CN210129523U - Fluorine and rubidium doped perovskite solar cell - Google Patents
Fluorine and rubidium doped perovskite solar cell Download PDFInfo
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Abstract
The utility model relates to a fluorine and rubidium mix perovskite solar cell includes substrate, conducting layer, TiO from bottom to top2Dense layer, TiO2The device comprises a mesoporous layer, a fluorine and rubidium doped perovskite light absorption layer, a hole transmission layer and a counter electrode; the fluorine and rubidium doped perovskite light absorption layer material is Cs1‑xRbxPbBrI2‑yFyX is 0-0.05, y is 0-0.3, and the thickness is 300-500 nm. The scheme is beneficial to improving the spectrum absorption performance of the light absorption layer and the overall efficiency of the battery; the decay speed of the battery performance is greatly reduced; is favorable to exciton dissociation and charge transfer and is used for later stageRelatively stable in cell attenuation; the packaging-free epoxy resin can be used in higher water oxygen content, and has good intrinsic stability.
Description
Technical Field
The utility model relates to a solar cell field specifically is a fluorine and rubidium mix perovskite solar cell and preparation method.
Background
The concentrated research on perovskite solar cells in the scientific community has been for decades, and the solar cells are continuously improved to gradually replace silicon solar cells. However, with CH3NH3Organic perovskite solar cells with PbI3 as the basic structure are not efficient and have poor stability, and thus the improvement space of such solar cells is still huge. In recent years, the substitution of CH with Cs + has been developed3NH3+ CsPbI2And (3) research of a Br inorganic perovskite solar cell system. Compared with an organic system, the solar cell has greatly increased stability. Therefore, the method is very beneficial to promoting the commercial application process of the solar cell, fully utilizes clean energy of solar energy and realizes effective protection of the natural environment.
Although the stability of inorganic perovskite solar cells is relatively good, the efficiency decay is still fast without encapsulating the cell, with oxygen and moisture, and there is some distance from commercial use. The doping of perovskite layer elements to further improve the stability of the battery is still a subject of researchers.
In perovskite ABX3In the structure, X halogen is Cl, Br and I which are applied much, and A cation is mainly Cs in an inorganic system. The biggest problem of inorganic perovskite solar cells is that the photoelectric conversion efficiency is low compared with an organic system; and, under the condition of not encapsulating, stability can be further improved. Therefore, a certain proportion of doping in A and X needs to be found out, and the problems are solved.
SUMMERY OF THE UTILITY MODEL
The utility model discloses the purpose is: the fluorine and rubidium doped perovskite solar cell has excellent comprehensive performance and stable performance.
The technical scheme of the utility model is that: a fluorine and rubidium doped perovskite solar cell comprises a substrate, a conductive layer and TiO from bottom to top2Dense layer, TiO2The device comprises a mesoporous layer, a fluorine and rubidium doped perovskite light absorption layer, a hole transmission layer and a counter electrode; the fluorine and rubidium doped perovskite light absorption layer material is Cs1-xRbxPbBrI2-yFyX is 0-0.05, y is 0-0.3, and the thickness is 300-500 nm.
Preferably, the TiO is2The mesoporous layer is arranged on the TiO2Above the dense layer; TiO 22The thickness of the compact layer is 25-50nm, TiO2The thickness of the mesoporous layer is 200-300 nm.
Preferably, the hole transport layer is a hole transport layer of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene; the hole transport layer thickness was 100-250 nm.
Preferably, the conductive layer is SnO doped with fluorine2And the conductive glass layer is called an FTO conductive layer.
Preferably, the counter electrode is a top electrode made of Ag and has a thickness of 50-100 nm.
A preparation method of a fluorine and rubidium doped perovskite solar cell comprises the following specific preparation steps:
A. preparing a conductive layer:
the substrate is transparent glass; forming a conductive layer on a substrate by laser etching;
B. TiO2dense layer and TiO2Preparing a mesoporous layer:
b1、TiO2preparing a compact layer, namely firstly ultrasonically cleaning a conductive layer by using deionized water, acetone and ethanol in sequence, and then carrying out UV ozone treatment for 15-25 min; then, adopting a spray pyrolysis method to dissolve diisopropyl bis (acetylacetonate) titanate in absolute ethyl alcohol at the temperature of 400-500 ℃ to obtain a dense layer precursor solution with the concentration of 0.3-0.5 mol/L; depositing on the conductive layer to form 20-40nm thick TiO2A dense layer;
b2、TiO2preparing a mesoporous layer; in TiO2Spin-coating the diluted mesoporous layer precursor solution on the compact layer at the rotating speed of 3000 plus 5000 rpm; the mesoporous layer precursor solution is titanium dioxide slurry, the time is 10-30s, and the annealing is carried out for 20-35min at the temperature of 400-2A mesoporous layer; diluting the mesoporous layer precursor solution by adopting absolute ethyl alcohol until the volume of the mesoporous layer precursor solution accounts for 30-50%;
b3、TiO2dense layer and TiO2After the preparation of the mesoporous layer, 0.02-0.04mol/L TiCl is used at 50-80 DEG C4Soaking in the solution for 10-30min to improve TiO2A mesoporous structure, and then annealing again for 10-45min at 300-600 ℃;
C. preparing a fluorine and rubidium doped perovskite light absorption layer;
with CsPbI2Based on Br inorganic system, CsBr and PbI2、PbF2And RbI are dissolved in a mixed solution of dimethyl sulfoxide and anhydrous N, N-dimethylformamide to prepare a doped light absorption layer precursor solution containing fluorine and rubidium; adding HI dropwise into the doped light absorption layer precursor solution, and performing magnetic stirring treatment; dropping a doped light-absorbing layer precursor solution to the TiO2On the mesoporous layer, one-step spin-coating method is adopted to coat on TiO2Growing on the mesoporous layer to obtain a fluorine and rubidium doped perovskite light absorption layer;
the concentration of the light absorption layer precursor solution is 0.6-1.0 mol/L; CsBr, PbI2、PbF2Is 1: 1: 0. 2: 1.7: 0.3, 2: 1.5: 0.5 or 2: 1.3: 0.7; the stoichiometric ratio of RbI accounts for 1-5% of the total components; the volume ratio of the anhydrous N, N-dimethylformamide to the dimethyl sulfoxide is 8:2-5: 5;
D. preparing a hole transport layer;
after a fluorine and rubidium doped perovskite light absorption layer is formed, cooling to room temperature, and spin-coating a chlorobenzene solution mixed with 50-80mmol of 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, 5-10mmol of lithium bistrifluoromethanesulfonylimide and 30-60mmol of tributyl phosphate at the rotation speed of 2500-;
E. preparing a counter electrode;
at 1X 10-4-8×10-4Carrying out thermal evaporation on the hole transport layer under the Pa vacuum condition to obtain an Ag top electrode with the thickness of 50-80 nm; and finishing the preparation of the solar cell.
Preferably, the amount of the HI dropwise added into the light absorption layer precursor solution is 20-40ul, and the concentration is 40-57 wt%; the magnetic stirring time is 6-12h at room temperature.
Preferably, the spin-coating speed in the one-step spin-coating method is 1500-3000rpm, and the time is 20-35 s; the annealing temperature is 90-170 ℃ and the time is 10-25 min.
The utility model has the advantages that:
1) rubidium ions are doped in the perovskite light absorption layer, so that the spectrum absorption performance of the light absorption layer and the overall efficiency of the battery are improved; compared with inorganic system CsPbI2The film-forming crystallinity of the light absorption layer is better in the preparation process of the Br perovskite solar cell, and the surface pores are greatly reduced;
2) fluorine ions are doped in the perovskite light absorption layer, and CsPbI can be prepared according to the calculation result of tolerance factors2The α -/delta heterogeneous junction is formed at the beginning, which is beneficial to the dissociation of excitons and the transmission of charges and is relatively stable in the later cell attenuation;
3) the rubidium and cesium doped solar cell is good in intrinsic stability, so that the rubidium and cesium doped solar cell can be used in an environment with 20% of relative humidity, 70% of initial photoelectric conversion efficiency can be maintained after 10 days, and the rubidium and cesium doped solar cell is beneficial to being used commercially;
4) the comprehensive performance of the doped inorganic solar cell is excellent; open circuit voltage of 1.0-1.2V and short circuit current density of 15-18mA cm2Filling factor is 0.6-0.8, photoelectric conversion efficiency is 12% -14%; without encapsulation, can be used in higher water oxygen content.
Drawings
The invention will be further described with reference to the following drawings and examples:
FIG. 1 is a schematic structural diagram of a fluorine and rubidium doped perovskite solar cell according to the scheme;
FIG. 2 is a graph of photoelectric conversion efficiency performance of a fluorine and rubidium doped perovskite solar cell described in the present disclosure at room temperature at 20% relative humidity;
wherein: 1. a substrate; 2. a conductive layer; 3. TiO 22A dense layer; 4. TiO 22A mesoporous layer; 5. fluorine and rubidium doped perovskite light absorption layer; 6. a hole transport layer; 7. a counter electrode.
Detailed Description
Example (b):
as shown in attached figures 1-2, the fluorine and rubidium doped perovskite solar cell comprises a substrate 1, a conducting layer 2 and TiO from bottom to top2Dense layer 3, TiO2The mesoporous layer 4, the fluorine and rubidium doped perovskite light absorption layer 5, the hole transport layer 6 and the counter electrode 7; the material of the fluorine and rubidium doped perovskite light absorption layer 5 is Cs1-xRbxPbBrI2-yFyX is 0-0.05, y is 0-0.3, and the thickness is 400 nm; the bottom substrate 1 is a glass substrate, and the conductive layer 2 is SnO doped with fluorine2A conductive glass layer, referred to as an FTO conductive layer; an FTO conductive layer with a width slightly narrower than that of the substrate is arranged on the top surface of the substrate 1, the length of the FTO conductive layer is consistent with that of the substrate 1, and TiO is arranged on the top surface of the FTO conductive layer2Dense layer 3 and TiO2A mesoporous layer 4; TiO 22The mesoporous layer 4 is fully paved on the TiO2Above the dense layer 3; TiO 22The thickness of the compact layer 3 is 30nm, TiO2The mesoporous layer 4 has a thickness of 250 nm. The TiO is2The top surface of the mesoporous layer 4 is provided with a fluorine and rubidium doped perovskite light absorption layer 5, the top surface of the fluorine and rubidium doped perovskite light absorption layer 5 is provided with a hole transmission layer 6, and the top surface of the hole transmission layer 6 is provided with a counter electrode 7. The hole transport layer 6 is 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino]-a hole transport layer of 9,9' -spirobifluorene (known as spiro-OMeTAD); the hole transport layer thickness was 150 nm. The counter electrode is a top electrode made of Ag and is 60nm thick.
A preparation method of a fluorine and rubidium doped perovskite solar cell comprises the following specific preparation steps:
A. preparing a conductive layer:
the substrate is transparent glass with the thickness of 2.2 mm; formation of fluorine-doped SnO on a substrate by laser etching2Conductive glass layer, preparationObtaining conductive glass;
B、TiO2dense layer and TiO2Preparing a mesoporous layer:
b1、TiO2preparing a compact layer, namely firstly ultrasonically cleaning the FTO conductive layer by using deionized water, acetone and ethanol in sequence, and then carrying out UV ozone treatment for 20 min; then, adopting a spray pyrolysis method to dissolve diisopropyl di (acetylacetonate) titanate in absolute ethyl alcohol at 450 ℃ to obtain a dense layer precursor solution, wherein the concentration is 0.46 mol/L; depositing on FTO conductive layer to form TiO 30nm thick2A dense layer;
b2、TiO2preparing a mesoporous layer; in TiO2Spin-coating diluted mesoporous layer precursor solution on the compact layer at the rotation speed of 4000 rpm; diluting the mesoporous layer precursor solution to 40% by volume with anhydrous ethanol; the mesoporous layer precursor solution is Dyesol titanium dioxide slurry 18 NR-T, the time is 20s, and annealing is carried out at 500 ℃ for 30min to obtain TiO with the thickness of 250nm2A mesoporous layer;
b3、TiO2dense layer and TiO2After the preparation of the mesoporous layer, 0.03mol/L TiCl was used at 70 DEG C4Soaking in the solution for 20min to improve TiO2A mesoporous structure is adopted, and then annealing is carried out again for 30min at 500 ℃;
C. preparing a fluorine and rubidium doped perovskite light absorption layer;
with CsPbI2Based on Br inorganic system, CsBr and PbI2、PbF2And RbI is dissolved in a mixed solution of dimethyl sulfoxide (named as DMSO) and anhydrous N, N-dimethylformamide (named as DMF) to prepare a doped light absorption layer precursor solution containing fluorine and rubidium; a small amount of HI is required to be dripped into the doped light absorption layer precursor solution, and the mixture is subjected to magnetic stirring treatment; dropping a doped light-absorbing layer precursor solution to the TiO2On the mesoporous layer, one-step spin-coating method is adopted to coat on TiO2Growing on the mesoporous layer to obtain a fluorine and rubidium doped perovskite light absorption layer;
the concentration of the doped light absorption layer precursor solution is 0.8 mol/L; CsBr, PbI2、PbF2Is 2: 1.5: 0.5; the stoichiometric ratio of RbI accounts for 1-5% of the total components. The volume ratio of anhydrous DMF to DMSO is 7:3；
the amount of HI dropwise added into the doped light absorption layer precursor solution is 33ul, and the concentration is 57 wt%; the magnetic stirring time is 12h at room temperature;
the spin coating speed in the one-step spin coating method is 2000rpm, and the time is 20-35 s; the annealing temperature is 150 ℃, and the time is 20 min;
D. preparing a hole transport layer;
after a fluorine and rubidium doped perovskite light absorption layer is formed, cooling to room temperature, and spin-coating a chlorobenzene solution mixed with 68mmol of spiroO-MeTAD, 9mmol of Li-TFSI and 55mmol of tributyl phosphate (named as TBP) at the rotation speed of 4000rpm for 20s to prepare a hole transport layer;
E. preparing a counter electrode;
at 7X 10-4Carrying out thermal evaporation on the hole transport layer under the high vacuum condition below Pa to obtain an Ag top electrode with the thickness of 50-80 nm; and finishing the preparation of the solar cell.
Placing the fluorine and rubidium doped perovskite solar cell in AM1.5 and 100mW/cm2Under the illumination condition, the J-V performance of the cell is tested by using Keithley 2400 to obtain that the open-circuit voltage of the solar cell is 1.1V, and the short-circuit current density is 14.5 mA-cm2The filling factor is 0.69, and the photoelectric conversion efficiency is 13.8%; as shown in fig. 2, the perovskite solar cell doped with both fluorine and rubidium has the best overall performance, the highest efficiency is slightly higher than that of the cell doped with only fluorine, and the stability is obviously higher than that of the cell without a doped inorganic system; such doped inorganic solar cells are advantageous for commercial applications.
The above embodiments are merely illustrative of the principles and effects of the present invention, and are not to be construed as limiting the invention. Modifications and variations can be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and technical concepts of the present invention be covered by the claims of the present invention.
Claims (5)
1. A fluorine and rubidium doped perovskite solar cell is characterized in that: comprises a substrate, a conductive layer and TiO from bottom to top2Dense layer, TiO2The device comprises a mesoporous layer, a fluorine and rubidium doped perovskite light absorption layer, a hole transmission layer and a counter electrode; the fluorine and rubidium doped perovskite light absorption layer material is Cs1-xRbxPbBrI2-yFyX is 0-0.05, y is 0-0.3, and the thickness is 300-500 nm.
2. A fluorine and rubidium doped perovskite solar cell as defined in claim 1, wherein: the TiO is2The mesoporous layer is arranged on the TiO2Above the dense layer; TiO 22The thickness of the compact layer is 25-50nm, TiO2The thickness of the mesoporous layer is 200-300 nm.
3. A fluorine and rubidium doped perovskite solar cell as defined in claim 1, wherein: the hole transport layer is a hole transport layer of 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene; the hole transport layer thickness was 100-250 nm.
4. A fluorine and rubidium doped perovskite solar cell as defined in claim 1, wherein: the conducting layer is SnO doped with fluorine2A conductive glass layer.
5. A fluorine and rubidium doped perovskite solar cell as defined in claim 1, wherein: the counter electrode is a top electrode made of Ag and has a thickness of 50-100 nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110416416A (en) * | 2019-06-26 | 2019-11-05 | 西交利物浦大学 | A kind of fluorine and rubidium adulterated with Ca and Ti ore solar battery and preparation method |
| WO2021226191A1 (en) * | 2020-05-05 | 2021-11-11 | Northwestern University | Oxygen- and fluorine-doped cesium and rubidium lead perovskite compounds for hard radiation detection |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110416416A (en) * | 2019-06-26 | 2019-11-05 | 西交利物浦大学 | A kind of fluorine and rubidium adulterated with Ca and Ti ore solar battery and preparation method |
| WO2021226191A1 (en) * | 2020-05-05 | 2021-11-11 | Northwestern University | Oxygen- and fluorine-doped cesium and rubidium lead perovskite compounds for hard radiation detection |
| EP4147279A4 (en) * | 2020-05-05 | 2024-05-22 | Northwestern University | Oxygen- and fluorine-doped cesium and rubidium lead perovskite compounds for hard radiation detection |
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