CN108250222A - (D-A) based on benzene thiophene -4,8- diketonen+1The synthesis and application of D type oligomer photovoltaic donor materials - Google Patents
(D-A) based on benzene thiophene -4,8- diketonen+1The synthesis and application of D type oligomer photovoltaic donor materials Download PDFInfo
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- 0 **c1c(-c2ccc[s]2)[s]c(-c([s]c(-c2cc(*)c(-c3ccc(-c4c(*)cc(C(CC(c5cc(*)c(-c6ccc[s]6)[s]5)=C5C(c6c(*)[s]c(*)c66)=O)=C5C6=O)[s]4)[s]3)[s]2)c2C(C3=C(*=I)SC(*)C33)=N)c2C3=*)c1 Chemical compound **c1c(-c2ccc[s]2)[s]c(-c([s]c(-c2cc(*)c(-c3ccc(-c4c(*)cc(C(CC(c5cc(*)c(-c6ccc[s]6)[s]5)=C5C(c6c(*)[s]c(*)c66)=O)=C5C6=O)[s]4)[s]3)[s]2)c2C(C3=C(*=I)SC(*)C33)=N)c2C3=*)c1 0.000 description 6
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Abstract
The present invention relates to one kind to be based on benzene [1,2 c:4,5 c'] 4,8 diketone (BDD) electron acceptor unit of 1,4-Dithiapentalene, there is (D A)n+1The synthesis of the oligomer photovoltaic donor material of D (n=1,2 ...) framework and its application in organic solar batteries.The oligomer pushes away electronics (D) unit, BDD and its derivative by electronics (A) unit comprising thiophene, benzene, benzene thiophene and its derivative, and a kind of donor material can be used as to be widely used in solution processing type organic solar batteries.When photoactive layer donor material be 5BDTBDD, acceptor material 3,9 two (2 methylene 3 (1,1 dicyan ylmethyl) indolone) 5,5,11,11 four (4 hexyl phenyl) two sulphur alkene [2,3d:2', 3'd] s indoles [1,2 b:5,6'] Dithiophene (ITIC), donor is with being 1 by body mass ratio:When 0.8, the highest energy transformation efficiency of body heterojunction oligomer solar energy reaches 7.89%.For the present invention using oligomer as electron donor material, non-fullerene ITIC builds organic solar batteries for electron acceptor material, realizes the efficient energy conversion of device.
Description
Technical field
The present invention relates to one kind based on benzene thiophene diketone (BDD) electron acceptor unit, have (D-A)n+1D (n=1,
2......) the oligomer photovoltaic donor material of framework synthesis and its application in oligomer solar cell device.It is this kind of
Oligomer can be widely used in solution processing type solar cell as electron donor material.When the electron acceptor material of device is 3,
- two sulphur alkene [2,3d of 9- bis- (2- methylene -3- (1,1- dicyan ylmethyl) indolone) -5,5,11,11- four (4- hexyls phenyl):
2', 3'd]-s- indoles [1,2-b:5,6'] Dithiophene (ITIC), donor is with being 1 by body mass ratio:When 0.8, body heterojunction
The highest energy transformation efficiency of oligomer solar device reaches 7.89%.The present invention is for the first time with (D-A)n+1D types oligomer is supplies
Body material, ITIC make organic solar batteries for non-fullerene acceptor material, realize the efficient energy conversion of device.
Background technology
Today of 21 century, solar energy is because have widely distributed, no territory restriction, inexhaustible, cleaning
The advantages that pollution-free, has become the developing direction of new energy.At present, human use's solar energy mainly includes three kinds of forms：Photoelectricity turns
It changes, photothermal conversion and photochemical conversion.Wherein, organic solar batteries (OSCs) can be realized by opto-electronic conversion to the sun
Directly utilizing and effectively storing for energy, is received significant attention.
Organic solar batteries mainly include polymer solar battery (P-OSCs), small molecule solar cell (SM-
) and oligomer solar cell (OM-OSCs) OSCs.The OM-OSCs researchs of early stage are main to concentrate oligomerisation benzene[1], oligomerisation benzene second
Support[2], Uniformpoly thiophene[3-5], Uniformpoly thiophene ethylene[6], oligomerisation fluorenes[7,8]Synthesis, structure and performance study, these oligomers
(OMs) most of is the homopolymer for including donor element.But oligomer photovoltaic material based on D-A block units and its too
The document report of positive energy battery is seldom[9-13].2014, Bazan et al. reported a series of alternate oligomer photovoltaic materials of D/A
Material[9,10], the energy conversion efficiency of body heterojunction oligomer solar cell reached 5.7-6.4%；South China Science ＆ Engineering University
Huang Fei seminar has studied the oligomerisation object light using traditional two octyloxy diazosulfides of 4,7- Dithiophenes -5,6- as block unit
Material is lied prostrate, obtains the OM-OSCs devices that energy conversion efficiency is 2.35%, but efficiency is less than the P-OSCs devices of phase emergencing copolymer
The energy conversion efficiency value of part[11].2015, the national auspicious seminars of nanometer scientific research center Wei Zhi were reported with two-dimentional two thiophene of benzo
The diazosulfide (dFBT) of fen (BDTT) and the substitution of double fluorine is to the oligomer photovoltaic material O-BDTd-FBT of/receptor unit[12], and the energy conversion efficiency of OM-OSCs devices is increased to 8.10%, higher than the P-OSCs of corresponding polymer P-BDTdFBT
The energy conversion efficiency value of device.Moreover, under the simple Devices preparation process handled without solution additive, based on O-
The energy conversion efficiency of the OM-OSCs devices of BDTdFBT has also reached 6.02%.The same year, Cha Ermusi universities of Sweden king two are firm
Seminar is reported by block unit, end of (3- octyloxyphenyls) quinoxalines of 5- thiophene 2,3- bis- be Rhodanine derivates by
Oligomer photovoltaic material (the TQ of body unitn- DR, n=5,7,9), the energy of body heterojunction oligomer solar cell device
It is 3.05% to measure transformation efficiency[13].Compared with P-OSCs and SM-OSCs devices, the efficiency of OM-OSCs devices is although relatively partially
It is low, but easily adjust since OMs materials have both organic small molecule structure, prepare reproducible, the advantages such as polymer film forming type is good,
OM-OSCs devices are considered to have larger development and application space.Develop the oligomer photovoltaic material and its height haveing excellent performance
The OM-OSCs devices of energy conversion efficiency by be new energy materials and device development important directions.
It is attached：Leading reference
[1]J.A.He,J.L.Crase,S.H.Wadumethrige,K.Thakur,L.Dai,S.Z.Zou,
R.Rathore,C.S.Hartley,J.Am.Chem.Soc.2010,132,13848-13857.
[2]H.Meier,J.Gerold,H.Kolshorn,W.Baumann,M.Bletz,Angew.Chem.,
Int.Edit.2001,41,292-295.
[3]T.Izumi,S.Kobashi,K.Takimiya,Y.Aso,T.Otsubo,J.Am.Chem.Soc.2003,
125,5286-5287.
[4]J.Gierschner,J.Cornil,H.J.Egelhaaf,Adv.Mater.2007,19,173-191.
[5]L.Zhang,N.S.Colella,F.Liu,S.Trahan,J.K.Baral,H.H.Winter,
S.C.Mannsfeld,A.L.Briseno,J.Am.Chem.Soc.2013,135,844-854.
[6]J.Roncali,Acc.Chem.Res.2000,33,147-156.
[7]Q.L.Wang,Y.Qu,H.K.Tian,Y.H.Geng,F.S.Wang,Macromolecules.2011,44,
1256-1260.
[8]J.H.Jo,C.Y.Chi,S.Hoger,G.Wegner,D.Y.Yoon,Chem-Eur.J.2004,10,2681-
2688.
[9]X.F.Liu,Y.M.Sun,B.B.Y.Hsu,A.Lorbach,L.Qi,A.J.Heeger,
G.C.Bazan.J.Am.Chem.Soc.2014,136,5697-5708.
[10]X.F.Liu,Y.M.Sun,L.A.Perez,W.Wen,M.F.Toney,A.J.Heeger,
G.C.Bazan.J.Am.Chem.Soc.2012,134,20609-20612.
[11]C.Zhou,Y.M.Liang,F.Liu,C.Sun,X.L.Huang,Z.X.Xie,F.Huang,J.Roncali,
T.P.Russell,Y.Cao,Adv.Funct.Mater.2014,24,7538-7547.
[12]L.Yuan,Y.F.Zhao,J.Q.Zhang,Y.J.Zhang,L.Y.Zhu,K.Lu,W.Yan,Z.X.Wei,
Adv.Mater.2015,27,4229-4233.
[13]W.Li,D.J.Wang,S.S.Wang,W.Ma,S.D.I.James,X.F.Xu,P.Persson,
S.Fabiano,M.Berggren,O.F.Huang,E.Wang,ACS Appl.Mater.Interfaces.2015,
7,27106-27114.
Invention content
Few for the document report of the oligomer photovoltaic material of current D-A block units, oligomer is taken into account polymer and is had
The advantages of machine small molecule photovoltaic material, does not fully demonstrate, and the relationship of molecular structure and performance is still unintelligible, and the energy of device turns
The problems such as efficiency is relatively low is changed, we have invented one kind to have (D-A)n+1The oligomer photovoltaic donor of D (n=1,2......) framework
Material, the molecular structure feature of such oligomer be with benzene thiophene diketone (BDD) for electron acceptor (A) unit, thiophene,
Benzene, benzene thiophene derivative are electron donor (D) unit.
D-A type oligomer photovoltaic donor material and its high-energy the purpose of the present invention is to provide a kind of intermediate band gap turn
Change efficiency, oligomer solar cell using non-fullerene as electron acceptor material.When non-fullerene is (the 2- methylenes of 3,9- bis-
Base -3- (1,1- dicyan ylmethyl) indolone)-two sulphur alkene [2,3d of -5,5,11,11- four (4- hexyls phenyl):2',3'd]-s-
Indoles [1,2-b:5,6'] during Dithiophene (ITIC), the highest energy transfer efficiency of this kind of oligomer solar cell reaches
7.89%, realize the efficient energy conversion of device.
It is this kind of that there is (D-A)n+1The molecular structure of the D-A type oligomer photovoltaic donor material of D (n=1,2......) framework
It can be any one of following molecule.
It is above-mentioned that there is (D-A)n+1The D-A type oligomer photovoltaic donor material of D (n=1,2......) framework, including following
Any derivative:
With benzene thiophene diketone (BDD) for electron-accepting group, the benzene thiophene (BDT) of alkylthrophene substitution is pushes away electricity
Subbase group has (D-A)n+1The oligomer photovoltaic material 5BDTBDD of D frameworks.
With benzene thiophene diketone (BDD) for electron-accepting group, three thiophene are electron donating group, are had (D-A)n+1D frameworks
Oligomer photovoltaic material 3T2BDD.
With benzene thiophene diketone (BDD) for electron-accepting group, four thiophene are electron donating group, are had (D-A)n+1D frameworks
Oligomer photovoltaic material 4T3BDD.
With benzene thiophene diketone (BDD) for electron-accepting group, five thiophene are electron donating group, are had (D-A)n+1D frameworks
Oligomer photovoltaic material 5T4BDD.
Above-mentioned oligomer photovoltaic material, synthetic schemes of the invention are as follows in order to obtain:
The synthesis of receptor unit benzene thiophene diketone:3,4- thiophene dicarboxylates are stirred to react 12h with bromine at room temperature,
Obtain bis- bromo- 3,4- thiophene dicarboxylates of 2,5-；Bis- bromo- 3,4- thiophene dicarboxylates of 2,5- react under DMF catalysis with oxalyl chloride
12h obtains 2,5-, bis- bromo- 3,4- diacid chlorides thiophene；Bis- bromo- 3,4- diacid chlorides thiophene of 2,5- under Catalyzed by Anhydrous Aluminium Chloride with
2,5- bis- (ethylhexyl) thiophene react, and obtain benzene thiophene diketone (BDD).
The synthesis of D-A type oligomer photovoltaic material 5BDTBDD：The bis- tin compounds of BDT are with BDT-2TBDD-Br in four (triphens
Base phosphine) under palladium chtalyst, Stille couplings occur, synthesis obtains D-A type oligomer 5BDTBDD, and crude product is obtained through column chromatography for separation
To sterling.
The synthesis of D-A type oligomer photovoltaic material 3T2BDD：T-BDD-Br is with the double tin compounds of thiophene in four (triphenyls
Phosphine) under palladium chtalyst, Stille couplings occur, synthesis obtains D-A type oligomer 3T2BDD, and crude product obtains pure through column chromatography for separation
Product.
The synthesis of D-A type oligomer photovoltaic material 4T3BDD：The mono- tin compounds of 2TBDD are with BDD in tetrakis triphenylphosphine palladium
Under catalysis, Stille couplings occur, synthesis obtains D-A type oligomer 4T3BDD, and crude product obtains sterling through column chromatography for separation；
The synthesis of D-A type oligomer photovoltaic material 5T4BDD：2TBDD-BDD-Br is with the double tin of thiophene in four (triphenylphosphines)
Stille couplings occur under palladium chtalyst, synthesis obtains D-A type oligomer 5T4BDD, and crude product obtains sterling through column chromatography for separation.
The present invention based on BDD electron acceptor units, have (D-A)n+1The oligomerisation object light of D (n=1,2......) framework
Donor material is lied prostrate compared with published most of oligomers, its main feature is that:(1) such oligomer is middle width strip gap material, and
There is higher molar absorption coefficient, can preferably absorb the solar energy of short wavelength；(2) the non-fullerene acceptor ITIC of narrow band gap
The energy of long wavelength's sunlight can be preferably absorbed, complementary absorption spectrum can be formed with the blending of such oligomer, improve device
Short circuit current (Jsc) and fill factor (FF)；(3) for the alkyl chain of thiophene in BDD, select the alkyl chain of different length can
Effectively to adjust the dissolubility of oligomer molecule；(4) what selection was different pushes away electronic unit, is made by being pushed away in molecule by structure
With the adjustable absorption spectrum of molecule and electron orbit energy level.Therefore, this kind of material builds photoactive layer with non-fullerene, can
To obtain the oligomer solar cell of high efficiency energy transformation efficiency.
The application of the present invention is：It is non-lipid using the oligomer photovoltaic material of design as photoactive layer electron donor material
Le alkene is photoactive layer electron acceptor material, builds oligomer solar cell, realizes the efficient photoelectricity treater conversion of device.
The oligomer solar cell device uses formal structure, structure Glass/ITO/ZnO/active
layer/MoO3/Ag.Including conductive glass electrode, indium tin oxide target (ITO), zinc oxide, photoactive layer, molybdenum oxide and silver cathode,
Photoactive layers material is oligomer photovoltaic material of the present invention and the non-fullerene acceptor materials of ITIC, and blending weight ratio is
1:0.8。
Description of the drawings
Fig. 1 is the uv-visible absorption spectra of 3BDTBDD chloroformic solutions of the present invention
Fig. 2 is the uv-visible absorption spectra in 3BDTBDD solid films of the present invention
Fig. 3 is the cyclic voltammetry curve in 3BDTBDD solid films of the present invention
Fig. 4 is 3BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL), in chloroform as solvent
In the case of, the J-V curves of the photovoltaic device of addition different proportion DIO
Fig. 5 is 3BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL) adds 0.2% DIO,
The EQE curves of active layer in the case where chloroform is as solvent
Fig. 6 is 3BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL) adds 0.2% DIO,
In the case where chloroform is as solvent, the J of single hole device1/2- V curves
Fig. 7 is 3BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL) adds 0.2% DIO,
In the case where chloroform is as solvent, the J of single-electron device1/2- V curves
Fig. 8, Fig. 9 are 3BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL), adds 0.2%
DIO, in the case where chloroform is as solvent, the atomic force microscope height map and phasor of active layer
Figure 10 is the uv-visible absorption spectra of 5BDTBDD chloroformic solutions of the present invention
Figure 11 is the uv-visible absorption spectra in 5BDTBDD solid films of the present invention
Figure 12 is the cyclic voltammetry curve in 5BDTBDD solid films of the present invention
Figure 13 is 5BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL), in chloroform as solvent
In the case of, the J-V curves of the photovoltaic device of addition different proportion DIO
Figure 14 is 5BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL) adds 0.2% DIO,
The EQE curves of active layer in the case where chloroform is as solvent
Figure 15 is 5BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL) adds 0.2% DIO,
In the case where chloroform is as solvent, the J of single hole device1/2- V curves
Figure 16 is 5BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL) adds 0.2% DIO,
In the case where chloroform is as solvent, the J of single-electron device1/2- V curves
Figure 17, Figure 18 are 5BDTBDD of the present invention and ITIC mixed proportions are 1:0.8 (w/w, 20mg/mL), addition 0.2%
DIO, in the case where chloroform is as solvent, the atomic force microscope height map and phasor of active layer
Figure 19 be 3T2BDD of the present invention, the uv-visible absorption spectra of 4T3BDD and 5T4BDD chloroformic solutions
Figure 20 is 3T2BDD of the present invention, the uv-visible absorption spectra in 4T3BDD and 5T4BDD solid films
Figure 21 is 3T2BDD of the present invention, the cyclic voltammetry curve in 4T3BDD and 5T4BDD solid films
Specific embodiment
The present invention main research idea be：
(1) such oligomer is middle width strip gap material, and has higher molar absorptivity absorption coefficient, can preferably be absorbed short
The energy of wavelength sunlight；(2) the non-fullerene acceptor material ITIC of narrow band gap can preferably absorb the energy of long wavelength's sunlight,
It is blended with such oligomer, complementary spectral absorption can be formed very well, improve short circuit current JscWith fill factor FF.
Below by specific embodiment, the invention will be further described, but these specific embodiments are not in any way
It limits the scope of the invention.
Embodiment 1
4,8- bis- bromo- two (2- ethylhexyls) benzo [1,2-c:4,5-c '] Dithiophene -4,8- diketone (M1) synthesis
The synthesis of 1.1 2,5-, bis- bromo- 3,4- thiophene dicarboxylates
3,4- thiophene dicarboxylates (5g, 29.04mmol) and 40mL glacial acetic acid are added sequentially in 100mL single port bottles, room
Temperature stirring, bromine (8.9mL, 174.24mol) is added in 25mL constant pressure funnels, is slowly dropped into reaction bulb, instead
Answer 12h.It treats after reaction, reaction solution is poured into the stirring of 500mL saturations sodium bisulfate until there is buff white solid analysis
Go out, decompression filters, and drying obtains buff white solid (8.2g, 85.6%), chemical formula C6H2Br2O4S,MS m/z:[M1] is
329.8。
The synthesis of 1.2 2,5-, bis- bromo- 3,4- diacid chlorides thiophene
By bis- bromo- 3,4- thiophene dicarboxylates (2g, 6.06mol) of 2,5-, the dichloromethane of 50mL dryings is added sequentially to
It in 100mL single port bottles, is stirred at room temperature, then adds in oxalyl chloride (6m, 68.5mol) and a drop DMF, 12h is stirred at room temperature.It treats anti-
After answering, by Rotary Evaporators distilling off solvent, without being further processed.
1.3 4,8-, bis- bromo- two (2- ethylhexyls) benzo [1,2-c:4,5-c '] Dithiophene -4,8- diketone synthesis
By 2,5-, bis- bromo- 3,4- diacid chlorides thiophene (0.83g, 2.26mmol), 2,5- bis- (2- ethylhexyls) thiophene
(0.69g, 2.26mmol) and 50mL anhydrous methylene chlorides are added sequentially in 100mL single port bottles, are placed at 0 DEG C and are stirred, in batches
Add in anhydrous AlCl3Powder continues after stirring 30min, is transferred to room temperature reaction 3h.Reaction solution is poured into 100mL 1M/L ice
Dilute hydrochloric acid solution, chloroform extraction three times, merge organic phase, dried with anhydrous magnesium sulfate, filter, pass through Rotary Evaporators
Distilling off solvent, crude product is with petroleum ether:Dichloromethane (v/v, 5:1) mixed solvent carries out column chromatography point as eluant, eluent
From obtaining faint yellow solid 0.41g, yield 30.3%.1H NMR(400MHz,CDCl3)δ3.47–3.15(m,2H),1.82–
1.70 (m, 1H), 1.47-1.17 (m, 7H), 0.89 (dt, J=11.1,7.3Hz, 5H)
Embodiment 2
4,8- bis--(5- bromothiophenes base)-two (2- ethylhexyls) benzo [1,2-c:4,5-c '] Dithiophene -4,8- diketone
(M2) synthesis
2.1 4,8- dithienyls-two (2- ethylhexyls) benzo [1,2-c:4,5-c '] Dithiophene -4,8- diketone conjunction
Into
By M1 (0.5g, 0.83mmol), tributylstamlyl thiophene (0.93g, 2.5mmol), four (triphenyl phosphorus) palladiums
(96mg), 30mL toluene are added sequentially in 100mL bottle with two necks, lead to nitrogen deoxidation.Heating, which is transferred at 110 DEG C, is stirred to react 12h.
Stop reaction, after reactant is cooled to room temperature, be poured into 100mL distilled water, dichloromethane extraction (3x 30mL).It closes
And organic phase, with anhydrous magnesium sulfate drying, filtering, solvent is distilled off in filtrate Jin Hang Minus pressures, and residue is matched with oil:Dichloromethane
Alkane mixed solution (v/v, 5:1) it is eluant, eluent, carries out column chromatography for separation, obtain 325mg yellow solids, yield 64.3%.1H NMR
(300MHz,CDCl3) δ 7.78-7.70 (m, 1H), 7.50 (dd, J=5.1,1.2Hz, 1H), 7.12 (dd, J=5.1,3.8Hz,
1H), 3.31 (d, J=7.4Hz, 2H), 1.76 (s, 1H), 1.33 (s, 8H), 1.01-0.78 (m, 6H)
2.2 4,8-, bis--(5- bromothiophenes base)-two (2- ethylhexyls) benzo [1,2-c:4,5-c '] Dithiophene -4,8- two
The synthesis of ketone (M2)
By 4,8- dithienyls-two (2- ethylhexyls) benzo [1,2-c:4,5-c '] Dithiophene -4,8- diketone (0.5g,
0.82mmol), 30mLTHF is added sequentially in 100mL bottle with two necks, and N- bromo-succinimides are added portionwise under the conditions of being protected from light
(NBS)(307mg,1.73mmo1).React at room temperature 12h.Stop reaction, pour into 100mL distilled water, dichloromethane extraction (3x
30mL).The organic phase of merging, with anhydrous magnesium sulfate drying, filtering, filtrate removes solvent by vacuum distillation, and crude product is with stone
Oily ether:Dichloromethane mixed solution (v/v, 6:1) it is eluant, eluent, carries out column chromatography for separation.Obtain 565mg yellow solids, yield
90%.1H NMR(400MHz,CDCl3)(ppm):7.39 (d, J=5.2,2H), 7.03 (d, J=5.2,2H), 3.27 (m, 4H),
1.74(m,2H),1.41-1.32(m,16H),0.94-0.90(m,12H)
Embodiment 3
2- tin trimethyls -4,8- two (5- (2- ethylhexyls) thienyl) benzo [1,2-b:4,5-b '] Dithiophene (M3)
Synthesis
By 4,8- bis- (5- (2- ethylhexyls) thienyl) benzo [1,2-b:4,5-b '] Dithiophene (0.3g,
0.52mmol), the anhydrous THF of 15mL are added sequentially in 50mL bottle with two necks, are led to nitrogen deoxidation, are transferred at -78 DEG C and cool down 15min,
It is slowly injected into n-BuLi (THF solution of 0.23mL, 0.57mmol, 2.5M/L), -78 DEG C of the reaction was continued 2h inject trimethyl chlorine
Change tin (THF solution of 0.57mL, 0.57mmol, 1M/L), -78 DEG C of the reaction was continued 0.5h are transferred to room temperature reaction 12h.Stop
Reaction adds in 10mL water quenchings and goes out, and reaction solution is poured into 100mL distilled water, is extracted (3x 30mL) with dichloromethane.What is merged has
Machine phase, with anhydrous magnesium sulfate drying, filtering, filtrate removes solvent by vacuum distillation, and drying without being further processed, obtains
3.7g light yellow viscous liquids, yield 88%.1H NMR(500MHz,CDCl3) δ 7.71 (s, 1H), 7.66 (d, J=5.7Hz,
1H), 7.45 (t, J=4.8Hz, 1H), 7.33 (s, 2H), 6.92 (s, 2H), 2.88 (s, 4H), 1.81-1.64 (m, 2H), 1.35
(s, 20H), 0.97 (s, 14H), 0.42 (d, J=2.5Hz, 9H)
Embodiment 4
2,2 '-two (tin trimethyl) -4,8- two (5- (2- ethylhexyls) thienyl) benzo [1,2-b:4,5-b '] two thiophenes
The synthesis of fen (M4)
By 4,8- bis- (5- (2- ethylhexyls) thienyl) benzo [1,2-b:4,5-b '] Dithiophene (0.5g,
0.86mmol), the anhydrous THF of 15mL are added sequentially in 50mL bottle with two necks, are led to nitrogen deoxidation, are transferred at -78 DEG C and cool down 15min,
It is slowly injected into n-BuLi (THF solution of 0.76mL, 1.9mmol, 2.5M/L), -78 DEG C of the reaction was continued 2h inject trimethyl ammonia chloride
Tin (THF solution of 1.9mL, 1.9mmol, 1M/L), -78 DEG C of the reaction was continued 0.5h are warmed to room temperature reaction 12h naturally.Stop anti-
Should, it adds in 10mL water quenchings and goes out, reaction solution is poured into 100mL distilled water, is extracted (3x 30mL) with dichloromethane.What is merged is organic
Phase, anhydrous magnesium sulfate is dry, filtering, and filtrate removes solvent by vacuum distillation, and drying without being further processed, obtains yellow
Viscous liquid 0.76g, yield 85%.1H NMR(300MHz,CDCl3) δ 7.78-7.63 (m, 1H), 7.31 (d, J=3.5Hz,
1H), 6.88 (t, J=9.2Hz, 1H), 2.87 (d, J=6.6Hz, 3H), 1.55 (s, 3H), 1.04-0.77 (m, 6H), 0.54-
0.24(m,9H).
Embodiment 5
The synthesis of compound 3BDTBDD
By M2 (0.167g, 0.22mmol), M3 (0.358g, 0.48mmol), four (triphenyl phosphorus) palladiums (15mg), 20mL first
Benzene is added sequentially in 50mL bottle with two necks, leads to nitrogen deoxidation.It is transferred at 110 DEG C and is stirred to react 12h.Stop reaction, treat reactant
It after being cooled to room temperature, is poured into 100mL distilled water, dichloromethane extraction (3x 30mL).Merge organic phase, anhydrous slufuric acid
Magnesium is dry, filtering, and solvent is distilled off in filtrate Tong Guo Minus pressures, and residue is with petroleum ether:Dichloromethane mixed solution (v/v, 4:1)
For eluant, eluent, column chromatography for separation is carried out, obtains 225mg aubergine solids, yield 61.9%.1H NMR(300MHz,CDCl3)δ7.72
(s, 1H), 7.65 (d, J=4.0Hz, 1H), 7.55 (d, J=5.7Hz, 1H), 7.38 (d, J=5.7Hz, 1H), 7.24 (s,
2H), 7.21 (d, J=4.0Hz, 1H), 6.84 (d, J=3.7Hz, 2H), 3.24 (d, J=8.1Hz, 2H), 2.81 (d, J=
4.0Hz, 4H), 1.78-1.53 (m, 4H), 1.48 (s, 2H), 1.30 (t, J=38.2Hz, 32H), 0.86 (s, 22H) ,-0.03
(s,2H),-0.09(s,1H).
Embodiment 6
The synthesis of oligomer 5BDTBDD
The synthesis of 6.1 compound BDT-BDD-Br
By M2 (0.24g, 0.31mmol), M3 (0.23g, 0.31mmol), four (triphenyl phosphorus) palladiums (11mg), 20mL toluene
It is added sequentially in 50mL bottle with two necks, leads to nitrogen deoxidation.It is transferred at 110 DEG C and is stirred to react 12h.Stop reaction, treat that reactant is cold
But it to after room temperature, is poured into 100mL distilled water, dichloromethane extraction (3x 30mL).Merge organic phase, use anhydrous slufuric acid
Magnesium is dry, filtering, and solvent is distilled off in filtrate Tong Guo Minus pressures.Residue is with petroleum ether:Dichloromethane mixed solution (v/v, 5:1)
For eluant, eluent, column chromatography for separation is carried out, obtains 120mg red solids, yield 46%.1H NMR(300MHz,CDCl3)δ7.78(s,
1H), 7.71 (d, J=4.0Hz, 1H), 7.62 (d, J=5.7Hz, 1H), 7.44 (dd, J=7.6,4.9Hz, 2H), 7.32 (t, J
=3.4Hz, 2H), 7.26 (d, J=2.0Hz, 1H), 7.04 (d, J=4.1Hz, 1H), 6.91 (dd, J=4.2,3.6Hz, 2H),
3.61-3.05 (m, 4H), 2.83 (dt, J=66.2,33.1Hz, 4H), 1.84-1.63 (m, 5H), 1.56 (s, 3H), 1.53-
1.18(m,36H),1.04–0.77(m,26H),0.02–-0.05(m,1H).
The synthesis of 6.2 compound 5BDTBDD
By M2 (0.24g, 0.31mmol), M3 (0.23g, 0.31mmol), four (triphenyl phosphorus) palladiums (11mg), 20mL toluene
It is added sequentially in 50mL bottle with two necks, leads to nitrogen deoxidation.It is transferred at 110 DEG C and is stirred to react 12h.Stop reaction, treat that reactant is cold
But it to after room temperature, is poured into 100mL distilled water, dichloromethane extraction (3x 30mL).Merge organic phase, use anhydrous slufuric acid
Magnesium is dry, filtering, and solvent is distilled off in filtrate Jin Hang Minus pressures, and residue is with petroleum ether:Dichloromethane mixed solution (v/v, 3:1)
For eluant, eluent, column chromatography for separation is carried out, obtains 120mg red solids, yield 46%.1H NMR(300MHz,CDCl3)δ7.79
(s, 1H), 7.75 (s, 1H), 7.71 (d, J=4.0Hz, 2H), 7.63 (s, 1H), 7.61 (s, 1H), 7.46 (s, 1H), 7.44
(s, 1H), 7.37-7.31 (m, 3H), 7.28-7.27 (m, 2H), 6.96 (d, J=3.5Hz, 1H), 6.94-6.90 (m, 2H),
3.43-3.21 (m, 5H), 2.95-2.85 (m, 6H), 1.75 (s, 6H), 1.39 (dd, J=45.3,22.2Hz, 42H), 1.04-
0.81(m,31H),0.00(s,13H).
Embodiment 7
The synthesis of oligomer 3T2BDD
By T-BDD (208mg, 0.35mmol), double methyl tin thiophene (62mg, 0.16mmol), four (triphenyl phosphorus) palladiums
(9.2mg), 20mL toluene are added sequentially in 50mL bottle with two necks, lead to nitrogen deoxidation.110 DEG C are warming up to, is stirred to react 12h.Stop
Reaction, after reactant is cooled to room temperature, is poured into 100mL distilled water, dichloromethane extraction (3x 30mL).It is associated with
Machine phase, with anhydrous magnesium sulfate drying, filtering, solvent is distilled off in filtrate Jin Hang Minus pressures, and residue is with petroleum ether:Dichloromethane mixes
Conjunction solution (v/v, 3:1) it is eluant, eluent, carries out column chromatography for separation, obtain 100mg red solids, yield 55%.1H NMR
(400MHz,CDCl3) δ 7.83 (s, 1H), 7.77 (dd, J=3.7,1.2Hz, 1H), 7.52 (dd, J=5.1,1.1Hz, 1H),
7.14 (dd, J=5.1,3.8Hz, 1H), 3.39-3.23 (m, 4H), 1.77 (s, 2H), 1.45-1.19 (m, 18H), 0.99-
0.80(m,12H).
Embodiment 8
The synthesis of oligomer 4T3BDD
By 2TBDD-Sn (153mg, 0.2mmol), BDD (48mg, 0.08mmol), four (triphenyl phosphorus) palladiums (9.2mg),
20mL toluene is added sequentially in 50mL bottle with two necks, leads to nitrogen deoxidation.110 DEG C are heated to, is stirred to react 12h.Stop reaction, treat anti-
It after object is answered to be cooled to room temperature, is poured into 100mL distilled water, dichloromethane extraction (3x 30mL).Merge organic phase, with nothing
Water magnesium sulfate is dry, filtering, and solvent is distilled off in filtrate Tong Guo Minus pressures, and residue is with petroleum ether:Dichloromethane mixed solution (v/
v,3:4) it is eluant, eluent, carries out column chromatography for separation, obtain 77mg aubergine solids, yield 65%.1H NMR(400MHz,CDCl3)δ
7.87-7.81 (m, 1H), 7.77 (dd, J=3.7,1.1Hz, 1H), 7.52 (dd, J=5.1,1.1Hz, 1H), 7.14 (dd, J=
5.1,3.8Hz,1H),3.44-3.23(m,4H),1.77(s,2H),1.48-1.18(m,14H),1.00-0.78(m,10H).
Embodiment 9
The synthesis of oligomer 5T4BDD
By 2TBDD-BDD (120mg, 0.1mmol), double methyl tin thiophene (21mg, 0.05mmol), four (triphenyl phosphorus) palladiums
(5.8mg), 20mL toluene are added sequentially in 50mL bottle with two necks, lead to nitrogen deoxidation.110 DEG C are heated to, is stirred to react 12h.Stop
Reaction, after reactant is cooled to room temperature, is poured into 100mL distilled water, dichloromethane extraction (3x 30mL).It is associated with
Machine phase, with anhydrous magnesium sulfate drying, filtering, solvent is distilled off in filtrate Jin Hang Minus pressures, and residue is with petroleum ether：Dichloromethane mixes
Conjunction solution (v/v, 2:1) it is eluant, eluent, carries out column chromatography for separation, obtain 60mg atropurpureus solids, yield 54%.1H NMR
(400MHz,CDCl3) δ 7.88 (d, J=4.8Hz, 3H), 7.80 (d, J=2.6Hz, 1H), 7.55 (d, J=3.9Hz, 1H),
7.19-7.15 (m, 1H), 3.31 (t, J=6.1Hz, 8H), 1.8 (s, 4H), 1.50-1.24 (m, 31H), 0.99 (ddd, J=
17.1Hz,13.9Hz,7.1Hz,23H).
Embodiment 10
Containing based on benzene thiophene diketone (BDD) receptor unit, have (D-A)n+1The D-A of D (n=1,2......) framework
The making and performance test of the performance characterization and its solar cell device of type oligomer photovoltaic donor material
1H-NMR and13C-NMR spectrum are purple by Bruker Dex-300NMR and Bruker Dex-400NMR Instrument measurings
Outside-visible absorption spectra is measured by HP-8453 ultraviolet-visible spectrometers.
Based on benzene thiophene diketone (BDD) receptor unit, have (D-A)n+1The D-A type of D (n=1,2......) framework
The solar cell device of oligomer photovoltaic donor material uses formal structure, structure Glass/ITO/ZnO/active
layer/MoO3/Ag.Including conductive glass electrode, indium tin oxide target (ITO), zinc oxide, photoactive layer, molybdenum oxide, silver cathode, light
Activation layer material is oligomer photovoltaic material of the present invention and the non-fullerene acceptor materials of ITIC, and blending weight ratio is 1:
0.8。
Embodiment 11
The optical physics of 3BDTBDD, electrochemistry and its solar cell device performance
Uv-visible absorption spectras of the 3BDTBDD in chloroformic solution is as shown in Figure 1.The oligomer is in 250-550nm tables
Strong absorption, wherein electron transition absorption peak of the absorption peak of 340nm or so for the π-π * of molecule, 484nm absorption peaks are showed
It can be attributed to electric charge transfer (ICT) the transition absorption peak of donor monomer BDT to receptor unit BDD.
Uv-visible absorption spectras of the 3BDTBDD in solid film is as shown in Figure 2.Compared with the absorption spectrum of solution, light
The peak type of spectrogram is not much different, but absorption peak red shift, plays peak position and is set to 610nm or so, calculates the light of the material
Band gap is 2.03eV.
Cyclic voltammetry curves of the 3BDTBDD in solid film is as shown in Figure 3.Reversible oxidation peak is presented, is calculated by figure
The HOMO energy levels for obtaining the material are -5.52eV.The HUMO energy levels that the material is calculated by reduction peak are -3.32eV.
3BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, the J-V curves of photovoltaic device are as shown in Figure 4.Under this condition, the short circuit current of device is 9.51mAcm2, open
Road voltage be 0.90V, fill factor 50.6%, PCEmaxIt is 4.33%.
3BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, the EQE curves of active layer are as shown in Figure 5.The EQE test scopes that the figure is shown are 300-800nm, in 670nm
There are maximum EQE values at place, is 47%.
3BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, the J of single-electron device1/2- V curves are as shown in fig. 6, its maximum hole mobility is 1.73 × 10- 5cm2V-1s-1。
3BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, the J of single-electron device1/2- V curves are as shown in fig. 7, its maximum electron mobility is up to 3.84 × 10- 5cm2V-1s-1。
3BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, atomic force microscope (AFM) figure such as Fig. 8 of active layer, shown in Fig. 9.Wherein Fig. 8 is height map, and Fig. 9 is phase
Figure.Roughness RMS is measured as 0.87nm.
Embodiment 12
The optical physics of 5BDTBDD, electrochemistry and its solar cell device performance
Ultra-violet absorption spectrums of the 5BDTBDD in chloroformic solution is as shown in Figure 10.The oligomer is demonstrated by 250-600nm
Strong absorption.Wherein, the absorption peak of 350nm or so is the π-π * electron transition absorption peaks of molecule, and 512nm absorption peaks can sum up
In electric charge transfer (ICT) the transition absorption peak of donor monomer BDT to receptor unit BDD.
Ultra-violet absorption spectrums of the 5BDTBDD in solid film is as shown in figure 11.Compared with the absorption spectrum of solution, solid film
Absorption spectrum have about 50nm red shift, this is mainly due to molecular motions to be limited, and intermolecular interaction force is caused to add
Caused by strong, moreover, in long wavelength region, there is a new apparent absorption peak, this absorption peak is due to molecule
Between pi-pi accumulation caused by.It has measured peak position and has been set to 663nm or so, the optical band gap for calculating the material is 1.87eV.
Cyclic voltammetry curves of the 5BDTBDD in solid film is as shown in figure 12.Reversible oxidation peak is presented, is calculated by figure
The HOMO energy levels for obtaining the material are -5.48eV.The lumo energy that the material is calculated by reduction peak is -3.36eV.
5BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, the J-V curves of photovoltaic device are as shown in figure 13.Under this condition, the short circuit current of device is 13.23mAcm2,
Open-circuit voltage is 0.91V, fill factor 65.6%, PCEmaxIt is 7.89%.
5BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, the EQE curves of active layer are as shown in figure 14.The EQE test scopes that the figure is shown are 300-800nm, 540-
EQE values are above 60% in the range of 710nm.
5BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, the J of single-electron device1/2- V curves are as shown in figure 15, and maximum hole mobility is 1.12 × 10- 4cm2V-1s-1。
5BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, the J of single-electron device1/2- V curves are as shown in figure 16, and maximum electron mobility is up to 8.93 ×
10-5cm2V-1s-1。
5BDTBDD is 1 with ITIC mixed proportions:0.8 (w/w, 20mg/mL) adds 0.2% DIO, in chloroform as molten
In the case of agent, atomic force microscope figure such as Figure 17 of active layer, shown in Figure 18.Wherein Figure 17 be height map, Tu18Wei
Phasor.Roughness RMS is measured as 1.23nm.
Embodiment 13
The optical physics and chemical property of 3T2BDD, 4T3BDD and 5T4BDD
The ultra-violet absorption spectrum of 3T2BDD, 4T3BDD and 5T4BDD in chloroformic solution is as shown in figure 19.The series oligomerisation
Object UV absorption is concentrated mainly between 400-600nm.Its maximum absorption band is donor monomer thiophene to receptor unit BDD
Electric charge transfer (ICT) transition absorption peak, respectively 441nm, 484nm, 487nm.
The ultra-violet absorption spectrum of 3T2BDD, 4T3BDD and 5T4BDD in solid film is as shown in figure 20.With the absorption of solution
Spectrum is compared, and the red shift of absorption spectrum difference about 80nm, 70nm, the 100nm of solid film, this is mainly due to molecular motions to be limited,
Cause caused by intermolecular interaction force reinforcement, moreover, in long wavelength region, a new apparent absorption occur
Peak, this absorption peak are caused by the pi-pi accumulation between dividing.It is respectively 616nm, 665nm to have measured peak position,
688nm.The optical band gap for calculating the series material is respectively 2.01,1.86,1.80eV.
The cyclic voltammetry curve of 3T2BDD, 4T3BDD and 5T4BDD in solid film is as shown in figure 21.It presents reversible
Oxidation peak, by figure be calculated the series material HOMO energy levels be respectively -5.46, -5.40, -5.27eV.
Despite the incorporation of preferred embodiment, the present invention is described, but the invention is not limited in above-described embodiment,
It should be understood that appended claims summarise the scope of the present invention.Under the guidance of present inventive concept, those skilled in the art
It will be appreciated that certain change that various embodiments of the present invention scheme is carried out, it all will be by claims of the present invention
Spirit and scope covered.
Claims (4)
1. one kind is based on benzene [1,2-c:4,5-c'] 1,4-Dithiapentalene -4,8- diketone (BDD) electron acceptor unit (D-A)n+1D(n
=1,2......) type oligomer photovoltaic material, it is characterised in that there is the molecular structure shown in Formulas I.
Formulas I：(n=1,2......)
Wherein D is：
A is：
One kind in group；
R1Independently selected from C6-C16One kind of alkyl；R2For H or independently selected from C6-C16One kind of alkyl；R3Independently selected from
C6-C16One kind of alkyl is OR1Or it is SR1。
2. (D-A) based on benzene thiophene diketone (BDD) receptor unit as described in claim 1 Formulas In+1D (n=1,
2......) type oligomer photovoltaic material, it is characterised in that for one kind (1-13) in following molecular structure.
3. the application of 1 and 2 material of claim, it is characterised in that using the oligomer photovoltaic material as donor material, with
3,9- bis- (2- methylene -3- (1,1- dicyan ylmethyl) indolones)) -5,5,11,11- tetra- (4- hexyls phenyl)-two sulphur alkene [2,
3d：2', 3'd]-s- indoles [1,2-b:5,6'] Dithiophene (ITIC) blending form photoactive layers and its organic solar batteries device
Part.
4. the application of material according to claim 3, in organic solar batteries, the material is blended feature with ITIC
Mass ratio is 1:0.8.
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| CN108864142A (en) * | 2018-07-27 | 2018-11-23 | 武汉理工大学 | A kind of novel method for synthesizing of ITIC derivative |
| CN111019095A (en) * | 2019-10-23 | 2020-04-17 | 苏州大学 | Ternary random conjugated polymer based on 2, 5-di (2-thienyl) thiazolo [5,4-d ] thiazolyl |
| CN111019095B (en) * | 2019-10-23 | 2021-08-31 | 苏州大学 | Ternary random conjugated polymer based on 2, 5-di (2-thienyl) thiazolo [5,4-d ] thiazolyl |
| CN113214456A (en) * | 2020-01-21 | 2021-08-06 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN113214456B (en) * | 2020-01-21 | 2023-10-13 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN111892696A (en) * | 2020-07-23 | 2020-11-06 | 华南理工大学 | Dithienobenzene fused ring quinoxaline conjugated polymer and preparation method and application thereof |
| CN111848649A (en) * | 2020-08-05 | 2020-10-30 | 中国科学院重庆绿色智能技术研究院 | Conjugated micromolecule semiconductor material containing halogen modified core group and preparation and application thereof |
| CN111909169A (en) * | 2020-08-10 | 2020-11-10 | 泰州市海创新能源研究院有限公司 | Hole transport material with benzodithiophene diketone as core, synthesis method and application in perovskite solar cell |
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