THECTA to synchronously realize CsPbI at 210 DEG C3Annealing and THECTA crosslinking in CsPbI3Coating CsPbI on the surface to form a complete cross-linked network structure3Surface, improved stability, and guaranteed CsPbI crosslinking at this temperature3The surface morphology structure, crystal size and crystallinity are not destroyed by thecta modification.
Further, the above-mentioned spin-coated TiO2The electron transport layer is specifically prepared by spin-coating a titanium n-butanol solution with a concentration of 0.15M on the surface of the pretreated conductive glass FTO, raising the speed to 2000rpm at a speed of 1000rpm/s, spin-coating for 26s, annealing at 125 ℃ for 5min, then annealing in air for 30min, and finally cleaning for 10min by an ultraviolet ozone machine.
Further, the spin-on P3HT hole transport layer was specifically spin-coated with P3HT at a concentration of 15mg/mL on CsPbI3The surface of the film was raised to 4000rpm at a rate of 2000rpm/s, spin-coated for 26 seconds, and then annealed at 100 ℃ for 3 min.
Further, the Ag metal electrode is deposited by adopting a thermal evaporation mode, the vacuum degree is pumped to 3.5 multiplied by 10 < -4 > Pa, and the deposition thickness is 80 nm.
Most specifically, the preparation method of the all-inorganic perovskite solar cell is characterized by comprising the following steps:
(1) pretreatment: washing the conductive glass FTO with a detergent, deionized water, acetone, ethanol and deionized water in sequence, then blowing and drying with nitrogen, and finally cleaning with an ultraviolet ozone cleaning instrument for 20 min;
(2) preparing an electron transport layer: spin-coating the pretreated FTO surface of conductive glass with titanium n-butanol solution with concentration of 0.15M at 1000rpIncreasing the speed of m/s to 2000rpm, spin-coating for 26s, annealing at 125 deg.C for 5min, annealing in air for 30min, and cleaning by ultraviolet ozone machine for 10min to obtain TiO2An electron transport layer;
(3) preparing an inorganic perovskite thin film: dissolving DMAPbI3 and CsI in DMF, and stirring at 60 deg.C for 12h to form CsPbI3Precursor solution of DMAPbI3CsPbI and DMF at a molar volume ratio of 1mol:1mol: 1.25-1.5 mL, and mixing CsPbI and DMF3Spin-coating the precursor solution on the surface of the electron transport layer prepared in the step (2), specifically spin-coating at 450-500 rpm for 5s, then spin-coating at 2800-3000 rpm for 30s, then spin-coating the surface of the electron transport layer with 1-5mg/mL THEICA chlorobenzene solution at 3000-3200 rpm for 30s, and finally annealing at 210 ℃ for 5 min;
(4) preparing a hole transport layer: spin-coated CsPbI with P3HT at a concentration of 15mg/mL3Raising the speed of the film surface to 4000rpm at 2000rpm/s, spin-coating for 26s, and then annealing at 100 ℃ for 3 min;
(5) preparing a metal electrode layer: adopting thermal evaporation method to make vacuum degree be 3.5X 10-4An Ag electrode with a thickness of 80nm was deposited under Pa.
The invention has the following technical effects:
the invention modifies CsPbI through THECTA3The film realizes one-step annealing treatment, ensures the complete appearance structure and crystal size of the film, simultaneously achieves good appearance, high crystallinity, low defect density and excellent temperature and humidity stability, and the prepared solar cell device has circuit voltage (V)oc) 1.05V, short-circuit current density (J)sc) Reaches 19.26mA/cm2The Fill Factor (FF) reached 78.2%, and the photoelectric conversion efficiency of the prepared solar cell was improved from the first 14.59% to 15.96%.
Drawings
FIG. 1: SEM images of the surface of thin films modified with thecta at different concentrations.
FIG. 2: thecta modified CsPbI in the invention3XRD pattern of the film.
FIG. 3: thecta modified CsPbI in the invention3Humidity stability and temperature of filmAnd (4) stability.
FIG. 4: photovoltaic properties of solar cell devices prepared in the present invention.
FIG. 5: comparative example 1 is a graph comparing the effect of different organic additives on film morphology and size.
FIG. 6: CsPbI prepared from precursor solutions of different organic additives in comparative example 13XRD pattern of the film.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
A preparation method of an all-inorganic perovskite solar cell comprises the following steps:
(1) pretreatment: washing the conductive glass FTO with a detergent, deionized water, acetone, ethanol and deionized water in sequence, then blowing and drying with nitrogen, and finally cleaning with an ultraviolet ozone cleaning instrument for 20 min;
(2) preparing an electron transport layer: spin-coating the pretreated FTO surface with 0.15M n-butanol solution of titanium, raising the speed to 2000rpm at 1000rpm/s, spin-coating for 26s, annealing at 125 deg.C for 5min, annealing in air for 30min, and cleaning with ultraviolet ozone machine for 10min to obtain TiO2An electron transport layer;
(3) preparing an inorganic perovskite thin film: dissolving DMAPbI3 and CsI in DMF, and stirring at 60 deg.C for 12h to form CsPbI3Precursor solution of DMAPbI3CsPbI and DMF at a molar volume ratio of 1mol:1mol:1.25mL3Spin-coating the precursor solution on the surface of the electron transport layer prepared in the step (2), specifically spin-coating at 450rpm for 5s, then spin-coating at 2800rpm for 30s, then spin-coating at 3000rpm on the surface of the electron transport layer with 1mg/mL of THEICA solution, spin-coating for 30s, and finally annealing at 210 ℃ for 5 min;
(4) hole transportLayer preparation: spin-coated CsPbI with P3HT at a concentration of 15mg/mL3Raising the speed of the film surface to 4000rpm at 2000rpm/s, spin-coating for 26s, and then annealing at 100 ℃ for 3 min;
(5) preparing a metal electrode layer: adopting thermal evaporation method to make vacuum degree be 3.5X 10-4An Ag electrode with a thickness of 80nm was deposited under Pa.
Example 2
A preparation method of an all-inorganic perovskite solar cell comprises the following steps:
(1) pretreatment: washing the conductive glass FTO with a detergent, deionized water, acetone, ethanol and deionized water in sequence, then blowing and drying with nitrogen, and finally cleaning with an ultraviolet ozone cleaning instrument for 20 min;
(2) preparing an electron transport layer: spin-coating the pretreated FTO surface with 0.15M n-butanol solution of titanium, raising the speed to 2000rpm at 1000rpm/s, spin-coating for 26s, annealing at 125 deg.C for 5min, annealing in air for 30min, and cleaning with ultraviolet ozone machine for 10min to obtain TiO2An electron transport layer;
(3) preparing an inorganic perovskite thin film: dissolving DMAPbI3 and CsI in DMF, and stirring at 60 deg.C for 12h to form CsPbI3Precursor solution of DMAPbI3CsPbI and DMF at a molar volume ratio of 1mol:1mol:1.5mL3Spin-coating the precursor solution on the surface of the electron transport layer prepared in the step (2), specifically spin-coating at 500rpm for 5s, then spin-coating at 3000rpm for 30s, then spin-coating the surface of the electron transport layer with 3mg/mL THEICA chlorobenzene solution at 3200rpm after the spin-coating is finished, spin-coating for 30s, and finally annealing at 210 ℃ for 5 min;
(4) preparing a hole transport layer: spin-coated CsPbI with P3HT at a concentration of 15mg/mL3Raising the speed of the film surface to 4000rpm at 2000rpm/s, spin-coating for 26s, and then annealing at 100 ℃ for 3 min;
(5) preparing a metal electrode layer: adopting thermal evaporation method to make vacuum degree be 3.5X 10-4An Ag electrode with a thickness of 80nm was deposited under Pa.
Example 3
A preparation method of an all-inorganic perovskite solar cell comprises the following steps:
(1) pretreatment: washing the conductive glass FTO with a detergent, deionized water, acetone, ethanol and deionized water in sequence, then blowing and drying with nitrogen, and finally cleaning with an ultraviolet ozone cleaning instrument for 20 min;
(2) preparing an electron transport layer: spin-coating the pretreated FTO surface with 0.15M n-butanol solution of titanium, raising the speed to 2000rpm at 1000rpm/s, spin-coating for 26s, annealing at 125 deg.C for 5min, annealing in air for 30min, and cleaning with ultraviolet ozone machine for 10min to obtain TiO2An electron transport layer;
(3) preparing an inorganic perovskite thin film: dissolving DMAPbI3 and CsI in DMF, and stirring at 60 deg.C for 12h to form CsPbI3Precursor solution of DMAPbI3CsPbI and DMF at a molar volume ratio of 1mol:1mol:1.3mL3Spin-coating the precursor solution on the surface of the electron transport layer prepared in the step (2), specifically spin-coating at 480rpm for 5s, then spin-coating at 2900rpm for 30s, after the spin-coating is completed, spin-coating the surface of the electron transport layer with a 5mg/mL THEICA chlorobenzene solution at 3100rpm for 30s, and finally annealing at 210 ℃ for 5 min;
(4) preparation of hole transport layer: spin-coated CsPbI with P3HT at a concentration of 15mg/mL3Raising the speed of the film surface to 4000rpm at 2000rpm/s, spin-coating for 26s, and then annealing at 100 ℃ for 3 min;
(5) preparing a metal electrode layer: adopting thermal evaporation method to make vacuum degree be 3.5X 10-4An Ag electrode with a thickness of 80nm was deposited under Pa.
THECTA surface treated CsPbI3The thin surface morphology of the perovskite was characterized by SEM (scale bar 500nm) as shown in fig. 1: initial CsPbI3The film has compact appearance without holes, and has a plurality of crystal grains with the size of more than 500nm, and the defects of the film can be reduced by the larger crystal grain size because the defects of the crystal are mainly concentrated at the crystal boundary, and the compact appearance is the basis for preparing the high-efficiency device. The perovskite thin film treated by the THECTA under different concentrations keeps the similar shape as the original film and also shows compact appearance and basically similar crystal grainsThe size shows that the appearance of the film cannot be influenced by the THECTA treatment, and the original appearance of the film is ensured.
XRD test is carried out on the thin film treated by the THECTA interface, and the crystallinity of the perovskite thin film treated by the THECTA interface is researched. As can be seen from FIG. 2a, the initial CsPbI3The XRD pattern of the film showed diffraction peaks at 14.36 and 28.95 corresponding to the gamma phase CsPbI3The (110) and (220) planes of the perovskite. We enlarged the diffraction region of XRD from 11-13 deg., and it can be seen that no DMAPbI is visible at 11.6 deg.3Peaks, no Cs at 11.9 ° and 12.1 °4PbI6Peaks, indicating total DMAPbI3Are used to form perovskites and no impurity phases are present. The diffraction region of 14-15 degrees of XRD is amplified, so that the addition of THECTA with different concentrations in the perovskite thin film can be seen, and the crystallinity and the positions of diffraction peaks of the perovskite thin film are not changed.
The humidity stability of thecta interface treated CsPbI3 was also tested at 18 ℃ and 40% relative humidity at various concentrations. As shown in fig. 3a, significant decay was seen after approximately 6 hours at 40% relative humidity for the initial CsPbI3 perovskite film, and after 12 hours of standing, the sample had substantially a yellow hue, indicating that the majority of the gamma phase CsPbI3 in the film had undergone a phase change. The film after the surface treatment of the THECTA obviously improves the humidity stability, the stability of the perovskite film is improved to 24 hours when the concentration of the THECTA is 1mg/mL, the concentration of the THECTA is continuously increased, and the stability of the THECTA can be further improved, which is probably related to the passivation effect of the THECTA. In addition, the moisture stability of the perovskite may also be improved in consideration of the water barrier effect. We also performed contact angle tests on the perovskite, and fig. 3b shows that the addition of thecta can actually increase the hydrophobicity, compared with 36 ° of the original film, in the concentration range of 1-5mg/mL, the hydrophobicity of the film can continuously increase with the increase of the concentration of the additive, and reaches up to 64 °, and the increase of the contact angle can also be one of the reasons for improving the stability of the perovskite, and the phenomenon of the increase of the contact angle with the increase of the concentration of the additive can be caused by the increase of the thickness of the thecta, which further indicates that the thecta exists in the perovskite film.
Comparative example 1:
preparing an inorganic perovskite solar cell device:
the prepared inorganic perovskite solar cell device has the following structure: FTO/TiO2/CsPbI3/P3HT/Ag。
The method comprises the following specific steps:
(1) pretreatment: washing the conductive glass FTO with a detergent, deionized water, acetone, ethanol and deionized water in sequence, then blowing and drying with nitrogen, and finally cleaning with an ultraviolet ozone cleaning instrument for 20 min;
(2) preparing an electron transport layer: spin-coating the pretreated FTO surface with 0.15M n-butanol solution of titanium, raising the speed to 2000rpm at 1000rpm/s, spin-coating for 26s, annealing at 125 deg.C for 5min, annealing in air for 30min, and cleaning with ultraviolet ozone machine for 10min to obtain TiO2An electron transport layer;
(3) preparing an inorganic perovskite thin film: 0.8mmol of DMAPbI30.8mmol CsI in 1mL DMF, DMAPbI3The mol volume ratio of CsI to DMF is 1mol:1mol:1.3mL, THECTA is added, the mass volume ratio of THECTA to DMF is 1mg/mL, the mixture is stirred for 12h at the temperature of 60 ℃, and CsPbI is formed3Precursor solution to form CsPbI3A precursor solution, coating a perovskite precursor on a substrate by using a spin coating method, respectively spin-coating for 5s and 30s at 500rpm and 3000rpm, annealing at 100 ℃ for 3min, and then annealing at 210 ℃ for 5 min;
(4) preparing a hole transport layer: spin-coating the CsPbI3 film surface with P3HT with concentration of 15mg/mL, raising to 4000rpm at 2000rpm/s, spin-coating for 26s, and annealing at 100 deg.C for 3 min;
(5) preparing a metal electrode layer: an Ag electrode with a thickness of 80nm was deposited by thermal evaporation under a vacuum of 3.5X 10-4 Pa.
Comparative example 1 an inorganic perovskite thin film was prepared, organic small molecule THEICA was dissolved in a system using DMF as organic solvent by bulk phase treatment, spin coated and then annealed at 210 ℃,
due to AA (acrylic acid) and THEIC (tri (acrylic acid) ((III))2-hydroxyethyl) isocyanurate) can be generated, and AA and THEIC are respectively adopted to replace THEICA to participate in the formation of CsPbI3The precursor solution is used for preparing the inorganic perovskite thin film, and the surface appearance (the scale of a scale bar is 1000nm) and the corresponding grain size of different organic small-molecule additives to the inorganic perovskite thin film are shown in figure 5: in the diagram a), thecta can be composed of two smaller monomers of AA and THEIC, wherein COOH groups of AA and OH groups in THEIC can generate THECTA through esterification. We introduced these three different substances and studied them separately for CsPbI3Influence of the thin film, FIG. b), initial CsPbI3The film has compact appearance and no holes, the perovskite film treated by different additives keeps the similar degree of compactness as the original film, but the size of crystal grains has certain change. The grain sizes of these 4 films were counted by the NanoMeasure software, as shown in fig. c), and it can be seen that the grain size of the film after adding AA was not much changed, while the grain sizes of the samples to which THEIC and thecta were added were significantly reduced, compared to the average 402nm grain size of the original film, wherein the grain reduction of thecta was the largest, and was only 267 nm.
As the grain size of the prepared film is changed due to the addition of the additive into the precursor solution, XRD tests are carried out on films treated by different types of additives, and the results show that the addition of AA and THECTA has no influence on the crystallinity of perovskite and both show pure gamma-phase CsPbI3And the crystallinity of the film is reduced after the THEIC additive is added, and a diffraction peak appears at 12.1 degrees, and the diffraction peak is considered to belong to Cs4PbI6It is shown that the addition of high concentrations of THEIC produces new species of impurities, as shown in FIG. 6.
The performance tests of the inorganic perovskite solar cell device prepared by the invention and the inorganic perovskite solar cell device prepared by the comparative example 1 are carried out under the standard light intensity condition of AM1.5G, and the performance data are shown in Table 1.
Table 1: photovoltaic parameters for inorganic perovskite solar cell devices prepared according to the present invention and comparative example 1
Comparative example 2:
preparing an inorganic perovskite solar cell device, wherein the structure of the prepared inorganic perovskite solar cell device is as follows: FTO/TiO2/CsPbI3/P3HT/Ag；
The method comprises the following specific steps: FTO pretreatment and TiO treatment of conductive glass2The preparation of the electron transport layer, the preparation of the P3HT hole transport layer and the preparation of the Ag electrode are the same as those in example 3, except that an organic solvent DMF is used to dissolve thecta in the step (2), and the spin coating and annealing processes are the same as those in example 3.
The stability of the inorganic perovskite thin film prepared in comparative example 2 is also improved to some extent, but the grain size in the perovskite thin film is reduced from about 500nm without coating with small organic molecules to about 300nm as in comparative example 1. Namely THEICA in CsPbI with DMF as solvent3After the surface is coated in a spinning mode, the effect of ensuring the stability and the invariability of the appearance and the crystal size of the film cannot be achieved when the film is annealed at 210 ℃, the reduction of the crystal size of the film increases the defects of the film, and the perovskite film which is good in appearance, high in crystallinity and low in defect density cannot be prepared.
Claims (7)
1. A preparation method of an all-inorganic perovskite solar cell is characterized by comprising the following steps:
(1) pretreating the conductive glass FTO;
(2) spin coating TiO on the surface of conductive glass2An electron transport layer;
(3) spin coating CsPbI on the surface of the electron transport layer prepared in the step (2)3Coating the perovskite precursor solution with chlorobenzene solution of tris (2-hydroxyethyl) isocyanuric acid (THEICA), and annealing at 210 deg.C for 5min to obtain CsPbI after interface treatment3A film;
(4) CsPbI prepared in step (3)3Spin-coating and depositing a hole transport layer on the surface of the film;
(5) and (5) depositing an Ag metal electrode on the surface of the hole transport layer prepared in the step (4).
2. The method of claim 1, wherein the method comprises: CsPbI as described in the step (3)3The precursor solution is DMAPbI3And CsI are dissolved in DMF, and the mixture is stirred for 10 to 12 hours at the temperature of 60 ℃ to form CsPbI3Precursor solution of DMAPbI3And the molar volume ratio of the CsI to the DMF is 1mol:1mol: 1.25-1.5 mL.
3. The method of manufacturing an all-inorganic perovskite solar cell as claimed in claim 1 or 2, wherein: the spin coating in the step (3) is spin coating for 5s at 450-500 rpm, and then spin coating for 30s at 2800-3000 rpm.
4. A method of manufacturing an all inorganic perovskite solar cell as claimed in any one of claims 1 to 3, wherein: the spin-coated TiO2The electron transport layer is specifically prepared by spin-coating a titanium n-butanol solution with a concentration of 0.15M on the surface of the pretreated conductive glass FTO, raising the speed to 2000rpm at a speed of 1000rpm/s, spin-coating for 26s, annealing at 125 ℃ for 5min, then annealing in air for 30min, and finally cleaning for 10min by an ultraviolet ozone machine.
5. The method of claim 4, wherein the method comprises: the spin-coating P3HT hole transport layer is specifically spin-coating CsPbI with P3HT with the concentration of 15mg/mL3The surface of the film was raised to 4000rpm at a rate of 2000rpm/s, spin-coated for 26 seconds, and then annealed at 100 ℃ for 3 min.
6. The method of claim 5, wherein the method comprises: the Ag metal electrode is deposited by adopting a thermal evaporation mode, the vacuum degree is pumped to 3.5 multiplied by 10 < -4 > Pa, and the deposition thickness is 80 nm.
7. A preparation method of an all-inorganic perovskite solar cell is characterized by comprising the following steps:
(1) pretreatment: washing the conductive glass FTO with a detergent, deionized water, acetone, ethanol and deionized water in sequence, then blowing and drying with nitrogen, and finally cleaning with an ultraviolet ozone cleaning instrument for 20 min;
(2) preparing an electron transport layer: spin-coating the pretreated FTO surface with 0.15M n-butanol solution of titanium, raising the speed to 2000rpm at 1000rpm/s, spin-coating for 26s, annealing at 125 deg.C for 5min, annealing in air for 30min, and cleaning with ultraviolet ozone machine for 10min to obtain TiO2An electron transport layer;
(3) preparing an inorganic perovskite thin film: dissolving DMAPbI3 and CsI in DMF, and stirring at 60 deg.C for 12h to form CsPbI3Precursor solution of DMAPbI3CsPbI and DMF at a molar volume ratio of 1mol:1mol: 1.25-1.5 mL, and mixing CsPbI and DMF3Spin-coating the precursor solution on the surface of the electron transport layer prepared in the step (2), specifically spin-coating at 450-500 rpm for 5s, then spin-coating at 2800-3000 rpm for 30s, then spin-coating the surface of the electron transport layer with a chlorobenzene solution of THEICA at 3000-3200 rpm for 30s, and finally annealing at 210 ℃ for 5 min;
(4) preparing a hole transport layer: spin-coated CsPbI with P3HT at a concentration of 15mg/mL3Raising the speed of the film surface to 4000rpm at 2000rpm/s, spin-coating for 26s, and then annealing at 100 ℃ for 3 min;
(5) preparing a metal electrode layer: adopting thermal evaporation method to make vacuum degree be 3.5X 10-4An Ag electrode with a thickness of 80nm was deposited under Pa.
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