CN111864084B - Preparation method of stable and efficient perovskite solar cell - Google Patents

Preparation method of stable and efficient perovskite solar cell Download PDF

Info

Publication number
CN111864084B
CN111864084B CN202010728431.5A CN202010728431A CN111864084B CN 111864084 B CN111864084 B CN 111864084B CN 202010728431 A CN202010728431 A CN 202010728431A CN 111864084 B CN111864084 B CN 111864084B
Authority
CN
China
Prior art keywords
solution
solar cell
deionized water
sno
stable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010728431.5A
Other languages
Chinese (zh)
Other versions
CN111864084A (en
Inventor
黄福志
郑循天
貊艳平
程一兵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Guangjing Energy Technology Co ltd
Original Assignee
Wuhan University of Technology WUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University of Technology WUT filed Critical Wuhan University of Technology WUT
Priority to CN202010728431.5A priority Critical patent/CN111864084B/en
Publication of CN111864084A publication Critical patent/CN111864084A/en
Application granted granted Critical
Publication of CN111864084B publication Critical patent/CN111864084B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • 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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • 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
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a preparation method of a stable and efficient perovskite solar cell, which comprises the steps of cleaning and etching a substrate FTO glass; soaking in Sn4+Sealing in the diluent, heating in a forced air drying oven until a little white flocculent precipitate appears, taking out and ultrasonically cleaning; soaking in Sn2+Sealing the diluted solution, heating the diluted solution in a blast drying oven to be milk white, taking out the diluted solution and ultrasonically cleaning the diluted solution; repeating the previous step twice, and annealing to obtain SnO2An electron transport layer; one-step antisolvent spin-coating process on SnO2Preparing a perovskite light absorption layer on the electron transmission layer; uniformly coating the surface of the cooled perovskite light absorption layer by using a Spiro-OMeTAD (HTL) solution as a hole transport layer; the gold film is evaporated as an electrode by a vacuum evaporation method. The preparation process is simple and has strong repeatability; has higher short-circuit current Jsc and higher photoelectric conversion efficiency.

Description

Preparation method of stable and efficient perovskite solar cell
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a preparation method of a stable and efficient perovskite solar cell
Background
The perovskite solar cell has outstanding advantages in both material formation and preparation process as a third generation novel photovoltaic device. Since the first report of efficient devices in 2012, the device attracts extensive attention worldwide and is rated as one of the ten technological advances in 2013 by the journal of science. In 7 years later, the certified photoelectric conversion efficiency of the perovskite solar cell device is increased from about 15% to 25.2%, and surpasses the efficiency of a polycrystalline silicon solar cell (23.3%). It can be seen that the perovskite photovoltaic technology has a basis for preliminary industrialization.
Currently, tin oxide (SnO) is widely used for planar heterostructure perovskite cells2) As an Electron Transport Layer (ETL), this is mainly due to: (1) SnO2With a deep conduction band and a more closely matched energy level position to the perovskite, the superior band of the ETL/perovskite interface will enhance the ability of the electron layer to extract electrons and block holes. (2) SnO2Having a height of up to 240cm2V-1S-1The high volume electron mobility and the high conductivity of the composite material can efficiently transmit electrons and reduce the electron hole recombination loss. (3) SnO2Has a wider optical band gap (3.6-4.0eV), has higher transmittance for visible light, and can ensure that most of light passes through and is absorbed by the perovskite. (4) SnO2The flexible solar cell is easy to process at low temperature (less than 200 ℃), can be made into a flexible solar cell and is easy to commercialize. (5) With TiO2SnO, or other ETL vs2Has excellent chemical stability, ultraviolet resistance and lower photocatalytic activity, which contributes to the overall stability of the device.
Containing Sn4+，Sn2+The compounds and solutions of (a) are commonly used in the fabrication of electron transport layers for perovskite solar cells as a conventional tin source. The radius of the particles, the thickness of the formed film and the like can be adjusted by changing the concentration of the solution, the annealing temperature and the annealing time, so that SnO with different crystal forms and different thicknesses can be obtained2Electron shell films. However, the tin oxide film prepared by the low-temperature solution method has more defects, and is unfavorable for the photovoltaic performance and stability of the perovskite solar cell.
Disclosure of Invention
The invention aims to improve the photoelectric conversion efficiency and stability requirements of a perovskite solar cell, and provides a preparation method of a stable and efficient perovskite solar cell.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of a stable and efficient perovskite solar cell comprises the following steps:
1) cleaning and etching the FTO glass substrate;
2) soaking the treated FTO glass into Sn4+Sealing in the diluent, heating in a forced air drying oven until a little white flocculent precipitate appears, taking out and ultrasonically cleaning; soaking in Sn2+Sealing the diluted solution, heating the diluted solution in a blast drying oven to be milk white, taking out the diluted solution and ultrasonically cleaning the diluted solution; repeating the previous stepTwice, annealing treatment to obtain SnO2An electron transport layer;
3) one-step antisolvent spin-coating process on SnO2Preparation of perovskite light absorption layer Cs on electron transport layer0.1FA0.9PbI3；
4) Uniformly coating the surface of the cooled perovskite light absorption layer by using a Spiro-OMeTAD (HTL) solution as a hole transport layer;
5) the gold film is evaporated as an electrode by a vacuum evaporation method.
Sn in step 2 according to the scheme4+The diluent is prepared by the following method:
anhydrous SnCl4Mixing with deionized water according to the volume ratio of 3:7, stirring in ice water bath for 12-24h, diluting the obtained mixed solution with deionized water by 18-20 times, and refrigerating in a refrigerator for later use.
Sn in step 2 according to the scheme2+The diluent is prepared by the following method:
adding a proper amount of urea and concentrated hydrochloric acid into deionized water to adjust the pH of the solution<1, adding 0.025 vt% thioglycolic acid and finally adding SnCl2·2H2Preparing SnCl with concentration of 0.010-0.012mmol/L from O2The solution was used diluted 6-fold with deionized water after three days of refrigeration in a refrigerator.
According to the scheme, Sn is soaked in the step 24+Blowing the diluted solution into a drying oven at 80-100 deg.C for 40-50 min.
According to the scheme, Sn is soaked in the step 22+The temperature of the air-blast drying oven after the dilution is 60-80 ℃ and the time is 1.5-2 h.
According to the scheme, the annealing temperature in the step 2 is 170-190 ℃, and the annealing time is 0.5-1.5 h.
SnO prepared by low-temperature solution method2The electron transport layer is easy to introduce oxygen vacancy, so that the overall defects of the perovskite solar cell are increased, the photoelectric conversion efficiency and the long-term stability of the device are reduced, and the invention utilizes Sn4+Can be hydrolyzed rapidly and has good crystallinity, and simultaneously introduces Sn2+Reduce the defects of the electron transport layer and passivate the perovskite layer and SnO2Electron transport layerThe interface of the device shows higher carrier mobility, reduces non-radiative recombination, obviously improves short-circuit current, and simultaneously improves the photoelectric conversion efficiency and long-term stability of the device.
The invention uses 2,2 ', 7, 7' -tetra [ N, N-di (4-methoxyphenyl) amino]-9, 9' -spirobifluorene (Spiro-OMeTAD) as a hole transport material and Cs0.1FA0.9PbI3(wherein FA refers to formamidine) is perovskite light-absorbing material, and anhydrous stannic chloride (SnCl) is used4) And stannous chloride dihydrate (SnCl)2·2H2O) as containing Sn4+，Sn2+The research shows that the charge transmission of the perovskite solar cell is obviously improved after the electron transmission layer is optimized, and a stable and efficient solar cell device is obtained.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the preparation process is simple and has strong repeatability;
2) the short-circuit current Jsc is higher and the photoelectric conversion efficiency is higher;
3) has better long-term stability.
Drawings
FIG. 1: examples SnO obtained2Electron scanning microscopy of the nano-film material;
FIG. 2: scanning electron micrographs of the perovskite thin film obtained in the examples.
Detailed Description
Example 1:
1)Sn2+preparation of a diluent: adding a proper amount of urea and concentrated hydrochloric acid into deionized water to adjust the pH of the solution<1, adding 0.025 vt% thioglycolic acid and finally adding SnCl2·2H2Preparing SnCl with concentration of 0.010mmol/L from O2The solution was used diluted 6-fold with deionized water after three days of refrigeration in a refrigerator.
2) And (3) femtosecond laser etching transparent conductive substrate FTO glass, 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.
3)SnO2Preparing a nano film: 120mL of Sn is taken2+The diluted solution was 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.
4) The perovskite light absorption layer 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; the anti-solvent ethyl acetate was added dropwise during the last 5 seconds of the spin coating process, and annealed on a 120 ℃ hot stage for 60min and then cooled.
5) 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.
The perovskite solar cell prepared by the experiment is tested, the test condition is a light intensity, and the test area is 0.16cm2The AAA level of the test light source shows that the photoelectric conversion efficiency of the reverse scanning of the cell is 18.39%, wherein the open-circuit voltage is 1058mV, and the short-circuit current is 23.89mA/cm2The fill factor is 0.73; the photoelectric conversion efficiency of the cell in forward scanning is 14.46 percent, wherein the open-circuit voltage is 996mV, and the short-circuit current is 23.91mA/cm2The fill factor is 0.61.
Example 2:
1)Sn2+preparation of a diluent: adding a proper amount of urea and concentrated hydrochloric acid into deionized water to adjust the pH of the solution<1, adding 0.025 vt% thioglycolic acid and finally adding SnCl2·2H2Preparing SnCl with concentration of 0.012mmol/L from O2The solution was used diluted 6-fold with deionized water after three days of refrigeration in a refrigerator. Sn (tin)4+Preparation of a diluent: anhydrous SnCl4Mixing with deionized water according to the volume ratio of 3:7, stirring in an ice-water bath for 12h, diluting the obtained mixed solution by 18 times with deionized water, and placing into a refrigerator for refrigeration for standby.
2) 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;
3)SnO2preparing a nano film: taking 100mL of Sn4+Diluting, mixing, pouring into a clean glass container, adding FTO glass cleaned and treated with ultraviolet irradiation for 15min, and sealing. Heating in oven at 90 deg.C for 40-50min until some white flocculent precipitate appears. Then the surface of the glass is directly washed clean by deionized water. And after washing, putting the glass into an ultrasonic machine for ultrasonic treatment for 5min, and then washing the surface of the glass by using deionized water. 120mL of Sn is taken2+The dilution was poured into a glass container, the glass was placed and sealed. Heating in 70 deg.C oven for 1.5-2 hr until the solution is milky white. Then the surface of the glass is directly washed clean by 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 twice. 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.
4) The perovskite light absorption layer 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 was 6000rpm for 30s, and the spin-coating was carried out while pouringThe anti-solvent ethyl acetate was added dropwise several seconds to 5 seconds, and the mixture was annealed in a 120 ℃ hot stage for 60 minutes and then cooled.
5) 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.
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 18.83%, wherein the open-circuit voltage is 1045mV, and the short-circuit current is 24.05mA/cm2The fill factor is 0.75; the photoelectric conversion efficiency of the cell in forward scanning is 16.37 percent, wherein the open-circuit voltage is 1012mV, and the short-circuit current is 24.06mA/cm2The fill factor is 0.67.
Example 3:
1)Sn2+preparation of a diluent: adding a proper amount of urea and concentrated hydrochloric acid into deionized water to adjust the pH of the solution<1, adding 0.025 vt% thioglycolic acid and finally adding SnCl2·2H2Preparing SnCl with concentration of 0.011mmol/L from O2The solution was used diluted 6-fold with deionized water after three days of refrigeration in a refrigerator. Sn (tin)4+Preparation of a diluent: anhydrous SnCl4Mixing with deionized water according to the volume ratio of 3:7, stirring in an ice-water bath for 24h, diluting the obtained mixed solution by 20 times with deionized water, and placing in a refrigerator for cold storage for later use.
2) And (3) femtosecond laser etching transparent conductive substrate FTO glass, 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.
3)SnO2Preparing a nano film: taking 100mL of Sn4+The diluted solution was poured into a clean glass container, and FTO glass cleaned and treated with ultraviolet irradiation for 15min was put in and sealed. Heating in an oven at 90 deg.C for 40 deg.C50min until some white floc precipitate appeared. Then the surface of the glass is directly washed clean by 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 twice. 120mL of Sn is taken2+The dilution was poured into a glass container, the glass was placed and sealed. Heating in 70 deg.C oven for 1.5-2 hr until the solution is milky white. Then the surface of the glass is directly washed clean by deionized water. And after washing, putting the glass into an ultrasonic machine for ultrasonic treatment for 5min, and then washing the surface of the glass by using deionized water. 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.
4) The perovskite light absorption layer 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, the time is 30s, the anti-solvent ethyl acetate is dripped in the last 5 seconds in the spin coating process, and the mixture is annealed on a 120 ℃ hot bench for 60min and then cooled.
5) 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.
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 15.57 percent, wherein the open-circuit voltage is 997mV, and the short-circuit current is 23.81mA/cm2The fill factor is 0.66; the forward scanning photoelectric conversion efficiency of the cell is 12.52 percent, wherein the open-circuit voltage is 960mV, and the short-circuit current is 23.79mA/cm2The fill factor is 0.55.
Example 4:
1)Sn4+preparation of a diluent: anhydrous SnCl4Mixing with deionized water according to the volume ratio of 3:7, stirring in an ice-water bath for 24h, diluting the obtained mixed solution by 19 times with deionized water, and placing in a refrigerator for cold storage for later use.
2) And (3) femtosecond laser etching transparent conductive substrate FTO glass, 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.
3)SnO2Preparing a nano film: taking 100mL of Sn4+The diluted solution was poured into a clean glass container, and FTO glass cleaned and treated with ultraviolet irradiation for 15min was put in and sealed. Heating in oven at 90 deg.C for 40-50min until some white flocculent precipitate appears. Then the surface of the glass is directly washed clean by 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 twice. 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.
4) The perovskite light absorption layer 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, the time is 30s, the anti-solvent ethyl acetate is dripped in the last 5 seconds in the spin coating process, and the mixture is annealed on a 120 ℃ hot bench for 60min and then cooled.
5) 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.
The perovskite solar cell prepared by the experiment is tested, the test condition is a light intensity, and the test area is 0.16cm2The AAA test light source is in grade, and the result shows that the photoelectric conversion efficiency of the reverse scanning of the cell is 14.55 percent, wherein the open-circuit voltage is 1004mV, and the short-circuit current is 23.46mA/cm2The fill factor is 0.62; the photoelectric conversion efficiency of the cell in forward scanning is 12.99%, wherein the open-circuit voltage is 969mV, and the short-circuit current is 23.45mA/cm2The fill factor is 0.57.
FIG. 1 is a SnO obtained from examples 1 to 42Scanning electron microscope image of nano-film material, wherein A is SnO prepared in example 12A nano-film; b is SnO prepared in example 22A nano-film; c is SnO prepared in example 32A nano-film; d is SnO prepared in example 42And (3) a nano film. A shows that the tin oxide electronic layer completely covers FTO, no obvious holes exist, but a small amount of particles appear; SnO prepared in B2The nano film is more smooth and uniform, and completely covered without holes; SnO in C2A very small amount of holes appear on the surface of the nano film; group D had more pronounced holes.
FIG. 2 is a scanning electron micrograph of the perovskite thin film obtained in examples 1 to 4, wherein A is the perovskite thin film prepared in example 1; b is the perovskite thin film prepared in example 2; c is the perovskite thin film prepared in example 3; d is the perovskite thin film prepared in example 4. The perovskite thin films obtained in the examples 1-4 have no obvious difference in morphology, the grain sizes are mostly between 200 and 400nm, and the surfaces of the perovskite thin films all contain a small amount of lead iodide.

Claims (5)

1. A preparation method of a stable and efficient perovskite solar cell is characterized by comprising the following steps:
1) cleaning and etching the FTO glass substrate;
2) soaking the treated FTO glass into Sn4+Sealing in the diluent, heating in a forced air drying oven until a little white flocculent precipitate appears, taking out and ultrasonically cleaning; soaking in Sn2+Mixing and sealing in diluentSealing, heating in an air-blast drying oven to milk white, taking out and ultrasonically cleaning; repeating the previous step twice, and annealing to obtain SnO2An electron transport layer;
3) one-step antisolvent spin-coating process on SnO2Preparation of perovskite light absorption layer Cs on electron transport layer0.1FA0.9PbI3；
4) Uniformly coating the surface of the cooled perovskite light absorption layer with a Spiro-OMeTAD solution, and drying to form a hole transport layer;
5) adopting a vacuum evaporation method to evaporate a gold film as an electrode;
wherein, the Sn in the step 2)2+The diluent is prepared by the following method:
adding a proper amount of urea and concentrated hydrochloric acid into deionized water to adjust the pH of the solution<1, adding 0.025 vt% thioglycolic acid and finally adding SnCl2·2H2Preparing SnCl with concentration of 0.010-0.012mmol/L from O2The solution was used diluted 6-fold with deionized water after three days of refrigeration in a refrigerator.
2. The method of claim 1, wherein the step 2) is performed by using Sn4 +The diluent is prepared by the following method:
anhydrous SnCl4Mixing with deionized water according to the volume ratio of 3:7, stirring in ice water bath for 12-24h, diluting the obtained mixed solution with deionized water by 18-20 times, and refrigerating in a refrigerator for later use.
3. The method for preparing a stable and efficient perovskite solar cell as claimed in claim 1, wherein the step 2) is soaking in Sn4+Blowing the diluted solution into a drying oven at 80-100 deg.C for 40-50 min.
4. The method for preparing a stable and efficient perovskite solar cell as claimed in claim 1, wherein the step 2) is soaking in Sn2+The temperature of the air-blast drying oven after the dilution is 60-80 ℃ and the time is 1.5-2 h.
5. The method for preparing a stable and efficient perovskite solar cell as claimed in claim 1, wherein the annealing temperature in step 2) is 170 ℃ and 190 ℃, and the annealing time is 0.5-1.5 h.
CN202010728431.5A 2020-07-24 2020-07-24 Preparation method of stable and efficient perovskite solar cell Active CN111864084B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010728431.5A CN111864084B (en) 2020-07-24 2020-07-24 Preparation method of stable and efficient perovskite solar cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010728431.5A CN111864084B (en) 2020-07-24 2020-07-24 Preparation method of stable and efficient perovskite solar cell

Publications (2)

Publication Number Publication Date
CN111864084A CN111864084A (en) 2020-10-30
CN111864084B true CN111864084B (en) 2022-03-01

Family

ID=72947057

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010728431.5A Active CN111864084B (en) 2020-07-24 2020-07-24 Preparation method of stable and efficient perovskite solar cell

Country Status (1)

Country Link
CN (1) CN111864084B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN114551723B (en) * 2021-12-30 2023-08-04 苏州科技大学 Perovskite battery based on acid treatment of tin oxide and preparation thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107919439A (en) * 2017-11-15 2018-04-17 武汉理工大学 A kind of perovskite solar cell of stabilization and preparation method thereof
CN110518125A (en) * 2019-08-01 2019-11-29 北京科技大学 A kind of preparation method of cation doping perovskite solar battery

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4105345A1 (en) * 1991-02-21 1992-08-27 Kronos Int Inc METHOD FOR PRODUCING FINE PARTICLE TITANIUM DIOXIDE AND FINE PARTICLE TITANIUM DIOXIDE
CN104157788B (en) * 2014-08-19 2017-03-29 武汉大学 It is a kind of to be based on SnO2Perovskite thin film photovoltaic cell and preparation method thereof
KR102027304B1 (en) * 2018-05-15 2019-10-01 (주)에이프로 Organic Light-Emitting Diodes
CN109103338B (en) * 2018-07-23 2020-06-19 武汉理工大学 Preparation method of large-area perovskite thin film and battery pack thereof
CN109354057B (en) * 2018-09-18 2021-09-14 鞍山七彩化学股份有限公司 Tin oxide nanocrystal and preparation method thereof and preparation method of solar cell
CN116546867A (en) * 2019-05-08 2023-08-04 昆山协鑫光电材料有限公司 Preparation method of flexible perovskite solar cell
CN110518131B (en) * 2019-07-02 2021-07-20 南昌航空大学 Perovskite quantum dot light-emitting diode containing composite electron transport layer and preparation method thereof
CN110828182A (en) * 2019-11-29 2020-02-21 南昌航空大学 Preparation method of magnesium-doped tin dioxide photo-anode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107919439A (en) * 2017-11-15 2018-04-17 武汉理工大学 A kind of perovskite solar cell of stabilization and preparation method thereof
CN110518125A (en) * 2019-08-01 2019-11-29 北京科技大学 A kind of preparation method of cation doping perovskite solar battery

Also Published As

Publication number Publication date
CN111864084A (en) 2020-10-30

Similar Documents

Publication Publication Date Title
CN111864084B (en) Preparation method of stable and efficient perovskite solar cell
CN108598268B (en) Method for preparing planar heterojunction perovskite solar cell by printing under environmental condition
CN108288675B (en) Iron salt doped cyclone-OMeTAD hole transport layer and solar cell comprising same
CN113903861B (en) Perovskite solar cell rapidly annealed in air and preparation method thereof
CN111710782B (en) Preparation method of high-quality perovskite thin film and perovskite solar cell
CN109378386A (en) It is a kind of regulate and control the method for unleaded perovskite solar battery pattern and the solar cell device of preparation
CN111864083A (en) Packaging method of perovskite solar cell
CN110299455A (en) It is a kind of regulate and control unleaded perovskite solar cell surface pattern preparation method
CN113659082B (en) Perovskite solar cell preparation method based on interface modification
CN114883493A (en) Solar cell based on three-dimensional/two-dimensional perovskite and preparation method thereof
CN114497390A (en) Perovskite solar cell and preparation method thereof
CN106784330B (en) A kind of translucent organic metal halide perovskite thin film solar battery and preparation method thereof
CN112993167A (en) Application of organic ammonium salt modified metal oxide nanoparticles in positive perovskite solar cell and preparation method of device
CN114805150B (en) Interface modification molecule applied to lead-based perovskite solar cell
CN116056469A (en) Perovskite solar cell based on ionic liquid interface modification
CN109888100A (en) A kind of preparation of rubidium Y-oxides doping film and application as hole transmission layer in perovskite solar battery
CN115528178A (en) Perovskite-polymer composite material, preparation method and perovskite solar cell
CN114583061A (en) Lead-free tin-based perovskite thin film with three-dimensional structure and preparation method of solar cell thereof
CN115188899A (en) Method for preparing perovskite solar cell by one-step printing in high-humidity air
CN110246969B (en) Preparation method of perovskite solar cell with pyridine modified tin oxide compact layer
CN109802045B (en) NaTaO3And PCBM as double electron transport layers for preparing perovskite solar cell
CN116507185B (en) Formamidine perovskite solar cell and preparation method thereof
CN111640868B (en) Preparation method of perovskite thin film photoelectric device based on electronic irradiation modification
CN115360303B (en) Interface in-situ induction layer and preparation method of photovoltaic device thereof
CN116507139B (en) Long-branched chain alkyl ammonium modified formamidine perovskite solar cell and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20221213

Address after: 528216 13th Floor, Building A, No. 28, Dongyang 3rd Road, Danzao Town, Nanhai District, Foshan City, Guangdong Province

Patentee after: Guangdong Guangjing Energy Technology Co.,Ltd.

Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122

Patentee before: WUHAN University OF TECHNOLOGY