CN104974335A - Pyridazinopyrrole diketone semiconducting organic polymer and application thereof - Google Patents
Pyridazinopyrrole diketone semiconducting organic polymer and application thereof Download PDFInfo
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- CN104974335A CN104974335A CN201510381717.XA CN201510381717A CN104974335A CN 104974335 A CN104974335 A CN 104974335A CN 201510381717 A CN201510381717 A CN 201510381717A CN 104974335 A CN104974335 A CN 104974335A
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- 0 Bc1c(*)c(*)c(-c(nnc(-c2c(*)c(*)c(*)[s]2)c2C(N3*)=O)c2C3=O)[s]1 Chemical compound Bc1c(*)c(*)c(-c(nnc(-c2c(*)c(*)c(*)[s]2)c2C(N3*)=O)c2C3=O)[s]1 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/549—Organic PV cells
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Abstract
The invention provides a pyridazinopyrrole diketone semiconducting organic polymer and application thereof. The semiconducting organic polymer has a structure as shown in a formula (I). In the formula, Ar is a substituted heteroarylene group containing at least a ring; R1 and R2 are selected from the group consisting of hydrogen or substituted/unsubstituted straight-chain/branched-chain alkyl groups with a carbon atom number of 6 to 20; R3 is a substituted/unsubstituted straight-chain/branched-chain alkyl group with a carbon atom number of 6 to 20; and n is a natural number in a range of 1 to 10000. The polymer provided by the invention has excellent photoelectric conversion and charge transfer performance, is an organic semiconductor material with good application prospects and can be applied to the fields of organic solar batteries and organic field effect transistors.
Description
Technical field
The invention belongs to organic semiconductor technologies field, be specifically related to a kind of pyridazine and pyrrole-dione semiconducting organic polymer and the application in organic solar batteries and organic field effect tube field thereof.
Background technology
In recent years, organic solar batteries, particularly cause educational circles based on the research of polymer thin-film solar cell and industrial community is paid close attention to widely, the advantage that this kind of battery has inorganic semiconductor solar cell incomparable, as low in cost, lightweight, preparation technology is simple, can be prepared into flexible device etc., presents considerable investigation and application prospect.By the regulation and control to polymer molecule energy level, absorption spectrum and accumulation mode, add the optimization to polymer solar cell device structure, the electricity conversion of polymer thin-film solar cell has breached 10% (J.B.You, L.T.Dou, K.Yoshimura, T.Kato, K.Ohya, T.Moriarty, K.Emery, C.C.Chen, J.Gao, G.Li, Y.Yang, Nat.Commun.2013,4,1446.), this result excites people's design, synthesizing new high-level efficiency polymer donor material further and continues to optimize the research enthusiasm of device architecture.
Pyridazine pyrrole-dione semiconducting organic polymer be a class using pyridazine and pyrroledione as electrophilic unit to-by copoly type polymkeric substance.Due to pyridazine and pyrroledione has very strong electron-withdrawing power, therefore compared to the benzopyrrole dione unit with it with similar structures, it is more obvious to the effect reducing polymkeric substance lumo energy.So build novel to-by making full use of pyridazine during copoly type polymkeric substance and this characteristic of pyrroledione comes energy level and the absorption spectrum of telomerized polymer, thus reach the object improving polymer solar cell device open circuit voltage and short-circuit current.
In addition, by changing length and the type of pyridazine alkyl chain on pyrroledione, the solvability of polymkeric substance in the conventional film forming solvents such as chloroform, chlorobenzene and orthodichlorobenzene can be regulated and controled on the one hand, thus ensure the homogeneous preparation of active coating film in polymer solar cell device; On the other hand, polymer molecule can also be regulated and controled whereby at suprabasil accumulation mode, thus reach and improve the charge mobility of polymer solar cell device and the object of packing factor.
In sum, pyridazine pyrroledione base polymer is the organic semiconductor material that a class possesses application potential in organic solar batteries and organic field effect tube field very much.
Summary of the invention
The object of the present invention is to provide a kind of novel pyridazine and pyrrole-dione semiconducting organic polymer, it has excellent photoelectric conversion and charge transport properties, is a kind of organic semiconductor material very with application prospect.
In order to achieve the above object, present invention employs following technical scheme:
A kind of pyridazine pyrrole-dione semiconducting organic polymer, have such as formula the structure shown in (I):
In formula, Ar is selected from the heteroarylidene containing at least one ring of replacement; R
1and R
2it is all the alkyl of the straight or branched of 6 to 20 independently selected from hydrogen or substituted or unsubstituted carbonatoms; R
3it is the alkyl of the straight or branched of 8 to 20 for substituted or unsubstituted carbonatoms; N is the natural number between 1 ~ 10000, such as, be 5,25,100,500,1000,5000,8500 etc.
As preferably, described Ar be selected from following group any one:
Wherein, the alkyl of R to be substituted or unsubstituted carbonatoms the be straight or branched of 6 to 20.
As preferably, described polymkeric substance has formula II or the structure shown in (III):
In formula, Ar is selected from the heteroarylidene containing at least one ring of replacement; R
1and R
2it is all the alkyl of the straight or branched of 6 to 20 independently selected from hydrogen or substituted or unsubstituted carbonatoms; R
3it is the alkyl of the straight or branched of 8 to 20 for substituted or unsubstituted carbonatoms; N is the natural number between 1 ~ 10000.
As preferably, the number-average molecular weight of described polymkeric substance is 5000 ~ 1000000, is preferably 10000 ~ 500000, more preferably 20000 ~ 300000.
An object of the present invention is also the preparation method providing a kind of polymkeric substance of the present invention, comprises the steps:
(1) under protection of inert gas, the compound unit shown in the compound shown in formula IV and formula (V) is reacted under katalysis;
(2) reaction adds the poor solvent precipitating of described polymkeric substance after terminating, and filters and is precipitated thing;
(3) throw out is extracted, concentrated extract, and by the poor solvent precipitating of described polymkeric substance, suction filtration obtains described pyridazine and pyrroledione base polymer:
In formula, Ar is selected from the heteroarylidene containing at least one ring of replacement; R
1and R
2it is all the alkyl of the straight or branched of 6 to 20 independently selected from hydrogen or substituted or unsubstituted carbonatoms; R
3it is the alkyl of the straight or branched of 8 to 20 for substituted or unsubstituted carbonatoms; N is the natural number between 1 ~ 10000.
As preferably, step (1) used catalyst is palladium catalyst.
Preferably, the temperature of described reaction is 80-150 DEG C, is preferably 110 DEG C.
Preferably, the time of described reaction is 8 ~ 24h, is preferably 12h.
Preferably, described reaction is carried out in a solvent.
Preferably, described solvent is one or more the mixture in toluene, DMF, chlorobenzene or orthodichlorobenzene.
Preferably, the mol ratio of the compound shown in the compound shown in described formula IV and formula (V) is 1:1.If both ratios are not the mol ratios of 1:1, a kind of compound so certainly will be had to be exactly excessive, the existence of excess reactant can affect the purification of the polymkeric substance of generation, is unfavorable for obtaining purer polymkeric substance.
Preferably, the poor solvent of described conjugated polymers is that methyl alcohol is or/and normal hexane.
Preferably, be extracted as described in step (3) and extract with methyl alcohol, acetone, normal hexane and chloroform successively, preferably use surname extraction.
Compound shown in formula (V) can with reference to prior art (Qun Ye, Wei Teng Neo, Ching Mui Cho, Shuo Wang Yang, Tingting Lin, Hui Zhou, Hong Yan, Xuehong Lu, Chunyan Chi, and Jianwei Xu.Org.Lett.2014,16,6386 – 6389.) disclosed in method preparation.
Two of object of the present invention is the purposes providing a kind of polymkeric substance of the present invention, and it can be used as active layer for the preparation of organic field effect tube device.
Three of object of the present invention is to provide a kind of semiconductor blend, and it comprises pyridazine of the present invention and pyrrole-dione semiconducting organic polymer and acceptor material.
Preferably, described acceptor material is fullerene derivate, is preferably [6,6]-phenyl C
61methyl-butyrate (PC
61and/or [6,6]-phenyl C BM)
71methyl-butyrate (PC
71bM).
Preferably, described polymkeric substance can mix according to arbitrary proportion with acceptor material, as being 1:1,1:2 or 1:3 etc. as the polymkeric substance of donor material and the mass ratio of acceptor material.
Four of object of the present invention is the purposes providing a kind of semiconductor blend of the present invention, and it can be used as active coating for the preparation of organic solar batteries device.
Compared with the prior art, the present invention has following beneficial effect:
With pyridazine provided by the invention and the benzopyrrole diones polymer phase ratio of pyrroledione base polymer and similar structures, energy level shows obvious reduction trend, and absorption spectrum is significantly widened.
Accompanying drawing explanation
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of polymer P 1 under chlorobenzene solution neutralized film state prepared by embodiment 2;
It is ITO/ZnO/ polymer P 1:PC that Fig. 2 shows structure
71bM/MoO
3the I-V curve of the organic solar batteries device of/Ag.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
Embodiment 1: the synthesis of compound 8
Chemical reaction flow process figure is as follows, concrete reactions steps and reaction conditions as follows:
772mg (0.8mmol) compound 6 and 167mg (0.8mmol) compound 7 are dissolved in 25mL phenyl ether, 160 DEG C, reaction 16 hours under argon atmosphere.Reaction terminates and pours in silicagel column by reaction solution after being chilled to room temperature, first falls phenyl ether with sherwood oil drip washing, then crosses post with sherwood oil mixing methylene dichloride, obtain 366mg compound 8 (red thick liquid), productive rate 40%.
MS(MALDI-TOF):m/z＝1144.7
1HNMR(400MHz,CDCl
3,ppm):δ8.544(s,2H),3.78(t,2H),2.58(d,4H),1.76(m,4H),1.31(m,74H),0.88(m,15H)。
Embodiment 2: the synthesis of polymer P 1
Chemical reaction flow process figure is as follows, concrete reactions steps and reaction conditions as follows:
In 50mL there-necked flask; add 228mg (0.2mmol) compound 8 and 98mg (0.2mmol) compound 9; add the super dry chlorobenzene of 10mL again; logical within 20 minutes, after argon gas, add rapidly three (dibenzalacetone) two palladium and three (o-methyl-phenyl-) phosphine; take out inflation again three times; slow afterwards temperature is risen to 130 DEG C, under argon shield, lucifuge reacts 24 hours.Question response terminates, after reaction system naturally cools to room temperature, reaction solution is instilled in 200mL methyl alcohol and carry out precipitating, leach throw out and transfer them in apparatus,Soxhlet's, carrying out extracting with methyl alcohol, acetone, normal hexane and chloroform successively, the concentrated chloroform extract finally obtained, and be added dropwise in 200mL methyl alcohol and carry out precipitating again, filter out and precipitate and carry out vacuum-drying, finally obtain 190mg polymer P 1, productive rate 77%.
Be the number-average molecular weight M that moving phase records this polymkeric substance at 140 DEG C by gel exclusion chromatography with trichlorobenzene
n=25.6K, dispersity PDI=3.2.
Embodiment 3: the synthesis of polymer P 2 ~ P20
The synthetic method of polymer P 2 ~ P20 is as above-described embodiment, and only need compound 8 to carry out reacting with following compound 10-28, chemical reaction flow process figure is as follows.
Embodiment 4: measure the ultraviolet-visible absorption spectroscopy of polymkeric substance under chlorobenzene solution neutralized film state and utilize experimental formula to calculate the optical band gap of polymkeric substance
Appropriate polymer dissolution is made into certain density solution in chlorobenzene and gets part solution and be spin-coated to film quartz plate being made polymkeric substance.
The ultraviolet-visible absorption spectroscopy that polymer P 1 prepared by embodiment 2 records under chlorobenzene solution neutralized film state as shown in Figure 1.The optical band gap of polymkeric substance uses formula (E
g=1240/ λ
absorb limit) calculate, wherein the maximum absorption band of P1 in chlorobenzene solution is 548nm, and the maximum absorption band under filminess is 588nm, and absorb limit at 698nm, optical band gap is 1.77eV.
Embodiment 5: preparation is characterize polymers solar cell device also
Transparent conducting glass with ITO is used successively each ultrasonic cleaning of deionized water, acetone, Virahol 15 minutes, ZnO colloidal sol is spin-coated on ITO, the rotating speed of spin coating is 3000 revs/min, and at 150 DEG C dry 15 minutes, obtain the negative pole decorative layer that thickness is 30nm.By polymkeric substance obtained in embodiment 2 and embodiment 3 and [6,6]-phenyl C in glove box
71methyl-butyrate (PC
71bM) be configured to the chlorobenzene solution of different concns according to the mass ratio of 1:1, and with certain rotating speed, this dissolution homogeneity be spin-coated on negative pole decorative layer, obtain the active material layer that thickness is 100-300nm.Last 2 × 10
-6by MoO under the vacuum tightness of holder
3evaporation, on active material layer, forms the positive pole decorative layer that thickness is 10nm; And 2 × 10
-6under the vacuum tightness of holder by Ag evaporation on positive pole decorative layer, forming thickness is the positive pole of 120nm, thus obtains polymer solar cell device.
Use the white light source that the filter set cooperation of 500W xenon lamp and AM 1.5 is simulated solar irradiation, the light intensity of adjusting means measured place is to 100mW/cm
-2, use Keithley to test the open circuit voltage of prepared polymer solar cell device, short-circuit current and packing factor three parameters.It is ITO/ZnO/ polymer P 1:PC that Fig. 2 shows structure
71bM/MoO
3the I-V curve of the organic solar batteries device of/Ag.
Based on the polymer P 1 of embodiment 2, according to the step preparation also characterize polymers solar cell device of embodiment 5.Wherein open circuit voltage V
oc=0.80V, short-circuit current J
sc=2.43mA/cm2, packing factor FF=60.9%, electricity conversion PCE=1.18%.
Applicant states, the present invention illustrates detailed construction of the present invention and composition by above-described embodiment, but the present invention is not limited to above-mentioned detailed construction and composition, does not namely mean that the present invention must rely on above-mentioned detailed construction and composition could be implemented.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. pyridazine a pyrrole-dione semiconducting organic polymer, has such as formula the structure shown in (I):
In formula, Ar is selected from the heteroarylidene containing at least one ring of replacement; R
1and R
2it is all the alkyl of the straight or branched of 6 to 20 independently selected from hydrogen or substituted or unsubstituted carbonatoms; R
3it is the alkyl of the straight or branched of 8 to 20 for substituted or unsubstituted carbonatoms; N is the natural number between 1 ~ 10000.
2. polymkeric substance according to claim 1, is characterized in that, described Ar be selected from following group any one:
Wherein, the alkyl of R to be substituted or unsubstituted carbonatoms the be straight or branched of 6 to 20.
3. polymkeric substance according to claim 1 and 2, is characterized in that, described polymkeric substance has formula II or the structure shown in (III):
In formula, Ar is selected from the heteroarylidene containing at least one ring of replacement; R
1and R
2it is all the alkyl of the straight or branched of 6 to 20 independently selected from hydrogen or substituted or unsubstituted carbonatoms; R
3it is the alkyl of the straight or branched of 8 to 20 for substituted or unsubstituted carbonatoms; N is the natural number between 1 ~ 10000.
4. the polymkeric substance according to any one of claim 1-3, is characterized in that, the number-average molecular weight of described polymkeric substance is 5000 ~ 1000000, is preferably 10000 ~ 500000, more preferably 20000 ~ 300000.
5. the pyridazine described in any one of claim 1-4 a preparation method for pyrroledione base polymer, comprise the steps:
(1) under protection of inert gas, the compound unit shown in the compound shown in formula IV and formula (V) is reacted under katalysis;
(2) reaction adds the poor solvent precipitating of described polymkeric substance after terminating, and filters and is precipitated thing;
(3) throw out is extracted, concentrated extract, and by the poor solvent precipitating of described polymkeric substance, suction filtration obtains described pyridazine and pyrroledione base polymer:
In formula, Ar is selected from the heteroarylidene containing at least one ring of replacement; R
1and R
2it is all the alkyl of the straight or branched of 6 to 20 independently selected from hydrogen or substituted or unsubstituted carbonatoms; R
3it is the alkyl of the straight or branched of 8 to 20 for substituted or unsubstituted carbonatoms; N is the natural number between 1 ~ 10000.
6. method as claimed in claim 5, it is characterized in that, step (1) used catalyst is palladium catalyst;
Preferably, the temperature of described reaction is 80-150 DEG C, is preferably 110 DEG C;
Preferably, the time of described reaction is 8 ~ 24h, is preferably 12h;
Preferably, described reaction is carried out in a solvent;
Preferably, described solvent is one or more the mixture in toluene, DMF, chlorobenzene or orthodichlorobenzene;
Preferably, the mol ratio of the compound shown in the compound shown in described formula IV and formula (V) is 1:1;
Preferably, the poor solvent of described conjugated polymers is that methyl alcohol is or/and normal hexane;
Preferably, be extracted as described in step (3) and extract with methyl alcohol, acetone, normal hexane and chloroform successively, preferably use surname extraction.
7. a semiconductor blend, is characterized in that, it comprises pyridazine described in any one of claim 1-4 and pyrrole-dione semiconducting organic polymer and acceptor material.
8. semiconductor blend according to claim 7, is characterized in that, described acceptor material is [6,6]-phenyl C
61methyl-butyrate and/or [6,6]-phenyl C
71methyl-butyrate.
9. a purposes for the semiconductor blend described in any one of claim 7-8, its as active coating for the preparation of organic solar batteries device.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012233098A (en) * | 2011-05-02 | 2012-11-29 | Konica Minolta Holdings Inc | Conjugated polymer and organic photoelectric conversion element using the same |
| CN104961884A (en) * | 2015-05-28 | 2015-10-07 | 合肥工业大学 | A-[pi]-A type conjugated semiconductor polymer based on pyridazino pyrroledione, and preparation method thereof |
-
2015
- 2015-07-02 CN CN201510381717.XA patent/CN104974335A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012233098A (en) * | 2011-05-02 | 2012-11-29 | Konica Minolta Holdings Inc | Conjugated polymer and organic photoelectric conversion element using the same |
| CN104961884A (en) * | 2015-05-28 | 2015-10-07 | 合肥工业大学 | A-[pi]-A type conjugated semiconductor polymer based on pyridazino pyrroledione, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YE QUN, ET AL: "Synthesis of Ultrahighly Electron-Deficient Pyrrolo[3,4-d]pyridazine-5,7-dione by Inverse electron Demand Diels-Alder Reaction and Its Application as Electrochromic Materials", 《ORGANIC LETTERS》 * |
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