CN105061730A - Fluorine-containing phenanthrene quinoxaline and thiophene conjugated polymer - Google Patents
Fluorine-containing phenanthrene quinoxaline and thiophene conjugated polymer Download PDFInfo
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- CN105061730A CN105061730A CN201510449945.6A CN201510449945A CN105061730A CN 105061730 A CN105061730 A CN 105061730A CN 201510449945 A CN201510449945 A CN 201510449945A CN 105061730 A CN105061730 A CN 105061730A
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- polymer
- quinoxaline
- fluorine
- thiophene
- containing phenanthrene
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000011737 fluorine Substances 0.000 title claims abstract description 24
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 20
- 229930192474 thiophene Natural products 0.000 title claims abstract description 20
- WULOGQDWUYTIAM-UHFFFAOYSA-N N1=CC=NC2=CC=CC=C12.C1=CC=CC=2C3=CC=CC=C3C=CC12 Chemical compound N1=CC=NC2=CC=CC=C12.C1=CC=CC=2C3=CC=CC=C3C=CC12 WULOGQDWUYTIAM-UHFFFAOYSA-N 0.000 title abstract 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 44
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 38
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 24
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 12
- 238000013087 polymer photovoltaic Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 125000005594 diketone group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 0 CC*c1cc2c(cc(cc3)O)c3c3nc(c(*(C)C)c(cc4-c5ccc(*(C)C)[s]5)F)c4nc3c2cc1 Chemical compound CC*c1cc2c(cc(cc3)O)c3c3nc(c(*(C)C)c(cc4-c5ccc(*(C)C)[s]5)F)c4nc3c2cc1 0.000 description 1
- QWSLPZWXFVAPPC-UHFFFAOYSA-N CC=1C(=C(SC1)C)C.[Sn] Chemical compound CC=1C(=C(SC1)C)C.[Sn] QWSLPZWXFVAPPC-UHFFFAOYSA-N 0.000 description 1
- 241001634884 Cochlicopa lubricella Species 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- -1 alkoxyl group quinoxalines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a fluorine-containing phenanthrene quinoxaline and thiophene conjugated polymer, the energy gap and the HOMO energy level of the polymer are reduced simultaneously, and needs of polymer photovoltaic cell photoactivity layer electron donor materials is met. The conjugated polymer has the structural general formula shown in the description. The polymer disclosed by the invention has deeper HOMO energy level than a polymer D and can be as deep as -5.67 eV, and high open circuit voltage of more than 0.89 V can be obtained when the polymer is applied in photovoltaic cells.
Description
Technical field
The invention belongs to filed of functional, be specifically related to the conjugated polymers of a kind of fluorine-containing phenanthrene for quinoxaline and thiophene.
Background technology
Polymer photovoltaic cell is a kind of photovoltaic device converted solar energy into electrical energy, and due to low cost, the manufacturing processed simple and light weight outstanding advantages such as to be easy to carry is subject to the favor of scientific research personnel.It is the current key technical problem being badly in need of solving in this field that the photoelectric transformation efficiency how improving battery makes it to commercially produce.By the core that the active coating forming to body and acceptor material is device, in view of current acceptor material multiselect be fullerene derivate (PCBM) when, therefore develop high-efficiency polymer donor material most important to raising cell photoelectric efficiency of conversion.
Polymkeric substance is as the chief component of device photoactive layer, and its absorption spectrum affects the short-circuit current of battery, and the difference of lowest unoccupied molecular orbital (LUMO) energy level of highest occupied molecular orbital (HOMO) energy level and PCBM determines the open circuit voltage of device.Therefore, desirable polymer materials should have wider absorption namely containing narrower optical energy gap, is conducive to the short-circuit current of boost device; There is lower HOMO energy level simultaneously, ensure that device can obtain larger open circuit voltage.One alternately will form D-A type conjugated polymer backbone to electric unit (D) and short of electricity unit (A), realize by intermolecular interaction the important channel method that material energy level and energy gap regulate being become to the efficient donor polymer of exploitation at present.
Quinoxaline molecule draws electrically stronger nitrogen-atoms because itself having two, has obtained good result in the devices, in recent years enjoy the concern of scientific research personnel as a class novel short of electricity unit application in polymkeric substance.Such as material FTQ (JournalofMaterialsChemistryC.2013,1,630-637), this polymkeric substance is formed by quinoxaline and thiophene copolymerization.Its absorption bands is positioned at 300-730nm, and absorb the strongest with 360nm and 622nm place, ABSORPTION EDGE is 730nm, and corresponding optical energy gap is 1.70eV; Oxidizing potential is 0.79V, and corresponding HOMO energy level is-5.51eV.The polymer battery best photoelectric conversion efficiency of this material and the blended preparation of PCBM is 5.27%, and wherein open circuit voltage is 0.87V, and short-circuit current is 10.11mA/cm
2.
Although above-mentioned materials has achieved good opto-electronic conversion result, but due to quinoxaline unit contained in such polymer molecular structure, they are 2 years old, 3 are all substituted by phenyl, consequent sterically hindered effect makes two phenyl ring and quinoxaline molecular backbone chain structure form certain torsion, can not be coexisted same plane, polymer molecule conjugated degree is caused to reduce, optical energy gap can not absorb sunlight more greatly effectively, produce comparatively multi-photon and carry out opto-electronic conversion, performance is that the short-circuit current of battery is less than normal in the devices, become the important bottleneck hindering device photoelectric efficiency of conversion to promote.
Summary of the invention
For the deficiencies in the prior art, the present invention develops a kind of based on the D-A type donor polymer material of fluorine-containing phenanthrene for quinoxaline-thiophene-structure, material property is optimized, the final object realizing lifting photovoltaic device photoelectric transformation efficiency by the molecular structure improving modified polymer.
To achieve these goals, the technical solution used in the present invention is as follows: utilize phenanthrenequione structural compounds to substitute quinoxaline unit 2, the substituting group phenyl ring of 3, containing 5 aromatic nucleus in the polymer molecule skeleton that program design obtains, thus the coplanar structure that composition one is complete, have higher conjugated degree compared with the molecule replaced with phenyl, the absorption spectrum can widening polymkeric substance further produces narrower optical energy gap, and performance in the devices can the short-circuit current of effective boost device.In addition, in polymer backbone conformation, retain the fluorine atom drawing electronic capability stronger equally, reduce the HOMO energy level of polymkeric substance, ensure that device has higher open circuit voltage.
Specifically, a kind of fluorine-containing phenanthrene of the present invention is for the conjugated polymers of quinoxaline and thiophene, and its general structure is such as formula shown in I:
In formula, R
1, R
2can identical also can be different,
Work as R
1during=H, R
2alkyl or the alkoxyl group of to be carbonatoms the be straight or branched of 4 to 20.
Work as R
2during=H, R
1alkyl or the alkoxyl group of to be carbonatoms the be straight or branched of 4 to 20.
Work as R
1=R
2time, be alkyl or the alkoxyl group of the straight or branched of 4 to 20.
The present invention has following technical characterstic:
Work as R
2during for hydrogen atom, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in II:
Work as R
1during for hydrogen atom, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in III:
When R1 and R2 is octyloxy, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in IV:
Fluorine-containing phenanthrene disclosed by the invention, for the conjugated polymers of quinoxaline and thiophene, carries out according to reaction mechanism as follows:
Concrete synthesis step is as follows:
(1) fluorine-containing phenanthrene is for the preparation of quinoxaline and derivative thereof
By 5 fluorine-containing 4,7-bis-bromo-2,1,3-diazosulfide is dissolved in dehydrated alcohol, adds sodium borohydride at 0 DEG C in batches, then reacts 20h under room temperature, reaction terminates rear distillation under vacuum and removes ethanol, adds suitable quantity of water, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying, crude product obtains fluorinated diamine through silica column purification, then with 2,3-dialkyl group/alkoxyl group phenanthrenequione take acetic acid as solvent reaction, obtained 11 fluorine-containing 10,13-bis-bromo-2,3-dialkyl group/alkoxyl group quinoxalines.
(2) fluorine-containing phenanthrene is for the preparation of the D-A type conjugated polymers of quinoxaline and thiophene
This reaction is carried out under nitrogen protection, by short of electricity unit 11 fluorine-containing 10, 13-bis-bromo-2, the molar weight of 3-dialkyl group/alkoxyl group quinoxaline is as matching criterion, with 2 of equimolar amount, 5-bis-(tin trimethyl) thiophene, join in two mouthfuls of dry flasks, toluene dissolves, fluorine-containing phenanthrene controls at about 0.03mol/L for quinoxaline monomer concentration, catalyzer three (dibenzylideneacetone) two palladium of 0.02 times of molar weight and the part tri-o-tolyl phosphorus of 0.08 times of molar weight is added after ventilation 0.5h, continue ventilation 0.5h, then heating is started, after back flow reaction 24h, stopped reaction, system is cooled to room temperature, reaction solution is instilled sedimentation in methyl alcohol, filter, the polymkeric substance collected is 50 DEG C of baking 12h in vacuum drying oven, use methyl alcohol successively, normal hexane, chloroform carries out surname extraction, concentrated chloroform extracted solution, with methyl alcohol sedimentation again, filter, obtain such as formula the conjugated polymers of the fluorine-containing phenanthrene shown in I for quinoxaline and thiophene.
Beneficial effect:
(1) the present invention has wider absorption spectrum, and compared with polymkeric substance D, absorption spectrum there occurs obvious red shift, significantly reduces the optical energy gap of polymkeric substance;
(2) the present invention has the HOMO energy level darker than polymkeric substance D, can be deep to-5.67eV, be applied in photovoltaic cell the high open circuit voltage obtaining >0.89V;
(3) the present invention possesses the feature of thin pillar and dark HOMO energy level, very useful to the photovoltaic performance improving photovoltaic device.
Accompanying drawing explanation
Fig. 1 is the abosrption spectrogram of polymer A, D.
Fig. 2 is the C-V figure of polymer A, D.
Fig. 3 is the I-V figure of polymer device A, D.
Embodiment
Below in conjunction with drawings and Examples, particular content of the present invention is described in more detail.
Below provide specific embodiments of the invention, it should be noted that the present invention is not limited to following specific embodiment, all equivalents done on technical scheme basis all fall into protection scope of the present invention.
Embodiment 1: the synthesis of intermediate
(1) preparation of fluoro-3,6-bis-bromo-1, the 2-phenylenediamines (compound 1) of 4-
Fluoro-4,7-bis-bromo-2,1, the 3-diazosulfides (5g, 0.016mol) of 5-are dissolved in 150ml dehydrated alcohol, add NaBH4 (11.1g, 0.29mol) in batches, then react 20h under room temperature at 0 DEG C.After reaction terminates, remove ethanol, add 160ml water, extraction into ethyl acetate, saturated common salt water washing organic phase with distillation under vacuum, last anhydrous MgSO4 is dry.Concentrated removal organic solvent, the thick product n-hexane/ethyl acetate obtained (volume ratio is 25:1) silica gel column chromatography, obtains fluoro-3,6-bis-bromo-1, the 2-phenylenediamine 3.5g of 4-, productive rate 78%.
The preparation of (2) 1,2-bis-(3-octyloxyphenyl) second diketone (compound 2)
To CuBr (4.33g, in THF solution 30.2mmol), (40ml) adds LiBr (5.25g, 60.4mmol), stirred at ambient temperature dissolves, under ice bath, temperature is down to 0 DEG C, start to drip a Grignard reagent [bromobenzene octyl ether (8.6g of bromobenzene octyl ether between brand-new, 30.2mmol), Mg (1g, 41.7mmol), THF (30ml)], after reaction 20min, start at 0 DEG C to drip oxalyl chloride (1.71g, 13.5mmol), dropwise, continue reaction 30min.Saturated NH4Cl solution cancellation reaction is added in system, extraction into ethyl acetate, salt water washing organic phase, anhydrous MgSO4 is dry, concentrated removal organic solvent, the thick product n-hexane/ethyl acetate obtained (volume ratio is 200:1) silica gel column chromatography, obtains 1,2-bis-(3-octyloxyphenyl) second diketone 3.46g, productive rate 55%.
The preparation of (3) 2,7-bis-octyloxy-9,10-phenanthrenequione (compound 3)
Under argon shield, 1,2-bis-(3-octyloxyphenyl) second diketone (0.70g, 1.5mmol) be dissolved in 80ml dry methylene chloride solution, add 0.25ml boron trifluoride diethyl etherate and trifluoro vanadyl (0.41g, 3.3mmol), 0 DEG C is stirred 10 minutes; Add molybdenum pentachloride (0.90g, 3.3mmol), stirring reaction 30min.The sodium hydrogen carbonate solution (50ml) of ice is added in system, suction filtration, extraction into ethyl acetate, anhydrous magnesium sulfate drying, concentrated removal organic solvent, the thick product n-hexane/ethyl acetate obtained (volume ratio is 100:1) silica gel column chromatography, obtain 2,7-bis-octyloxy-9,10-phenanthrenequione 0.56g, productive rate 80%.
(4) preparation of fluoro-10,13-bis-bromo-2, the 7-bis-octyloxy benzodiazepine anthracenes (compound 4) of 11-
Fluoro-3,6-bis-bromo-1, the 2-phenylenediamines (0.59g, 1.9mmol) of 4-and 2,7-bis-octyloxy-9,10-phenanthrenequione (0.88g, 1.9mmol) are dissolved in 40ml acetic acid, are warming up to 60 DEG C, close heating, react 2h under room temperature.Suction filtration, washing with alcohol filter cake, obtains fluoro-10,13-bis-bromo-2, the 7-bis-octyloxy benzodiazepine anthracene 1.28g of 11-, productive rate 95%.Nuclear-magnetism characterization data is: 1HNMR (CDCl3,500MHz, ppm), δ: 8.40 (d, 2H), 8.04 (d, 2H), 7.84 (d, 1H), 7.15 (s, 2H), 4.09 (t, 4H), 1.85 (s, 4H), 1.37 (m, 20H), 0.85 (s, 6H).
Embodiment 2: polymer A
Reaction is carried out under nitrogen protection, 11-fluoro-10, 13-bis-bromo-2, 7-bis-octyloxy benzodiazepine anthracene (213.7mg, 0.3mmol) He 2, two (tin trimethyl) thiophene (198.6mg of 5-, 0.3mmol) be dissolved in 10ml toluene, logical nitrogen 0.5h, add catalyzer three (dibenzylideneacetone) two palladium (5.5mg) and part tri-o-tolyl phosphorus (9.8mg), heating is started after continuing ventilation 0.5h, back flow reaction 24h, system is naturally cooling at room temperature, dropwise add to sedimentation in methyl alcohol, filter, the polymkeric substance vacuum drying oven 50 DEG C collected dries 12h, the polymkeric substance obtained uses methyl alcohol successively, normal hexane, chloroform surname extraction, concentrated chloroform extracted solution, again drop to sedimentation in methyl alcohol, obtain polymer A 175mg, for atropurpureus fibrous solids, productive rate 88%, number-average molecular weight 192.38kDa, distribution coefficient 2.94.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, platinum wire electrode is to electrode, and Ag/Ag+ electrode is reference electrode, and Bu4NPF6 makes ionogen, in acetonitrile solvent, initial oxidation current potential through cyclic voltammetry polymer A film is 0.95V, and according to calculation formula-(4.72+ initial oxidation current potential/V) eV of HOMO energy level, the HOMO energy level obtaining polymer A is-5.67eV, see accompanying drawing 1, reduce 0.16eV than polymkeric substance D.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: the sandwich battery structure of PC71BM/PFN/Al, polymer A and acceptor material PC71BM are made photovoltaic cell according to weight ratio 1:3, useful area 0.16cm2, current-voltage test is carried out under NewportThermalOriel69911 simulated solar light source, utilize Keithley2611 source to show to gather, open circuit voltage is 0.92V, short-circuit current density 11.6mA/cm2, packing factor 54.1%, photoelectric transformation efficiency is 5.77%.
Embodiment 3: polymer B
With embodiment 2, short of electricity unit is changed into fluoro-10,13-bis-bromo-3, the 6-bis-octyloxy benzodiazepine anthracenes of 11-, adopt identical polymerization process to obtain polymer B, productive rate 76%, number-average molecular weight 153.67kDa, distribution coefficient 2.75.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag+ electrode is reference electrode, Bu4NPF6 makes ionogen, in acetonitrile solvent, can be-5.58eV through the HOMO of cyclic voltammetry polymer B film.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: the sandwich battery structure of PC71BM/LiF/Al, polymer B and acceptor material PC71BM are made photovoltaic cell according to certain weight ratio, useful area 0.16cm2, current-voltage test is carried out under NewportThermalOriel69911 simulated solar light source, Keithley2611 source is utilized to show to gather, open circuit voltage is 0.89V, and photoelectric transformation efficiency is 5.42%.
Embodiment 4: polymkeric substance C
With embodiment 3, short of electricity unit changes fluoro-10,13-bis-bromo-2,3,6, the 7-bis-octyloxy benzodiazepine anthracenes of 11-into, adopts identical polymerization process to obtain polymkeric substance C, productive rate 72%, number-average molecular weight 90.78kDa, distribution coefficient 2.43.
Electro-chemical test: with CHI660D type electrochemical workstation, employing glass-carbon electrode is working electrode, and platinum wire electrode is to electrode, Ag/Ag
+electrode is reference electrode, Bu
4nPF
6making ionogen, in acetonitrile solvent, can be-5.63eV through the HOMO of cyclic voltammetry polymkeric substance C film.
Photovoltaic performance is studied: adopt ITO/PEDOT:PSS/ polymkeric substance: PC
71the sandwich battery structure of BM/PFN/Al, by polymkeric substance C and acceptor material PC
71bM makes photovoltaic cell according to certain weight ratio, useful area 0.16cm
2, under NewportThermalOriel69911 simulated solar light source, carry out current-voltage test, utilize Keithley2611 source to show to gather, open circuit voltage is 0.91V, and photoelectric transformation efficiency is 5.58%.
The HOMO energy level of table 1 polymkeric substance
Claims (4)
1. fluorine-containing phenanthrene is for a conjugated polymers for quinoxaline and thiophene, and it is characterized in that, general structure is such as formula shown in I:
In formula, R
1, R
2can identical also can be different;
Work as R
1during=H, R
2alkyl or the alkoxyl group of to be carbonatoms the be straight or branched of 4 to 20;
Work as R
2during=H, R
1alkyl or the alkoxyl group of to be carbonatoms the be straight or branched of 4 to 20;
Work as R
1=R
2time, be alkyl or the alkoxyl group of the straight or branched of 4 to 20.
2. fluorine-containing phenanthrene as claimed in claim 1 is for the conjugated polymers of quinoxaline and thiophene, it is characterized in that, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in II:
3. fluorine-containing phenanthrene as claimed in claim 1 is for the conjugated polymers of quinoxaline and thiophene, it is characterized in that, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in III:
4. fluorine-containing phenanthrene as claimed in claim 1 is for the conjugated polymers of quinoxaline and thiophene, it is characterized in that, described fluorine-containing phenanthrene for the structure of the conjugated polymers of quinoxaline and thiophene such as formula shown in IV:
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| CN108276559A (en) * | 2018-01-16 | 2018-07-13 | 华南协同创新研究院 | Phenanthro-containing tri-heterocyclic conjugated polymer and application thereof in organic photoelectric device |
| WO2018131766A1 (en) * | 2017-01-10 | 2018-07-19 | 건국대학교 산학협력단 | Phenazine derivative having increased solubility, and polymer for organic photovoltaic conversion device, using same |
| CN108976392A (en) * | 2018-05-28 | 2018-12-11 | 华南师范大学 | The conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline and its application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102159617A (en) * | 2008-09-19 | 2011-08-17 | 默克专利股份有限公司 | Polymers derived from bis(thienocyclopenta)benzothiadiazole and their use as organic semiconductors |
| CN103724283A (en) * | 2013-12-17 | 2014-04-16 | 华南理工大学 | 2,7-alkyl substituted phenanthro [9,10-b] pyrazine derivative monomer, preparation method of 2,7-alkyl substituted phenanthro [9,10-b] pyrazine derivative monomer and polymer |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102159617A (en) * | 2008-09-19 | 2011-08-17 | 默克专利股份有限公司 | Polymers derived from bis(thienocyclopenta)benzothiadiazole and their use as organic semiconductors |
| CN103724283A (en) * | 2013-12-17 | 2014-04-16 | 华南理工大学 | 2,7-alkyl substituted phenanthro [9,10-b] pyrazine derivative monomer, preparation method of 2,7-alkyl substituted phenanthro [9,10-b] pyrazine derivative monomer and polymer |
Non-Patent Citations (1)
| Title |
|---|
| RENEE KROON ET AL.: ""New quinoxaline and pyridopyrazine-based polymers for solution-processable photovoltaics"", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018131766A1 (en) * | 2017-01-10 | 2018-07-19 | 건국대학교 산학협력단 | Phenazine derivative having increased solubility, and polymer for organic photovoltaic conversion device, using same |
| CN108276559A (en) * | 2018-01-16 | 2018-07-13 | 华南协同创新研究院 | Phenanthro-containing tri-heterocyclic conjugated polymer and application thereof in organic photoelectric device |
| CN108276559B (en) * | 2018-01-16 | 2020-01-17 | 华南协同创新研究院 | A kind of conjugated polymer containing phenanthrene triheterocycle and its application in organic optoelectronic devices |
| CN108976392A (en) * | 2018-05-28 | 2018-12-11 | 华南师范大学 | The conjugated polymer photoelectric material of the condensed ring of acid imide containing quinoxaline and its application |
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