CN113651757B - Hole transport material containing spiro [ fluorene-heterocycle ] structure, and preparation method and application thereof - Google Patents
Hole transport material containing spiro [ fluorene-heterocycle ] structure, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a hole transport material containing spiro [ fluorene-heterocycle ] structure, a preparation method and application thereof. The material takes spiro [ fluorene-9, 4' -imidazoline ] -2',5' -diketone or spiro [ fluorene-9, 4' -imidazoline ] -2',5' -dithione with hydrocarbon groups connected on nitrogen as a central core, takes diphenylamine, carbazole, phenothiazine or phenoxazine with methoxy or methylthio groups as end groups, and in the preparation, under the action of trifluoroacetic acid or sulfonic acid compounds, the 9, 10-phenanthrenequinone type compound reacts with urea or urea derivatives to synthesize the spiro [ fluorene-9, 4' -imidazoline ] -2',5' -diketone type compound, the reaction condition is mild, the preparation is simple and convenient, and a novel method is provided for synthesizing the spiro skeleton structure type compound.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to preparation of a hole transport material containing a spiro [ fluorene-heterocycle ] structure and application of the hole transport material in perovskite solar cells.
Background
In recent years, organic-inorganic hybrid Perovskite Solar Cells (PSCs) become a research hot spot of a new generation of solar cells due to the advantages of wide material sources, simple preparation process, high Photoelectric Conversion Efficiency (PCE) and the like. In 2009, japanese scientist Miyasaka et al applied perovskite light absorbing materials to solar cells for the first time, and achieved a photoelectric conversion efficiency of 3.8% (Kojima a, teshima K, shirai Y, miyasaka t.journal of the American Chemical Society,2009,131 (17): 6050-6051). With the continuous and deep research of PSCs by scientific researchers, the current authentication photoelectric conversion efficiency of perovskite solar cells has broken through 25%, and the perovskite solar cells show good application development prospect.
As an important component of perovskite solar cells, hole Transport Materials (HTMs) play an indispensable role in accelerating hole extraction and transport, inhibiting carrier recombination, protecting perovskite layers from corrosion, and the like, and the performance of the materials directly affects the photovoltaic performance of PSCs. Currently, the most used hole transport material in perovskite solar cells is 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (spiro-ome tad). However, the synthesis of the spiro-OMeTAD is complicated in steps and complicated in purification, so that the spiro-OMeTAD is high in price and is unfavorable for the commercialization development of perovskite solar cells. Therefore, the development and preparation of the hole transport material with simple preparation and excellent performance are one of the important research points in the field of perovskite solar cells, and have important significance for promoting the commercialization process of the perovskite solar cells.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a hole transport material containing a spiro [ fluorene-heterocycle ] structure, a preparation method thereof and application thereof in perovskite solar cells. The material takes spiro [ fluorene-9, 4 '-imidazoline ] -2',5 '-diketone or spiro [ fluorene-9, 4' -imidazoline ] -2',5' -dithione with hydrocarbon groups connected on nitrogen as a central core, takes diphenylamine, carbazole, phenothiazine or phenoxazine with methoxy or methylthio groups as end groups, heteroatoms in the central spiro [ fluorene-heterocycle ] core can passivate the surface defect of a perovskite layer, and meanwhile, due to low symmetry, material molecules can form compact and uniform films, and both are beneficial to improving the performance of perovskite solar cells; in the preparation, under the action of trifluoroacetic acid or a sulfonic acid compound, the 9, 10-phenanthrenequinone type compound reacts with urea or a urea derivative to synthesize the spiro [ fluorene-9, 4' -imidazoline ] -2',5' -diketone type compound, the reaction condition is mild, the preparation is simple and convenient, and a novel method is provided for synthesizing the spiro framework structure type compound.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a hole transport material containing spiro [ fluorene-heterocycle ] structure has a chemical structural general formula shown in formula I:
wherein X is an oxygen atom or a sulfur atom; r is a C1-C12 hydrocarbyl group; g is any one of the following structural formulas:
preferably, R is a C1-C6 hydrocarbyl group.
More preferably G isR is methyl, and a hole transport material with a chemical structure shown as SFHc- (1) or SFHc- (2) is obtained:
the preparation method of the hole transport material containing the spiro [ fluorene-heterocycle ] structure.
The synthesis steps of the SFHc- (1) are as follows:
s1: under the protection of inert gas, adding 2, 7-dibromo-9, 10-phenanthrenequinone, 1, 3-dimethylurea, acid and a first solvent into a reactor with a water separator, and reacting for 10-12 hours at 100-120 ℃ to obtain a spiro compound 1;
wherein, the mol ratio of the 2, 7-dibromo-9, 10-phenanthrenequinone, the 1, 3-dimethylurea and the acid is 1:1 to 3: 1-5, wherein the solvent dosage is 2-20 mL of solvent added to each millimole of 2, 7-dibromo-9, 10-phenanthrenequinone;
the acid is one or more of trifluoroacetic acid or a sulfonic acid compound; the sulfonic acid compound is p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid or camphorsulfonic acid.
S2: under the protection of inert gas, adding the compound 1, 4' -dimethoxy diphenylamine, strong alkali, a catalyst and a second solvent into a reactor, and reacting for 10-15 hours at 105-115 ℃ to obtain a hole transport material SFHc- (1);
wherein, the mol ratio of the compound 1 to the 4,4' -dimethoxy diphenylamine is 1:2.5 to 3.5, the mole ratio of the strong alkali, the catalyst and the compound 1 is 2 to 6:0.03 to 2:1, a step of; 2 to 20mL of the second solvent is added per millimole of compound 1.
The reaction is that strong alkali is sodium tert-butoxide or potassium tert-butoxide, catalyst is tri (dibenzylideneacetone) dipalladium and substance M, substance M is tri-tert-butylphosphine or tri-tert-butylphosphine tetrafluoroborate, and the molar ratio is that tri (dibenzylideneacetone) dipalladium and substance M=0.01-1: 0.02 to 1.
The synthesis steps of the SFHc- (2) are as follows:
under the protection of inert gas, the third solvent, the compound SFHc- (1) and the Lawson reagent are reacted for 9-11 h at 105-115 ℃ to obtain the hole transport material SFHc- (2).
Preferably, the molar ratio of SFHc- (1) to lawsen reagent is 1:2 to 4, and 2 to 20mL of a third solvent is added to each millimole of the compound SFHc- (1).
The first solvent, the second solvent and the third solvent are all toluene.
Preferably, the inert gas in the above reaction step is argon or nitrogen.
The invention also provides a perovskite solar cell which sequentially comprises a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer and a metal electrode from bottom to top, wherein the hole transport layer is formed by any hole transport material based on a spiro [ fluorene-heterocycle ] structure.
Preferably, the transparent conductive substrate is FTO conductive glass.
Preferably, the electron transport layer is composed of a dense titania layer and a mesoporous titania layer.
Preferably, the material composition of the perovskite layer is APbB 3 Wherein A is one or more of Cs, FA and MA, and B is one or two of I and Br;
further preferably Cs 0.05 FA 0.85 MA 0.10 Pb(I 0.97 Br 0.03 ) 3 。
Preferably, the metal electrode is gold (Au).
Preferably, the thickness of the dense titanium dioxide layer is 0.01-30 nm; the thickness of the mesoporous titanium dioxide layer is 60-280 nm; the thickness of the perovskite layer is 200-550 nm; the thickness of the hole transport layer is 40-170 nm; the thickness of the metal electrode is 60-100 nm.
The preparation method of the perovskite solar cell comprises the following steps:
s1: carrying out ultrasonic cleaning and drying on the transparent conductive substrate, and then carrying out ozone ultraviolet treatment;
s2: preparing compact TiO on the treated transparent conductive substrate by a spray pyrolysis method 2 A layer.
S3: tiO is mixed with 2 Dense TiO spin-coated to S2 after slurry dilution 2 Sintering the film to obtain mesoporous TiO 2 A layer;
s4: preparing perovskite precursor liquid, and spin-coating the perovskite precursor liquid to mesoporous TiO of S3 2 Annealing treatment is carried out on the film to generate a perovskite layer;
s5: preparing a hole transport material containing a spiro [ fluorene-heterocycle ] structure into a solution, and spin-coating the solution on the surface of the perovskite film of S4 to obtain a hole transport layer;
s6: the metal electrode is deposited onto the hole transport layer by vacuum evaporation.
Preferably, the cleaning treatment in the step S1 is ultrasonic cleaning with cleaning agent, deionized water, acetone and ethanol for 10-30 min and ozone ultraviolet treatment for 10-30 min.
Preferably, in the step S2, the spraying solution is ethanol, titanium acetylacetonate and acetylacetone according to the proportion of 40-45: 2 to 5:2 (volume ratio) and evenly mixing the solution, and pyrolyzing the solution for 10 to 30 minutes at the temperature of 400 to 500 ℃.
Preferably, in step S3, tiO 2 Slurry ethanol according to 1: 5-7 (mass ratio), the spin coating rotating speed is 3000-5000 rpm, and the sintering treatment condition is 400-500 ℃ for 20-45 min.
Preferably, in the step S4, a mixed solvent of DMF/DMSO with the volume ratio of 3-5:1 of the perovskite precursor solution is prepared, and the heating and dissolving temperature is 60-80 ℃; adopting two spin coating processes to spin-coat perovskite precursor liquid, wherein the first process is 1500-3000 rpm spin-coat for 6-15 s, and the second process is 4000-7000 rpm spin-coat for 15-25 s; dripping 80-120 mu L of chlorobenzene 3-8 s before ending the second process; the annealing condition is 100-130 ℃ for 10-30 min.
Preferably, in the step S5, the concentration of the hole transport material containing the spiro [ fluorene-heterocycle ] structure is 10-80 mmol/mL, the solvent is chlorobenzene, 15-25 mu L of 4-tertiary butyl pyridine and 7-15 mu L of lithium bis (trifluoromethanesulfonyl) imide (acetonitrile solution with the concentration of 500-550 mg/mL) are added into each milliliter of chlorobenzene solution; spin coating conditions are 3000-5000 rpm for 10-30 s.
Compared with the prior art, the invention has the following beneficial effects:
1. the hole transport material containing the spiro [ fluorene-heterocycle ] structure provided by the invention has the advantages of simple synthetic route, readily available raw materials and easy purification; meanwhile, the hole transport material containing the spiro [ fluorene-heterocycle ] structure has good solubility, film forming property and thermal stability.
2. The hole transport material containing the spiro [ fluorene-heterocycle ] structure provided by the invention is applied to perovskite solar cells, and test results show that the cell device can obtain good photoelectric conversion efficiency (up to 21 percent), and has a wide application prospect.
Drawings
FIG. 1 shows the UV-visible absorption spectra (10) of the hole transport materials SFHc- (1) and SFHc- (2) according to the invention - 5 mol/L, dichloromethane solution);
FIG. 2 is a TGA curve of the hole transport material SFHc- (1) according to the present invention;
FIG. 3 is a TGA curve of the hole transport material SFHc- (2) according to the present invention;
FIG. 4 is a DSC curve of a hole transporting material SFHc- (1) according to the present invention;
FIG. 5 is a DSC curve of a hole transporting material SFHc- (2) according to the present invention;
FIG. 6 is a schematic view of the device structure of the perovskite solar cell of the invention;
FIG. 7 is a J-V curve of a perovskite solar cell device based on SFHc- (1) and SFHc- (2) according to the invention.
Detailed Description
The present invention will be further illustrated by the following specific examples to better understand the present invention, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1: synthesis of spiro [ fluorene-heterocycle ] hole transport materials SFHc- (1) and SFHc- (2).
The synthetic routes for SFHc- (1) and SFHc- (2) are as follows:
synthesis of intermediate 1: to a 50mL round bottom flask was added 2, 7-dibromo-9, 10-phenanthrenequinone (1.76 g,4.8 mmol), 1, 3-dimethylurea (0.86 g,9.8 mmol) and toluene (20 mL) in this order, and after stirring at room temperature for 2min, trifluoroacetic acid (2.23 g,19.6 mmol) was added, a water separator and a reflux condenser were installed, and the reflux reaction was allowed to proceed under argon atmosphere (110.6 ℃ C.) for 12h. After the reaction was completed, the reaction mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the mixture was separated by column chromatography (petroleum ether: dichloromethane=1:2) to obtain 1.07g of a white solid product in a yield of 51%. 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.62-7.57(m,4H),7.41(s,2H),3.21(s,3H),2.60(s,3H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):170.6,156.6,141.3,139.7,133.8,126.9,122.5,122.4,74.6,26.0,25.9.
Synthesis of compound SFHc- (1): to a 50mL round bottom flask was added in order intermediate 1 (1.31 g,3 mmol), 4' -dimethoxydiphenylamine (2.06 g,9 mmol), tris (dibenzylideneacetone) dipalladium (0.28 g,0.3 mmol), sodium t-butoxide (1.49 g,15.5 mmol), tris-t-butylphosphinothiotetraborate (0.21 g,0.72 mmol) and toluene (20 mL) and the reaction was refluxed under argon (110.6 ℃ C.) for 12h. Cooling to room temperature, removing the solvent in vacuo, separating by column chromatography (petroleum ether: ethyl acetate=2:1) followed by ethyl acetate andn-hexane was further recrystallized and purified to obtain 1.14g of pale yellow solid with a yield of 52%. 1 H NMR(400MHz,Acetone-d 6 )δ(ppm):7.55(d,J＝8.4Hz,2H),7.02(d,J＝7.2Hz,8H),6.89(d,J＝8.4Hz,12H),3.78(s,12H),2.88(s,3H),2.51(s,3H). 13 C NMR(100MHz,Acetone-d 6 )δ(ppm):169.8,154.7,146.8,140.0,139.2,132.9,124.9,120.7,118.9,114.0,113.2,73.3,53.3,23.3,23.1.HRMS(ESI):calcd for C 45 H 40 N 4 O 6 [M + ]732.2942,found 732.2952.
Synthesis of compound SFHc- (2): to a 50mL round bottom flask was added compound SFHc- (1) (0.97 g,1.32 mmol), lawson's reagent (CAS number: 19172-47-5,1.07g,2.65 mmol) and toluene (20 mL), and after reflux reaction under argon atmosphere for 10h, the temperature was lowered to room temperature, the solvent was removed in vacuo, and after separation by column chromatography (petroleum ether: dichloromethane=1:1), further recrystallization from dichloromethane and n-hexane was performed to give 0.49g of yellow solid in 49% yield. 1 H NMR(400MHz,CDCl 3 )δ(ppm):7.34(d,J＝8.4Hz,2H),6.99(d,J＝8.4Hz,8H),6.91(d,J＝8.0Hz,2H),6.80(d,J＝8.4Hz,8H),6.67(s,2H),3.79(s,12H),3.62(s,3H),2.91(s,3H). 13 C NMR(100MHz,CDCl 3 )δ(ppm):202.3,181.3,155.8,148.4,143.3,140.6,134.0,126.1,123.0,120.3,115.9,114.7,86.4,55.4,33.7,31.7.HRMS(ESI):calcd for C 45 H 40 N 4 O 4 S 2 [M + ]764.2485,found 764.2491.
The thermal decomposition temperatures of the compounds SFHc- (1) and SFHc- (2) prepared in example 1 were measured, with the weight loss of 5% as a standard, and the results are shown in FIG. 2 and FIG. 3, which show that both compounds have good thermal stability.
The glass transition temperatures of the compounds SFHc- (1) and SFHc- (2) prepared in example 1 were measured and the results (see FIGS. 4 and 5) were 120℃and 111℃respectively.
Example 2: the compound SFHc- (1) is used as a hole transport material and applied to perovskite solar cell devices, and the preparation method is as follows:
(1) Sequentially cleaning fluorine-doped tin oxide glass with an etching tank, deionized water and acrylicUltrasonic cleaning ketone and ethanol respectively for 20min, and adding N 2 Blow-drying followed by 20min of O 3 UV treatment.
(2) Ethanol, titanium acetylacetonate and acetylacetone are measured according to 45:3:2 (volume ratio) and spraying nitrogen as carrier gas onto FTO substrate in 450 deg.C heating state, heating for 20min, and naturally cooling to form compact TiO 2 A layer.
(3) TiO is mixed with 2 Slurry and ethanol according to 1:6 (mass ratio) and then carrying out ultrasonic treatment and stirring to uniformly disperse the mixture, and spin-coating the mixture on compact TiO at 4000rpm 2 On the layer, sintering at 450 ℃ for 30min to form mesoporous TiO 2 A layer; the thickness was 220nm.
(4) Weighing PbI 2 (1.58 mmol), FAI (1.28 mmol), MABr (0.15 mmol), csI (0.08 mmol) were added in a 1mL volume ratio of 4:1, heating to 70 ℃ to dissolve the DMF/DMSO mixed solvent to obtain a precursor solution. The precursor solution (60. Mu.L) was spin-coated onto TiO by two spin-coating processes 2 Spin-coating at 2000rpm for 10s in the first process, spin-coating at 6000rpm for 20s in the subsequent process, dripping 100 mu L of chlorobenzene 5s before the end of the second process, and annealing on a hot table at 120 ℃ for 20min immediately after the spin-coating is finished to form a perovskite film; the thickness was 450nm.
(5) SFHc- (1) was weighed and dissolved in chlorobenzene to prepare a 40mmol/mL solution, then 4-t-butylpyridine (23.667. Mu.L) and lithium bistrifluoromethylsulfonylimide (10.673. Mu.L) in acetonitrile (520 mg/mL) were added per mL solution, followed by spin coating on the perovskite film surface at 4000rpm for 20s; the thickness was 70nm.
(6) Vacuum evaporating a layer of 80nm gold electrode on the surface of the film obtained in the step (5) to obtain a perovskite solar cell with an effective area of 0.16cm 2 。
Example 3: the compound SFHc- (2) is used as a hole transport material and applied to perovskite solar cell devices.
The other steps are the same as in example 2 except that SFHc- (1) is replaced with SFHc- (2) in step (5).
Photovoltaic performance test:
use of xenon lamp in glove box under nitrogen atmosphereSolar simulator, AM 1.5G intensity (100 mW/cm 2 ) The perovskite solar cell device prepared as described above was tested for current density-voltage (J-V) curves as follows.
The J-V curve after the test is shown in FIG. 7. The perovskite solar cell device corresponding to the compound SFHc- (2) has a short-circuit current density (Jsc) of 24.18mA/cm 2 Open circuit voltage (Voc) of 1.100V, fill Factor (FF) of 0.809, energy conversion efficiency (PCE) of 21.52%; as can be seen from fig. 7, this result is superior to the photovoltaic performance of the perovskite solar cell device based on SFHc- (1) under the same conditions (jsc= 24.01mA/cm 2 ，Voc＝0.975V，FF＝0.721，PCE＝16.87％)。
The foregoing description of the preferred embodiment of the present invention is provided for illustration only, and not for limiting the scope of the invention, and it will be appreciated by those skilled in the art that changes, substitutions and modifications may be made to the embodiment without departing from the spirit and scope of the invention, and these changes, substitutions and modifications are intended to be included in the scope of the invention.
The invention is not a matter of the known technology.
Claims (10)
1. A hole transport material containing spiro [ fluorene-heterocycle ] structure is characterized in that the chemical structural general formula of the compound is shown as formula I:
，
wherein X is an oxygen atom or a sulfur atom; r is a C1-C12 hydrocarbyl group; g is any one of the following structural formulas:
。
2. a spiro [ fluorene-containing heterocycle according to claim 1]The hole transport material of the structure is characterized in that G isR is methyl, and a hole transport material with a chemical structure shown as SFHc- (1) or SFHc- (2) is obtained:
。
3. the method for producing a hole transporting material having a spiro [ fluorene-heterocycle ] structure according to claim 2, wherein one of the following two methods is adopted:
the method comprises the following steps: the synthesis steps of the SFHc- (1) are as follows:
s1: under the protection of inert gas, adding 2, 7-dibromo-9, 10-phenanthrenequinone, 1, 3-dimethylurea, acid and a first solvent into a reactor with a water separator, and reacting for 10-12 hours at 100-120 ℃ to obtain a spiro compound 1, wherein the formula is as follows:
；
wherein, the mol ratio of the 2, 7-dibromo-9, 10-phenanthrenequinone, the 1, 3-dimethylurea and the acid is 1:1 to 3: 1-5, wherein the solvent dosage is 2-20 mL of 2, 7-dibromo-9, 10-phenanthrenequinone per millimole;
the acid is one or more of trifluoroacetic acid or a sulfonic acid compound; the sulfonic acid compound is p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid or camphorsulfonic acid;
s2: under the protection of inert gas, adding the compound 1, 4' -dimethoxy diphenylamine, strong alkali, a catalyst and a second solvent into a reactor, and reacting for 10-15 hours at 105-115 ℃ to obtain a hole transport material SFHc- (1);
wherein, the mol ratio of the compound 1 to the 4,4' -dimethoxy diphenylamine is 1:2.5 to 3.5, the mole ratio of the strong alkali, the catalyst and the compound 1 is 2 to 6:0.03 to 2:1, a step of; adding 2-20 g/m of mL second solvent to each mmol of compound 1;
the reaction is that strong alkali is sodium tert-butoxide or potassium tert-butoxide, catalyst is tri (dibenzylideneacetone) dipalladium and substance M, substance M is tri-tert-butylphosphine or tri-tert-butylphosphine tetrafluoroborate, and the molar ratio is that tri (dibenzylideneacetone) dipalladium and substance M=0.01-1: 0.02 to 1;
or, in the second method, the synthesis steps of the SFHc- (2) are as follows:
under the protection of inert gas, the third solvent, the compound SFHc- (1) and the Lawson reagent react for 9-11 h at 105-115 ℃ to obtain a hole transport material SFHc- (2);
the molar ratio of SFHc- (1) to Lawsen reagent is 1:2 to 4, and 2 to 20mL of a third solvent are added per millimole of the compound SFHc- (1).
4. The method for producing a hole transporting material having a spiro [ fluorene-heterocycle ] structure according to claim 3, wherein the first solvent, the second solvent and the third solvent are toluene.
5. The method for producing a hole transporting material having a spiro [ fluorene-heterocycle ] structure according to claim 3, wherein the inert gas is argon or nitrogen.
6. A perovskite solar cell, which is characterized by comprising a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer and a metal electrode from bottom to top in sequence, wherein the hole transport layer is formed by the hole transport material based on a spiro [ fluorene-heterocycle ] structure as claimed in claim 1 or claim 2;
the electron transport layer is composed of a dense titanium dioxide layer and a mesoporous titanium dioxide layer.
7. The perovskite solar cell of claim 6 wherein the transparent conductive substrate is FTO conductive glass;
the material composition of the perovskite layer is APbT 3 Wherein A is one or more of Cs, FA and MA, and T is one or two of I and Br;
the metal electrode is gold;
the thickness of the dense titanium dioxide layer is 0.01-30 nm; the thickness of the mesoporous titanium dioxide layer is 60-280 nm; the thickness of the perovskite layer is 200-550 nm; the thickness of the hole transport layer is 40-170 a nm a; the thickness of the metal electrode is 60-100 nm.
8. The perovskite solar cell of claim 6 wherein the perovskite layer material is Cs 0.05 FA 0.85 MA 0.10 Pb(I 0.97 Br 0.03 ) 3 。
9. The method for manufacturing a perovskite solar cell as claimed in claim 6, comprising the steps of:
s1: carrying out ultrasonic cleaning and drying on the transparent conductive substrate, and then carrying out ozone ultraviolet treatment;
s2: preparing compact TiO on the treated transparent conductive substrate by a spray pyrolysis method 2 A layer;
s3: tiO is mixed with 2 Dense TiO spin-coated to S2 after slurry dilution 2 Sintering the film to obtain mesoporous TiO 2 A layer;
s4: preparing perovskite precursor liquid, and spin-coating the perovskite precursor liquid to mesoporous TiO of S3 2 Annealing treatment is carried out on the film to generate a perovskite layer;
s5: preparing a hole transport material containing a spiro [ fluorene-heterocycle ] structure into a solution, and spin-coating the solution on the surface of the perovskite film of S4 to obtain a hole transport layer;
s6: the metal electrode is deposited onto the hole transport layer by vacuum evaporation.
10. The method for preparing a perovskite solar cell according to claim 9, wherein the cleaning treatment in the step S1 is ultrasonic cleaning with a cleaning agent, deionized water, acetone and ethanol for 10-30 min and ozone ultraviolet treatment for 10-30 min;
the spraying solution in the step S2 is ethanol, titanium acetylacetonate and acetylacetone according to the volume ratio of 40-45: 2 to 5:2, uniformly mixing the prepared solution, and pyrolyzing for 10-30 min at the temperature of 400-500 ℃;
step (a)In S3, tiO 2 Ethanol for slurry is prepared according to the mass ratio of 1: 5-7, the spin coating rotating speed is 3000-5000 rpm, and the sintering treatment condition is 400-500 ℃ for 20-45 min;
in the step S4, preparing a mixed solvent of DMF/DMSO with the volume ratio of 3-5:1 as a solvent of the perovskite precursor solution, and heating and dissolving at the temperature of 60-80 ℃; adopting two spin coating processes to spin-coat perovskite precursor liquid, wherein the first process is 1500-3000 rpm spin coating 6-15 s, and the second process is 4000-7000 rpm spin coating 15-25 s; dripping 80-120 mu L of chlorobenzene 3-8 s before the second process is finished; annealing at 100-130 deg.c for 10-30 min;
in the step S5, the concentration of a hole transport material containing a spiro [ fluorene-heterocycle ] structure is 10-80 mmol/mL, a solvent is chlorobenzene, 15-25 mu L of 4-tert-butylpyridine and 7-15 mu L of acetonitrile solution of lithium bis (trifluoromethanesulfonyl) imide are added into each milliliter of chlorobenzene solution, and the concentration of the lithium bis (trifluoromethanesulfonyl) imide is 500-550 mg/mL; spin coating conditions are 3000-5000 rpm spin coating 10-30 s.
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