CN106518691B - Synthesis and application of triphenylamine derivative as modification material in perovskite solar cell - Google Patents
Synthesis and application of triphenylamine derivative as modification material in perovskite solar cell Download PDFInfo
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- CN106518691B CN106518691B CN201610956969.5A CN201610956969A CN106518691B CN 106518691 B CN106518691 B CN 106518691B CN 201610956969 A CN201610956969 A CN 201610956969A CN 106518691 B CN106518691 B CN 106518691B
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- 239000000463 material Substances 0.000 title claims abstract description 14
- 125000006617 triphenylamine group Chemical group 0.000 title claims description 10
- 238000012986 modification Methods 0.000 title abstract description 5
- 230000004048 modification Effects 0.000 title abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000010189 synthetic method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 238000004528 spin coating Methods 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 150000001651 triphenylamine derivatives Chemical class 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical class OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- SRGBSEMMGLSUMI-UHFFFAOYSA-N BrCCOc(cc1)ccc1Br Chemical compound BrCCOc(cc1)ccc1Br SRGBSEMMGLSUMI-UHFFFAOYSA-N 0.000 description 1
- CDLTYSHLBNEMHL-UHFFFAOYSA-N C(C)O.C(=O)(OC(C)(C)C)OC(=O)OC(C)(C)C Chemical compound C(C)O.C(=O)(OC(C)(C)C)OC(=O)OC(C)(C)C CDLTYSHLBNEMHL-UHFFFAOYSA-N 0.000 description 1
- VDCSLLPTWPVDAB-UHFFFAOYSA-N CC(C)(C)OC(NCCOc(cc1)ccc1N(c1ccccc1)c1ccccc1)=O Chemical compound CC(C)(C)OC(NCCOc(cc1)ccc1N(c1ccccc1)c1ccccc1)=O VDCSLLPTWPVDAB-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N Cc(cc1)ccc1O Chemical compound Cc(cc1)ccc1O IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WLLGXSLBOPFWQV-UHFFFAOYSA-N MGK 264 Chemical compound C1=CC2CC1C1C2C(=O)N(CC(CC)CCCC)C1=O WLLGXSLBOPFWQV-UHFFFAOYSA-N 0.000 description 1
- OZCHWBNRSSPBOA-UHFFFAOYSA-N NOc(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound NOc(cc1)ccc1N(c1ccccc1)c1ccccc1 OZCHWBNRSSPBOA-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 0 [*+]CCOc(cc1)ccc1N(c1ccccc1)c1ccccc1 Chemical compound [*+]CCOc(cc1)ccc1N(c1ccccc1)c1ccccc1 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
- 239000011149 active material Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000002027 dichloromethane extract Substances 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/92—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the nitrogen atom of at least one of the amino groups being further bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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- 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
- H10K30/451—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a metal-semiconductor-metal [m-s-m] structure
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- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- 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
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Abstract
The method is mainly used for designing and synthesizing triphenylamine derivatives, and the triphenylamine derivatives are used as a modification material to modify the interface of a perovskite/electron transmission layer in an inverted structure. The method specifically comprises the steps of spin-coating a layer of modification material on a perovskite film, utilizing the interaction of amino groups and I-ions in a molecular structure and inorganic Pd2+ in a perovskite layer to increase the stability of the perovskite layer, utilizing benzene rings and alkyl chain components in the molecular structure to improve interface compatibility, reducing surface defects, introducing dipole moment to regulate and control interface energy level, improving carrier injection efficiency and finally realizing the high-performance solar cell.
Description
Technical field
The present invention relates to the design of triphenylamine derivative chemical constitution, synthesis and as perovskite in perovskite solar cell
The application of layer decorative material.
Background technology
Currently, it is extremely urgent to substitute traditional energy with clean regenerative resource for energy and environment problem getting worse.It closes
Reason is to solve the problems, such as this effective means using solar energy.A kind of effective method for converting the solar into electric energy is to prepare
Solar cell based on photovoltaic effect.
Solar cell includes first generation crystal silicon solar energy battery (occupation rate of market 85%), second generation thin film solar
Battery and the third generation solar cell based on solution preparation process.The third generation solar cell efficiency does not surmount silicon substrate electricity
Pond, but it is a kind of in recent years swift and violent for the novel solar cell development of light active material with perovskite (perovskites).Based on having
Machine-inorganic hybridization perovskite material (CH3NH3PbX3) prepare perovskite solar cell (PSCs), realize in recent years
Rising violently for photoelectric conversion efficiency, 3.8% from 2009 rise to 20.2%.Perovskite solar cell, because its have compared with
The high absorption coefficient of light, relatively low cost, higher mobility and the advantages such as easily prepared, by international highest academic journal《Section
It learns》One of " ten big sciences are broken through within 2013 " is chosen as, has become one of research hotspot of novel solar battery at present.
Although perovskite solar cell current situation is good, but still there are several key factors to restrict perovskite solar-electricity
The development in pond：1) stability of battery is poor, and efficiency attenuation is serious in an atmosphere；2) contain soluble heavy metal Pb in absorbed layer,
Easily pollute the environment；3) theoretical research of perovskite solar cell is also to be reinforced.
Modifying interface passes through as the stability of perovskite solar cell, the important channel of electricity conversion is improved
Carrier blocking layers, electrode or calcium titanium ore bed are modified, the transmission and collection of charge can not only be enhanced, while improve interface and connect
Touch (Zhongmin Zhou, Shuping Pang, * Zhihong Liu, Hongxia Xu and Guanglei Cui*
J.Mater.Chem.A, 2015,3,19205-19217).
Triphenylamine and its derivative are a kind of important hole mobile materials, generally with relatively low HOMO energy levels and higher
Hole mobility, be widely used in the numerous areas such as organic semiconductor, Organic Light Emitting Diode, organic solar batteries.
This patent is mainly designed with synthesizing a kind of triphenylamine derivative, and as decorative material, in inverted structure
The interface of perovskite/electron transfer layer is modified.Specific method is by one layer of decorative material of spin coating in perovskite film, profit
With amido, the I in molecular structure-Ion and the inorganic Pd in calcium titanium ore bed2+Interaction increase the stabilization of calcium titanium ore bed
Property, improve interface compatibility using the phenyl ring in molecular structure and alkyl chain component, reduce surface defect, while introduce dipole moment
Regulate and control interface energy level, improve Carrier Injection Efficiency, finally realize high performance solar cells.
Invention content
1. the invention is characterized in that providing a kind of compound of triphenylamine derivative, structure is as follows：
Note：N=1-16
2. it is another feature that providing synthetic method is used for above-mentioned triphenylamine derivative.
3. another feature of the present invention is triphenylamine derivative answering in the modification of perovskite solar cell calcium titanium ore bed
With and characterization.
Description of the drawings
The above and other feature and advantage of the present invention will be more clearly understood that with reference to drawings described below and detailed description,
In：
Fig. 1 perovskite solar battery structure schematic diagrames；
Fig. 2 4- (2- ethamine oxygroup)-triphenylamine hydriodate nucleus magnetic hydrogen spectrum
Fig. 3 modifies the J with unmodified perovskite solar cell with triphenylamine derivativesc(mA/cm2)-Voc(V) curve
Scheme (VocRepresent open-circuit voltage, JscShort-circuit current density is represented, FF represents fill factor, and PCE represents photoelectric conversion efficiency).
Specific embodiment
The preferred implementation case of the present invention is described in detail below, so that advantages and features of the invention can be easier to
It is readily appreciated by one skilled in the art.Illustrate the chemical synthesis of material by taking n=2 as an example below.
Case study on implementation 1：
The synthesis of decorative material：
1. the preparation method of triphenylamine derivative hydriodate, reaction formula are as follows：
(1) 4- (2- bromine oxethyls)-bromobenzene
In 50ml two mouth flasks, add in 30ml water, 4- bromophenols (2.00g, 5.78mmol), sodium hydroxide (0.96g,
24.0mmol), 1,2- Bromofumes (5.0ml, 34.6mmol), back flow reaction 17h.After reaction three are extracted with dichloromethane
It is secondary, merge organic phase, add in appropriate anhydrous MgSO4, stand half an hour.It is filtered to remove MgSO4, rotary evaporation removing dichloromethane,
Chromatographic column separating-purifying (petroleum ether is leacheate), obtains white solid, yield 65%.1H NMR(300MHz；CDCl3)：δ
3.63 (t, 2H), 4.26 (t, 2H), 6.80 (d, 2H), 7.39 (d, 2H).
(2) 4- [(2- phthalimide-baseds)-ethyoxyl]-bromobenzene
In 100ml two mouth flasks, 40ml DMF, 4- (2- bromine oxethyls)-bromobenzene (9.48g, 47mmol), adjacent benzene are added in
Dicarboximide potassium (10.47g, 56mmol) reacts 2h at 90 DEG C.Revolving removes DMF after reaction, is then extracted with chloroform
Three times, merge organic phase, add in appropriate anhydrous MgSO4, stand half an hour.It is filtered to remove MgSO4, revolving removing chloroform, chromatographic column
Separating-purifying (dichloromethane is leacheate) obtains white solid, yield 85%.1H NMR (300MHz, CDCl3)：δ 4.08 (t,
2H), 4.18 (t, 2H), 6.74 (d, 2H), 7.31 (d, 2H), 7.71 (m, 2H), 7.85 (m, 2H).
(3) 4- [(2- t-butylcarbamates)-ethyoxyl]-bromobenzene
In 150ml two mouth flasks, 50ml methanol, 4- [(2- phthalimide-baseds)-ethyoxyl]-bromobenzene are added in
(2.89g, 10mmol), hydrazine hydrate (0.65ml, 11mmol), is heated to reflux 2h.After reaction, revolving removes methanol, then
With dichloromethane extraction three times, merge organic phase, remove solvent, obtain colourless oil liquid.At 0 DEG C, into colourless liquid
Add in 15ml ethyl alcohol and triethylamine (2.0ml, 15mmol), be added dropwise di-tert-butyl dicarbonate ethanol solution (2.6g, 12mmol,
It is dissolved in 15ml ethyl alcohol).After completion of dropwise addition, room temperature is warming up to, stirs 12h.After reaction, revolving removes solvent, uses dichloro
Methane extracts three times, merges organic phase, adds in appropriate anhydrous MgSO4, half an hour filtering is stood, revolving removes organic solvent.Layer
Post separation purification (ethyl acetate: petroleum ether=1: 6 be leacheate) is analysed, obtains white solid, yield 91%.1H NMR
(300MHz, CDCl3)：δ 1.45 (s, 9H), 3.51 (d, 2H), 3.98 (t, 2H), 6.77 (d, 2H), 7.37 (d, 2H).
(4) 4- [(2- t-butylcarbamates)-ethyoxyl]-triphenylamine
In 50ml two mouth flasks, 20ml dry toluenes, 4- [(2- t-butylcarbamates)-ethyoxyl]-bromine are added in
Benzene (2mmol, 630mg), diphenylamines (2mmol, 338mg) lead to nitrogen 15min, add in sodium tert-butoxide (5mmol, 480mg), vinegar
Sour palladium (0.06mmol, 13mg), tri-tert-butylphosphine (0.06mmol, 12mg) are heated to reflux 12h under nitrogen protection.Reaction terminates
Afterwards, with chloroform extraction three times, MgSO is used4It is dry, it is filtered after standing half an hour, revolving removes solvent.Chromatographic column separating-purifying (second
Acetoacetic ester: petroleum ether=1: 9 be leacheate), yield 41%.1H NMR (300MHz, CDCl3)：δ 1.46 (s, 9H), 3.53 (d,
2H), 4.01 (t, 2H), 6.83 (d, 2H), 6.95 (t, 2H), 7.05 (t, 6H), 7.21 (t, 4H).
(5) preparation of 4- (2- ethamine oxygroup)-triphenylamine hydriodate
In 25ml two mouth flasks, addition 4- [(2- t-butylcarbamates)-ethyoxyl]-triphenylamine (1mmol,
404mg), 10ml methanol, hydroiodic acid (1ml, 12mmol), stirring at normal temperature 12h.After reaction, rotary evaporation removes solvent.Add
Enter 10ml water, washed three times with chloroform.Merge inorganic phase, revolving removes water, obtains product 348mg, yield 81%.1H NMR
(300MHz, CD3OD)：δ 3.36 (t, 2H), 4.22 (t, 2H), 6.94 (m, 4H), 6.97 (m, 4H), 7.03 (m, 2H), 7.21
(t, 4H).
Case study on implementation 2：
The preparation and representation of solar cell：
(1) the ITO substrates for being cut into 1.5cm x 1.5cm are etched using the mixed liquor of dilute hydrochloric acid and zinc powder, is used after etching
Cotton balls is wiped, and is rinsed with water totally, and deionized water ultrasound 15 minutes is cleaned surface with acetone, dried up with nitrogen, shone in UV- ozone
It penetrates 20 minutes.
(2) add modification layer device ITO/PEDOT：PSS/perovskite/ decorative materials/PCBM/C60The system of/BCP/Al
It is standby：
First by PEDOT：PSS is spun on processed ITO substrates, is annealed 30 minutes under conditions of 120 DEG C；Then will
Lead iodide (the PbI of 1M2) solution is spun to ITO/PEDOT：On PSS, and then one layer of methylpyridinium iodide ammonium of spin coating at once immediately exists
It anneals 5 minutes or so under conditions of 100 DEG C；Following spin coating decorative material；Then the dichlorobenzene solution of the PCBM prepared is revolved
It is coated onto on perovskite, and places 10 minutes or more at normal temperatures；Finally by C60, BCP buffer layers and Al electrodes vapor deposition get on.
(3) preparation of normal component：
Method is with (1), (2), and the difference lies in no decorative layers.
(4) battery performance test：
Device is tested for the property using Keithley2400：Under the conditions of the sunlight irradiation of the AM 1.5G of simulation
(luminous intensity 100mW/cm2) photoelectric current-voltage curve can be obtained, scanning voltage range is reverse scan 1.2V → -1.2V, just
To scanning -1.2V → 1.2V, sweep speed 50mV/S.
One layer of decorative material of spin coating on calcium titanium ore bed, utilizes amido, the I in molecular structure-In ion and calcium titanium ore bed
The interaction of inorganic pd2+ increase the stability of calcium titanium ore bed, changed using the phenyl ring in molecular structure and alkyl chain component
Kind interface compatibility, reduces surface defect, while introduces dipole moment to regulate and control interface energy level, improves Carrier Injection Efficiency, carries
High current density and fill factor, efficiency are increased to 11.16% from 7.64%.
Claims (3)
1. the perovskite solar cell decorative material based on triphenylamine derivative, structure are as follows：
Wherein, n=1-16.
2. the synthetic method of triphenylamine derivative according to claim 1, wherein, n=2 includes the following steps：
3. application of the triphenylamine derivative in perovskite solar cell according to claim 1.
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| WO2015049031A1 (en) * | 2013-10-02 | 2015-04-09 | Merck Patent Gmbh | Hole transport material |
| CN105037179A (en) * | 2015-05-29 | 2015-11-11 | 中山大学 | Novel hole transport material, and preparation method and application thereof |
| CN105161622A (en) * | 2015-07-01 | 2015-12-16 | 中国华能集团清洁能源技术研究院有限公司 | Solar cell based on graphene transparent electrode |
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| WO2015049031A1 (en) * | 2013-10-02 | 2015-04-09 | Merck Patent Gmbh | Hole transport material |
| CN105037179A (en) * | 2015-05-29 | 2015-11-11 | 中山大学 | Novel hole transport material, and preparation method and application thereof |
| CN105161622A (en) * | 2015-07-01 | 2015-12-16 | 中国华能集团清洁能源技术研究院有限公司 | Solar cell based on graphene transparent electrode |
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