CN114927623A - Preparation method of organic-inorganic hybrid double perovskite thin film and solar cell - Google Patents
Preparation method of organic-inorganic hybrid double perovskite thin film and solar cell Download PDFInfo
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Abstract
The invention belongs to the technical field of perovskite solar cells, and particularly relates to an organic-inorganic hybrid double perovskite thin film and a preparation method of a solar cell, wherein C is 6 H 4 NH 2 I, AgI and BiI 3 Dissolving in DMF and DMSO mixed solvent to obtain double perovskite precursor solution, spin-coating on substrate, heating after spin-coating, and annealing to obtain (C) 6 H 4 NH 2 ) 2 AgBiI 6 A thin film of a double perovskite compound in (C) 6 H 4 NH 2 ) 2 AgBiI 6 Preparing a hole transport layer on the double perovskite thin film, and then evaporating a counter electrode on the surface of the hole transport layer to form the organic-inorganic hybrid double perovskite solar cell. The invention adopts a solution method to anneal in high humidity air to prepare high quality (C 6 H 4 NH 2 ) 2 AgBiI 6 A double perovskite thin film.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to an organic-inorganic hybrid double perovskite thin film and a preparation method of a solar cell.
Background
In recent years, the efficiency of the lead-containing perovskite solar cell is greatly broken through, but the stability and toxicity of the lead-containing perovskite solar cell are not beneficial to the development of industrialization. While non-toxic, environmentally friendly and stable lead-free halide double perovskite materials are considered to be one of the most promising alternatives to lead-based perovskite materials. For example, CN112331557A adopts vacuum single-source thermal evaporation method to prepare inorganic lead-free double perovskite thin film. The solution method for preparing the film material has the advantage of low cost, but at present, the lead-free halide double perovskite material has some defects: (1) the solubility difference among the components, the film prepared by the solution method has poor quality, a plurality of surface or crystal boundary defects and serious carrier recombination; (2) most of double perovskite materials have wide band gaps and poor light absorption capacity, and are not beneficial to the improvement of the photoelectric performance of devices. Therefore, how to prepare high-quality double perovskite thin films with appropriate band gaps by a solution method is a challenging task at present.
The method aims to solve the problems of high toxicity and inherent instability of lead in the lead-halogen perovskite material. CN109830550A discloses a preparation method of lead-free double perovskite single crystal, which is prepared by mixing MAI and BiI 3 Dissolving in hydriodic acid mixed with AgI, heating at 140-160 deg.C for 5 hr until the solution is clear and completely dissolved, and dissolving MA 2 AgBiI 6 The precursor solution is cooled and crystallized for three times to generate the lead-free perovskite single crystal with the size of about 3 mm. CN110927769A produced MA 2 AgBiBr 6 A double perovskite single crystal material. However, MA 2 AgBiI 6 And MA 2 AgBiBr 6 Contains MA + Restricted by MA + The prepared double perovskite single crystal needs 373K annealing in nitrogen or inert gas for 2 h to prepare a single crystal device, and the single crystal device cannot be prepared in air. Compared with double perovskite single crystal, the double perovskite thin film has much larger specific surface area and large contact surface with air, and is limited by MA + The method of CN109830550A or CN110927769A is difficult to prepare high-quality double perovskite thin film in air.
Disclosure of Invention
The invention aims to provide a preparation method of an organic-inorganic hybrid double perovskite thin film and a solar cell, which adopts 2-iodoaniline (C) with strong hydrophobicity 6 H 4 NH 2 I) Replacing MAI or MABr which is easy to absorb moisture, and mixing with AgI and BiI 3 Blending appropriate band gaps can be grown in high humidity (RH = 60-70%) air by solution methods: (E g =1.67 eV) and dense (C) 6 H 4 NH 2 ) 2 AgBiI 6 And the double perovskite thin film is used for further assembling the stable and efficient n-i-p type solar cell.
The invention is realized by the following technical scheme. A method for preparing organic-inorganic hybrid double perovskite thin film comprises mixing 2-iodoaniline (C) 6 H 4 NH 2 I) With AgI, BiI 3 Dissolving in DMF and DMSO mixed solvent to obtain double perovskite precursor solution, spin-coating on a substrate, heating after the spin-coating is finished, and annealing to obtain (C) 6 H 4 NH 2 ) 2 AgBiI 6 A double perovskite thin film.
Further, the volume ratio of DMF to DMSO in the mixed solvent was 3: 1.
further, filtering and removing impurities from the double perovskite precursor solution; spreading on the surface of a substrate, and then using segmented spin coating, wherein the parameters of the segmented spin coating process are as follows, in the first segment: spin-coating at 500 rpm for 8 s; and a second stage: spin-coating at 3000 r/min for 30s, and adding 80 dropwise when the second spin-coating time is 15s
Chlorobenzene as an anti-solvent.
Further, the mass concentration of the double perovskite precursor liquid is 46-49 wt%.
Further, the annealing temperature is 100-120 ℃.
Further, the substrate is prepared with SnO on the surface of FTO 2 Layer was obtained.
A method for preparing an organic-inorganic hybrid double perovskite solar cell, which is prepared by the method (C) 6 H 4 NH 2 ) 2 AgBiI 6 And preparing a hole transport layer on the double perovskite thin film, and then evaporating a counter electrode on the surface of the hole transport layer to form the organic-inorganic hybrid double perovskite solar cell.
Use of an organic-inorganic hybrid double perovskite thin film, resulting (C) 6 H 4 NH 2 ) 2 AgBiI 6 The double perovskite thin film is applied to a perovskite solar cell light absorption layer.
Compared with the prior art, the invention has the beneficial effects that: the invention relates to a strong hydrophobicity C 6 H 4 NH 2 I and AgI, BiI 3 Organic combinations prepared by solution annealing in high humidity (RH = 60-70%) air with appropriate band gaps (E g =1.67 eV) of high quality (C) 6 H 4 NH 2 ) 2 AgBiI 6 Double perovskite thin film and simultaneously overcomes Cs prepared by a solution method 2 AgBiX 6 The poor film-forming quality of the double perovskite material and the band gap larger than 2eV result in the poor photoelectric performance of the device and the narrow band gap (smaller than 2 eV) of the organic-inorganic hybrid MA 2 AgBiI 6 And MA 2 AgBiBr 6 The double perovskite material is easy to absorb moisture and has the strict requirement of annealing in a nitrogen or inert gas atmosphere, and the preparation of the double perovskite material and the assembly of a device under the condition of high air humidity are realized.
Drawings
FIG. 1 is a surface SEM image of a double perovskite thin film prepared in example 2.
FIG. 2 is a surface SEM image of a double perovskite thin film prepared in example 4.
FIG. 3 is a surface SEM image of a double perovskite thin film prepared in example 6.
FIG. 4 is an EDS spectrum of the double perovskite thin film prepared in example 6.
FIG. 5 is an EDS spectrum of the double perovskite thin film prepared in example 4.
Fig. 6 is an XRD pattern of the double perovskite thin film prepared in example 4.
Fig. 7 is a uv-vis absorption spectrum of the double perovskite thin films prepared in examples 4 and 6.
FIG. 8 is the Tauc relationship for the double perovskite thin film prepared in example 4.
FIG. 9 is a schematic representation of a double perovskite solar cell prepared in examples 4 and 6J-VA characteristic curve.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The invention relates to a preparation method of an organic-inorganic hybrid double perovskite film, which comprises the following specific steps:
step 1: cleaning an FTO substrate by adopting a glass detergent, deionized water, acetone and absolute ethyl alcohol in sequence, blow-drying by using nitrogen and treating the surface of the FTO by using an ultraviolet ozone cleaning machine for later use;
and 2, step: cooling to room temperature, and spin-coating 0.1mol/L SnCl on the surface of the FTO conductive glass obtained in the step 1 4 ·5H 2 Baking O/absolute ethyl alcohol solution in air at 150 ℃ for 30min to obtain SnO 2 A layer;
and step 3: preparing (C) with a certain mass concentration 6 H 4 NH 2 ) 2 AgBiI 6 Using a mixed solvent of DMSO and DMF, fully stirring to obtain a perovskite precursor solution, and filtering by using a nylon filter screen filter head of 0.22 micron; spreading the double perovskite precursor solution on FTO/SnO obtained in step 2 in high humidity (RH = 60-70%) air 2 The method comprises the following steps of (1) carrying out segmented spin coating on the surface of a substrate, wherein the process parameters of the segmented spin coating are as follows: spin-coating at 500 rpm for 8 s; and a second stage: spin-coating at 3000 rpm for 30s, and adding 80 dropwise when 15s remain in the second spin-coating period
The chlorobenzene antisolvent is transferred to a heating table to be heated and annealed for a period of time at a certain temperature after the spin coating is finished to obtain (C) 6 H 4 NH 2 ) 2 AgBiI 6 A double perovskite thin film.
A method for preparing an organic-inorganic hybrid double perovskite solar cell as described in (C) 6 H 4 NH 2 ) 2 AgBiI 6 On the basis of the double perovskite thin film, 4wt% of TBAPF is prepared 6 Preparing a hole transport layer on the double perovskite thin film by using a doped Spiro-OMeTAD/dichloromethane solution (the content of Spiro-OMeTAD in the Spiro-OMeTAD/dichloromethane solution is 72.3 mg) and corresponding spin coating parameters; depositing Au with a certain thickness on the surface of the obtained hole transport layer as a counter electrode to complete device assemblyJ-VAnd (6) testing.
Example 1
Step 1: mixing 1.5 x 1.5cm 2 The FTO substrate is sequentially cleaned for 30min by adopting a glass detergent, deionized water, acetone and absolute ethyl alcohol, and then is dried by nitrogen and then is treated on the surface of the FTO for 30min by an ultraviolet ozone cleaning machine for standby;
and 2, step: cooling to room temperature, and spin-coating 0.1mol/L SnCl on the surface of the FTO conductive glass obtained in the step 1 4 ·5H 2 Baking O/absolute ethyl alcohol solution in air at 150 ℃ for 30min to obtain SnO 2 A layer;
and 3, step 3: 46wt% of (C) was prepared 6 H 4 NH 2 ) 2 AgBiI 6 A double perovskite precursor solution, using a mixed solvent of DMSO and DMF, wherein the volume ratio of the DMF to the DMSO is 3: 1, fully stirring to obtain perovskite precursor liquid, and filtering by using a 0.22 micron nylon filter head; spreading the double perovskite precursor solution on FTO/SnO obtained in step 2 in high humidity (RH = 60-70%) air 2 And (3) carrying out segmented spin coating on the surface of the substrate, wherein the segmented spin coating has the following process parameters: spin-coating at 500 rpm for 8 s; and a second stage: spin-coating at 3000 r/min for 30s, and adding 80 dropwise when the second spin-coating time is 15s
The chlorobenzene antisolvent is transferred to a heating table for annealing at 110 ℃ for 60min after the spin coating is finished to obtain (C) 6 H 4 NH 2 ) 2 AgBiI 6 A double perovskite thin film;
and 4, step 4: 4wt% of tetrabutyl hexafluoro compound is preparedAmmonium Phosphate (TBAPF) 6 ) Preparing a hole transport layer on the double perovskite thin film by using a doped Spiro-OMeTAD/dichloromethane solution (the content of Spiro-OMeTAD in the Spiro-OMeTAD/dichloromethane solution is 72.3 mg) and corresponding spin coating parameters; 4wt% TBAPF 6 Spreading the doped Spiro-OMeTAD/dichloromethane solution on the surface of perovskite, spin-coating at the rotating speed of 3000 r/min for 30s, and naturally airing to obtain a Spiro-OMeTAD film after the spin-coating is finished;
and 5: and (4) evaporating 60nm Au on the surface of the hole transport layer obtained in the step (4) to be used as a counter electrode to complete device assemblyJ-VAnd (6) testing.
Example 2
The other steps are the same as example 1 except that in step 3 (C) 6 H 4 NH 2 ) 2 AgBiI 6 The annealing temperature of the double perovskite thin film is 120 ℃.
Example 3
The other steps are the same as example 1 except that in step 3 (C) 6 H 4 NH 2 )AgBiI 6 The mass concentration of the double perovskite precursor solution is 49 wt%.
Example 4
The other steps are the same as those in example 2 except that in step 3, (C) 6 H 4 NH 2 ) 2 AgBiI 6 The mass concentration of the double perovskite precursor solution is 49 wt%.
Example 5
The other steps are the same as example 1 except that in step 3 (C) 6 H 4 NH 2 ) 2 AgBiI 6 The annealing temperature of the double perovskite thin film is 100 ℃.
Example 6
The other steps are the same as example 3 except that in step 3 (C) 6 H 4 NH 2 ) 2 AgBiI 6 The annealing temperature of the double perovskite thin film is 100 ℃.
And (3) testing and characterizing the double perovskite thin film:
FIG. 1 is a surface SEM image of a double perovskite thin film prepared in example 2; FIG. 2 is a surface SEM image of a double perovskite thin film prepared in example 4; FIG. 3 is a surface SEM image of a double perovskite thin film prepared in example 6. FIG. 4 is an EDS spectrum of the double perovskite thin film prepared in example 6, and Table 1 is the EDS spectrum analysis result of FIG. 4; fig. 5 is an EDS spectrum of the double perovskite thin film prepared in example 4, and table 2 is the EDS spectrum analysis result of fig. 5.
Fig. 6 is an XRD pattern of the double perovskite thin film prepared in example 4. Fig. 7 is a uv-vis absorption spectrum of the double perovskite thin films prepared in examples 4 and 6. FIG. 8 is the Tauc relationship for the double perovskite thin film prepared in example 4. In the course of the experiment, (C) 6 H 4 NH 2 ) 2 AgBiI 6 When the mass concentration of the double perovskite precursor liquid is 49wt%, the precursor liquid is completely dissolved after being continuously stirred for 2-3h, and when the mass concentration of the precursor liquid is 46wt% (C) 6 H 4 NH 2 ) 2 AgBiI 6 It only needs about 0.5h to be completely dissolved. As can be seen from FIGS. 1-3, when (C) 6 H 4 NH 2 ) 2 AgBiI 6 When the mass concentration of the double perovskite precursor liquid is 49wt% and the annealing temperature is 100 ℃, the grain size of the formed double perovskite is larger than 2 microns but the corresponding film is discontinuous, and sufficient light absorption required by high-efficiency double perovskite solar energy cannot be ensured; whereas, when the annealing temperatures were 110 ℃ (example 2) and 120 ℃ (example 4), the formed high-quality double perovskite thin film was dense and continuous (ensuring sufficient light absorption in the visible light range to construct a high-efficiency double perovskite solar cell), although the surface was not flat enough from the surface SEM view, due to the increased annealing temperature, which accelerated solvent evaporation. The EDS spectrum results of FIGS. 4-5 show that (C) is formed when the annealing temperature is 100 deg.C (example 6) and 120 deg.C (example 4) 6 H 4 NH 2 ) 2 AgBiI 6 The double perovskite thin film is consistent with the SEM analysis result. As can be seen from the XRD pattern results of the double perovskite thin film of FIG. 6, we successfully prepared (C) 6 H 4 NH 2 ) 2 AgBiI 6 Double calciumTitanium ore, XRD diffraction peak and C thereof 6 H 4 NH 2 I、AgI、BiI 3 The characteristic peaks of the powder do not correspond to each other and they correspond to C reported in the prior art 6 H 4 NH 2 BiI 4 And AgBiI 4 The characteristic peaks of the perovskite are inconsistent, and the EDS analysis result is further proved. As can be seen from fig. 7, the high quality (dense and continuous) double perovskite thin film prepared in example 4 has higher light absorption than the high quality double perovskite thin film prepared in example 6 (discontinuous), which is also consistent with the previous SEM and EDS analysis results. The appropriate band gap is key to achieving high performance perovskite solar cells, so we have obtained high quality (dense and continuous) (C) by uv-vis absorption testing 6 H 4 NH 2 ) 2 AgBiI 6 The Tauc relationship of the double perovskite thin film can be preliminarily estimated from the Tauc relationship (C) 6 H 4 NH 2 ) 2 AgBiI 6 Of double perovskitesE g And (4) =1.67eV, and the perovskite solar cell is further assembled into an n-i-p type perovskite solar cell for performance test.
And (3) analyzing the performance of the double perovskite solar cell:
FIG. 9 shows the results of the double perovskite solar cells prepared in examples 4 and 6J-VCharacteristic curve. Of double perovskite solar cellsJ-VThe characteristic curves show that the short-circuit current density of the double perovskite solar cell prepared in example 6 (cJ sc ) Is 1.09 mA cm -2 Open circuit voltage (V oc ) 0.95V, a Fill Factor (FF) of 0.65 and a Photoelectric Conversion Efficiency (PCE) of 0.67%; while that of the double perovskite solar cell prepared in example 4J sc Is 3.47mA cm -2 ，V oc 0.95V, FF 0.62 and PCE 2.04%. The above performance results are also consistent with previous SEM, EDS, XRD and uv-vis absorption spectroscopy results, since the double perovskite thin film prepared in example 4 is dense and continuous by annealing at 120 ℃, the defects of grain boundaries, pinholes and the like of the prepared thin film are effectively reduced, and the light response of the corresponding double perovskite thin film in the visible light range is improvedFinally, the performance of the corresponding device is greatly improved. In addition, the double perovskite thin film can be prepared in high-humidity air, and has excellent air stability and moisture stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A preparation method of an organic-inorganic hybrid double perovskite thin film is characterized by comprising the following steps: c is to be 6 H 4 NH 2 I and AgI, BiI 3 Dissolving in DMF and DMSO mixed solvent to obtain double perovskite precursor solution, spin-coating on substrate, heating after spin-coating, and annealing to obtain (C) 6 H 4 NH 2 ) 2 AgBiI 6 A double perovskite thin film.
2. The method for preparing an organic-inorganic hybrid double perovskite thin film according to claim 1, which is characterized in that: the volume ratio of DMF to DMSO in the mixed solvent is 3: 1.
3. the method for preparing an organic-inorganic hybrid double perovskite thin film according to claim 1, wherein the method comprises the following steps: filtering and removing impurities from the double perovskite precursor solution; spreading on the surface of a substrate, and then using segmented spin coating, wherein the parameters of the segmented spin coating process are as follows, in the first segment: spin-coating at 500 rpm for 8 s; and a second stage: spin-coating at 3000 r/min for 30s, and adding 80 dropwise when the second spin-coating time is 15s
Chlorobenzene antisolvent.
4. The method for preparing an organic-inorganic hybrid double perovskite thin film according to claim 1, which is characterized in that: the mass concentration of the double perovskite precursor liquid is 46-49 wt%.
5. The method for preparing an organic-inorganic hybrid double perovskite thin film according to claim 1, which is characterized in that: the annealing temperature is 100-120 ℃.
6. The method for preparing an organic-inorganic hybrid double perovskite thin film according to claim 1, which is characterized in that: the substrate is SnO prepared on the surface of FTO 2 The layers are obtained.
7. The method for preparing an organic-inorganic hybrid double perovskite thin film according to claim 1, which is characterized in that: the annealing temperature was 120 ℃.
8. A preparation method of an organic-inorganic hybrid double perovskite solar cell is characterized by comprising the following steps: (C) produced by the production method according to any one of claims 1 to 7 6 H 4 NH 2 ) 2 AgBiI 6 Preparing a hole transport layer on the double perovskite thin film, and then evaporating a counter electrode on the surface of the hole transport layer to form the organic-inorganic hybrid double perovskite solar cell.
9. The application of an organic-inorganic hybrid double perovskite thin film is characterized in that: (C) 6 H 4 NH 2 ) 2 AgBiI 6 The double perovskite thin film is applied to a perovskite solar cell light absorption layer.
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