CN108493340B - Method for preparing perovskite solar cell with assistance of steam - Google Patents
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- CN108493340B CN108493340B CN201810257299.7A CN201810257299A CN108493340B CN 108493340 B CN108493340 B CN 108493340B CN 201810257299 A CN201810257299 A CN 201810257299A CN 108493340 B CN108493340 B CN 108493340B
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Abstract
The invention belongs to the field of solar cells, and particularly relates to a method for preparing a perovskite solar cell by steam assistance, which specifically comprises the following steps: evaporating an electron transport layer on a substrate; evaporating PbI on the electron transmission layer2A layer; mixing FAI and I2Dissolving in isopropanol, spraying on another glass sheet, and mixing with PbI2The layers are placed in opposition and heated in a vacuum environment to sublime FAI and iodine molecules to PbI2The invention adopts a steam-assisted method to obtain a continuous, uniform, compact and high-quality perovskite thin film through slow gas-solid phase reaction, and simultaneously excess iodine is doped in the perovskite light-absorbing layer to ensure that α -FAPBI with photosensitivity in the perovskite is prepared3The proportion of (A) is increased, the crystal defect concentration is reduced, and the photoelectric conversion efficiency of the cell is improved.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a method for preparing a perovskite solar cell by steam assistance.
Background
Energy is an important basic condition for social and economic development, and until now, the development of human society mainly depends on fossil energy. Non-renewable energy sources represented by fossil energy sources such as petroleum, coal, natural gas and the like have limited reserves, high development cost, environmental pollution easily caused in the use process and other factors, cannot meet the increasingly expanded energy requirements and environmental protection requirements, and people pay attention to alternative clean energy sources, while solar cell power generation is considered to be one of the most promising methods. The solar cell can directly convert solar energy into electric energy, can provide inexhaustible clean energy for the development of human society, and is an important countermeasure for the human society to deal with energy crisis, solve environmental problems and seek sustainable development.
The perovskite solar cell has the advantages of high photoelectric conversion efficiency, low cost, simple preparation process and the like, and is a novel photovoltaic device with the greatest prospect at present. The film forming quality of the perovskite thin film is an important factor for restricting the efficiency of the battery, improving the stability and even large-area application. How to prepare the high-quality perovskite light absorption layer thin film determines the photoelectric conversion efficiency of a solar cell device to a great extent, the traditional perovskite thin film preparation method is mainly a solution method, the advantages can be fully exerted on the preparation of a small-area cell, but the traditional perovskite thin film preparation method has great limitations, the problems brought by a spin coating method are more serious along with the increase of the area of the cell to be prepared, and the solution method is a liquid phase reaction to quickly generate perovskite, so that the growth of perovskite crystals is difficult to control, and the thin film is rough and porous. In addition, most of the existing materials for preparing perovskite light absorption layers adopt MAI, but MAPbI3Is not good in thermal stability and fails the 'double 85 test', while FAPBI3Good thermal stability, but easily produces β -FAPBI without photosensitivity when pure FAI is used for preparing perovskite light absorption layer3(yellow phase) resulting in a severe drop in cell efficiency, and the prior art has not been able to prepare FAPbI of large size3The perovskite light absorption layer seriously restricts the commercialization process of the perovskite solar cell.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a perovskite solar cell by steam assistance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method of vapor-assisted production of a perovskite solar cell, comprising the steps of:
1) washing the substrate through a substrate cleaning process, drying the substrate by using nitrogen, and irradiating the substrate by using UV (ultraviolet);
2) evaporating an electron transport layer on a substrate;
3) evaporating PbI on the electron transmission layer2Layer, for standby; mixing FAI and I2Dissolved in isopropylAlcohol spray coating on another glass sheet to form FAI/I2Layer, for standby; will PbI2Layer and FAI/I2The layers are placed in opposition and then heated in a vacuum environment to sublime FAI and iodine molecules into PbI2Reaction of coating surface to form FAPBI3Perovskite crystals; annealing to obtain perovskite light absorption layer;
4) spin coating solution Spiro-OMeTAD on the perovskite light absorption layer to prepare a hole transport layer;
5) and (4) evaporating a metal counter electrode on the hole transport layer to finally obtain the perovskite solar cell.
In the scheme, the heating temperature in the step (3) is 150-170 ℃, and the heating time is 30-60 min.
In the scheme, the annealing temperature in the step (3) is 150-160 ℃, and the annealing time is 5-10 min.
In the scheme, the thickness of the electron transmission layer is 10-15 nm; the thickness of the perovskite light absorption layer is 300-500 nm; the thickness of the hole transport layer is 150-250 nm; the thickness of the metal counter electrode is 70-100 nm.
In the scheme, the substrate is a transparent ITO conductive glass substrate.
In the above scheme, the electron transport layer is C60。
In the scheme, the spin-coating rotating speed is 3000-4000 rpm; the metal counter electrode is an Au electrode or an Ag electrode.
The invention has the advantages that when the large-area perovskite light absorption layer is prepared by adopting a steam-assisted method, a continuous, uniform, compact and high-quality perovskite thin film can be obtained by slowly carrying out gas-solid phase reaction, and meanwhile, X-bit element regulation (excessive iodine doping) is carried out in the perovskite light absorption layer to ensure that the X-bit element in the perovskite is excessive, so that α -FAPBI with photosensitivity in the perovskite3The proportion of (black phase) is increased, the concentration of crystal defects is reduced, and the photoelectric conversion efficiency of the cell is improved; the large-size perovskite thin film absorption layer prepared by the method has good commercial prospect in the application of perovskite batteries.
Drawings
Fig. 1 is a graph comparing current density versus voltage curves for perovskite solar cells made in example 1 and perovskite solar cells made without excess iodine.
FIG. 2 is a graph comparing the X-ray diffraction patterns of perovskite light absorbing layers produced in example 1 with perovskite light absorbing layers produced without excess iodine.
FIG. 3 is a comparison of large-size perovskite light-absorbing layer films prepared by solution and vapor-assisted methods.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the content of the present invention, but the content of the present invention is limited only to the following examples.
Example 1
A method of vapor-assisted production of a perovskite solar cell, comprising the steps of:
1) taking a clean piece of ITO conductive glass, and etching by using laser; ultrasonically cleaning the glass substrate by using soap water, pure water and ethanol for 10 minutes respectively, and drying the glass substrate by using nitrogen to obtain a conductive glass substrate;
2) UV irradiating the conductive glass substrate and then evaporating C60As electron transport layer, evaporation rate
The thickness is 10 nm;
3) evaporating PbI on conductive substrate with electron transport layer2A layer, 165nm thick, for use; adding 0.5g of FAI and 0.00762g of iodine simple substance (the concentration is about 3mmol/L) into 10ml of isopropanol, stirring to obtain a precursor solution, and spraying the precursor solution on another piece of common glass by using a spray gun at a small air amount to form FAI/I2Layer, for standby; will PbI2Layer and FAI/I2The layers are oppositely arranged, the middle of the layers is spaced by 3-5 cm, the layers are placed in a chemical vapor deposition tube furnace, the chemical vapor deposition tube furnace is vacuumized and heated at 160 ℃ for 50min, and FAI molecules and iodine molecules are sublimated to PbI2FAPBI generated by coating surface reaction3(ii) a Annealing at 160 deg.C for 5min to obtain perovskite light-absorbing layer;
4) spin-coating Spiro-OMeTAD on the perovskite light absorption layer at the rotation speed of 3500rpm as a hole transport layer;
5) the Au counter electrode is evaporated on the obtained hole transport layer at the evaporation speed
And the thickness is about 70-100 nm, so that the perovskite solar cell is obtained.
As shown in fig. 1, the current density-voltage curves of the perovskite solar cell produced in this example were compared with those of the perovskite solar cell produced without excess iodine. The perovskite solar cell prepared in this example was rounded to an open circuit voltage of 941.76mV and a short circuit current density of 19.28mA/cm2The filling factor is 0.59, and the photoelectric conversion efficiency is 10.71%; the square is an excess iodine perovskite solar cell, the open-circuit voltage is 908.52mV, and the short-circuit current density is 18.85mA/cm2The fill factor was 0.56, and the photoelectric conversion efficiency was 9.59%. The method indicates that the photoelectric conversion efficiency of the perovskite solar cell can be improved by doping excessive iodine in a vapor-assisted method.
As shown in FIG. 2, the X-ray diffraction patterns of the perovskite light-absorbing layer of this example were compared with those obtained without excess iodine-the perovskite obtained in the above example and that obtained without excess iodine- α -FAPBI at 14.0 °, 28.0 °, 31.4 °, 40.1 ° and 42.5 °3The diffraction peaks (black phase) were β -FAPBI at 26.0 °, 38.9 ° and 52.6 °3(yellow phase) diffraction peaks it is shown that β -FAPBI was made in the perovskite by the X-site ion excess method in the examples3The proportion of (yellow phase) is reduced, and the quality of the perovskite thin film is improved.
The invention further adopts a solution method and a steam-assisted method to prepare the perovskite light absorption layer film with large area (10cm multiplied by 10 cm). The results are shown in FIG. 3, wherein the left side is an object image and a micrograph of the perovskite light absorption layer thin film prepared by the solution method, and the right side is an object image and a micrograph of the perovskite light absorption layer thin film prepared by the steam-assisted method, and the results in FIG. 3 show that when the solution method is used for preparing the perovskite light absorption layer thin film with a large area (10cm × 10cm), the spin coating method is adopted for deposition on a substrate with a large area, the precursor solution is unevenly spread, the perovskite thin film has cracks during high-speed spin coating, the quality of the perovskite light absorption layer thin film is poor, and the rough thin film and many holes can be seen by a microscope; on the contrary, when the vapor-assisted method is adopted to prepare the large-area perovskite thin film, the perovskite thin film which is very uniform and compact can be obtained, the holes of the thin film are obviously reduced as seen from a microscope picture, and the quality of the thin film is much higher than that of the thin film prepared by the solution method.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (7)
1. A method for vapor-assisted preparation of a perovskite solar cell, characterized by comprising the steps of:
(1) washing the substrate through a substrate cleaning process, drying the substrate by using nitrogen, and irradiating the substrate by using UV (ultraviolet);
(2) evaporating an electron transport layer on a substrate;
(3) evaporating PbI on the electron transmission layer2Layer, for standby; 0.5g of FAI and 0.00762g I2Dissolved in isopropanol and sprayed on another piece of glass to form FAI/I2Layer, for standby; will PbI2Layer and FAI/I2The layers are placed in opposition and then heated in a vacuum environment to sublime FAI and iodine molecules into PbI2Reaction of coating surface to form FAPBI3Perovskite crystals; then annealing to obtain a perovskite light absorption layer;
(4) spin coating solution Spiro-OMeTAD on the perovskite light absorption layer to prepare a hole transport layer;
(5) and (4) evaporating a metal counter electrode on the hole transport layer to finally obtain the perovskite solar cell.
2. The production method according to claim 1, wherein the temperature of heating in the step (3)
The temperature is 150-170 ℃, and the heating time is 30-60 min.
3. The method of claim 1, wherein the annealing of step (3)
The temperature is 150-160 ℃, and the time is 5-10 min.
4. The method according to claim 1, wherein the electron transport layer has a thickness of
10-15 nm; the thickness of the perovskite light absorption layer is 300-500 nm; the thickness of the hole transport layer is 150-250 nm; the thickness of the metal counter electrode is 70-100 nm.
5. The method according to claim 1, wherein the substrate is transparent ITO conductive glass
A glass substrate.
6. The method according to claim 1, wherein the electron transport layer is C60。
7. The method of claim 1, wherein the spin coating speed is
3000-4000 rpm; the metal counter electrode is an Au electrode or an Ag electrode.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110350094A (en) * | 2019-06-12 | 2019-10-18 | 安徽鑫民玻璃股份有限公司 | A method of it iodinates and improves perovskite thin film stability |
| CN111321467A (en) * | 2020-03-11 | 2020-06-23 | 中物院成都科学技术发展中心 | Preparation method of inorganic perovskite crystal and product thereof |
| CN111682116B (en) * | 2020-05-21 | 2023-07-14 | 常州大学 | Method for preparing perovskite solar cell based on ion exchange |
| CN112038490A (en) * | 2020-09-14 | 2020-12-04 | 甘肃泰达春晖新能源科技有限公司 | Method for preparing perovskite solar cell by improved steam assistance |
| CN112675922B (en) * | 2020-12-10 | 2022-04-12 | 复旦大学 | Titanium dioxide photocatalytic film with three-layer structure and preparation method thereof |
| CN112593190B (en) * | 2020-12-15 | 2022-11-01 | 华能新能源股份有限公司 | Preparation method of double-element co-evaporated FA-based perovskite film |
| CN113193122B (en) * | 2021-04-08 | 2022-10-14 | 电子科技大学 | Perovskite thin film based on PbCl2 buffer layer and preparation method and application thereof |
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| CN105552237A (en) * | 2016-02-14 | 2016-05-04 | 桂林理工大学 | Preparation method of organic-inorganic hybrid perovskite thin film |
| WO2016094966A1 (en) * | 2014-12-19 | 2016-06-23 | Commonwealth Scientific And Industrial Research Organisation | Process of forming a photoactive layer of an optoelectronic device |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016094966A1 (en) * | 2014-12-19 | 2016-06-23 | Commonwealth Scientific And Industrial Research Organisation | Process of forming a photoactive layer of an optoelectronic device |
| CN105552237A (en) * | 2016-02-14 | 2016-05-04 | 桂林理工大学 | Preparation method of organic-inorganic hybrid perovskite thin film |
| CN106252460A (en) * | 2016-08-15 | 2016-12-21 | 常州大学 | The manufacture method of a kind of large area perovskite solaode and system |
Non-Patent Citations (1)
| Title |
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| 《Accelerated degradation of methylammonium lead iodide perovskites induced by exposure to iodine vapour》;Shenghao Wang, et al.;《NATURE ENERGY》;20161222;第2卷;(16195)1-8 * |
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