CN113611802A - Perovskite solar cell modified by organic small molecules, preparation method and application - Google Patents
Perovskite solar cell modified by organic small molecules, preparation method and application Download PDFInfo
- Publication number
- CN113611802A CN113611802A CN202111004262.1A CN202111004262A CN113611802A CN 113611802 A CN113611802 A CN 113611802A CN 202111004262 A CN202111004262 A CN 202111004262A CN 113611802 A CN113611802 A CN 113611802A
- Authority
- CN
- China
- Prior art keywords
- perovskite
- transport layer
- layer
- solar cell
- electron transport
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000003384 small molecules Chemical class 0.000 title claims description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000010409 thin film Substances 0.000 claims abstract description 32
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000005622 photoelectricity Effects 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 44
- 238000004528 spin coating Methods 0.000 claims description 38
- 239000000654 additive Substances 0.000 claims description 34
- 230000005525 hole transport Effects 0.000 claims description 33
- 230000000996 additive effect Effects 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000010408 film Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 10
- -1 halide salt Chemical class 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- JAHFQMBRFYOPNR-UHFFFAOYSA-N iodomethanamine Chemical compound NCI JAHFQMBRFYOPNR-UHFFFAOYSA-N 0.000 claims description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical group 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical group 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 claims description 4
- DDQAGDLHARKUFX-UHFFFAOYSA-N acetic acid;methanamine Chemical compound [NH3+]C.CC([O-])=O DDQAGDLHARKUFX-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 claims description 4
- 238000005956 quaternization reaction Methods 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 abstract description 7
- 150000004820 halides Chemical class 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- CPIVYSAVIPTCCX-UHFFFAOYSA-N 4-methylpentan-2-yl acetate Chemical compound CC(C)CC(C)OC(C)=O CPIVYSAVIPTCCX-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical group NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- OGQSCIYDJSNCMY-UHFFFAOYSA-H iron(3+);methyl-dioxido-oxo-$l^{5}-arsane Chemical compound [Fe+3].[Fe+3].C[As]([O-])([O-])=O.C[As]([O-])([O-])=O.C[As]([O-])([O-])=O OGQSCIYDJSNCMY-UHFFFAOYSA-H 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 3
- 229940006461 iodide ion Drugs 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Chemical group CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- OUVNAZAUHZDDSD-UHFFFAOYSA-N butanoic acid;methanamine Chemical compound [NH3+]C.CCCC([O-])=O OUVNAZAUHZDDSD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Chemical group CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- DYWODRJVMZCPDO-UHFFFAOYSA-N ethylammonium formate Chemical compound CC[NH3+].[O-]C=O DYWODRJVMZCPDO-UHFFFAOYSA-N 0.000 description 2
- BAONHUZQTANSBI-UHFFFAOYSA-N formic acid;methanamine Chemical compound [NH3+]C.[O-]C=O BAONHUZQTANSBI-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- AUJBWBGETPUHHU-UHFFFAOYSA-N methylazanium;propanoate Chemical compound [NH3+]C.CCC([O-])=O AUJBWBGETPUHHU-UHFFFAOYSA-N 0.000 description 2
- 125000005496 phosphonium group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Images
Classifications
-
- 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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- 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
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Materials Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a modifier, an interfacial active material, a perovskite solar cell and a preparation method, and belongs to the field of organic photoelectricity. The modifier comprises methyl acrylate or methyl methacrylate with R1‑CH＝CHCOO‑R2Organic micromolecules with the structure are matched with ionic liquid to modify halide perovskite, so that the photoelectric property and the environmental stability of the halide perovskite are improved, the open voltage of the perovskite solar cell is obviously improved, and the performance of the perovskite solar cell is finally improved. The preparation method contacts halide perovskite with an organic molecular modifier, and carries out annealing treatment to prepare the perovskite thin film material with excellent photoelectric property. The process is simple, has high repeatability, can be prepared in the environment, can optimize organic molecules according to the actual application requirements,the photoelectric property of the halide perovskite thin film is exerted to the maximum extent, and excellent device performance is realized.
Description
Technical Field
The invention belongs to the field of organic photoelectricity, and relates to an additive, a preparation method and a perovskite solar cell.
Background
Perovskite solar cells are the hot direction in the photovoltaic field due to their excellent photoelectric properties, however, many problems of perovskite solar cells are still not solved. In the field of photovoltaic technology, efficiency, cost, and lifetime (or stability) are often used to judge the commercial viability of a solar module. Efficiency and stability are the key issues of concern among the three elements, particularly perovskite stability, which has been the focus of research.
Further studies of the stability of perovskite layers must be carried out in order to translate the attractive photovoltaic properties of perovskites into higher device performance and continue toward achieving 30% of their theoretical PCE limit. In the development of crystalline silicon solar cells, the use of high quality silicon wafers combined with efficient surface passivation and contact passivation strategies brought experimental operating voltages close to their theoretical limits and device efficiencies as high as 26.7%. In addition, in the field of perovskite solar cells, interface engineering is an important method for improving the stability and efficiency of perovskite, and in the interface engineering, for example, macromolecular polymers such as PDMS and PMMA are used for passivating defects and isolating water and oxygen.
Disclosure of Invention
The invention aims to provide a high-efficiency and stable perovskite solar cell preparation method aiming at the problems and the defects of the existing perovskite solar cell. The photoelectric property and the environmental stability of the perovskite film are improved through interface modification, so that the multielement organic molecular modifier and the perovskite preparation method thereof are provided. The invention effectively improves the photoelectric conversion efficiency of the perovskite solar cell, realizes long-term stability and simultaneously effectively improves the open-circuit voltage of the perovskite solar cell. The invention has the advantages of simple process, environmental manufacture, low temperature and low cost for preparing the perovskite solar cell device with stable water and oxygen.
In order to solve the technical problem of the invention, the technical scheme is as follows: a perovskite thin-film solar cell modified by organic micromolecules comprises a transparent conductive substrate, an electron transmission layer and a transparent conductive substrate with R1-CH＝CHCOO-R2(R1、R2One of aryl, alkyl or hydrogen atoms) structure, a hole transport layer and a counter electrode layer sequentially form a laminated structure, or the laminated structure comprises a transparent conductive substrate, an electron transport layer, the perovskite light absorption layer and a transparent conductive substrate with R1-CH＝CHCOO-R2(R1、R2One of aryl, alkyl or hydrogen atoms), a hole transport layer and a counter electrode layer sequentially form a laminated structure;
the transparent conductive substrate is Indium Tin Oxide (ITO) or fluorine-doped SnO2(FTO) or Al-doped zinc oxide (AZO) as conductive layer;
the electron transport layer is TiO2Or SnO2A film;
the perovskite light absorption layer is ABXmY3-mA material of a crystalline structure of the formula, wherein A is CH3NH3Or C4H9NH3B is Pb or Sn, X, Y is Cl, Br or I, and m is 1, 2 or 3;
the hole transport layer is one or a mixture of more than two of NiO, CuO, CuSCN, CuI, tungsten trioxide, molybdenum trioxide, vanadium pentoxide, 2',7,7' -tetra [ N, N-diamino ] -9,9' -spirobifluorene Spiro-OMETAD, P3HT, PTAA, NPB and TPD in any proportion.
Preferably, the perovskite solar cell has two structures: reverse and forward planar heterojunction perovskite solar cells.
In order to solve the technical problem of the invention, another technical scheme is provided as follows: the preparation method of the perovskite thin-film solar cell modified by the organic small molecules comprises the following steps:
(1) preparing an ionic liquid: synthesizing ionic liquid in one step through acid-base neutralization reaction or quaternization reaction; or preparing halide salt containing target cations through a two-step reaction through a quaternization reaction, and then replacing halogen ions with target anions or adding Lewis acid to obtain target ionic liquid;
(2) ABXmY3-mDissolving perovskite powder in ionic liquid according to a certain proportionAnd in the bulk solution, adding the additive into the precursor solution or directly spin-coating the solution of the additive on the perovskite active layer.
(3) The precursor solution is continuously stirred at 50-100 ℃ for 3-24 hours, and thenAddingAdding 1-20 mul of organic micromolecules, and continuously stirring for 0.5-6 hours at 50-80 ℃ to prepare perovskite precursor solution;
or independently preparing an additive organic micromolecule solution, and stirring the solution at room temperature for 0.5 to 2 hours in a dark place;
(4) spin coating a hole or electron transport material on the transparent conductive ITO glass;
(5) spin-coating the prepared perovskite precursor solution on an ITO conductive substrate with a hole transport layer or an electron transport layer, and annealing at 70-150 ℃ for 5-15min to obtain a compact and uniform active layer;
(6) spin-coating an electron or hole transport layer on the perovskite layer;
(7) and (3) evaporating a modification layer and a metal electrode on the electron or hole transport layer in vacuum.
Preferably, the method comprises the following steps:
(1) preparing an ionic liquid: mixing acetic acid and methylamine according to a certain stoichiometric ratio, and stirring to prepare methylamine acetate;
(2) mixing lead iodide and iodomethylamine according to the ratio of 1:1, then stirring for 8 hours at 50-100 ℃, then adding 5 mul of methyl acrylate (5 mul/ml), and continuously stirring for 2 hours at 50-80 ℃ to prepare a perovskite precursor solution;
(3) spin coating a hole or electron transport material on the transparent conductive ITO glass;
(4) spin-coating the prepared perovskite precursor solution on an ITO conductive substrate with a hole transport layer or an electron transport layer, and annealing at 100 ℃ for 5min to obtain a compact and uniform active layer;
(5) spin-coating an electron or hole transport layer on the perovskite layer;
(6) and (3) evaporating a modification layer and a metal electrode on the electron or hole transport layer in vacuum.
Preferably, the acetic acid and the methylamine in the step (1) are stirred for 2 hours in an ice-water bath;
the concentration of the perovskite precursor solution in the step (2) is 200-500 mg/ml.
Preferably, the organic small molecule added in step (2) is one or both of methyl acrylate and methyl methacrylate.
Preferably, the hole transport layer spin-coated on the transparent conductive ITO glass in step (3) is PEDOT: PSS, the electron transport layer is SnO2(ii) a The method comprises the following specific steps:
(3) PSS, annealing at 120 ℃ for 30 min;
(4) SnO2Dissolving in deionized water at a concentration of 10 mg/ml; spin coating on ITO, and annealing at 150 deg.C for 30 min;
preferably, the electron transport layer spin-coated on the perovskite layer is PCBM, and the hole transport layer is Spiro-MeOTAD; the method comprises the following specific steps:
(3) dissolving PCBM in chlorobenzene at a concentration of 18 mg/ml;
(4) dissolving 72.6mg/ml Spiro-MeOTAD in chlorobenzene, stirring for 0.5-1.5h, adding 14.4. mu.L of lithium bistrifluoromethylsulfinamide dissolved in acetonitrile at a concentration of 520mg/ml, and finally adding 28.8. mu.L of 4-tert-butylpyridine;
preferably, the modification layer is LiF and MoO respectively3The metal electrode is Ag or Au; the method comprises the following specific steps:
(4) LiF is evaporated on the electron transport layer with the reverse structure, and the thickness of the electron transport layer is 2 nm;
(5)MoO3the layer is evaporated on the hole transport layer of the positive structure, and the thickness is 5 nm;
(6) the thickness of the metal electrode is 100 nm;
in order to solve the technical problem of the invention, another technical scheme is provided for the application of the perovskite thin-film solar cell modified by the organic small molecules in the photoelectric field.
The formal structure comprises an ITO electrode containing a transparent substrate, an electron transport layer, a perovskite active layer (containing an additive), a hole transport layer and a positive electrode in sequence; the trans-structure comprises an ITO electrode containing a transparent substrate, a hole transport layer, a perovskite active layer (containing an additive), an electron transport layer and a negative electrode in sequence.
The chemical formula of the perovskite active layer is ABX3Wherein A is a cation; b is at least one of lead and tin atoms; x is halide ion(s). Including CH3NH3PbI3、CH3NH3PbI3-xClx、(FAPbI3)1-x(MAPbBr3)xOr (CsFAMA) PbI3-xBrxAnd the like.
The invention also provides a preparation method of the perovskite active material, which comprises the following steps: mixing halide perovskite with an organic molecular modifier, and carrying out annealing treatment to obtain the perovskite active material.
The additive is an organic polymerization monomer with self-polymerization and strong coordination: methyl Acrylate (MA), Methyl Methacrylate (MMA), etc. have CH2One or more of organic molecules of the characteristic structure CHCOO-R (note: R is an organic molecular chain).
The addition amount of the additive is 5-15 mu l/ml.
The ionic liquid is methylamine acetic acid, methylamine formic acid, methylamine propionic acid, methylamine butyric acid, ethylamine formic acid, etc. (the cation is ionic liquid of imidazole, pyrrolidine, pyridine, morpholine, piperidine, quaternary ammonium, quaternary phosphonium, guanidine, etc.).
Preparing a precursor solution: MAX or FAX PbX2Is dissolved in 1ml MAAc ionic liquid, and the molar ratio of (1: 1) is dissolved in 1ml MAAc ionic liquid. 5 microliters of methyl acrylate (or other additives mentioned above) was added and magnetically stirred at 60 ℃ for 6-12 hours.
The additive participates in the formation of the perovskite thin film in the perovskite precursor liquid, and organic molecules and the perovskite thin film can be bonded through one step or multiple steps.
The temperature of the annealing treatment is 70-150 ℃, and the time is 5-15 min; preferably, the temperature of the annealing treatment is 100 ℃ and the time is 5min
The annealing process of the present invention is operated in an outdoor environment.
The additive is also suitable for preparing perovskite solar cells by an anti-solvent method.
The invention has the following advantages:
(1) the perovskite solar cell prepared by the method can reduce the influence degree of external factors on the performance of the perovskite thin film and keep the stability of the perovskite thin film under the condition of exposed water and oxygen even under the condition of no encapsulation.
(2) The invention has good interface passivation and iodide ion anchoring effects under the synergistic catalysis of the ionic liquid, and as can be seen from figure 3, the open-circuit voltage of the device in practical application is improved by about 8%. And the photoelectric response performance is improved, the perovskite efficiency is improved to 22.4% from 20% before modification, and finally the performance of the perovskite solar cell is improved.
(3) The invention prepares the perovskite solar cell with high efficiency and stability at low temperature in the environment, thereby greatly reducing the operation difficulty and the cost. The method has the advantages of wide application range, simplicity in operation and high repeatability, and is beneficial to commercialization of the perovskite solar cell.
(4) The invention has the advantages that the methyl acrylate monomer with a very small amount avoids the defect of large resistance of macromolecular polymers and can play a role in isolating water vapor.
(5) The invention not only realizes interface modification, but also can reasonably regulate and control the morphology and the photoelectric property of the perovskite thin film.
(6) Provides a general idea of perovskite optimization, and can optimize organic molecular components according to the requirements of practical application.
(7) The cell can maintain long-term stability through the crystal phase transformation of perovskite (XRD shown in figure 5 can see that the perovskite solar cell added with acrylate has a stronger low-dimensional crystal phase peak and a weaker lead iodide peak for decomposing perovskite, and the opposite is true for a control group without the additive).
(8) Good stability in high humidity environment. FIG. 6 erosion experiments readily show that: the A group (with additive) is not affected by water erosion, the film is kept intact for a long time in contact with water, and the B group (without additive) film is greatly eroded.
(9) Greatly enhancing the stability of the perovskite high-dimensional crystalline phase: as can be seen from the XRD pattern of fig. 2, after a long time of standing, the peak value of lead iodide produced by decomposition of perovskite of a (with additive) was greatly reduced compared to that of B (without additive).
(10) On the basis of the above item (7), the free iodide ions are captured by the additive and form low-vitamin perovskite, which functions to reduce the iodide ion concentration and inhibit the iodide ion migration. Reducing the defects formed by perovskite decomposition enhances carrier lifetime, as can be seen in fig. 4: cells incorporating the MA additive have longer carrier lifetimes.
(11) The perovskite film forming quality of the added additive can be greatly improved, the perovskite crystal is more complete, and the improvement is mutually verified with the opening pressure enhancement, the stability enhancement and the carrier service life enhancement.
Drawings
Fig. 1 is a schematic structural view of a perovskite solar cell of the present invention. In the figure: 1. a metal electrode; 2. a hole transport layer; 3. a perovskite light absorbing layer and a methyl acrylate additive therein; 4. an electron transport layer; 5. transparent conductive substrate
FIG. 2 is an X-ray single crystal diffraction pattern of a perovskite thin film A modified by a modifier in example 1 of the present invention compared with a perovskite thin film B unmodified by a comparative example, which was continuously heated at 85 ℃ for 14 days.
FIG. 3 is a J-V curve of the energy conversion efficiency of the present invention modified with a modifier.
FIG. 4 is a PL profile of the transient fluorescence spectra before (curve: control) and after (curve: MA) modification.
FIG. 5 is an X-ray single crystal diffraction pattern for 14 days at ambient conditions before (curve: A) and after (curve: B) modification.
FIG. 6 is a graph showing the effect of the water droplet erosion test before modification (group A) and after modification (group B).
FIG. 7 is SEM images before (left) and after (right) modification.
Detailed Description
Reference will now be made in detail to the embodiments of the present invention, some of which are illustrated in the drawings and are not intended to be exhaustive or to limit the invention to the precise forms disclosed. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, belong to the protection scope of the present invention.
The embodiments do not specify specific experimental procedures or conditions, and the procedures or conditions can be performed according to the conventional experimental procedures described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be purchased in the market.
The chemical formula of the perovskite active layer is ABX3Wherein A is a cation; b is at least one of lead and tin atoms; x is halide ion(s). Including CH3NH3PbI3、CH3NH3PbI3-xClx、(FAPbI3)1-x(MAPbBr3)xOr (CsFAMA) PbI3-xBrxAnd the like.
Methyl methacrylate is an unpolymerized organic monomer molecule.
The ionic liquid is methylamine acetic acid, methylamine formic acid, methylamine propionic acid, methylamine butyric acid, ethylamine formic acid, etc. (the cation is ionic liquid of imidazole, pyrrolidine, pyridine, morpholine, piperidine, quaternary ammonium, quaternary phosphonium, guanidine, etc.).
The stable perovskite solar cell through interface modification comprises a formal structure or a trans-structure.
Example 1
The preparation method of the stable perovskite solar cell provided by the invention has the following specific implementation mode.
(1) Synthesis of MAAc: glacial acetic acid (15.3mL, 0.327mol) and methylamine (27.8mL, 0.491mol, 40%) were added to a 250mL round-bottomed flask in an ice bath and stirred for 2 hours. The resulting solution was then rotary evaporated at 80 ℃ for 1 hour to yield a recovered solution that was the synthetic liquid chemical MAAc. The liquid product crystallized after 2 hours in a refrigerator. Washing the obtained solid product with diethyl ether for 3 times, dissolving with ethanol, and rotary evaporating at 80 deg.C for 1h for recovery. Finally, the resulting liquid was cooled to room temperature before use.
(2) Preparing a precursor solution: MAI (89.28mg) and lead iodide (302.02mg) were stirred in MAAc (1mL) at 60 ℃ for 6 hours. The molar ratio of the lead iodide to the iodomethylamine is 1: 1. thereafter, 3 to 10. mu.l, preferably 5. mu.l, of methyl acrylate are added to the solution and stirring is continued for 2 to 6 hours.
(3) And cleaning the ITO glass substrate electrode.
(4) The electron transport layer is spin coated on the substrate.
(5) And spin-coating the perovskite precursor solution on a pretreated substrate at the speed of 4000r/s under the outdoor condition at the substrate temperature of 75-90 ℃ (the spin-coating time is 20-25 s). And after the spin coating is finished, the substrate is placed on a 100 ℃ hot bench for annealing for 5min to prepare the perovskite thin film.
(6) And spin-coating a hole transport layer on the prepared perovskite thin film in an anhydrous environment (or an environment with the relative humidity of less than 30 wt%).
(7) A100 nm thick metal Ag electrode was evaporated under vacuum (1X 10-5 Pa). The structure of the device is schematically shown in figure 1.
The method for preparing the perovskite solar cell is simple and high in repeatability. And the film forming quality and the photoelectric performance of the battery are obviously improved. The experimental efficiency results are shown in fig. 3, and the open-circuit voltage can reach about 1.19V, which is improved by 7% compared with that before addition. The device shown in fig. 2 with the additive added (curve a) maintains better crystal stability.
Example 2
The embodiment provides a perovskite solar cell and a preparation method thereof. The preparation method comprises the following steps:
(1) synthesis of MAAc: glacial acetic acid (15.3mL, 0.327mol) and methylamine (27.8mL, 0.491mol, 40%) were added to a 250mL round-bottomed flask in an ice bath and stirred for 2 hours. The resulting solution was then rotary evaporated at 80 ℃ for 1 hour to yield a recovered solution that was the synthetic liquid chemical MAAc. The liquid product crystallized after 2 hours in a refrigerator. Washing the obtained solid product with diethyl ether for 3 times, dissolving with ethanol, and rotary evaporating at 80 deg.C for 1h for recovery. Finally, the resulting liquid was cooled to room temperature before use.
(2) Preparation of precursor solution: MAI (89.28mg) and lead iodide (302.02mg) were stirred in MAAc (1mL) at 60 ℃ for 6 hours. The molar ratio of the lead iodide to the iodomethylamine is 1: 1.
(3) preparation of methyl acrylate solution: in an anhydrous environment (or an environment with a relative humidity of less than 30 wt%), 5-20 microliters (preferably 10 microliters) of methyl acrylate are dissolved in 1ml of toluene and stirred at room temperature for 30 min.
(4) And cleaning the ITO glass substrate electrode.
(5) The electron transport layer is spin coated on the substrate.
(6) And spin-coating the perovskite precursor solution on a pretreated substrate at the speed of 4000r/s under the outdoor condition at the substrate temperature of 75-90 ℃ (the spin-coating time is 20-25 s). And after the spin coating is finished, the substrate is placed on a 100 ℃ hot bench for annealing for 5min to prepare the perovskite thin film.
(7) The prepared methyl acrylate solution was spin-coated onto the prepared perovskite layer at a speed of 4000 r/s.
(8) Spin coating the hole transport layer material on the film obtained in (7) in an anhydrous environment (or an environment with a relative humidity of less than 30 wt%).
(9) A100 nm thick metal Ag electrode was evaporated under vacuum (1X 10-5 Pa).
The experimental results are shown in fig. 4, and the mobility (curve: MA) of the device carrier with the additive added is effectively improved. And it can be seen from fig. 6 that the battery (group a) with the additive added thereto is better resistant to water erosion.
The scheme plays a role in isolating water and oxygen on the basis of continuing the advantages of example 1, and provides an encapsulation scheme for the perovskite solar cell.
Example 3
The embodiment provides a perovskite solar cell and a preparation method thereof. The preparation method comprises the following steps:
(1) synthesis of MAFA: solution A: 15ml of formic acid was placed in a beaker and then diluted with 62.5ml of anhydrous methanol. Solution B: 62.5ml of methylamine (33% ethanol solution) was put into a flask, stirred at-16 ℃ and then diluted with 25ml of absolute ethanol. After solution B was stabilized in temperature, solution A was slowly dropped into solution B. During this time, solution B was maintained at-16 ℃ with constant stirring. Finally, after 2 hours of continuous stirring, the solution was rotary evaporated at 55 ℃ to remove the remaining solvent to obtain the product MAFA.
The liquid product crystallized after 2 hours in a refrigerator. Washing the obtained solid product with diethyl ether for 3 times, dissolving with ethanol, and rotary evaporating at 80 deg.C for 1h for recovery. Finally, the resulting liquid was cooled to room temperature before use.
(2) Preparation of PbI2MAFA precursor solution of (a): 1.5M lead iodide powder was dissolved in 1 mM FA solvent, and then heated and stirred at 60 ℃ for 2 hours in an anhydrous environment (or an environment having a relative humidity of less than 30 wt%). Thereafter, 5. mu.l of methyl acrylate were added and stirring was continued for 1 h.
(3) IPA precursor solution of FAI: FAI: 90mg, MACl: 9mg was dissolved in 1mL of isopropanol solution and stirred for 2h under anhydrous environment (or environment with a relative humidity of less than 30 wt%).
(4) And cleaning the ITO glass substrate electrode.
(5) The electron transport layer is spin coated on the substrate.
(6) The MAFA precursor solution of PbI2 was added to ITO/SnO at 4000rpm under ambient conditions2The substrate was spin coated for 30s and then annealed at 120 ℃ for 4 min.
(7) After cooling to room temperature, IPA precursor solution of FAI is coated on MAFA film of PbI2 in a rotary way at constant temperature, and then annealing is carried out for 4 minutes at 150 ℃ in ambient air (70-95% humidity) to form FAPBI3A perovskite thin film. All device fabrication processes were carried out in ambient air under high humidity environment.
(8) Spin coating the hole transport layer material on the film obtained in (7) in an anhydrous environment (or an environment with a relative humidity of less than 30 wt%).
(9) A100 nm thick metal Ag electrode was evaporated under vacuum (1X 10-5 Pa).
The experimental method is based on the two examples, and the experimental mechanism is expanded to the example 3. Example 3 improvement of photoelectric properties, further demonstration of the correctness of the mechanism of examples 1 and 2, and the universality of the additive to the experimental method.
Experimental efficiency results on the basis of results similar to those of examples 1 and 2, higher on-voltage and device stability were maintained, and high-dimensional to low-dimensional conversion occurred in the crystal form shown in fig. 5.
Example 4
The preparation method of the stable perovskite solar cell provided by the invention has the following specific implementation mode.
(1) Synthesis of MAAc: glacial acetic acid (15.3mL, 0.327mol) and methylamine (27.8mL, 0.491mol, 40%) were added to a 250mL round-bottomed flask in an ice bath and stirred for 2 hours. The resulting solution was then rotary evaporated at 80 ℃ for 1 hour to yield a recovered solution that was the synthetic liquid chemical MAAc. The liquid product crystallized after 2 hours in a refrigerator. Washing the obtained solid product with diethyl ether for 3 times, dissolving with ethanol, and rotary evaporating at 80 deg.C for 1h for recovery. Finally, the resulting liquid was cooled to room temperature before use.
(2) Preparing a precursor solution: MAI (89.28mg) and lead iodide (302.02mg) were stirred in MAAc (1mL) at 60 ℃ for 6 hours. The molar ratio of the lead iodide to the iodomethylamine is 1: 1. thereafter, 3 to 10. mu.l, preferably 5. mu.l, of methyl acrylate are added to the solution and stirring is continued for 2 to 6 hours.
(3) And cleaning the ITO glass substrate electrode.
(4) SnO is coated on a substrate by spinning2An electron transport layer.
(5) And spin-coating the perovskite precursor solution on a pretreated substrate at the speed of 4000r/s under the outdoor condition at the substrate temperature of 75-90 ℃ (the spin-coating time is 20-25 s). And after the spin coating is finished, the substrate is placed on a 100 ℃ hot bench for annealing for 5min to prepare the perovskite thin film.
(6) And (3) spin-coating a Spiro-OMETAD hole transport layer on the prepared perovskite thin film in an anhydrous environment (or an environment with the relative humidity of less than 30 wt%).
(7) A100 nm thick metal Ag electrode was evaporated under vacuum (1X 10-5 Pa). The structure of the device is schematically shown in figure 1.
The method for preparing the perovskite solar cell is simple and high in repeatability. And the film forming quality and the photoelectric performance of the battery are obviously improved. The experimental efficiency results are shown in fig. 3, and the open-circuit voltage can reach about 1.19V, which is improved by 7% compared with that before addition. The device shown in fig. 2 with the additive added (curve a) maintains better crystal stability.
Example 5
The preparation method of the stable perovskite solar cell provided by the invention has the following specific implementation mode.
(1) Synthesis of MAAc: glacial acetic acid (15.3mL, 0.327mol) and methylamine (27.8mL, 0.491mol, 40%) were added to a 250mL round-bottomed flask in an ice bath and stirred for 2 hours. The resulting solution was then rotary evaporated at 80 ℃ for 1 hour to yield a recovered solution that was the synthetic liquid chemical MAAc. The liquid product crystallized after 2 hours in a refrigerator. Washing the obtained solid product with diethyl ether for 3 times, dissolving with ethanol, and rotary evaporating at 80 deg.C for 1h for recovery. Finally, the resulting liquid was cooled to room temperature before use.
(2) Preparing a precursor solution: MAI (89.28mg) and lead iodide (302.02mg) were stirred in MAAc (1mL) at 60 ℃ for 6 hours. The molar ratio of the lead iodide to the iodomethylamine is 1: 1. thereafter, 3 to 10. mu.l, preferably 5. mu.l, of methyl acrylate are added to the solution and stirring is continued for 2 to 6 hours.
(3) And cleaning the ITO glass substrate electrode.
(4) Spin coating on a substrate to obtain a TIO2An electron transport layer.
(5) And spin-coating the perovskite precursor solution on a pretreated substrate at the speed of 4000r/s under the outdoor condition at the substrate temperature of 75-90 ℃ (the spin-coating time is 20-25 s). And after the spin coating is finished, the substrate is placed on a 100 ℃ hot bench for annealing for 5min to prepare the perovskite thin film.
(6) And (3) spin-coating a PTAA hole transport layer on the prepared perovskite thin film in an anhydrous environment (or an environment with the relative humidity of less than 30 wt%).
(7) A layer of 100nm thick metal Au electrode was evaporated under vacuum (1X 10-5 Pa). The structure of the device is schematically shown in figure 1.
The method for preparing the perovskite solar cell is simple and high in repeatability. And the film forming quality and the photoelectric performance of the battery are obviously improved. The experimental efficiency results are shown in fig. 3, and the open-circuit voltage can reach about 1.19V, which is improved by 7% compared with that before addition. The device shown in fig. 2 with the additive added (curve a) maintains better crystal stability.
Comparative example 1
The preparation method of the stable perovskite solar cell provided by the invention has the following specific implementation mode.
(1) Synthesis of MAAc: glacial acetic acid (15.3mL, 0.327mol) and methylamine (27.8mL, 0.491mol, 40%) were added to a 250mL round-bottomed flask in an ice bath and stirred for 2 hours. The resulting solution was then rotary evaporated at 80 ℃ for 1 hour to yield a recovered solution that was the synthetic liquid chemical MAAc. The liquid product crystallized after 2 hours in a refrigerator. Washing the obtained solid product with diethyl ether for 3 times, dissolving with ethanol, and rotary evaporating at 80 deg.C for 1h for recovery. Finally, the resulting liquid was cooled to room temperature before use.
(2) Preparing a precursor solution: MAI (89.28mg) and lead iodide (302.02mg) were stirred in MAAc (1mL) at 60 ℃ for 6 hours. The molar ratio of the lead iodide to the iodomethylamine is 1: 1.
(3) and cleaning the ITO glass substrate electrode.
(4) The electron transport layer is spin coated on the substrate.
(5) And spin-coating the perovskite precursor solution on a pretreated substrate at the speed of 4000r/s under the outdoor condition at the substrate temperature of 75-90 ℃ (the spin-coating time is 20-25 s). And after the spin coating is finished, the substrate is placed on a 100 ℃ hot bench for annealing for 5min to prepare the perovskite thin film.
(6) And spin-coating a hole transport layer on the prepared perovskite thin film in an anhydrous environment (or an environment with the relative humidity of less than 30 wt%).
(7) A100 nm thick metal Ag electrode was evaporated under vacuum (1X 10-5 Pa). The structure of the device is schematically shown in figure 1.
This scheme compares to example 1, perovskite solar cells of the same composition made under the same conditions without the addition of additives. The battery cell stability (fig. 2: curve B) performed much worse compared to the additive package (fig. 2: curve a). It can also be seen in the steady state photovoltage of fig. 4 that the cell carrier lifetime without additive is greatly reduced compared to the additive package.
The above examples are merely illustrative for clarity, and the present additives are applicable to both trans-perovskite structures and non-ionic liquid solvents. Variations or modifications in other variations may occur to those skilled in the art upon reading the foregoing description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A perovskite thin-film solar cell modified by organic small molecules is characterized in that: comprises a transparent conductive substrate, an electron transport layer, a transparent conductive layer, an electron transport layer, a transparent conductive layer, an electron transport layer, a transparent conductive layer, an electron transport layer, a transparent conductive layer, an electron transport layer, a transparent conductive1-CH＝CHCOO-R2(R1、R2One of aryl, alkyl or hydrogen atoms) structure, a hole transport layer and a counter electrode layer sequentially form a laminated structure, or the laminated structure comprises a transparent conductive substrate, an electron transport layer, the perovskite light absorption layer and a transparent conductive substrate with R1-CH＝CHCOO-R2(R1、R2One of aryl, alkyl or hydrogen atoms), a hole transport layer and a counter electrode layer sequentially form a laminated structure;
the transparent conductive substrate is Indium Tin Oxide (ITO) or fluorine-doped SnO2(FTO) or Al-doped zinc oxide (AZO) as conductive layer;
the electron transport layer is TiO2Or SnO2A film;
the perovskite light absorption layer is ABXmY3-mA material of a crystalline structure of the formula, wherein A is CH3NH3Or C4H9NH3B is Pb or Sn, X, Y is Cl, Br or I, and m is 1, 2 or 3;
the hole transport layer is one or a mixture of more than two of NiO, CuO, CuSCN, CuI, tungsten trioxide, molybdenum trioxide, vanadium pentoxide, 2',7,7' -tetra [ N, N-diamino ] -9,9' -spirobifluorene Spiro-OMETAD, P3HT, PTAA, NPB and TPD in any proportion.
2. The perovskite thin-film solar cell modified by the organic small molecule as claimed in claim 1, wherein: the perovskite solar cell has two structures: reverse and forward planar heterojunction perovskite solar cells.
3. The preparation method of the perovskite thin-film solar cell modified by the organic small molecule according to claim 1, is characterized in that: the method comprises the following steps:
(1) preparing an ionic liquid: synthesizing ionic liquid in one step through acid-base neutralization reaction or quaternization reaction; or preparing halide salt containing target cations through a two-step reaction through a quaternization reaction, and then replacing halogen ions with target anions or adding Lewis acid to obtain target ionic liquid;
(2) ABXmY3-mDissolving perovskite powder in an ionic liquid solution in proportion, adding additive organic micromolecules into a precursor solution or directly spin-coating the solution of the additive organic micromolecules on the perovskite active layer;
(3) continuously stirring the precursor solution at 50-100 ℃ for 3-24 hours, then adding 1-20 mul of organic micromolecules, and continuously stirring at 50-80 ℃ for 0.5-6 hours to prepare a perovskite precursor solution;
or independently preparing an additive organic micromolecule solution, and stirring the solution at room temperature for 0.5 to 2 hours in a dark place;
(4) spin coating a hole or electron transport material on the transparent conductive ITO glass;
(5) spin-coating the prepared perovskite precursor solution on an ITO conductive substrate with a hole transport layer or an electron transport layer, and annealing at 70-150 ℃ for 5-15min to obtain a compact and uniform active layer;
(6) spin-coating an electron or hole transport layer on the perovskite layer;
(7) and (3) evaporating a modification layer and a metal electrode on the electron or hole transport layer in vacuum.
4. The method for preparing the perovskite thin-film solar cell modified by the organic small molecule as claimed in claim 3, wherein the method comprises the following steps: the method comprises the following steps:
(1) preparing an ionic liquid: mixing acetic acid and methylamine according to a certain stoichiometric ratio, and stirring to prepare methylamine acetate;
(2) mixing lead iodide and iodomethylamine according to the ratio of 1:1, then stirring for 8 hours at 50-100 ℃, then adding 5 mul of methyl acrylate (5 mul/ml), and continuously stirring for 2 hours at 50-80 ℃ to prepare a perovskite precursor solution;
(3) spin coating a hole or electron transport material on the transparent conductive ITO glass;
(4) spin-coating the prepared perovskite precursor solution on an ITO conductive substrate with a hole transport layer or an electron transport layer, and annealing at 100 ℃ for 5min to obtain a compact and uniform active layer;
(5) spin-coating an electron or hole transport layer on the perovskite layer;
(6) and (3) evaporating a modification layer and a metal electrode on the electron or hole transport layer in vacuum.
5. The method for preparing the perovskite thin-film solar cell modified by the organic small molecule as claimed in claim 4, wherein the method comprises the following steps:
stirring acetic acid and methylamine in the step (1) for 2 hours in an ice-water bath;
the concentration of the perovskite precursor solution in the step (2) is 200-500 mg/ml.
6. The method for preparing the perovskite thin-film solar cell modified by the organic small molecule as claimed in claim 3, wherein the method comprises the following steps: the organic micromolecules added in the step (2) are one or two of methyl acrylate and methyl methacrylate.
7. The method for preparing the perovskite thin-film solar cell modified by the organic small molecule as claimed in claim 3, wherein the method comprises the following steps: the method is characterized in that: the hole transport layer spin-coated on the transparent conductive ITO glass in the step (3) is PEDOT: PSS, the electron transport layer is SnO2(ii) a The method comprises the following specific steps:
(1) PSS, annealing at 120 ℃ for 30 min;
(2) SnO2Dissolving in deionized water at a concentration of 10 mg/ml; spin-coating on ITOThen, annealing was carried out at 150 ℃ for 30 min.
8. The method for preparing the perovskite thin-film solar cell modified by the organic small molecule as claimed in claim 3, wherein the method comprises the following steps: the electron transport layer spin-coated on the perovskite layer is PCBM, and the hole transport layer is Spiro-MeOTAD; the method comprises the following specific steps:
(1) dissolving PCBM in chlorobenzene at a concentration of 18 mg/ml;
(2) 72.6mg/ml of Spiro-MeOTAD was dissolved in chlorobenzene, and after stirring for 0.5-1.5h 14.4. mu.L of lithium bistrifluoromethylsulfinamide dissolved in acetonitrile was added at a concentration of 520mg/ml, and finally 28.8. mu.L of 4-tert-butylpyridine was added.
9. The method for preparing the perovskite thin-film solar cell modified by the organic small molecule as claimed in claim 3, wherein the method comprises the following steps: the modification layers are respectively LiF and MoO3The metal electrode is Ag or Au; the method comprises the following specific steps:
(1) LiF is evaporated on the electron transport layer with the reverse structure, and the thickness of the electron transport layer is 2 nm;
(2)MoO3the layer is evaporated on the hole transport layer of the positive structure, and the thickness is 5 nm;
(3) the thickness of the metal electrode is 100 nm.
10. Application of the perovskite thin-film solar cell modified by the organic small molecule according to claim 1 or 2 in the field of photoelectricity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111004262.1A CN113611802B (en) | 2021-08-30 | 2021-08-30 | Perovskite solar cell modified by small organic molecules, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111004262.1A CN113611802B (en) | 2021-08-30 | 2021-08-30 | Perovskite solar cell modified by small organic molecules, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113611802A true CN113611802A (en) | 2021-11-05 |
| CN113611802B CN113611802B (en) | 2023-10-31 |
Family
ID=78309702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111004262.1A Active CN113611802B (en) | 2021-08-30 | 2021-08-30 | Perovskite solar cell modified by small organic molecules, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113611802B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685314A (en) * | 2022-03-28 | 2022-07-01 | 桂林理工大学 | Steady-state alpha-phase FAPBI3Is manufactured by |
| CN114824105A (en) * | 2022-05-07 | 2022-07-29 | 深圳职业技术学院 | Perovskite solar cell and preparation method thereof |
| WO2023227122A1 (en) * | 2022-05-27 | 2023-11-30 | 北京曜能光电科技有限公司 | Solar cell transport layer, mixed transport-layer material, and solar cell |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019141044A1 (en) * | 2018-01-17 | 2019-07-25 | 杭州纤纳光电科技有限公司 | Perovskite solar cell having interface modification layer and preparation method thereof |
| WO2019148326A1 (en) * | 2018-01-30 | 2019-08-08 | 南方科技大学 | Method for preparing perovskite thin film and application thereof |
| CN111584715A (en) * | 2020-04-02 | 2020-08-25 | 深圳大学 | Modifier, perovskite active material, preparation method and perovskite solar cell |
| CN111710780A (en) * | 2020-06-18 | 2020-09-25 | 西北工业大学 | Preparation method of cathode in-situ modified perovskite solar cell without electron transport layer |
| CN111952456A (en) * | 2020-08-20 | 2020-11-17 | 南京工业大学 | Efficient and stable perovskite solar cell based on novel ionic liquid methylamine formate and preparation method and application thereof |
-
2021
- 2021-08-30 CN CN202111004262.1A patent/CN113611802B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019141044A1 (en) * | 2018-01-17 | 2019-07-25 | 杭州纤纳光电科技有限公司 | Perovskite solar cell having interface modification layer and preparation method thereof |
| WO2019148326A1 (en) * | 2018-01-30 | 2019-08-08 | 南方科技大学 | Method for preparing perovskite thin film and application thereof |
| CN111584715A (en) * | 2020-04-02 | 2020-08-25 | 深圳大学 | Modifier, perovskite active material, preparation method and perovskite solar cell |
| CN111710780A (en) * | 2020-06-18 | 2020-09-25 | 西北工业大学 | Preparation method of cathode in-situ modified perovskite solar cell without electron transport layer |
| CN111952456A (en) * | 2020-08-20 | 2020-11-17 | 南京工业大学 | Efficient and stable perovskite solar cell based on novel ionic liquid methylamine formate and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685314A (en) * | 2022-03-28 | 2022-07-01 | 桂林理工大学 | Steady-state alpha-phase FAPBI3Is manufactured by |
| CN114824105A (en) * | 2022-05-07 | 2022-07-29 | 深圳职业技术学院 | Perovskite solar cell and preparation method thereof |
| WO2023227122A1 (en) * | 2022-05-27 | 2023-11-30 | 北京曜能光电科技有限公司 | Solar cell transport layer, mixed transport-layer material, and solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113611802B (en) | 2023-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shahiduzzaman et al. | The benefits of ionic liquids for the fabrication of efficient and stable perovskite photovoltaics | |
| CN113611802B (en) | Perovskite solar cell modified by small organic molecules, preparation method and application | |
| KR101707050B1 (en) | Preparation for method of perovskite absorber layer and perovskite solar cells comprising the perovskite absorber layer thereby | |
| CN108389969B (en) | Green solvent system and mixed solution for preparing perovskite layer of perovskite solar cell | |
| CN112542549A (en) | Wide-band-gap perovskite solar cell and preparation and application thereof | |
| CN113480569A (en) | Titanium-oxygen cluster compound, preparation thereof and application thereof as electron transport material | |
| CN111525038B (en) | Perovskite solar cell doped with multifunctional additive and preparation method thereof | |
| CN114678472A (en) | FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same | |
| CN112349845A (en) | Phase stabilizer and method for preparing perovskite solar cell by using same | |
| CN113725368A (en) | NH (hydrogen sulfide)4NO3Interface modified perovskite solar cell | |
| CN111063806B (en) | Perovskite solar cell and preparation method thereof | |
| CN116056469A (en) | Perovskite solar cell based on ionic liquid interface modification | |
| CN114539290B (en) | Conjugated organic molecule and preparation method and application thereof | |
| CN115161012A (en) | Perovskite material, thin film, solar cell device and preparation method thereof | |
| CN113087636A (en) | Iodide and preparation method thereof, and all-inorganic perovskite solar cell based on iodide and preparation method thereof | |
| Aziz et al. | Synthesizing and characterization of Lead Halide Perovskite Nanocrystals solar cells from reused car batteries | |
| CN113644199B (en) | Perovskite solar cell with phytic acid dipotassium complexed with tin dioxide and preparation method thereof | |
| CN111092156B (en) | Perovskite solar cell and preparation method thereof | |
| Reddy et al. | Degradation conceptualization of an innovative perovskite solar cell fabricated using SnO 2 and P3HT as electron and hole transport layers | |
| CN220307715U (en) | Perovskite solar cell with double light absorption layer structure | |
| CN114267798A (en) | One-step method for preparing amidino FAPBI in air at medium and low temperature3Method and application of perovskite solar cell | |
| Panchu et al. | Highly Stable Inorganic Hole Transport Materials in Perovskite Solar Cells | |
| CN116322094A (en) | Perovskite solar cell passivated by sulfur-containing passivating agent | |
| CN117720511A (en) | Side chain-regulated additive-free organic photovoltaic cell receptor material and application thereof | |
| CN116847666A (en) | Interface modified electron transport layer, perovskite solar cell and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |