CN111138440B - Preparation and application of organic hole transport material with triptycene-tripeptizine as core - Google Patents
Preparation and application of organic hole transport material with triptycene-tripeptizine as core Download PDFInfo
- Publication number
- CN111138440B CN111138440B CN202010008496.2A CN202010008496A CN111138440B CN 111138440 B CN111138440 B CN 111138440B CN 202010008496 A CN202010008496 A CN 202010008496A CN 111138440 B CN111138440 B CN 111138440B
- Authority
- CN
- China
- Prior art keywords
- hole transport
- transport material
- triptycene
- reaction
- ometpa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 73
- 230000005525 hole transport Effects 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 claims abstract description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- -1 (4-methoxyphenyl) aminobenzoyl Chemical group 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- ZJPTYHDCQPDNBH-UHFFFAOYSA-N 4-methoxy-n-(4-methoxyphenyl)-n-phenylaniline Chemical compound C1=CC(OC)=CC=C1N(C=1C=CC(OC)=CC=1)C1=CC=CC=C1 ZJPTYHDCQPDNBH-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 5
- 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 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- UUIMDJFBHNDZOW-UHFFFAOYSA-N 2-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC=N1 UUIMDJFBHNDZOW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/14—Ortho-condensed systems
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses preparation and application of a novel organic hole transport material taking triptycene and tripeptidine as cores, and belongs to the field of perovskite solar cell application. The hole transport material disclosed by the invention is simple in synthetic route, low in cost, good in solubility, easy to purify and good in stability, and can be used as the hole transport material to be applied to a planar perovskite solar cell. The planar perovskite solar cell prepared from the organic hole transport material taking triptycene and tripeptidine as cores, which is designed by the invention, has high photoelectric conversion efficiency and good stability. The organic hole transport material taking triptycene and tripeptidine as the core provides a new design idea for the hole transport material of the planar perovskite solar cell.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric functional materials, and particularly relates to an organic hole transport material taking triptycene and tripeptidyl pyrazine as a core, a preparation method thereof, and application thereof in a planar perovskite solar cell.
Background
Perovskite solar cells have been subject to dramatic development over the past decade, and laboratory photoelectric conversion efficiency records have exceeded 25% (www.nrel.gov/pv/cell-efficiency. The perovskite solar cell as a novel solar power generation technology brings new hopes for technical innovation of the photovoltaic industry, and has wide application prospects. As an important component in the perovskite solar cell, the performance of a Hole Transport Material (HTM) has an important influence on the photoelectric conversion efficiency and stability of the cell, and the development, design and preparation of a hole transport layer material with simple structure and excellent performance is one of the important research points in the research field of the perovskite solar cell, and has a very important significance in promoting the industrialization process of the perovskite solar cell.
At present, the reported hole transport materials applied to planar perovskite solar cells and obtaining higher photoelectric conversion efficiency are mostly two materials of polymer hole transport material PTAA (poly [ bis (4-phenyl) (2, 4, 6- (trimethylphenyl) amine ]) and organic small molecule hole transport material Spiro-OMeTAD (2, 2 ', 7, 7 ' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9 ' -spirobifluorene), however, PTAA and Spiro-OMeTAD have poor conductivity and low hole mobility, and need to use P-type dopants and additives, such as tert-butylpyridine (TBP), lithium bistrifluoromethaneimide (LiTFSI) and the like, to improve the conductivity of the hole transport layer, however, the use of these dopants and additives can reduce the stability of the cell on one hand, on the other hand, the manufacturing cost of the battery is increased. In addition, the synthesis and purification process of the Spiro-OMeTAD is complex, and the manufacturing cost of the battery is further increased. Therefore, the hole transport material which is simple in design, development and preparation, easy to purify, good in film forming property, excellent in performance and high in stability has very important significance for the commercial application of the perovskite solar cell.
Disclosure of Invention
The invention constructs a novel organic hole transport material by molecular design, taking triptycene and tripeptidine as cores and introducing arylamine substituent groups. The material has the advantages of molecular energy level matched with that of a perovskite material, good solubility and high stability, and can be used as a hole transport material to be applied to a planar perovskite solar cell. The hole transport material TT-OMeTPA can be applied to the preparation of perovskite solar cells under the condition of not using dopants and additives, the higher photoelectric conversion efficiency is obtained, the stability of the cells is improved, the manufacturing cost is reduced, and the hole transport material TT-OMeTPA has potential application value.
The invention also aims to provide a preparation method of the organic hole transport material taking triptycene and tripeptidine as cores, which has the advantages of simple preparation operation process, mild reaction conditions and simple purification process, avoids the noble metal catalytic coupling reaction required in the synthesis of most hole transport materials, reduces the manufacturing cost and has higher application value.
The invention provides an organic hole transport material taking triptycene and tripeptidine as cores, which has a chemical structural formula (I):
the synthesis method of the organic hole transport material TT-OMeTPA taking triptycene and tripeptidine as cores comprises the following steps: carrying out nitration reaction on triptycene in a mixed solution of fuming nitric acid and concentrated sulfuric acid to obtain hexanitrotriptycene; reducing the mixed solution of ethanol and concentrated acid salt of stannous chloride to generate a compound hexaamino triptycene hydrochloride; then the target organic hole transport material TT-OMeTPA is generated by condensation reaction with 4-di (4-methoxyphenyl) aminobenzoyl.
(1) According to a reference method (J.Org.chem.2011, 76, 6389-6393), concentrated sulfuric acid is dropwise added into fuming nitric acid solution of an ice salt bath, then a compound triptycene is added in batches, after the reaction is finished, the ice salt bath is kept for 30min, then the temperature is slowly raised to 85 ℃, the reaction is carried out for 24h, after the reaction is finished, the reaction is cooled to room temperature, a large amount of water is added, the reaction is washed to be neutral, then a large amount of white powder is precipitated, then the reaction is carried out by suction filtration, and the obtained solid is dried and recrystallized to obtain the compound hexanitrotriptycene. Adding hexanitrotriptycene into a mixed solution of ethanol of stannous chloride and concentrated acid salt, uniformly stirring under the protection of nitrogen at room temperature, heating to 85 ℃, reacting for 24 hours, cooling to room temperature after the reaction is finished, separating out solid, filtering the separated out solid, and freeze-drying to obtain hexanitrotriptycene hydrochloride.
(2) Adding aluminum trichloride into ice-bath anhydrous dichloromethane, continuously stirring, dropwise adding a dichloromethane solution of N, N-bis (4-methoxyphenyl) aniline into the mixed solution, finally dropwise adding oxalyl chloride into the mixed solution, reacting at room temperature overnight, after the reaction is finished, spin-drying the mixed solvent, adding water into the residue, extracting dichloromethane, washing with saturated saline solution, collecting an organic phase, adding anhydrous sodium sulfate, drying, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain 4-bis (4-methoxyphenyl) aminobenzoyl.
(3) Adding the intermediate hexa-amino triptycene hydrochloride and 4-bis (4-methoxyphenyl) aminobenzoyl into a mixed solution of ethanol and glacial acetic acid, uniformly stirring under the protection of nitrogen at room temperature, heating, and reacting overnight. And cooling to room temperature after the reaction is finished. And (2) drying the mixed solvent by spinning, adding water into the residue, extracting by using dichloromethane, washing by using saturated saline solution, collecting an organic phase, adding anhydrous sodium sulfate, drying, removing the organic solvent by reducing pressure, separating and purifying the obtained solid, and drying in vacuum to obtain the triptycene and tripeptidine-based organic hole transport material TT-OMeTPA.
The synthesis process comprises the following steps:
in the step (1), the volume ratio of fuming nitric acid to concentrated sulfuric acid is 4: 1, the reaction temperature is 85 ℃, and the reaction time is 24 hours; the volume ratio of the ethanol to the concentrated hydrochloric acid is 2: 1, the reaction temperature is 85 ℃, and the reaction time is 24 hours.
In the step (2), the molar ratio of oxalyl chloride to N, N-bis (4-methoxyphenyl) aniline to aluminum trichloride is 1: 2-4: 8, the reaction temperature is 0-30 ℃, and the reaction time is 8-20 hours.
In the step (3), the molar ratio of the intermediate hexaaminopteritrine hydrochloride to the 4-bis (4-methoxyphenyl) aminobenzoyl is 1: 4-6, the reaction temperature is 80-120 ℃, and the reaction time is 24-36 hours.
The organic hole transport material TT-OMeTPA taking triptycene and tripeptidine as the core prepared by the invention is applied to the perovskite solar cell as a hole transport layer, the planar perovskite solar cell is composed of a transparent conductive substrate, an electron transport layer, a perovskite absorption layer, a hole transport layer and a metal electrode, and the specific steps are as follows:
(1) cutting a transparent conductive substrate into a fixed size, carrying out etching treatment, carrying out ultrasonic cleaning on the etched conductive substrate in different solvents respectively, and then carrying out ultraviolet ozone treatment on the conductive substrate;
(2) spin-coating a precursor solution of the electron transport material on the treated transparent conductive substrate, and then annealing to obtain an electron transport layer;
(3) transferring the conductive substrate coated with the electron transport layer into a glove box, and spin-coating perovskite precursor liquid on the electron transport layer by a spin-coating method to form a perovskite absorption layer;
(4) preparing a hole transport layer from an arylamine organic hole transport material taking triptycene and tripeyrazine as cores by a spin coating method;
(5) and depositing a metal electrode on the hole transport layer by a vacuum evaporation method.
The transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or a flexible substrate;
The electron transport material solution is nano SnO2(the particle size is about 5nm) in water (the mass percentage concentration is about 2-5%);
the perovskite precursor liquid is prepared by the following steps: methylamine hydrobromide (CH)3NH3Br), formamidine hydroiodide (nhchh)3I) Lead bromide (PbBr)2) And lead iodide (PbI)2) Stirring at 50 ℃ to 1 ℃Obtaining a precursor solution of the perovskite material after 3 hours;
the hole transport material solution is prepared by dissolving 80mg of hole transport material in 1mL of chlorobenzene;
the metal electrode is one of gold and silver.
The invention has the following advantages:
the organic hole transport material designed by the invention adopts triptycene and tripezine as the core, has simple synthetic route, good solubility, easy purification and good stability, and can be used as a non-doped organic hole transport material to be applied to a planar perovskite solar cell. The planar perovskite solar cell prepared from the organic hole transport material taking triptycene and tripeptidine as cores has high photoelectric conversion efficiency and good device stability. The organic hole transport material TT-OMeTPA which is designed and developed by the invention and takes triptycene and tripeptidine as cores provides a new design idea for the organic hole transport material based on the planar perovskite solar cell.
Drawings
FIG. 1 shows the molecular structure of TT-OMeTPA, a hole transport material synthesized in example 1 of the present invention.
FIG. 2 shows the NMR spectrum of TT-OMeTPA, a hole transport material synthesized in inventive example 1.
FIG. 3 is a nuclear magnetic resonance carbon spectrum of a hole transport material TT-OMeTPA synthesized in example 1 of the present invention.
FIG. 4 is a chart showing an ultraviolet-visible absorption spectrum of a hole transporting material TT-OMeTPA synthesized in example 1 of the present invention. As can be seen, the hole transport material TT-OMeTPA has strong absorption in the ultraviolet region.
FIG. 5 is a thermogravimetric analysis Test (TGA) curve of the hole transport material TT-OMeTPA synthesized in example 1 of the present invention.
As can be seen, the hole transport material TT-OMeTPA has a decomposition temperature of 400 ℃, which indicates that the material has high thermal stability.
FIG. 6 is a Cyclic Voltammogram (CV) of TT-OMeTPA, a hole transport material synthesized in example 1 of the present invention. As can be seen from the figure, the hole transport material TT-OMeTPA has good oxidation reduction performance, and the HOMO energy level is calculated to be about 5.28 eV.
Fig. 7 is a J-V plot of a perovskite solar cell based on the hole transport material TT-ome tpa synthesized in example 1 of the present invention, with voltage on the abscissa and current density on the ordinate. The perovskite solar cell based on TT-OMeTPA obtains 18.83% of photoelectric conversion efficiency (current density (J) SC) Is 23.28mA/cm2Voltage (V)OC) 1.067V, Fill Factor (FF) 0.758).
FIG. 8 is a perovskite solar cell stability test chart based on the hole transport material TT-OMeTPA synthesized in example 1 of the present invention. The result shows that the planar perovskite solar cell based on the hole transport material TT-OMeTPA has better stability.
Detailed Description
Example 1:
the synthesis of hole transport material TT-OMeTPA and the application thereof in perovskite solar cells:
(1) the intermediates hexanitrotriptycene and hexaneaminotripterene hydrochloride can be prepared according to the literature (J.org.chem.2011, 76, 6389-6393).
(2) 1.1g (8.27mmol) of aluminum trichloride was added to anhydrous dichloromethane in an ice bath with continuous stirring, and thereafter a dichloromethane solution of 3.6g (12mmol) of N, N-bis (4-methoxyphenyl) aniline was added dropwise to the mixed solution, and finally 500mg (4.0mmol) of oxalyl chloride was added dropwise to the mixed solution, and reacted overnight at room temperature, after the reaction was completed, the mixed solvent was dried by spinning, water was added to the residue, dichloromethane was extracted, followed by washing with saturated brine, the organic phase was collected, after drying with anhydrous sodium sulfate, the organic solvent was removed under reduced pressure, and the resulting solid was isolated, purified, and dried under vacuum to obtain 1.6g (yield: 61.5%) of 4-bis (4-methoxyphenyl) aminobenzoyl. 1H NMR(CDCl3，600MHz)：δ7.72(d，J＝9.0Hz，4H)，7.10(d，J＝9.0Hz，8H)，6.87(d，J＝9.0Hz，8H)，6.78(d，J＝9.0Hz，4H)，3.80(s，12H).13C NMR(CDCl3，600MHz)：δ193.59，157.49，154.14，138.81，131.84，128.17，124.27，116.74，115.17，55.62.HR-MS：(ESI)m/z：C42H36N2O6Calculated value 664.2573; found 664.2560.
(3) Hexaaminotridetriptycene hydrochloride (25mg, 0.045mmol) and 4-bis (4-methoxyphenyl) aminobenzoyl (150mg, 0.225mmol) were dissolved in a mixed solvent of ethanol and glacial acetic acid, stirred uniformly at room temperature under nitrogen protection, then heated to reflux, and reacted overnight. After the reaction is finished, cooling to room temperature. After the solvent was dried by spinning, water was added to the residue, extraction was performed with dichloromethane, and then washing was performed with saturated brine, the organic phase was collected, dried with anhydrous sodium sulfate, the organic solvent was removed under reduced pressure, and the obtained solid was separated, purified, and dried under vacuum to obtain an organic hole transport material TT-omtpa centered on triptycene-tripeptidine, 64mg (yield: 65%).1H NMR(CDCl3，600MHz)：δ8.14(s，6H)，7.32(d，J＝9.0Hz，12H)，7.06(d，J＝8.4Hz，24H)，6.82-6.84(m，36H)，5.98(s，2H)，3.79(s，36H).13C NMR(CDCl3，400MHz)：δ156.27，153.09，149.32，143.65，140.55，140.23，130.84，130.68，127.11，123.55，119.30，114.83，55.61.HR-MS：(ESI)m/z：C146H116N12O12，Calculated value 2228.8836; found 2228.8818.
The hole transport material TT-OMeTPA synthesized by the method is applied to the perovskite solar cell, and the preparation process comprises the following steps:
ITO (indium tin oxide) conductive glass having a size of 20mm × 15mm was used as a transparent conductive electrode, and etching was performed chemically using zinc powder and hydrochloric acid. And washing the etched conductive glass by using a detergent, sequentially carrying out ultrasonic cleaning for 15min by using deionized water, acetone and ethanol, and then treating for 10min in an ultraviolet ozone machine. Nano SnO at normal temperature 2The aqueous dispersion (particle size about 5nm, mass percent concentration about 2.67%) was spin-coated onto an ITO conductive glass substrate at a speed of 3000rpm for 30 seconds, and then at 150 deg.CAnnealing for 30min to form an electron transport layer; 0.05mmol of methylamine hydrobromide (CH)3NH3Br), 0.95mmol formamidine hydroiodide (NHCHNH)3I) 0.05mmol of lead bromide (PbBr)2) And 0.95mmol of lead iodide (PbI)2) Dissolving in 1mL of dimethyl sulfoxide, and stirring at 50 ℃ for 2h to prepare a perovskite material precursor solution. 50 μ L of the perovskite precursor solution was spin-coated on the electron transport material thin film at room temperature with the rotation speed controlled to 1000rpm for 10s, followed by the rotation speed controlled to 4000rpm for 30s, during which 200 μ L of chlorobenzene was dropped on the film, and the perovskite thin film was annealed and calcined at 100 ℃ for 30 min. After cooling to room temperature, a hole transport material solution (80mg TT-OMeTPA dissolved in 1mL chlorobenzene) was spin-coated onto the surface of the perovskite layer at a rotation speed of 3000rpm for a spin-coating time of 30s, and sintered at 70 ℃ for 5 min. The device was then transferred to a vacuum evaporation chamber, the cell area was set to 5mm x 5mm using a reticle, and about 100nm of Au was deposited onto the device film by vacuum evaporation.
Claims (8)
1. An organic hole transport material with triptyceno-pyrazine as a core, which is characterized by having a chemical structural formula of formula (I):
2. the preparation method of the triptycene-tripeptidyl pyrazine-based organic hole transport material TT-OMeTPA as claimed in claim 1, characterized by comprising the following steps:
(1) preparing intermediate hexanitrotriptycene and hexaamino triptycene hydrochloride; dropwise adding concentrated sulfuric acid into fuming nitric acid solution of an ice salt bath, then adding a compound triptycene in batches, after the reaction is finished, maintaining the ice salt bath for 30min, slowly heating to 85 ℃, reacting for 24h, after the reaction is finished, cooling to room temperature, adding a large amount of water, washing to be neutral, separating out a large amount of white powder, then performing suction filtration, drying the obtained solid, and recrystallizing to obtain a compound hexanitrotriptycene; adding hexanitrotriptycene into a mixed solution of ethanol of stannous chloride and concentrated acid salt, uniformly stirring under the protection of nitrogen at room temperature, heating to 85 ℃, reacting for 24 hours, cooling to room temperature after the reaction is finished, separating out solid, carrying out suction filtration on the separated out solid, and freeze-drying to obtain hexanitrotriptycene hydrochloride;
(2) preparation of 4-bis (4-methoxyphenyl) aminobenzoyl: adding aluminum trichloride into ice-bath anhydrous dichloromethane, continuously stirring, dropwise adding a dichloromethane solution of N, N-bis (4-methoxyphenyl) aniline into the mixed solution, finally dropwise adding oxalyl chloride into the mixed solution, reacting at room temperature overnight, after the reaction is finished, spin-drying the solvent, adding water into the residue, extracting dichloromethane, washing with saturated saline solution, collecting an organic phase, adding anhydrous sodium sulfate, drying, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain 4-bis (4-methoxyphenyl) aminobenzoyl;
(3) Dissolving hexaamino triptycene hydrochloride in a mixed solution of glacial acetic acid and ethanol, adding 4-bis (4-methoxyphenyl) aminobenzoyl, uniformly stirring at room temperature under the protection of nitrogen, heating, and reacting overnight; cooling to room temperature after the reaction is finished; and (2) after the solvent is mixed by spinning, adding water into the reaction solution, extracting by dichloromethane, washing by saturated saline solution, collecting an organic phase, adding anhydrous sodium sulfate, drying, removing the organic solvent by decompression, separating and purifying the obtained solid, and drying in vacuum to obtain the triptycene-tripeptidine core organic hole transport material TT-OMeTPA.
3. The preparation method of the triptycene-tripeptidyl pyrazine-based organic hole transport material TT-OMeTPA as claimed in claim 2, characterized in that the synthesis method comprises the following steps: in the step (1), the volume ratio of fuming nitric acid to concentrated sulfuric acid is 4: 1, the reaction temperature is 85 ℃, and the reaction time is 24 hours; the molar ratio of the hexanitrotriptycene to the stannous chloride is 1: 40, the volume ratio of the ethanol to the concentrated hydrochloric acid is 2: 1, the reaction temperature is 85 ℃, and the reaction time is 24 hours.
4. The method for preparing the triptycene-tripeptidine-based organic hole transport material TT-OMeTPA as claimed in claim 2, wherein the synthesis method comprises the following steps: in the step (2), the molar ratio of oxalyl chloride to N, N-bis (4-methoxyphenyl) aniline to aluminum trichloride is 1: 2-4: 2, the reaction temperature is 0-30 ℃, and the reaction time is 8-20 hours.
5. The preparation method of the arylamine organic hole transport material TT-OMeTPA taking triptycene and tripeptidine as the core as claimed in claim 2, wherein the synthesis method comprises the following steps: in the step (3), the molar ratio of hexa-amino triptycene hydrochloride to 4-bis (4-methoxyphenyl) aminobenzoyl is 1: 4-6, the reaction temperature is 80-120 ℃, and the reaction time is 24-36 hours.
6. Use of the triptycene-triazine-based organic hole transport material as claimed in claim 1 as a hole transport layer in planar perovskite solar cells.
7. The application of claim 6, wherein the planar perovskite solar cell is composed of a transparent conductive substrate, an electron transport layer, a perovskite absorption layer, a hole transport layer and a metal electrode, and the preparation steps are as follows:
(1) cutting a transparent conductive substrate into a fixed size, carrying out etching treatment, respectively carrying out ultrasonic cleaning on the etched conductive substrate in different solvents, and then carrying out ultraviolet ozone treatment on the substrate;
(2) performing spin coating on the precursor of the electron transport material on the treated transparent conductive substrate, and then performing annealing treatment to obtain an electron transport layer;
(3) The conductive substrate coated with the electron transmission layer is moved into a glove box, and the perovskite precursor liquid is coated on the electron transmission layer in a rotary coating manner to form a perovskite absorption layer;
(4) preparing an organic hole transport material TT-OMeTPA taking triptycene and tripeptidine as cores into a hole transport layer by a solution spin-coating method;
(5) and depositing a metal electrode on the hole transport layer by a vacuum evaporation method.
8. The use according to claim 7,
(1) the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or a flexible substrate;
(2) the electron transport material precursor is nano SnO2The mass percentage concentration of the dispersion liquid in water is 2-5 percent;
(3) the perovskite precursor liquid is prepared by the following steps: methylamine hydrobromide (CH)3NH3Br), formamidine hydroiodide (nhchh)3I) Lead bromide (PbBr)2) And lead iodide (PbI)2) Mixing and dissolving the materials in dimethyl sulfoxide according to a certain molar ratio, and stirring the mixture for 1 to 3 hours at the temperature of 50 ℃ to obtain a precursor solution of the perovskite material;
(4) the hole transport material solution is prepared by dissolving 80mg of hole transport material in 1mL of chlorobenzene;
(5) the metal electrode is one of gold and silver.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010008496.2A CN111138440B (en) | 2020-01-03 | 2020-01-03 | Preparation and application of organic hole transport material with triptycene-tripeptizine as core |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010008496.2A CN111138440B (en) | 2020-01-03 | 2020-01-03 | Preparation and application of organic hole transport material with triptycene-tripeptizine as core |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111138440A CN111138440A (en) | 2020-05-12 |
| CN111138440B true CN111138440B (en) | 2022-05-24 |
Family
ID=70523668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010008496.2A Expired - Fee Related CN111138440B (en) | 2020-01-03 | 2020-01-03 | Preparation and application of organic hole transport material with triptycene-tripeptizine as core |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111138440B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194630A (en) * | 2020-10-30 | 2021-01-08 | 南京林业大学 | Preparation and application of organic hole transport material with imidazole derivative as core |
| CN116478164B (en) * | 2022-01-14 | 2024-03-19 | 南京林业大学 | Preparation and application of arylamine hole transport material with benzo-bipyrazine as core |
| CN115819365A (en) * | 2022-07-29 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Organic compound, solar cell and preparation method thereof |
| CN116120328B (en) * | 2023-04-07 | 2023-06-20 | 季华实验室 | Triptycene compound, preparation method thereof and light-emitting device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108659019A (en) * | 2017-04-01 | 2018-10-16 | 南京理工大学 | Perovskite hole mobile material and preparation method thereof based on triptycene parent nucleus |
-
2020
- 2020-01-03 CN CN202010008496.2A patent/CN111138440B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108659019A (en) * | 2017-04-01 | 2018-10-16 | 南京理工大学 | Perovskite hole mobile material and preparation method thereof based on triptycene parent nucleus |
Non-Patent Citations (4)
| Title |
|---|
| Homoconjugation enhances the photophysical and electrochemical properties of a new 3D intramolecular charge transfer iptycene displaying deep blue emission;Stephanie Montanaro,等;《Journal of Materials Chemistry C: Materials for Optical and Electronic Devices》;20190909;第7卷(第41期);12886-12890 * |
| Robust MOFs of tsg Topology Based on Trigonal Prismatic Organic and Metal Cluster SBUs: Single Crystal to Single Crystal Postsynthetic Metal Exchange and Selective CO2 Capture;Pujari Chandrasekhar，等;《Chemistry - A European Journal》;20171231;第23卷(第30期);7297-7305 * |
| Soluble Tetraaminotriptycene Precursors;Nicholas G. White，等;《J. Org. Chem.》;20150804;第80卷(第16期);8390-8397 * |
| 一类基于三蝶烯骨架的电池受体材料;刘晓凤，等;《山东化工》;20181231;第47卷(第24期);3-5 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111138440A (en) | 2020-05-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111138440B (en) | Preparation and application of organic hole transport material with triptycene-tripeptizine as core | |
| CN111909169B (en) | Hole transport material with benzodithiophene dione as core, synthesis method and application of hole transport material in perovskite solar cell | |
| CN109265410B (en) | Hole transport material with phenoxazine as core structure and synthesis method and application thereof | |
| CN111533757B (en) | Dithienobenzimidazole-based undoped hole transport material, preparation method thereof and application thereof in perovskite solar cell | |
| CN104031245B (en) | A kind of Polymer photovoltaic materials, preparation method and its usage | |
| CN106876589A (en) | The perovskite solar cell of novel hole transport layer material and its composition | |
| CN110343119B (en) | Non-doped hole transport material containing benzothiadiazole unit, and preparation and application thereof | |
| CN114276353B (en) | Synthetic method and application of hole transport material with polyfluoro-substituted pyrrole- [3,2-b ] pyrrole as core | |
| CN114181229B (en) | Organic micromolecular photovoltaic material based on benzopyrazine donor cores, and preparation method and application thereof | |
| CN110148672B (en) | Hole transport material, preparation method and application thereof, and perovskite solar cell comprising hole transport material | |
| CN109336852B (en) | Non-fullerene electron transport material and synthetic method and application thereof | |
| CN109851571B (en) | Conjugated organic small molecule interface modification material, preparation method and organic solar cell formed by conjugated organic small molecule interface modification material | |
| CN110128399B (en) | Organic molecular material based on dibenzo five-membered aromatic heterocycle, synthetic method thereof and application of organic molecular material as hole transport layer | |
| CN115746059A (en) | Imide molybdenum-oxygen cluster organic-inorganic hybrid material and preparation method and application thereof | |
| CN115472749A (en) | Perovskite solar cell based on modification of bisfluorenylidene quinoid thiophene derivative | |
| CN110845503B (en) | Preparation and application of arylamine substituted benzodiindole organic hole transport material | |
| CN112194630A (en) | Preparation and application of organic hole transport material with imidazole derivative as core | |
| CN116478164B (en) | Preparation and application of arylamine hole transport material with benzo-bipyrazine as core | |
| CN110204545B (en) | Organic photovoltaic material based on perylene bisimide and preparation method and application thereof | |
| CN112646130B (en) | N-type water/alcohol-soluble conjugated polyelectrolyte based on double free radical benzobisthiadiazole, and preparation and application thereof | |
| CN111454262B (en) | Cathode interface modification layer material and perovskite solar cell | |
| CN109096163B (en) | Organic molecular material, synthesis method thereof and application of organic molecular material as hole transport layer | |
| CN109651197B (en) | Phthalocyanin derivative, preparation method thereof, metal phthalocyanine derivative, preparation method and application thereof | |
| CN115873016B (en) | Condensed ring organic small molecule and preparation method and application thereof | |
| CN111349104B (en) | Organic small-molecule semiconductor material containing rhodanine fused isatin and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220524 |