CN103570743B - Two-dimensional conjugated organic molecule photovoltaic material of solution processable and preparation method thereof and application - Google Patents

Two-dimensional conjugated organic molecule photovoltaic material of solution processable and preparation method thereof and application Download PDF

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CN103570743B
CN103570743B CN201310516056.8A CN201310516056A CN103570743B CN 103570743 B CN103570743 B CN 103570743B CN 201310516056 A CN201310516056 A CN 201310516056A CN 103570743 B CN103570743 B CN 103570743B
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李永舫
张婧
何畅
申素玲
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Abstract

The invention discloses a kind of solution processable organic molecule photovoltaic material based on two-dimensional conjugated benzene 1,4-Dithiapentalene and preparation method thereof and application.The two-dimensional conjugated benzene 1,4-Dithiapentalene that this quasi-molecule replaces with thiophene is core, two ends symmetry connects thiofuran ethylene indone or bithiophene ethene indone conjugated structure unit, and its structural formula is such as formula shown in I.They have good solubility common are in machine solvent (as methylene dichloride, trichloromethane, tetrahydrofuran (THF) etc.), can prepare high-quality film by solution methods; And compared with polymer materials easier purifying, the material that purity is very high can be obtained.This kind of organic molecule is used for the donor material of organic solar batteries, and effciency of energy transfer is more than 6.5%.

Description

Two-dimensional conjugated organic molecule photovoltaic material of solution processable and preparation method thereof and application
Technical field
The present invention relates to two-dimensional conjugated organic molecule photovoltaic material of a kind of solution processable and preparation method thereof and application.
Background technology
1986, Kodak doctor Deng Qingyun uses CuPc to be that acceptor (A) has prepared the organic photovoltaic devices (C.W.Tang with D/A heterojunction bilayers structure to body (D), perylene, Appl.Phys.Lett., 1986,48:183-185.), under simulated solar irradiation, effciency of energy transfer is close to 1%.Nineteen ninety-five, the Yu Gang etc. of black square study group invented the conjugated polymers/solubility C of solution processable 60derivative blended type " body heterojunction " (bulk heterojunction) polymer solar battery (G.Yu J.Gao J.C.Hummelen, F.Wudl, A.J.Heeger, Science, 1995,270:1789-1791.).Bulk heteroj junction type solar cell simplifies preparation technology, by expanding to acceptor interface area and shortening exciton transfer distance and improve effciency of energy transfer, thus organic polymer solar cell research is afterwards all mainly adopt bulk heteroj unction structure.
Recent years, the organic molecule solar cell of solution processable because have that polymer solar battery preparation technology is simple, cost is low simultaneously, lightweight, can flexible device be prepared into, and the advantage that organic molecular structure is determined, purity is high and device performance easily repeats and be subject to extensive concern (Y.Z.Lin, Y.F.Li, X.W.Zhan, Chem.Soc.Rev., 2012,41,4245-4272.).In solution processable organic molecule photovoltaic material, molecule containing triphenylamine is especially paid attention to due to excellent solvability ((a) C.He, Q.G.He, Y.P.Yi, G.L.Wu, F.L.Bai, Z.G.Shuai, Y.F.Li, J.Mater.Chem.2008, 18, 4085-4090. (b) J.Zhang, Y.Yang, C.He, Y.J.He, G.J.Zhao, Y.F.Li, Macromolecules, 2009, 42, 7619-7622. (c) J.Zhang, D.Deng, C.He, Y.J.He, M.J.Zhang, Z.-G.Zhang, Z.J.Zhang, Y.F.Li, Chem.Mater., 2011, 23, 817-822. (d) H.X.Shang, H.J.Fan, Y.Liu, W.P.Hu, Y.F.Li, X.W.Zhan, Adv.Mater., 2011, 23, 1554 – 1557.).But due to the nonplanarity of triphenylamine, the interaction between molecule is more weak, causes lower hole mobility and lower photovoltaic device packing factor, thus limit the efficiency of photovoltaic device.Recently, by planarity D-A multipolymer to the inspiration of body photovoltaic material, planarity solution processable organic molecule arouses attention, and reach 5-6%((a based on the efficiency of this kind of solution processable organic molecule solar cell) Y.Liu, X.Wan, F.Wang, J.Zhou, G.Long, J.Tian, J.You, Y.Yang and Y.Chen, Adv.Energy Mater., 2011, 1, 771. (b) Y.Liu, X.Wan, F.Wang, J.Zhou, G.Long, J.Tian and Y.Chen, Adv.Mater., 2011, 23, 5387. (c) Y.Sun, G.C.Welch, W.L.Leong, C.J.Takacs, G.C.Bazan and A.J.Heeger, Nat.Mater., 2012, 11, 44.).
Two-dimentional conjugation benzene 1,4-Dithiapentalene with thiophene side chain has been proved to be to form high-efficiency polymer to important structural unit ((a) L.J.Huo of body photovoltaic material, S.Q.Zhang, X.Guo, F.Xu, Y.F.Li, J.H.Hou, Angew.Chem.Int.Ed., 2011, 50, 9697-9702. (b) Y.Huang, X.Guo, F.Liu, L.J.Huo, Y.M.Chen, T.P.Russell, C.C.Han, Y.F.Li, J.H.Hou, Adv.Mater.2012, 24, 3383 – 3389.), this structural unit has large π coplanar structure, the air stability etc. that strong electron donation is become reconciled.This two-dimensional conjugated benzo two thiophene unit is incorporated in solution processable organic molecule photovoltaic material by the present invention, has prepared the two-dimensional conjugated organic molecule photovoltaic material of efficient solution processable.
Summary of the invention
The object of this invention is to provide that a kind of the two-dimentional conjugation benzene 1,4-Dithiapentalene (2D-BDT) of thiophene conjugation side chain is core to be with, two ends symmetry connects two-dimensional conjugated organic molecule of solubility of thiofuran ethylene indone conjugated structure unit and preparation method thereof.
The general structure of the two-dimensional conjugated organic molecule of solubility provided by the present invention is such as formula shown in I:
In formula I, R 1and R 3be all straight chained alkyl or the branched-chain alkyl of 6-12 independently selected from the total number of carbon atoms, R 2for direct-connected alkyl or branched-chain alkyl that hydrogen atom or the total number of carbon atoms are 6-12, n=1-3.
The method of solubility organic molecule shown in preparation formula I (n=1-3), comprise the steps: under the katalysis of tetrakis triphenylphosphine palladium, compound shown in compound and formula III shown in formula II is reacted, obtains the solubility organic molecule (n=1-3) shown in formula I.
In formula II, R 1, R 2definition cotype I; In formula III, n, R 3definition cotype I.
In aforesaid method, shown in formula II, the molar ratio of compound shown in compound and formula III is 1:2-2.1, preferred 1:2.
The molar ratio of compound shown in described tetrakis triphenylphosphine palladium and formula III is 0.02 ~ 0.05:1, preferred 0.02:1.
Described reaction is carried out in organic solvent.Described organic solvent specifically can be chlorobenzene, dimethylbenzene or toluene.
The temperature of reaction of described reaction is 100-115 DEG C, preferably 115 DEG C; Reaction times is 12-48 hour, preferably 24 hours.
The invention provides the method for monomer (n=1-3) shown in a kind of preparation formula III; comprise step as follows: the compound shown in formula IV, formula V and piperidines and dried acetonitrile are mixed in reactor, then 70 DEG C-90 DEG C (preferably 80 DEG C) backflow 12-24 hour (preferably 24 hours) under nitrogen protection.By reaction mixture cool to room temperature, be then dissolved in methylene dichloride, wash with salt subsequently, anhydrous magnesium sulfate drying, after solvent is fallen in vacuum-evaporation, adopts methylene dichloride/sherwood oil (1/5, V/V) cross chromatographic column to purify, obtain yellow solid and be compound shown in formula III.Wherein reaction raw materials mol ratio is formula IV compound: the compound=1:2-2.2 shown in formula V, preferred 1:2.1.
In formula V, n, R 3definition cotype III.
Shown in the formula I of said n=3, solubility organic molecule also can be prepared as follows, comprises the steps:
1) under the katalysis of tetrakis triphenylphosphine palladium, compound shown in compound and formula V shown in formula II is reacted, obtains compound shown in formula VI;
In formula II, R 1, R 2definition cotype I; In formula III, n, R 3definition cotype I; In formula VI, R 1, R 2, R 3, the definition cotype I of n;
2) in an inert atmosphere, carry out back flow reaction by after the compound shown in formula IV, VI and piperidines and toluene mixing, obtain the solution containing the solubility organic molecule (n=3) shown in formula I.
Wherein, shown in step 1) Chinese style II, the molar ratio of compound shown in compound and formula V is 1:2 ~ 2.1, preferred 1:2.The molar ratio of compound shown in described tetrakis triphenylphosphine palladium and formula V is 0.02 ~ 0.05:1, preferred 0.02:1.Described reaction is carried out in organic solvent.Described organic solvent specifically can be chlorobenzene, dimethylbenzene or toluene.The temperature of reaction of described reaction is 80-100 DEG C, preferably 90 DEG C; Reaction times is 12-48 hour, preferably 24 hours.
Step 2) described in reaction temperature of reaction be 100-110 DEG C, preferably 110 DEG C; Reaction times is 12-48 hour, preferably 24 hours.The mol ratio that feeds intake of described formula IV compound and the compound shown in formula VI is 1:2-2.2, preferred 1:2.1.
Aforesaid method also comprises following purification step: by the described solution cool to room temperature containing the solubility organic molecule (n=3) shown in formula I, then be dissolved in methylene dichloride, wash with salt subsequently, anhydrous magnesium sulfate drying, after solvent is fallen in vacuum-evaporation, employing methylene dichloride and sherwood oil volume ratio are that chromatographic column purification crossed by the mixed solvent of 1:3, obtain solubility organic molecule shown in formula I.
Solubility organic molecule shown in above-mentioned formula I is preparing the application in organic solar batteries, and the application particularly in the donor material preparing organic solar batteries, also all belongs to protection scope of the present invention.
In the design that the concept of two-dimentional conjugation is applied to solution processable organic molecule photovoltaic material by the present invention and synthesis, synthesize the two-dimensional conjugated organic molecule of solubility that the two-dimentional conjugation benzene 1,4-Dithiapentalene replaced with thiophene is core, two ends symmetry connects thiophene or bithiophene ethene indone conjugated structure unit.They have good solubility common are in machine solvent (as methylene dichloride, trichloromethane, tetrahydrofuran (THF) etc.), can prepare high-quality film by solution methods; And compared with polymer materials easier purifying, the material that purity is very high can be obtained.Meanwhile, these molecules have wide visible region and absorb, the band gap of suitable HOMO and lumo energy and relative narrower.Be to body, PC with this type of organic molecule 60bM or PC 70bM is that acceptor has prepared body heterojunction organic solar batteries, and the highest energy efficiency of conversion after its optimization can more than 6.5%.
Accompanying drawing explanation
Fig. 1 is 2,6-di-thiofuran ethylene indone 4,8-bis-thiophene benzos [1 provided by the invention, 2-b:4,5-b '] two thiophene (TVIBDT-T), 2,6-bigeminy thiofuran ethylene indone 4,8-bis-thiophene benzos [1,2-b:4,5-b '] two thiophene (DTVIBDT-T) and 2,6-terthienyl ethene indone 4,8-bis-thiophene benzo [1,2-b:4,5-b '] synthetic route chart of two thiophene (TTVIBDT-T).
Fig. 2 is TVIBDT-T, DTVIBDT-T and TTVIBDT-T solution of embodiment 5 ~ 8 preparation and the absorption spectrum of solid film.
Fig. 3 is be to the structural representation of body and the PCBM acceptor blend film organic solar batteries that is active coating with TVIBDT-T, DTVIBDT-T and TTVIBDT-T.
Fig. 4 is based on current-voltage curve figure (a) of the organic solar batteries of TVIBDT-T/PC60BM and DTVIBDT-T/PC70BM (mass ratio 1.5:1) and external quantum efficiency figure (b); Fig. 4 (c) is the current-voltage curve figure of the organic solar batteries of TTVIBDT-T/PC70BM (mass ratio 1.5:1).
Fig. 5 is the cyclic voltammogram based on TVIBDT-T and DTVIBDT-T film.
Fig. 6 is the J-V figure of the hole mobility measuring TVIBDT-T and DTVIBDT-T.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
The synthesis of embodiment 1, α-Bromine β-hexyl thiophene ethene indone (in formula III, R 3=C 6h 13, the compound of n=1)
By the indone (formula IV) of 3.03g, the compound (formula V, n=1, R of 6.25g 3=C 6h 13), 2ml piperidines and dried 22.8ml acetonitrile join reactor mixed dissolution, then 80 DEG C of backflows 24 hours under nitrogen protection.By reaction mixture cool to room temperature, then be dissolved in methylene dichloride, wash with salt subsequently, anhydrous magnesium sulfate drying, after solvent is fallen in vacuum-evaporation, adopt methylene dichloride/sherwood oil (1/5, V/V) to cross chromatographic column and purify, obtain 5g yellow solid α-Bromine β-hexyl thiophene ethene indone, productive rate: 60%.GC/MS:402(M+)。
Structural identification data are as follows: 1h NMR (400MHz, CDCl 3) δ (ppm): 7.96-7.95(t, 2H), 7.835 (s, 1H), 7.81-7.77 (m, 2H), 7.599(s, 1H), 2.64-2.60(t, 2H), 1.66-1.58(m, 3H), 1.38-1.25(m, 6H), 0.91-0.88(t, 2H).
The synthesis of embodiment 2, α-Bromine β-hexyl di-thiofuran ethylene indone (in formula III, R 3=C 6h 13, the compound of n=2)
By the indone (formula IV) of 1.34g, the compound (formula V, n=2, R of 4.0g 3=C 6h 13), 2ml piperidines and dried 22.8ml acetonitrile join reactor mixed dissolution, then 80 DEG C of backflows 24 hours under nitrogen protection.By reaction mixture cool to room temperature, then be dissolved in methylene dichloride, wash with salt subsequently, anhydrous magnesium sulfate drying, after solvent is fallen in vacuum-evaporation, adopt methylene dichloride/sherwood oil (1/5, V/V) to cross chromatographic column and purify, obtain 5g yellow solid α-Bromine β-hexyl di-thiofuran ethylene indone, productive rate: 60%.MALDI-TOF:MS:569.1, the C calculated 30h 33brO 2s 2mass-to-charge ratio be 569.62.
Structural identification data are as follows: 1h NMR (400MHz, CDCl 3) δ (ppm): 8.09-8.07 (s, 1H), 7.97-7.94 (t, 2H), (7.78-7.75 t, 2H), 7.21 (s, 1H), 7.07 (s, 1H), 2.94-2.90 (t, 2H), 2.62-2.57 (t, 2H), 1.71-1.60 (m, 4H), 1.42-1.25 (s, 12H), 0.93-0.88 (s, 6H).
Embodiment 3, α-Bromine β-hexyl join three thiofuran ethylene indones synthesis (in formula III, R 3=C 6h 13, the compound of n=3)
By indone (formula IV), formula V compound (n=3, R 3=C 6h 13), piperidines and dried acetonitrile join reactor mixed dissolution, then 80 DEG C of backflows 24 hours under nitrogen protection.By reaction mixture cool to room temperature, be then dissolved in methylene dichloride, wash with salt subsequently, anhydrous magnesium sulfate drying, after solvent is fallen in vacuum-evaporation, adopts methylene dichloride/sherwood oil (1/5, V/V) cross chromatographic column to purify, obtain yellow solid α-Bromine β-hexyl and join three thiofuran ethylene indones.Structural identification data show product for the purpose of gained compound really.
The synthesis of embodiment 4,2,6-terthienyl hexenal 4,8-bis-thiophene benzo [1,2-b:4,5-b '] two thiophene (in formula VI, R 1=C 6h 13, R 2=H, R 3=C 6h 13, the compound of n=3)
Monomer-type II (the R of 0.509g is added in the there-necked flask of 50mL 1=C 6h 13, R 2=H), 0.523g monomer α-Bromine β-hexyl three connects thiofuran ethylene aldehyde (R in formula V 3=C 6h 13, n=3) and 20mL toluene, logical nitrogen, after 15 minutes, adds 30mg tetrakis triphenylphosphine palladium (0.015mmol), is warming up to 90 DEG C of stirring reactions 24 hours.Reaction terminates, and is cooled to room temperature, reaction solution is fallen to 200mL methyl alcohol, then suction filtration, collects red solid.Then adopt methylene dichloride/sherwood oil (5/1, v/v) to cross chromatographic column separating-purifying product, obtain red molecular solid 0.503g.Productive rate: 75.4%.MALDI-TOF:MS:1408.6, the C calculated 30h 33brO 2s 2mass-to-charge ratio be 1408.25.
Structural identification data are as follows: 1h NMR (400MHz, CDCl 3) δ (ppm): 9.96 (s, 2H), 7.63 (s, 2H), 7.33 (d, 2H), 7.21 (d, 2H), 7.06 (d, 2H), 7.03 (d, 4H), 6.93 (d, 2H), 2.95-2.88 (m, 8H), 2.81 (t, 4H), 1.82-1.70 (m, 4H), 1.68-1.64 (m, 9H), 1.49 (t, 4H), 1.44-1.35 (m, 33H), (1.32 m, 18H).
The synthesis of embodiment 5,2,6-di-thiofuran ethylene indone 4,8-bis-thiophene benzo [1,2-b:4,5-b '] two thiophene (TVIBDT-T) (in formula I, R 1=R 3=C 6h 13, R 2the compound of=H, n=1)
Monomer-type II (the R of 0.523g is added in the there-necked flask of 50mL 1=C 6h 13, R 2=H), 0.5g monomer α-Bromine β-hexyl thiophene ethene indone (embodiment 1 prepare compound) and 20mL toluene, logical nitrogen is after 15 minutes, add 30mg tetrakis triphenylphosphine palladium (0.015mmol), be warming up to 115 DEG C of stirring reactions 24 hours.Reaction terminates, and is cooled to room temperature, reaction solution is fallen to 200mL methyl alcohol, then suction filtration, collects black solid.Then adopt methylene dichloride/sherwood oil (1/1, v/v) to cross chromatographic column separating-purifying product, obtain 0.575g black molecule TVIBDT-T solid, productive rate 80%.MALDI-TOF:m/z1166.6. the C calculated 70h 70o 4s 6mass-to-charge ratio be 1166.36.
Structural identification data are as follows: 1h NMR (400MHz, CDCl 3) δ (ppm): 7.97-7.95(t, 4H), 7.87-7.83(t, 6H), 7.77-7.75(t, 4H), 7.38-7.37(d, 2H), 6.98-6.97(d, 2H), 2.96-2.95(t, 4H), 2.90-2.86(t, 4H), 1.87-1.80(m, 4H), 1.75-1.70(m, 4H), 1.57-1.50(d, 6H), 1.47-1.25(m, 20H), 0.95-0.91(m, 10H). 13c NMR (CDCl 3, 400MHz) and δ (ppm): 190.23,189.65,147.81,145.11,144.59,142.46,142.09,140.56,139.71,137.38,136.82,136.11,136.03,135.53,135.08,134.85,128.30,124.68,124.43,124.17,123.70,123.05,122.85,31.69,31.67,31.64,30.41,30.29,29.61,29.36,29.12,22.71,14.18,14.17.
This compound is at methylene dichloride, and trichloromethane, tetrahydrofuran (THF), dissolves good in the common solvent such as toluene.
The absorption spectrum of organic molecule TVIBDT-T prepared by this example is shown in Fig. 2 (a).
(between 400 ~ 750nm, have wide absorption, ABSORPTION EDGE is at about 810nm, and corresponding optical band gap is 1.62eV, shows that this is the organic semiconductor material of a narrow band gap for this compound film.
The synthesis of embodiment 6,2,6-bigeminy thiofuran ethylene indone 4,8-bis-thiophene benzo [1,2-b:4,5-b '] two thiophene (DTVIBDT-T) (in formula I, R 1=R 3=C 6h 13, R 2the compound of=H, n=2)
The monomer-type II of 0.41g, 0.6g monomer α-Bromine β-hexyl bithiophene ethene indone (compound prepared by embodiment 2) and 20mL toluene is added in the there-necked flask of 50mL, logical nitrogen is after 15 minutes, add 30mg tetrakis triphenylphosphine palladium (0.015mmol), be warming up to 115 DEG C of stirring reactions 24 hours.Reaction terminates, and is cooled to room temperature, reaction solution is fallen to 200mL methyl alcohol, then suction filtration, collects black solid.Then adopt methylene dichloride/sherwood oil (1/1, v/v) to cross chromatographic column separating-purifying product, obtain 0.120g black molecule DTVIBDT-T solid, productive rate is 50%.MALDI-TOF:m/z1498.8. the C calculated 90h 98o 4s 8mass-to-charge ratio be 1498.52.
Structural identification data are as follows: 1h NMR (400MHz, CDCl 3) δ (ppm): 8.04 (s, 2H), 7.95-7.91 (t, 4H), 7.75-7.73 (m, 4H), 7.73 (s, 2H), 7.37-7.36 (s, 2H), 7.31 (s, 2H), 7.12 (s, 2H), 6.97-6.96 (d, 2H), 2.99-2.95 (t, 4H), 2.92-2.88 (t, 4H), 2.84-2.80 (t, 4H), 1.85-1.82 (m, 4H), 1.71-1.68 (m, 8H), 1.37-1.33 (m, 36H), 0.96-0.91 (m, 18H). 13cNMR (CDCl 3, 300MHz) and δ (ppm): 192.48,158.97,147.74,142.19,140.54,137.14,136.81,134.89,133.49,133.03,129.94,128.14,126.98,126.50,124.59,122.93,122.28,31.92,30.61,29.68,29.49,29.15,22.77,14.22,11.86.
This compound is at methylene dichloride, and trichloromethane, tetrahydrofuran (THF), dissolves good in the common solvent such as toluene.
The absorption spectrum of organic molecule DTVIBDT-T prepared by this example is shown in Fig. 2 (b).Compound film adopts method film forming on quartz plate of solution spin coating, this compound film has wide absorption between 400 ~ 800nm, ABSORPTION EDGE is at about 850nm, and corresponding optical band gap is 1.46eV, shows that this is the organic semiconductor material of a narrow band gap.
The film absorption of this compound absorbs with the solution of this compound to be compared, and it absorbs width and broadens, and absorbs the obvious red shift in position.
Fig. 5 is the cyclic voltammogram based on TVIBDT-T and DTVIBDT-T film.Being coated on platinum electrode by the chloroform soln of TVIBDT-T and DTVIBDT-T, is reference electrode with Ag/AgCl, waits to dry film forming and be placed in phosphofluoric acid 4-butyl amine acetonitrile solution and measure.From figure, obtain initial oxidation current potential and initial reduction current potential be respectively TVIBDT-T:0.9V and-0.72V. then by formula HOMO=-e(Eoxonset+4.4) (eV)=-5.3eV, LOMO=-e (Eredonset+4.4) (eV)=-3.68eV.DTVIBDT-T:0.8V and-0.75V, then by formula HOMO=-e(E ox onset+ 4.4) (eV)=-5.2eV, LOMO=-e (E red onset+ 4.4) (eV)=-3.65eV.
The synthesis (TTVIBDT-T) of embodiment 7,2,6-terthienyl ethene indone 4,8-bis-thiophene benzo [1,2-b:4,5-b '] two thiophene (in formula I, R 1=R 3=C 6h 13, R 2the compound of=H, n=3)
In the there-necked flask of 50mL, add formula II monomer-type II, monomer α-Bromine β-hexyl joins three thiofuran ethylene indones (embodiment 3 prepare compound) and toluene, logical nitrogen is after 15 minutes, add 30mg tetrakis triphenylphosphine palladium (0.015mmol), be warming up to 115 DEG C of stirring reactions 24 hours.Reaction terminates, and is cooled to room temperature, reaction solution is fallen to 200mL methyl alcohol, then suction filtration, collects black solid.Then adopt methylene dichloride/sherwood oil (1/1, v/v) to cross chromatographic column separating-purifying product, obtain product.MALDI-TOF:MS:1663.8, the C calculated 30h 33brO 2s 2mass-to-charge ratio be 1664.51.
Structural identification data are as follows: 1h NMR (400MHz, CDCl 3) δ (ppm): 7.85 (s, 1H), 7.72-7.69 (m, 3H), (7.67-7.65 t, 3H), 7.34 (s, 1H), (7.01 s, 4H), 2.98-2.86 (d, 6H), 2.10(m, 17H), 1.86 (t, 3H), 1.68-1.52 (m, 11H), 1.41-1.25 (m, 23H), 0.97-0.92 (t, 12H).
Structural identification data show product for the purpose of gained compound really.
The synthesis of embodiment 8,2,6-terthienyl ethene indone 4,8-bis-thiophene benzo [1,2-b:4,5-b '] two thiophene (TTVIBDT-T) (in formula I, R 1=R 3=C 6h 13, R 2the compound of=H, n=3)
The compound embodiment 4 of the indone (formula IV) of 146mg, 352mg prepared, 0.2ml piperidines and dried 22.8ml toluene join reactor mixed dissolution, then 110 DEG C of backflows 24 hours under nitrogen protection.By reaction mixture cool to room temperature, be then dissolved in methylene dichloride, wash with salt subsequently, anhydrous magnesium sulfate drying, after solvent is fallen in vacuum-evaporation, adopts methylene dichloride/sherwood oil (1/3, V/V) cross chromatographic column to purify, obtain 202mg purple solid product, productive rate: 48.5%.MALDI-TOF:MS:1663.8, the C calculated 30h 33brO 2s 2mass-to-charge ratio be 1664.51.
Structural identification data are as follows: 1h NMR (400MHz, CDCl 3) δ (ppm): 7.85 (s, 1H), 7.72-7.69 (m, 3H), (7.67-7.65 t, 3H), 7.34 (s, 1H), (7.01 s, 4H), 2.98-2.86 (d, 6H), 2.10(m, 17H), 1.86 (t, 3H), 1.68-1.52 (m, 11H), 1.41-1.25 (m, 23H), 0.97-0.92 (t, 12H).
This compound is at methylene dichloride, and trichloromethane, tetrahydrofuran (THF), dissolves good in the common solvent such as toluene.
The absorption spectrum of organic molecule TTVIBDT-T prepared by this example is shown in Fig. 2 (c).Compound film adopts method film forming on quartz plate of solution spin coating, this compound film has wide absorption between 400 ~ 800nm, ABSORPTION EDGE is at about 750nm, and corresponding optical band gap is 1.64eV, shows that this is the organic semiconductor material of a narrow band gap.
The Photovoltaic Properties of embodiment 9, TVIBDT-T
Be to body, PC with TVIBDT-T 60bM is that acceptor has prepared organic solar batteries device by solution spin coating.Fig. 3 is the schematic diagram of organic solar batteries device.
Device architecture is ITO/PEDOT:PSS/TVIBDT-T:PC 60bM/Ca/Al.
Preparation method is as follows: be dissolved in by TVIBDT-T with the solution of obtained 12mg/mL in trichloromethane, then with the PC of 50wt.% 60blended (TVIBDT-T and the PC of BM 60bM mass ratio is 1.5:1).The glass substrate that transparent indium tin oxide (ITO) is coated with manufactures organic solar batteries.The film of poly-(3,4-ethylenedioxythiophene) (PEDOT:PSS) that adulterated by conductive polymer poly (styrene sulfonate) is spin-coated to ITO surface with the interface of more being mated.The thickness of the PEDOT:PSS layer using Dektek profilograph to record is about 30nm.Then, the blend solution spin coating thin layer as above manufactured is used to be about 60nm.Then, about 10 -4under the pressure of Pa, the thin layer of evaporation calcium and aluminium in succession, obtains organic solar batteries device.At filling N 2glove box in use the AM1.5G intensity (100mW/cm of xenon lamp solar simulator 2) under the open circuit voltage of prepared organic solar batteries device, short-circuit current and these three parameters of packing factor are tested, described xenon lamp solar simulator uses silicon diode (having KG5 Vis filter) to correct in National Renewable Energy Laboratory (NREL).
The current-voltage curve that Fig. 4 (a) is this device.The open circuit voltage of this device is 1.02V, and short-circuit current is 10.15mA/cm 2, packing factor is 57.2%, and energy conversion efficiency is 5.92%; B Photocurrent action spectra that () is this device, it is consistent with the absorption spectrum trend of material that its device obtains optogalvanic spectra, and illustrate that the absorption of this material all has contribution to photoelectric current generation, it reaches 57% in the maximum external quantum efficiency value of main absorption peak.
The Photovoltaic Properties of embodiment 10, DTVIBDT-T
Be to body, PC with DTVIBDT-T 70bM is that acceptor has prepared organic solar batteries device by solution spin coating.Fig. 3 is the schematic diagram of organic solar batteries device.Device architecture is ITO/PEDOT:PSS/DTVIBDT-T:PC 70bM/Ca/Al.
Preparation method is as follows: be dissolved in by DTVIBDT-T with the solution of obtained 12mg/mL in trichloromethane, then with PC 70bM blended (DTVIBDT-T) and PC 70bM mass ratio is 1.5:1).The glass substrate that transparent indium tin oxide (ITO) is coated with manufactures organic solar batteries.The film of poly-(3,4-ethylenedioxythiophene) (PEDOT:PSS) that adulterated by conductive polymer poly (styrene sulfonate) is spin-coated to ITO surface with the interface of more being mated.The thickness of the PEDOT:PSS layer using Dektek profilograph to record is about 30nm.Then, the blend solution spin coating thin layer 60nm as above manufactured is used.Then, about 10 -4under the pressure of Pa, the thin layer of evaporation calcium and aluminium in succession, obtains organic solar batteries device.At filling N 2glove box in use the AM1.5G intensity (100mW/cm of xenon lamp solar simulator 2) under the open circuit voltage of prepared organic solar batteries device, short-circuit current and these three parameters of packing factor are tested, described xenon lamp solar simulator uses silicon diode (having KG5 Vis filter) to correct in National Renewable Energy Laboratory (NREL).
The current-voltage curve that Fig. 4 (a) is this device.The open circuit voltage of this device is 0.92V, and short-circuit current is 11.05mA/cm 2, packing factor is 66.4%, and energy conversion efficiency is 6.75%; B Photocurrent action spectra that () is this device, it is consistent with the absorption spectrum trend of material that its device obtains optogalvanic spectra, and illustrate that the absorption of this material all has contribution to photoelectric current generation, it reaches 60% in the maximum external quantum efficiency value of main absorption peak.
The Photovoltaic Properties of embodiment 11, TTVIBDT-T
Compound with prepared by TTVIBDT-T(embodiment 8) be to body, PC 70bM is that acceptor has prepared organic solar batteries device by solution spin coating.Fig. 3 is the schematic diagram of organic solar batteries device.Device architecture is ITO/PEDOT:PSS/TTVIBDT-T:PC 70bM/Ca/Al.
Preparation method is as follows: be dissolved in by TTVIBDT-T with the solution of obtained 12mg/mL in trichloromethane, then with PC 70blended (DTVIBDT-T and the PC of BM 70bM mass ratio is 1.5:1).The glass substrate that transparent indium tin oxide (ITO) is coated with manufactures organic solar batteries.The film of poly-(3,4-ethylenedioxythiophene) (PEDOT:PSS) that adulterated by conductive polymer poly (styrene sulfonate) is spin-coated to ITO surface with the interface of more being mated.The thickness of the PEDOT:PSS layer using Dektek profilograph to record is about 30nm.Then, the blend solution spin coating thin layer 60nm as above manufactured is used.Then, about 10 -4under the pressure of Pa, the thin layer of evaporation calcium and aluminium in succession, obtains organic solar batteries device.At filling N 2glove box in use the AM1.5G intensity (100mW/cm of xenon lamp solar simulator 2) under the open circuit voltage of prepared organic solar batteries device, short-circuit current and these three parameters of packing factor are tested, described xenon lamp solar simulator uses silicon diode (having KG5 Vis filter) to correct in National Renewable Energy Laboratory (NREL).
The current-voltage curve that Fig. 4 (c) is this device.The open circuit voltage of this device is 0.87V, and short-circuit current is 8.8mA/cm 2, packing factor is 70%, and energy conversion efficiency is 5.36%.
The present invention designs that this two-dimensional conjugated organic molecule is photoabsorption in order to widen organic molecule, the hole mobility that reduces band gap, improve organic semiconductor material, mobility schematic diagram is shown in that the mobility of accompanying drawing 6, TVIBDT-T and DTVIBDT-T is respectively 1.85 × 10 -4cm 2v -1s -1with 1.84 × 10 -4cm 2v -1s -1.This is conducive to the raising of organic semiconductor photovoltaic performance.
The present invention is described with reference to specific embodiment and embodiment.But the present invention is not limited to only described embodiment and embodiment.Those of ordinary skill in the art it should be understood that based on instruction herein, can carry out many changes and substitute not departing under the scope of the present invention that claims limit.

Claims (7)

1. general structure is such as formula the compound shown in I:
In formula I, R 1and R 3be all straight chained alkyl or the branched-chain alkyl of 6-12 independently selected from the total number of carbon atoms, R 2for straight chained alkyl or branched-chain alkyl that hydrogen or the total number of carbon atoms are 6-12, n=3.
2. prepare the synthetic method of compound shown in claim 1 Chinese style I, comprise the steps: under the katalysis of tetrakis triphenylphosphine palladium, compound shown in compound and formula III shown in formula II is reacted, obtains the compound shown in formula I;
In formula II, R 1, R 2definition cotype I; In formula III, n and R 3definition cotype I.
3. method according to claim 2, is characterized in that: shown in described formula II, shown in compound and formula III, the molar ratio of compound is 1:2 ~ 2.1;
The molar ratio of compound shown in described tetrakis triphenylphosphine palladium and formula III is 0.02 ~ 0.05:1;
The temperature of reaction of described reaction is 100 ~ 115 DEG C; Reaction times is 12 ~ 48 hours; Described reaction is carried out in organic solvent; Described organic solvent is specially toluene, chlorobenzene or dimethylbenzene.
4. method according to claim 3, is characterized in that: shown in described formula II, shown in compound and formula III, the molar ratio of compound is 1:2;
The molar ratio of compound shown in described tetrakis triphenylphosphine palladium and formula III is 0.02:1;
The temperature of reaction of described reaction is 115 DEG C; Reaction times is 24 hours; Described organic solvent is specially toluene, chlorobenzene or dimethylbenzene.
5. the compound shown in claim 1 Chinese style I is preparing the application in photovoltaic device.
6. application according to claim 5, is characterized in that: described photovoltaic device is organic solar batteries.
7. general structure is such as formula the compound shown in III:
In formula III, R 3independently selected from straight chained alkyl or branched-chain alkyl that the total number of carbon atoms is 6-12, n=3.
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