CN106633000A - D-A type broad-band gap polymer photovoltaic materials based on benzodithiophene-2,6-diformate and application of D-A type broad-band gap polymer photovoltaic materials - Google Patents

D-A type broad-band gap polymer photovoltaic materials based on benzodithiophene-2,6-diformate and application of D-A type broad-band gap polymer photovoltaic materials Download PDF

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CN106633000A
CN106633000A CN201610836131.2A CN201610836131A CN106633000A CN 106633000 A CN106633000 A CN 106633000A CN 201610836131 A CN201610836131 A CN 201610836131A CN 106633000 A CN106633000 A CN 106633000A
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band gap
polymer
polymer photovoltaic
materials
gap polymer
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朱卫国
陶强
谭华
王亚飞
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Changzhou University
Xiangtan University
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Xiangtan University
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Abstract

The invention relates to synthesizing of a D-A type broad-band gap polymer photovoltaic materials based on benzodithiophene-2,6-diformate acceptor units and application of the D-A type broad-band gap polymer photovoltaic materials to polymer photovoltaic devices. The electron-donating (D) units of the D-A type broad-band gap polymer materials are thiophene, benzodithiophene and the derivatives of the benzodithiophene, and the electron-accepting (A) units of the D-A type broad-band gap polymer materials are benzodithiophene-2,6-diformate. The D-A type broad-band gap polymer photovoltaic materials can be used as the donor materials to be applied to solution processing type polymer solar cells (PSCs) devices. When the acceptor materials of the devices are fullerenes, the maximum energy conversion efficiency and open-circuit voltage of the bulk heterojunction polymer solar cells devices respectively reach up to 7.49% and 1.03V. By the arrangement, efficient energy conversion of the broad-band gap polymer photovoltaic materials in the PSCs is achieved.

Description

D-A type wide band gap polymer photovoltaic material based on benzene thiophene -2,6- dicarboxylic acid esters Material and its application
Technical field
The present invention relates to organic polymer solar cell field, a more particularly to class is based on benzene thiophene -2,6- Dicarboxylic acid esters are by the synthesis of the D-A type wide band gap polymer photovoltaic material of electronic unit and its in polymer solar cell device In application.
Technical background
The development of economic society be unable to do without the energy.Now in the fossil energy dual system that increasingly deficient and environment is urgently protected Under about, the energy and environmental problem have become whole world emphasis in the urgent need to address and difficulties.It is taken because solar energy has Not to the utmost, it is nexhaustible, the unrivaled advantage such as safe and pollution-free, no regional limitation, exploitation and the application of solar energy, Become the focus of global green novel energy source research.Wherein, the solar battery technology for converting solar energy into electric energy is in recent years Solar energy development and the primary study direction applied.
Organic solar batteries (OSCs) with material selection range width, structure due to easily adjusting, preparation process is simple, device The advantages of part easy large area flexible, it has also become the main development direction of solar battery technology, and obtain and quickly send out Exhibition[1-6].At present organic solar batteries mainly include polymer solar battery (PSCs) and organic molecule solar cell (SMs-OSCs).The energy conversion efficiency difference of body heterojunction (BHJ) individual layer OSCs wherein, based on polymer and small molecule Reach 11.7%[7]With 10.08%[8], respectively reached based on the energy conversion efficiency of polymer and the lamination OSCs of small molecule 11.83%[9]With 10.1%[10].These efficient organic solar batteries are made a general survey of, its light active material is mainly using narrow The conjugated polymer and small molecule of band gap, farthest to absorb solar photon, obtains high short circuit current (Jsc).Compared to Narrow band gap (Eg<1.8eV) photovoltaic material, broad-band gap (Eg>1.9eV) the research of photovoltaic material relatively lags behind, its solar cell Energy conversion efficiency greatly below 7%[11]。
Laminated organic solar cell is the mutual supplement with each other's advantages using two kinds or more photovoltaic donor materials to solar absorption, The high performance solar batteries constructed.Wherein, broad-band gap conjugated polymer is its important part.Therefore, develop efficiently wide Band gap Polymer photovoltaic materials, are the key that laminated organic solar cell realizes high-energy conversion efficiency and the key for intending to solve Bottleneck problem[12]。
It is attached：Leading reference
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[6].Y.M.Sun,G.C.Welch,W.L.Leong,C.J.Takacs,G.C.Bazan,A.J.Heeger, Nat.Mater.,2012,11,44.
[7].J.B.Zhao,Y.K.Li,G.F.Yang,K.Jiang,H.Lin,H.Ade,W.Ma,H.Yan, Nat.Energy,2016,1,15027.
[8].B.Kan,M.Li,Q.Zhang,F.Liu,X.Wan,Y.Wang,W.Ni,G.Long,X.Yang,H.Feng, Y.Zuo,M.Zhang,F.Huang,Y.Cao,T.P.Russell,Y.Chen,J.Am.Chem.Soc.,2015,137,3886- 3893.
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[11].(a)S.C.Price,A.C.Stuart,L.Yang,H.Zhou and W.You,J.Am.Chem.Soc., 2011,133,4625–4631.(b)J.Wolf,F.Cruciani,A.E.Labban and P.M.Beaujuge, Chem.Mater.,2015,27,4184–4187.(c)W.Gao,T.Liu,M.Hao,K.Wu,C.Zhang,Y.Sun,C.Yang, Chem.Sci.,2016,DOI:10.1039/c6sc01791f.
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The content of the invention
For current wide band gap photovoltaic description of materials it is few, energy conversion efficiency is low the problems such as, invented a class new Benzene thiophene -2,6- dicarboxylic acid esters are by electronics (A) unit and its D-A type wide band gap polymer photovoltaic material.Such material Molecular structure feature is that, with thiophene -2 of benzo two, 6- dicarboxylic acid esters are that, by electronics (A) unit, thiophene, benzene thiophene derivative are Push away electronics (D) unit.Using this kind of D-A type polymer photovoltaic donor material and fullerene acceptor material, processed by solution, system Make polymer solar battery (PSCs), realize efficient energy conversion of the wide band gap polymer photovoltaic material in PSCs.
It is an object of the invention to provide a class has the broad-band gap D-A type polymer photovoltaic material of high-energy conversion efficiency Material.Such material has relatively low HOMO energy levels, and preferable film forming has stronger absorption in 300-600nm wave-length coverages And spectral response.When with PC71When BM is blended, its solvent processing type body heterojunction PSCs device obtains high energy conversion effect Rate (PCE) and open-circuit voltage (Voc)。
The molecular structure of this kind of D-A type Polymer photovoltaic materials can be any one of following molecule.
Formula one：PV-BDTC1
Formula two：PV-BDTC2
Formula three：PV-BDTC3T
Formula four：PV-BDTC3TO
Above-mentioned D-A type wide band gap polymer photovoltaic material, including following any derivative：
With benzene thiophene -2,6- dicarboxylic acid esters (V-BDTC) are electron-accepting group, the benzene thiophene that alkoxyl replaces (BDT) it is electron donating group, the Polymer photovoltaic materials PV-BDTC1 with D-A structure.
With benzene thiophene -2,6- dicarboxylic acid esters (V-BDTC) are electron-accepting group, the benzo two that alkylthrophene base replaces Thiophene (BDTT) be electron donating group, the Polymer photovoltaic materials PV-BDTC2 with D-A structure.
With benzene thiophene -2,6- dicarboxylic acid esters (V-BDTC) are electron-accepting group, and alkylthrophene derivative (3T) is to push away Electron group, the Polymer photovoltaic materials PV-BDTC3T with D-A structure.
With benzene thiophene -2,6- dicarboxylic acid esters (V-BDTC) are electron-accepting group, and alkoxy thiophene derivative (3TO) is Electron donating group, the Polymer photovoltaic materials PV-BDTC3TO with D-A structure.
In order to obtain above-mentioned Polymer photovoltaic materials, the synthetic schemes of the present invention is as follows：
The synthesis of novel receptor unit benzene thiophene -2,6- dicarboxylic acid esters：The bromo- 2,5- dimethylbenzene of 1,4- bis- is in three oxidations In the presence of chromium and the concentrated sulfuric acid, the bromo- benzaldehydes of 2,5- bis- of Isosorbide-5-Nitrae-two are oxidized to；Two benzaldehyde derivative further with sulfydryl second Acetoacetic ester is condensed to yield benzene thiophene -4,6- dicarboxylic acid ethyl esters (V-BDTC)；Ester exchange is carried out using alkylol and V-BDTC Reaction, obtains different alkyl-substituted benzene thiophene -4,6- dicarboxylic acid esters.The dicarboxylic acid esters and Br2Generation parental materials are anti- Should, obtain benzene thiophene -4 that double bromines replace, 6- dicarboxylic acid esters.Jing column chromatography for separation obtains sterling；The benzene that double bromines are replaced 1,4-Dithiapentalene -4,6- dicarboxylic acid esters successively obtain 4,8- bis--(2- with 2- tributyl tins thiophene Still cross-couplings and NBS brominations (5- bromothiophene bases) benzo [1,2-b:4,5-b'] Dithiophene -2,6- two [formic acid (2- butyl) monooctyl ester].
The synthesis of one-dimensional D-A type Polymer photovoltaic materials PV-BDTC1：4,8- bis--(2- (5- bromothiophene bases) benzo [1,2- b:4,5-b'] Dithiophene -2,6- two [formic acid (2- butyl) monooctyl ester] and bis-alkoxy benzene thiophene Fluorescence Properties of Pyrene Derivatives thing (BDTSnMe3) there is the reaction of Still coupling polymerizations under three (dibenzalacetone) two palladium chtalyst, synthesis obtains polymer P V- BDTC1 crude products, through methyl alcohol sedimentation, surname extraction washing, then settle and obtain polymer P V-BDTC1 net products.
The synthesis of two-dimentional D-A type Polymer photovoltaic materials PV-BDTC2：Containing 4,8- bis--(2- (5- bromothiophene bases) benzo [1, 2-b:4,5-b'] Dithiophene -2,6- two [formic acid (2- butyl) monooctyl ester] takes with double alkylthrophene base benzene thiophene tin trimethyls For thing (BDTTSnMe3) there is the reaction of Still coupling polymerizations under three (dibenzalacetone) two palladium chtalyst, synthesis is polymerized Thing PV-BDTC2 crude products, through methyl alcohol sedimentation, surname extraction washing, then settle and obtain polymer P V-BDTC2 net products.
The synthesis of D-A type Polymer photovoltaic materials PV-BDTC3T：4,8- dibromo benzo [1,2-b:4,5-b'] Dithiophene- 2,6- bis- [formic acid (2- butyl monooctyl esters] connect three thiophene Fluorescence Properties of Pyrene Derivatives thing (3TSnMe with alkylation3) in three (dibenzylidenes third Ketone) there is the reaction of Still coupling polymerizations under two palladium chtalysts, synthesis obtains polymer P V-BDTC3T crude products, and poly- Jing methyl alcohol sinks Drop, surname extraction washing, then settle and obtain polymer P V-BDTC3T net products.
The synthesis of D-A type Polymer photovoltaic materials PV-BDTC3TO：4,8- dibromo benzo [1,2-b:4,5-b'] Dithiophene- 2,6- bis- [formic acid (2- butyl monooctyl esters] connect three thiophene Fluorescence Properties of Pyrene Derivatives thing (3TOSnMe with alkoxylate3) in three (two benzal Benzylacetone) there is the reaction of Still coupling polymerizations under two palladium chtalysts, synthesis obtains polymer P V-BDTC3TO crude products, Jing Guojia Alcohol is settled, surname extraction washing, then is settled and obtained polymer P V-BDTC3TO net products.
The present invention is new big with published by electronic unit 4,8- dibromo benzene thiophene -2,6- dicarboxylic acid esters V-BDTC Majority is compared by electronic unit, is characterized in：(1) HOMO of polymer molecule can be effectively reduced with the connected mode of 4,8 Energy level, obtains a larger open-circuit voltage；The modification of (2) 2,6 two ester groups can be effectively increased whole benzene thiophene unit By electronic capability；(3) alkyl chain of selection different length can effectively adjust the dissolubility of polymer molecule；(4) select not The same presence for pushing away electronic unit, pushing away by structure in molecule, can adjust the absorption spectrum and electron orbit energy level of molecule.Therefore, This kind of material is the very promising Polymer photovoltaic materials of a class.
The present invention application be：Using the Polymer photovoltaic materials of design as photoactive layer donor material, with PC71BM exists It is blended under different proportion, makes polymer solar cell device, realizes the efficient photoelectricity treater conversion of device.
Described organic polymer solar cell device includes indium tin oxide target (ITO) electro-conductive glass anode, anode modification Layer, photoactive layer, negative electrode.Wherein anode modification layer be poly- ethylenedioxythiophene, poly styrene sulfonate (PEDOT/PSS, 30nm) coating；Negative electrode is the sedimentary of Ca (10nm)/Al (100nm)；Activation layer material is polymer photovoltaic of the present invention Material and PC71BM, its blending weight ratio is 1:2.
Description of the drawings
Fig. 1 is the thermogravimetric curve of PV-BDTC1 of the present invention
Fig. 2 is the differential calorimetry curve of PV-BDTC1 of the present invention
Fig. 3 is the uv-visible absorption spectra of PV-BDTC1 chloroformic solutions of the present invention
Fig. 4 is the uv-visible absorption spectra of PV-BDTC1 solid films of the present invention
Fig. 5 is the cyclic voltammetry curve of PV-BDTC1 solid films of the present invention
Fig. 6 is PV-BDTC1/PC of the present invention71The J-V curves of BM polymer solar cell devices
Fig. 7 is PV-BDTC1/PC of the present invention71The EQE curves of BM polymer solar cell devices
Fig. 8 is the thermogravimetric curve of PV-BDTC2 of the present invention
Fig. 9 is the differential scanning amount curve of PV-BDTC2 of the present invention
Figure 10 is the uv-visible absorption spectra of PV-BDTC2 chloroformic solutions of the present invention
Figure 11 is the uv-visible absorption spectra of PV-BDTC2 solid films of the present invention
Figure 12 is the cyclic voltammetry curve of PV-BDTC2 solid films of the present invention
Figure 13 is the present invention under addition 3%DIO, PV-BDTC2/PC71The J-V of BM polymer solar cell devices is bent Line
Figure 14 is the present invention under addition 3%DIO, PV-BDTC2/PC71The EQE of BM polymer solar cell devices is bent Line
Figure 15 is PV-BDTC2/PC of the present invention71The J-V curves of the mono- hole transport devices of BM
Figure 16 is PV-BDTC2/PC of the present invention71The J-V curves of BM single electron transmission apparatus
Figure 17 is PV-BDTC2/PC of the present invention71The TEM figures of BM photoactive layers
Figure 18 is the present invention under addition 3%DIO, PV-BDTC2/PC71The TEM figures of the photoactive layer of BM
Figure 19 is the uv-visible absorption spectra of PV-BDTC3T chloroformic solutions of the present invention
Figure 20 is the uv-visible absorption spectra of PV-BDTC3T solid films of the present invention
Figure 21 is the cyclic voltammetry curve of PV-BDTC3T solid films of the present invention
Figure 22 is the uv-visible absorption spectra of PV-BDTC3TO chloroformic solutions of the present invention
Figure 23 is the uv-visible absorption spectra of PV-BDTC3TO solid films of the present invention
Figure 24 is the cyclic voltammetry curve of PV-BDTC3TO solid films of the present invention
Specific embodiment
Below by specific embodiment, the invention will be further described, but these specific embodiments are never in any form Limit the scope of the invention.
Embodiment 1
4,8- dibromo benzo [1,2-b:4,5-b'] Dithiophene -2,6- two [formic acid (2- butyl) monooctyl ester] synthesis
The synthesis of 1.1 2,5- dibromobenzene -1,4- dicarbaldehydes
In 100mL single port bottles, by the bromo- Isosorbide-5-Nitrae-dimethyl benzenes (3.9g, 15mmol) of 2,5- bis- be dissolved in 20mL acetic acid and In the mixed solution of 40mL acetic anhydride, magnetic agitation after the concentrated sulfuric acid (14mL) is slowly added dropwise at 0 DEG C, is dividedly in some parts CrO3 (6.0g), 3h is reacted at 0 DEG C.After question response terminates, reactant liquor is poured into 100mL frozen water, separate out a large amount of white solids, taken out Filter, washing.Solid is transferred in 100mL single port bottles, 20mL water, 20mL ethanol and the 2mL concentrated sulfuric acids is added, 12h is heated to reflux. Natural cooling, suction filtration, solid water, methyl alcohol alternately wash multiple.Vacuum drying, obtain faint yellow solid (2.0g, 48.0%) 。1H NMR(400MHz,CDCl3)δ10.39(s,2H),8.20(s,2H).13C NMR(100MHz,CDCl3)δ10.39,8.20, 7.31,1.66,0.04.
1.2 benzo [1,2-b:4,5-b'] Dithiophene -2,6- two (Ethyl formate) synthesis
In 100mL single port bottles, 2,5- dibromobenzenes-Isosorbide-5-Nitrae-dicarbaldehyde (2.7g, 9.3mmol), ethyl thioglycolate are added (3.0g, 28mmol), potassium carbonate (4.1g, 30mmol), cupric oxide (180mg, 0.3mmol), DMF (DMF) (100mL) 80 DEG C, under nitrogen atmosphere, are heated with stirring to, 24h is reacted, room temperature is cooled to.Reactant mixture is extracted with chloroform Take (3 × 20mL), with watery hydrochloric acid water washing repeatedly, anhydrous magnesium sulfate is dried the organic layer of merging, distillation, and residue is with oil Ether/dichloromethane mixed solution be eluant, eluent (v/v, 1:1) column chromatography for separation is carried out, obtains faint yellow acicular crystal 1.2g, yield 38.7%.1H NMR(400MHz,CDCl3) δ 8.37 (s, 2H), 8.10 (s, 2H), 4.43 (d, J=6.7Hz, 4H), 1.69- 1.31(m,6H).13C NMR(100MHz,CDCl3)δ162.55,139.23,138.32,135.87,129.42,119.34, 110.02,61.88,14.35.
1.3 benzo [1,2-b:4,5-b'] Dithiophene -2,6- two [formic acid (2- butyl) monooctyl ester] synthesis
In 100mL single port bottles, benzo [1,2-b is added:4,5-b'] Dithiophene -2,6- two (Ethyl formate) (1.0g, 3.0mmol), 2- butyl octanol (2.0g), toluene (40mL), acetylacetone,2,4-pentanedione oxygen titanium (40mg), back flow reaction uses water-separator Remove the ethanol that reaction is produced.After reaction 10h, 2- butyl octanols (1.0g) and acetylacetone,2,4-pentanedione oxygen titanium (160mg) are added, continue anti- Answer 4h.Solvent is distilled off by rotary evaporator, residue with petroleum ether/dichloromethane mixed solution (v/v, 2:1) to wash De- agent, carries out column chromatography for separation, obtains light yellow bulk solid 1.36g, yield 74.1%.1H NMR(400MHz,CDCl3)δ8.38 (s, 2H), 8.09 (s, 2H), 4.28 (d, J=5.6Hz, 4H), 1.80 (d, J=5.6Hz, 2H), 1.47-1.12 (m, 32H), 0.89(m,12H).13C NMR(100MHz,CDCl3)δ162.64,141.35,139.27,138.34,136.72,135.95, 129.89,129.30,122.31,119.32,69.88,68.62,66.72,37.45,34.15,31.82,31.44,31.11, 29.63,29.00,27.78,26.76,23.74,23.00,22.66,15.21,14.10,14.05.
1.4 4,8- dibromo benzo [1,2-b:4,5-b'] Dithiophene -2,6- two [formic acid (2- butyl monooctyl esters] synthesis
In 250mL single port bottles, benzo [1,2-b is added:4,5-b'] Dithiophene -2,6- two [formic acid (2- butyl) monooctyl ester] (1.36g, 2.2mmol), bromine (0.4mL, 4.6mmol), FeCl3(150mg), chloroform 80mL, lucifuge back flow reaction 24h.Natural cooling, adds water and reaction is quenched, and organic layer sodium sulfite aqueous solution is washed repeatedly, is dried, by rotary evaporator Be distilled off solvent, residue with petroleum ether/dichloromethane mixed solution (v/v, 2:1) it is eluant, eluent, carries out column chromatography for separation, Faint yellow solid 1.4g, yield 82.0%.1H NMR(400MHz,CDCl3) δ 8.27 (s, 2H), 4.30 (d, J=5.6Hz, 4H), 1.82 (d, J=5.6Hz, 2H), 1.48-1.16 (m, 32H), 0.91 (dt, J=15.6,6.4Hz, 12H).13C NMR (100MHz,CDCl3)δ161.99,141.20,137.68,136.93,129.74,111.46,69.08,37.39,31.84, 31.42,31.09,29.62,29.01,26.76,23.00,22.68,14.14,14.09.
Embodiment 2
4,8- bis--(2- (5- bromothiophene bases) benzo [1,2-b:4,5-b'] [formic acid (2- butyl) is pungent for Dithiophene -2,6- two Ester] synthesis (M1)
Benzo [the 1,2-b of 2.1 4,8- bis--(2- thienyls):4,5-b'] [formic acid (2- butyl) is pungent for Dithiophene -2,6- two Ester] synthesis
In 100mL single port bottles, (4,8- dibromo benzos [1,2-b are sequentially added:4,5-b'] [the formic acid of Dithiophene -2,6- two (2- butyl) monooctyl ester] (0.77g, 1.0mmol), four (triphenyl phosphorus) palladiums (60mg), 2- tributyl tin thiophene (1.12g, 3.0mmol), 30mL toluene, the protection of system nitrogen.100 DEG C of stirring reactions 18h of temperature control.Stop reaction, question response thing is cooled to room Wen Hou, in being poured into 100mL distilled water, dichloromethane extraction (3 × 30mL).The organic phase of merging is dry with anhydrous magnesium sulfate Dry, filtration, filtrate carries out vacuum distillation and removes solvent, and residue is with petroleum ether:Dichloromethane mixed solution (v/v, 2:1) to wash De- agent, carries out column chromatography for separation, obtains 720mg yellow solids, yield 92.5%.1H NMR(400MHz,CDCl3)δ8.30(s, 2H), 7.59 (d, J=4.9Hz, 2H), 7.51 (d, J=3.0Hz, 2H), 7.34-7.27 (m, 2H), 4.23 (d, J=5.8Hz, 4H), 1.77 (d, J=4.9Hz, 2H), 1.63 (dd, J=15.6,8.2Hz, 2H), 1.47-1.09 (m, 32H), 0.90 (dt, J =15.2,7.0Hz, 12H).13C NMR(100MHz,CDCl3)δ162.58,141.27,137.95,137.51,136.07, 129.72,128.70,127.77,127.29,126.23,68.82,37.37,31.77,31.45,31.10,29.59,28.96, 28.29,26.77,26.72,22.96,22.64,17.31,14.09,14.03,13.58.
2.2 bis--(2- (5- bromothiophene bases) benzo [1,2-b of 4,8-:4,5-b'] [formic acid (the 2- fourths of Dithiophene -2,6- two Base) monooctyl ester] synthesis (M1)
In 100mL single port bottles, 4,8- bis--(2- thienyls) benzos [1,2-b:4,5-b'] [the formic acid of Dithiophene -2,6- two (2- butyl) monooctyl ester] (0.72g, 0.93mmol), dry tetrahydrofuran (THF) 30mL is dissolved in, under the conditions of lucifuge, it is dividedly in some parts N- bromo-succinimides (NBS) (344mg, 1.95mmol).Room temperature reaction 24h.Stop reaction, in pouring 100mL distilled water into, Dichloromethane extracts (3 × 30mL).The organic phase of merging anhydrous magnesium sulfate is dried, filters, and filtrate is by vacuum distillation except molten Agent, residue is with petroleum ether:Dichloromethane mixed solution (v/v, 2:1) it is eluant, eluent, carries out column chromatography for separation.Finally use ethanol 700mg yellow solids, yield 90% are recrystallized to obtain with tetrahydrofuran.1H NMR(400MHz,CDCl3) δ 8.28 (d, J=0.8Hz, 2H), 7.29 (m, 4H), 4.27 (d, J=5.8Hz, 4H), 1.82 (s, 2H), 1.51-1.18 (m, 32H), 0.91 (dd, J= 12.3,6.7Hz,12H).13C NMR(100MHz,CDCl3)δ162.36,141.13,139.25,137.37,136.42, 130.68,129.25,129.17,125.46,114.53,68.99,37.31,31.80,31.41,31.08,29.61,28.96, 26.72,23.00,22.68,14.15,14.10.
Embodiment 3
The synthesis of polymer P V-BDTC1
In 25mL two-mouth bottles, M1 (154mg, 0.2mmol) is sequentially added, tin trimethyl benzene thiophene (187mg, 0.2mmol), three (dibenzalacetone) two palladium (3mg), three (o-tolyl) phosphorus (6mg), deoxygenated toluene 6mL.Protect in nitrogen stream Under shield, 110 DEG C of reaction 24h of temperature control.Natural cooling, adds 10mL dilution with toluene reactant liquors, is added drop-wise in 100mL methyl alcohol and settles. Suction filtration, polymer solids thing carries out surname extraction with methyl alcohol, ether, chloroform successively, by the concentration of chloroform extract, drop Enter in methyl alcohol and settle.Suction filtration, collection solids, vacuum drying.Obtain red solid 200mg, yield 90%.
Embodiment 4
The synthesis of polymer P V-BDTC2
In 25mL two-mouth bottles, M1 (154mg, 0.15mmol), 4,8- bis- (2- (5- alkylthrophene bases) benzos are sequentially added Dithiophene tin trimethyl (187mg, 0.15mmol), three (dibenzalacetone) two palladium (3mg), three (o-tolyl) phosphorus (6mg), Deoxygenated toluene 6mL.Under nitrogen stream protection, 110 DEG C of temperature control reacts 24h to system.Natural cooling, adds the reaction of 10mL dilution with toluene Liquid, is added drop-wise in 100mL methyl alcohol and settles.Suction filtration, polymer solids thing carries out Soxhlet and carries with methyl alcohol, ether, chloroform successively Take.By the concentration of chloroform extract, instill in methyl alcohol and settle.Suction filtration, collection solids, vacuum drying.Obtain red solid 150mg, yield 73%.
The synthesis of polymer P V-BDTC3T
In 25mL two-mouth bottles, 4,8- dibromos benzo [1,2-b is sequentially added:4,5-b'] [the formic acid of Dithiophene -2,6- two (2- butyl) monooctyl ester] (154mg, 0.2mmol), (3,3 "-dioctyl-[2,2':5', 2 "-three thienyls] -5,5 " two trimethyls Tin (160mg, 0.2mmol), three (dibenzalacetone) two palladium (3mg), three (o-tolyl) phosphorus (6mg), deoxygenated toluene 6mL. Under nitrogen stream protection, 110 DEG C of temperature control reacts 24h to system.Natural cooling, adds 10mL dilution with toluene reactant liquors, is added drop-wise to Settle in 100mL methyl alcohol.Suction filtration, polymer solids thing carries out surname extraction with methyl alcohol, ether, chloroform successively.By trichlorine Methane extract is concentrated, and is instilled in methyl alcohol and is settled.Suction filtration, collection solids, vacuum drying.Orange red solid 125mg is obtained, is produced Rate 72%.
The synthesis of polymer P V-BDTC3TO
In 25mL two-mouth bottles, 4,8- dibromos benzo [1,2-b is sequentially added:4,5-b'] [the formic acid of Dithiophene -2,6- two (2- butyl) monooctyl ester] (154mg, 0.2mmol), (3,3 "-two hexyloxies-[2,2':5', 2 "-three thienyls] -5,5 " two front threes Ji Xi (160mg, 0.2mmol), three (dibenzalacetone) two palladium (3mg), three (o-tolyl) phosphorus (6mg), deoxygenated toluene 6mL.Under nitrogen stream protection, 110 DEG C of temperature control reacts 24h to system.Natural cooling, adds 10mL dilution with toluene reactant liquors, is added dropwise Settle in 100mL methyl alcohol.Suction filtration, polymer solids thing carries out surname extraction with methyl alcohol, ether, chloroform successively.By three Chloromethanes extract is concentrated, and is instilled in methyl alcohol and is settled.Suction filtration, collection, vacuum drying.Obtain black solid 75mg, yield 53%.
Embodiment 5
The property of the D-A type wide band gap polymer photovoltaic material containing new benzene thiophene -2,6- dicarboxylic acid esters receptor units The making and performance test of energy sign and its photovoltaic optical device
All intermediates of novel receptor unit and building-up process1H NMR and13C NMR spectras pass through Bruker Dex-400NMR Instrument measurings, the uv-visible absorption spectra of novel receptor cells D-A molded breadth band gap Polymer photovoltaic materials leads to Cross HP-8453 ultraviolet-visible spectrometers measure.
Included based on the organic solar batteries device of D-A type wide band gap polymer photovoltaic material：Indium tin oxide target (ITO) is led Electric glass anode layer, poly styrene sulfonate (PEDOT/PSS) anode modification layer, photoactive layer and negative electrode.Photoactive layer is by institute State Polymer photovoltaic materials and PC71BM blendings are constituted, and its blending ratio is 1:2.Negative electrode is by Ca (10nm)/Al (100nm) layer structure Into.
Embodiment 6
The Photophysics and its polymer solar cell device performance of PV-BDTC1
The thermogravimetric curve of PV-BDTC1 is as shown in Figure 1.Heat decomposition temperature during its thermal weight loss 5% is 326 DEG C.
The differential scanning amount curve of PV-BDTC1 is as shown in Figure 2.In 50-300 DEG C of temperature range, gentle temperature-fall period point is risen Do not occur in that melting peak and peak crystallization.
Ultra-violet absorption spectrums of the PV-BDTC1 in chloroformic solution is as shown in Figure 3.The polymer is demonstrated by 250-550nm Strong absorption.The absworption peak of 483nm can be attributed to donor monomer BDT and jump to the electric charge transfer (ICT) of receptor unit V-BDTC Absworption peak is moved, extinction coefficient herein is 35Lg-1cm-1。
Ultra-violet absorption spectrums of the PV-BDTC1 in solid film is as shown in Figure 4.Compared with the absorption spectrum of solution, spectrogram It is roughly the same, but absworption peak has different degrees of red shift, and this is due to packing of molecules in solid film.The peak position meter by The optical band gap for calculating the material is 2.07eV.
Cyclic voltammetry curves of the PV-BDTC1 in solid film is as shown in Figure 5.Present reversible oxidation peak, it follows that The HOMO energy levels of the material are -5.56eV.
In PV-BDTC1 and PC71The doping ratio of BM is 1:In the case of 2 (w/w, 10mg/mL), PV-BDTC1/PC71BM The J-V curves of photovoltaic device are as shown in Figure 6.Under this condition, the short circuit current of device is 5.90mA/cm2, open-circuit voltage is 0.93V, fill factor, curve factor is 59.39%, and photovoltaic efficiency is 3.15%.
In PV-BDTC1 and PC71The mixed proportion of BM is 1:In the case of 2 (w/w, 10mg/mL), the EQE of photoactive layer is bent Line is as shown in Figure 7.The EQE test scopes that the figure shows are 300-600nm, there is maximum EQE values at 480nm, are 51%.
Embodiment 7
PV-BDTC2 Photophysics and its polymer photovoltaics performance
The thermogravimetric curve of PV-BDTC2 is as shown in Figure 8.Heat decomposition temperature during its thermal weight loss 5% is 357 DEG C.PV- The differential scanning amount curve of BDTC2 is as shown in Figure 9.In 50-300 DEG C of temperature range, the gentle temperature-fall period of liter occurs in that respectively molten Melt peak and peak crystallization.
Ultra-violet absorption spectrums of the PV-BDTC2 in chloroformic solution is as shown in Figure 10.The polymer is showed in 250-550nm Strong absorption.Wherein the absworption peak of 350nm or so for molecule π-π * transition absorptions peak, the absworption peak of 480nm or so is Electric charge transfer (ICT) transition absorption peak of the donor monomer (BDT) to receptor unit (V-BDTC).
Ultra-violet absorption spectrums of the PV-BDTC2 in solid film is as shown in figure 11.Compared with the absorption spectrum of solution, its peak Shape is roughly the same, but absworption peak has different degrees of red shift, and this is due to packing of molecules in solid film.The peak position by The band gap for calculating the material is 2.09eV.
Cyclic voltammetry curves of the PV-BDTC2 in solid film is as shown in figure 12.Reversible oxidation peak is presented, thus The HOMO energy levels for going out the material are -5.67eV.
In PV-BDTC2 and PC71The mixed proportion of BM is 1:In the case of 2 (w/w, 10mg/mL), PV-BDTC2/PC71BM The J-V curves of photovoltaic device are as shown in figure 13.Under this condition, the short circuit current of device is 10.37mA/cm2, open-circuit voltage is 1.03V, fill factor, curve factor is 70.0%, and photovoltaic efficiency is 7.49%.
In PV-BDTC2 and PC71The mixed proportion of BM is 1:In the case of 2 (w/w, 10mg/mL), the EQE curves of photoactive layer Figure is as shown in figure 14.The EQE test scopes that the figure shows are 300-600nm, have maximum EQE values at 500nm or so places, are 70%.
As PV-BDTC2 and PC71The mixed proportion of BM is 1:When 2 (w/w, 16mg/mL), the J of its single-electron device1/2- V is bent As shown in figure 15, its maximum hole mobility is 9.72 × 10 to line-4cm2V-1s-1。
As PV-BDTC2 and PC71The mixed proportion of BM is 1:When 2 (w/w, 16mg/mL), the J of its single-electron device1/2- V is bent As shown in figure 16, its maximum electron mobility is 2.32 × 10 to the maximum to line-3cm2V-1s-1。
As PV-BDTC2 and PC71The mixed proportion of BM is 1:When 2 (w/w, 10mg/mL), its transmission electron microscope (TEM) figure is as schemed Shown in 17, polymer and PCBM show certain aggregation, and phase separation domain is than larger.
As PV-BDTC2 and PC71The mixed proportion of BM is 1:When 2 (w/w, 10mg/mL) and addition 3%DIO, its transmission electricity Mirror TEM figures are as shown in figure 18, and polymer and PCBM are uniformly dispersed, and are demonstrated by good inierpeneirating network structure.
Embodiment 8
PV-BDTC3T Photophysics and its small molecule photovoltaic device performance
Ultra-violet absorption spectrums of the PV-BDTC3T in dichloromethane solution is as shown in figure 19.The wherein absorption of 310nm or so Peak is intramolecular π-π * transition absorptions peak, and the absworption peak of 480nm or so is that donor monomer (3T) arrives receptor unit (V-BDTC) Electric charge transfer (ICT) transition absorption peak.
Ultra-violet absorption spectrums of the PV-BDTC3T in solid film is as shown in figure 20.Compared with the absorption spectrum of solution, its light Spectrogram shape is roughly the same, but absworption peak has different degrees of red shift, and this is due to packing of molecules in solid film.The peak position by Put calculate the material band gap be 2.05eV.
Cyclic voltammetry curves of the PV-BDTC3T in solid film as shown in figure 21, presents reversible oxidation peak, thus The HOMO energy levels for going out the material are -5.60eV.
Embodiment 9
PV-BDTC3TO Photophysics and its small molecule photovoltaic device performance
Ultra-violet absorption spectrums of the PV-BDTC3TO in chloroformic solution is as shown in figure 22.The wherein absworption peak of 320nm or so Absworption peak for intramolecular π-π * transition absorptions peak, 510nm or so is that donor monomer (3TO) arrives receptor unit (V-BDTC) Electric charge transfer (ICT) transition absorption peak.
Ultra-violet absorption spectrums of the PV-BDTC3TO in solid film is as shown in figure 23.Compared with the absorption spectrum of solution, its The peak shape of abosrption spectrogram is roughly the same, but absworption peak has different degrees of red shift, and this is due to packing of molecules in solid film It is caused.The band gap that peak position calculates the material by is 1.80eV.
Cyclic voltammetry curves of the PV-BDTC3TO in solid film is as shown in figure 24.Reversible oxidation peak is presented, thus The HOMO energy levels for drawing the material are -5.23eV.
Describe the present invention despite the incorporation of preferred embodiment, but the invention is not limited in above-described embodiment, It should be understood that claims summarise the scope of the present invention.Under the guidance of present inventive concept, those skilled in the art It should be recognized that certain change that various embodiments of the present invention scheme is carried out, all will be by claims of the present invention Spirit and scope covered.

Claims (4)

1. a class is based on benzene thiophene -2, and 6- dicarboxylic acid esters receive the D-A type wide band gap polymer photovoltaic material of electronic unit, its The molecular structure being characterized by shown in Formulas I.
Formulas I：
Wherein, D is
It is a kind of in group；
R is independently selected from C8～C16It is a kind of in alkyl；R ' is H or independently selected from C6～C16It is a kind of in alkyl.
2. the D-A type wide band gap polymer photovoltaic material as described in claim 1 Formulas I, it is characterised in that for following molecular structure In one kind (1-12).
3. the application of material described in claim 1 and 2, it is characterised in that with the Polymer photovoltaic materials as donor material, with PC71BM is blended the photoactive layers and its polymer solar cell device to form polymer solar battery.
4. the application of material according to claim 3, it is characterised in that the material of polymer solar battery and PCBM Blending mass ratio is 1:2.
CN201610836131.2A 2016-09-20 2016-09-20 D-A type broad-band gap polymer photovoltaic materials based on benzodithiophene-2,6-diformate and application of D-A type broad-band gap polymer photovoltaic materials Pending CN106633000A (en)

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CN107634142A (en) * 2017-09-16 2018-01-26 华南理工大学 A kind of new A D A conjugation small molecules and its application in the opto-electronic device
WO2018196792A1 (en) * 2017-04-25 2018-11-01 The Hong Kong University Of Science And Technology Vertical benzodithiophene-based donor-acceptor polymers for electronic and photonic applications
CN114736232A (en) * 2022-05-11 2022-07-12 江西师范大学 Diester-base bithiophene non-condensed ring electron acceptor material, preparation method and application

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CN102762545A (en) * 2010-02-15 2012-10-31 默克专利股份有限公司 Semiconducting polymers
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WO2018196792A1 (en) * 2017-04-25 2018-11-01 The Hong Kong University Of Science And Technology Vertical benzodithiophene-based donor-acceptor polymers for electronic and photonic applications
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