CN117603215A - Star-shaped porphyrin compound, preparation method and application thereof, and organic solar cell - Google Patents
Star-shaped porphyrin compound, preparation method and application thereof, and organic solar cell Download PDFInfo
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- CN117603215A CN117603215A CN202311393080.7A CN202311393080A CN117603215A CN 117603215 A CN117603215 A CN 117603215A CN 202311393080 A CN202311393080 A CN 202311393080A CN 117603215 A CN117603215 A CN 117603215A
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- -1 porphyrin compound Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical group 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 15
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000004032 porphyrins Chemical class 0.000 abstract description 35
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000004220 aggregation Methods 0.000 abstract description 7
- 230000021615 conjugation Effects 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 3
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 108020003175 receptors Proteins 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QNVKZKOSAXYVFZ-UHFFFAOYSA-N 2-(3-oxoinden-1-ylidene)propanedinitrile Chemical compound C1=CC=C2C(=O)CC(=C(C#N)C#N)C2=C1 QNVKZKOSAXYVFZ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 101150050192 PIGM gene Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229930002868 chlorophyll a Natural products 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 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
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 108020000597 porphyrin receptors Proteins 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C07D487/22—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 four or more hetero rings
-
- 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
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to the technical field of solar cells, and discloses a star porphyrin compound, a preparation method and application thereof, and an organic solar cell. The star porphyrin compound has a structure shown in a formula (I), wherein an electron-withdrawing unit in the compound forms a plane with porphyrin, and the plane interacts with pi electrons of an aromatic porphyrin ring to enhance conjugation and reduce self-aggregation in a film forming process. The self-aggregation property in the blend film can be improved and the photoelectric conversion efficiency can be improved by using the polymer as a receptor material in a solar cell.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a star porphyrin compound, a preparation method and application thereof, and an organic solar cell.
Background
Porphyrin molecules play a very important role in photosynthesis, respiration, etc. Porphyrin derivative chlorophyll a absorbs photons in plants and converts light energy into chemical energy through a charge transfer process. Porphyrin is a tetrapyrrole macrocyclic molecule whose core has 18 pi electron resonances, which give it a higher molar absorptivity. Although porphyrin has high structural stability under different temperature and pH conditions, the structure of porphyrin can be changed by adding substituent groups on the peripheral structure or adding metal ions in the center, so that the physical and chemical properties of porphyrin can be adjusted, and the physical and chemical properties can be used for an Organic Photovoltaic (OPV) solar cell.
The study of porphyrin-based organic solar cells has been a difficult task and porphyrin has been used as a donor and acceptor for organic solar cells at present, but conventional solar cells using porphyrin have not achieved satisfactory advantages. Through research, porphyrin molecules are easy to gather in the blend membrane, so that the photoelectric conversion efficiency is affected.
Gou et al (Guo Y, zhang A, li C, et al, A near-infrared porphyrin-based electron acceptor for non-fullerene organic solar cells [ J ]. Chinese Chemical Letters,2018,29 (3): 371-373.) report a star-shaped electron acceptor with porphyrin as the core, rhodamine-benzothiadiazole as the end group, and both linked by an ethynyl group. The porphyrin receptor is prepared by connecting four intermediate acetylene bridges surrounded by four Benzothiadiazole (BT) units as weak electron-withdrawing units with a rhodanine (Rh) end group to improve the energy efficiency of the organic solar cell. However, the efficiency of solar cell devices is not greatly improved due to the attachment of two different electron withdrawing groups to the porphyrin core, and the synthesis of such molecules is difficult.
Therefore, there is an urgent need to provide a novel porphyrin compound, which has a simple preparation method, has a single strong electron withdrawing group as a terminal group, has good solubility in an organic solar cell blend film, and has a very wide absorption band to improve the photoelectric conversion efficiency of an organic solar cell device.
Disclosure of Invention
The invention aims to overcome the defects of narrow ultraviolet-visible absorption and strong self-aggregation of a blending film in a photoelectric conversion device.
The invention takes porphyrin as a core and 2- (2, 3-dihydro-3-oxo-1H-indene-1-subunit) malononitrile (IC) as a terminal group, and a star-shaped electron acceptor is designed and synthesized through an acetylene bridge. In this structure, porphyrin is used as an electron donor unit, and an electron withdrawing group is connected through an acetylene bridge, so that Internal Charge Transfer (ICT) is realized. Because of the conjugation of the low energy end groups and the extension, a low energy level is created, so we link the thiophene group with 2- (2, 3-dihydro-3-oxo-1H-inden-1-ylidene) malononitrile (IC) via four ethylene bridges. The extended conjugation from porphyrin to electron withdrawing unit is beneficial to charge generation, and at the same time, the electron withdrawing unit forms a plane with porphyrin, interacts with pi electrons of aromatic porphyrin ring and enhances conjugation, and reduces energy band gap, thereby enhancing absorption band and reducing self-aggregation property in film forming process. Since porphyrin macromolecules and aromatic molecules are not easy to dissolve in organic solvents, the self-aggregation property can be reduced, the solubility can be improved, and the planeness of the molecules is not influenced by introducing thiophene groups with long alkyl chains into porphyrin molecules.
In order to achieve the above object, a first aspect of the present invention provides a star porphyrin compound having a structure represented by formula (I):
wherein in formula (I), R is C 5 -C 15 Is a hydrocarbon group.
Preferably, in formula (I), R is C 6 -C 10 Is a hydrocarbon group.
Preferably, R is 2-ethylhexyl.
In a second aspect, the present invention provides a process for preparing a star porphyrin compound represented by the formula (I), which comprises the steps of: in the presence of a protective atmosphere,
(1) In the presence of a solvent I, tetra (triphenylphosphine) palladium and CuI, carrying out first mixing on a compound shown in a formula (A) and a compound shown in a formula (B) to obtain a compound shown in a formula (C);
(2) In the presence of a solvent II, carrying out second mixing on the compound shown in the formula (C) and the compound shown in the formula (D) to obtain a star porphyrin compound shown in the formula (I);
wherein in the formulae (B), (C) and (I), R is correspondingly the same as the definition of the first aspect.
Preferably, in the step (1), the molar ratio of the compound shown in the formula (a) to the compound shown in the formula (B), tetrakis (triphenylphosphine) palladium and CuI is 1: (5-14): (0.1-0.3): (0.2-0.5).
Preferably, the molar ratio of the compound shown in the formula (A) to the compound shown in the formula (B), the tetrakis (triphenylphosphine) palladium and the CuI is 1: (11-14): (0.15-0.25): (0.3-0.4).
Preferably, in the step (1), the solvent I is at least one selected from a mixed solution of triethylamine and tetrahydrofuran, triethylamine, and diethylamine.
Preferably, the solvent I is a mixed solution of triethylamine and tetrahydrofuran, and the dosage volume ratio of the triethylamine to the tetrahydrofuran is 1:1-3.
Preferably, the solvent I is used in an amount of 250 to 350mL relative to 1mmol of the compound represented by the formula (A).
Preferably, in the step (2), the molar ratio of the compound represented by the formula (C) to the compound represented by the formula (D) is 1:5-7.
Preferably, in the step (2), the solvent II is a mixed solution of chloroform and pyridine, and the usage volume ratio of chloroform to pyridine is 20-30:1.
preferably, the protective atmosphere is at least one selected from nitrogen and argon.
Preferably, in step (1), the conditions of the first mixing at least satisfy: the temperature is 70-90 ℃ and the time is 48-72h.
Preferably, in step (2), the conditions of the second mixing at least satisfy: the temperature is 60-70 ℃ and the time is 12-24h.
A third aspect of the present invention provides the use of a star porphyrin compound according to the first aspect as acceptor material in the preparation of an organic solar cell.
A fourth aspect of the present invention provides an organic solar cell comprising a metal electrode layer as an anode, a hole transport layer, an active layer containing the star-shaped porphyrin compound of the first aspect, an electron transport layer, and an Indium Tin Oxide (ITO) layer as a transparent electrode.
The star-shaped porphyrin compound provided by the application is connected with large-size electron-rich electrons serving as a central core at a meso position of porphyrin, and porphyrin-based receptor molecules are synthesized in a non-planar geometry, so that favorable microstructures are formed in the blend membrane, and the self-aggregation property of the porphyrin is reduced. Porphyrin is connected with a thiophene group through ethynyl, and then the thiophene group is connected with 2- (2, 3-dihydro-3-oxo-1H-indene-1-subunit) malononitrile (IC) through vinyl, so that an electron withdrawing unit and porphyrin form a planar structure, and the electron withdrawing unit interacts with pi electrons of an aromatic porphyrin ring to enhance conjugation. Meanwhile, the introduction of thiophene units with branched alkyl groups into porphyrin molecules is beneficial to improving the solubility of large-size porphyrin structures in the blend membrane.
The star porphyrin compound provided by the application is used as an acceptor material in the preparation of the solar cell, can improve the photoelectric conversion efficiency and stability of the solar cell in the blend film, and is beneficial to commercialization of the solar cell.
Drawings
FIG. 1 is a MALDI-TOF-MS diagram of star porphyrin compound por-TIC.
FIG. 2 is a graph of ultraviolet-visible absorption spectra of star porphyrin compound por-TIC in chloroform and thin film.
FIG. 3 is an electrochemical pattern of star porphyrin compound por-TIC.
Fig. 4 is a schematic diagram of the device energy level in test example 3.
FIG. 5 is a J-V curve of PTB7-Th: pore-TIC based organic solar cell.
FIG. 6 is an EQE curve of an organic solar cell based on PTB7-Th: pore-TIC.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Term interpretation:
“C 5 -C 15 the "alkyl group" of (a) represents an alkyl group having 5 to 15 carbon atoms, and includes a straight-chain alkyl group and a branched-chain alkyl group; for example, a branched or straight-chain alkyl group having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 carbon atoms may be used, and for example, n-pentyl, n-hexyl, n-decyl, 2-ethylhexyl and the like may be used. For "C 6 -C 10 The "alkyl group" of (2) has a similar explanation to this except that the number of carbon atoms is different.
As described above, the first aspect of the present invention provides a star porphyrin compound having a structure represented by formula (I):
wherein in formula (I), R is C 5 -C 15 Is a hydrocarbon group.
Preferably, in formula (I), R is C 6 -C 10 Is a hydrocarbon group.
More preferably, R is 2-ethylhexyl. The inventors of the present invention found that in this preferred case, the obtained star porphyrin compound can better reduce its self-aggregation in the blend film.
As previously described, a second aspect of the present invention provides a process for preparing a star porphyrin compound represented by the formula (I), which comprises the steps of: in the presence of a protective atmosphere,
(1) In the presence of a solvent I, tetra (triphenylphosphine) palladium and CuI, carrying out first mixing on a compound shown in a formula (A) and a compound shown in a formula (B) to obtain a compound shown in a formula (C);
(2) In the presence of a solvent II, carrying out second mixing on the compound shown in the formula (C) and the compound shown in the formula (D) to obtain a star porphyrin compound shown in the formula (I);
wherein in the formulae (B), (C) and (I), R is correspondingly the same as the definition of the first aspect.
Preferably, the method further comprises: in the step (1), carrying out post-treatment on the materials obtained after the first mixing; in the step (2), the material obtained after the second mixing is subjected to post-treatment.
Preferably, the post-treatment comprises at least one of cooling, rotary evaporation, extraction, washing, filtration, drying, column chromatography. The specific modes of operation of the rotary distillation, extraction, washing, filtration, drying, column chromatography are not particularly limited, and may be carried out by those skilled in the art using methods known in the art, and those skilled in the art should not be construed as limiting the present invention.
Preferably, in the step (1), the molar ratio of the compound represented by the formula (a) to the compound represented by the formula (B), tetrakis (triphenylphosphine) palladium, cuI is 1: (5-14): (0.1-0.3): (0.2-0.5). More preferably, the molar ratio of the compound shown in the formula (A) to the compound shown in the formula (B), the tetrakis (triphenylphosphine) palladium and the CuI is 1: (11-14): (0.15-0.25): (0.3-0.4).
Preferably, the solvent I is used in an amount of 250 to 350mL relative to 1mmol of the compound represented by the formula (A).
Preferably, in the step (1), the solvent I is at least one selected from a mixed solution of triethylamine and tetrahydrofuran, triethylamine, and diethylamine. More preferably, the solvent I is a mixed solution of triethylamine and tetrahydrofuran, and the dosage volume ratio of the triethylamine to the tetrahydrofuran is 1:1-3.
Preferably, in the step (2), the molar ratio of the compound represented by the formula (C) to the compound represented by the formula (D) is 1:5-7.
Preferably, in the step (2), the solvent II is a mixed solution of chloroform and pyridine, and the usage volume ratio of chloroform to pyridine is 20-30:1.
preferably, the solvent II is used in an amount of 200 to 300mL relative to 1mmol of the compound represented by the formula (C).
Preferably, the protective atmosphere is at least one selected from nitrogen and argon. More preferably, the protective atmosphere is nitrogen.
According to a preferred embodiment, in step (1), the conditions of the first mixing at least satisfy: the temperature is 70-90 ℃ and the time is 48-72h.
According to another preferred embodiment, in step (2), the conditions of the second mixing at least satisfy: the temperature is 60-70 ℃ and the time is 12-24h.
The compound represented by the formula (a), the compound represented by the formula (B), and the compound represented by the formula (D) of the present invention may be purchased directly or prepared by methods known in the art, and those skilled in the art should not be construed as limiting the present invention.
As described above, the third aspect of the present invention provides the use of the star porphyrin compound described in the first aspect as a receptor material in the preparation of an organic solar cell.
As described above, the fourth aspect of the present invention provides an organic solar cell comprising a metal electrode layer as an anode, a hole transport layer, an active layer containing the star-shaped porphyrin compound of the first aspect, an electron transport layer, and an Indium Tin Oxide (ITO) layer as a transparent electrode.
Preferably, the material of the active layer contains the compounds PTB7-Th, optionally with additives.
Preferably, the additive is at least one of pyridine, 1, 8-diisooctane and 1-chloronaphthalene; the compound PTB7-Th has the following structure:
preferably, the thickness of the active layer is 50-100nm.
Preferably, the material of the metal electrode layer is an Ag electrode.
Preferably, the electron transport layer is a metal oxide layer selected from zinc oxide, snO 2 And TiO 2 At least one of them.
Preferably, the electron transport layer has a thickness of 10 to 100nm.
Preferably, the hole transport layer is made of MoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The thickness of the hole transport layer is 1-20nm.
The invention will be described in detail below by way of examples. In the following examples, the reagents used are commercially available products, and are not particularly limited unless otherwise specified. The water used in the examples below was deionized water, and room temperature was 25.+ -. 3 ℃.
Example 1
Star porphyrin Compounds Por-TIC, among Compound 2, compound 3, and Compound Por-TIC, -C were prepared according to the following synthetic route 2 H 5 Represents ethyl, -C 4 H 9 Represents n-butyl:
reference W.Yen, S.Lo, M.Kuo, C.Mai, G.Lee, S.Peng, and C.Yeh, org.Lett.,2006,8,4239-4242 prepared compound 1; reference Z.Tian, M.Huang, B.Zhao, H.Huang, X.Feng, Y.Nie, P.Shen, S.Tan, dyes pigm, 2010,87,181-187, prepares compound 2 or purchased directly.
At N 2 A mixed solution of Compound 1 (0.19 mmol), compound 2 (2.5 mmol), triethylamine (20 mL) and anhydrous tetrahydrofuran (40 mL) was deoxygenated under protection for 15 min, then under N 2 Pd (PPh 3) added downwards 4 (0.04 mmol) and CuI (0.07 mmol). At N 2 The solution was refluxed at 80 ℃ for 48 hours under protection. After cooling to room temperature, the mixture was extracted with diethyl ether and dried over anhydrous magnesium sulfate. The solvent was then evaporated on a rotary evaporator to give a solid residue which was purified by silica gel column chromatography to give compound 3 as a black solid (yield 65%).
1 HNMR(500MHZ,CDCl3)δ:10.2(s,4H),8.21-8.1(m,8H),7.57.2(m,4H),2.5(m,4H),2.1(m,8H),1.55(m,16H)1.32(m,16H),1.1-09(m,24H).
At N 2 Under protection, compound 3 (0.11 mmol) and compound 4 (0.68 mmol) were deoxygenated in 25mL of chloroform for 15 min, and 1mL of pyridine was added to the solution. At N 2 The solution was refluxed at 65 ℃ for 16 hours under protection. After cooling to room temperature, the solvent was evaporated on a rotary evaporator to give a solid residue, which was purified by silica gel column chromatography to give the dark solid star porphyrin compound por-TIC (55% as yield).
The star porphyrin compound was characterized by MALDI-TOF-MS, and the results are shown in FIG. 1, MALDI-TOF (m/z): calcd.for (C) 128 H 100 N 12 O 4 S 4 Zn):2063.91；Found,2063.909.。
Test example 1
The ultraviolet-visible absorption spectrum of the compound pro-TIC in chloroform solution and film was determined by the following method (as shown in fig. 2). A0.02 mg/mL solution of the por-TIC was prepared by adding 0.2mg of the por-TIC to 10mL of chloroform solution, and then UV-visible absorption was measured using an ultraviolet-visible spectrophotometer, with a wavelength set to 300nm-1200nm. Similarly, 1mg of the por-TIC solution was added to 100. Mu.L of the chloroform solution, and then a film was prepared using a spin coater, and the absorption of the film was measured.
The pore-TIC has absorption bands at 443-535nm, 585-655nm (soret band) and 758-829nm (Q band) in chloroform solution. The por-TIC film state showed strong absorption at 458-558nm, 580-642nm and 780-888nm, with an initial absorption wavelength of 1002nm, corresponding to an optical bandgap of 1.28ev. We note that the Q band shifts to the near infrared region, indicating the presence of Intramolecular Charge Transfer (ICT) between porphyrin and 2- (2, 3-dihydro-3-oxo-1H-inden-1-ylidene) malononitrile (IC).
Test example 2 electrochemical Performance
Electrochemical properties of the por-TIC were measured by cyclic voltammetry, and cyclic voltammetry curves are shown in fig. 3. The ferrocene/ferrocenium (Fc/Fc+) redox couple is used as an internal standard, the redox potential of the ferrocene/ferrocenium is 0.534eV, and the calculation formula of HOMO and LUMO energy levels is adopted: e (E) HOMO ＝-e[E ox +4.80-E (Fc/Fc+) ]，E LUMO ＝-e[E re +4.80-E (Fc/Fc+) ]The method comprises the steps of carrying out a first treatment on the surface of the The HOMO and LUMO levels of the por-TIC were calculated to be-5.36 and-3.71 eV, respectively. According to the formula a E g,opt ＝1240/λonset, b Band gap of the obtained compound a E g,opt . The specific test results are shown in Table 1.
TABLE 1 electrochemical and optical Properties of por-TIC
Test example 3 determination of the photovoltaic Properties of the por-TIC
To investigate the photovoltaic properties of the por-TIC as receptor, PTB7-Th was chosen as donor, and ITO/ZnO (30 nm)/PTB 7-Th: por-TIC (100 nm)/MoO was prepared 3 The specific preparation method of the solar cell device with the inverted structure of (8.5 nm)/Ag (100 nm) and the film resistance of the ITO electrode of 15 omega/square is as follows:
(1) Before using, the ITO glass substrate is cleaned by detergent, and then distilled water, acetone, isopropanol and secondary water are sequentially used for super-cleaningAnd making sound for 20min. Then spin-drying the water by a spin coater, then drying the water on a hot table at 150 ℃, and then using UV-O 3 Activating for 20min.
(2) A ZnO precursor solution was prepared by dissolving zinc acetate dihydrate (1 g) and ethanolamine (0.28 g) in 2-methoxyethanol (10 mL) with vigorous stirring for 12 hours, and performing hydrolysis reaction in air. Spin-coating ZnO precursor solution on an ITO glass substrate at 3500r/min, and baking at 200deg.C for 20min to obtain 30nm thick electron transport layer.
(3) 5.2mg of por-TIC and 4mg of PTB7-Th were dissolved in 1mL of 1, 2-dichlorobenzene in pyridine (V 1, 2-dichlorobenzene solution :V Pyridine compound =99:1) in the mixed solution. Wherein the PTB7-Th concentration is 4.0mg/mL, stirring at 110deg.C under nitrogen for 1 hr to ensure sufficient dissolution, and spin coating the prepared mixed solution on ZnO to obtain active layer thickness of about 100nm.
(4) Transferring the prepared ITO sheet of the active layer into a vacuum coating box, and placing the ITO sheet in a vacuum coating box at 10 -5 Vacuumizing Pa for 3h, and then evaporating MoO with the thickness of 8.5nm 3 Ag as a hole transport layer and 100nm thick was used as an electrode. Each substrate contains 6 devices, and the effective area of each device is 0.04cm 2 。
The energy levels of the solar cell device described above are shown in fig. 4. As can be seen from FIG. 4, the donor PTB7-Th and the porphyrin compound por-TIC as the acceptor match well with each other. The current density versus voltage (J-V) curve is shown in FIG. 5. When the device efficiency is optimal, the energy conversion efficiency is 3.82%, the open circuit voltage V is 0.77V, and the short circuit current density Jsc is 9.65mA.cm 2 The fill factor FF was 51.44%. To obtain accurate short circuit current density data, the external quantum efficiency EQE was tested in experiments, as shown in fig. 6. The JV value obtained from the EQE curve integral correction was 5%, consistent with the results obtained from the J-V test.
Device comparative example
The present device comparative example a solar cell device having an inverted structure was prepared by a method similar to that in test example 3. The difference is that: step (3) is different; specifically:
5.2mg of RhBT-Por and 4mg of PDPP5T were dissolved in 1mL1, 2-dichlorobenzyl-pyridine (V) 1, 2-dichlorobenzene solution :V Pyridine compound =99:1) in the mixed solution. Wherein the concentration of PTB7-Th is 4.0mg/mL, stirring for 1h at 110 ℃ in nitrogen environment to ensure sufficient dissolution, and spin-coating the prepared mixed solution on ZnO to obtain an active layer with a thickness of about 100nm;
the remaining steps were the same as those of test example 3.
The specific structures of RhBT-Por and PDPP5T are as follows:
optimized Power Conversion Efficiency (PCE), open circuit voltage (V) of solar cell devices made from the comparative compound (RhBT-Por) oc ) Density of short-circuit current (J) sc ) And Fill Factor (FF) of 1.8%, 0.53V, 7.3mA.cm, respectively 2 And 47.32%.
The results show that in the case where star-shaped porphyrin is surrounded by electron withdrawing groups as the central core, the effect of the acetylene group linkage to the electron donating unit (thiophene) is more excellent than that of the electron withdrawing unit (benzothiadiazole), which can not only improve the morphology during film formation but also reduce the tendency of porphyrin to self-aggregate.
Meanwhile, when the compound provided by the invention is used in an organic solar cell, as porphyrin is connected with four electron withdrawing (IC) end groups at the meso position of porphyrin (the position of carbon in porphyrin, and carbon atoms 5, 10, 15 and 20) through ethynyl, pi-conjugation is prolonged, intramolecular Charge Transfer (ICT) effect is enhanced, very wide absorption is generated in a near infrared region, the structure is more soluble in a solvent due to the adhesion of an alkyl chain on the 3-position of thiophene, and the structure can be well coordinated with a donor in the film forming process of the solar cell, so that excellent energy conversion efficiency (3.82%) is obtained. In addition, the synthesis method of the compound shown in the formula (I) is simple and is suitable for large-scale synthesis.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A star porphyrin compound characterized by having a structure represented by formula (I):
wherein in formula (I), R is C 5 -C 15 Is a hydrocarbon group.
2. The compound of claim 1, wherein in formula (I), R is C 6 -C 10 Alkyl of (a);
preferably, R is 2-ethylhexyl.
3. A process for preparing a star porphyrin compound represented by the formula (I), which comprises the steps of: in the presence of a protective atmosphere,
(1) In the presence of a solvent I, tetra (triphenylphosphine) palladium and CuI, carrying out first mixing on a compound shown in a formula (A) and a compound shown in a formula (B) to obtain a compound shown in a formula (C);
(2) In the presence of a solvent II, carrying out second mixing on the compound shown in the formula (C) and the compound shown in the formula (D) to obtain a star porphyrin compound shown in the formula (I);
wherein in the formulae (B), (C) and (I), R is correspondingly the same as defined in claim 1 or 2.
4. A method according to claim 3, wherein in step (1), the molar ratio of the compound of formula (a) to the compound of formula (B), tetrakis (triphenylphosphine) palladium, cuI is 1: (5-14): (0.1-0.3): (0.2-0.5);
preferably, the molar ratio of the compound shown in the formula (A) to the compound shown in the formula (B), the tetrakis (triphenylphosphine) palladium and the CuI is 1: (11-14): (0.15-0.25): (0.3-0.4).
5. The method according to claim 3 or 4, wherein in step (1), the solvent I is selected from at least one of a mixed solution of triethylamine and tetrahydrofuran, triethylamine, diethylamine;
preferably, the solvent I is a mixed solution of triethylamine and tetrahydrofuran, and the dosage volume ratio of the triethylamine to the tetrahydrofuran is 1:1-3;
preferably, the solvent I is used in an amount of 250 to 350mL relative to 1mmol of the compound represented by the formula (A).
6. The method according to any one of claims 3 to 5, wherein in the step (2), the molar ratio of the compound represented by the formula (C) to the compound represented by the formula (D) is 1:5-7.
7. The method according to any one of claims 3 to 6, wherein in the step (2), the solvent II is a mixed solution of chloroform and pyridine, and the volume ratio of the chloroform to the pyridine is 20 to 30:1, a step of;
preferably, the protective atmosphere is at least one selected from nitrogen and argon.
8. The method according to any one of claims 3-7, wherein in step (1), the first mixing conditions at least satisfy: the temperature is 70-90 ℃ and the time is 48-72h;
preferably, in step (2), the conditions of the second mixing at least satisfy: the temperature is 60-70 ℃ and the time is 12-24h.
9. Use of a star porphyrin compound as claimed in claim 1 or 2 as acceptor material in the preparation of an organic solar cell.
10. An organic solar cell comprising a metal electrode layer as an anode, a hole transport layer, an active layer, an electron transport layer, and an indium tin oxide layer as a transparent electrode, wherein the active layer contains the star porphyrin compound described in claim 1 or 2.
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