CN110112301A - It is a kind of regulate and control calcium titanium ore bed crystal growth method and its application in solar cells - Google Patents
It is a kind of regulate and control calcium titanium ore bed crystal growth method and its application in solar cells Download PDFInfo
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- CN110112301A CN110112301A CN201910309877.1A CN201910309877A CN110112301A CN 110112301 A CN110112301 A CN 110112301A CN 201910309877 A CN201910309877 A CN 201910309877A CN 110112301 A CN110112301 A CN 110112301A
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- titanium ore
- ore bed
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- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002109 crystal growth method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 26
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 19
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 14
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960001484 edetic acid Drugs 0.000 claims abstract description 13
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910005855 NiOx Inorganic materials 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000004528 spin coating Methods 0.000 claims description 13
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 229910052745 lead Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000012296 anti-solvent Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 100
- 239000010409 thin film Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical compound [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- 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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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of methods of regulation calcium titanium ore bed crystal growth, prepare decorative layer in anodic interface layer surface, then prepare calcium titanium ore bed in modification layer surface；The decorative layer is one of 2,2'- bipyridyl, 4,4'- bipyridyl, 1,10- phenanthroline, ethylenediamine tetra-acetic acid or a variety of.The present invention is easily combined with introducing additive, mixed solvent system, using the methods of anti-solvent, can it is more efficiently obtain homogeneity, high coverage rate film and big crystalline size, help to further increase and be inverted perovskite solar battery efficiency, for promoting the commercialization process of perovskite solar battery to be of great significance.
Description
Technical field
The present invention relates to perovskite technical field of solar batteries, more particularly, to a kind of regulation calcium titanium ore bed crystal
The method of growth and its application in solar cells.
Background technique
The chemical general formula that solar battery based on hybrid inorganic-organic perovskite active material has is AMX3, and A is represented
Cs, CH3NH3(MA) or HC (NH2)2(FA), M represents Pb or Sn, and X represents halogen Cl, Br, I.Traditional proton type is organic-nothing
Machine perovskite MAPbI3 has the bandwidth of tetragonal and 1.4eV~1.6eV, wherein MA, Pb are replaced by element, or
The element of the position I can synthesize a kind of perovskite structure.It is absorbed since hybrid inorganic-organic perovskite solar cell has
By force, mobility is high, carrier lifetime is long and can the potential advantages such as inexpensive solution processing, become the new weight of field of solar energy utilization
Want research direction.Currently, the energy conversion efficiency of its laboratory small-area devices is from the 3.8% of report in 2009
(J.Am.Chem.Soc., 2009,131,6050-6051) is improved to 22.1% (NREL, Best Research-Cell
Efficiencies, http://www.nrel.gov, accessed:November 2016), the energy of module device converts effect
Rate becomes most potential solar cell technology up to 8.7% (Energy Environ.Sci.2014,7,2642).Regulate and control calcium
The pattern of titanium ore layer is the key that obtain high efficiency solar cell such as homogeneity, high coverage rate and big crystalline size.Compared with
It include introducing additive, mixed solvent system, using anti-solvent etc. commonly to regulate and control method.However, these current methods pair
It is limited in the effect for improving perovskite pattern, develop new calcium titanium ore bed crystal growth strategy, and will in combination with the above method
Help to further increase solar battery efficiency.
Summary of the invention
It is an object of the invention to overcoming the above-mentioned deficiency of the prior art, a kind of regulation calcium titanium ore bed crystal growth is provided
Method.By improving the nucleation process of perovskite, thus effectively control perovskite crystal growth, in conjunction with existing regulation side
Method, such as mixed solvent system use the methods of anti-solvent, effective raising inversion perovskite solar battery efficiency.
A second object of the present invention is to provide the methods to prepare the application in solar battery.
Third object of the present invention is to provide a kind of perovskite solar cell devices.
Fourth object of the present invention is to provide the preparation method of the perovskite solar cell device.
Above-mentioned purpose of the invention is to give realization by the following technical programs:
A method of regulation calcium titanium ore bed crystal growth is to prepare decorative layer in anodic interface layer surface, is then repairing
Decorations layer surface prepares calcium titanium ore bed；The decorative layer is 2,2'- bipyridyl, 4,4'- bipyridyl, 1,10- phenanthroline, ethylenediamine tetraacetic
One of acetic acid is a variety of.
The research of the invention finds that in one layer of 2,2'- bipyridyl of anode interface layer surface modification, 4,4'- bipyridyl, 1,10-
One of phenanthroline or ethylenediamine tetra-acetic acid or it is a variety of after, then calcium titanium ore bed is prepared on decorative layer, the perovskite after modification
Film morphology is substantially better than NiOx layers of unmodified perovskite thin film, after introducing above-mentioned decorative layer, controllable perovskite at
Film property, so that the crystal morphology of perovskite improves, chemical property is improved.
Specifically decorative layer solution is spin-coated in anode interface layer under protective atmosphere, decorative layer is made；Again
Calcium titanium ore bed is made in the spin coating perovskite solution on decorative layer.
Preferably, the perovskite structure of the calcium titanium ore bed be ABX3, which is characterized in that any one of A Pb, Sn or
Two kinds, any one of B MA, FA, Cs or two kinds, X ClpBrqI3-p-q, the value range of p, q are 0~3.
Preferably, the anode interface layer is NiOx layers；There is many Lacking oxygens in NiOx, join pyrrole using above-mentioned 2,2'-
One of pyridine, 4,4'- bipyridyl, 1,10- phenanthroline or ethylenediamine tetra-acetic acid or a variety of modifiers can be with the nickel in NiOx
Atom is coordinated, and vacancy is filled up, and improves hole mobility, while improving the wellability on the surface NiOx.
Preferably, the concentration of the decorative layer solution is 0.01mg/mL~1mg/mL (preferably 1mg/mL).
Preferably, the concentration of the perovskite solution is 1.0mol/L~1.5mol/L (preferably 1.5mol/L).
It preferably, further include load step before the spin coating, the time of the load is 30s~300s.
Preferably, further include annealing steps after the spin coating, the temperature of the annealing is 50~100 DEG C, annealing when
Between be 6h~12h.
Preferably, the spin coating the specific steps are first low speed rotations, then high speed rotation；The revolving speed of the low speed rotation is
800~1200rpm；The high-speed rotating revolving speed is 4500~6000rpm.
It preferably, further include solvent being added dropwise, the solvent includes chlorobenzene and acetic acid second in the high-speed rotation
Ester.
The perovskite solar cell device with interface-modifying layer, therefore this hair can be further prepared using the above method
The bright the method that is also claimed is preparing the application in perovskite solar cell device.
A kind of perovskite solar cell device, including be cascading conductive glass electrode, anode interface layer, repair
Adorn layer, calcium titanium ore bed, electron transfer layer and metal electrode；The decorative layer is 2,2'- bipyridyl, 4,4'- bipyridyl, 1,10-
One of phenanthroline, ethylenediamine tetra-acetic acid are a variety of；For upper in the anode interface layer spin coating 2,2'- bipyridyl, 4,4'-
One of bipyridyl, 1,10- phenanthroline, ethylenediamine tetra-acetic acid or a variety of ethanol solutions are modified, then on decorative layer
Spin coating perovskite solution liquid forms calcium titanium ore bed.
It preferably, also include metal electrode decorative layer, the metal electrode between electron transfer layer and metal electrode layer
Decorative layer is ZrAcac；ZrAcac film facilitates the extraction of electronics as electron transfer layer, is effectively improved device photoelectric stream and fills out
The factor is filled, is a kind of good cathode modification layer material.
Preferably, the conductive glass electrode is ITO, FTO or AZO (preferably ITO electro-conductive glass).
Preferably, the anode interface layer is NiOx；Thickness is about 40nm.
Preferably, the calcium titanium ore bed is ABX3, which is characterized in that any one of A Pb, Sn or two kinds, B MA,
Any one of FA, Cs or two kinds, X ClpBrqI3-p-q, the value range of p, q are 0~3.
Preferably, the electron transfer layer is PCBM.
The preparation method of above-mentioned perovskite solar cell device is also claimed in the present invention, includes the following steps: that S1. exists
Anode interface layer is prepared on the substrate of transparent conductive substrate；S2. decorative layer is prepared in anode interface layer；S3. on decorative layer
Prepare calcium titanium ore bed；S4. electron transfer layer S5. is prepared on calcium titanium ore bed prepares metal electrode modification on the electron transport layer
Layer；S6. evaporation metal electrode obtains the perovskite solar-electricity with interface-modifying layer as back electrode on electrode modification layer
Pond device.
Specifically, described to be prepared as continuously being coated with by spin coating, blade coating, slit, spraying or print etc. modes for target
Layer preparation is on upper one layer；Preferably spin coating.
Compared with prior art, the invention has the following advantages:
The method that the present invention regulates and controls calcium titanium ore bed crystal growth, by preparing one between anode interface layer and calcium titanium ore bed
Layer decorative layer, the decorative layer are one of 2,2'- bipyridyl, 4,4'- bipyridyl, 1,10- phenanthroline, ethylenediamine tetra-acetic acid
Or it is a variety of；The film forming of the above-mentioned controllable perovskite of decorative layer improves perovskite thin film so that the crystal morphology of perovskite improves
Fluorescence intensity.The photovoltaic property of the perovskite solar cell device with interface-modifying layer further prepared simultaneously is relatively free of
The perovskite solar cell device of decorative layer significantly improves.The present invention is easily with introducing additive, mixed solvent system, using anti-
The methods of solvent combine, can it is more efficiently obtain homogeneity, high coverage rate film and big crystalline size, facilitate
It further increases and is inverted perovskite solar battery efficiency, for promoting the commercialization process of perovskite solar battery that there is weight
Want meaning.
Detailed description of the invention
Fig. 1 is the calcium titanium ore bed SEM exterior view and particle diameter distribution of Example 1 and Example 2 of the present invention preparation；A is SEM
Figure, b is grain size distribution.
Fig. 2 is the calcium titanium ore bed XRD diagram of Example 1 and Example 2 of the present invention preparation.
Fig. 3 is the calcium titanium ore bed fluorescence emission spectrum test curve of Example 1 and Example 2 of the present invention preparation.
Fig. 4 is the current density voltage curve of perovskite solar battery prepared by the embodiment of the present invention 5.
Specific embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
Embodiment 1
A method of regulation calcium titanium ore bed crystal growth prepares 2,2'- bipyridyl layer on the surface anode interface layer NiOx,
Then, calcium titanium ore bed (FAPbI is prepared on its surface3)0.85(MAPbI3)0.15.Specific preparation process is as follows:
It is first that quartz glass plate is successively clear by ultrasound through deionized water, acetone, detergent, deionized water and isopropanol
It washes, every each 20min of step.After drying in an oven, handled 4 minutes using PLASMA (oxygen plasma).Then above-mentioned processed
Quartz glass on piece, spin coating layer of Ni Ox film, thickness is about 40nm,.2,2'- is joined into pyrrole in the glove box of nitrogen atmosphere
The ethanol solution of pyridine is spin-coated on NiOx layer, and concentration is 1mg mL–1, revolving speed 3000rpm, 100 DEG C of annealing 10h.Then, will
(FAPbI3)0.85(MAPbI3)0.15Solution is spin-coated on 2,2'- bipyridyl layer, and solvent is the mixed solvent (volume of DMF and DMSO
Than for 4:1), concentration is 1.5mmol mL–1, revolving speed is improved to 5000rpm after revolving speed 1000rpm, 10s, and 100 μ are added dropwise after 15s
L ethyl acetate solution, then after rotating 10s, 100 DEG C of annealing 40min.
Embodiment 2
A method of regulation calcium titanium ore bed crystal growth prepares 4,4'- bipyridyl layer on the surface anode interface layer NiOx,
Then, calcium titanium ore bed (FAPbI is prepared on its surface3)0.85(MAPbI3)0.15.Specific preparation process is same as Example 1.
Embodiment 1 and the calcium titanium ore bed for implementing 2 preparations are compared with the calcium titanium ore bed that do not modify, SEM figure
With grain size distribution as shown in Figure 1, pattern and particle diameter distribution by the perovskite crystal after observation modification can react
The nucleation rate and crystal growth of crystal out, the partial size for being nucleated faster crystal is smaller, it will be seen from figure 1 that repairing on the surface NiOx
One layer of 2,2'- bipyridyl or 4 is adornd, after 4'- bipyridyl, more unmodified small of the partial size of perovskite crystal shows introducing 2,2'- connection
Pyridine or 4,4'- bipyridyl decorative layer can control the nucleation rate of perovskite crystal, influence the pattern of crystal.Its XRD diagram is such as
Shown in Fig. 2, PbI is respectively represented in 12.8 ° and 14.2 °2And perovskite, PbI after modification2The weakened at peak and perovskite peak
Intensity become strong, show that the crystallization of perovskite after modification becomes more completely.
Embodiment 1 and the calcium titanium ore bed for implementing 2 preparations are carried out fluorescence emission spectrum test: concrete outcome is shown in Fig. 1, due to
The mode of carrier termination only has defective effect and is quenched, and perovskite pattern is better, and defect is fewer, and electron hole is quenched just more
More, spectrally fluorescence intensity is with regard to stronger, it will be seen from figure 1 that in one layer of 2,2'- bipyridyl of NiOx surface modification or 4,4'-
After bipyridyl, perovskite thin film fluorescence intensity is better than NiOx layers of unmodified perovskite thin film, in conjunction with the result of Fig. 1, it is seen that
Perovskite thin film pattern after one layer of 2,2'- bipyridyl of NiOx surface modification or 4,4'- bipyridyl is substantially better than NiOx layers not
The perovskite thin film of modification, shows introducing 2,2'- bipyridyl or 4, and the film forming of controllable perovskite, makes after 4'- bipyridyl layer
The crystal morphology for obtaining perovskite improves.
Embodiment 3
A method of regulation calcium titanium ore bed crystal growth prepares 1,10- phenanthroline layer on the surface anode interface layer NiOx,
Then, calcium titanium ore bed (FAPbI is prepared on its surface3)0.85(MAPbI3)0.15.Specific preparation process is same as Example 1.As a result
After being shown in one layer of 1,10- phenanthroline of NiOx surface modification, perovskite thin film fluorescence intensity is better than NiOx layers of unmodified calcium titanium
Mine film, it is seen that the perovskite thin film pattern after one layer of 1,10- phenanthroline of NiOx surface modification be substantially better than NiOx layers it is unmodified
Perovskite thin film, show introducing 1, the film forming of controllable perovskite after 10- phenanthroline layer, so that the crystal morphology of perovskite
Improve.
Embodiment 4
A method of regulation calcium titanium ore bed crystal growth prepares ethylenediamine tetra-acetic acid on the surface anode interface layer NiOx
Layer, then, is prepared on its surface calcium titanium ore bed (FAPbI3)0.85(MAPbI3)0.15.Specific preparation process is same as Example 1.
As the result is shown after one layer of ethylenediamine tetra-acetic acid of NiOx surface modification, perovskite thin film fluorescence intensity be better than NiOx layers it is unmodified
Perovskite thin film, it is seen that the perovskite thin film pattern after one layer of ethylenediamine tetra-acetic acid of NiOx surface modification is substantially better than NiOx layers not
The perovskite thin film of modification shows the film forming of controllable perovskite after introducing ethylenediamine tetra-acetic acid, so that the crystal of perovskite
Pattern improves.
Embodiment 5
A kind of calcium perovskite solar cell device, including be cascading conductive glass electrode, anode interface layer,
Decorative layer, calcium titanium ore bed, electron transfer layer, metal electrode decorative layer and metal electrode；The conductive glass electrode is ITO conductive
Sheet glass, anode interface layer NiOx, decorative layer 2,2'- bipyridyl layer (2,2'-Dipyridyl), calcium titanium ore bed are
(FAPbI3)0.85(MAPbI3)0.15, electron transfer layer PC61BM, metal electrode decorative layer be ZrAcac, metal electrode Ag,
Its structure may be expressed as: ITO/NiOx/2,2'-Dipyridyl/Perovskite/PC61BM/ZrAcac/Ag.Specifically prepared
Journey is as follows:
It is first 15 Ω square by resistance–1Tin indium oxide (ITO) electro-conductive glass piece successively through deionized water, acetone,
Detergent, deionized water and isopropanol pass through ultrasonic cleaning, every each 20min of step.After drying in an oven, using PLASMA (oxygen
Plasma) processing 4 minutes.Then in above-mentioned processed tin indium oxide (ITO) electro-conductive glass on piece, spin coating layer of Ni Ox is thin
Film, thickness are about 40nm,.The ethanol solution of 2,2'- bipyridyl is spin-coated on NiOx layer in the glove box of nitrogen atmosphere, it is dense
Degree is 1mg mL–1, revolving speed 3000rpm, 100 DEG C of annealing 10h.Then, by (FAPbI3)0.85(MAPbI3)0.15Solution is spin-coated on
On 2,2'- bipyridyl layers, solvent is the mixed solvent (volume ratio 4:1) of DMF and DMSO, and concentration is 1.5mmol mL–1, revolving speed
For 1000rpm, revolving speed is improved to 5000rpm after 10s, and 100 μ L ethyl acetate solutions are added dropwise after 15s, then after rotating 10s, and 100 DEG C
Anneal 40min.Then, one layer of PCBM film of spin coating, concentration 20mg/mL, revolving speed 2500rpm.One layer of acetylacetone,2,4-pentanedione of spin coating
Zirconium film (ZrAcac), concentration 2mg/mL.Finally, < 5 × 10-4Under the vacuum of Pa, evaporation metal Ag.Battery device has
Effect area is 0.0576cm2.Except the preparation process of NiOx film is completed in atmospheric environment, remaining all link is in nitrogen
It is completed in the glove box of gas atmosphere.
Meanwhile the reference device that preparation does not modify anode interface layer NiOx, structure are as follows: ITO/NiOx/
Perovskite/PC61BM/ZrAcac/Ag。
Carry out photovoltaic property test to the above-mentioned perovskite device being prepared: its result is as shown in table 1 and Fig. 2, tentatively
Characterization, normal component do not modify anode interface layer NiOx, energy conversion efficiency 15.2%, and current density is
20.56mA cm-2, open-circuit voltage 1.00V, fill factor 74.26%.In contrast, one layer 2 is prepared on the surface NiOx,
2'-Dipyridyl, resulting devices efficiency have been increased to 5%.Wherein, energy conversion efficiency 15.95%, current density are
20.34mA cm-2, open-circuit voltage 1.064V, fill factor 75.37%.Show using this method to anodic interface layer surface
It is modified, can effectively regulate and control calcium titanium ore bed crystal growth, improve the photovoltaic property of perovskite device.
The preliminary characterization result of 1 organic photovoltaic battery device of table
Remarks: light intensity is 100mW cm-2。
The above results show by preparing one layer of decorative layer, the decorative layer between anode interface layer and calcium titanium ore bed
For one of 2,2'- bipyridyl, 4,4'- bipyridyl, 1,10- phenanthroline, ethylenediamine tetra-acetic acid or a variety of；Above-mentioned decorative layer can
Regulate and control the film forming of perovskite, so that the crystal morphology of perovskite improves, improves perovskite thin film fluorescence intensity and electrochemistry
Energy；The photovoltaic property of the perovskite solar cell device with interface-modifying layer further prepared simultaneously is relatively free of decorative layer
Perovskite solar cell device significantly improve, have biggish application prospect.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method of regulation calcium titanium ore bed crystal growth, which is characterized in that prepare decorative layer in anodic interface layer surface, so
Calcium titanium ore bed is prepared in modification layer surface afterwards；The decorative layer is 2,2'- bipyridyl, 4,4'- bipyridyl, 1,10- phenanthroline, second
One of ethylenediamine tetraacetic acid (EDTA) is a variety of.
2. the method according to claim 1, wherein decorative layer solution is spin-coated on sun under protective atmosphere
On the boundary layer of pole, decorative layer is made；Calcium titanium ore bed is made in the spin coating perovskite solution on decorative layer again.
3. method according to claim 1 or 2, which is characterized in that the perovskite structure of the calcium titanium ore bed is ABX3,
It is characterized in that, any one of A Pb, Sn or two kinds, any one of B MA, FA, Cs or two kinds, X ClpBrqI3-p-q,
P, the value range of q is 0~3.
4. according to right want 1 or 2 described in method, which is characterized in that the anode interface layer be NiOx layers.
5. any the method for Claims 1 to 4 is preparing the application in perovskite solar cell device.
6. a kind of perovskite solar cell device, which is characterized in that including conductive glass electrode, the anode being cascading
Boundary layer, decorative layer, calcium titanium ore bed, electron transfer layer and metal electrode；The decorative layer is 2,2'- bipyridyl, 4,4'- connection pyrrole
One of pyridine, 1,10- phenanthroline, ethylenediamine tetra-acetic acid are a variety of.
7. perovskite solar cell device according to claim 6, which is characterized in that in electron transfer layer and metal electricity
It also include metal electrode decorative layer between the layer of pole, the metal electrode decorative layer is ZrAcac.
8. perovskite solar cell device according to claim 6, which is characterized in that the conductive glass electrode is
ITO, FTO or AZO.
9. perovskite solar cell device according to claim 6, which is characterized in that the electron transfer layer is
PCBM。
10. the preparation method of perovskite solar cell device as claimed in claim 7, which comprises the steps of:
S1. anode interface layer is prepared on the substrate of transparent conductive substrate；S2. decorative layer is prepared in anode interface layer；S3. it is modifying
Calcium titanium ore bed is prepared on layer；S4. electron transfer layer S5. is prepared on calcium titanium ore bed prepare metal electrode on the electron transport layer repair
Adorn layer；S6. evaporation metal electrode obtains the perovskite solar energy with interface-modifying layer as back electrode on electrode modification layer
Battery device.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403596A (en) * | 2020-03-20 | 2020-07-10 | 电子科技大学 | Surface treatment method for stripping single crystal film by ion implantation |
| CN111525038A (en) * | 2020-04-30 | 2020-08-11 | 陕西师范大学 | Perovskite solar cell doped with multifunctional additive and preparation method thereof |
| CN112864329A (en) * | 2021-01-08 | 2021-05-28 | 苏州大学张家港工业技术研究院 | Perovskite solar cell and preparation method thereof |
| CN114394968A (en) * | 2022-03-25 | 2022-04-26 | 中国长江三峡集团有限公司 | Conjugated organic ionic salt, preparation method and application in perovskite solar cell |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105244449A (en) * | 2015-09-13 | 2016-01-13 | 北京化工大学 | Perovskite type solar cell |
| CN106159095A (en) * | 2016-09-21 | 2016-11-23 | 深圳市先进清洁电力技术研究有限公司 | The preparation method of a kind of perovskite solaode and perovskite solaode |
| CN107104189A (en) * | 2016-02-23 | 2017-08-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | perovskite thin film solar cell and preparation method thereof |
| EP3333170A1 (en) * | 2016-12-06 | 2018-06-13 | Merck Patent GmbH | Asymmetrical polycyclic compounds for use in organic semiconductors |
| CN108258133A (en) * | 2018-01-22 | 2018-07-06 | 苏州大学 | perovskite light emitting diode and preparation method thereof |
| JP2018190928A (en) * | 2017-05-11 | 2018-11-29 | 国立研究開発法人物質・材料研究機構 | Perovskite solar battery and manufacturing method therefor |
| US20180358571A1 (en) * | 2015-06-25 | 2018-12-13 | Global Frontier Center For Multiscale Energy Syste | Perovskite-based solar cell using graphene as conductive transparent electrode |
-
2019
- 2019-04-17 CN CN201910309877.1A patent/CN110112301A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180358571A1 (en) * | 2015-06-25 | 2018-12-13 | Global Frontier Center For Multiscale Energy Syste | Perovskite-based solar cell using graphene as conductive transparent electrode |
| CN105244449A (en) * | 2015-09-13 | 2016-01-13 | 北京化工大学 | Perovskite type solar cell |
| CN107104189A (en) * | 2016-02-23 | 2017-08-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | perovskite thin film solar cell and preparation method thereof |
| CN106159095A (en) * | 2016-09-21 | 2016-11-23 | 深圳市先进清洁电力技术研究有限公司 | The preparation method of a kind of perovskite solaode and perovskite solaode |
| EP3333170A1 (en) * | 2016-12-06 | 2018-06-13 | Merck Patent GmbH | Asymmetrical polycyclic compounds for use in organic semiconductors |
| JP2018190928A (en) * | 2017-05-11 | 2018-11-29 | 国立研究開発法人物質・材料研究機構 | Perovskite solar battery and manufacturing method therefor |
| CN108258133A (en) * | 2018-01-22 | 2018-07-06 | 苏州大学 | perovskite light emitting diode and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| O.YU.GORBENKO等: "Crystal structure of copper(II) pivaloyltrifluoracetonate adducts with o-phenanthroline and 2,2′-dipyridyl", 《POLYHEDRON》 * |
| 张婧 等: "钙钛矿太阳能电池中小分子空穴传输材料的研究进展", 《物理化学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403596A (en) * | 2020-03-20 | 2020-07-10 | 电子科技大学 | Surface treatment method for stripping single crystal film by ion implantation |
| CN111403596B (en) * | 2020-03-20 | 2022-07-26 | 电子科技大学 | Surface treatment method for stripping single crystal film by ion implantation |
| CN111525038A (en) * | 2020-04-30 | 2020-08-11 | 陕西师范大学 | Perovskite solar cell doped with multifunctional additive and preparation method thereof |
| CN111525038B (en) * | 2020-04-30 | 2023-07-25 | 陕西师范大学 | Perovskite solar cell doped with multifunctional additive and preparation method thereof |
| CN112864329A (en) * | 2021-01-08 | 2021-05-28 | 苏州大学张家港工业技术研究院 | Perovskite solar cell and preparation method thereof |
| CN112864329B (en) * | 2021-01-08 | 2023-10-20 | 苏州大学张家港工业技术研究院 | Perovskite solar cell and preparation method thereof |
| CN114394968A (en) * | 2022-03-25 | 2022-04-26 | 中国长江三峡集团有限公司 | Conjugated organic ionic salt, preparation method and application in perovskite solar cell |
| CN114394968B (en) * | 2022-03-25 | 2022-06-21 | 中国长江三峡集团有限公司 | Conjugated organic ionic salt, preparation method and application in perovskite solar cell |
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