CN106531888A - Porphyrin derivative for interface modification of hole transport layer/perovskite layer in inverted perovskite solar cell - Google Patents
Porphyrin derivative for interface modification of hole transport layer/perovskite layer in inverted perovskite solar cell Download PDFInfo
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- CN106531888A CN106531888A CN201610652091.6A CN201610652091A CN106531888A CN 106531888 A CN106531888 A CN 106531888A CN 201610652091 A CN201610652091 A CN 201610652091A CN 106531888 A CN106531888 A CN 106531888A
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- perovskite
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- porphyrin
- hole transport
- transport layer
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- 238000012986 modification Methods 0.000 title abstract description 9
- 230000004048 modification Effects 0.000 title abstract description 9
- 230000005525 hole transport Effects 0.000 title abstract 6
- 150000004033 porphyrin derivatives Chemical class 0.000 title abstract 2
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 32
- 230000005540 biological transmission Effects 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 11
- 238000004528 spin coating Methods 0.000 abstract description 6
- 238000002347 injection Methods 0.000 abstract description 5
- 239000007924 injection Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 33
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 11
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 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 3
- -1 CH3NH3 + Chemical class 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical class O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 125000005429 oxyalkyl group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AJRXEXGVDMEBCT-UHFFFAOYSA-M [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] Chemical compound [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] AJRXEXGVDMEBCT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
-
- 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
- H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
-
- 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
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
-
- 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
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
-
- 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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to an application of a porphyrin derivative in an interface modification aspect of a hole transport layer/perovskite layer in an inverted perovskite solar cell. A device structure is an ITO/hole transport layer/perovskite layer/electron transport layer/cathode. Porphyrin is used for an interface of the hole transport layer/perovskite layer in the perovskite solar cell. Firstly, the shape and form of the perovskite layer can be adjusted, the defect density in a film is reduced and the quality of the perovskite layer is improved; and secondly, a porphyrin interface modification layer is introduced, transportation of electrons from perovskite to the hole transport layer can be effectively blocked, and meanwhile, injection and transportation of holes from the perovskite to the hole transport layer are facilitated, thereby facilitating improvement of the device efficiency. Furthermore, since the solubility of the porphyrin is relatively good, the porphyrin can be introduced into the perovskite solar cell through a solution spin-coating method, the operation is very simple and the repeatability is good.
Description
Technical field
The present invention relates to derivatives of porphyrin is on the boundary for being inverted Ca-Ti ore type solaode hole-transporting layer/calcium titanium ore bed
Application in terms of the modification of face.
Background technology
Since 21 century, energy problem becomes increasingly conspicuous, and the non-renewable fossil energy such as current coal, oil is today's society
Main energy sources, but they exploitation, transport processing and use during can cause serious environmental pollution, such as greenhouse
Effect, haze, soil block etc., therefore it is extremely urgent to develop reproducible clean energy resource.Wherein, solar energy resources take no
It is most, nexhaustible, and cleanliness without any pollution, can use safely, so being reasonably solve energy problem effective using solar energy
One of approach, and solar energy can be directly translated into electric energy by solaode, be constantly subjected to the concern of researchers.
Since being reported from solaode, its development course can be divided into for four generations：The first generation is with monocrystal silicon, polysilicon
For the silica-based solar cell for representing；The second filial generation is the thin film sun with cadmium telluride (CdTe) and CIGS (CIGS) as representative
Can battery；The third generation is with dye sensitization (DSSC), organic (OPV) and solaode of the quantum dot as representative；Forth generation is
Novel solar battery with perovskite as representative.Wherein-, secondary solaode have been achieved with commercialization, but this
The large-scale production of a little solar battery technologies there are problems that big production power consumption, high cost and.By contrast,
Third and fourth generation solaode low cost, easily prepared, development prospect is wide, especially emerging perovskite solaode
Since being reported from 2009, its photoelectric transformation efficiency (PCE) has brought up to more than 22% by initial 3.8%, development speed
Degree is very surprising, it has also become the study hotspot of photovoltaic art.
Perovskite solaode is using perovskite as light absorbing zone.The basic structure of perovskite material is regular octahedron
Type, chemical composition are ABX3(A represents organoammonium cations, such as CH3NH3 +、HC(NH2)2 +；B represents divalent metal, such as
Pb2+、Sn2+；X represents halide ion, such as I-、Cl-、Br-).Perovskite itself has wider optical absorption spectra, energy gap scalable, carries
Stream carrier diffusion length and last a long time and the advantages of inexpensive, preparation process is simple.The film-forming process of perovskite has variation,
It is broadly divided into a step spin-coating method, two step spin coatings or infusion method and vacuum vapour deposition etc.；Ca-Ti ore type solar cell device is tied
Structure also has variation, is broadly divided into two types, and one kind is traditional structure：FTO electro-conductive glass/electron transfer layer/perovskite
Layer/hole transmission layer/metal electrode (gold or silver), another kind is inverted structure：ITO electro-conductive glass/hole transmission layer/perovskite
Layer/electron transfer layer/metal electrode.The operation principle of perovskite solaode be related to calcium titanium ore bed to the absorption of photon and
The generation process of exciton, electronics, hole are respectively to electronics, the injection of hole transmission layer and transmitting procedure, the collection process of electrode.
Wherein, the extraction of carrier and injection occurs in perovskite/electron transfer layer, perovskite/hole transmission layer and electronics, hole
Between the interface of transport layer/electrode, the property of boundary layer has very big impact for the quality of device performance, therefore, to boundary
It is to obtain one of effective way of high performance solar cells that surface layer carries out modification.Not only can be improved by modifying interface
Open-circuit voltage, the hysteretic phenomenon for reducing or eliminating photoelectric current, while the modifying interface between carrier blocking layers and calcium titanium ore bed
Calcium titanium ore bed is effectively protected not to be corroded, so as to improve the stability of device to a certain extent.Ogomi et al. is before this in electricity
Sub- transport layer titanium dioxide (TiO2HOCO-R-NH is introduced between)/calcium titanium ore bed3 +I-Self assembled monolayer, can suppress TiO2
In middle electronics and perovskite, hole is compound, so as to improve the performance of device；Fullerene (C60) and its single point of derivative self-assembled
Sublayer is used to modify TiO2Interface between/perovskite, while open-circuit voltage and fill factor, curve factor are improved, so as to further improve battery
Efficiency；Other are used for modifying electron transfer layer (TiO2, Zinc Oxide) material with the interface of perovskite, such as alanine, 4- ammonia
Yl benzoic acid, organosilan etc., can pass through to improve the quality of perovskite film, so as to be conducive to the raising of device photoelectric performance.This
Outward, C12The hydrophobic molecules such as-silane are introduced on the interface of perovskite/hole transmission layer (spiro-OMeTAD), can be certain
The corrosion to perovskite film such as water, oxygen is reduced in degree, so as to improve the stability of device.
At present, the work majority in terms of the modifying interface of perovskite device reported is both for traditional device
Structure, for inverted device architecture modifying interface in terms of work it is even few.The present invention is mainly by inverted
The interface of the hole transmission layer/calcium titanium ore bed in perovskite device is modified, derivant of the decorative material for porphyrin.Porphyrin point
Son has the pi-conjugated structure of larger plane, compared with strong light absorption, unique photoelectron and magnetic performance and excellent thermally-stabilised
Property.The interface of hole transmission layer/calcium titanium ore bed that porphyrin is used in perovskite solaode, first, scalable calcium titanium
The pattern of ore bed, reduces the defect concentration in film, improves the quality of calcium titanium ore bed；Secondly, porphyrin interface-modifying layer is introduced, can be with
Effectively stop transmission of the electronics from perovskite to hole transmission layer, while being conducive to hole from perovskite to hole transmission layer
Injection and transmission, so as to be conducive to the raising of device efficiency.Further, since the dissolubility of porphyrin is preferably, solution spin coating can be passed through
Method is introduced in perovskite solaode, and operation is very simple, favorable repeatability.
Goal of the invention
The present invention seeks to derivatives of porphyrin is applied to inverted perovskite solaode hole-transporting layer/calcium titanium
The modifying interface of ore bed.
The content of the invention
1. it is a kind of based on derivatives of porphyrin inversion perovskite solaode hole-transporting layer/calcium titanium ore bed interface
Modification, molecular structural formula are as follows：
N=1-16, M=Zn2+, Fe2+, Co2+, Ni2+, Cu2+, X=-SAc
2. preparation method of the porphyrin in hole transmission layer modifying interface, including spin-coating method, vapour deposition method, self assembly etc..
3. based on porphyrin modified hole transmission layer/calcium titanium ore bed solaode preparation.
Description of the drawings
Fig. 1：Device architecture schematic diagram (PEDOT based on porphyrin modified perovskite solaode：PSS represents poly- 3,
4- ethylenedioxy thiophenes/poly styrene sulfonate, Porphyrin represent porphyrin, and Perovskite represents perovskite, and PCBM is represented
A kind of fullerene derivate, C60Fullerene is represented, BCP represents dimethyl -4, and 7- diphenyl -1,10- phenanthrene quinolines, Al represent aluminum)
Fig. 2：Based on porphyrin modified density of photocurrent-voltage curve (V with unmodified solaodeocRepresentative is opened
Road voltage, JscShort-circuit current density is represented, FF represents fill factor, curve factor, and PCE represents photoelectric transformation efficiency)
Specific embodiment
Case study on implementation 1
Zinc (II) 5,10,15,20- tetra- [5- (penta oxyalkyl of acetyl group sulfydryl) phenyl] porphyrin is used as into perovskite solar energy
Poly- 3,4-ethylene dioxythiophene/poly styrene sulfonate (PEDOT in battery：The interface-modifying layer of PSS)/perovskite, its molecule
Structural formula is as follows：
Step one：ITO substrates are cleaned
The ITO substrates of 1.5cmx1.5cm are etched using the mixed liquor of zinc powder and dilute hydrochloric acid, then by the ITO after etching point
It is each not in deionized water, acetone and isopropanol to be cleaned by ultrasonic 15 minutes, finally dried up with nitrogen and irradiated in UV- ozone
15 minutes.
Step 2：It is prepared by device
(1) add modification layer device ITO/PEDOT：PSS/porphyrin/perovskite/PCBM/C60The system of/BCP/Al
It is standby：
First by PEDOT：PSS be spun on the ITO substrates that ozone was processed (6000 revs/min (rpm), 60 seconds (S)) and
Anneal 30 minutes under conditions of 120 DEG C, be transferred in nitrogen atmosphere glove box afterwards；Again by zinc (II) 5,10,15,
The dichlorobenzene solution (0.5mM) of 20- tetra- [5- (penta oxyalkyl of acetyl group sulfydryl) phenyl] porphyrin is spun to ITO/PEDOT：On PSS
(6000rpm, 30S), and the dried overnight under normal temperature condition；Then by the lead iodide (PbI of 1M2) solution is spun to ITO/
PEDOT：On PSS/ porphyrins (3000rpm, 40S), one layer of methylpyridinium iodide ammonium (3000rpm, 40S) of spin coating at once immediately, and then
Anneal 5 minutes or so under conditions of 100 DEG C；Next the dichlorobenzene solution of the PCBM of 20mg/ml is spun on perovskite
(6000rpm, 30S), and place more than 10 minutes at normal temperatures；Finally by C60(20nm), BCP (8nm) cushions and Al
(100nm) electrode evaporation gets on.
(2) without polishing layer device ITO/PEDOT：PSS/perovskite/PCBM/C60The preparation of/BCP/Al：
Using same preparation technology, difference is no porphyrin decorative layers.
Step 3：Battery performance test
Performance test is carried out to device using Keithley2400：Under the conditions of the sunlight of the AM 1.5G of simulation
(light intensity is 100mW/cm2) photoelectric current-voltage curve can be obtained, scanning voltage scope is reverse scan 1.2V → -1.2V, just
To scanning -1.2V → 1.2V, sweep speed 50mV/S.
In PEDOT：The interface of PSS/ perovskites introduces zinc (II) 5,10,15,20- tetra- [5- (penta oxygen alkane of acetyl group sulfydryl)
Phenyl] porphyrin, porphyrin can be by-SCOCH thereon3Group chemical adsorbs in PEDOT：PSS surfaces, this intermolecular electrostatic
Interaction can increase perovskite film in PEDOT：Surface coverage on PSS, while the PEDOT after modification：PSS surfaces
Hydrophobicity strengthens, and perovskite film can reduce the density of heterogeneous nucleation point in its shaping surface, so as to be conducive to larger crystalline substance in film
The formation of grain, improves the quality of calcium titanium ore bed.Additionally, the highest occupied molecular orbital (HOMO) of porphyrin does not occupy track with minimum
(LUMO) energy level is matched with Perovskite Phase, can effectively stop electronics from perovskite to PEDOT：The transmission of PSS, while favorably
In hole from perovskite to PEDOT：The injection of PSS and transmission, eventually pass through the efficiency of the device after modification by original
11.35% has brought up to 13.55%.
Summarize result above and show have through the device performance of the perovskite solaode of porphyrin modified mistake and substantially carry
Height, and prepare that the method for boundary layer is simple and favorable repeatability.
Hole transmission layer of the above derivatives of porphyrin provided by the embodiment of the present invention in perovskite solaode
Modifying interface is described in detail, and applies specific case and the principle and embodiment of the present invention are set forth, the above
Embodiment is only intended to help and understands the method for the present invention and its core concept, and content should not be construed as limiting the invention.
Claims (3)
1. a kind of modifying interface material of the perovskite solaode hole-transporting layer/calcium titanium ore bed based on derivatives of porphyrin
Material, molecular structural formula are as follows：
Wherein, n=1-16, M=Zn2+, Fe2+, Co2+, Ni2+, Cu2+, X=-SAc.
2. if the porphyrin in claim 1 is in the preparation method of hole transmission layer modifying interface.
3. porphyrin modified hole transmission layer/calcium titanium ore bed is applied in solar cells.
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| CN109860394A (en) * | 2019-03-01 | 2019-06-07 | 兰州大学 | A method of the preparation of efficient stable large area perovskite solar battery is realized based on Porphyrin-doped |
| CN110212093A (en) * | 2019-04-18 | 2019-09-06 | 上海黎元新能源科技有限公司 | A kind of solar battery and preparation method thereof |
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