CN116669510A - Perovskite photovoltaic device with BCP (binary coded decimal) used for photoelectrode modification and preparation method thereof - Google Patents
Perovskite photovoltaic device with BCP (binary coded decimal) used for photoelectrode modification and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000004048 modification Effects 0.000 title abstract description 11
- 238000002715 modification method Methods 0.000 title description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 52
- 238000004528 spin coating Methods 0.000 claims abstract description 30
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- -1 ammonium halide salt Chemical class 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000009472 formulation Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 19
- 239000010931 gold Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001246 colloidal dispersion Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
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- 238000007738 vacuum evaporation Methods 0.000 description 1
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
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Abstract
The invention discloses a perovskite photovoltaic device with BCP used for photoelectrode modification and a preparation method thereof, comprising the following steps: preparing BCP solution and spin-coating on an ITO substrate; preparing SnO 2 Solution and spin-coating on BCP; formulation of PbI 2 Solution and spin coating on SnO 2 Applying; preparing mixed solution of ammonium halide salt and spin-coating on PbI 2 Applying; preparing PEAI solution and spin-coating on ammonium halide salt; preparing and spin-coating the spiro-OMeTAD on PEAI to obtain ITO/BCP/SnO 2 perovskite/PEAI/spiro-OMeTAD samples; and (5) evaporating an electrode. The invention uses BCP to process ITAfter the O substrate is treated, blocking of holes and transmission of electrons are facilitated; second, BCP versus SnO 2 The electron transport layer is subjected to interface modification, so that interface defects are reduced; in addition, a small amount of BCP contacts with the perovskite interface, promoting the growth of perovskite grains.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a perovskite photovoltaic device with BCP for photoelectrode modification and a preparation method thereof.
Background
The main energy source in the current age is fossil energy, but with the combustion of fossil fuels, the environment is irreversibly destroyed, the fossil fuels are not renewable, and people have to find a clean renewable energy source to replace the traditional fossil fuels, so solar energy, wind energy and the like are generated. Under the background, the efficient conversion of solar energy into electric energy becomes urgent, and in addition, compared with the traditional silicon-based solar cell, the perovskite photovoltaic device has the advantages of simple preparation process and high first-order rate. In addition, after the BCP modification is added, the crystallinity of the (111) crystal face of the device is better (Science, 2023, 379 (6628): 173-178), the stability is improved, and a new method is provided for preparing the perovskite photovoltaic device with higher efficiency and stability.
Disclosure of Invention
The invention aims to provide a perovskite photovoltaic device with BCP used for photoelectrode modification and a preparation method thereof. The invention improves the interface defect problem and the charge accumulation recombination problem of the electron transport layer.
By spin coating BCP on ITO/SnO 2 Modification of SnO at the interface 2 The bottom is beneficial to the transmission of electrons and the blocking of holes; furthermore, snO 2 The layer is made of nano SnO 2 Dispersion liquidWhen the perovskite layer is manufactured, part of perovskite solution is contacted with bottom ITO/BCP through the gaps, BCP is directly contacted with perovskite crystal grains after film formation, and the strong interaction between the BCP and the perovskite crystal grains is beneficial to promoting the directional growth of the perovskite crystal grains, namely the growth along the (111) plane, so that the photoelectric conversion efficiency and the stability of the device are improved, and the perovskite photovoltaic device with high efficiency and stability is manufactured.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a perovskite photovoltaic device with BCP used for photoelectrode modification comprises the following steps:
(1) Cleaning an ITO (indium tin oxide) substrate, respectively using a glass cleaning agent, acetone and isopropanol to carry out ultrasonic cleaning, drying by nitrogen, and then treating the substrate by ultraviolet ozone;
(2) Preparing and spin-coating a BCP solution, and performing ultraviolet ozone treatment to obtain an ITO/BCP sample;
(3) Preparing SnO 2 Spin coating SnO on ITO/BCP substrate 2 The solution is annealed and treated by ultraviolet ozone to obtain ITO/BCP/SnO 2 A sample;
(4) Formulation of PbI 2 Spin-coating PbI on the sample obtained in the step (3) in a nitrogen glove box 2 Solution, annealing treatment to obtain ITO/BCP/SnO 2 /PbI 2 A sample;
(5) ITO/BCP/SnO obtained in the step (4) 2 /PbI 2 Spin-coating ammonium halide salt mixed solution on the sample under the protection of nitrogen, and annealing to obtain ITO/BCP/SnO 2 Perovskite sample;
(6) Preparing PEAI solution, and obtaining ITO/BCP/SnO in the step (5) 2 Spin coating PEAI solution on perovskite sample to obtain ITO/BCP/SnO 2 perovskite/PEAI sample;
(7) ITO/BCP/SnO obtained in step (6) 2 Spin-coating of spiro-OMeTAD on perovskite/PEAI sample to obtain ITO/BCP/SnO 2 Samples of perovskite/PEAI/spiro-OMeTAD structure.
(8) Obtained in step (7)ITO/BCP/SnO 2 Evaporating gold electrode on sample with perovskite/PEAI/spiro-OMeTAD structure to obtain ITO/BCP/SnO 2 Perovskite photovoltaic devices of the/perovskite/PEAI/spiro-OMeTAD/Au structure.
Preferably, in step (2), the BCP solution is prepared as follows: and adding BCP powder into isopropanol, and stirring for 5-7 hours to prepare 0.5mg/ml BCP solution. The spin-coating amount of the BCP solution is 20-30 mu L/cm 2 。
Preferably, in step (3), snO 2 The preparation process of (2) is as follows: snO is prepared 2 Diluting the colloidal dispersion (15 wt%) with deionized water to 10wt%, and stirring for 20min to obtain SnO 2 A solution; in step (3), annealing means annealing at 100℃for 5 minutes and at 150℃for 10 minutes.
In the step (1), (2) and (3), the wavelength of ultraviolet rays is 180-190 nm, and the temperature of the treatment process is 40-45 ℃.
Preferably, in step (4), pbI 2 The specific preparation process of the solution is as follows: pbI is prepared 2 Dissolving in a mixed solution of DMF and DMSO in a volume ratio of 9:1, and stirring for 10-15 hours to obtain 1.5 mmol/mL PbI 2 A solution; annealing in step (4) means annealing at 70℃for 1 minute. PbI 2 The spin coating amount of the solution is 7-8 mu L/cm 2 。
Preferably, in the step (5), the specific preparation process of the mixed solution of ammonium halide salt is as follows: adding FAI, MAI, MACl into isopropanol to prepare ammonium halide salt mixed solution with the concentration of 105.36 mg/mL; in step (5), annealing means annealing at 150 ℃ in air with humidity of 30% -40% for 15 minutes. The spin coating amount of the ammonium halide salt mixed solution is 20-30 mu L/cm 2 。
Preferably, in step (6), the PEAI is formulated as follows: dissolving PEAI in isopropanol to prepare PEAI solution; the spin coating amount of PEAI solution is 15-25 mu L/cm 2 。
Preferably, in step (7), the preparation process of the spiro-OMeTAD is as follows, 72.5mg of spiro-OMeTAD is taken, 1mL of chlorobenzene, 18. Mu.l of lithium bis (trifluoromethanesulfonyl) imide acetonitrile solution (520 mg/mL), 28.5. Mu.l of 4-tert-butylpyridine is added, and stirred for 12 hours;
BCP prepared by the preparation method is used for photoelectrode modified perovskite photovoltaic devices, in particular SnO 2 The thickness of the layer is 40nm, the thickness of the perovskite layer is about 650nm, the thickness of the spiro-OMeTAD layer is about 160nm, and the thickness of the gold is 80nm.
The invention uses BCP to modify ITO surface, to reduce the defect problem of interface, while BCP is used as hole blocking layer material to block hole transmission and conduct electron transmission. Furthermore, snO 2 The film layer is easy to generate nano gaps, so that BCP is in direct contact with perovskite, and strong interaction exists between the BCP and the perovskite, so that the crystallization direction of the perovskite can be regulated and controlled, the purpose of directional growth is achieved, and the perovskite film which is beneficial to preparing a high-performance photovoltaic device is realized.
Drawings
Fig. 1 is a schematic view of a battery structure according to the present invention;
FIG. 2 is ITO/BCP/SnO 2 perovskite/PEAI/spiro-OMeTAD/Au and ITO/SnO 2 Current density-voltage (J-V) curve contrast plot for a photovoltaic device of perovskite/PEAI/Spiro-OMeTAD/Au structure;
FIG. 3 is ITO/BCP/SnO 2 Cross-sectional Scanning Electron Microscope (SEM) images of perovskite;
FIG. 4 is ITO/BCP/SnO 2 Perovskite and ITO/SnO 2 X-ray diffraction (XRD) patterns of perovskite thin films of both perovskite structures;
FIG. 5 is a non-encapsulated ITO/BCP/SnO 2 perovskite/PEAI/spiro-OMeTAD/Au and ITO/SnO 2 Photovoltaic devices of two structures, perovskite/PEAI/spiro-OMeTAD/Au: (a) long term stability in nitrogen atmosphere; (b) thermal stability in a nitrogen environment with continued heating at 85 ℃; (c) Continuous illumination in a nitrogen atmosphere (illumination intensity of 100 mW cm) -2 ) Is not limited, and is not limited.
Detailed Description
The technical scheme of the present invention will be further described in detail with reference to the accompanying drawings and examples, but the scope of the present invention is not limited thereto.
Table 1 description of materials used in the experiments
Example 1
A preparation method of a perovskite photovoltaic device modified by a BCP (binary coded decimal) for a photoelectrode comprises the following steps of:
(1) BCP solution was formulated in a nitrogen glove box: adding BCP powder into isopropanol, stirring for 6 hours, and preparing 0.5mg/mL BCP solution;
(2) Preparing SnO 2 Solution of SnO 2 The solution (15 wt%) was diluted with deionized water at a volume ratio of 2:1, and stirred for 30 minutes after dilution to give 10wt% SnO 2 A solution;
(3) Preparation of PbI in a Nitrogen glove box 2 1.5mmol of PbI was taken from the solution 2 Powder, dissolved in 1mL volume ratio of 9:1 in DMF and DMSO, stirring for 12 hours to obtain PbI 2 A solution;
(4) A mixed solution of ammonium halide salt was prepared, and 90mg (0.52 mmol) of FAI, 6.36mg (0.04 mmol) of MAI, and 9mg (0.13 mmol) of MACl were dissolved in 1mL of isopropyl alcohol and stirred for 12 hours;
(5) Preparing PEAI solution, and preparing 5mg/ml PEAI solution by using isopropanol as solvent;
(6) A solution of spiro-OMeTAD was prepared in a nitrogen glove box by taking 72.5mg of spiro-OMeTAD, adding 1mL of chlorobenzene thereto, stirring for one hour, and then adding 28.5. Mu.l of 4-tert-butylpyridine and 18. Mu.l of lithium bis (trifluoromethanesulfonyl) imide in acetonitrile (520 mg of Li-TFSI in 1mL of acetonitrile) thereto to prepare a solution of spiro-OMeTAD.
(7) Will be 2X 2 cm 2 Respectively carrying out ultrasonic treatment for 45 minutes by using a glass cleaning agent, deionized water, acetone and isopropanol in sequence, drying the glass substrate by using nitrogen, and then carrying out ultraviolet treatment for 20 minutes in an ultraviolet ozone cleaning machine generating 185nm ultraviolet rays, wherein the temperature of the treatment process is 40-45 ℃;
(8) Spin-coating 100 mu L of BCP solution on a conductive glass substrate with ITO at a rotating speed of 4500rmp for 20 seconds, and then performing ultraviolet treatment in an ultraviolet ozone cleaning machine for 20 minutes, wherein the ultraviolet ray is generated at 185nm, and the temperature of the treatment process is 40-45 ℃;
(9) To prepare SnO 2 Filtering the solution by using a water system filter head with the thickness of 0.22mm, spin-coating 100 mu l of the solution at the rotating speed of 5500rmp for 10 seconds, annealing at the temperature of 100 ℃ for 5 minutes and then at the temperature of 150 ℃ for 10 minutes after spin-coating, and then carrying out ultraviolet treatment for 60 minutes in an ultraviolet ozone cleaning machine generating 185nm ultraviolet rays, wherein the treatment temperature is 40-45 ℃ to obtain SnO 2 Is about 40nm thick;
(10) PbI is prepared 2 After the solution was filtered with a 0.22mm organic filter, 30. Mu.l of the solution was spin-coated on ITO/BCP/SnO 2 The sample is annealed for 1 minute at 70 ℃ at the rotating speed of 1500rmp for 1 minute, and cooled to room temperature to obtain ITO/BCP/SnO 2 /PbI 2 A sample;
(11) The ammonium halide salt mixed solution was filtered using a 0.22mm organic filter head, and 100. Mu.l of the solution was spin-coated on ITO/BCP/SnO 2 /PbI 2 The sample is subjected to spin coating for 30 seconds at the rotating speed of 2000rmp, then is transferred to air with the humidity of 30% -40% for annealing at the annealing temperature of 150 ℃ for 15 minutes, and is cooled to room temperature to obtain ITO/BCP/SnO 2 Perovskite sample, the thickness of the resulting perovskite film was about 650 a nm a;
(12) ITO/BCP/SnO 2 The perovskite sample was transferred again into a glove box and 80. Mu.l of PEAI solution was spin-coated on ITO/BCP/SnO 2 On a perovskite sample, the rotating speed is 5000rmp, the spin coating time is 30 seconds, and the ITO/BCP/SnO is obtained 2 perovskite/PEAI sample;
(13) A0.22 mm organic filter head was used to filter the spiro-OMeTAD solution, and 20. Mu.l of the solution was spin-coated on ITO/BCP/SnO 2 On perovskite/PEAI, the rotating speed is 4500rmp, the spin coating time is 20 seconds, and the thickness of the spin-on-OMeTAD film obtained by spin coating is about 160nm;
(14) Finally, on the obtained sample, a vacuum evaporation instrument is used for evaporating a gold electrode, the thickness of gold is about 80nm, and the area of the device is 4mm 2 . Through the steps, the ITO/BCP/SnO with the structure is obtained 2 Calcium titaniumThe structure of the photovoltaic device of ore/PEAI/spira-OMeTAD/Au (labeled as optimized device) is shown in FIG. 1.
Reference device ITO/SnO for comparison 2 The procedure for the preparation of/perovskite/PEAI/spiro-OMeTAD/Au was as in example 1, except that steps (1) and (8) were omitted.
FIG. 2 is ITO/BCP/SnO 2 perovskite/PEAI/spiro-OMeTAD/Au and ITO/SnO 2 The comparison graph of current-voltage (J-V) of the perovskite/PEAI/spiro-OMeTAD/Au (marked as a reference device) photovoltaic device can show that the performance of the perovskite photovoltaic device with the BCP modified layer is obviously improved, and the efficiency, the short-circuit current density, the open-circuit voltage and the filling factor of the device are respectively 20.07 cm and 25.22mA cm -2 1.093V, 72.28% to 22.03%, 25.72mA cm -2 、1.113V、77.02%。
FIG. 3 is ITO/BCP/SnO 2 Cross-sectional Scanning Electron Microscope (SEM) pictures of perovskite structure, the growth of grains of each layer can be seen from fig. 3 (the thickness of BCP in the figure is not marked because it is too thin);
FIG. 4 is ITO/BCP/SnO 2 Perovskite and ITO/SnO 2 After adding the BCP modification layer, the main peak of the perovskite film is obviously enhanced, which proves that the optimized perovskite film has better crystallinity. At the same time, for ITO/BCP/SnO 2 The XRD curve of the perovskite shows that the diffraction intensity of the (111) crystal face is obviously stronger than that of the (100) crystal face, which shows that after the BCP modification layer is added, the perovskite crystal orientation is optimized, and the perovskite film with the (111) crystal face orientation is beneficial to preparing high-performance photovoltaic devices.
FIG. 5 is ITO/BCP/SnO 2 perovskite/PEAI/spiro-OMeTAD/Au and ITO/SnO 2 FIG. 5 (a) is a graph comparing the stability of two unpackaged photovoltaic devices of the perovskite/PEAI/spiro-OMeTAD/Au structure, and shows the long-term stability of the two devices in a nitrogen atmosphere, wherein after 1200 hours of storage, the photoelectric conversion efficiency of the optimized device is maintained at more than 70% of the initial value, while the reference device only remains about 35% of the initial efficiency under the same test conditions, FIG. 5 @b) As a result of the thermal stability test of the two devices under the condition of continuous heating at 85℃in a nitrogen atmosphere, it can be seen that the photoelectric conversion efficiency of the optimized device was maintained at 77% of its initial value after the lapse of 630 hours of continuous heating, while the reference device was attenuated to about 30% of its initial value, and FIG. 5 (c) shows the continuous irradiation of the two devices under a nitrogen atmosphere (irradiation intensity of 100 mW cm -2 ) After 475 hours of continuous illumination, the photoelectric conversion efficiency of the optimized device remained around 80% of its initial value, while the reference device had decayed to around 40% of its initial value. The result shows that the normal temperature stability, the thermal stability and the illumination stability of the photovoltaic device with the BCP modified layer added in the nitrogen atmosphere are obviously improved.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any changes or substitutions that do not undergo the inventive effort should be construed as falling within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope defined by the claims.
Claims (10)
1. A method for preparing a perovskite photovoltaic device modified by a BCP (binary coded decimal) used for a photoelectrode, which is characterized by comprising the following steps of:
(1) Cleaning an ITO substrate, drying the ITO substrate by nitrogen, and then treating the substrate by ultraviolet ozone;
(2) Preparing and spin-coating a BCP solution, and performing ultraviolet ozone treatment to obtain an ITO/BCP sample;
(3) Preparing SnO 2 Spin coating SnO on ITO/BCP substrate 2 The solution is annealed and treated by ultraviolet ozone to obtain ITO/BCP/SnO 2 A sample;
(4) Formulation of PbI 2 Spin-coating PbI on the sample obtained in step (3) 2 Solution, annealing treatment to obtain ITO/BCP/SnO 2 /PbI 2 A sample;
(5) ITO/BCP/SnO obtained in the step (4) 2 /PbI 2 Spin-coating ammonium halide salt mixed solution of sample under the protection of nitrogen, annealingObtaining ITO/BCP/SnO 2 Perovskite sample;
(6) Preparing PEAI solution, and obtaining ITO/BCP/SnO in the step (5) 2 Spin coating PEAI solution on perovskite sample to obtain ITO/BCP/SnO 2 perovskite/PEAI sample;
(7) ITO/BCP/SnO obtained in step (6) 2 Spin-coating of spiro-OMeTAD on perovskite/PEAI sample to obtain ITO/BCP/SnO 2 perovskite/PEAI/spiro-OMeTAD samples;
(8) ITO/BCP/SnO obtained in step (7) 2 Evaporating gold electrode on perovskite/PEAI/spiro-OMeTAD sample to obtain ITO/BCP/SnO 2 Perovskite photovoltaic devices of the/perovskite/PEAI/spiro-OMeTAD/Au structure.
2. The method of claim 1, wherein in step (2), the BCP solution is prepared as follows: and adding isopropanol into the BCP powder, and stirring for 5-7 hours to prepare 0.5mg/mL BCP solution.
3. The method of producing a perovskite photovoltaic device according to claim 1, wherein in step (3), snO 2 The preparation process of the solution is as follows: 15wt% SnO 2 Diluting the colloidal dispersion with deionized water to 10wt%, and stirring to obtain SnO 2 A solution.
4. The method of claim 1, wherein in step (4), pbI 2 The specific preparation process of the solution is as follows: pbI is prepared 2 Dissolving in a mixed solution of DMF and DMSO in a volume ratio of 9:1 to obtain 1.5mol/L PbI 2 A solution.
5. The method of producing a perovskite photovoltaic device according to claim 1, wherein in the step (5), the specific preparation process of the ammonium halide salt mixed solution is as follows: FAI, MAI, MACl is added into isopropanol according to a molar ratio of 52:4:13 to prepare a mixed solution of ammonium halide salt, wherein the total concentration of FAI, MAI, MACl in isopropanol is 105.36mg/mL.
6. The method of claim 1, wherein in step (6), the PEAI is formulated as follows: PEAI was dissolved in isopropanol to prepare a 5mg/mL PEAI solution.
7. The method of claim 1, wherein in step (7), the spiro-ome tad is formulated as follows: 72.5mg of spiro-OMeTAD was taken, 1ml of chlorobenzene, 18. Mu.l of lithium bistrifluoromethylsulfonylimide and 28.5. Mu.l of 4-tert-butylpyridine were added, and stirred for 10 to 15 hours.
8. The method of claim 1, wherein in step (3), annealing means annealing at 100 ℃ for 5 minutes and further annealing at 150 ℃ for 10 minutes; annealing in the step (4) means annealing at 70 ℃ for 1 minute; in the step (5), annealing refers to annealing at 150 ℃ for 15 minutes in air with the humidity of 30% -40%.
9. BCP prepared by the preparation method of any one of claims 1 to 8 for use in photoelectrode-modified perovskite photovoltaic devices.
10. The perovskite photovoltaic device of claim 9, wherein SnO 2 The thickness of the layer is 40nm, the thickness of the perovskite layer is 650nm, the thickness of the spiro-OMeTAD layer is 160nm, and the thickness of the gold is 80nm.
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