CN102653587A - N,N'-di-substituted isoindigo and 2,7-carbazole copolymer and preparation method and application thereof - Google Patents
N,N'-di-substituted isoindigo and 2,7-carbazole copolymer and preparation method and application thereof Download PDFInfo
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- CN102653587A CN102653587A CN2011100510405A CN201110051040A CN102653587A CN 102653587 A CN102653587 A CN 102653587A CN 2011100510405 A CN2011100510405 A CN 2011100510405A CN 201110051040 A CN201110051040 A CN 201110051040A CN 102653587 A CN102653587 A CN 102653587A
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- 0 CC(C)(C)c(cc1)cc2c1c(ccc(C(C=C[C@]1C3=C(c4ccc(C(C)(C)C)cc4N4*)C4=O)=CC1N(*)C3=O)c1)c1[n]2* Chemical compound CC(C)(C)c(cc1)cc2c1c(ccc(C(C=C[C@]1C3=C(c4ccc(C(C)(C)C)cc4N4*)C4=O)=CC1N(*)C3=O)c1)c1[n]2* 0.000 description 3
- LTSJENDLAJQJAH-CCEZHUSRSA-N CN(c1cc(Br)ccc1/C1=C(/c(ccc(Br)c2)c2N2)\C2=O)C1=O Chemical compound CN(c1cc(Br)ccc1/C1=C(/c(ccc(Br)c2)c2N2)\C2=O)C1=O LTSJENDLAJQJAH-CCEZHUSRSA-N 0.000 description 1
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Abstract
The invention discloses an N,N'-di-substituted isoindigo and 2,7-carbazole copolymer. A molecular structure general formula of the copolymer is shown as the following formula (I) in the specification, wherein in the formula (I), R1 is C8-C20 alkyl, R2 is C1-C20 alkyl or C1-C20 alkoxy monosubstituted phenyl, and n is a positive integer ranging from 2 to 100. The N,N'-di-substituted isoindigo and 2,7-carbazole copolymer has excellent dissolving property and thermal stability, and the HOMO and LUMO energy level of the copolymer can be effectively regulated, so that the absorption range becomes wider, and the energy conversion efficiency is greatly improved. The copolymer is simple in preparation process, high in yield, easy to operate and control, low in production cost, and applicable to the fields such as photoelectricity.
Description
Technical field
The invention belongs to the organic cpds synthesis technical field, relate to a kind of N specifically, N '-two replaces isoindigo and 2,7-carbazole multipolymer.
Background technology
Energy problem is the significant problem that countries in the world are extremely paid close attention to.Sun power is following human optimal substitute energy, is that the solar cell of electric energy also is the focus of research with solar energy converting.The conjugated polymer thin films solar cell of rising in recent years has that cost is low, in light weight, manufacture craft is simple, can be prepared into outstanding advantage such as flexible device.In addition, organic materials is of a great variety, designability is strong, is hopeful to improve Solar cell performance through the design and the optimization of material.
Recently contain unitary acceptor systems small molecules, the conjugated polymers given of pyrrolopyrrole diketone (DPP) and appear in the newspapers frequently, be respectively 4.7% and 4.4% based on polymkeric substance/PCBM of DPP with based on the effciency of energy transfer of the small molecules solar cell of DPP.But it is still much lower than the efficiency of conversion of inorganic solar cell; The main restricting factor that limiting performance improves has: the carrier mobility that organic semiconductor device is relatively low; The spectral response of device and solar radiation spectrum do not match, the red light district of high photon flux be not used effectively and the electrode collection effciency of current carrier low etc.Simultaneously; Contain unitary acceptor systems small molecules, the conjugated polymers given of pyrrolopyrrole diketone and in actual application, still have deficiency, restricted its further application at photoelectric field like poor performance such as thermal stability, solubility property and film forming propertiess.In order to make polymer solar battery obtain actual application, the material of development of new increases substantially the top priority that its effciency of energy transfer is still this research field.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art; Providing a kind of passes through N; N '-two replaces isoindigo structural unit and 2, and the multipolymer that the unit copolymerization of 7-carbazole structure forms, this multipolymer have the HOMO and the lumo energy of good solubility property and thermal stability, this multipolymer to be regulated effectively; Absorption region broadens, and has increased substantially effciency of energy transfer.
Another object of the present invention is to provide that a kind of technology is simple, productive rate is high, be easy to operate and control N, N '-two replaces isoindigo and 2,7-carbazole copolymer method.
Further aim of the present invention is to provide above-mentioned N, and N '-two replaces isoindigo and 2,7-carbazole multipolymer at organic photoelectrical material, solar cell, organic electroluminescence device or/and the application in the organic field effect tube.
In order to realize the foregoing invention purpose, technical scheme of the present invention is following:
A kind of N, N '-two replaces isoindigo and 2,7-carbazole multipolymer, its general formula of molecular structure is following (I):
In the formula, R
1Be C
8～C
20Alkyl, R
2Be C
1～C
20Alkyl or C
1～C
20The alkoxyl group monosubstituted phenyl; N is 2～100 positive integer.
And, a kind of N, N '-two replaces isoindigo and 2, and 7-carbazole copolymer method comprises the steps:
The compd A, the B that provide following structural formula to represent respectively, wherein, R
1Be C
8～C
20Alkyl, R
2Be C
1～C
20Alkyl or C
1～C
20The alkoxyl group monosubstituted phenyl,
Under the condition that in oxygen-free environment, exists with organo-metallic catalyst, organic solvent, compd A, B are carried out the Suzuki coupling reaction, obtain the N of following general structure for (I) expression, N '-two replaces isoindigo and 2,7-carbazole multipolymer,
In the general structure (I), n is 2～100 positive integer.
Further, N of the present invention, N '-two replaces isoindigo and 2,7-carbazole multipolymer at organic photoelectrical material, solar cell, organic electroluminescence device or/and the application in the organic field effect tube.
N of the present invention, N '-two replaces isoindigo and 2, and 7-carbazole multipolymer possesses following advantage at least:
1. at N, N '-two replaces isoindigo and 2, and in the 7-carbazole multipolymer, N, N '-two replace the isoindigo structural unit and introduce alkyl and 2, and alkyl or alkoxyl group are introduced in 7-carbazole structure unit, have significantly improved its solvability.
2. the N in the multipolymer, N '-two replace the isoindigo structural unit and contain centrosymmetry pyrrolidone nuclear, and the alkylated reaction on the N on the N atom becomes and is very easy to carry out; The carbazole structure unit is good hole transport unit, N, and N '-two replaces isoindigo and 2; The copolymerization of 7-carbazole makes N, and N '-two replaces isoindigo and 2; 7-carbazole multipolymer has good thermostability, solvability and film-forming properties, the range of application of having widened this multipolymer; Effectively regulated simultaneously band gap and the HOMO and the lumo energy of multipolymer, the absorption region of this multipolymer to light broadened, improved its utilization ratio sunshine.
3. N of the present invention, N '-two replaces isoindigo and 2,7-carbazole multipolymer be with the measured response thing in suitable reaction environment; Thereby just can react through controlled temperature makes title product, and therefore, preparation technology is simple; Be easy to operate and control, production cost is low, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is embodiment of the invention N, and N '-two replaces isoindigo and 2, the synoptic diagram of 7-carbazole copolymer molecule general structure;
Fig. 2 is embodiment of the invention N, and N '-two replaces isoindigo and 2, the schema of 7-carbazole copolymer method;
Fig. 3 is the N of embodiment 1 preparation, and N '-two replaces isoindigo and 2,7-carbazole multipolymer abosrption spectrogram;
Fig. 4 is with embodiment of the invention N, and N '-two replaces isoindigo and 2, and 7-carbazole multipolymer is as the preparation of the solar cell device of active coating:
Fig. 5 is with embodiment of the invention N, and N '-two replaces isoindigo and 2, and 7-carbazole multipolymer is as the structural representation of doing the organic electroluminescence device of luminescent layer;
Fig. 6 is with embodiment of the invention N, and N '-two replaces isoindigo and 2, and 7-carbazole multipolymer is as the structural representation of the organic field effect tube device of organic semiconductor layer.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention will be solved, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, show a kind of N of the embodiment of the invention, N '-two replaces isoindigo and 2,7-carbazole copolymer molecule general structure, and it is following (I):
In the formula, R
1Be C
8～C
20Alkyl, R
2Be C
1～C
20Alkyl or C
1～C
20The alkoxyl group monosubstituted phenyl; N is 2～100 positive integer.Particularly, R
1Be preferably C
10～C
18Alkyl, R
2Be C
2～C
12Alkyl or C
2～C
12The alkoxyl group monosubstituted phenyl, this R
1, R
2The preferred group of institute can effectively improve present embodiment N, and N '-two replaces isoindigo and 2, the solvability of 7-carbazole multipolymer; N is preferably 5～50 positive integer.
The invention described above embodiment N, N '-two replaces isoindigo and 2, and the N in the 7-carbazole multipolymer, N '-two replace the isoindigo structural unit and contain centrosymmetry pyrrolidone nuclear, and the alkylated reaction on the N atom becomes and is very easy to carry out; The carbazole structure unit is good hole transport unit, N, and N '-two replaces isoindigo and 2, the copolymerization of 7-carbazole; Make N, N '-two replaces isoindigo and 2, and 7-carbazole multipolymer has good thermostability; Solvability and film-forming properties have improved its processing characteristics, have enlarged its Application Areas; Effectively regulated simultaneously band gap and the HOMO and the lumo energy of multipolymer, the absorption region of this multipolymer to light broadened, improved its utilization ratio sunshine.N, N '-two replace the isoindigo structural unit and introduce alkyl and 2, and alkyl or alkoxyl group are introduced in 7-carbazole structure unit, have significantly improved N, and N '-two replaces isoindigo and 2,7-carbazole multipolymer solvability.
Present embodiment also provides above-mentioned N, and N '-two replaces isoindigo and 2, and 7-carbazole copolymer method sees also Fig. 2.This N, N '-two replaces isoindigo and 2, and 7-carbazole multipolymer comprises the steps:
S1: the compd A, the B that provide following structural formula to represent respectively, wherein, R
1Be C
8～C
20Alkyl, R
2Be C
1～C
20Alkyl or C
1～C
20The alkoxyl group monosubstituted phenyl,
S2: under the condition that in oxygen-free environment, exists, compd A, B are carried out the Suzuki coupling reaction, obtain the N of following general structure for (I) expression with organo-metallic catalyst, organic solvent; N '-two replaces isoindigo and 2; 7-carbazole multipolymer, in the general structure (I), n is 2～100 positive integer.The Suzuiki coupling reaction formula of this step S2 can be represented as follows:
Particularly, above-mentioned N, N '-two replaces isoindigo and 2, and among the step S1 of 7-carbazole copolymer method, compd A, B can directly buy from market or prepare through existing compound method.Wherein, the R in the compd A
1Be preferably C
10～C
18Alkyl, R
2Be preferably C
2～C
12Alkyl or C
2～C
12The alkoxyl group monosubstituted phenyl.
Above-claimed cpd B can be with reference to " advanced material " Advanced Materials, 2007,19,2295 said method preparations.Compd A can be by following method preparation, and its chemical reaction is following:
The first step: 6; The preparation of 6 '-dibromo isoindigo: 6-bromo indole ketone, 6-bromo-isatin, Glacial acetic acid min. 99.5 and hydrochloric acid are joined in the flask reflux, stopped reaction and be cooled to room temperature more respectively; Water, ethanol, ETHYLE ACETATE are washed respectively then to filter the solid that obtains; At last with final product at vacuum drying oven, obtain brown 6,6 '-dibromo isoindigo.
Second step: 6,6 '-two bromo-N, the preparation of N '-two (2-ethylhexyl) isoindigo: under nitrogen protection, with 6 of above-mentioned preparation, 6 '-dibromo isoindigo and salt of wormwood, N, dinethylformamide and Br-R
1Join respectively in the there-necked flask, mixture is at 100 ℃ of following stirring reactions, and the stopped reaction postcooling is to room temperature; Mixture is poured in the water, organic phase is used dichloromethane extraction again, then washes with saturated common salt; Use the anhydrous magnesium sulfate drying organic phase then, rotary evaporation solvent, last crude product adopt (methylene dichloride/normal hexane=1: 1) to obtain dark red solid product 6 for leacheate separates through silica gel column chromatography; 6 '-two bromo-N, N '-two (2-ethylhexyl) isoindigo.Wherein, R
1Be C
8～C
20Alkyl.
Particularly, above-mentioned N, N '-two replaces isoindigo and 2; Among the step S2 of 7-carbazole copolymer method; The Suzuiki coupling reaction needs organic metal catalyst, and this organo-metallic catalyst is preferably the organic palladium catalyzer, perhaps the mixture of organic palladium catalyzer and organophosphorus ligand.Wherein, the organic palladium catalyzer is preferably Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2Deng, the preferred P of organophosphorus ligand (o-Tol)
3Deng.This organo-metallic catalyst addition is preferably 0.05%～50% of compd B molar percentage.When organo-metallic catalyst is the mixture of organic palladium catalyzer and organophosphorus ligand, the mol ratio of organic palladium catalyzer and organophosphorus ligand is preferably 1: 2～and 20.
Among the above-mentioned steps S2, the organic solvent in the Suzuiki coupling reaction is preferably one or more in benzene, chlorobenzene, the toluene, and its consumption should guarantee carrying out smoothly of Suzuiki coupling reaction at least.The temperature of Suzuiki coupling reaction is preferably 90～110 ℃, and the time is preferably 48～96 hours.
Among the above-mentioned steps S2, compd A, B reactant consumption mol ratio are preferably 1: 1.Like this, in the Suzuiki coupling reaction, can guarantee that compd A, B fully react, thereby improve the productive rate of conduction hole type electroluminescent material.Wherein, N, N '-two replaces isoindigo and 2, and the n in the 7-carbazole copolymer structure general formula (I) is preferably 5～50 positive integer.
Among the above-mentioned steps S2, the Suzuiki coupling reaction also need carry out in oxygen-free environment, and this is in order to prevent organo-metallic catalyst and the oxygen reaction in the Suzuiki coupling reaction, to guarantee activity of such catalysts.This oxygen-free environment can adopt vacuum or be full of rare gas element and realize, preferably is full of rare gas element and realizes oxygen-free environment, and this rare gas element is a present technique field rare gas element commonly used, like nitrogen, argon gas etc.
At above-mentioned N, N '-two replaces isoindigo and 2, in the 7-carbazole copolymer method; Only need that reactant is pressed ratio and add, need not special devices and environmental requirement, its preparation method technology is simple; Productive rate is high, and mild condition, is easy to operate and control; Reduce production cost, be suitable for suitability for industrialized production.
The above-mentioned N that provides, N '-two replaces isoindigo and 2, and 7-carbazole multipolymer is because the molecular structure of self; Make it have good solubility property and thermal stability; The HOMO and the lumo energy of this multipolymer are regulated effectively, and absorption region broadens, and has increased substantially effciency of energy transfer.Formal because embodiment of the invention N, N '-two replaces isoindigo and 2, and 7-carbazole multipolymer has above-mentioned good performance, makes it can be at organic photoelectrical material, solar cell, organic electroluminescence device or/and be able to application in the organic field effect tube.
Combine embodiment at present, the present invention is further elaborated.
Present embodiment N, N '-two (2-ethylhexyl) isoindigo-9-(9 '-heptadecyl)-2,7-carbazole conjugated polymers (PIDCZ1) and preparation thereof, the following I of its structural formula
1Shown in:
The preparation process of above-mentioned polymkeric substance is following:
1) 6,6 '-two bromo-N, the preparation of N '-dialkyl group isoindigo, its reaction formula is following:
This 6,6 '-two bromo-N, the concrete preparation process of N '-dialkyl group isoindigo is following:
1.1) 6, the preparation of 6 '-dibromo isoindigo: with 6-bromo indole ketone (500mg, 2.36mmol), 6-bromo-isatin (533mg; 2.36mmol), 15mL Glacial acetic acid min. 99.5 and 0.1mL hydrochloric acid joins respectively in the flask, behind the reflux 24h, stopped reaction also is cooled to room temperature; Refilter obtain solid respectively water, ethanol, ETHYLE ACETATE wash, at last that final product is dry at vacuum drying oven, obtain brown 6; 6 '-dibromo isoindigo, productive rate are 95%.
This 6, the test result of 6 '-dibromo isoindigo is:
1H NMR (300MHz, CDCl
3): 10.7 (bs, 2H), 9.14 (d, 2H), 7.22-7.15 (m, 4H).
1.2) 6,6 '-two bromo-N, the preparation of N '-two (2-ethylhexyl) isoindigo: under the nitrogen protection; With 6, and 6 '-dibromo isoindigo (420mg, 1mmol), salt of wormwood (829mg; 5mmol), 20mL N, (425g 2.2mmol) joins in the there-necked flask respectively for dinethylformamide and 1-bromo-2-ethyl hexane; Mixture is behind 100 ℃ of following stirring reaction 15h, and stopped reaction also is cooled to room temperature, and mixture is poured in the 100mL water; Organic phase is used dichloromethane extraction, with the saturated common salt washing, uses the anhydrous magnesium sulfate drying organic phase then again; Rotary evaporation solvent, last crude product adopt (methylene dichloride/normal hexane=1: 1) to obtain dark red solid 2 for leacheate separates through silica gel column chromatography, and productive rate is 85%.
This 6,6 '-two bromo-N, the test result of N '-two (2-ethylhexyl) isoindigo is:
1H NMR (300MHz, CDCl
3): 9.00 (d, 2H), 7.13 (dd, 2H), 6.81 (d, 2H), 3.60-3.48 (m, 4H), 1.90-1.72 (m, 2H), 1.43-1.20 (m, 16H), 0.95-0.82 (m, 12H).
2) N, N '-dialkyl group replaces isoindigo-9-(9 '-heptadecyl)-2, the preparation of 7-carbazole conjugated polymers, its reaction formula is following:
Concrete preparation process is: under nitrogen protection, and with 9-(9 '-heptadecyl)-2,7-carbazole hypoboric acid ester (reference literature " advanced material " Advanced Materials; 2007,19,2295 said methods are synthetic) (236.7mg; 0.36mmol), 6,6 '-two bromo-N, N '-two (2-ethylhexyl) isoindigo (231.8mg; 0.36mmol), (2.0mol/L 4.5mL) joins respectively in the two-mouth bottle of 50mL, behind the fully logical about 20min of nitrogen purge gas for 15mL toluene and solution of potassium carbonate; Add the 20mg tetra-triphenylphosphine palladium, after continuing again to lead to the about 10min of nitrogen purge gas, at 95 ℃ of stirring reaction 96h; Stop polyreaction after the cooling then, in flask, add 40mL methyl alcohol precipitating, use methyl alcohol and normal hexane extracting 24h successively after filtering through apparatus,Soxhlet's; Then be that solvent extraction is extremely colourless, collect chloroform solvent and also revolve the dried garnet solid that obtains, collect the back and under vacuum, be polymkeric substance I behind 50 ℃ of dry 24h with the chloroform
1Productive rate is 46%.
This N, N '-dialkyl group replaces isoindigo-9-(9 '-heptadecyl)-2, and the test result of 7-carbazole conjugated polymers is: Molecular weight (GPC, THF, R.I): M
n=59500, M
w/ M
n=1.8).
With the PIDCZ1 absorption spectrum test of present embodiment preparation, test result is as shown in Figure 3.Can be known that by Fig. 3 present embodiment PIDCZ1 is wide to the absorption region of sunshine, wherein, be that the sunshine of 500-600nm absorbs the strongest to wavelength.
Embodiment 2
Present embodiment N, N '-two (2-ethylhexyl) isoindigo-9-(4 '-octyloxy benzene)-2, the synthetic preparation of 7-carbazole conjugated polymers (PIDCZ2), the following I of its structural formula
2Shown in, its reaction formula is following:
1) 6,6 '-two bromo-N, the preparation of N '-dialkyl group isoindigo, its preparation method sees also the step (1) among the embodiment 1.
2) N, N '-two (2-ethylhexyl) isoindigo-9-(4 '-octyloxy benzene)-2, the preparation of 7-carbazole conjugated polymers:
Under nitrogen protection, with 9-(4 '-octyloxy benzene)-2,7-carbazole hypoboric acid ester (reference literature " advanced material " Advanced Materials; 2007,19,2295 said methods are synthetic) (236.7mg; 0.36mmol), 6,6 '-two bromo-N, N '-two (2-ethylhexyl) isoindigo (231.8mg; 0.36mmol), the 15mL volume ratio is 1: 1 chlorobenzene or toluene, and solution of potassium carbonate (2.0mol/L 4.5mL) joins respectively in the two-mouth bottle of 50mL; Behind the fully logical about 20min of nitrogen purge gas, adding 20mg mol ratio is 1: 2 Pd
2(dba)
3/ P (o-Tol)
3, after continuing again to lead to the about 10min of nitrogen purge gas, at 110 ℃ of stirring reaction 48h; Stop polyreaction after the cooling then; In flask, adding 40mL methyl alcohol precipitating, use methyl alcohol and normal hexane extracting 24h successively after filtering through apparatus,Soxhlet's, then is that solvent extraction is to colourless with the chloroform; Collect chloroform solvent and revolve the dried garnet solid that obtains, collect the back and under vacuum, be polymkeric substance I behind 50 ℃ of dry 24h
2Productive rate is 58%.
This N, N '-two (2-ethylhexyl) isoindigo-9-(4 '-octyloxy benzene)-2, the test result of 7-carbazole conjugated polymers is: Molecular weight (GPC, THF, R.I): M
n=66420, M
w/ M
n=2.0).
Application implementation example 3
With embodiment of the invention N, N '-two replaces isoindigo and 2, and 7-carbazole multipolymer is as the preparation of the solar cell device of active coating:
See also Fig. 4, this solar cell device comprises glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14, the negative electrode 15 that stacks gradually.Transparent anode 12 can adopt tin indium oxide (abbreviating ITO as), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Middle supplementary layer 13 adopts and gathers 3,4-Ethylenedioxy Thiophene and PS-sulfonic acid matrix material (abbreviating PEDOT:PSS as).Active coating 14 comprises electron donor material and electron acceptor material, and electron donor material adopts the PIDCZ1 of embodiment 1 preparation, and electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (abbreviating PCBM as).Negative electrode 15 can adopt aluminium electrode or double-metal layer electrode, for example Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 30nm, 130nm or 60nm.Glass-base 11 can be used as bottom, during making, chooses ito glass; And after ultrasonic cleaning, handle supplementary layer 13 in the middle of on ito glass, applying with oxygen-Plasma; Again the polymkeric substance of embodiment 1 preparation and electron acceptor material are coated on the supplementary layer 13 of centre after through blend; Form active coating 14, and then, obtain above-mentioned solar cell device through vacuum evaporation technology deposition cathode 15 on active coating 14.This solar cell device also needs to heat 4 hours down through 110 degrees centigrade of air tight conditions; Drop to room temperature again; Can effectively increase order and the regularity of arranging between each group of intramolecularly and molecule segment after device is annealed; Improve the transmission speed and the efficient of carrier mobility, and then improve photoelectric transformation efficiency.In the present embodiment, the thickness of negative electrode 15Al layer is respectively 170nm.
As shown in Figure 4, under illumination, light transmission glass-base 11 and ITO electrode 12; Conduction hole type electroluminescent material in the active coating 14 absorbs luminous energy, and produces exciton, and these excitons are moved to electron donor(ED)/acceptor material at the interface again; And give electron acceptor material with transfer transport, like PCBM, realize the separation of electric charge; Thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to metallic cathode transmission and collected by negative electrode; Freely the hole along electron donor material to ito anode transmission and collected by anode, thereby form photoelectric current and photovoltage, realize opto-electronic conversion; During external load 16, can supply power to it.In this process, conduction hole type electroluminescent material can utilize luminous energy more fully because it has very wide spectral response range, 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 make through technology such as spin coatings, is convenient to large batch of preparation.
Application implementation example 4
With N, N '-two replaces isoindigo and 2, and the preparation of the organic electroluminescence device of luminescent layer is done in the conduct of 7-carbazole multipolymer:
See also Fig. 5; Show and adopt N in the foregoing description; N '-two replaces isoindigo and 2, the organic electroluminescence device of 7-carbazole multipolymer, and it comprises glass-base 21, anode 22, hole injection layer 23, luminescent layer 24, impact plies 25 and the negative electrode 26 that is cascading.Anode 22 can adopt tin indium oxide (abbreviating ITO as), is preferably the tin indium oxide that square resistance is 10-20 Ω/; Hole injection layer 23 can be 3,4-Ethylenedioxy Thiophene (PEDOT) and polystyrolsulfon acid (PSS) mixture layer; Luminescent layer 24 comprises the PIDCZ2 of the foregoing description 2 preparations; Impact plies 25 can adopt LiF etc., but is not limited thereto.Negative electrode 26 can be but be not limited to metal A l.Thereby present embodiment organic electroluminescence device structural table is shown: glass/ITO/PEDOT:PSS/PIDCZ2/LiF/Al.
The manufacturing processed of this organic electroluminescence device is following:
1) ito glass is carried out ultrasonic cleaning, and, form glass-base 21 and anode 22 bonded substrates with after oxygen-Plasma processing;
2) at ito anode 22 surperficial spin coating one deck PEDOT as hole injection layer 23, the conjugated polymers PIDCZ2 that in embodiment 2, prepares at hole injection layer 23 surperficial spin coating one decks then forms luminescent layer 24;
3) on luminescent layer 24, adopt vacuum evaporation technology to apply one deck LiF and form impact plies 25;
4) at impact plies 25 surface vacuum evaporation metal aluminium, form metal aluminium lamination 26 as negative electrode, obtain organic electroluminescence device; Wherein, the thickness of metal aluminium lamination 26 is 170nm.
Certainly, the thickness of metal aluminium lamination 26 can also be 30nm, 130nm, 60nm.
Application implementation example 5
Contain N, N '-two replaces isoindigo and 2, the preparation of 7-carbazole multipolymer organic field effect tube:
See also Fig. 6, this organic field effect tube comprises substrate 31, insulation layer 32, decorative layer 33, the organic semiconductor layer 34 that is cascading and is located at source electrode 35 and the drain electrode 36 on the organic semiconductor layer 34.Wherein, substrate 31 can be but be not limited to highly doped silicon chip (Si) that insulation layer 32 can be but be not limited to micro-nano (like 450nm) thick SiO
2 Organic semiconductor layer 34 adopts the PIDCZ2 of the foregoing description 2 preparations.Source electrode 35 all can adopt with drain electrode 36 but be not limited to gold.Decorative layer 33 can be but be not limited to octadecyl trichlorosilane (OTS).
The manufacturing processed of this organic field effect tube is following:
1) clean doped silicon substrate 31, deposition has the SiO of insulating effect
2Layer 32;
2) at SiO
2Apply OTS on the insulation layer 32, form OTS layer 33;
3) on OTS layer 33, apply the PIDCZ2 of one deck, form organic semiconductor layer 34 in embodiment 2 preparations;
4) the source electrode 35 and drain electrode 36 of metallic gold material are set on organic semiconductor layer 34, obtain organic field effect tube.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. N, N '-two replaces isoindigo and 2,7-carbazole multipolymer, its general formula of molecular structure is following (I):
In the formula, R
1Be C
8～C
20Alkyl, R
2Be C
1～C
20Alkyl or C
1～C
20The alkoxyl group monosubstituted phenyl; N is 2～100 positive integer.
2. N according to claim 1, N '-two replaces isoindigo and 2, and 7-carbazole multipolymer is characterized in that: R
1Be C
10～C
18Alkyl, R
2Be C
2～C
12Alkyl or C
2～C
12The alkoxyl group monosubstituted phenyl; N is 5～50 positive integer.
3. N, N '-two replaces isoindigo and 2, and 7-carbazole copolymer method comprises the steps:
The compd A, the B that provide following structural formula to represent respectively, wherein, R
1Be C
8～C
20Alkyl, R
2Be C
1～C
20Alkyl or C
1～C
20The alkoxyl group monosubstituted phenyl,
Under the condition that in oxygen-free environment, exists with organo-metallic catalyst, organic solvent, compd A, B are carried out the Suzuki coupling reaction, obtain the N of following general structure for (I) expression, N '-two replaces isoindigo and 2,7-carbazole multipolymer,
In the general structure (I), n is 2～100 positive integer.
4. N according to claim 3, N '-two replaces isoindigo and 2, and 7-carbazole copolymer method is characterized in that: the temperature of said Suzuki coupling reaction is 90～110 ℃, and the time is 48～96 hours.
5. N according to claim 3, N '-two replaces isoindigo and 2, and 7-carbazole copolymer method is characterized in that: the organo-metallic catalyst addition is 0.05%～50% of a compd B molar percentage.
6. according to claim 3 or 5 described N, N '-two replaces isoindigo and 2, and 7-carbazole copolymer method is characterized in that: said organo-metallic catalyst is the organic palladium catalyzer, perhaps the mixture of organic palladium catalyzer and organophosphorus ligand.
7. N according to claim 6, N '-two replaces isoindigo and 2, and 7-carbazole copolymer method is characterized in that: said organic palladium catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2In at least a; Said organophosphorus ligand is P (o-Tol)
3
8. N according to claim 6; N '-two replaces isoindigo and 2; 7-carbazole copolymer method is characterized in that: when said organo-metallic catalyst was the mixture of organic palladium catalyzer and organophosphorus ligand, the mol ratio of said organic palladium catalyzer and organophosphorus ligand was 1: 2～20.
9. N according to claim 3, N '-two replaces isoindigo and 2, and 7-carbazole copolymer method is characterized in that: the organic solvent of said Suzuki coupling reaction is one or more in benzene, chlorobenzene, the toluene.
10. according to each described N of claim 1 to 2, N '-two replaces isoindigo and 2,7-carbazole multipolymer at organic photoelectrical material, solar cell, organic electroluminescence device or/and the application in the organic field effect tube.
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| CN101343350A (en) * | 2008-09-04 | 2009-01-14 | 南昌航空大学 | Fluorine-carbazole blue electroluminescence copolymer material containing cavity transmission arborescence macromolecule side chain and preparation thereof |
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| LIJUN HUO, ET AL.: "Bandgap and Molecular Level Control of the Low-Bandgap Polymers Based on 3,6-Dithiophen-2-yl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione toward Highly Efficient Polymer Solar Cells", 《MACROMOLECULES》 * |
| NICOLAS BLOUIN, ET AL.: "A Low-Bandgap Poly(2,7-Carbazole) Derivative for Use in High-Performance Solar Cells", 《ADVANCED MATERIALS》 * |
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| CN103804271A (en) * | 2012-11-06 | 2014-05-21 | 北京大学 | Isoindigo compound containing electron-withdrawing groups, and preparation and application thereof |
| CN103804271B (en) * | 2012-11-06 | 2016-08-10 | 北京大学 | Isoindigo green grass or young crops compounds containing electron withdraw group and preparation thereof and application |
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