CN117320518A - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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- CN117320518A CN117320518A CN202211231130.7A CN202211231130A CN117320518A CN 117320518 A CN117320518 A CN 117320518A CN 202211231130 A CN202211231130 A CN 202211231130A CN 117320518 A CN117320518 A CN 117320518A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 230000005525 hole transport Effects 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000012986 modification Methods 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- ZZMQTTUJZFEWMD-UHFFFAOYSA-N 2-phenylethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCC1=CC=CC=C1 ZZMQTTUJZFEWMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 238000007781 pre-processing Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 24
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 15
- XIOYECJFQJFYLM-UHFFFAOYSA-N 2-(3,6-dimethoxycarbazol-9-yl)ethylphosphonic acid Chemical compound COC=1C=CC=2N(C3=CC=C(C=C3C=2C=1)OC)CCP(O)(O)=O XIOYECJFQJFYLM-UHFFFAOYSA-N 0.000 claims description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 10
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- 239000012296 anti-solvent Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 6
- 150000001409 amidines Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001771 vacuum deposition Methods 0.000 claims description 4
- KIMPAVBWSFLENS-UHFFFAOYSA-N 2-carbazol-9-ylethylphosphonic acid Chemical compound C1=CC=CC=2C3=CC=CC=C3N(C1=2)CCP(O)(O)=O KIMPAVBWSFLENS-UHFFFAOYSA-N 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 3
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002648 laminated material Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 238000010345 tape casting Methods 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 10
- 238000005286 illumination Methods 0.000 abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 238000002207 thermal evaporation Methods 0.000 description 9
- 238000007738 vacuum evaporation Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 5
- 239000011799 hole material Substances 0.000 description 5
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- -1 phenethyl phosphoric acid (Phenethylphosphonic Acid) Chemical compound 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910005855 NiOx Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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 relates to a perovskite solar cell and a preparation method thereof, wherein the preparation method comprises the steps of preparing a precursor solution, preprocessing a substrate, preparing a hole transport layer, preparing a perovskite film layer, preparing an electron transport layer, preparing an electrode and preparing a hole transport layer modification film layer, wherein the hole transport layer modification film layer is formed by depositing phenethyl phosphoric acid on the hole transport layer by a solution method. The invention effectively reduces the defect state density of the film layer, improves the efficiency by 7.2 percent compared with an untreated perovskite battery, and greatly improves the illumination stability.
Description
Technical Field
The invention relates to a solar cell and a preparation method thereof, in particular to a perovskite solar cell and a preparation method thereof.
Background
Perovskite solar cells are of great interest due to their higher power conversion efficiency and lower manufacturing costs. Compared with the perovskite battery with the positive structure (n-i-p), the perovskite battery with the negative structure (p-i-n) has lower preparation temperature and lower preparation cost, and is more suitable for industrial expansion. As a critical layer of material in the inversion structure, hole transport layers are of interest. In general, the organic hole transport layer is relatively matched to the perovskite layer deposited thereon, enabling superior performance to be achieved. However, the organic hole layer is expensive and intrinsicThe stability of the product is poor, and the matching performance with the industrialization requirement is low. In contrast, inorganic hole materials, such as nickel oxide (NiO) x ) The material has various excellent performances such as larger band gap, proper mobility, matched energy level, excellent intrinsic stability, lower cost and the like, and can meet the requirement of large scale.
However, the performance of inverted perovskite batteries based on nickel oxide and like inorganic hole materials is generally lower than that based on organic hole materials, in most cases due to lower open circuit voltages and poorer stability. Research shows that the source of such attenuation is mainly that electrochemical reactions occurring at the interface of the nickel oxide material and the perovskite film layer accelerate the degradation of the perovskite at the interface. In addition, the halogen in the perovskite can be combined with part of Ni in the nickel oxide 3+ And reacting to form a defect state at the interface. The defect is used as a recombination center of carriers, and can limit part of carriers, so that recombination at an interface is increased, and the photoelectric performance and the stability of a device are reduced. Therefore, how to reduce the defect state of the perovskite film layer and improve the stability of the perovskite solar cell under high working conditions is of great significance to the photovoltaic industry.
Disclosure of Invention
The invention aims to: the invention aims to improve the stability of perovskite solar cells.
The technical scheme adopted for the purposes is as follows: in one aspect, the invention provides a method for preparing a perovskite solar cell, comprising the following steps:
(1) Preparing a precursor solution;
(2) Pretreatment of a substrate;
(3) Preparing a hole transport layer;
(4) Preparation of the modification layer: dissolving phenethyl phosphoric acid (Phenethylphosphonic Acid) in an N, N-Dimethylformamide (DMF) solvent, and spin-coating on the hole transport layer;
(5) Preparation of perovskite film layer: lead iodide (PbI) 2 ) Lead bromide (PbBr) 2 ) A mixed solution of cesium iodide (CsI), rubidium iodide (RbI), amidine iodide (FAI), methylamine chloride (MACl) and methylamine bromide (MABr) is deposited in the airThe hole transport layer can be spin-coated, knife-coated, spray-coated, etc., and the auxiliary crystallization can be anti-solvent dripping, vacuum drying, heating auxiliary, etc. Annealing and cooling for standby after forming a film;
(6) Preparing an electron transport layer;
(7) Preparation of the electrode.
Further, the material used for preparing the electron transport layer in the step (3) is tin dioxide (SnO) 2 ) Titanium dioxide (TiO) 2 ) 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (BCP), fullerene (C) 60 ) At least one of fullerene derivative (PCBM) and zinc oxide (ZnO) material, and the preparation method can be vacuum deposition or solution deposition.
Further, the hole transport layer in the step (6) is made of nickel oxide (NiO) x ) Poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine](PTAA), me-2PACz (2- (3, 6-Dimethyl-9H-carbazol-9-yl) ethyl) phosphoric acid), me-4PACz (cas: 2747959-96-0), (2- (3, 6-dimethoxy-9H-carbazole-9-yl) ethyl) phosphonic acid (MeO-2 PACz), and (2- (9H-carbazole-9-yl) ethyl) phosphonic acid (2 PACz) or a mixture material or a laminated material formed by a plurality of materials, wherein the hole transport layer is prepared by vacuum deposition or solution deposition.
Further, the conversion efficiency of the perovskite solar cell was 17.22%.
Further, the pretreatment method of the substrate in the step (2) comprises the following steps: and ultrasonically cleaning the substrate in deionized water, ultrasonically cleaning the substrate in an organic solvent, drying the substrate, and then treating the substrate in an ultraviolet ozone processor.
In another aspect, there is provided a perovskite solar cell manufactured by the above manufacturing method.
The method selects the mode of post-processing the hole transport layer film layer by utilizing the modification layer, reduces the defect density of the interface between the hole layer and the perovskite film, and improves the performance and stability of the battery.
The beneficial effects are that: the perovskite battery with the interface modified is prepared by the method, the defect state density of a film layer is effectively reduced, the efficiency is improved by 7.2% compared with an untreated perovskite battery, and the illumination stability is greatly improved.
The nickel oxide film is modified by using phenethyl phosphoric acid (Phenethylphosphonic Acid) material, and a molecular thin layer of phenethyl phosphoric acid material is inserted between perovskite and nickel oxide. The material has phosphate radical capable of anchoring with NiOx layer, passivating the NiOx interface defect effectively, reducing composite center and preventing perovskite and NiO to some extent x The direct contact of the materials prevents the diffusion of halogen at the interface to form defects, thereby greatly improving the photoelectric performance and stability. The modified material has good effect on the hole transport layer of MeO-2PACz besides the NiOx.
Drawings
FIG. 1 is an I-V curve of perovskite cells treated and untreated with a modification layer of example 1 and comparative example 1;
FIG. 2 is a graph of the light stability of perovskite cells treated and untreated with a modification layer for example 2 and comparative example 2;
FIG. 3 is an SEM image of an unmodified perovskite film layer of comparative example 3;
fig. 4 is an SEM image of the perovskite film layer treated with the finishing layer of example 3.
Detailed Description
The present invention will be explained in detail by way of examples, but it should be understood that the scope of the present invention is not limited to the examples.
Example 1
The preparation method of the perovskite solar cell comprises the following steps:
(1) Preparing a precursor solution:
a perovskite layer solution: lead iodide (PbI) 2 ) Mixed solution of amidine (FAI) and methylamine chloride (MACl);
PbI 2 and FAI in a ratio of 1:1 in a mixed solution of DMF and DMSO, wherein the mixed solution comprises 20% of MACl additive, the volume ratio of DMF and DMSO is 4:1, and the concentration of the solution is 45wtThe mixture was stirred at 70℃for 60min until complete dissolution and filtered through a 0.22 μm filter cartridge for further use.
b modification layer solution: a phenethyl phosphoric acid solution;
phenethyl phosphoric acid was dissolved in DMF solvent at a concentration of 0.3% mmol/mL.
c hole transport layer solution: niO x A nanoparticle solution;
25mg of NiO was reacted with x The nanocrystalline solution of (2) was mixed with 1mL of deionized water, stirred with shaking, and filtered using a 0.45 μm filter cartridge for use.
(2) Pretreatment of a substrate:
the ITO glass substrate was first ultrasonically cleaned in deionized water for 30 minutes, then in acetone for 30 minutes, finally in isopropyl alcohol (IPA) for 30 minutes, then blow-dried with a nitrogen gun, and treated in an ultraviolet ozone treater for 30 minutes for use.
(3) Preparation of hole transport layer:
filtering NiO x The nanoparticle solution was spin coated on the ITO substrate at a spin rate of 3000rpm for 30s, followed by annealing at 120℃for 30min.
(4) Preparation of the modification layer:
spin-coating phenethyl phosphoric acid solution on NiO of hole transport layer x On top of this, the speed was 1700rpm for 20s, followed by annealing of the film layer at 130℃for 2 minutes.
(5) Preparation of perovskite film layer:
spin-coating the prepared lead iodide, methyliodide and methylamine chloride solution on the modified NiO x And (3) dropwise adding 0.5mL of anti-solvent chlorobenzene on the film layer at the speed of 4000rpm for 40s, and then annealing for 20min at 140 ℃ in air, wherein the humidity is controlled to be 30-40%, and cooling for standby after annealing.
(6) Preparation of an electron transport layer:
evaporating C by thermal evaporation using vacuum evaporation equipment 60 20nm of material, 5nm of BCP material, and controlling the vacuum degree to 7 x 10 -4 Pa or below.
(7) Preparation of an electrode:
using a vacuum evaporation device, evaporating 150nm copper (Cu) on the surface of BCP by using a thermal evaporation method as an electrode, wherein the vacuum degree is controlled at 7×10 -4 Pa or below.
Comparative example 1
The difference from example 1 is that the preparation without the modification layer comprises the following specific steps:
(1) Preparing a precursor solution:
a lead iodide (PbI) 2 ) Mixed solution of amidine (FAI) and methylamine chloride (MACl);
PbI 2 and FAI was dissolved in a ratio of 1:1 in a mixed solution of DMF and DMSO, including 20% MACl additive, at a volume ratio of DMF to DMSO of 4:1, at a concentration of 45wt%, heated to 70℃for 60min to complete dissolution, and filtered using a 0.22 μm filter cartridge for use.
b NiO x A nanoparticle solution;
25mg of NiO was reacted with x The nanocrystalline solution of (2) was mixed with 1mL of deionized water, stirred with shaking, and filtered using a 0.45 μm filter cartridge for use.
(2) Pretreatment of a substrate:
the ITO glass substrate was first ultrasonically cleaned in deionized water for 30 minutes, then in acetone for 30 minutes, finally in isopropyl alcohol (IPA) for 30 minutes, then blow-dried with a nitrogen gun, and treated in an ultraviolet ozone treater for 30 minutes for use.
(3) Preparation of hole transport layer:
filtering NiO x The nanoparticle solution was spin coated on the ITO substrate at a spin rate of 3000rpm for 30s, followed by annealing at 120℃for 30min.
(4) Preparation of perovskite film layer:
spin-coating the prepared lead iodide, methyliodide and methylamine chloride solution on the modified NiO x And (3) dropwise adding 0.5mL of anti-solvent chlorobenzene on the film layer at the speed of 4000rpm for 40s, and then annealing for 20min at 140 ℃ in air, wherein the humidity is controlled to be 30-40%, and cooling for standby after annealing.
(5) Preparation of an electron transport layer:
evaporating C by thermal evaporation using vacuum evaporation equipment 60 20nm of material, 5nm of BCP material, and controlling the vacuum degree to 7 x 10 -4 Pa or below.
(6) Preparation of an electrode:
using a vacuum evaporation device, evaporating 150nm copper (Cu) on the surface of BCP by using a thermal evaporation method as an electrode, wherein the vacuum degree is controlled at 7×10 -4 Pa or below.
The current and voltage of the perovskite solar cell obtained in example 1 and comparative example 1 were monitored and plotted as a graph, as shown in fig. 1, the perovskite cell treated with the modification layer improved the efficiency by 7.2% over the untreated cell, and exhibited significant advantages in terms of open circuit voltage, short circuit current, fill factor, and conversion efficiency, as shown in table 1.
Table 1 perovskite cell photoelectric parameters treated and untreated with modifier
Example 2
The preparation method of the perovskite solar cell comprises the following steps:
(1) Preparing a precursor solution:
a perovskite layer solution
19.5mg of CsI,15.9mg of RbI,8.4mg of MABr,219.5mg of FAI,656.9mg of PbI 2 27.5mg of PbBr 2 Dissolved in 1mL of a mixed solution of DMF and DMSO at a volume ratio of 7:1, stirred at 60℃for 1 hour, and filtered using a 0.22 μm filter cartridge for use.
b hole transport layer solution
0.55mg of MeO-2PACz powder was dissolved in 1mL of ethanol, stirred with shaking, and filtered using a 0.45 μm filter cartridge for use.
c modifying layer solution
Phenethyl phosphoric acid was dissolved in DMF solvent at a concentration of 0.26% mmol/mL.
(2) Pretreatment of a substrate:
the ITO glass substrate was first ultrasonically cleaned in deionized water for 30 minutes, then in acetone for 30 minutes, finally in isopropyl alcohol (IPA) for 30 minutes, then blow-dried with a nitrogen gun, and treated in an ultraviolet ozone treater for 30 minutes for use.
(3) Preparation of hole transport layer:
the filtered MeO-2PACz solution was spin-coated onto the UV-treated ITO substrate at a spin rate of 3000rpm for 30s, followed by annealing at 100deg.C for 10min.
(4) Preparation of the modification layer:
the phenethyl phosphoric acid solution was spin coated onto the hole transport layer at 2500rpm for 20s, followed by annealing of the film layer at 130 ℃ for 1 minute.
(5) Preparation of perovskite film layer:
the prepared perovskite solution is spin-coated on a modified MeO-2PACz film layer at the speed of 4000rpm for 40s, 0.4mL of anti-solvent chlorobenzene is added dropwise on the film layer at the 18 th s of spin-coating, and then the film layer is annealed at 100 ℃ for 30min and cooled for later use.
(6) Preparation of an electron transport layer:
evaporating C by thermal evaporation using vacuum evaporation equipment 60 20nm of material, 5nm of BCP material, and controlling the vacuum degree to 7 x 10 -4 Pa or below.
(7) Preparation of an electrode:
using a vacuum evaporation device, evaporating 120nm silver (Ag) on the surface of BCP by using a thermal evaporation method as an electrode, wherein the vacuum degree is controlled at 7×10 -4 Pa or below.
Comparative example 2
The difference from example 2 is that: no modification layer was prepared between the hole transport layer and the perovskite film layer. The method comprises the following specific steps:
(1) Preparing a precursor solution:
a perovskite layer solution 19.5mg CsI,15.9mg RbI,8.4mg MABr,219.5mg FAI,656.9mg PbI 2 27.5mg of PbBr 2 Dissolved in 1mL of a mixed solution of DMF and DMSOThe volume ratio of DMF and DMSO was 7:1, stirred at 60℃for 1 hour and filtered using a 0.22 μm filter cartridge for use.
b hole transport layer solution: 0.55mg of MeO-2PACz powder was dissolved in 1mL of ethanol, stirred with shaking, and filtered using a 0.45 μm filter cartridge for use.
(2) Pretreatment of a substrate:
the ITO glass substrate was first ultrasonically cleaned in deionized water for 30 minutes, then in acetone for 30 minutes, finally in isopropyl alcohol (IPA) for 30 minutes, then blow-dried with a nitrogen gun, and treated in an ultraviolet ozone treater for 30 minutes for use.
(3) Preparation of hole transport layer:
the filtered MeO-2PACz solution was spin-coated onto the UV-treated ITO substrate at a spin rate of 3000rpm for 30s, followed by annealing at 100deg.C for 10min.
(4) Preparation of perovskite film layer:
the prepared perovskite solution is spin-coated on a modified MeO-2PACz film layer at the speed of 4000rpm for 40s, 0.4mL of anti-solvent chlorobenzene is added dropwise on the film layer at the 18 th s of spin-coating, and then the film layer is annealed at 100 ℃ for 30min and cooled for later use.
(5) Preparation of an electron transport layer:
evaporating C by thermal evaporation using vacuum evaporation equipment 60 20nm of material, 5nm of BCP material, and controlling the vacuum degree to 7 x 10 -4 Pa or below.
(6) Preparation of an electrode:
using a vacuum evaporation device, evaporating 120nm silver (Ag) on the surface of BCP by using a thermal evaporation method as an electrode, wherein the vacuum degree is controlled at 7×10 -4 Pa or below.
The perovskite solar cell obtained in example 2 and comparative example 2 was tested for stability in an illumination environment, and after 1000 hours of illumination time, the modified cell stability remained above 85% and the unmodified cell stability was reduced to below 80%, as shown in fig. 2.
Example 3
The preparation method of the perovskite solar cell comprises the following steps:
(1) Preparing a precursor solution:
a perovskite layer solution
142.8mg of FAI,44.2mg of CsI,461mg of PbI 2 25mg of MACl,96uL of NMP was dissolved in 600uL of DMF and stirred at 60℃for 1 hour and filtered using a 0.22 μm filter cartridge for further use.
b modification layer solution
Phenethyl phosphoric acid was dissolved in DMF solvent at a concentration of 0.3% mmol/mL.
c hole transport layer solution
Dissolving 0.55mg of MeO-2PACz powder in 1mL of ethanol, dissolving 0.55mg of 2PACz powder in 1mL of ethanol, mixing the two powders according to the volume ratio of 1:2.5, vibrating and stirring, and filtering by using a filter element of 0.45 mu m for later use;
d. electron transport layer solution:
PCBM is dissolved in chlorobenzene with the concentration of 20mg/mL, and stirred for 2 hours at room temperature for dissolution;
BCP was dissolved in isopropanol at a concentration of 0.45mg/mL and stirred at room temperature for 2 hours.
(2) Pretreatment of a substrate:
the ITO glass substrate was first ultrasonically cleaned in deionized water for 30 minutes, then in acetone for 30 minutes, finally in isopropyl alcohol (IPA) for 30 minutes, then blow-dried with a nitrogen gun, and treated in an ultraviolet ozone treater for 30 minutes for use.
(3) Preparation of hole transport layer:
the filtered hole transport layer solution was spin coated on an ITO substrate at a spin rate of 3000rpm for 30s, followed by annealing at 100deg.C for 10min.
(4) Preparation of the modification layer:
the phenethyl phosphoric acid solution was spin coated onto the hole transport layer at 2500rpm for 20s, followed by annealing of the film layer at 130 ℃ for 2 minutes.
(5) Preparation of perovskite film layer:
spin-coating the prepared perovskite solution on the modified hole transport layer at the speed of 4500rpm for 40s, dropwise adding 0.5mL of anti-solvent chlorobenzene on the film layer at the 18s of spin-coating, annealing for 20min at 140 ℃ in air, controlling the humidity to be 30-40%, and cooling for later use.
(6) Preparation of an electron transport layer:
spin-coating PCBM solution on the perovskite film layer, wherein the rotating speed is 3000rpm, and the time is 60s; the BCP solution was spin coated on PCBM film at 4000rpm for 60 seconds.
(7) Preparation of an electrode:
using a vacuum evaporation device, evaporating 120nm silver (Ag) on the surface of BCP by using a thermal evaporation method as an electrode, wherein the vacuum degree is controlled at 7×10 -4 Pa or below.
Comparative example 3
The difference compared to example 3 is only that no modification layer is provided between the hole transport layer and the perovskite layer.
The perovskite layer material structures obtained in example 3 and comparative example 3 were observed by SEM, and as shown in fig. 3 and 4, the unmodified perovskite layer particles were small, and the number of defects was large, and the modified perovskite layer particles were uniform, and the number of defects was greatly reduced.
Claims (7)
1. The preparation method of the perovskite solar cell comprises the steps of preparing a precursor solution, preprocessing a substrate, preparing a hole transport layer, preparing a perovskite film layer, preparing an electron transport layer and preparing an electrode, and is characterized in that: the preparation method also comprises the preparation of a hole transport layer modification film layer, wherein the hole transport layer modification film layer is formed by depositing phenethyl phosphoric acid on the hole transport layer by a solution method.
2. The method of manufacturing a perovskite solar cell according to claim 1, wherein: the perovskite film layer is prepared specifically as follows: (1) Depositing a mixed solution of lead iodide, lead bromide, cesium iodide, rubidium iodide, methyl amidine iodide, methyl amine chloride and methyl amine bromide on the hole transport layer in one of spin coating, knife coating and spray coating;
(2) Auxiliary crystallization film forming: the mode is one or a combination of a plurality of anti-solvent dripping, vacuumizing and drying and heating assistance;
(3) And annealing and cooling after forming the film.
3. The method of manufacturing a perovskite solar cell according to claim 1, wherein: the electron transport layer is prepared from at least one of tin dioxide, titanium dioxide, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, fullerene derivative and zinc oxide material by vacuum deposition or solution deposition.
4. The method of manufacturing a perovskite solar cell according to claim 1, wherein: the hole transport layer is prepared from nickel oxide, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ], me-2PACz, me-4PACz, (2- (3, 6-dimethoxy-9H-carbazole-9-yl) ethyl) phosphonic acid, a mixture material of one or more of (2- (9H-carbazole-9-yl) ethyl) phosphonic acid or a laminated material formed by a plurality of materials, and is prepared by vacuum deposition or solution deposition.
5. The method of manufacturing a perovskite solar cell according to claim 1, wherein: the conversion efficiency of the perovskite solar cell was 17.22%.
6. The method of manufacturing a perovskite solar cell according to claim 1, wherein: the pretreatment method of the substrate comprises the following steps: and (3) ultrasonically cleaning the substrate in deionized water, then ultrasonically cleaning the substrate in an organic solvent, and drying the substrate and then treating the substrate in an ultraviolet ozone processor.
7. A perovskite solar cell produced by the production method according to any one of claims 1 to 6.
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