CN104513369A - Quinoxaline based copolymer, preparation method and applications thereof - Google Patents
Quinoxaline based copolymer, preparation method and applications thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic solar cell materials, and discloses a quinoxaline based copolymer, a preparation method and applications thereof. The structural formula of the copolymer is shown in the description, in the formula, the R1 and R2 individually represent a C1-C20 alkyl group and the n represents an integer in a range of 17 to 85. In the provided quinoxaline based copolymer, quinoxaline is an excellent electron acceptor unit and is advantageously for being applied to organic solar cells. The phenyl ring is modified by an alkyloxy chain so as to improve the solubility and film-forming ability of the copolymer. Phenanthrene is a compound with a large planar rigid structure, and thus has high thermal stability and a strong fluorescence performance. The light conversion rate of an organic solar cell device can be improved by applying the provided quinoxaline based copolymer to the solar cells of the organic solar cell device.
Description
Technical field
The present invention relates to organic solar battery material field, particularly relate to a kind of quinoxalinyl multipolymer and its preparation method and application.
Background technology
Utilize cheap material prepares low cost, dynamical solar cell is photovoltaic art always study hotspot and difficult point.High due to complex manufacturing, cost for the silicon wafer battery on ground at present, make it apply and be restricted.In order to reduce battery cost, expansive approach scope, people are finding novel solar cell material always for a long time.Organic semiconductor material is easy to get with its raw material, cheap, preparation technology is simple, environmental stability good, have the advantages such as good photovoltaic effect to receive much concern.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C
60between Photo-induced electron transfer phenomenon after, people have dropped into large quantity research in polymer solar battery, and achieve development at full speed, but still much lower than the efficiency of conversion of inorganic solar cell.The main restricting factor that limiting performance improves has: the spectral response of organic semiconductor material is not mated with solar radiation spectrum, the electrode collection effciency etc. of the carrier mobility that organic semiconductor is relatively low and lower current carrier.In order to make polymer solar battery be on the actual application, the material of development of new, and then the top priority increasing substantially that its effciency of energy transfer is still this research field.
Summary of the invention
Problem to be solved by this invention is the quinoxalinyl multipolymer providing a kind of light conversion efficiency higher.
Technical scheme of the present invention is as follows:
Quinoxalinyl multipolymer provided by the invention, its structure is such as formula shown:
In formula, R
1, R
2be C
1~ C
20alkyl, n is the integer of 17 ~ 85.
The present invention also provides a kind of preparation method of quinoxalinyl multipolymer described above, comprises the steps:
The compd A providing following structural formula to represent respectively and B,
Under oxygen-free environment, be after the organic solvent dissolution that is added into containing catalyzer and alkaline solution of the compd A of 1:1 ~ 1.2 and B by mol ratio, Suzuki coupling reaction is carried out 12 ~ 96 hours at 70 ~ 130 DEG C, stopped reaction cool to room temperature, separating-purifying reaction solution, obtains the described quinoxalinyl multipolymer that following structural formula represents:
Wherein, R
1, R
2be C
1~ C
20alkyl, n is the integer of 17 ~ 85.
In the preparation method of described quinoxalinyl multipolymer, described catalyzer is bis-triphenylphosphipalladium palladium dichloride or tetra-triphenylphosphine palladium; Or described catalyzer is mol ratio is the organic palladium of 1:4 ~ 8 and the mixture of organophosphorus ligand, and described organic palladium is palladium or three or two argon benzyl acetone two palladiums, described organophosphorus ligand is three (o-methyl-phenyl-) phosphines or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl; The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
In the preparation method of described quinoxalinyl multipolymer, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and in alkaline solution, the mol ratio of alkali solute and compd A is 20:1.
In the preparation method of described quinoxalinyl multipolymer, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
In the preparation method of described quinoxalinyl multipolymer, Suzuki coupling reaction, preferable reaction temperature is 90 ~ 120 DEG C, and the reaction times is 24 ~ 72 hours.
In the preparation method of described quinoxalinyl multipolymer, the oxygen-free environment of one or both compositions in described oxygen-free environment preferred nitrogen, argon gas.
In the preparation method of described quinoxalinyl multipolymer, separating-purifying reaction solution comprises:
After reaction stops, in reaction solution, add methyl alcohol carry out precipitating, then methyl alcohol and normal hexane extracting is used successively after the reaction solution after filtering precipitating by apparatus,Soxhlet's, then be solvent extracting again with chloroform, collect chloroformic solution and be spin-dried for, obtain red powder, the red powder after collection is the dry 24h of 50oC under vacuo, obtains described quinoxalinyl multipolymer.
The present invention also provides the application as electron donor material in organic solar batteries device active layer of above-mentioned quinoxalinyl multipolymer.
In quinoxalinyl multipolymer of the present invention, quinoxaline is an excellent electron acceptor(EA) unit, is very potentially applied in organic solar batteries, through the modification of oxyalkyl chain on phenyl ring, is conducive to improving polymer dissolution performance and film forming properties; Phenanthrene is a kind of compound with large plane rigid structure, and it has higher thermostability and strong fluorescence property; Above-mentioned quinoxalinyl multipolymer is applied in solar cell, the light turnover ratio of organic solar batteries device can be improved.
The preparation method of above-mentioned quinoxalinyl multipolymer, have employed better simply synthetic route, thus reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And obtained material structure is novel, solubility property is good, and film forming properties is excellent, and thermostability is high, is applicable to organic solar batteries device.This material has higher electricity conversion.
Accompanying drawing explanation
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of the quinoxalinyl multipolymer that embodiment 1 obtains;
Fig. 2 is the organic solar batteries device architecture schematic diagram of embodiment 6.
Embodiment
In order to understand the content of patent of the present invention better, further illustrate technology case of the present invention below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein, compd A and compd B are all purchased from scientific and technological in lark prestige.
Embodiment 1: the quinoxalinyl multipolymer of the present embodiment, i.e. poly-{ 2,2'-(9,10-bis-(n-octyloxy) luxuriant and rich with fragrance-2,7-bis-base-co-5,8-bis-base-2,3-dimethyl-6,7-bis-(n-octyloxy) quinoxaline } (P1), (wherein, R1 is octane base, and R2 is octane base, n=52), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under argon shield, by 2,2'-(9,10-bis-(n-octyloxy) luxuriant and rich with fragrance-2,7-bis-tetramethyl ethylene ketone boric acid ester (137mg, 0.2mmol), 5, bromo-2,3-dimethyl-6,7-bis-(n-octyloxy) quinoxaline (114mg of 8-bis-, 0.2mmol) add in the flask filling 10ml toluene solvant, after abundant dissolving, salt of wormwood (2mL, 2mol/L) solution is joined in flask, vacuumize deoxygenation and be filled with argon gas, then bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol) is added; Flask is heated to 100 DEG C and carries out Suzuki coupling reaction 48h.Subsequently, after cooling, stop polyreaction, drip in flask in 50ml methyl alcohol and carry out sedimentation; Methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, obtain product P 1, productive rate 82% after 50 DEG C of dry 24h under vacuo.
Test result is: Molecular weight (GPC, THF, R.I): Mn=36.4kDa, M
w/ M
n=2.2.
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of the quinoxalinyl multipolymer that embodiment 1 obtains; As shown in Figure 1, result shows, this co-polymer has comparatively large wider absorption between 300nm ~ 700nm, and wherein maximum absorption band is positioned at about 579nm.
Embodiment 2: the quinoxalinyl multipolymer of the present embodiment, i.e. poly-{ 2,2'-(9,10-bis-(methoxyl group) luxuriant and rich with fragrance-2,7-bis-base-co-5,8-bis-base-2,3-dimethyl-6,7-bis-(NSC 62789 oxygen base) quinoxaline } (P2), (wherein, R1 is methyl, and R2 is NSC 62789 base, n=17), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and argon gas gas mixture are protected; by 2; 2'-(9; 10-bis-(methoxyl group) luxuriant and rich with fragrance-2; 7-bis-tetramethyl ethylene ketone boric acid ester (147mg; 0.3mmol), 5; bromo-2,3-dimethyl-6,7-bis-(the NSC 62789 oxygen base) quinoxaline (273mg of 8-bis-; 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF); after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min, then tetra-triphenylphosphine palladium (4mg, 0.003mmol) is added wherein; sodium bicarbonate (3mL, 2mol/L) solution is added again after abundant dissolving.After the gas mixture air-discharging of fully logical nitrogen and argon gas is about 10min again, two-mouth bottle is joined 70 DEG C and carry out Suzuki coupling reaction 96h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, obtain product P 2 after 50 DEG C of dry 24h under vacuo.Productive rate is 76%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=14.7kDa, M
w/ M
n=2.4.
Embodiment 3: the quinoxalinyl multipolymer of the present embodiment, i.e. poly-{ 2,2'-(9,10-bis-(NSC 62789 oxygen base) luxuriant and rich with fragrance-2,7-bis-base-co-5,8-bis-base-2,3-dimethyl-6,7-bis-(methoxyl group) quinoxaline } (P3), (wherein, R1 is NSC 62789 base, and R2 is methyl, n=85), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by 2,2'-(9,10-bis-(NSC 62789 oxygen base) luxuriant and rich with fragrance-2,7-bis-tetramethyl ethylene ketone boric acid ester (307mg, 0.3mmol), 5,8-bis-bromo-2,3-dimethyl-6,7-bis-(methoxyl group) quinoxaline (124mg, 0.33mmol), palladium (3.5mg, 0.015mmol) and three (o-methyl-phenyl-) phosphine (21mg, 0.06mmol) joins the N filling 12mL, in the flask of dinethylformamide, salt of wormwood (3mL, 2mol/L) solution is added, after logical nitrogen purge gas is about 30min in flask subsequently after abundant dissolving; Flask is heated to 130 DEG C and carries out Suzuki coupling reaction 12h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively; Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuo after 50 DEG C of dry 24h, be product P 3, productive rate is 85%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=91.3kDa, M
w/ M
n=2.1.
Embodiment 4: the quinoxalinyl multipolymer of the present embodiment, i.e. poly-{ 2,2'-(9,10-bis-(n-butoxy) luxuriant and rich with fragrance-2,7-bis-base-co-5,8-bis-base-2,3-dimethyl-6,7-bis-(n-decyloxy) quinoxaline } (P4), (wherein, R1 is normal-butyl, and R2 is positive decyl, n=40), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection; by 2; 2'-(9; 10-bis-(n-butoxy) luxuriant and rich with fragrance-2; 7-bis-tetramethyl ethylene ketone boric acid ester (172mg; 0.3mmol), 5,8-bis-bromo-2,3-dimethyl-6; 7-bis-(n-decyloxy) quinoxaline (226mg; 0.36mmol), three or two argon benzyl acetones two palladium (9mg, 0.009mmol) and 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg; 0.072mmol) join the N filling 12mL; in the flask of dinethylformamide, after fully dissolving, add sodium bicarbonate (3mL, 2mol/L) solution.After in flask, logical nitrogen purge gas is about 30min subsequently; Flask is heated to 120 DEG C and carries out Suzuki coupling reaction 24h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively; Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuo after 50 DEG C of dry 24h, be product P 4, productive rate is 80%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=28.2kDa, M
w/ M
n=2.3.
Embodiment 5: the quinoxalinyl multipolymer of the present embodiment, i.e. poly-{ 2,2'-(9,10-bis-(n-dodecane oxygen base) luxuriant and rich with fragrance-2,7-bis-base-co-5,8-bis-base-2,3-dimethyl-6,7-bis-(positive hexyloxy) quinoxaline } (P5), (wherein, R1 is dodecyl, and R2 is n-hexyl, n=52), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and argon gas gas mixture are protected; by 2; 2'-(9; 10-bis-(n-dodecane oxygen base) luxuriant and rich with fragrance-2; 7-bis-tetramethyl ethylene ketone boric acid ester (239mg; 0.3mmol), 5; bromo-2,3-dimethyl-6,7-bis-(positive hexyloxy) quinoxaline (155mg of 8-bis-; 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene; after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min, then tetra-triphenylphosphine palladium (8mg, 0.006mmol) is added wherein; add salt of wormwood (3mL, 2mol/L) solution again.After the gas mixture air-discharging of fully logical nitrogen and argon gas is about 10min again, two-mouth bottle is joined 90 DEG C and carry out Suzuki coupling reaction 72h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, obtain product P 5 after 50 DEG C of dry 24h under vacuo.Productive rate is 77%.Test result is: Molecular weight (GPC, THF, R.I): M
n=58.9kDa, M
w/ M
n=2.2.
Embodiment 6:
Originally organic solar batteries device is embodied as, its quinoxalinyl multipolymer obtained with the embodiment of the present invention 1, namely { 2 are gathered, 2'-(luxuriant and rich with fragrance-2, the 7-bis-base-co-5 of 9,10-bis-(n-octyloxy), 8-bis-base-2,3-dimethyl-6,7-bis-(n-octyloxy) quinoxaline } as the electron donor material of active layer, the quinoxalinyl multipolymer that embodiment 2 to 5 can certainly be adopted obtained is as electron donor material.
As shown in Figure 2, this organic solar batteries device 60 comprises substrate 61, anode layer 62, buffer layer 63, active coating 64 and negative electrode 65; And anode 62, buffer layer 63, active coating 64 and negative electrode 65 are formed on substrate 61 successively.
In the present embodiment, substrate 61 is glass.
Anode 62 is formed at a side surface of substrate 61.In the present embodiment, anode 62 is ITO(tin indium oxide), preferably, the tin indium oxide of ITO to be square resistance be 10-20 Ω/, ITO is prepared in glass surface by magnetron sputtering technique.
Buffer layer 63 is formed at anode layer 62 surface; The material of buffer layer 63 is poly-3,4-Ethylenedioxy Thiophenes (PEDOT) and the mixture of polystyrene-sulfonic acid matrix material (PSS), is expressed as PEDOT:PSS; Buffer layer is prepared in ITO surface by spin coating technique.
Active coating 64 is formed at buffer layer 63 surface.Active coating 64 comprises electron donor material and electron acceptor material, and the mol ratio of electron donor material and electron acceptor material is 1:2, and wherein electron acceptor material is (6,6) phenyl-C
61-methyl-butyrate (PCBM), electron donor material is that the present invention prepares pyrrolo-pyrrole-dione based polyalcohol, in present embodiment, poly-{ 2,2'-(9, the 10-bis-(n-octyloxy) luxuriant and rich with fragrance-2 of preparation in the embodiment 1 that electron donor material is, 7-bis-base-co-5,8-bis-base-2,3-dimethyl-6,7-bis-(n-octyloxy) quinoxaline } (being expressed as P1).
Negative electrode 65 is formed at the surface of active coating 64.Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 150nm, 130nm or 60nm.In present embodiment, the material of negative electrode 65 is aluminium, and thickness is 170nm.
In another embodiment, buffer layer 63 can omit, and now active coating 64 is directly formed at anode 62 surface.
The manufacturing processed of this organic solar batteries device 60 is as follows:
Anode 62 is formed at the laggard row ultrasonic cleaning of a side surface of substrate 61, and after processing with oxygen-Plasma, is coated with the PEDOT:PSS formation buffer layer 63 that last layer plays modification on anode 62 surface.
Buffer layer 64 applies one deck active coating 64.This active coating 64 comprises electron donor material and electron acceptor material, and wherein electron acceptor material is PCBM, the P1 of preparation in the embodiment one that electron donor material is.
Negative electrode 65 is formed on active coating 64 surface.In present embodiment, negative electrode 65 is the aluminium lamination formed by vacuum evaporation.The thickness of negative electrode 65 is 170nm.
In the present embodiment, this organic solar batteries device 60 was through lower 4 hours of 110 degrees Celsius of air tight conditions, drop to room temperature again, the order and regularity that arrange between each group and molecule segment in molecule effectively can be increased after this organic solar batteries device is annealed, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.
Test is improved to organic solar batteries device effciency of energy transfer.At AM1.5G100mW/cm
2under illumination, be that the effciency of energy transfer of the body heterojunction organic solar batteries device 60 of electron donor material is 3.7% based on the copolymer p 1 in embodiment 1.
When this organic solar batteries device 60 uses, under light illumination, light transmission substrate 61 and anode 62, the conduction hole type solar cell material in active coating 64 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by transfer transport to electron acceptor material, as PCBM, realize the separation of electric charge, thus form current carrier freely, i.e. electronics and hole freely.These freely electronics to transmit along electron acceptor material to negative electrode 65 and collected by negative electrode, hole to be transmitted and collected by anode 62 along electron donor material anode 62 freely, thus forms photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In the process, conduction hole type solar cell material has very wide spectral response range due to it, can utilize luminous energy more fully, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can be made by technology such as spin coatings, be convenient to large batch of preparation.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a quinoxalinyl multipolymer, is characterized in that, its structural formula is as follows:
In formula, R
1, R
2be C
1~ C
20alkyl, n is the integer of 17 ~ 85.
2. a preparation method for quinoxalinyl multipolymer as claimed in claim 1, is characterized in that, comprise the steps:
The compd A providing following structural formula to represent respectively and B,
Under oxygen-free environment, be after the organic solvent dissolution that is added into containing catalyzer and alkaline solution of the compd A of 1:1 ~ 1.2 and B by mol ratio, Suzuki coupling reaction is carried out 12 ~ 96 hours at 70 ~ 130 DEG C, stopped reaction cool to room temperature, separating-purifying reaction solution, obtains the described quinoxalinyl multipolymer that following structural formula represents:
Wherein, R
1, R
2be C
1~ C
20alkyl, n is the integer of 17 ~ 85.
3. the preparation method of quinoxalinyl multipolymer according to claim 2, is characterized in that, described catalyzer is bis-triphenylphosphipalladium palladium dichloride or tetra-triphenylphosphine palladium, and the mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
4. the preparation method of quinoxalinyl multipolymer according to claim 2, it is characterized in that, described catalyzer is mol ratio is the organic palladium of 1:4 ~ 8 and the mixture of organophosphorus ligand, and the mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
5. the preparation method of quinoxalinyl multipolymer according to claim 4, is characterized in that, described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Described organophosphorus ligand is three (o-methyl-phenyl-) phosphines or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl.
6. the preparation method of quinoxalinyl multipolymer according to claim 2, it is characterized in that, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution, and in alkaline solution, the mol ratio of alkali solute and compd A is 20:1.
7., according to the preparation method of the arbitrary described quinoxalinyl multipolymer of claim 2 to 6, it is characterized in that, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
8., according to the preparation method of the arbitrary described quinoxalinyl multipolymer of claim 2 to 6, it is characterized in that, the temperature of reaction of Suzuki coupling reaction is 90 ~ 120 DEG C, and the reaction times is 24 ~ 72 hours.
9. the preparation method of quinoxalinyl multipolymer according to claim 2, is characterized in that, separating-purifying reaction solution comprises:
After reaction stops, in reaction solution, add methyl alcohol carry out precipitating, then methyl alcohol and normal hexane extracting is used successively after the reaction solution after filtering precipitating by apparatus,Soxhlet's, then be solvent extracting again with chloroform, collect chloroformic solution and be spin-dried for, obtain red powder, the red powder after collection is 50 DEG C of dry 24h under vacuo, obtain described quinoxalinyl multipolymer.
10. a quinoxalinyl multipolymer according to claim 1 in organic solar batteries device active layer as the application of electron donor material.
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| WO2017010847A3 (en) * | 2015-07-15 | 2017-05-11 | 건국대학교 산학협력단 | Organic hole transporting compound using p-doped conjugated polymer electrolyte, organic electronic device using same, and manufacturing method therefor |
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| WO2017010847A3 (en) * | 2015-07-15 | 2017-05-11 | 건국대학교 산학협력단 | Organic hole transporting compound using p-doped conjugated polymer electrolyte, organic electronic device using same, and manufacturing method therefor |
| EP3323871A4 (en) * | 2015-07-15 | 2019-01-23 | Konkuk University Industrial Cooperation Corp. | Organic hole transporting compound using p-doped conjugated polymer electrolyte, organic electronic device using same, and manufacturing method therefor |
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