CN104877113A - Organic photoelectric polymer material based on dibenzothiophene unit and quinoxaline unit as well as preparation method and application of organic photoelectric polymer material - Google Patents
Organic photoelectric polymer material based on dibenzothiophene unit and quinoxaline unit as well as preparation method and application of organic photoelectric polymer material Download PDFInfo
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Abstract
The invention discloses an organic photoelectric polymer material based on a dibenzothiophene unit and a quinoxaline unit as well as a preparation method and application of the organic photoelectric polymer material. The structural formula of the polymer is shown by a formula I, wherein R1 and R2 represent straight or branched alkyl with 8-10 carbon atoms, and n represents the number of repeated units of the polymer and is a natural number between 5 and 1000. The polymer material disclosed by the invention can be applied to the photoelectric field such as the field of polymer solar cells.
Description
Technical field
The invention belongs to organic photoelectric polymer field of material technology, be specifically related to a kind of organic photoelectric polymer material based on benzo two thiophene unit and quinoxaline unit and preparation method thereof and application.
Background technology
Since from the eighties in last century, Kodak develops organic solar batteries, particularly after 2002, organic solar batteries technology day crescent benefit, especially in developing material, novel material continues to bring out, and the efficiency of battery is also improving constantly.Organic (comprising polymkeric substance) photovoltaic device because of its have lightweight, cost is low, technique is simple and the easy outstanding advantages such as the flexible broad area device of preparation, become the study hotspot of solar cell, its highest energy transformation efficiency reaches 8-10%, (Samuel C.Price, Andrew C.Stuart, Liqiang Yang, Huaxing Zhou, Wei You, J.Am.Chem.Soc.2011,133,4625 – 4631; Ta-Ya Chu, Jianping Lu, Serge Beaupre, Yanguang Zhang, Jean-Remi Pouliot, Salem Wakim, Jiayun Zhou, Mario Leclerc, Zhao Li, Jianfu Ding, Ye Tao, J.Am.Chem.Soc.2011,133,4250 – 4253; YongyeLiang, Zheng Xu, Jiangbin Xia, Szu-Ting Tsai, Yue Wu, Gang Li, Claire Ray, Luping Yu, Adv.Mater.2010,22, E135 – E138; Hsiang-Yu Chen, JianhuiHou, Shaoqing Zhang, Yongye Liang, Guanwen Yang, Yang Yang, Luping Yu, YueWu, Gang Li NATURE PHOTONICS, 2009,3,649-653; Ming-Shin Su, Chih-YinKuo, Mao-Chuan Yuan, U-Ser Jeng, Chun-Jen Su, Kung-Hwa Wei Adv.Mater.2011,23,3315 – 3319; ) progressively promoting of organic solar batteries efficiency bring the dawn of its commercial applications.
The polymkeric substance or organic small molecule material (donor material) and fullerene (C that possess photoelectric activity is depended in organic solar batteries
60and C
70derivative) material (acceptor material) forms photoactive layer (being called body heterojunction) and absorbs sunlight and be translated into and can utilize electric energy.Therefore photoelectric activity material is the research core of organic solar batteries, particularly donor material aspect, determines the performance perameter (open circuit voltage, short-circuit current and photoelectric transformation efficiency) of battery to a great extent.
Bibliographical information shows, the planarity of benzo [1,2-b:4,5-b '] two thiophene units (BDT) is fine, and the stronger Pi-Pi between molecular chain piles up and more easily forms high mobility.Utilize the characteristic of this plane symmetry and high mobility, it is incorporated in organic photovoltaic material molecule, high efficiency organic photovoltaic devices can be obtained.Therefore, the Optimized Approaches of the novel Polymer Optoelectronic active material based on BDT unit of design and development and exploration material is extremely important and significant.
Summary of the invention
In order to solve above-mentioned prior art Problems existing, the object of the present invention is to provide a kind of organic photoelectric polymer material based on benzo two thiophene unit and quinoxaline unit and preparation method thereof and application, combination between benzene 1,4-Dithiapentalene BDT unit and quinoxaline Qx unit can modulate the high performance material being suitable for organic photovoltaic battery, the invention provides the efficient combination mode of benzene 1,4-Dithiapentalene BDT unit and quinoxaline Qx unit and obtain organic photoelectric polymer PBQx, be applied in organic photovoltaic battery, further prepare the high efficiency solar cell based on organic materials by the weight ratio of modulation polymer and additive.
For reaching above object, the present invention adopts following technical scheme:
Based on an organic photoelectric polymer material for benzo two thiophene unit and quinoxaline unit, the structural formula of described organic photoelectric polymer material is such as formula shown in I:
Comprise benzene 1,4-Dithiapentalene BDT unit and quinoxaline Qx unit in described formula I, be connected with thiophene singly-bound therebetween, obtained by the polymerization of Stille cross-coupling; Wherein, R
1, R
2representative has the straight or branched alkyl of 8 to 10 carbon atoms; The repeating unit number of n representation polymer is the natural number between 5-1000;
The number-average molecular weight of described organic photoelectric polymer material is 1000 to 1,000,000.
Usually, described R
1, R
2representative has the straight or branched alkyl of 10 carbon atoms; The number-average molecular weight of described organic photoelectric polymer material is 2000 to 1,000,000.About 3000 to 500 can be had further, the number-average molecular weight of 000, and about 20 can be had further, the number-average molecular weight of 000 to 200,000.Should understand and can change molecular weight with aggregation properties.Such as, lower molecular weight can guarantee solubleness, and higher molecular weight can guarantee good film-forming quality.
The preparation method of organic photoelectric polymer material described above, it is characterized in that: the compound 2 shown in described organic photoelectric polymer material through type II, 6-X-4, two (5-alkyl (the R1)-4-fluorine thiophene-2-base) benzo [1 of 8-, 2-b:4,5-b '] compound 5 shown in two thiophene and formula III, two (5-Y benzene-2 base)-6 of 8-, 7-bis-fluoro-1, there is copolyreaction in 2 pairs of (3-alkoxyl group (OR2)) phenyl quinoxalines, obtain polymer materials shown in formula I under the effect of catalyzer;
Reaction formula is as follows:
In formula II and formula III, R
1, R
2definition cotype I;
The Y that X in formula II relies in formula III selects;
X in formula II is selected from boric acid base group, borate group, magnesium halide group, zinc halide group or trialkyltin groups, and the Y in formula III is selected from I, Br or Cl;
Y in formula III is selected from I, Br or Cl, and the X in formula II is selected from boric acid base group, borate group, zinc halide group or trialkyltin groups;
Wherein, described boric acid base group is selected from and includes but not limited to: 1,3,2-dioxaborinate-2-base, 4,4,5,5-tetramethyl--1,2,3-dioxaborolanes-2-bases or 5,5-dimethyl-1,3,2-dioxaborinate-2-base; Described magnesium halide group is selected from and includes but not limited to: magnesium chloride, magnesium bromide or magnesium iodide; Described zinc halide group is preferred: zinc chloride or zinc bromide; Described trialkyltin groups is selected from and includes but not limited to: tin trimethyl, triethyltin or tributyl tin.
Definition and name:
Unless otherwise noted, otherwise the present invention is not limited to specific raw material, reagent or reaction conditions, but can change.Term used herein " alkyl " refers to branching or nonbranched saturated alkyl, and it is usually but not necessarily containing 1 to 30 carbon atom, as methyl, ethyl, n-propyl, sec.-propyl, n-octyl, iso-octyl, decyl etc.; And cycloalkyl, as cyclopentyl, cyclohexyl etc.
The present invention also protects a kind of semiconductor composition, is made up of polymer materials shown in formula I described above and adulterating agent; Described adulterating agent is selected from least one in soccerballene or derivatives thereof; Described soccerballene or derivatives thereof is specially [6,6]-phenyl C
61methyl-butyrate or [6,6]-phenyl C
71methyl-butyrate or containing indenes soccerballene.
Described adulterating agent is generally a kind of compound, selects this compound to make, when the excitaton source comprising light or voltage is applied to this combination, Charger transfer and/or energy trasfer to occur between adulterating agent and polymkeric substance.Such as, described adulterating agent can be soccerballene, as: C
60, C
70or C
80, or some fullerene compounds replaced, as PCBM ([6,6]-phenyl C
61methyl-butyrate) and containing indenes soccerballene.
In semiconductor composition, polymkeric substance shown in described formula I and adulterating agent can mix according to any mass ratio, as mixed according to mass ratio 1:2.
The present invention also protects a kind of solar cell device, and the active material layer in described solar cell device adopts polymer materials shown in formula I described above.
Described a kind of solar cell device, comprises the second electrode that the first electrode and described first electrode space are opened and at least one deck active material layer arranged between described first electrode and the second electrode.
When one deck active material layer is set between described first electrode and the second electrode, also comprise the electrode transition layer be arranged between active material layer and the first electrode and/or the second electrode; When multilayer active material layer is set between described first electrode and the second electrode, also comprise the transparent electrode layer be arranged between adjacent two layers active material layer.
Described first electrode and/or the second electrode are transparency electrode.
Compared to the prior art comparatively, the present invention possesses following advantage:
The invention provides a kind of organic photoelectric polymer material based on benzo two thiophene unit and quinoxaline unit and preparation method thereof and application, go out to be suitable for the high performance material of organic photovoltaic battery based on the hybrid modulation between high-level efficiency benzene 1,4-Dithiapentalene BDT unit and quinoxaline Qx unit; The present invention has prepared high-level efficiency organic photoelectric polymer PBQx, and by optimizing battery structure and technique, prepares the high efficiency solar cell device based on organic materials.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention prepares monomer M 1 (2, two (tin trimethyl)-4 of 6-, two (5-(2-the ethylhexyl)-4-fluorine thiophene-2-base) benzo of 8-[1,2-b:4,5-b '] two thiophene) chemical reaction flow process figure.
Fig. 2 is the structural representation of outsourcing reagent monomer M 4.
Fig. 3 is the chemical equation that the present invention prepares polymer P BQx.
Fig. 4-1, Fig. 4-2 are the abosrption spectrogram after the normalization method of polymkeric substance prepared by embodiment 2, wherein, and the absorption in the solution of Fig. 4-1 representation polymer, the absorption of Fig. 4-2 representation polymer in solid film.
Fig. 5 shows polymeric film provided by the invention on platinum electrode at 0.1mol/L Bu
4nPF
6acetonitrile solution in electrochemistry cyclic voltammogram.
Fig. 6 is thermogravimetric analysis (TGA) figure of polymkeric substance.
Fig. 7 is a kind of structural representation of solar cell device of the present invention.
Fig. 8 is the another kind of structural representation of solar cell device of the present invention.
Fig. 9-1 for PBQx be donor material with fullerene derivative receptor material (PC
71bM) the I-V curve of the battery device of Different Weight ratio; Fig. 9-2 is be donor material with PBQx, fullerene derivate (PC
71bM) for acceptor material is under fixed proportion, the battery device I-V curve of different ratios additive in active coating solution, is added.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail.
When describing embodiment of the present invention, for the sake of clarity, employ specific term.But the present invention is not intended to be confined to selected particular term.Should be appreciated that each particular element comprises similar method and runs with all technically equivalent ones realizing similar object.
Practice of the present invention can adopt the routine techniques of the polymer chemistry in art technology.In the examples below, endeavour to ensure the accuracy of numeral used (amount of comprising, temperature, reaction times etc.), but some experimental errors and deviation should be considered.Temperature used is in the examples below DEG C to represent, pressure is normal atmosphere or close to normal atmosphere.All solvents are all buy with HPLC level, and respond is carried out under argon inert atmosphere.Unless otherwise noted, otherwise all reagent be all business obtain.
The synthesis of embodiment 1, monomer M 1 (two (5-(2-the octyl group)-4-fluorine thiophene-2-base) benzos of 2,6-two (tin trimethyl)-4,8-[1,2-b:4,5-b '] two thiophene)
Chemical reaction flow process figure as shown in Figure 1, concrete reactions steps and reaction conditions as follows:
(i) compound 1 (4, two (the bromo-5-of 4-(2-octyl group) thiophene-2-base) benzo [1 of 8-, 2-b:4,5-b '] two thiophene) synthesis: under ar gas environment, temperature controls at subzero 78 DEG C, the bromo-2-of 3-(2-octyl group) thiophene (9.1g, 33mmol) be dissolved in distilled tetrahydrofuran (THF) (THF, 35ml), stir, dropwise add lithium diisopropylamine (LDA, 18.2mL, 2M), keep subzero 78 DEG C of lower magnetic force stirring reactions afterwards 1 hour, be then warming up to 50 DEG C of reactions 15 minutes; Above-mentioned reaction is cooled to room temperature, adds benzo [1,2-b:4,5-b '] two thiophene-4,8-diketone (2.4g, 10.9mmol), is warming up to 50 DEG C of reactions 2 hours; Last 10% hydrochloric acid (30ml) solution adding two hydration tindichloride (17.5g, 77mmol) in said mixture, keeps 50 DEG C of stirrings 1 hour, and then mixture goes out with shrend and with extracted with diethyl ether 3 times.The further purification of product adopts chromatographic column to purify (sherwood oil is eluent).Final product is yellow solid (5g, productive rate 63%).
(ii) compound 2 (2, two (trimethyl silicane)-4 of 6-, two (the bromo-5-of 4-(2-octyl group) thiophene-2-base) benzo [1 of 8-, 2-b:4,5-b '] two thiophene) synthesis: compound 1 (3.86g, 5mmol) is dissolved in THF (50ml), control temperature is at subzero 78 DEG C, dropwise add LDA (6.5ml, 2M), and stir 1 hour at this temperature; Add trimethyltin chloride (4ml) subsequently, be warming up to room temperature, stir 1 hour; React afterwards and go out with shrend, product with diethyl ether three times, and purifies (sherwood oil is for eluent) with chromatographic column.Final product is faint yellow solid (3.6g, productive rate 78%).
(iii) compound 3 (2, two (trimethyl silicane)-4 of 6-, two (5-(2-the octyl group)-4-fluorine thiophene-2-base) benzo [1 of 8-, 2-b:4,5-b '] two thiophene) synthesis: compound 2 (2.2g, 3mmol) is dissolved in 30mlTHF, after being cooled to subzero 78 DEG C, dropwise add butyllithium (2.6ml, 2.5M), keep this temperature to stir 1 hour; N-fluoro two benzsulfamide (2.4g, 7.6mmol) is dissolved in 20mlTHF and adds in above-mentioned reactant; Stirred at ambient temperature reacts 2 hours afterwards, then goes out with shrend, diethyl ether three times.Product is purified with chromatographic column, (sherwood oil is eluent).Final product is faint yellow solid (1.13g, productive rate 50%).
(iv) compound 4 (4, two (5-(2-the octyl group)-4-fluorine thiophene-2-base) benzo [1 of 8-, 2-b:4,5-b '] two thiophene) synthesis: compound 3 (3g, add 10ml trifluoroacetic acid in dichloromethane solution 4mmol), stirring is spent the night; Product with dichloromethane extraction, and purifies (sherwood oil is for elutriant) with chromatographic column.Final product is faint yellow solid (2.2g, productive rate 90%).
(v) monomer M 1 (2, two (tin trimethyl)-4 of 6-, two (5-(2-the octyl group)-4-fluorine thiophene-2-base) benzo [1 of 8-, 2-b:4,5-b '] two thiophene) synthesis: compound 4 (2.2g, 3mmol) be dissolved in 30mlTHF and dropwise add butyllithium (3.6ml, 2.5M) under subzero 78 DEG C of conditions, keep this temperature to stir 1 hour; Add 3ml trimethyltin chloride subsequently, rise to room temperature and continue stirring 1 hour; Product goes out with shrend, and with diethyl ether three times, purifies (sherwood oil is for eluent) afterwards with chromatographic column.Final product is faint yellow solid (2.4g, productive rate 85%).
The synthesis of embodiment 2, Inventive polymers PBQx.
Chemical reaction flow process figure as shown in Figure 3, concrete reactions steps and reaction conditions as follows:
Get as shown in Figure 1 monomer M 1 and as shown in Figure 2 monomer M 4 (outsourcing) by Stille cross-coupling polymerization obtain polymer P BQx.Reaction conditions is as follows: argon gas air-discharging 5 minutes, then adds catalyzer tetrakis triphenylphosphine palladium (0) and continue air-discharging 25 minutes afterwards.Then at refluxing toluene temperature, be polymerized 16 as a child stopped.Polymers soln is cooled to room temperature, and slowly pour in methyl alcohol (50mL), the solid polymer separated out carrys out wash-out with methyl alcohol, normal hexane successively in apparatus,Soxhlet's.After finally dissolving with trichloromethane, precipitating is in methyl alcohol, and filter, vacuum-drying obtains the polymkeric substance of solid powdery for 1 day.Polymer yield 69%, the polymericular weight that gel chromatography (GPC) records and being distributed as: Mn=23.4KPa, Mw=44.46KPa, PDI=1.9.
The workability of embodiment 3, Inventive polymers and utilize the measurement of optical band gap of absorption spectrum
Polymkeric substance obtained in embodiment 2 is mixed with various organic solvent, described organic solvent comprises chlorinated solvent, as chloroform, methylene dichloride, chlorobenzene and dichlorobenzene, and other solvents, as methyl alcohol, toluene, tetrahydrofuran (THF).Find that polymer P BQx series has good solubleness in chlorinated solvent, but soluble in methyl alcohol.By the dichlorobenzene solution of polymkeric substance being spin-coated to obtained high quality thin film on sheet glass.
Embodiment 4, the absorption spectrum that the polymkeric substance of preparation records under chloroformic solution and membrane stage are shown in Fig. 4-1 and Fig. 4-2.Optical band gap use experience formula (the Eg=1240/ λ of polymkeric substance
absorb initial, wherein: Eg is the optical band gap of polymkeric substance; λ
absorb initialfor absorption spectrum is in the starting point in long wave direction) calculate and be shown in Table 1.
The optical absorption of table 1. polymkeric substance 1 and electrochemistry and molecular entergy level Theoretical Calculation data
athe energy level that cyclic voltammetry measurement obtains
Embodiment 5, the highest molecular orbital(MO) (HOMO) that takies utilizing electrochemical cyclic voltammetry are measured, and result as shown in Figure 5.
Embodiment 6, polymkeric substance provided by the invention adopt thermogravimetric analyzer to test its thermostability, specific embodiments, and get 10mg polymkeric substance and heat under nitrogen protection environment, analysis chart is shown in Fig. 6, and the glass transition temperature of polymer recorded is T
d=369 DEG C.
Embodiment 7, prepare polymer solar cell device
Polymkeric substance (10mg) obtained is in example 2 dissolved in the solution of obtained 10mg/mL in chlorobenzene, then with the PC of Different Weight
71bM is blended, by preparing organic photovoltaic battery and test performance discovery, as polymer P BQx and PC
71when BM weight ratio is 1:2, the performance of photovoltaic cell reaches best, further, at polymer P BQx and PC
71add universal additive 1,8-diiodo-octane (DIO) in the blend solution of BM, obtain the organic photovoltaic battery of top efficiency.The glass substrate that transparent indium tin oxide (ITO) is coated with manufactures polymer solar battery.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.Then, about 10
-4under the pressure of Pa, the thin layer of evaporation calcium and aluminium in succession, obtains polymer solar cell 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 polymer solar cell 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).
Being illustrated in figure 7 a kind of structural representation of solar cell device of the present invention, is the schematic diagram of solar cell device 100.This solar cell device 100 has the first electrode 102, obtains the second electrode 104 with the first electrode 102 is spaced apart, and the active material layer 106 arranged between the first electrode and the second electrode.Such as, this solar cell device 100 can have multi-electrode transition layer 108 between electrode and active material layer.Described active material layer can comprise the conjugated polymer material of one or more embodiment of the present invention.In embodiments more of the present invention, one of the first electrode 102 and the second electrode 104 or both can be transparency electrode.
Being illustrated in figure 8 the another kind of structural representation of solar cell device of the present invention, is the schematic diagram of solar cell device 200.This solar cell device 200 have the first electrode 202, with isolated second electrode 204 of the first electrode 202, and the first active coating 206 arranged between the first electrode and the second electrode.This embodiment is the example between the first electrode 202 and the second electrode 204 with the solar cell device of the second active coating 210.This solar cell device 200 can have other material layer between active material layer and electrode and/or between two active coatings.Such as, transparency conducting layer 208 can be there is between the first active coating 206 and the second active coating 210.Solar cell device according to the present invention is not limited to only one or two active material layer; In some embodiments of the present invention, they can have multiple active material layer.The schematic diagram of Fig. 7 and Fig. 8 shows as an example.Device is according to a further embodiment of the present invention not limited to these specific examples.
Embodiment 8
Based on the polymkeric substance of embodiment 2, according to the program manufacture of embodiment 7 and characterize polymers solar cell device, and test its performance index, graphic representation is shown in Fig. 9-1 and Fig. 9-2, and data are shown in table 2.Wherein best performance perameter is as follows: polymer P BQx, open circuit voltage Voc=0.876V, short-circuit current Jsc=13.58mA/cm
2, packing factor FF=70.24%, transformation efficiency PCE=8.55%.
Table 2
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 (12)
1., based on an organic photoelectric polymer material for benzo two thiophene unit and quinoxaline unit, it is characterized in that: the structural formula of described organic photoelectric polymer material is such as formula shown in I:
Comprise benzene 1,4-Dithiapentalene BDT unit and quinoxaline Qx unit in described formula I, be connected with thiophene singly-bound therebetween, obtained by the polymerization of Stille cross-coupling; Wherein, R
1, R
2representative has the straight or branched alkyl of 8 to 10 carbon atoms; The repeating unit number of n representation polymer is the natural number between 5-1000;
The number-average molecular weight of described organic photoelectric polymer material is 1000 to 1,000,000.
2. a kind of organic photoelectric polymer material based on benzo two thiophene unit and quinoxaline unit according to claim 1, is characterized in that: described R
1, R
2representative has the straight or branched alkyl of 10 carbon atoms; The number-average molecular weight of described organic photoelectric polymer material is 2000 to 1,000,000.
3. a kind of organic photoelectric polymer material based on benzo two thiophene unit and quinoxaline unit according to claim 2, is characterized in that: the number-average molecular weight of described organic photoelectric polymer material is 3000 to 500,000.
4. a kind of organic photoelectric polymer material based on benzo two thiophene unit and quinoxaline unit according to claim 2, is characterized in that: the number-average molecular weight of described organic photoelectric polymer material is 20,000 to 200,000.
5. the preparation method of organic photoelectric polymer material according to claim 1, it is characterized in that: the compound 2 shown in described organic photoelectric polymer material through type II, 6-X-4, two (5-alkyl (the R1)-4-fluorine thiophene-2-base) benzo [1 of 8-, 2-b:4,5-b '] compound 5 shown in two thiophene and formula III, two (5-Y benzene-2 base)-6 of 8-, 7-bis-fluoro-1, there is copolyreaction in 2 pairs of (3-alkoxyl group (OR2)) phenyl quinoxalines, obtain polymer materials shown in formula I under the effect of catalyzer;
Chemical equation is as follows:
In formula II and formula III, R
1, R
2definition cotype I;
The Y that X in formula II relies in formula III selects;
X in formula II is selected from boric acid base group, borate group, magnesium halide group, zinc halide group or trialkyltin groups, and the Y in formula III is selected from I, Br or Cl;
Y in formula III is selected from I, Br or Cl, and the X in formula II is selected from boric acid base group, borate group, zinc halide group or trialkyltin groups;
Wherein, described boric acid base group is selected from and includes but not limited to: 1,3,2-dioxaborinate-2-base, 4,4,5,5-tetramethyl--1,2,3-dioxaborolanes-2-bases or 5,5-dimethyl-1,3,2-dioxaborinate-2-base; Described magnesium halide group is selected from and includes but not limited to: magnesium chloride, magnesium bromide or magnesium iodide; Described zinc halide group is preferred: zinc chloride or zinc bromide; Described trialkyltin groups is selected from and includes but not limited to: tin trimethyl, triethyltin or tributyl tin.
6. a semiconductor composition, is characterized in that: be made up of polymer materials shown in the formula I described in claim 1 or 2 and adulterating agent; Described adulterating agent is selected from least one in soccerballene or derivatives thereof; Described soccerballene or derivatives thereof is specially [6,6]-phenyl C
61methyl-butyrate or [6,6]-phenyl C
71methyl-butyrate or containing indenes soccerballene.
7. a kind of semiconductor composition according to claim 6, is characterized in that: shown in described formula I, polymkeric substance and adulterating agent mix according to any mass ratio.
8. a kind of semiconductor composition according to claim 6, is characterized in that: polymer materials shown in described formula I and adulterating agent mix according to mass ratio 1:2.
9. a solar cell device, is characterized in that: the active material layer in described solar cell device adopts polymer materials shown in the formula I described in claim 1 or 2.
10. a kind of solar cell device according to claim 9, is characterized in that: comprise the second electrode that the first electrode and described first electrode space are opened and at least one deck active material layer arranged between described first electrode and the second electrode.
11. a kind of solar cell devices according to claim 9, it is characterized in that: when one deck active material layer is set between described first electrode and the second electrode, also comprise the electrode transition layer be arranged between active material layer and the first electrode and/or the second electrode; When multilayer active material layer is set between described first electrode and the second electrode, also comprise the transparent electrode layer be arranged between adjacent two layers active material layer.
12. a kind of solar cell devices according to claim 9, is characterized in that: described first electrode and/or the second electrode are transparency electrode.
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| WO2019137329A1 (en) * | 2018-01-10 | 2019-07-18 | The Hong Kong University Of Science And Technology | Chlorinated benzodithiophene-based polymers for electronic and photonic applications |
| TWI688637B (en) * | 2018-06-21 | 2020-03-21 | 國立交通大學 | Active layer of solar cells and polymer solar cells |
| CN110938067A (en) * | 2019-12-13 | 2020-03-31 | 中南大学 | Asymmetric quinoxaline receptor unit material, polymer material for further copolymerization thereof and application thereof |
| CN113024779A (en) * | 2021-03-05 | 2021-06-25 | 中国科学院化学研究所 | Application of p-type D-A copolymer containing quinoxaline unit in high-efficiency organic and perovskite solar cell |
| CN113214456A (en) * | 2020-01-21 | 2021-08-06 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN113527641A (en) * | 2021-07-31 | 2021-10-22 | 常州大学 | Polymer material based on ester side chain substituted quinoxaline derivative and application thereof |
| CN113929880A (en) * | 2021-10-29 | 2022-01-14 | 武汉工程大学 | Ester thiazole wide band gap polymer and application thereof in photoelectric device |
| WO2023070569A1 (en) * | 2021-10-29 | 2023-05-04 | 武汉工程大学 | Ester group thiazole-type wide band-gap polymer and use thereof in photoelectric device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827088A (en) * | 2012-08-30 | 2012-12-19 | 西安近代化学研究所 | Chloroquinoxaline compound |
| CN102827358A (en) * | 2012-08-30 | 2012-12-19 | 西安近代化学研究所 | Conjugated polymer of 4,8-di(5-isooctyl thiophene)phenyl [1,2-b; 3,4-b]bithiophene and chloroquinoxaline |
| CN104086752A (en) * | 2014-05-16 | 2014-10-08 | 中国华能集团清洁能源技术研究院有限公司 | Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it |
| CN104513367A (en) * | 2013-09-26 | 2015-04-15 | 海洋王照明科技股份有限公司 | Quinoxaline based copolymer, preparation method and applications thereof |
-
2015
- 2015-05-18 CN CN201510253029.5A patent/CN104877113A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827088A (en) * | 2012-08-30 | 2012-12-19 | 西安近代化学研究所 | Chloroquinoxaline compound |
| CN102827358A (en) * | 2012-08-30 | 2012-12-19 | 西安近代化学研究所 | Conjugated polymer of 4,8-di(5-isooctyl thiophene)phenyl [1,2-b; 3,4-b]bithiophene and chloroquinoxaline |
| CN104513367A (en) * | 2013-09-26 | 2015-04-15 | 海洋王照明科技股份有限公司 | Quinoxaline based copolymer, preparation method and applications thereof |
| CN104086752A (en) * | 2014-05-16 | 2014-10-08 | 中国华能集团清洁能源技术研究院有限公司 | Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it |
Non-Patent Citations (3)
| Title |
|---|
| DONGFENG DANG ET AL.: "Manipulating backbone structure with various conjugated spacers to enhance photovoltaic performance of D-A-type two-dimensional copolymers", 《ORGANIC ELECTRONICS》 * |
| LONG YE ET AL.: "Molecular Design toward Highly Efficient Photovoltaic Polymers Based on Two-Dimensional Conjugated Benzodithiophene", 《ACCOUNTS OF CHEMICAL RESEARCH》 * |
| QUNPING FAN ET AL.: "Improved photovoltaic performance of a 2D-conjugated benzodithiophene-based polymer by the side chain engineering of quinoxaline", 《POLYMER CHEMISTRY》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019137329A1 (en) * | 2018-01-10 | 2019-07-18 | The Hong Kong University Of Science And Technology | Chlorinated benzodithiophene-based polymers for electronic and photonic applications |
| CN111278888A (en) * | 2018-01-10 | 2020-06-12 | 香港科技大学 | Chlorinated benzodithiophene-based polymers for photovoltaic applications |
| TWI688637B (en) * | 2018-06-21 | 2020-03-21 | 國立交通大學 | Active layer of solar cells and polymer solar cells |
| CN110938067A (en) * | 2019-12-13 | 2020-03-31 | 中南大学 | Asymmetric quinoxaline receptor unit material, polymer material for further copolymerization thereof and application thereof |
| CN113214456A (en) * | 2020-01-21 | 2021-08-06 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN113214456B (en) * | 2020-01-21 | 2023-10-13 | 位速科技股份有限公司 | Copolymer and organic photovoltaic element |
| CN113024779A (en) * | 2021-03-05 | 2021-06-25 | 中国科学院化学研究所 | Application of p-type D-A copolymer containing quinoxaline unit in high-efficiency organic and perovskite solar cell |
| CN113527641A (en) * | 2021-07-31 | 2021-10-22 | 常州大学 | Polymer material based on ester side chain substituted quinoxaline derivative and application thereof |
| CN113527641B (en) * | 2021-07-31 | 2022-06-17 | 常州大学 | Polymer material based on ester side chain substituted quinoxaline derivative and application thereof |
| CN113929880A (en) * | 2021-10-29 | 2022-01-14 | 武汉工程大学 | Ester thiazole wide band gap polymer and application thereof in photoelectric device |
| WO2023070569A1 (en) * | 2021-10-29 | 2023-05-04 | 武汉工程大学 | Ester group thiazole-type wide band-gap polymer and use thereof in photoelectric device |
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