CN111446374A - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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- CN111446374A CN111446374A CN202010155144.XA CN202010155144A CN111446374A CN 111446374 A CN111446374 A CN 111446374A CN 202010155144 A CN202010155144 A CN 202010155144A CN 111446374 A CN111446374 A CN 111446374A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 29
- 230000004048 modification Effects 0.000 claims abstract description 29
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
- 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 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 38
- 238000004528 spin coating Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002207 thermal evaporation Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 230000031700 light absorption Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 3
- 238000001771 vacuum deposition Methods 0.000 claims description 3
- 238000000861 blow drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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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
- H10K30/80—Constructional details
- H10K30/81—Electrodes
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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
- 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
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- 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
- 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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- 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
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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
- 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
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Abstract
The invention discloses a perovskite solar cell and a preparation method thereof, and the perovskite solar cell comprises glass, cathode ITO and cathode modification layer PVP-SnO from bottom to top2Perovskite light absorbing layer (FAPbI)3)0.97(MAPbBr3)0.03A first anode modification layer Spiro-OMeTAD and a second anode modification layer MoO3And anode silver. The invention adds PVP into SnO2The PVP-SnO can improve the electron transmission performance of the perovskite solar cell by doping2Electron mobility of (2) is higher than that of pure SnO2Is high, thereby improving the photoelectric conversion performance of the solar cell and showing less hysteresis.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a perovskite solar cell and a preparation method thereof.
Background
Perovskite solar cells with simple planar structures have the advantages of high efficiency, low cost and easy processing, and have become one of the most competitive and promising next-generation photovoltaic technologies in the future. Due to its high absorption coefficient and long carrier diffusion length, the power conversion efficiency of perovskite solar cells is rapidly increased from 3.8% to over 20% within 10 years. Although perovskite solar cells have excellent performance, many planar perovskite solar cells are still unstable and have severe hysteresis due to ion migration and interface defects in the device. Research shows that the interface between the perovskite layer and the electron transport layer is changed, and the hysteresis phenomenon in the perovskite solar cell can be greatly eliminated. To date, it has been agreed that electron transport layers are critical for the fabrication of efficient and lag-free perovskite solar cells.
To avoid charge accumulation at the electron transport layer/perovskite interface, polymers are incorporated into the electron transport layer to further enhance the electron mobility of the electron transport layer, thereby improving the performance of the planar perovskite solar cell. The invention provides for the incorporation of PVP (polyvinylpyrrolidone) into SnO2The electron transport layer of the perovskite solar cell.
Disclosure of Invention
The invention aims to provide a perovskite solar cell and a preparation method thereof, wherein the perovskite solar cell is provided with PVP-SnO2The cathode modification layer of (1).
Therefore, the first technical scheme of the invention is as follows: a perovskite solar cell, characterized in that: the structure comprises glass, cathode ITO and cathode modification layer PVP-SnO from bottom to top2Perovskite light absorbing layer (FAPbI)3)0.97(MAPbBr3)0.03A first anode modification layer Spiro-OMeTAD and a second anode modification layer MoO3Anodic silver.
Wherein the light absorbing layer (FAPBI)3)0.97(MAPbBr3)0.03Means of FAPBI3With MAPbBr3Is 0.97: 0.03.
In the electron transport layer of the perovskite solar cell, SnO is arranged2The solution was doped with PVP.
The second technical scheme of the invention is as follows: a preparation method of a perovskite solar cell comprises the following steps:
1) cleaning the ITO glass substrate: sequentially carrying out ultrasonic cleaning in glass detergent, deionized water, acetone and isopropanol solution for 10min, blow-drying with nitrogen, and treating in an ultraviolet ozone cleaning machine for 30 min;
2) preparation of PVP-SnO2Cathode modification layer: spin-coating PVP-SnO on the cleaned ITO glass substrate by a spin coater2The solution is annealed in the air for 20min at the speed of 4000rpm for 40s at the temperature of 180 ℃;
3) treating the annealed sample in an ultraviolet ozone cleaning machine for 10 min;
4) preparing a perovskite light absorption layer: transferring the substrate to a nitrogen glove box, spin-coating a perovskite layer by a two-step method, and spin-coating PbI by a spin coater2The solution, at a speed of 1500rpm for 30s, was subsequently annealed at a temperature of 70 ℃ for 2 min; and then spin-coating FAI: MACl: MABr solution, spin-coating speed is 1700rpm, time is 30s, then annealing in air at 135 deg.C for 15 min;
5) preparing a first anode modification layer: spin-coating a Spiro-OMeTAD solution at 2500rpm for 30 s;
6) preparing a second anode modification layer: transferring the substrate to a vacuum coating machine, and depositing MoO by thermal evaporation3The thickness is 7.5 nanometers;
7) preparing an anode: the silver is deposited by a thermal evaporation method, and the thickness of the silver is 100 nanometers.
Preferably, the PVP-SnO in the step 2)2The preparation method of the solution comprises the following steps: firstly, 15 percent of SnO by mass ratio2Aqueous solution diluted in water, SnO2The volume ratio of the aqueous solution to water is 1:3, 0.1% of x-100 triton and 0.2% of piperidine are added, and then SnO with the volume ratio of 1m L23mg of PVP and 0.5m L methanol solution containing 0.1g of azobisisobutyronitrile are added into the solution to finally obtain PVP-SnO2The solution was then stirred in air for 4 h.
Preferably, the spin coating method of the perovskite layer in the step 4) is a two-step method, and two solutions, respectively PbI, are used in the process2Mixed solution of the solution and FAI, MACl and MABr, wherein PbI2The solution is PbI2Dissolving in mixed solution of DMF and DMSO at a volume ratio of 9:1, PbI2The concentration of the solution was 1.3M, wherein the mixed solution of FAI, MACl and MABr was 60mg of FAI, 6mg of MACl and 6mg of MABr in 1M L of isopropanol.
Compared with the traditional pure SnO2Cathode modification layer of PVP-SnO2Has higher electron mobility and is based on PVP-SnO2The device achieves higher photoelectric conversion efficiency. Meanwhile, PVP-SnO in the invention2The preparation method adopts the spin-coating method, has simple and easy process, and provides a simple and feasible method for improving the performance of the perovskite solar cell.
Drawings
The following detailed description is made with reference to the accompanying drawings and embodiments of the present invention
FIG. 1 is a schematic diagram of a prior art perovskite solar cell;
FIG. 2 is a schematic structural diagram of a perovskite solar cell of an embodiment of the invention;
FIG. 3 shows the electron mobility of the electron transport layer according to the embodiment of the present invention, wherein S1 is PVP-SnO22.75*10- 3cm2V-1s-1S2 is SnO22.24*10-3cm2V-1s-1；
FIG. 4 is an I-V test curve (AM1.5, 100 mW/cm) of an embodiment of the present invention2At 25 ℃), wherein P1 is PVP-SnO2PCE 19.55%, P2 SnO2PCE＝17.50％。
Detailed Description
See the drawings. The structure of a traditional perovskite solar cell is shown in fig. 1, and the perovskite solar cell comprises a substrate, a cathode modification layer, a perovskite light absorption layer, an anode modification layer and an anode; the substrate is glass, the cathode is ITO, and the cathode modification layer is SnO2A thin film, the perovskite light absorption layer is (FAPBI)3)0.97(MAPbBr3)0.03The anode modification layers are Spiro-OMeTAD and MoO3The anode is silver.
This embodiment provides a perovskite solar cell, as shown in fig. 2, the perovskite solar cell includes ITO glass, cathode modification layer PVP-SnO arranged in sequence2Perovskite light-absorbing layer (FAPBI)3)0.97(MAPbBr3)0.03A first anode modification layer Spiro-OMeTAD and a second anode modification layer MoO3And a silver electrode Ag. Wherein the cathode modification layer is PVP-doped SnO2A film.
Wherein the light absorbing layer (FAPBI)3)0.97(MAPbBr3)0.03Means of FAPBI3With MAPbBr3Is 0.97: 0.03. The first anode modification layer Spiro-OMeTAD is 2, 2 ', 7, 7' -tetra [ N, N-di (4-methoxyphenyl) amino]-9, 9' -spirobifluorene.
The preparation method of the perovskite solar cell comprises the following steps:
1) cleaning the ITO glass: sequentially carrying out ultrasonic treatment on the ITO glass substrate in glass detergent, deionized water, acetone and isopropanol for 10 minutes respectively, then blowing the ITO glass substrate with nitrogen, and then treating the ITO glass substrate in an ultraviolet ozone cleaning machine for 30 minutes;
2) preparing a cathode modification layer: firstly SnO is carried out2(15% aqueous solution) in water, SnO2The volume ratio of (15% aqueous solution) to water is 1:3, 0.1% of x-100 triton and 0.2% of piperidine are added, and then SnO is added at 1m L23mg of PVP and 0.5m L methanol solution containing 0.1g of azobisisobutyronitrile are added into the solution to finally obtain PVP-SnO2And (3) solution. Then spin-coating PVP-SnO on the substrate by a spin coater in air2The solution is annealed in the air at the rotation speed of 4000rpm for 40s at the annealing temperature of 150-250 ℃ for 20 min;
3) treating the annealed sample for 10 minutes by using an ultraviolet ozone cleaning machine;
4) preparing a perovskite light absorption layer: the substrate was transferred to a nitrogen glove box and the perovskite light absorbing layer (FAPBI) was prepared in a two-step process3)0.97(MAPbBr3)0.03First, PbI is mixed2Solution spin coating on the electron transport layerAt a speed of 1500rpm for 30s, followed by annealing at a temperature of 70 ℃ for 2 min. Then spin coating FAI: MACl: MABr solution at 1700rpm for 30s, followed by annealing in air at 135 deg.C for 15 min;
wherein PbI2The formula of the solution is as follows: will PbI2Dissolving in mixed solution of dimethyl formamide (DMF) and anhydrous dimethyl sulfoxide (DMSO) at a volume ratio of DMF to DMSO of 9:1, and adding PbI2The concentration of the solution was 1.3M;
wherein, the FAI is MACl, the formula of MABr solution is that 60mgFAI, 6mgMACl and 6mgMABr are dissolved in isopropanol of 1m L;
5) preparing a first anode modification layer: spin-coating a Spiro-OMeTAD solution at 2500rpm for 30 s;
6) preparing a second anode modification layer: transferring the substrate to a vacuum coating machine, and depositing MoO by thermal evaporation3The thickness is 7.5 nanometers;
7) preparing an anode: the silver is deposited by a thermal evaporation method, and the thickness of the silver is 100 nanometers.
Pure SnO was then tested2And PVP-SnO2Electron mobility of (2) when in SnO as shown in FIG. 32When PVP is added, SnO can be effectively improved2Test I-V curves characterizing the performance of solar cells, as shown in fig. 4, and based on SnO2Compared with the device, the PVP doped SnO is used2(PVP-SnO2) Being an electron transport layer of a perovskite solar cell can further improve the efficiency of the device and also show less hysteresis.
Claims (4)
1. A perovskite solar cell, characterized in that: comprises glass, cathode ITO and cathode modification layer PVP-SnO from bottom to top2Perovskite light absorbing layer (FAPbI)3)0.97(MAPbBr3)0.03A first anode modification layer Spiro-OMeTAD and a second anode modification layer MoO3Anodic silver.
2. A method of making the perovskite solar cell of claim 1, wherein: the method comprises the following steps:
1) cleaning the ITO glass substrate: sequentially carrying out ultrasonic cleaning in glass detergent, deionized water, acetone and isopropanol solution for 10min, blow-drying with nitrogen, and treating in an ultraviolet ozone cleaning machine for 30 min;
2) preparation of PVP-SnO2Cathode modification layer: spin-coating PVP-SnO on the cleaned ITO glass substrate by a spin coater2The solution is annealed in the air for 20min at the speed of 4000rpm for 40s at the temperature of 180 ℃;
3) treating the annealed sample in an ultraviolet ozone cleaning machine for 10 min;
4) preparing a perovskite light absorption layer: transferring the substrate to a nitrogen glove box, spin-coating a perovskite layer by a two-step method, and spin-coating PbI by a spin coater2The solution, at a speed of 1500rpm for 30s, was subsequently annealed at a temperature of 70 ℃ for 2 min; and then spin-coating FAI: MACl: MABr solution, spin-coating speed is 1700rpm, time is 30s, then annealing in air at 135 deg.C for 15 min;
5) preparing a first anode modification layer: spin-coating a Spiro-OMeTAD solution at 2500rpm for 30 s;
6) preparing a second anode modification layer: transferring the substrate to a vacuum coating machine, and depositing MoO by thermal evaporation3The thickness is 7.5 nanometers;
7) preparing an anode: the silver is deposited by a thermal evaporation method, and the thickness of the silver is 100 nanometers.
3. The method of claim 2, wherein: PVP-SnO in step 2)2The preparation method of the solution comprises the following steps: firstly, 15 percent of SnO by mass ratio2Aqueous solution diluted in water, SnO2The volume ratio of the aqueous solution to water is 1:3, 0.1% of x-100 triton and 0.2% of piperidine are added, and then SnO with the volume ratio of 1m L23mg of PVP and 0.5m L methanol solution containing 0.1g of azobisisobutyronitrile are added into the solution to finally obtain PVP-SnO2The solution was then stirred in air for 4 h.
4. The method of claim 2, wherein: the spin coating method of the perovskite layer in the step 4) is a two-step method, two solutions are used in the process, and the two solutions are respectively PbI2Mixed solution of the solution and FAI, MACl and MABr, wherein PbI2The solution is PbI2Dissolving in mixed solution of DMF and DMSO at a volume ratio of 9:1, PbI2The concentration of the solution was 1.3M, wherein the mixed solution of FAI, MACl and MABr was 60mg of FAI, 6mg of MACl and 6mg of MABr in 1M L of isopropanol.
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