CN102504208B - Organic copolymerized semiconductor material containing EDOT (3,4-ethylenedioxy thiophene)( 3,4-ethylenedioxythiophene) electron donor cell - Google Patents

Organic copolymerized semiconductor material containing EDOT (3,4-ethylenedioxy thiophene)( 3,4-ethylenedioxythiophene) electron donor cell Download PDF

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CN102504208B
CN102504208B CN2011103116896A CN201110311689A CN102504208B CN 102504208 B CN102504208 B CN 102504208B CN 2011103116896 A CN2011103116896 A CN 2011103116896A CN 201110311689 A CN201110311689 A CN 201110311689A CN 102504208 B CN102504208 B CN 102504208B
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semiconductor material
organic semiconductor
organic
ring structure
copolymerized
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CN102504208A (en
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李宛飞
周明
刘扬
张清泉
黄泽柱
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SUZHOU NAKAI TECHNOLOGY CO LTD
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Abstract

The invention relates to an organic copolymerized semiconductor material containing a 3,4-ethylenedioxy thiophene (EDOT) electron donor cell, which has a structural formula as shown in formula II, wherein one of A and D is a heteroaromatic ring structure containing nitrogen atoms while the other one is a heteroaromatic ring structure containing sulfur atoms, and R1 and R2 are hydrogen, cyan, alkyl or alkoxy, and n is an integer valued from 10 to 100. The organic copolymerized semiconductor material disclosed by the invention has better photoelectric properties and interface properties with respect to electrodes, so that using the organic copolymerized semiconductor material is good for increasing the conversion efficiency of photoelectric energy of an organic solar energy battery. According to the invention, the organic copolymerized semiconductor material is prepared through a Suzuki or Still coupling reaction, and has the advantages of simple preparation method, mild and controllable reaction conditions, high reaction yield and capability, and applicability to large-scale production.

Description

The copolymerization organic semiconductor material that contains EDOT electron donor(ED) unit
Technical field
The invention belongs to the organic semiconductor material field, be specifically related to a class and contain copolymerization organic semiconductor material of EDOT electron donor(ED) unit and preparation method thereof
Background technology
Having quality is light, flexible, production cost is low and be easy to realize the advantages such as big area production organic solar batteries (organic photovoltaic or plastic solar cell) and utilize in low cost and shown great potential aspect sun power, is the most noticeable in research and development field and the organic electronic industry that is surging forward and have new technology and a product innovation of great market prospect in recent years.The successful design of the organic semiconducting polymer of strong absorption of novel arrowband system material, the photovoltaic energy conversion efficient that development and application makes organic solar batteries constantly are refreshed.Further improve this class organic polymer semiconductor material photoelectric properties by the functional unit who introduces superior photoelectric characteristic, organic solar batteries photovoltaic energy conversion efficient is further improved, be significant to finally realizing the organic solar batteries industrialization.
In view of containing 3, the macromolecular material of 4-ethene dioxythiophene (EDOT) group has good photoelectronic property, wherein PEDOT[Poly (3,4-ethylenedioxythiophene), poly-3, the 4-ethylenedioxy thiophene] be widely used in comprising in the various opto-electronic devices of organic solar batteries, PEDOT/PSS(poly-3,4-ethylenedioxy thiophene/poly styrene sulfonate, structure are seen the formula I) electrically conductive ink plays vital effect as the electrode modification material to the performance of organic solar batteries.Can infer, be can have very great help for the photoelectric properties of improving this class material in the organic polymer semiconductor material if 3,4-rthylene dioxythiophene (EDOT) group is incorporated into the arrowband.
Figure 799434DEST_PATH_IMAGE001
Ⅰ。
Summary of the invention
The objective of the invention is by being the copolymerization organic semiconductor material to provide class photoelectric properties to be improved in the organic semiconductor material system with introducing arrowband, EDOT electron donor(ED) unit, it can be applicable in organic solar batteries.
Another object of the present invention is to provide the preparation method of above-mentioned copolymerization organic semiconductor material.
For achieving the above object, the present invention takes following technical scheme:
A kind of copolymerization organic semiconductor material that contains EDOT electron donor(ED) unit, its structural formula be suc as formula shown in II,
Figure 2011103116896100002DEST_PATH_IMAGE002
Ⅱ
Wherein, one in A and D is the hetero-aromatic ring structure of nitrogen atom, and another is the hetero-aromatic ring structure of sulfur atom-containing, R 1 And R 2 Be hydrogen, cyano group, alkyl or alkoxyl group, n is integer, and n=10 ~ 100.
Preferably, R 1 =R 2 =H.
Preferably, the hetero-aromatic ring structure of described nitrogen atom is any in following structure:
（1）
Figure 184672DEST_PATH_IMAGE003
；（2）
Figure 238079DEST_PATH_IMAGE004
；（3）
Figure 140176DEST_PATH_IMAGE005
；（4）
Figure 620836DEST_PATH_IMAGE006
； （5）
Figure 726326DEST_PATH_IMAGE007
；（6） ；（7）
Figure 340027DEST_PATH_IMAGE009
；
Wherein, R is alkyl.
Further preferably, the hetero-aromatic ring structure of described nitrogen atom is a kind of in following two kinds of structures:
（1）
Figure 303173DEST_PATH_IMAGE003
；（2）
Figure 348489DEST_PATH_IMAGE004
。
Preferably, the hetero-aromatic ring structure of described sulfur atom-containing is any in following structure:
（8） ； （9）
Figure 167858DEST_PATH_IMAGE011
；（10）
Figure 255899DEST_PATH_IMAGE012
；
（11）
Figure 585249DEST_PATH_IMAGE013
；（12）
Figure 784150DEST_PATH_IMAGE014
；（13）
Figure 513682DEST_PATH_IMAGE015
；（14）
Figure 834942DEST_PATH_IMAGE016
；（15）
Figure 589271DEST_PATH_IMAGE017
；
Wherein, R is alkyl, R 3 Be ester group, acid amides, ketone group or alkyl, R 4 Be alkyl or alkoxyl group.
Further preferably, the hetero-aromatic ring structure of described sulfur atom-containing is a kind of in following three kinds of structures:
（9）
Figure 139333DEST_PATH_IMAGE011
；（10）
Figure 725035DEST_PATH_IMAGE012
；（11） 。
Above-mentioned copolymerization organic semiconductor material is by Suzuki or the preparation of Still linked reaction, and concrete synthetic route is as follows:
Figure 504827DEST_PATH_IMAGE018
Wherein, one in X and Y is haloid element Br, Cl or I, and another is boric acid or tin alkyl group.
Due to the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The present invention contains the copolymerization organic semiconductor material of EDOT electron donor(ED) unit, has more excellent photoelectric properties, with electrode, better interfacial characteristics is arranged, and therefore also more is conducive to the lifting of organic solar batteries photoelectric energy transformation efficiency;
The preparation method of copolymerization organic semiconductor material of the present invention is simple, and the reaction conditions gentleness is controlled, and reaction yield is high, is suitable for scale operation.
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment, but be not limited to these embodiment.
Embodiment 1
3,8-two (2-thienyl)-1,10-phenanthroline (formula 1) synthetic:
Add 3,8-, two bromo-1,10-phenanthroline (35.3 g in the there-necked flask of 2L with mechanical stirring, spherical condensating tube, 104.4 mmol), 2-thienyl boric acid (29.3g, 208.7 mmol), four (triphenyl phosphorus) palladium (14.1 g, 12.5 mmol), salt of wormwood (72.1 g, 521.8 mmol), Tetrabutyl amonium bromide (42.3 g, 135.7 mmol), toluene (705 mL), ethanol (529 mL), water (235 mL).Oil bath reflux 60 h under nitrogen protection react complete, and reaction solution is down to room temperature; add 1 L water in reaction solution; standing demix is isolated organic phase, the water layer dichloromethane extraction; dry; concentrated organic phase, take normal hexane: methylene dichloride: triethylamine=6:2:1 purifies as the moving phase column chromatography, with the mixed solvent recrystallization of methylene dichloride and normal hexane; obtain target product (13.1 g), productive rate is 36%.MS?(MALDI-TOF):?Calcd,?344.0442;?Found,?344.0441。
Synthetic route is as follows:
Figure 2011103116896100002DEST_PATH_IMAGE019
Embodiment 2
3,8-two (5-bromo-2-thienyl)-1,10-phenanthroline (formula 2) synthetic:
Under nitrogen protection, add 3,8-two (2-thienyl)-1 in 100 mL single port bottles; 10-phenanthroline (2.0 g; 5.8 mmol), use DMF(30 mL) and chloroform (10 mL) dissolving, drip NBS(2.1g under ice-water bath; 11.9 DMF(10 mL mmol)) solution; dropwise under 50 ℃ and reacted 5 hours, reaction is down to 0 ℃ of filtration with reaction solution after finishing, and washes drying with water; obtain target product (2.9 g), yield 99%.MS?(MALDI-TOF):?Calcd,?499.8652;?Found,?499.8650。
Synthetic route is as follows:
Figure 858579DEST_PATH_IMAGE020
Embodiment 3
3,8-two [5-(3,4-ethylenedioxy thiophene-2 base) thienyl]-1,10-phenanthroline (formula 3) synthetic:
Under nitrogen protection; add 3,8-two (5-bromo-2-thienyl)-1 in 100 mL single port bottles, 10-phenanthroline (1.0 g; 2.0 mmol); four (triphenyl phosphorus) palladium (0.5 g, 0.4 mmol), 3; 4-ethylenedioxy thiophene-5-tributyl tin (2.2 g; 5 mmol), DMF(75 mL), reaction is 15 hours under 135 ℃; react complete; reaction solution is poured into water, uses dichloromethane extraction, dry organic phase; be spin-dried for; purify with column chromatography, obtain the finished product (0.8 g), yield 64%.MS?(MALDI-TOF):?Calcd,?624.0306;?Found,?624.0301。
Synthetic route is as follows:
Figure 2011103116896100002DEST_PATH_IMAGE021
Embodiment 4
3,8-two [5-(7-bromo-3,4-ethylene dioxythiophene-2 base) thienyl]-1,10-phenanthroline (formula 4) synthetic:
Under nitrogen protection, add 3,8-, two [5-(3 in 100 mL single port bottles; 4-ethylenedioxy thiophene-2 base) thienyl]-1,10-phenanthroline (1.0 g, 1.6 mmol); use DMF(15 mL) and chloroform (5 mL) dissolving; drip NBS(0.6 g under ice-water bath, 3.3 mmol) DMF(5 mL) solution, dropwised under 50 ℃ reaction 5 hours; reaction is down to 0 ℃ of filtration with reaction solution after finishing; wash drying with water, obtain target product (1.1 g), yield 90%.MS?(MALDI-TOF):?Calcd,?779.8516;?Found,?779.8500。
Synthetic route is as follows:
Figure 878881DEST_PATH_IMAGE022
Embodiment 5
3,8-two [5-(7-tin trimethyl-3,4-ethylene dioxythiophene-2 base) thienyl]-1,10-phenanthroline (formula 5) synthetic:
Under nitrogen protection; add 3 in 100 mL single port bottles; 8-two [5-(3; 4-ethylenedioxy thiophene-2 base) thienyl]-1; 10-phenanthroline (1.0 g; 1.6 mmol); with anhydrous THF(30 mL) dissolving, under-78 ℃, drip n-BuLi(2 mL/1.6M; 3.2 mmol) reaction is one hour; add again trimethyltin chloride (0.64 g, 3.2 mmol), then react after one hour and to recover room temperature and reacted again 12 hours; reaction finishes to purify by column chromatography and obtains target product (1.2 g), yield 80%.MS?(MALDI-TOF):?Calcd,?951.9602;?Found,?951.9610。
Synthetic route is as follows:
Figure 2011103116896100002DEST_PATH_IMAGE023
Embodiment 6
Copolymerization organic semiconductor material-polymer P 1 Synthetic:
Take respectively the prepared monomer 4(782 of embodiment 4 mg, 1mmol in the round-bottomed flask of 25 mL), 2,6-two (tin trimethyl)-4,8-two (2-ethyl hexyl oxy) benzo [1,2-b:4,5-b '] two thiophene (being monomer 6) (772 mg, 1 mmol) and Pd(PPh 3 ) 4 (50mg), after then substituting argon gas three times, inject respectively dry DMF (5 mL) and dry toluene (15 mL).The lower 120 ℃ of reaction 12h of argon shield.Polymer fluid is sedimentation in methyl alcohol, and filtration obtains thick product and again is dissolved in chloroform, removes metal catalyst with diatomite filtration, and filtered liquid precipitates with hexane, filters, and obtains the finished product, and vacuum-drying obtains solid phase prod 960 mg(90%).GPC：Mw（35×10 3 ?g/mmol），PDI（1.34）。
Synthetic route is as follows:
Figure 276364DEST_PATH_IMAGE024
Embodiment 7
Copolymerization organic semiconductor material-polymer P 2 Synthetic:
Take respectively the prepared monomer 4(782 of embodiment 4 mg, 1mmol in the round-bottomed flask of 25 mL), N-9-heptadecyl carbazole-2,7-two (pinacol borate) (being monomer 7) (657 mg, 1 mmol) and Pd(PPh 3 ) 4 (50mg), after then substituting argon gas three times, inject respectively dry DMF (5 mL) and dry toluene (15 mL).The lower 120 ℃ of reaction 12h of argon shield.Polymer fluid is sedimentation in methyl alcohol, and filtration obtains thick product and again is dissolved in chloroform, removes metal catalyst with diatomite filtration, and filtered liquid precipitates with hexane, filters, and obtains the finished product, and vacuum-drying obtains solid phase prod 874 mg(85%).GPC：Mw（26×10 3 ?g/mmol），PDI（1.20）。
Figure 2011103116896100002DEST_PATH_IMAGE025
Embodiment 8
Copolymerization organic semiconductor material-polymer P 3 Synthetic:
Take respectively the prepared monomer 5(950 of embodiment 5 mg in the round-bottomed flask of 25 mL, 1mmol), 1-(4,6-two bromo-3-fluorine thieno-[3,4-b] thiophene-2-yls)-2-ethylhexyl-1-ketone (being monomer 8) (442 mg, 1 mmol) and Pd(PPh 3 ) 4 (50mg), after then substituting argon gas three times, inject respectively dry DMF (5 mL) and dry toluene (15 mL).React 12h in 120 ℃ under argon shield.Polymer fluid is sedimentation in methyl alcohol, and filtration obtains thick product and again is dissolved in chloroform, removes metal catalyst with diatomite filtration, and filtered liquid precipitates with hexane, filters, and obtains the finished product, and vacuum-drying obtains solid phase prod 860 mg(95%).GPC：Mw（58×10 3 ?g/mmol），PDI（1.26）。
Figure 880652DEST_PATH_IMAGE026
Embodiment 9
The polymer P that embodiment 6 is prepared 1 Be used for making organic solar cell device as P-type semiconductor, device architecture is ITO/PEDOT:PSS/ P 1 : PC71BM/LiF/Al.ITO is ultrasonic and use after with oxygen plasma treatment in the plasma clean device in ultrasonic cleaner with deionized water, acetone, methyl alcohol; P1 and PC71BM 1:3 in mass ratio mix, and are mixed with massfraction and are 1% o-dichlorobenzene solution; With the first spin coating PEDOT:PSS layer (25nm) on the ITO conductive glass of spin coating instrument, spin coating P1:PC71BM layer (100nm) again after vacuum-drying, vacuum moulding machine LiF(5nm respectively again after vacuum-drying 48h) and Al(200nm).At AM1.5G standard analog sunlight (100mW/cm 2 ) irradiation write, the photoelectric transformation efficiency that characterizes this device can reach 5.6%.
Above the present invention has been done detailed description; its purpose is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit protection scope of the present invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention

Claims (4)

1. copolymerization organic semiconductor material that contains EDOT electron donor(ED) unit is characterized in that: the structural formula of described copolymerization organic semiconductor material is suc as formula shown in II,
Figure 281140DEST_PATH_IMAGE001
Ⅱ
Wherein, one in A and D is the hetero-aromatic ring structure of nitrogen atom, and another is the hetero-aromatic ring structure of sulfur atom-containing, R 1And R 2Be hydrogen, cyano group, alkyl or alkoxyl group, n is integer, and n=10 ~ 100, and the hetero-aromatic ring structure of described nitrogen atom is:
；
The hetero-aromatic ring structure of described sulfur atom-containing is any in following two kinds of structures:
（1）
Figure 978017DEST_PATH_IMAGE003
；（2）
Figure 435543DEST_PATH_IMAGE004
Wherein, R 3Be ester group, acid amides, ketone group or alkyl, R 4Be alkyl or alkoxyl group.
2. copolymerization organic semiconductor material according to claim 1, is characterized in that: R 1=R 2=H.
3. copolymerization organic semiconductor material according to claim 1, it is characterized in that: described copolymerization organic semiconductor material comprises the polymkeric substance of following several structures:
P1
Figure 249916DEST_PATH_IMAGE005
, and P3
Figure 134695DEST_PATH_IMAGE006
Wherein, n is integer, and n=10 ~ 100.
4. the preparation method of the described copolymerization organic semiconductor material of any one in claim 1 ~ 3 is characterized in that: described copolymerization organic semiconductor material is by Suzuki or the preparation of Still linked reaction, and concrete synthetic route is as follows:
Figure 401728DEST_PATH_IMAGE007
Wherein, one in X and Y is haloid element Br, Cl or I, and another is boric acid or tin alkyl group.
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