CN106531888B - A kind of modifying interface material - Google Patents
A kind of modifying interface material Download PDFInfo
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- CN106531888B CN106531888B CN201610652091.6A CN201610652091A CN106531888B CN 106531888 B CN106531888 B CN 106531888B CN 201610652091 A CN201610652091 A CN 201610652091A CN 106531888 B CN106531888 B CN 106531888B
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
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Abstract
The present invention relates to application of the derivatives of porphyrin in terms of being inverted Ca-Ti ore type solar battery hole-transporting layer/calcium titanium ore bed modifying interface, device architectures are as follows: ITO/ hole transmission layer/calcium titanium ore bed/electron transfer layer/cathode.Porphyrin is used for hole transmission layer/calcium titanium ore bed interface in perovskite solar battery, firstly, the pattern of adjustable calcium titanium ore bed, reduces the defect density in film, improve the quality of calcium titanium ore bed；Secondly, introducing porphyrin interface-modifying layer, it can effectively stop transmission of the electronics from perovskite to hole transmission layer, while being conducive to injection and transmission of the hole from perovskite to hole transmission layer, to be conducive to the raising of device efficiency.It further, since the dissolubility of porphyrin is preferable, can be introduced by solution spin-coating method in perovskite solar battery, operate very simple, favorable repeatability.
Description
Technical field
The present invention relates to derivatives of porphyrin to be inverted Ca-Ti ore type solar battery hole-transporting layer/calcium titanium ore bed circle
The application of face modification aspect.
Background technique
Since 21 century, energy problem becomes increasingly conspicuous, and the non-renewable fossil energy such as coal, petroleum is today's society at present
Main energy sources, but they will cause serious environmental pollution, such as greenhouse in exploitation, transport processing and use during
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, it can use safely, so being reasonably the effective of solution energy problem using solar energy
One of approach, and solar energy can be directly translated into electric energy by solar battery, be constantly subjected to the concern of researchers.
Since solar battery is reported, development course can be divided into for four generations: the first generation is with monocrystalline silicon, polysilicon
For the silica-based solar cell of representative；The second generation is the film sun with cadmium telluride (CdTe) and copper indium gallium selenide (CIGS) for representative
It can battery；The third generation is using dye sensitization (DSSC), organic (OPV) and quantum dot as the solar battery of representative；Forth generation is
Using perovskite as the novel solar battery of representative.Wherein-, two generation solar batteries have been achieved with commercialization, but this
There is produce the problems such as consuming energy big, at high cost and environmental pollution for the large-scale production of a little solar battery technologies.In contrast,
Third and fourth generation solar battery is at low cost, easily prepared, and development prospect is wide, especially emerging perovskite solar battery
Since 2009 are reported, photoelectric conversion efficiency (PCE) has been increased to 22% or more by initial 3.8%, development speed
It spends very surprising, it has also become the research hotspot of photovoltaic art.
Perovskite solar battery is using perovskite as light absorbing layer.The basic structure of perovskite material is regular octahedron
Type, chemical composition 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 that optical absorption spectra is wider, energy gap is adjustable, carries
The advantages that flowing carrier diffusion length and lasting a long time and is inexpensive, preparation process is simple.The film-forming process of perovskite has diversification,
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 knot
Structure also has diversification, is broadly divided into two types, and one is traditional structures: 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 working principle of perovskite solar battery be related to calcium titanium ore bed to the absorption of photon and
The generation process of exciton, the injection and transmission process to electronics, hole transmission layer respectively of electronics, hole, the collection process of electrode.
Wherein, the extraction and injection of carrier occur in perovskite/electron transfer layer, perovskite/hole transmission layer and electronics, hole
Between transport layer/electrode interface, the property of boundary layer has the superiority and inferiority of device performance very big influence, therefore, to boundary
It is one of the effective way for obtaining high performance solar cells that surface layer, which carries out modification,.It 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
It is effectively protected calcium titanium ore bed not to be corroded, to improve the stability of device to a certain extent.Ogomi et al. existed before this
Electron transfer layer titanium dioxide (TiO2HOCO-R-NH is introduced between)/calcium titanium ore bed3 +I-Self assembled monolayer can inhibit
TiO2Middle electronics in perovskite hole it is compound, to improve the performance of device；Fullerene (C60) and its derivative self-assembled
Monolayer is for modifying TiO2Interface between/perovskite, while open-circuit voltage and fill factor are improved, to further mention
The efficiency of high battery；Other are used to modify electron transfer layer (TiO2, zinc oxide) material with the interface of perovskite, such as the third ammonia
Acid, 4-aminobenzoic acid, organosilan etc., can be by the quality of raising perovskite film, to be conducive to device photoelectric performance
It improves.In addition, C12The hydrophobic molecules such as silane are introduced in the interface of perovskite/hole transmission layer (spiro-OMeTAD)
On, the corrosion to perovskite film such as water, oxygen can be reduced to a certain extent, to improve the stability of device.
Currently, the reported work majority in terms of the modifying interface of perovskite device 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
Hole transmission layer/calcium titanium ore bed interface in perovskite device is modified, and decorative material is the derivative of porphyrin.Porphyrin point
Son has the pi-conjugated structure of larger plane, compared with strong light absorption, unique photoelectron and magnetic performance and excellent thermostabilization
Property.Porphyrin is used for hole transmission layer/calcium titanium ore bed interface in perovskite solar battery, firstly, adjustable calcium titanium
The pattern of ore bed reduces the defect density in film, improves the quality of calcium titanium ore bed；Secondly, porphyrin interface-modifying layer is introduced, it 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, to be conducive to the raising of device efficiency.Further, since the dissolubility of porphyrin is preferable, solution spin coating can be passed through
Method is introduced into perovskite solar battery, operates very simple, favorable repeatability.
Goal of the invention
Object of the present invention is to derivatives of porphyrin is applied to inverted perovskite solar battery hole-transporting layer/calcium titanium
The modifying interface of ore bed.
Summary of the invention
1. a kind of inversion perovskite solar battery hole-transporting layer/calcium titanium ore bed interface based on derivatives of porphyrin
Modification, molecular structural formula are as follows:
N=1-16, M=Zn2+, Fe2+, Co2+, Ni2+, Cu2+, X=-SAc
2. porphyrin is in preparation method of hole transmission layer modifying interface, including spin-coating method, vapour deposition method, self assembly etc..
3. the preparation based on porphyrin modified hole transmission layer/calcium titanium ore bed solar battery.
Detailed description of the invention
Fig. 1: based on porphyrin modified perovskite solar battery device architecture schematic diagram (PEDOT:PSS represents poly- 3,
4- ethylenedioxy thiophene/poly styrene sulfonate, Porphyrin represent porphyrin, and Perovskite represents perovskite, PCBM generation
A kind of fullerene derivate of table, C60Fullerene is represented, BCP represents dimethyl -4,7- diphenyl -1,10- ferrosin, and Al is represented
Aluminium)
Fig. 2: based on porphyrin modified density of photocurrent-voltage curve (V with unmodified solar batteryocRepresentative is opened
Road voltage, JscShort-circuit current density is represented, FF represents fill factor, and PCE represents photoelectric conversion efficiency)
Specific embodiment
Case study on implementation 1
[5- (the 4- acetyl mercapto amoxy) phenyl] porphyrin of zinc (II) 5,10,15,20- tetra- is used as perovskite solar-electricity
Chi Zhongju 3,4-ethylene dioxythiophene/poly styrene sulfonate (PEDOT:PSS)/perovskite interface-modifying layer, molecule knot
Structure formula is as follows:
Step 1: ITO substrate cleaning
The ITO substrate of 1.5cm x 1.5cm is etched using the mixed liquor of zinc powder and dilute hydrochloric acid, then by the ITO after etching
Respectively it is cleaned by ultrasonic 15 minutes in deionized water, acetone and isopropanol respectively, finally with being dried with nitrogen and shine in UV- ozone
It penetrates 15 minutes.
Step 2: device preparation
(1) add modification layer device ITO/PEDOT:PSS/porphyrin/perovskite/PCBM/C60The system of/BCP/Al
It is standby:
PEDOT:PSS is first spun on the ITO substrate that ozone treatment is crossed (6000 revs/min (rpm), 60 seconds (S)) simultaneously
It anneals 30 minutes under conditions of 120 DEG C, is transferred into nitrogen atmosphere glove box later；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:PSS
Upper (6000rpm, 30S), and be dried overnight under normal temperature conditions；Then by the lead iodide (PbI of 1M2) solution is spun to ITO/
On PEDOT:PSS/ porphyrin (3000rpm, 40S), one layer of methylpyridinium iodide ammonium (3000rpm, 40S) of spin coating at once immediately, and then
It anneals 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 10 minutes at normal temperature or more；Finally by C60(20nm), BCP (8nm) buffer layer and Al
(100nm) electrode vapor deposition gets on.
(2) without polishing layer device ITO/PEDOT:PSS/perovskite/PCBM/C60The preparation of/BCP/Al:
Using same preparation process, the difference is that there is no porphyrin decorative layer.
Step 3: battery performance test
Device is tested for the property using Keithley2400: under the conditions of the irradiation of the sunlight of the AM 1.5G of simulation
(luminous intensity is 100 mW/cm2) can get photoelectric current-voltage curve, scanning voltage range is reverse scan 1.2V → -1.2V,
Forward scan -1.2V → 1.2V, sweep speed 50mV/S.
Zinc (II) 5,10,15,20- tetra- [5- (penta oxygen alkane of acetyl group sulfydryl) is introduced at the interface of PEDOT:PSS/ perovskite
Phenyl] porphyrin, porphyrin can pass through-SCOCH thereon3Group chemical is adsorbed on the surface PEDOT:PSS, this intermolecular electrostatic
Interaction can increase surface coverage of the perovskite film on PEDOT:PSS, while the PEDOT:PSS table after modification
The enhancing of face hydrophobicity, perovskite film can reduce the density of heterogeneous nucleation point in its shaping surface, to be conducive to larger in film
The formation of crystal grain improves the quality of calcium titanium ore bed.In addition, 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 transmission of the electronics from perovskite to PEDOT:PSS, have simultaneously
Injection from perovskite to PEDOT:PSS and transmission conducive to hole from, the efficiency of the device after eventually passing through modification is by original
11.35% has been increased to 13.55%.
Summarize the above result shows that, the device performance of the perovskite solar battery by porphyrin modified mistake, which has, obviously to be mentioned
Height, and the method for preparing boundary layer is simple and favorable repeatability.
It is provided for the embodiments of the invention hole transmission layer of the derivatives of porphyrin in perovskite solar battery above
Modifying interface is described in detail, and applies that a specific example illustrates the principle and implementation of the invention, above
Embodiment is merely used to help understand method and its core concept of the invention, and content should not be construed as limiting the invention.
Claims (1)
1. a kind of derivatives of porphyrin is in perovskite solar battery as hole transmission layer/calcium titanium ore bed modifying interface material
Application, the molecular structural formula of such derivatives of porphyrin is as follows:
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| CN201610652091.6A CN106531888B (en) | 2016-08-04 | 2016-08-04 | A kind of modifying interface material |
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| CN106531888B true CN106531888B (en) | 2019-06-21 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107833970B (en) * | 2017-10-19 | 2020-04-28 | 华中科技大学鄂州工业技术研究院 | Surface modification method of perovskite film |
| CN108832002B (en) * | 2018-06-20 | 2022-04-22 | 南京邮电大学 | Perovskite solar cell based on PVA (polyvinyl alcohol) modified hole transport layer |
| CN109860394B (en) * | 2019-03-01 | 2021-06-22 | 兰州大学 | Method for realizing efficient and stable large-area perovskite solar cell preparation based on porphyrin doping |
| 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 |
| CN110311042B (en) * | 2019-05-31 | 2022-10-14 | 南京邮电大学 | Preparation method of self-assembled monolayer and perovskite solar cell |
| CN110289354A (en) * | 2019-06-10 | 2019-09-27 | 上海交通大学 | A kind of solar cell preparation method based on calcium titanium ore bed bilateral passivation film |
| CN110429180A (en) * | 2019-07-16 | 2019-11-08 | 上海黎元新能源科技有限公司 | A kind of solar battery and preparation method thereof |
| CN113943301B (en) * | 2020-07-17 | 2022-12-16 | 厦门稀土材料研究所 | Metalloporphyrin hole transport material for perovskite solar cell |
| CN113651825B (en) * | 2021-08-17 | 2022-07-26 | 华侨大学 | Fullerene derivative, preparation method thereof and perovskite solar cell |
| CN113754893B (en) * | 2021-09-01 | 2022-10-04 | 兰州大学 | Method for preparing perovskite solar cell by porphyrin complex self-assembly supermolecule |
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| CN103943781A (en) * | 2014-03-26 | 2014-07-23 | 中国科学院长春应用化学研究所 | Polymer solar cell active layer ink liquid, high-stability polymer solar cell and manufacturing methods of polymer solar cell active layer ink liquid and high-stability polymer solar cell |
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| CN103943781A (en) * | 2014-03-26 | 2014-07-23 | 中国科学院长春应用化学研究所 | Polymer solar cell active layer ink liquid, high-stability polymer solar cell and manufacturing methods of polymer solar cell active layer ink liquid and high-stability polymer solar cell |
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| Title |
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| "Electrochemical metallization of self-assembled porphyrin monolayers";Thomas Nann et al.;《Anal Bioanal Chem》;20020612;第373卷;第749-753页 |
| "Gold and silver anchored cobalt porphyrins used for catalytic water splitting";Miguel A. Morales Vásquez,et al.;《Materials Chemistry and Physics》;20150401;第159卷;第159-166页 |
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