CN111864083A - Packaging method of perovskite solar cell - Google Patents
Packaging method of perovskite solar cell Download PDFInfo
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- CN111864083A CN111864083A CN202010721379.0A CN202010721379A CN111864083A CN 111864083 A CN111864083 A CN 111864083A CN 202010721379 A CN202010721379 A CN 202010721379A CN 111864083 A CN111864083 A CN 111864083A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H10K30/88—Passivation; Containers; Encapsulations
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a packaging method of a perovskite solar cell, which comprises the steps of cleaning and etching a substrate FTO glass; preparation of SnO on FTO glass surface by using chemical bath deposition method2An electron transport layer; in SnO by one-step antisolvent method2Spin coating on surface of electron transport layer to prepare perovskite light absorption layer Cs0.1FA0.9PbI3(ii) a Uniformly coating the prepared Spiro-OMeTAD solution on the surface of the cooled perovskite light absorption layer, and finally evaporating a layer of gold film as an electrode to obtain a perovskite solar cell device; and (3) spin-coating the n-hexane solution of the hydrophobic material on the surface of the complete perovskite solar cell device by using a one-step spin coating method, and heating for 50-70s at 70-90 ℃. The method is simple and easy to operate, high in process parameter controllability and repeatability, and small in influence on intrinsic stability of the device.
Description
Technical Field
The invention belongs to the field of perovskite solar cells, and particularly relates to a packaging method of a perovskite solar cell.
Background
With the gradual depletion of fossil energy, environmental problems, natural disasters, and energy crisis are increasingly aggravated. Solar energy is gradually paid attention to people as a clean energy source due to the advantages of being rich in storage, renewable, convenient and easy to obtain and the like, how to efficiently utilize the solar energy becomes an important research direction of scientists, and solar cells are produced at the same time. Among a plurality of solar cells, perovskite solar cells are used as third-generation novel photovoltaic devices, and have the advantages of simple preparation process, low-temperature preparation, high photoelectric conversion efficiency and the like, so that the perovskite solar cells are rapidly developed in recent years. Among them, the organic-inorganic hybrid perovskite solar cell which is newly emerging in recent years has a photoelectric conversion efficiency which rapidly develops from 3.8% in 2009 to a current authentication efficiency of 25.2%, and is considered as one of the most potential novel high-efficiency solar cells.
At present, the efficiency of perovskite solar cells is continuously improved, but the commercialization progress is seriously influenced by the stability problems of perovskite materials and devices. The perovskite device is easy to be attacked in a high-humidity environment, so that the perovskite material is irreversibly degraded, and the device is damaged.
Disclosure of Invention
The invention aims to provide a packaging method of a perovskite solar cell, which is simple and easy to operate, has high controllability of process parameters and high repeatability, and has small influence on the intrinsic stability of a device.
In order to achieve the purpose, the technical scheme is as follows:
a method of encapsulating a perovskite solar cell, comprising the steps of:
1) cleaning and etching the FTO glass substrate;
2) preparation of SnO on FTO glass surface by using chemical bath deposition method2An electron transport layer;
3) in SnO by one-step antisolvent method2Spin coating on surface of electron transport layer to prepare perovskite light absorption layer Cs0.1FA0.9PbI3；
4) Uniformly coating the prepared Spiro-OMeTAD solution on the surface of the cooled perovskite light absorption layer, and finally evaporating and plating a gold film on the Spiro-OMeTAD solution to be used as an electrode to obtain a perovskite solar cell device;
5) and (3) spin-coating the n-hexane solution of the hydrophobic material on the surface of the complete perovskite solar cell device by using a one-step spin coating method, and heating for 50-70s at 70-90 ℃.
According to the scheme, the hydrophobic material is octadecyl trichlorosilane, perfluoro decyl trichlorosilane or perfluoro decyl triethoxysilane solution.
According to the scheme, the concentration of the n-hexane solution of the hydrophobic material in the step 5 is 10 vt%.
According to the scheme, the hydrophobic material in the step 5 is octadecyl trichlorosilane, the spin-coating parameter is 5000rpm, and the time is 30 s.
The invention uses tin oxide (SnO)2) 2,2 ', 7, 7' -tetrakis [ N, N-di (4-methoxyphenyl) amino as electron transport material]-9, 9' -spirobifluorene (Spiro-OMeTAD) as hole transport material, Cs0.1FA0.9PbI3(wherein FA refers to formamidine) is a perovskite light absorption material, and the efficient flat-plate perovskite solar cell is prepared. On the basis, the device is packaged by using different super-hydrophobic materials, wherein the hydrophobic materials comprise octadecyl trichlorosilane, perfluoro decyl trichlorosilane and perfluoro decyl triethoxysilane. The method is simple, easy to operate, high in controllability of process parameters and high in repeatability. The packaging is carried out on the basis of the complete device, and the influence on the intrinsic stability of the device is small.
Compared with the prior art, the invention has the following beneficial effects:
(1) a strategy of modifying the surface of the perovskite by using a hydrophobic group is introduced, and a super-hydrophobic coating is formed by hydrolysis and polycondensation, so that the aim of packaging the perovskite solar cell is fulfilled.
(2) The method is simple, easy to operate, high in controllability of process parameters and high in repeatability.
(3) The packaging is carried out on the basis of the complete device, and the influence on the intrinsic stability of the device is small.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1:
1) etching transparent conductive substrate FTO glass by femtosecond laser, respectively ultrasonically cleaning the FTO glass by using liquid detergent, deionized water and ethanol for 15min, blow-drying the FTO glass by using a dry air gun, and removing residual organic matters on the surface by ultraviolet-ozone treatment for 10 min;
2)SnO2preparing a nano film: 5g of urea, 5mL of concentrated hydrochloric acid, 100. mu.L of thioglycolic acid and 1.096g of SnCl2·2H2And adding O into 400mL of deionized water in sequence, uniformly mixing, and refrigerating in a refrigerator for three days for use. 20mL of SnCl is taken2The mother liquor of (1) and 100mL of deionized water were mixed well and poured into a clean glass container, and FTO glass cleaned and treated with ultraviolet irradiation for 15min was put in and sealed. The glass was heated in an oven at 70 ℃ for 90min until a slightly white precipitate appeared, after which the glass surface was rinsed clean with deionized water. And after washing, putting the glass into an ultrasonic machine for ultrasonic treatment for 5min, washing the surface of the glass by using deionized water, and repeating the step for three times. After the surface moisture is blown off by an air gun, the material is placed on a titanium-based heating table at 180 ℃ for heating for 1h, and annealing is carried out.
3) The perovskite thin film is prepared by a one-step method: preparation of perovskite precursor solution, 33mg CsI, 200mg FAI, 629mg PbI2Dissolved in 800. mu.L of a mixed DMF/DMSO solution (volume ratio DMF: DMSO. RTM.4: 1). Cleaning the FTO substrate with the prepared electron transport layer in a UV machine for 15min, and adding ethyl acetate dropwise as an anti-solvent in SnO2And preparing a perovskite thin film which is completely covered and well crystallized on the thin film. The spin coating speed is 6000rpm, and the time is 30 s; the anti-solvent ethyl acetate is added dropwise at the last 5s in the spin coating process, and the mixture is annealed on a hot bench at 120 ℃ for 60min and then cooled.
4) 73mg/mL of Spiro-OMeTAD solution was prepared as a hole transport material using chlorobenzene as a solvent, and 30. mu.L of 4-tert-butylpyridine, 29. mu.L of a cobalt salt solution, and 18. mu.L of a lithium salt solution were added. And (3) uniformly coating the prepared Spiro-OMeTAD solution on the surface of the cooled perovskite thin film, and spin-coating for 30s at the rotating speed of 3000 rpm. An Au thin film with the thickness of 80nm is evaporated on the surface of the hole transport layer by adopting a vacuum coating film to be used as a metal electrode.
5) Using normal hexane as a solvent, preparing a solution (volume ratio) with the concentration of octadecyl trichlorosilane being 10%, spin-coating the solution on the surface of a device by using a spin-coating method at the rotation speed of 5000rpm for 30s, immediately placing the device on a hot table at the temperature of 80 ℃ after the spin-coating is finished, heating the device for 60s, taking the device down, standing the device, and cooling the device to room temperature.
6) The devices (5-8) are placed in an environment box with the temperature of 20 ℃ and the relative humidity of 85 percent at constant temperature and constant humidity, and the photovoltaic performance of the devices in different time periods is tested.
The perovskite solar cell prepared by the experiment is tested, the test condition is a light intensity, and the test area is 0.16cm2And the test light source is AAA level, and the result shows that: before the stability test, the photoelectric conversion efficiency of the reverse scanning of the cell is 16.97 percent, wherein the open-circuit voltage is 1042mV, and the short-circuit current is 24.18mA/cm2The fill factor is 0.67; after 200h of humidity stability test, the reverse scanning photoelectric conversion efficiency of the cell is 10.74 percent, wherein the open-circuit voltage is 942mV, and the short-circuit current is 21.87mA/cm2The fill factor is 0.52.
Example 2:
1) etching transparent conductive substrate FTO glass by femtosecond laser, respectively ultrasonically cleaning the FTO glass by using liquid detergent, deionized water and ethanol for 15min, blow-drying the FTO glass by using a dry air gun, and removing residual organic matters on the surface by ultraviolet-ozone treatment for 10 min;
2)SnO2preparing a nano film: 5g of urea, 5mL of concentrated hydrochloric acid, 100. mu.L of thioglycolic acid and 1.096g of SnCl2·2H2And adding O into 400mL of deionized water in sequence, uniformly mixing, and refrigerating in a refrigerator for three days for use. 20mL of SnCl is taken2The mother liquor of (1) and 100mL of deionized water were mixed well and poured into a clean glass container, and FTO glass cleaned and treated with ultraviolet irradiation for 15min was put in and sealed. The glass was heated in an oven at 70 ℃ for 90min until a slightly white precipitate appeared, after which the glass surface was rinsed clean with deionized water. And after washing, putting the glass into an ultrasonic machine for ultrasonic treatment for 5min, washing the surface of the glass by using deionized water, and repeating the step for three times. After the surface moisture is blown off by an air gun, the material is placed on a titanium-based heating table at 180 ℃ for heating for 1h, and annealing is carried out.
3) The perovskite is prepared by a one-step method, and perovskite precursor liquid, 33mg CsI, 200mg FAI and 629mg PbI are prepared2Dissolved in 800. mu.L of a mixed DMF/DMSO solution (volume ratio DMF: DMSO. RTM.4: 1). Cleaning the FTO substrate with the prepared electron transport layer in a UV machine for 15min, and adding ethyl acetate dropwise as an anti-solvent in SnO2Preparing perovskite film with complete coverage and good crystallization on filmAnd (3) a membrane. The spin speed was 6000rpm for 30 s. Ethyl acetate was added dropwise within the reciprocal 5s during the spin coating, and the mixture was annealed on a 120 ℃ hot stage for 60min and then cooled.
4) 73mg/mL of Spiro-OMeTAD solution was prepared as a hole transport material using chlorobenzene as a solvent, and 30. mu.L of 4-tert-butylpyridine, 29. mu.L of a cobalt salt solution, and 18. mu.L of a lithium salt solution were added. And (3) uniformly coating the prepared Spiro-OMeTAD solution on the surface of the cooled perovskite thin film, and spin-coating for 30s at the rotating speed of 3000 rpm. An Au thin film with the thickness of 80nm is evaporated on the surface of the hole transport layer by adopting a vacuum coating film to be used as a metal electrode.
5) Respectively taking normal hexane as a solvent to prepare a solution (volume ratio) with the concentration of octadecyl trichlorosilane of 10%, spin-coating hydrophobic materials with different concentrations to the surface of a device by using a spin-coating method at the rotation speed of 5000rpm for 30s, immediately placing the device on a hot table at the temperature of 90 ℃ after the spin-coating is finished, heating the device for 50s, taking down the device, standing the device, and cooling the device to room temperature.
6) The device spin-coated with the octadecyltrichlorosilane is placed in a constant-temperature and constant-humidity environment box with the temperature of 20 ℃ and the relative humidity of 85 percent, and the photovoltaic performance of the device in different time periods is tested.
The perovskite solar cell prepared by the experiment is tested, the test condition is a light intensity, and the test area is 0.16cm2The test light source is AAA grade, and the result shows that the photoelectric conversion efficiency of the reverse scanning of the cell is 16.93 percent before the stability test, wherein the open-circuit voltage is 1036mV, and the short-circuit current is 24.29mA/cm2The fill factor is 0.67; after 200h of humidity stability test, the reverse scanning photoelectric conversion efficiency of the cell is 12.76%, wherein the open-circuit voltage is 1006mV, and the short-circuit current is 19.61mA/cm2The fill factor is 0.65.
Example 3:
1) etching transparent conductive substrate FTO glass by femtosecond laser, respectively ultrasonically cleaning the FTO glass by using liquid detergent, deionized water and ethanol for 15min, blow-drying the FTO glass by using a dry air gun, and removing residual organic matters on the surface by ultraviolet-ozone treatment for 10 min;
2)SnO2preparing a nano film: 5g of urea, 5mL of concentrated hydrochloric acid, 100. mu.L of thioglycolic acid and 1.096g SnCl2·2H2And adding O into 400mL of deionized water in sequence, uniformly mixing, and refrigerating in a refrigerator for three days for use. 20mL of SnCl is taken2The mother liquor of (1) and 100mL of deionized water were mixed well and poured into a clean glass container, and FTO glass cleaned and treated with ultraviolet irradiation for 15min was put in and sealed. The glass was heated in an oven at 70 ℃ for 90min until a slightly white precipitate appeared, after which the glass surface was rinsed clean with deionized water. And after washing, putting the glass into an ultrasonic machine for ultrasonic treatment for 5min, washing the surface of the glass by using deionized water, and repeating the step for three times. After the surface moisture is blown off by an air gun, the material is placed on a titanium-based heating table at 180 ℃ for heating for 1h, and annealing is carried out.
3) The perovskite is prepared by a one-step method, and perovskite precursor liquid, 33mg CsI, 200mg FAI and 629mg PbI are prepared2Dissolved in 800. mu.L of a mixed DMF/DMSO solution (volume ratio DMF: DMSO. RTM.4: 1). Cleaning the FTO substrate with the prepared electron transport layer in a UV machine for 15min, and adding ethyl acetate dropwise as an anti-solvent in SnO2And preparing a perovskite thin film which is completely covered and well crystallized on the thin film. The spin coating speed is 6000rpm, and the time is 30 s; ethyl acetate was added dropwise within the reciprocal 5s during the spin coating, and the mixture was annealed on a 120 ℃ hot stage for 60min and then cooled.
4) 73mg/mL of Spiro-OMeTAD solution was prepared as a hole transport material using chlorobenzene as a solvent, and 30. mu.L of 4-tert-butylpyridine, 29. mu.L of a cobalt salt solution, and 18. mu.L of a lithium salt solution were added. And (3) uniformly coating the prepared Spiro-OMeTAD solution on the surface of the cooled perovskite thin film, and spin-coating for 30s at the rotating speed of 3000 rpm. An Au thin film with the thickness of 80nm is evaporated on the surface of the hole transport layer by adopting a vacuum coating film to be used as a metal electrode.
5) Respectively taking normal hexane as a solvent to prepare a solution (volume ratio) with the concentration of perfluorodecyl trichlorosilane of 10%, spin-coating hydrophobic materials with different concentrations to the surface of a device by using a spin-coating method at the rotation speed of 5000rpm for 30s, immediately placing the device on a hot table at 70 ℃ after the spin-coating is finished, heating the device for 70s, taking down the device, standing the device, and cooling the device to room temperature.
6) The device spin-coated with the perfluorodecyl trichlorosilane is placed in a constant-temperature and constant-humidity environment box with the temperature of 20 ℃ and the relative humidity of 85%, and the photovoltaic performance of the device in different time periods is tested.
The perovskite solar cell prepared by the experiment is tested, the test condition is a light intensity, and the test area is 0.16cm2The test light source is AAA grade, and the result shows that the photoelectric conversion efficiency of the reverse scanning of the cell is 16.23 percent before the stability test, wherein the open-circuit voltage is 1025mV, and the short-circuit current is 24.17mA/cm2The fill factor is 0.66; after the constant temperature and humidity stability test of 200h, the photoelectric conversion efficiency of the reverse scanning of the battery is 11.29 percent, wherein the open-circuit voltage is 983mV, and the short-circuit current is 19.78mA/cm2The fill factor is 0.58.
Example 4:
1) etching transparent conductive substrate FTO glass by femtosecond laser, respectively ultrasonically cleaning the FTO glass by using liquid detergent, deionized water and ethanol for 15min, blow-drying the FTO glass by using a dry air gun, and removing residual organic matters on the surface by ultraviolet-ozone treatment for 10 min;
2)SnO2preparing a nano film: 5g of urea, 5mL of concentrated hydrochloric acid, 100. mu.L of thioglycolic acid and 1.096g of SnCl2·2H2And adding O into 400mL of deionized water in sequence, uniformly mixing, and refrigerating in a refrigerator for three days for use. 20mL of SnCl is taken2The mother liquor of (1) and 100mL of deionized water were mixed well and poured into a clean glass container, and FTO glass cleaned and treated with ultraviolet irradiation for 15min was put in and sealed. The glass was heated in an oven at 70 ℃ for 90min until a slightly white precipitate appeared, after which the glass surface was rinsed clean with deionized water. And after washing, putting the glass into an ultrasonic machine for ultrasonic treatment for 5min, washing the surface of the glass by using deionized water, and repeating the step for three times. After the surface moisture is blown off by an air gun, the material is placed on a titanium-based heating table at 180 ℃ for heating for 1h, and annealing is carried out.
3) The perovskite is prepared by a one-step method, and perovskite precursor liquid, 33mg CsI, 200mg FAI and 629mg PbI are prepared2Dissolved in 800. mu.L of a mixed DMF/DMSO solution (volume ratio DMF: DMSO. RTM.4: 1). Cleaning the FTO substrate with the prepared electron transport layer in a UV machine for 15min, and adding ethyl acetate dropwise as an anti-solvent in SnO2And preparing a perovskite thin film which is completely covered and well crystallized on the thin film. The spin speed was 6000rpm and the acceleration was 1000rpm/s for 30 s; the anti-solvent ethyl acetate is added dropwise at the last 5s in the spin coating process, and the mixture is annealed on a hot bench at 120 ℃ for 60min and then cooled.
4) 73mg/mL of Spiro-OMeTAD solution was prepared as a hole transport material using chlorobenzene as a solvent, and 30. mu.L of 4-tert-butylpyridine, 29. mu.L of a cobalt salt solution, and 18. mu.L of a lithium salt solution were added. And (3) uniformly coating the prepared Spiro-OMeTAD solution on the surface of the cooled perovskite thin film, and spin-coating for 30s at the rotating speed of 3000 rpm. An Au thin film with the thickness of 80nm is evaporated on the surface of the hole transport layer by adopting a vacuum coating film to be used as a metal electrode.
5) Respectively taking normal hexane as a solvent to prepare a solution (volume ratio) with the concentration of perfluorodecyl triethoxysilane of 10%, spin-coating hydrophobic materials with different concentrations to the surface of a device at the rotation speed of 5000rpm for 30s, immediately placing the device on a hot table at 80 ℃ after the spin-coating is finished, heating the device for 60s, taking down the device, standing the device, and cooling the device to room temperature.
6) And (3) placing the device spin-coated with the perfluorodecyl triethoxysilane in the step in a constant-temperature and constant-humidity environment box with the temperature of 20 ℃ and the relative humidity of 85%, and testing the photovoltaic performance of the device in different time periods.
The perovskite solar cell prepared by the experiment is tested, the test condition is a light intensity, and the test area is 0.16cm2The test light source is AAA grade, and the result shows that the photoelectric conversion efficiency of the reverse scanning of the cell is 16.68 percent before the stability test, wherein the open-circuit voltage is 1024mV, and the short-circuit current is 24.26mA/cm2The fill factor is 0.67; after the constant temperature and humidity stability test of 200h, the reverse scanning photoelectric conversion efficiency of the cell is 10.30 percent, wherein the open-circuit voltage is 975mV, and the short-circuit current is 18.00mA/cm2The fill factor is 0.57.
Claims (4)
1. A method of encapsulating a perovskite solar cell, characterized by comprising the steps of:
1) cleaning and etching the FTO glass substrate;
2) preparation of SnO on FTO glass surface by using chemical bath deposition method2An electron transport layer;
3) by usingOne step antisolvent process in SnO2Spin coating on surface of electron transport layer to prepare perovskite light absorption layer Cs0.1FA0.9PbI3；
4) Uniformly coating the prepared Spiro-OMeTAD solution on the surface of the cooled perovskite light absorption layer, and finally evaporating and plating a gold film on the Spiro-OMeTAD solution to be used as an electrode to obtain a perovskite solar cell device;
5) and (3) spin-coating the n-hexane solution of the hydrophobic material on the surface of the complete perovskite solar cell device by using a one-step spin coating method, and heating for 50-70s at 70-90 ℃.
2. The method for encapsulating a perovskite solar cell as claimed in claim 1, wherein the hydrophobic material is octadecyl trichlorosilane, perfluorodecyl trichlorosilane or a perfluorodecyl triethoxysilane solution.
3. The method for encapsulating a perovskite solar cell as claimed in claim 1, wherein the concentration of the n-hexane solution of the hydrophobic material in step 5 is 10 vt%.
4. The method for encapsulating a perovskite solar cell as claimed in claim 1, wherein the hydrophobic material in step 5 is octadecyltrichlorosilane, the spin coating parameter is 5000rpm, and the time is 30 s.
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| CN113725369A (en) * | 2021-08-04 | 2021-11-30 | 武汉理工大学 | Method for rapidly preparing large-area and uniform perovskite cell tin oxide electron transport layer in batch mode and perovskite solar cell |
| CN113809238A (en) * | 2021-08-24 | 2021-12-17 | 杭州电子科技大学 | Method for improving conversion efficiency of perovskite battery |
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