CN103554100B - The preparation method of a kind of organic solar battery material and application thereof - Google Patents

The preparation method of a kind of organic solar battery material and application thereof Download PDF

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CN103554100B
CN103554100B CN201310494877.6A CN201310494877A CN103554100B CN 103554100 B CN103554100 B CN 103554100B CN 201310494877 A CN201310494877 A CN 201310494877A CN 103554100 B CN103554100 B CN 103554100B
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organic solar
thiophene
solar battery
battery material
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CN103554100A (en
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赖文勇
黄维
范晓春
李祥春
陈垚
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Nanjing Post and Telecommunication University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

The present invention relates to the preparation of a kind of organic solar battery material and application thereof, many arm configurations compound of this material is to take phenyl carbazole as core, thiophene-benzothiazole derivant be branch arm, its formula is as shown in the formula shown in I:Wherein, X is thiophene derivant, is selected from one of following group:R1��R4For independent hydrogen, C1-C12 alkyl or alkoxyl group; N is 0��6; N is nitrogen-atoms, and S is sulphur atom. This material has good non-crystalline state characteristic and solvability, it is possible to prepare high-quality film by solution method, and compared with existing polymer materials easier purifying and obtain high purity material.

Description

The preparation method of a kind of organic solar battery material and application thereof
Technical field
The invention belongs to field of photovoltaic technology, it is specifically related to a kind of organic solar battery material, relate more specifically to a kind of star-type multi-arm structured material and application thereof; This material take phenyl carbazole as core, and the star type polysubstitution compound by branch arm of thiophene-diazosulfide derivative, this material can be used as organic solar batteries active coating, light is caught or electron donor material is applied to organic solar batteries device.
Background technology
Sun power is the long-expected renewable and clean energy resources of the mankind. Although inorganic solar cell material and various device architecture obtain and develop on a large scale very much, but the cost of its costliness and serious photoetch cause its energy share still very low, limit the development of inorganic solar cell. Therefore, developing novel material makes solar energy utilize the road going on Sustainable development to seem particularly urgent. Based on the organic solar batteries of organic/polymer semiconducting material owing to its cost is low, light weight, can flexibility, big area the significant advantage such as can prepare so that it is become most promising energy technology of future generation.
Polymer solar battery makes the repeatable poor of device due to the polymolecularity of polymkeric substance itself, and its purity is also difficult to control in addition.But when fabricate devices, the solution processable characteristic of polymkeric substance has that cost is low and advantage easily. And organic molecule has clear and definite molecular structure and the molecular weight determined, by the strict purifying of experimental technique, the favorable repeatability of device. Therefore, develop the organic solar battery material of high purity single dispersing solution processable, it is possible to the solution having polymer materials concurrently can the feature of processing characteristics and organic small molecule material high purity.
By molecular structure optimization design, the organic solar battery material of development of new is particularly important. For material, molecular designing is become hub-and-spoke configuration, be conducive to preventing intermolecular tightly packed, effectively suppress the crystallinity of material, it is to increase amorphous performance. In conjunction with previous work basis, inventive design has synthesized a kind of star-shaped material take phenyl carbazole as core, thiophene-diazosulfide derivative being branch arm. The phenyl carbazole group of rigidity is conducive to improving the cavity transmission ability of material, phenyl carbazole is as giving the derivative of body and diazosulfide as the interaction between acceptor simultaneously, make bill of material reveal lower HOMO value and narrower energy gap, contribute to obtaining bigger open circuit voltage and higher efficiency of light absorption. Diazosulfide has specific absorbance height, Heat stability is good, feature that oxidizing potential is higher, and it is widely used in organic solar battery material. Introducing alkyl chain in thiphene ring can the solvability of strongthener. This kind of star-shaped material can prepare organic solar battery material by easy solution film forming mode.
Summary of the invention
Technical problem: it is an object of the invention to provide a kind of organic solar battery material and preparation method and application thereof, makes the film-forming properties of material, thermostability etc. be increased dramatically, and can be used as active material and is applied to and prepares organic solar batteries device.
Technical scheme: the present invention proposes a kind of organic solar battery material, many arm configurations compound of this material is to take phenyl carbazole as core, thiophene-diazosulfide derivative be branch arm, its formula is as shown in the formula shown in I:
Wherein, X is thiophene derivant, is selected from one of following group:
R1��R4For independent hydrogen, C1-C12 alkyl or alkoxyl group; N is 0��6; N is nitrogen-atoms, and S is sulphur atom.
Preparation method based on many arm configurations compound of phenyl carbazole to be core, thiophene-diazosulfide derivative a be arm comprises the following steps:
1) by carbazole and paradibromobenzene reaction preparation 9-(4-bromophenyl) carbazole core, through bromination, acid esterification, by Suzuki linked reaction and thiophene-benzothiazole list bromine substitution compound reaction, to prepare phenyl carbazole be core, thiophene-benzothiazole derivant is the compound of an arm, bromination, last and capping group X is obtained by reacting end product;
2) by obtained 9-(4-bromophenyl) after carbazole is dissolved in solvent orange 2 A, slowly drips under lucifuge and condition of ice bath and add NBS solution, under room temperature, react 3-8h, through cancellation, washing, extraction, drying, obtain crude product separation and purify;
3) product of step 2 gained is dissolved in solvent B, at-78 DEG C, slowly drips and add butyllithium, then inject Virahol tetramethyl ethylene ketone boric acid ester fast, continue reaction 6-12h. After frozen water cancellation, extraction, drying, take out filter, obtain crude product separation and purify;
4) benzothiazole bromination is obtained 4,7-bis-bromo-2,1,3-diazosulfide, by first for alkylthrophene bromination again acid esterification obtain alkylthrophene list boric acid ester, by the two alkylthrophene substitutive derivative of Suzuki linked reaction benzothiazole, then control reaction conditions and carry out single bromine replacement, obtain thiophene-benzothiazole list bromine substitution compound;
5) under inert atmosphere, benzo carbazole three boric acid ester obtained by step 3), thiophene-benzothiazole list bromine substitution compound that step 4) is obtained, Pd (pph3)4, it is dissolved in solvent C, adds K2CO3The aqueous solution, temperature control 85-110 DEG C backflow, be poured into water, extract after reaction 48-72h, dry, column chromatography obtain solid;
6) under inert atmosphere, step 5 products therefrom is dissolved in the organic solvent D such as toluene and auxiliary agent, adds capping group X and react, through washing, extraction, dry, column chromatography, obtain end product.
Wherein:
Step 2) in solvent orange 2 A be one or more in methylene dichloride DCM, tetrahydrofuran THF or DMF, reactant 9-(4-bromophenyl) mole number of carbazole and the volume ratio of solvent orange 2 A be 1mmol:5mL��15mL, the mol ratio of reactant phenyl carbazole and NBS is 1:1.8��2.5.
Solvent B in step 3) is one or more in chloroform, tetrahydrofuran THF or DMF, reactions steps 2) mole number of product and the volume ratio of solvent B be 1mmol:5mL��15mL, reactions steps 2) mol ratio of product and Virahol tetramethyl ethylene ketone boric acid ester is 1:8.0��9.0.
Solvent C in step 5) is one or more in toluene, chloroform, tetrahydrofuran THF, reactions steps 3) mole number of product and the volume ratio of solvent B be 1mmol:5mL��15mL, reactions steps 3) product, step 4) product, K2CO3With Pd (pph3)4Mol ratio is 1:3.0:25��35:0.1��0.5.
Solvent D in step 6) is one or more in toluene, chloroform, tetrahydrofuran THF, and auxiliary agent is triethylamine or piperidines, and temperature of reaction is 80��100 DEG C, and the reaction times is 48��72h.
This material of this material as organic solar batteries active coating, light is caught or electron donor material is applied to organic solar batteries device.
Useful effect: the organic solar battery material that the present invention proposes has following feature: the molecular structure of (1) star type, significantly increase the space steric effect of target material, be conducive to preventing intermolecular tightly packed, effectively suppress the crystallinity of material, it is to increase amorphous performance; (2) phenyl carbazole and diazosulfide contribute to obtaining bigger open circuit voltage and higher efficiency of light absorption; (3) second-order transition temperature height, thermostability height can be formed, even compact without sizing film; (4) thin-film device can be prepared by easy solution film forming mode. Therefore, it may also be useful to this material, as the red emission that can obtain efficient stable to the organic solar batteries device of body, excellent spectrum and stabilizing device performance, is a kind of organic solar battery material with important application prospect.
Accompanying drawing explanation
Fig. 1 is the normalization method ultra-violet absorption spectrum of compound in tetrahydrofuran (THF) and normalization method fluorescence emission spectrum.
Embodiment
The organic solar battery material that the present invention proposes, many arm configurations compound of its to take phenyl carbazole as core, thiophene-diazosulfide derivative be branch arm, its formula is as shown in the formula shown in I:
Wherein, X is thiophene derivant, is selected from one of following group:
R1��R4For independent hydrogen, C1-C12 alkyl or alkoxyl group; N is 0��6; N is nitrogen-atoms, and S is sulphur atom.
Below by way of some embodiments, the present invention will be further described, but embodiment does not limit the covering scope of the present invention.
Embodiment 1:
[reaction scheme figure]
According to reaction scheme, 2-(4-hexyl thiophene-2-base)-4,4,5,5-tetramethyl--1,3,2-two oxygen is mixed borine, 2-(3-hexyl thiophene-2-base)-4,4,5,5-tetramethyl--1, the assorted borine of 3,2-bis-oxygen and 4-(4-hexyl thiophene-2-base)-7-(5-bromo-4-hexyl thiophene-2-base) diazosulfide occurs Suzuki linked reaction to obtain compound T1 when four triphenyl phosphorus palladiums make catalyzer.
Embodiment 2:
[reaction scheme figure]
According to reaction scheme figure, 2-(4-hexyl thiophene-2-base)-4,4,5,5-tetramethyl--1,3,2-two oxygen is mixed borine, 2-(3-hexyl thiophene-2-base)-4,4,5,5-tetramethyl--1, the assorted borine of 3,2-bis-oxygen and 4-(4-hexyl thiophene-2-base)-7-(5-bromo-4-hexyl thiophene-2-base) diazosulfide occurs Suzuki linked reaction to obtain compound T2 when four triphenyl phosphorus palladiums make catalyzer.
Although we are in conjunction with exemplary enforcement mode, it is specifically described the present invention, but it will be understood and appreciated by those or skill in the art that when not departing from the spirit and scope of the present invention that the claims limit, it is possible to make various modification and change in form and details.

Claims (2)

1. an organic solar battery material, it is characterised in that many arm configurations compound of this material is to take phenyl carbazole as core, thiophene-diazosulfide derivative be branch arm, its formula is as shown in the formula shown in I:
Wherein, X is thiophene derivant, is selected from one of following group:
R1��R4For independent hydrogen, C1-C12 alkyl or alkoxyl group; N is 0��6; N is nitrogen-atoms, and S is sulphur atom.
2. the application of a kind of organic solar battery material according to claim 1, it is characterized in that this material as organic solar batteries active coating, light is caught or electron donor material is applied to organic solar batteries device.
CN201310494877.6A 2013-10-21 2013-10-21 The preparation method of a kind of organic solar battery material and application thereof Active CN103554100B (en)

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CN106588867B (en) * 2016-12-05 2020-11-20 南京工业大学 Chemical synthesis and application research of cyano-containing functional material for modifying perovskite layer in perovskite solar cell
CN108409755B (en) * 2017-02-10 2021-03-26 中国科学院宁波材料技术与工程研究所 Organic photoelectric conversion material, preparation method and application thereof
CN110452241B (en) * 2019-07-26 2020-11-24 华南理工大学 Organic small-molecule non-fullerene acceptor material containing spirofluorene group and preparation method and application thereof
CN114685469B (en) * 2022-05-19 2024-06-21 浙江工业大学 Thiophene derivative based on 9-phenyl-carbazole and preparation and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747374A (en) * 2010-01-21 2010-06-23 中国科学院长春应用化学研究所 Compound containing phosphorus-oxygen groups and organic electroluminescent device comprising compound containing phosphorus-oxygen groups and preparation method thereof
KR20120087485A (en) * 2011-01-28 2012-08-07 주식회사 동진쎄미켐 Novel organic dye and preparation thereof
CN103073541B (en) * 2013-01-07 2015-08-19 中国科学院宁波材料技术与工程研究所 Triphenylamine star-shaped material, its preparation method and purposes that electron-withdrawing group is modified

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747374A (en) * 2010-01-21 2010-06-23 中国科学院长春应用化学研究所 Compound containing phosphorus-oxygen groups and organic electroluminescent device comprising compound containing phosphorus-oxygen groups and preparation method thereof
KR20120087485A (en) * 2011-01-28 2012-08-07 주식회사 동진쎄미켐 Novel organic dye and preparation thereof
CN103073541B (en) * 2013-01-07 2015-08-19 中国科学院宁波材料技术与工程研究所 Triphenylamine star-shaped material, its preparation method and purposes that electron-withdrawing group is modified

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"A Solution-Processable Star-Shaped Molecule for High-Performance Organic Solar Cells";Huixia Shang等;《Adv. Mater.》;20110207;第23卷(第13期);第1555页 Scheme 1、第1556页右栏第2段 *
"New star-shaped molecules derived from thieno[3,2-b]thiophene unit and triphenylamine";N. Metri等;《Tetrahedron Letters》;20121215;第51卷;第6673-6676页 *
"Star-Shaped D−A Small Molecules Based on Diketopyrrolopyrrole and Triphenylamine for Efficient Solution-Processed Organic Solar Cells";Pan Jun-Ying等;《ACS Applied Matericals & Interfaces》;20130115;第5卷;第972-980页 *

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