CN102617835A - Conjugated polymer of polyacenaphthylene and quinoxaline, as well as preparation method and application of conjugated polymer - Google Patents
Conjugated polymer of polyacenaphthylene and quinoxaline, as well as preparation method and application of conjugated polymer Download PDFInfo
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Abstract
The invention relates to novel conjugated polymer of polyacenaphthylene and quinoxaline, a preparation method of the conjugated polymer, as well as an application of the conjugated polymer in polymer solar cells. The conjugated polymer of polyacenaphthylene and quinoxaline, provided by the invention, has the structure formula as follows: Ar takes electron-rich aromatic ring as a structure unit; R1 is a linear chain or branch chain alkyl with the hydrogen atom number or carbon atom number of 1 to 20; and R2 is a linear chain or branch chain alkoxy with the hydrogen atom number or carbon atom number of 1 to 20.
Description
Technical field
The present invention relates to acenaphthene and quinoxaline polymkeric substance and preparation method, and the utilization of such conjugated polymers in polymer solar battery.
Background technology
In recent years, polymer solar battery is because advantages such as its cheapness, flexibility, big area become the research focus of cleaning, renewable energy source research field.Through the researcher unremitting effort, in the short time about ten years, be accompanied by continually developing of novel material, its photoelectric transformation efficiency is just from 10
-2-10
-3% has brought up to 9.2% [Service, R. F. Science 2011,332; 293.]; But satisfying the practicability demand, still need further to improve photoelectric transformation efficiency, is one of most important means of realizing this goal and seek the Optical Properties of Novel Conjugated material.
The efficiency of conversion of solar cell is the open circuit voltage (V by device
OC), short-circuit current (J
SC) and packing factor (FF) determined that the emphasis of novel material research and development mainly concentrates on controlled material and has lower energy gap (to obtain higher J
SC), lower HOMO energy level is (to obtain higher V
OC) and higher carrier mobility (to obtain higher J
SCAnd FF).On the main chain of polymkeric substance, introduce the inflexible slab construction; The face face that helps polymer segment is piled up; Thereby reduce the energy level of material and improve the carrier mobility of polymkeric substance, thereby become a kind of strategy of very effective design organic solar batteries novel material.From 2009; The Zhenan Bao seminar of Stanford Univ USA has reported a series of based on the naphthyl thiophene pyrazine base polymer with massive plate structure, and is applied to organic solar batteries, regrettably the photovoltaic performance of these materials and unsatisfactory; The open circuit voltage that mainly comes from device too low (Voc=0.515 ~ 0.725 V) [H. A. Becerril; R. Mondal, Z. Bao, et al.
J. Mater. Chem. 2009, 19,591.; N. M. Mondal, H. Becerril, J. E. Norton, et al.
Chem. Mater. 2009, 21,3618.; Rajib Mondal, H.A.B., Eric Verploegen, Zhenan Bao, et al.
J. Mater. Chem. 2010, 20,5823].
For reducing the HOMO energy level of acenaphthene thiophthene pyrazine base polymer; The present invention is with phenyl substituted thiophene base; Novel massive plate structural unit---acenaphthene and quinoxaline have been synthesized in design, with benzo two thiophene, thiophene, 3, and 6-carbazole, fluorenes and the two thiophene unit copolymerization of two-dimentional benzo; Obtained the material of a series of dark HOMO energy levels, prepared organic solar batteries device has obtained higher open circuit voltage.
Summary of the invention
One of the object of the invention is to prepare a kind of Optical Properties of Novel Conjugated material based on polyacenaphthylene and quinoxaline, and said material contains and has the massive plate rigid structure unit, can be used for organic solar batteries.
Polyacenaphthylene of the present invention and quinoxaline conjugated polymers, its constitutional features is to have following formula I:
In the formula I,
Said Ar is to be tectonic element with the electric aromatic ring of richness; R
1Be to be the alkyl of the straight or branched of 1-20 with Wasserstoffatoms or carbonatoms; R
2Be to be the alkoxyl group of the straight or branched of 1-20 with Wasserstoffatoms or carbonatoms.
Said Ar is preferably any among the following monomer 1-5:
Monomer 5
Wherein, the R in the different monomers can be Wasserstoffatoms respectively or carbonatoms is the alkyl or the alkoxyl group of the straight or branched of 1-20.
Two of the object of the invention is to provide the preparation method of polyacenaphthylene and quinoxaline Optical Properties of Novel Conjugated, it is characterized in that step and condition are following:
With 5,8-two (2-bromo-3-alkyl 5-thienyl)-acenaphthene and quinoxaline monomer are the molar weight matching criterion, with two pink salt monomers or the boric acid ester of the Ar of equimolar amount; 0.05 doubly the catalyzer tetra-triphenylphosphine palladium of molar weight adds in the reactor drum, under the argon shield, and heating reflux reaction 72 h; Reaction finishes, with resulting polymkeric substance at sedimentation in methyl alcohol, suction filtration; The polymkeric substance of collecting carries out Suo Shi with acetone and normal hexane successively and extracts 48 h, 40 ℃ of vacuum-drying 24 h.
Three of the object of the invention is to provide the purposes of polyacenaphthylene of the present invention and quinoxaline Optical Properties of Novel Conjugated.
Acenaphthene of the present invention and quinoxaline conjugated polymers have stronger absorption like Fig. 1, shown in 2 at 300～800 nm; Absorption to sunshine is very favourable aspect the polymer solar battery being applied to; And has dull and stereotyped conjugated structure; Helping the transmission of current carrier, is a kind of material of preparation optically functional device of excellent property, particularly on polymer solar battery, can be used widely.
This polymer solar cell device structure is as shown in Figure 3; 1 is ITO (tin indium oxide) glass; 2 are PEDOT:PSS [gathering (3,4-two oxidative ethane thiophene): gather (styrene sulfonate)], and its thickness is 30-40 nm; 3 for containing the conjugated polymers and acceptor material [6, the 6]-phenyl-C of acenaphthene and quinoxaline
61-methyl-butyrate (hereinafter to be referred as: blend film PCBM), its thickness are 60-120 nm, and 4 is Bphen; Its thickness is 5-10 nm; 5 is the Ag electrode, and its thickness is 60-100 nm, and described acenaphthene and quinoxaline conjugated polymers are as the photoactive layer of solar cell.
Beneficial effect
The present invention adopts Suzuki or Stille linked reaction that one type of novel polyacenaphthylene and quinoxaline conjugated polymers are provided, and its beneficial effect is:
(1) lower HOMO energy level is arranged.Obtain acenaphthene and quinoxaline through the thienyl in the acenaphthene thiophthene pyrazine is replaced with phenyl, the novel polyacenaphthylene of preparation and the HOMO of quinoxaline conjugated polymers (5.53 ~-5.60 eV) energy level is than acenaphthene thiophthene pyrazine class conjugated polymers low (0.4-0.8 eV).
(2) obtained higher open circuit voltage.The HOMO energy level of such novel polyacenaphthylene and quinoxaline conjugated polymers is (5.53 ~-5.60 eV), and low HOMO energy level helps obtaining higher open circuit voltage.So the open circuit voltage of acenaphthene provided by the invention and quinoxaline conjugated polymers PF-DTAQx made solar cell device is the highest can to reach 0.84V, this is up to now about the mxm. in the photovaltaic material of acenaphthenequinone base polymer.The photoactive layer of polymer P F-DTAQx provided by the present invention and acceptor material PCBM blend preparation has extraordinary microphase-separated and quite smooth pattern (see figure 4).
(3) modifiability of acenaphthene and quinoxaline structure is stronger.Can pass through at 5 of acenaphthene and quinoxaline, the alkoxyl group of 6-introducing long-chain improves the solvability of polymer molecule, improves the molecular weight of polymkeric substance, thereby improves the pattern of active coating, finally improves the photovoltaic performance of solar cell.
Description of drawings
Fig. 1 is conjugated polymers PBDT-DTAQx and the ultraviolet-visible absorption spectroscopy of PT-DTAQx (concrete structure is seen among the embodiment) in o-dichlorobenzene solution.
Fig. 2 is the ultraviolet-visible absorption spectroscopy of conjugated polymers PBDT-DTAQx and PT-DTAQx solid film, also is Figure of abstract simultaneously.
Fig. 3 is the structural representation of polymer solar cell device.
Fig. 4 is the three-dimensional collection of illustrative plates of AFM of polymer P F-DTAQx and PCBM blend (mass ratio 1:3) preparation photoactive layer.
Embodiment
Embodiment 1The preparation of polymer P BDT-DTAQx
(1) 5,8-two (2-bromo-3-substituted thiophene base)-5-acenaphthene and monomeric preparation of quinoxaline
With reference to Angewandte Chemie International Edition 2009,48, the disclosed compound method of 1664-1668; With the O-Phenylene Diamine is starting raw material; With sulfur oxychloride prepared in reaction diazosulfide, warp and liquid bromine reaction preparation 4,7-dibromo diazosulfide; Obtain 3 through sodium borohydride reduction then, 6-dibromo O-Phenylene Diamine.With 3,6-dibromo O-Phenylene Diamine and acenaphthenequinone condensation make 5, and 8-dibromo acenaphthene and quinoxaline promptly obtain polymerization single polymerization monomer 5,8-two (2-bromo-3-dodecyl-5-thienyl)-acenaphthene and quinoxaline through Suzuki Coupling and bromo at last.
With 5, the example that is prepared as of 8-two (2-bromo-3-dodecyl-5-thienyl)-acenaphthene and quinoxaline specifies below, and synthesis step is following:
(1) preparation of diazosulfide
Under argon shield, with sulfur oxychloride dropwise slowly splash into O-Phenylene Diamine (5g, 46.25mmol), (18.7g in methylene dichloride 185mmol) (150mL) solution (under the ice bath), drips off and continue to stir 10 minutes triethylamine, and 5 h then reflux.After reaction finishes, revolve and desolventize, add 100mL water, the pH with solution transfers to about 2 with hydrochloric acid; Use steam distillation instead, use dichloromethane extraction at last, anhydrous sodium sulfate drying spends the night; Revolve and desolventize, vacuum-drying promptly obtains white solid 4.2 g, yield: 64%.
The preparation of (2) 4,7-dibromo diazosulfides
Under the room temperature, (2g 18.35mmol) is dissolved in the Hydrogen bromide of 30mL 40%, then with bromine (7.04g with diazosulfide; 55.05mmol) and the mixing solutions of 40% Hydrogen bromide (20mL) be added drop-wise in the diazosulfide, the control rate of addition 2 seconds/about dripping, drip off reflux 7h; Naturally cool to room temperature, add sodium sulfite anhy 96 and go out excessive bromine, suction filtration; And with a large amount of water washings, vacuum-drying promptly obtains yellow solid 3.88g, yield: 89%.
The preparation of (3) 5,8-dibromo acenaphthenes and quinoxaline
Under argon shield, with 4,7-dibromo diazosulfide (1.45g; Absolute ethyl alcohol 5mmol) (50mL) solution stirs 10min under ice bath, divide 5 batches Peng Qinghuana added in the reaction flask then, adds in one hour; Naturally return to room temperature, continuation was stirred 1 day, revolved to desolventize; Add an amount of zero(ppm) water, suction filtration obtains white solid 0.93g.Then with acenaphthenequinone (0.64g; 3.5mmol) acetonitrile, acetic acid mixed solvent (30 mL V1/V2=1) stir 4h down at 100 ℃, have a large amount of yellow solids to separate out, naturally cool to room temperature; Suction filtration; Use a large amount of water, washing with alcohol respectively, vacuum-drying obtains yellow solid 1.29g, yield 90%.
1H?NMR(400?MHz,?CDCl
3,?ppm):?8.50?(d,?2H),?8.10?(d,?2H),?7.86?(s,?2H),?7.81?(t,?2H)。
(4) preparation of 3-dodecyl thiophene
(2.52 g, 105 mmol) join in the 250 mL three-necked bottles that fill the anhydrous THF of 30 mL with magnesium chips, add dodecyl bromide (24.92 g, 100 mmol) again.Under argon shield; The reaction of reflux to MAGNESIUM METAL 99 finishes, and ice bath adds 540 mg Ni (dppp) Cl2 and 3 bromo thiophene (16.3 g, 100 mmol) down then; Drip off and pour in the 2 ice-cold mol/L aqueous hydrochloric acids of 200 mL after nature returns to room temperature continuation stirring 24 h; Organic layer merges organic phase with extracted with diethyl ether (30 mL * 3), spends the night with anhydrous magnesium sulfate drying.Suction filtration revolves and desolventizes, and underpressure distillation obtains 3-dodecyl thiophene colorless oil 18.40 g, productive rate 93%.
1H?NMR?(400?MHz,?CDCl
3,?ppm)：7.22(dd,2H)，6.93～6.89(m,2H)，2.62(t,2H)，1.61(m,2H)，1.29～1.25(m,18H)，0.88(m,3H)。
(5) preparation of 3-dodecyl-5-thiophene pinacol ester
Under argon shield, in the 100mL three-necked bottle, with 3-dodecyl thiophene (10.08g; 40mmol) mix with the 80mL anhydrous tetrahydro furan after, be chilled to-78 ℃, slowly drip hexane solution (17.6 mL of 2.5 M n-Butyl Lithiums; 44 mmol), mixture continues to be chilled to-78 ℃ at-78 ℃ of following stirring reaction 1h; Inject 10 mL trimethyl borates rapidly, reaction mixture rises to room temperature and continues reaction 24h.At last, heavy-gravity white milky mixt is poured in the HCl aqueous solution of 2 ice-cold N of 100mL, organic phase is with extracted with diethyl ether 3 times; With saturated common salt water washing 2 times, use anhydrous magnesium sulfate drying again, can directly add tetramethyl ethylene ketone (5.9g in this drying process; 50mmol), behind the placement 5h, steaming desolventizes; Crude product obtains white solid 6g through column chromatography, yield 40%.
1H?NMR?(400?MHz,?CDCl
3,?ppm):?7.46?(s,?1H),?7.19?(s,?1H),?2.61?(t,?2H),?1.60?(m,?2H),?1.30?(m,?30H),?0.87?(t,?3H).
(6) 5,8-two (2-bromo-3-dodecyl-5-thienyl)-acenaphthene and quinoxaline
Under argon shield, with 3-dodecyl-5-thiophene pinacol ester (1.09g, 3mmol), 5,8-dibromo acenaphthene and quinoxaline (0.41g; 1mmol) (69mg 0.06mmol) mixes, and adds toluene (20mL) and 2M salt of wormwood (20mL) solution with syringe with catalyzer four triphenyl phosphorus palladiums; At 90-95 ℃ of lucifuge reaction 48h, reaction naturally cools to room temperature after finishing, and uses extracted in toluene; Washing, anhydrous sodium sulfate drying spends the night, and revolves to desolventize; Ethyl alcohol recrystallization, vacuum-drying obtain yellow solid 0.45g, yield 60%.
1H?NMR?(400?MHz,?CDCl
3,?ppm):?8.48～8.46?(dd,?2H),?8.13～8.11?(dd,?4H),?7.89～7.85?(t,?2H),?7.78?(s,?2H),?7.17?(s,?2H),?2.75～2.71?(t,?4H),?1.79～1.53?(m,?12H),?1.29～1.25?(br,?28H),?0.87～0.83?(t,?6H).
(7) 5,8-two (2-bromo-3-dodecyl 5-thienyl)-acenaphthene and quinoxaline
With 5, (0.45g 0.6mmol) is dissolved among the 18mL DMF for 8-two (3-dodecyl thienyl)-5-acenaphthene and quinoxaline; (0.22g, DMF 1.32mmol) (12mL) solution continue after dropwising to stir 2h down at-20 ℃ to splash into NBS-20 ℃ of following lucifuges; Naturally return to room temperature, stirred overnight, suction filtration then; Use ethyl alcohol recrystallization, vacuum-drying obtains red solid 0.49g, yield 90%.
1H?NMR?(400?MHz,?CDCl
3,?ppm):?8.47～8.41?(dd,?2H),?8.11～8.09?(t,?2H),?8.02～7.98?(d,?2H),?7.88～7.83?(dd,?2H),?7.52～7.49?(d,?2H),?2.67～2.63?(t,?4H),?1.72～1.66?(m,?4H),?1.55?(m,?8H),?1.26?(br,?28H),?0.88～0.85?(t,?6H).
(2) preparation of polymer P BDT-DTAQx
With 5,8-two (2-bromo-3-dodecyl 5-thienyl)-acenaphthene and quinoxaline (585 mg, 0.64 mmol), 2,6-two (tin trimethyl)-4,8-two (2-ethylhexyl) benzo [1,2-
b; 3,4-
b'] two thiophene (495 mg, 0.64 mmol), tetra-triphenylphosphine palladium (32 mg) adds in the reaction flask, with high-purity argon gas displacement three times; The reinject toluene of anhydrous and oxygen-free, under argon shield, heating reflux reaction 72 h, reaction finishes; With the sedimentation in methyl alcohol of resulting polymkeric substance, suction filtration, the polymkeric substance of collecting carry out Suo Shi with acetone and normal hexane successively and extract 24 h; 40 ℃ of vacuum-drying 24 h obtain atropurpureus solid 0.62 g, productive rate 79%.
1H?NMR?(400?MHz,?CDCl
3,?ppm)?:?8.46～8.33?(br,?2H),?8.11～7.90?(br,?3H),?7.84～7.61?(br,?5H),?7.58～7.44?(br,?2H),?4.19～4.05?(br,?4H),?2.97～2.63?(br,?4H),?1.57～1.02?(br,?64H),?1.04～0.96?(br,?12H).
Embodiment 2The preparation of polymer P T-DTAQx
With 5,8-two (2-bromo-3-dodecyl 5-thienyl)-acenaphthene and quinoxaline (725 mg, 0.79 mmol), 2; 5-two (tributyl tin)-thiophene (526 mg, 0.79 mmol), tetra-triphenylphosphine palladium (45 mg) add in the reaction flask, with high-purity argon gas displacement three times; The reinject toluene of anhydrous and oxygen-free, under argon shield, heating reflux reaction 72 h, reaction finishes; In the methyl alcohol sedimentation, suction filtration, the polymkeric substance of collecting carry out Suo Shi with acetone and normal hexane successively and extract 24 h with resulting polymkeric substance; 40 ℃ of vacuum-drying 24 h obtain black solid 0.42 g, productive rate 62%.
1H?NMR?(400?MHz,?CDCl
3,?ppm)?:?8.46?(br,?2H),?8.11?(br,?4H),?7.86～7.66?(br,?4H),?7.57～7.52?(br,?2H),?2.87～2.73?(br,?4H),?1.56～1.25?(br,?40H),?0.87?(br,?6H).
Embodiment 3The preparation of polymer PC-DTAQx
Under argon shield, with 5,8-two (2-bromo-3-dodecyl 5-thienyl)-acenaphthene and quinoxaline (343 mg, 0.38 mmol), N-(2-ethylhexyl)-3,6-carbazole two pinacol esters (200 mg, 0.38mmol), Pd (PPh
3)
4(22 mg), 10 mL toluene and 10 ml, 2 M solution of potassium carbonate join in the two neck bottles, under lucifuge, are heated to 90-95 ℃, stirring reaction 72 h.Reaction naturally cools to room temperature after finishing, chloroform extraction, saturated common salt water washing, and anhydrous magnesium sulfate drying spends the night.The filtering siccative revolves and desolvates, and uses with a large amount of methyl alcohol sedimentations, and suction filtration, the polymkeric substance of collecting carry out Suo Shi with acetone and normal hexane successively and extract 24 h, and 40 ℃ of vacuum-drying 24 h obtain black solid 0.22 g, productive rate 52%.
1H?NMR?(400?MHz,?CDCl
3,?ppm):?8.36～8.33?(br,2H),?8.07～8.05?(br,4H),?7.96～7.70?(br,8H),?7.51～7.42?(br,2H),?4.35～4.28?(br,2H),?3.73～3.71?(br,1H),?2.87～2.64?(br,4H),?1.79～1.10?(br,48H),?0.89～0.81?(br,12H)。
Embodiment 4The preparation of polymer P F-DTAQx
Under argon shield, with 5,8-two (2-bromo-3-dodecyl 5-thienyl)-acenaphthene and quinoxaline (366 mg, 0.73 mmol), 9,9-dihexyl-2,7-two (trimethylene) fluorenes boric acid ester (666 mg, 0.73mmol), Pd (PPh
3)
4(42 mg), 13 mL toluene and 13 ml, 2 M solution of potassium carbonate join in the two neck bottles, under lucifuge, are heated to 90-95 ℃, stirring reaction 72 h.Reaction naturally cools to room temperature after finishing, chloroform extraction, saturated common salt water washing, and anhydrous magnesium sulfate drying spends the night.The filtering siccative revolves and desolvates, and uses with a large amount of methyl alcohol sedimentations, and suction filtration, the polymkeric substance of collecting carry out Suo Shi with acetone and normal hexane successively and extract 24 h, and 40 ℃ of vacuum-drying 24 h obtain black solid 0.52 g, productive rate 47%.
1H?NMR?(400?MHz,?CDCl
3,?ppm)?:?8.38?(br,2H),?8.06?(br,4H),?7.87～7.65?(br,10H),?2.83～2.64?(br,4H),?2.16～2.08?(br,4H),?1.80～1.70?(br,6H),?1.29～1.18?(br,50H),?0.89～0.80?(br,12H)。
Embodiment 5The preparation of polymkeric substance 2DPBDT-DTAQx
With 5,8-two (2-bromo-3-dodecyl 5-thienyl)-acenaphthene and quinoxaline (585 mg, 0.64 mmol), 2,6-two (tributyl tin)-4,8-two (5-dodecyl-2-thienyl) benzo [1,2-
b; 3,4-
b'] two thiophene (812 mg, 0.64 mmol), tetra-triphenylphosphine palladium (32 mg) adds in the reaction flask, with high-purity argon gas displacement three times; The reinject toluene of anhydrous and oxygen-free, under argon shield, heating reflux reaction 72 h, reaction finishes; With the sedimentation in methyl alcohol of resulting polymkeric substance, suction filtration, the polymkeric substance of collecting carry out Suo Shi with acetone and normal hexane successively and extract 24 h; 40 ℃ of vacuum-drying 24 h obtain atropurpureus solid 0.66 g, productive rate 70%.
1H?NMR?(400?MHz,?CDCl
3,?ppm)?:?8.46～8.33?(br,?2H),?8.21～7.90?(br,?7H),?7.84～7.61?(br,?5H),?7.58～7.44?(br,?2H),?2.97～2.63?(br,?8H),?1.57～1.02?(br,?68H),?1.04～0.96?(br,?24H).
Embodiment 6The preparation of polymkeric substance 2DPBDT-DTOctOxyAQx
With 5,8-two (2-bromo-3-dodecyl-5-thienyl)-6,7-two octyloxies-acenaphthene and quinoxaline (584mg; 0.50 mmol) (with reference to 5; The compound method of 8-two (2-bromo-3-dodecyl-5-thienyl)-acenaphthene and quinoxaline), 2,6-two (tributyl tin)-4; 8-two (5-dodecyl-2-thienyl) benzo [1,2-
b; 3,4-
b'] two thiophene (635 mg, 0.50 mmol), tetra-triphenylphosphine palladium (22 mg) adds in the reaction flask, with high-purity argon gas displacement three times; The reinject toluene of anhydrous and oxygen-free, under argon shield, heating reflux reaction 72 h, reaction finishes; With the sedimentation in methyl alcohol of resulting polymkeric substance, suction filtration, the polymkeric substance of collecting carry out Suo Shi with acetone and normal hexane successively and extract 24 h; 40 ℃ of vacuum-drying 24 h obtain atropurpureus solid 0.65 g, productive rate 75%.
1H?NMR?(400?MHz,?CDCl
3,?ppm)?:?8.46～8.33?(br,?2H),?8.21～7.90?(br,?7H),?7.84～7.61?(br,?3H),?7.58～7.44?(br,?2H),?4.19～4.05?(br,?4H),?2.97～2.63?(br,?12H),?1.57～1.02?(br,?82H),?1.04～0.96?(br,?36H).
Embodiment 7The preparation of polymer P BDT-DTAQx solar cell device
6 mg PBDT-DTAQx mix with 24 mg PCBM, add 1 mL orthodichlorobenzene heating for dissolving, on the ito glass substrate of PEDOT:PSS modified, are preparing film through the spin coating mode, and vacuum evaporation Bphen and Ag prepare negative electrode then.
The absorption spectrum of this polymkeric substance is positioned at UV, visible light and near-infrared region (300-700 nm), and device performance is: white light 1.5 G (100 mW/cm
2) shine down open circuit voltage (V
Oc)=0.58 V, short-circuit current (J
Sc)=2.68 mA/cm
2, packing factor (FF)=0.58, electricity conversion (PCE)=0.90%.
Embodiment 8The preparation of polymer P T-DTAQx solar cell device
6 mg PT-DTAQx mix with 24 mg PCBM, add 1 mL orthodichlorobenzene heating for dissolving, on the ito glass substrate of PEDOT:PSS modified, are preparing film through the spin coating mode, and vacuum evaporation Bphen and Ag prepare negative electrode then.
Device performance is: white light 1.5 G (100 mW/cm
2) shine down open circuit voltage (V
Oc)=0.06 V, short-circuit current (J
Sc)=0.97 mA/cm
2, packing factor (FF)=0.23, electricity conversion (PCE)=0.01%.
Embodiment 9The preparation of polymer P F-DTAQx solar cell device
6 mg PF-DTAQx mix with 24 mg PCBM, add 1 mL orthodichlorobenzene heating for dissolving, on the ito glass substrate of PEDOT:PSS modified, are preparing film through the spin coating mode, and vacuum evaporation Bphen and Ag prepare negative electrode then.
Device performance is: white light 1.5 G (100 mW/cm
2) shine down open circuit voltage (V
Oc)=0.84 V, short-circuit current (J
Sc)=1.94 mA/cm
2, packing factor (FF)=0.29, electricity conversion (PCE)=0.48%.
Embodiment 10The preparation of polymkeric substance 2DPBDT-DTAQx solar cell device
7.5 mg 2DPBDT-DTAQx mixes with 22.5 mg PCBM, adds 1 mL orthodichlorobenzene heating for dissolving, on the ito glass substrate of PEDOT:PSS modified, is preparing film through the spin coating mode, vacuum evaporation Bphen and Ag prepare negative electrode then.
Device performance is: white light 1.5 G (100 mW/cm
2) shine down open circuit voltage (V
Oc)=0.70 V, short-circuit current (J
Sc)=3.94 mA/cm
2, packing factor (FF)=0.46, electricity conversion (PCE)=1.27%.
Embodiment 11The preparation of polymkeric substance 2DPBDT-DTOtcOxyAQx solar cell device
7.5 mg 2DPBDT-DTOtcOxyAQx mixes with 22.5 mg PCBM, adds 1 mL orthodichlorobenzene heating for dissolving, on the ito glass substrate of PEDOT:PSS modified, is preparing film through the spin coating mode, vacuum evaporation Bphen and Ag prepare negative electrode then.
Device performance is: white light 1.5 G (100 mW/cm
2) shine down open circuit voltage (V
Oc)=0.80 V, short-circuit current (J
Sc)=7.38 mA/cm
2, packing factor (FF)=0.43, electricity conversion (PCE)=2.54%.
Claims (9)
1. polyacenaphthylene and quinoxaline conjugated polymers, its constitutional features is to have following general formula I:
Among the formula I,
Said Ar is to be tectonic element with the electric aromatic ring of richness; R
1Be that Wasserstoffatoms or carbonatoms are the alkyl of the straight or branched of 1-20; R
2Be that Wasserstoffatoms or carbonatoms are the alkoxyl group of the straight or branched of 1-20.
2. acenaphthene and quinoxaline conjugated polymers according to claim 1 is characterized in that said Ar is the monomer of structure suc as formula II, and wherein R is that Wasserstoffatoms or carbonatoms are the alkyl or the alkoxyl group of the straight or branched of 1-20.
3.
formula II
Acenaphthene and quinoxaline conjugated polymers is characterized in that said Ar is the monomer of structure suc as formula III according to claim 1, and wherein R is that Wasserstoffatoms or carbonatoms are the alkyl or the alkoxyl group of the straight or branched of 1-20.
4.
formula III
Acenaphthene and quinoxaline conjugated polymers is characterized in that said Ar is the monomer of structure suc as formula IV according to claim 1, and wherein R is that Wasserstoffatoms or carbonatoms are the alkyl or the alkoxyl group of the straight or branched of 1-20.
5.
formula IV
Acenaphthene and quinoxaline conjugated polymers is characterized in that said Ar is the monomer of structure suc as formula V according to claim 1, and wherein R can be Wasserstoffatoms or carbonatoms is the alkyl or the alkoxyl group of the straight or branched of 1-20.
6.
formula V
Acenaphthene and quinoxaline conjugated polymers is characterized in that said Ar is the monomer of structure suc as formula VI according to claim 1, and wherein R is that Wasserstoffatoms or carbonatoms are the alkyl or the alkoxyl group of the straight or branched of 1-20.
7.
formula VI
Preparing method like the conjugated polymers of said arbitrary acenaphthene of claim 1 to 6 and quinoxaline is characterized in that step and condition are following:
With 5,8-two (2-bromo-3-alkyl 5-thienyl)-acenaphthene and quinoxaline monomer are the molar weight matching criterion, with two pink salt monomers or the boric acid ester of the Ar of equimolar amount; 0.05 doubly the catalyzer tetra-triphenylphosphine palladium of molar weight adds in the reactor drum, under the argon shield, and heating reflux reaction 72 h; Reaction finishes, with resulting polymkeric substance at sedimentation in methyl alcohol, suction filtration; The polymkeric substance of collecting carries out Suo Shi with acetone and normal hexane successively and extracts 48 h, 40 ℃ of vacuum-drying 24 h.
8. like said arbitrary acenaphthene of claim 1 to 6 and the application of quinoxaline in preparation photoelectric functional device.
9. application as claimed in claim 8 is characterized in that said photoelectric functional device is a polymer solar battery.
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| CN103570743A (en) * | 2012-10-26 | 2014-02-12 | 中国科学院化学研究所 | Soluble liquid machining two-dimensional conjugated organic molecular photovoltaic material as well as preparation method and application thereof |
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