CN109686846A - A kind of modifying interface method of organic metal halide perovskite solar cell - Google Patents
A kind of modifying interface method of organic metal halide perovskite solar cell Download PDFInfo
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- CN109686846A CN109686846A CN201811442868.1A CN201811442868A CN109686846A CN 109686846 A CN109686846 A CN 109686846A CN 201811442868 A CN201811442868 A CN 201811442868A CN 109686846 A CN109686846 A CN 109686846A
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- phthalocyanine
- perovskite
- metal halide
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910001507 metal halide Inorganic materials 0.000 title claims abstract description 15
- 150000005309 metal halides Chemical class 0.000 title claims abstract description 15
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012296 anti-solvent Substances 0.000 claims abstract description 14
- 230000005525 hole transport Effects 0.000 claims abstract description 6
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 49
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000004528 spin coating Methods 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 230000001133 acceleration Effects 0.000 claims description 9
- 230000005540 biological transmission Effects 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 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 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 3
- 238000000137 annealing Methods 0.000 claims 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound 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 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 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 1
- 238000002156 mixing Methods 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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
- H10K71/311—Purifying organic semiconductor materials
-
- 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
- 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
-
- 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
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to solar cell fields, more particularly to a kind of modifying interface method of organic metal halide perovskite solar cell, proposes and a kind of modify perovskite crystal grain boundary and perovskite/hole transport bed boundary method in organic metal halide perovskite solar cell.Phthalocyanine is added into the anti-solvent for prepare battery, by the weak interaction between Phthalocyanine and perovskite presoma cation, Phthalocyanine is made to be attached to perovskite crystal grain boundary and perovskite/hole transport bed boundary.Relative to the perovskite solar cell of no phthalocyanine modifying interface, stability of the perovskite solar cell under atmospheric environment and under illumination after modification is increased dramatically, and corresponding battery efficiency is also higher.This method has great importance to the industrialization of the following perovskite solar cell.This method can improve stability of the organic metal halide calcium titanium ore bed under atmospheric environment and under illumination, and improve the efficiency of perovskite solar cell.
Description
Technical field
The invention belongs to solar cell fields, refer in particular to a kind of interface for organic metal halide perovskite solar cell
Method of modifying.
Background technique
In all kinds of solar cells, organic metal halide perovskite solar cell (hereinafter referred to as perovskite battery) is simultaneous
Have inexpensive solution processing and excellent photoelectric conversion performance.By the development of 6-7 year, laboratory device energy conversion effect
Rate has broken through 23%, is the fastest-rising a kind of solar cell of efficiency of American National Renewable Energy Laboratory (NREL) statistics,
It therefore is considered as a kind of photovoltaic technology of great potential.However, perovskite solar cell efficiency is far from reaching
The Schockley-Queisser limit, this may with it is compound related caused by the defect of perovskite solar cell interface.In addition, calcium
It is added to hygroscopic lithium salts in the most common hole mobile material of titanium ore solar cell, causes the stability of perovskite thin film
Deterioration.Research accordingly, with respect to regulation perovskite solar cell interface is a hot spot of perovskite battery research field.
Summary of the invention
The present invention is directed to caused by the defect of perovskite solar cell interface that device photoelectric transfer efficiency is not high and stability
The problems such as bad, develops and a kind of utilizes Phthalocyanine modification perovskite crystal grain boundary and perovskite/hole transport bed boundary
Method, to improve the photoelectric conversion efficiency and stability of device.
Technical solution of the present invention: for the photoelectric conversion efficiency and stability for improving perovskite solar cell, one kind is provided
The method of modifying of device interfaces.Using Phthalocyanine as modifying interface layer material, preparation method includes: this method
1) it cleans FTO glass: FTO glass being sequentially placed into washing powder solution, deionized water, acetone and ethyl alcohol and is surpassed respectively
Sound cleans half an hour, is dried with nitrogen, then handles 15min with UV ozone；
2) TiO is prepared2Electron transfer layer: by 2.25ml TiCl4It is slowly dropped to ice face made of 100ml deionized water
On, TiCl is obtained after ice-out4The cleaned FTO glass of step 1) is immersed TiCl by aqueous solution4In aqueous solution, at 70 DEG C
1h is heated, is rinsed with water, is dried with nitrogen later, dry 1h, obtains FTO/TiO at 100 DEG C2；
3) it prepares perovskite precursor solution: weighing 208.30mg carbonamidine hydriodate (FAI), 587.79mg first
PbI2It dissolves in 1ml mixed solvent (N,N-dimethylformamide (DMF): dimethyl sulfoxide (DMSO)=4:1 (v/v)) and is configured to
Solution A；Then 159.6mg methylamine hydrobromate (MABr), 550.5mg PbBr are taken2Dissolve in 1ml mixed solvent (DMF:DMSO=
4:1 (v/v)) in be configured to B solution；Then it takes 77.94mg CsI to dissolve in 400 μ l DMSO solvents and is configured to C solution.By A,
B, tri- kinds of solution of C stir 8h to uniform dissolution respectively, and tri- kinds of 880 μ l of solution of A, B, C, 132 μ l, 88 μ l is finally taken to be mixed into respectively
Solution D, and it is stirred for 8h, obtain perovskite precursor solution.
4) it adds the preparation of the anti-solvent solution of phthalocyanine: weighing 0.01-10mg phthalocyanine and be added in 1ml methyl phenyl ethers anisole, stir
8h is completely dissolved to it, obtains the anti-solvent solution added with phthalocyanine.
5) hole transmission layer solution: first by Li-TFSI (Lithium-bis (trifluoromethanesulphonyl)
Imide) be dissolved in acetonitrile be made concentration be 520mg/ml Li-TFSI solution, then by 72.3mg spiro-MeOTAD (2,
2',7,7'-Tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spiro-bifluo rene)、28.8ul
4- tert .-butylpyridine and 17.5ul Li-TFSI solution dissolve in 1ml chlorobenzene, stir 12h, obtain hole transmission layer solution；
6) in the TiO of the substrate of step 2) preparation2Surface spin-coating step 3) preparation perovskite precursor solution (D is molten
Liquid), spin coating proceeding is as follows:
1. revolving speed 1000rpm/min, acceleration a=200rpm/s, spin coating are held time t=12s；
2. revolving speed 5000rpm/min, acceleration a=1500rpm/s, spin coating are held time t=45s, in the process of spin coating
Middle dropwise addition anti-solvent；
7) perovskite thin film prepared by step 6) is placed in thermal station annealed (110 DEG C, 20min)；
8) spin-coating step 5 on the calcium titanium ore bed that step 7) prepares) preparation hole transmission layer solution (revolving speed
5000rpm/min, acceleration a=2000rpm/s, spin coating are held time t=25s), finally using physical vaporous deposition in sky
Gold electrode is deposited in the transport layer of cave.
Wherein, the step 4) phthalocyanine include 2,9,16,23- tetra-tert -29H, 31H- phthalocyanines, Isosorbide-5-Nitrae, 8,11,15,
Eight butoxy -29H, 31H- phthalocyanine of 18,22,25-, 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25- 16
Fluoro- 29H, 31H- Cobalt Phthalocyanine (II) etc..
Preferably, step 4) weighs 0.1-1mg phthalocyanine.
Anti-solvent, preferably 25s is added dropwise in step 6) in the time interval of 15-30s after 2. spin-coating step starts, is added dropwise
Amount is 50-150 μ l.
Step 8) the gold electrode with a thickness of 50-150nm.
Step 3) -8) completed in glove box, preferably, the water oxygen concentration of glove box is controlled in 10ppm or less.
Technical effect of the invention: the method for the present invention adds phthalocyanine into the anti-solvent for prepare battery, passes through phthalocyanine point
Weak interaction (Van der Waals force, hydrogen bond, induction force, dipole-dipole force etc.) between son and perovskite presoma cation makes Phthalocyanine
It is attached to perovskite crystal grain boundary and perovskite/hole transport bed boundary.Research shows that: the calcium relative to no phthalocyanine modifying interface
Titanium ore solar cell, stability of the perovskite solar cell under atmospheric environment and under illumination after modification are increased dramatically,
And corresponding battery efficiency is also higher.Stability caused by phthalocyanine modifying interface and improved efficiency are mainly due to Phthalocyanine
Play the role of modifying interface and passivation and perovskite is adulterated.Phthalocyanine hydrophobicity and chemical stability are strong, when its is attached
Can obstruct hydrone in perovskite crystal grain boundary and perovskite/hole transport bed boundary and enter calcium titanium ore bed, to improve
The stability of perovskite solar cell.Furthermore Phthalocyanine may also suppress the generation of perovskite interface defect, and pass through doping
Perovskite regulates and controls the position of energy band of perovskite, therefore can reduce the compound of interface and promote transporting for carrier, to improve
The efficiency of battery.This method has great importance to the industrialization of the following perovskite solar cell.
Detailed description of the invention
Fig. 1 is the schematic diagram that phthalocyanine modifies perovskite solar cell interface.
Fig. 2 is the surface topography of the perovskite thin film without phthalocyanine decorative layer.
Fig. 3 is the surface topography of the perovskite thin film of the decorative layer containing phthalocyanine.
Specific embodiment
The technical characteristic that the present invention is further illustrated by the following examples, but protection scope of the present invention is not
It is limited to the following example.
Comparative example 1
Step 1: FTO glass (1.5*2.5cm, commercially available) is sequentially placed into washing powder solution, deionized water, acetone and ethyl alcohol
It is middle to be cleaned by ultrasonic half an hour respectively, it is dried with nitrogen, then handle 15min with UV ozone；
Step 2: by 2.25ml TiCl4(AR, commercially available) is slowly dropped in ice face made of 100ml deionized water, to ice
The cleaned FTO glass of step 1 is immersed into TiCl after thawing4In aqueous solution, 1h is heated at 70 DEG C, is rinsed with water later, nitrogen
Air-blowing is dry, and dry 1h, obtains FTO/TiO at 100 DEG C2；
Step 3: weighing 208.30mg FAI (AR, commercially available), 587.79mg PbI first2(AR, commercially available) dissolves in 1ml mixing
Solution A is configured in solvent (DMF:DMSO=4:1 (v/v))；Then 159.6mg MABr (AR, commercially available), 550.5mg are taken
PbBr2(AR, commercially available), which dissolves in 1ml mixed solvent (DMF:DMSO=4:1 (v/v)), is configured to B solution；Then 77.94mg is taken
CsI (AR, commercially available), which dissolves in 400 μ l DMSO solvents, is configured to C solution.By tri- kinds of solution of A, B, C stir respectively 8h to uniformly it is molten
Solution, finally takes tri- kinds of 880 μ l of solution of A, B, C, 132 μ l, 88 μ l to be mixed into solution D, and be stirred for 8h, before obtaining perovskite respectively
Drive liquid solution.Above-mentioned solvent is commercially available, purity AR.
Step 4: Li-TFSI (AR, commercially available) is dissolved in acetonitrile (AR, commercially available) concentration is made first is 520mg/ml's
Li-TFSI solution, then by 72.3mg spiro-MeOTAD (AR, commercially available), 28.8ul 4- tert .-butylpyridine (AR, commercially available) and
17.5ul Li-TFSI solution dissolves in 1ml chlorobenzene (AR, commercially available), stirs 12h, obtains hole transmission layer solution；
Step 5: in the TiO of substrate prepared by step 22(D is molten for perovskite precursor solution prepared by surface spin-coating step 3
Liquid), spin coating proceeding is as follows:
1. revolving speed 1000rpm/min, acceleration a=200rpm/s, spin coating are held time t=12s；
2. revolving speed 5000rpm/min, acceleration a=1500rpm/s, spin coating are held time t=45s, dripped as t=25s
Add 85 μ l of anti-solvent methyl phenyl ethers anisole (AR, commercially available)；
Step 6: being annealed (110 DEG C, 20min) to perovskite thin film；
Step 7: the hole transmission layer solution (revolving speed that on the calcium titanium ore bed that step 5 prepares prepared by spin-coating step 4
5000rpm/min, acceleration a=2000rpm/s, spin coating are held time t=25s), finally using physical vaporous deposition in sky
Gold electrode (80nm) is deposited in the transport layer of cave.
FTO/TiO prepared by 1 step 6 of comparative example2/ perovskite thin film carries out SEM characterization, and surface SEM schemes such as
Shown in Fig. 2.Fig. 2 shows that perovskite thin film is made of perovskite crystal grain.Intercrystalline gap can make steam be easy to invade perovskite
Film causes stability poor.In addition, also resulting in charge recombination, the efficiency of battery is influenced.It is bent that I-V is carried out to the battery of preparation
Line (under the simulated solar irradiation of AM 1.5G) test, efficiency 17.1%.Under conditions of unencapsulated, by the battery storing
In the atmospheric environment under 50% humidity, about the 50% (8.5%) of original efficiency is dropped to behind efficiency within 1 week.At the beginning of the battery
Efficiency decaying after beginning efficiency is lower than embodiment 1,1 week is also much higher than embodiment 1, shows unmodified perovskite interface to electricity
The stability and efficiency in pond have adverse effect.
Comparative example 2
Firstly, weighing 1mg fullerene C60(AR, commercially available) is added in 1ml methyl phenyl ethers anisole, and stirring 8h is completely dissolved to it.It connects
, it is added dropwise in 1 step 5 of comparative example and has dissolved fullerene C60100 μ l of methyl phenyl ethers anisole.
I-V curve (under the simulated solar irradiation of AM 1.5G) test, efficiency 17.5% are carried out to the battery of preparation.
Under conditions of unencapsulated, by the battery storing in the atmospheric environment under 50% humidity, original effect was dropped to behind efficiency in 1 week
60% (10.5%) of rate.The starting efficiency of the battery is higher than comparative example 1, and the decaying under the same terms is real also superior to comparison
Example 1 is applied, this should be attributed to C60Modification to perovskite interface.However, C60The poor chemical stability of itself, cannot be to perovskite
It is suitably adulterated, therefore the starting efficiency of the battery is still below embodiment, the decaying under the same terms is also faster than embodiment.
Embodiment 1
Firstly, weighing 2,9,16,23- tetra-tert -29H, 31H- phthalocyanine (AR, commercially available) of 0.25mg is added to 1ml benzene first
In ether, stirring 8h is completely dissolved to it.Then, the 85 μ l of methyl phenyl ethers anisole for having dissolved phthalocyanine is added dropwise in 1 step 5 of comparative example.
FTO/TiO prepared by 1 step 6 of embodiment2/ perovskite thin film carries out SEM characterization, and surface SEM schemes such as Fig. 3 institute
Show.Fig. 3 shows that perovskite thin film is still made of perovskite crystal grain, but intercrystalline gap is covered by phthalocyanine mostly, can make steam
It is difficult to invade perovskite thin film, to improve the stability of battery.I-V curve is carried out (in the mould of AM 1.5G to the battery of preparation
Under quasi- sunlight) test, efficiency 19.8%.It is under conditions of unencapsulated, the battery storing is big under 50% humidity
In compression ring border, 80% or more (16.2%) of original efficiency is dropped within 1 week with behind efficiency.Compared with comparative example 1, phthalocyanine
Battery starting efficiency after modification is higher, efficiency decaying is slower, has confirmed the Phthalocyanine added in anti-solvent and can play interface and has repaired
Decorations and passivation and the effect to perovskite doping.
Embodiment 2
Firstly, weighing 2,9,16,23- tetra-tert -29H, 31H- phthalocyanine (AR, commercially available) of 0.1mg is added to 1ml benzene first
In ether, stirring 8h is completely dissolved to it.Then, the 110 μ l of methyl phenyl ethers anisole for having dissolved phthalocyanine is added dropwise in 1 step 5 of comparative example.
I-V curve (under the simulated solar irradiation of AM 1.5G) test, efficiency 18.5% are carried out to the battery of preparation.
Under conditions of unencapsulated, by the battery storing in the atmospheric environment under 50% humidity, original effect was dropped to behind efficiency in 1 week
70% or more (13.0%) of rate.
Embodiment 3
Firstly, 1mg Isosorbide-5-Nitrae is weighed, the addition of 8,11,15,18,22,25- eight butoxy -29H, 31H- phthalocyanines (AR, commercially available)
Into 1ml methyl phenyl ethers anisole, stirring 8h is completely dissolved to it.Then, the benzene for having dissolved phthalocyanine is added dropwise in 1 step 5 of comparative example
100 μ l of methyl ether.
I-V curve (under the simulated solar irradiation of AM 1.5G) test, efficiency 18.2% are carried out to the battery of preparation.
Under conditions of unencapsulated, by the battery storing in the atmospheric environment under 50% humidity, original effect was dropped to behind efficiency in 1 week
80% or more (14.7%) of rate.
Compared with comparative example 2, after phthalocyanine modification battery starting efficiency is also higher, efficiency decaying is also slower, table
The modifying interface effect of bright phthalocyanine is better than C60。
Embodiment 4
Firstly, 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25- ten hexafluoro -29H of 5mg is weighed,
31H- Cobalt Phthalocyanine (II) (AR, commercially available) is added in 1ml methyl phenyl ethers anisole, and stirring 8h is completely dissolved to it.Then, in comparative example
The 150 μ l of methyl phenyl ethers anisole for having dissolved phthalocyanine is added dropwise in 1 step 5.
I-V curve (under the simulated solar irradiation of AM 1.5G) test, efficiency 18.0% are carried out to the battery of preparation.
Under conditions of unencapsulated, by the battery storing in the atmospheric environment under 50% humidity, original effect was dropped to behind efficiency in 1 week
85% or more (15.5%) of rate.
Embodiment 5
It is added in 1ml methyl phenyl ethers anisole, stirs firstly, weighing 2,9,16,23- tetra-tert -29H, 31H- phthalocyanine of 0.1mg
8h is completely dissolved to it.Then, it is added dropwise when the 15s after 2. spin-coating step starts in 1 step 5 of comparative example and has dissolved phthalocyanine
85 μ l of methyl phenyl ethers anisole.
I-V curve (under the simulated solar irradiation of AM 1.5G) test, efficiency 18.0% are carried out to the battery of preparation.
Under conditions of unencapsulated, by the battery storing in the atmospheric environment under 50% humidity, original effect was dropped to behind efficiency in 1 week
70% or more (12.7%) of rate.
Claims (8)
1. a kind of modifying interface method of organic metal halide perovskite solar cell, it is characterised in that: the method step
It is as follows:
1) clean FTO glass: it is clear that FTO glass is sequentially placed into washing powder solution, deionized water, acetone and ethyl alcohol ultrasound respectively
Half an hour is washed, is dried with nitrogen, then handles 15min with UV ozone；
2) TiO is prepared2Electron transfer layer: by 2.25ml TiCl4It is slowly dropped in ice face made of 100ml deionized water, to
TiCl is obtained after ice-out4The cleaned FTO glass of step 1) is immersed TiCl by aqueous solution4In aqueous solution, heated at 70 DEG C
1h is rinsed with water later, is dried with nitrogen, and dry 1h, obtains FTO/TiO at 100 DEG C2；
3) it prepares perovskite precursor solution: weighing 208.30mg carbonamidine hydriodate (FAI), 587.79mg PbI first2It dissolves in
1ml is matched by N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) according to the in the mixed solvent that the volume ratio of 4:1 obtains
Solution A is made；Then 159.6mg methylamine hydrobromate (MABr), 550.5mg PbBr are taken2Dissolve in 1ml by DMF and DMSO according to
The in the mixed solvent that the volume ratio of 4:1 obtains is configured to B solution；Then 77.94mg CsI is taken to dissolve in 400 μ l DMSO solvents
It is configured to C solution；Tri- kinds of solution of A, B, C are stirred into 8h to uniform dissolution respectively, finally take respectively tri- kinds of 880 μ l of solution of A, B, C,
132 μ l, 88 μ l are mixed into solution D, and are stirred for 8h, obtain perovskite precursor solution；
4) it adds the preparation of the anti-solvent solution of phthalocyanine: weighing 0.01-10mg phthalocyanine and be added in 1ml methyl phenyl ethers anisole, stirring 8h is extremely
It is completely dissolved, and obtains the anti-solvent solution added with phthalocyanine；
5) it is molten that Li-TFSI hole transmission layer solution: is dissolved in the Li-TFSI that obtained concentration is 520mg/ml in acetonitrile first
Liquid, then 72.3mg spiro-MeOTAD, 28.8ul 4- tert .-butylpyridine and 17.5ul Li-TFSI solution are dissolved in into 1ml chlorobenzene
In, 12h is stirred, hole transmission layer solution is obtained；
6) in the FTO/TiO of step 2) preparation2TiO2Surface spin-coating step 3) preparation perovskite precursor solution；
The spin coating proceeding is as follows:
1. revolving speed 1000rpm/min, acceleration a=200rpm/s, spin coating are held time t=12s；
2. revolving speed 5000rpm/min, acceleration a=1500rpm/s, spin coating are held time t=45s, when 2. spin-coating step starts
Anti-solvent is added dropwise in the time interval of 15-30s afterwards；
7) perovskite thin film prepared by step 6) is placed in thermal station and is annealed；
8) spin-coating step 5 on the calcium titanium ore bed that step 7) prepares) preparation hole transmission layer solution, finally utilize physics gas
Gold electrode is deposited in phase sedimentation on the hole transport layer.
2. the modifying interface method of organic metal halide perovskite solar cell as described in claim 1, it is characterised in that:
Step 4) the phthalocyanine includes 2,9,16,23- tetra-tert -29H, 31H- phthalocyanine, eight fourth oxygen of 1,4,8,11,15,18,22,25-
Ten hexafluoro -29H, 31H- phthalein of base -29H, 31H- phthalocyanine or 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-
Cyanines cobalt (II).
3. the modifying interface method of organic metal halide perovskite solar cell as described in claim 1, it is characterised in that:
It weighs 0.1-1mg phthalocyanine described in step 4) to be added in 1ml methyl phenyl ethers anisole, stirring 8h is completely dissolved to it, is obtained added with phthalocyanine
Anti-solvent solution.
4. the modifying interface method of organic metal halide perovskite solar cell as described in claim 1, it is characterised in that:
Step 6) is described to be added dropwise anti-solvent when 2. spin-coating step starts 25s, and the anti-solvent amount of dropwise addition is 50-150 μ l.
5. the modifying interface method of organic metal halide perovskite solar cell as described in claim 1, it is characterised in that:
Step 7) the annealing temperature is 110 DEG C, annealing time 20min.
6. the modifying interface method of organic metal halide perovskite solar cell as described in claim 1, it is characterised in that:
The revolving speed 5000rpm/min of step 8) the spin coating hole transmission layer solution, acceleration a=2000rpm/s, spin coating are held time
T=25s；Gold electrode with a thickness of 50-150nm.
7. the modifying interface method of organic metal halide perovskite solar cell as described in claim 1, it is characterised in that:
The step 3) -8) completed in glove box.
8. the modifying interface method of organic metal halide perovskite solar cell as claimed in claim 7, it is characterised in that:
The water oxygen concentration of the glove box is controlled in 10ppm or less.
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| CN117279406A (en) * | 2023-08-01 | 2023-12-22 | 兰州大学 | Hole transport composition of perfluoro phthalocyanine metal complex and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111435705A (en) * | 2019-06-12 | 2020-07-21 | 杭州纤纳光电科技有限公司 | Repairing agent and repairing method thereof and method for preparing photoelectric film |
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| CN113388385A (en) * | 2020-03-11 | 2021-09-14 | 南京工业大学 | Non-lead metal halide luminescent material and preparation method and device thereof |
| CN113388385B (en) * | 2020-03-11 | 2022-08-19 | 南京工业大学 | Non-lead metal halide luminescent material and preparation method and device thereof |
| CN117279406A (en) * | 2023-08-01 | 2023-12-22 | 兰州大学 | Hole transport composition of perfluoro phthalocyanine metal complex and application thereof |
| CN117279406B (en) * | 2023-08-01 | 2024-09-27 | 兰州大学 | Hole transport composition of perfluoro phthalocyanine metal complex and application thereof |
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