CN104319100A - Double-charge organic hole-transport material for fully-solid-state quantum dot sensitized solar cell - Google Patents
Double-charge organic hole-transport material for fully-solid-state quantum dot sensitized solar cell Download PDFInfo
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Abstract
The invention discloses double-charge organic hole-transport material for a fully-solid-state quantum dot sensitized solar cell. The double-charge organic hole-transport material is characterized in that m-dinitrobenzene and azoxybenzene serve as two active centers of the organic hole-transport material, when the cell works, two holes can be transported, R1 is any one of hydroxyl and carboxyl, n ranges from 1 to 6, and R2 is a hydrogen atom and can also be alkane with the number of carbon atoms being less than 6.
Description
[technical field]: the invention belongs to technical field of solar batteries, especially relates to the application of class double charge organic hole transport material in all solid state quantum dot sensitized solar cell.
[background technology]: quantum dot sensitized solar cell adopts the inorganic semiconductor of the inorganic-quantum-dot of narrow with gap (quantum dots, QDs) material wide with gap as CdSe, CdS etc. are adsorbed on as titanium dioxide makes as light anode.The inorganic-quantum-dot material tool of this narrow with gap has the following advantages: 1) the with gap of QDs can realize controllable adjustment by the size changing particle, and then can regulate and control the spectral response range of QDs, to reach the coupling good with solar spectrum; 2) QDs has high molar extinction coefficient, can improve the utilance of sunlight; 3) quantum dot sensitized solar cell can utilize hot electron to produce multiple electron hole pair, therefore has higher theoretical conversion efficiency (44%).
Electrolyte, as the important composition material of quantum dot sensitized solar cell, is generally be dissolved in specific solvent by oxidation-reduction pair to prepare.In the work of battery, realize the regeneration of QDs by transmitting electronics to QDs, and make by accepting electronics at photocathode battery complete a complete circulation.Therefore, the efficiency of electrolytical performance on quantum dot sensitized solar cell has vital impact.At present conventional electrolyte take water as many sulphur electrolyte of solvent.But inevitably there is the problem that volatilization is revealed in this electrolyte making solvent with water, has had a strong impact on the stability of battery, be difficult to the needs meeting practical application.Adopt organic hole transport material to replace liquid electrolyte can be assembled into all solid state quantum dot sensitized solar cell, the volatilization leakage problem of liquid electrolyte can be solved.The organic hole transport material spiro-OMeDAT of current report, also be lend from DSSC, well can not meet the needs of quantum dot sensitization solar battery, therefore efficiency very low (being far smaller than 1%), efficient organic hole transport material electrolyte also is not developed out.
Organic hole transport material for quantum dot sensitized solar cell should have: the hole mobility that (1) is higher, effectively can realize charge migration, multiple electron hole pair is produced in order to mate quantum dot sensitized battery hot electron, hole mobile material preferably has multiple hole transport center, realizes energy level Optimized Matching; (2) contact between organic hole transport material and the titanium dioxide film of porous will be got well; 3) dark reaction be injected between the electronics in titanium dioxide film and the hole in hole mobile material is little.
Based on this, this patent proposes the double charge organic hole transport material of a class for all solid state quantum dot sensitized solar cell, it is characterized in that described organic hole transport material is using meta-dinitro-benzent and azoxybenzene as two activated centres, when battery operated, two holes can be transmitted.R
1for any one of hydroxyl or carboxyl, add the contact of hole mobile material and titanium dioxide film on the one hand, on the other hand, this effect inhibits the compound in the electronics in titanium dioxide and the hole in hole mobile material, reduce dark reaction, achieve good effect.The patent announced and document are retrieved, does not find related content.Patent of the present invention has obvious practicality, novelty and novelty.
[summary of the invention]: when quantum dot sensitized solar cell working, quantum dot sensitized solar cell can utilize hot electron to produce multiple electron hole pair, therefore, design has the organic hole transport material of double charge transfer function, can be good at mating the feature that hot electron produces multiple electron hole pair, this is not suggested in research paper in the past and patent, and the present invention proposes this concept first.As realizing carrier, the present invention proposes the double charge organic hole transport material of a class for all solid state quantum dot sensitized solar cell, it is characterized in that described organic hole transport material is to have following molecular structure, wherein, meta-dinitro-benzent and azoxybenzene are respectively as two activated centres, when battery operated, two holes can be transmitted, R
1for any one of hydroxyl and carboxyl, n=1 ~ 6, R
2for hydrogen atom, the alkane that also can be less than 6 for carbon number.
When battery operated, hole on quantum dot can pass to meta-dinitro-benzent and azoxybenzene two hole receiving units, different according to hole energy level, generally, high level hole is tended to be combined with meta-dinitro-benzent unit, and more easily and the combination of azoxybenzene center, this is conducive to the rapidly and efficiently transfer realizing electric charge in low-lying level hole, also can improve open circuit voltage, finally obtain higher electricity conversion.Meanwhile, R
1for any one of hydroxyl and carboxyl, these two kinds of groups effectively can be adsorbed on the surface of titanium dioxide, are conducive to combining closely of hole mobile material and quantum dot.Wherein, n=1 ~ 6, R
2for hydrogen atom, the alkane that also can be less than 6 for carbon number, the alkyl chain of this prolongation contributes to the flexibility increasing hole mobile material, suppresses crystallization.
[technical scheme of the present invention]:
The present invention proposes the double charge organic hole transport material of a class for all solid state quantum dot sensitized solar cell, it is characterized in that described organic hole transport material is using meta-dinitro-benzent and azoxybenzene as two activated centres, when battery operated, two holes can be transmitted, R
1for any one of hydroxyl and carboxyl, n=1 ~ 6, R
2for hydrogen atom, the alkane that also can be less than 6 for carbon number.
The present invention proposes double charge organic hole transport material, and realizes being one of new meaning of the present invention respectively as two activated centres with dinitro benzene and azoxybenzene; Utilize organic molecule and the interactional concept of inorganic semiconductor to design the electrolyte of quantum dot sensitization solar battery, and creationary utilization is carried out to carboxyl and hydroxyl, be another new meaning of the present invention, the battery assembled achieves good transformation efficiency, and result has certain advance.
The assembling process of described all solid state quantum dot sensitized solar cell is as follows:
1) method of silk screen printing is adopted to be printed on by titania slurry on electro-conductive glass (1), thickness is controlled by the number of times of printing, by printed titanium dioxide film high-temperature calcination, to remove the organic substance in slurry, and improve the contact tightness degree between titania nanoparticles; 2) titanium dioxide film (2) after calcining immerses the aqueous solution of cysteine, then clean with acetone, finally put into the toluene solution of CdSe quantum dot, CdSe quantum dot (3) is adsorbed on titanium dioxide electrodes and obtains light anode, 3) be dissolved in volatile acetonitrile, carrene, any one solvent of ethanol by double charge organic hole transport material (4), concentration is 0.01 ~ 0.5mol/L; 4) method of above-mentioned solution spin coating is dripped on light anode, to make organic hole transport material solution better immerse in light anode, and the volatilization of accelerated solvent; 5) on the light anode containing organic hole transport material, steam gold, as to electrode (5), obtain complete all solid state quantum dot sensitized solar cell.
The all solid state quantum dot sensitized solar cell of described material assembling reaches ~ electricity conversion of 4%.
[advantage of the present invention and effect]: patent of the present invention provides a class for the double charge organic hole transport material of all solid state quantum dot sensitized solar cell, and it has the following advantages and beneficial effect: 1) containing double charge center: meta-dinitro-benzent and azoxybenzene.Different according to hole energy level, high level hole is tended to be combined with meta-dinitro-benzent unit, and more easily and the combination of azoxybenzene center, this is conducive to the rapidly and efficiently transfer realizing electric charge in low-lying level hole, also can improve open circuit voltage, finally obtain higher electricity conversion.2) on double charge organic hole transport material, hydroxyl or carboxyl is introduced, hydroxyl or carboxyl and titanium dioxide film is utilized to act on, add the contact of hole mobile material and titanium dioxide film on the one hand, on the other hand, this effect inhibits the compound in the electronics in titanium dioxide and the hole in hole mobile material, reduce dark reaction, achieve good effect.3) cyano group is as strong electron-withdrawing group group, has guide effect, improve charge mobility to the displacement of electric charge.
[accompanying drawing explanation]:
Fig. 1 is the structural representation of all solid state quantum dot sensitized solar cell based on double charge organic hole transport material.
[embodiment]:
Be described further content of the present invention below in conjunction with embodiment, but scope is not limited only to following examples, every technical scheme belonging to content of the present invention and be equal to, all belongs to the protection range of this patent.
1) adopt the method for silk screen printing to be printed on by titania slurry on electro-conductive glass (1), the formula of titania slurry is: 0.26g ethyl cellulose and 0.95g titania nanoparticles (P25) are dispersed in 5mL terpinol.Print 1 layer, obtain the titanium dioxide film of 2 micron thickness, printed titanium dioxide 450 DEG C is calcined half an hour, to remove the organic substance in slurry, and improves the contact tightness degree between titania nanoparticles; 2) titanium dioxide film (2) prepared immerses the aqueous solution of cysteine, places 1 hour, then clean with acetone at 70 DEG C.Finally put into the toluene solution of CdSe quantum dot, 24 hours, obtain the titanium dioxide electrodes of quantum dot (3) sensitization, i.e. light anode; 3) by double charge organic hole transport material (4), be dissolved in acetonitrile, concentration is 0.25mol/L; 4) method of above-mentioned solution spin coating is dripped on light anode, to make organic hole transport material solution better immerse in light anode, and the volatilization of accelerated solvent; 5) treat that solvent evaporates is done, the light anode containing organic hole transport material steams gold, as to electrode (5), the thickness of gold is 100nm, obtains complete all solid state quantum dot sensitized solar cell.The electricity conversion of battery is 4%.
Claims (2)
1. a class is used for the double charge organic hole transport material of all solid state quantum dot sensitized solar cell, it is characterized in that described organic hole transport material is using meta-dinitro-benzent and azoxybenzene as two activated centres, when battery operated, two holes can be transmitted, R
1for any one of hydroxyl and carboxyl, n=1 ~ 6, R
2for hydrogen atom, the alkane that also can be less than 6 for carbon number
2. a class according to claim 1 is used for the double charge organic hole transport material of all solid state quantum dot sensitized solar cell, it is characterized in that quantum dot sensitized solar cell is assembled by following step: be first dissolved in by organic hole transport material in acetonitrile, carrene, any one solvent of ethanol, be made into the weak solution that concentration is 0.01 ~ 0.5mol/L; Then dripped in the light anode of quantum dot sensitized solar cell by the method for spin coating, allow solvent evaporates; Finally gold evaporation is obtained complete battery above-mentioned containing on the light anode of organic hole transport material.
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| JP2008063390A (en) * | 2006-09-05 | 2008-03-21 | Gunma Univ | Dye for dye-sensitized solar battery, photoelectric transfer element using the dye, and dye-sensitized solar battery |
| CN101694813A (en) * | 2009-09-30 | 2010-04-14 | 中国科学院等离子体物理研究所 | Liquid crystal electrolyte solution for dye-sensitized nano film solar battery |
| CN102603542A (en) * | 2012-03-02 | 2012-07-25 | 河北联合大学 | Saccharide-modified triphenylamine organic hole transport material for all-solid-state quantum dot dye-sensitized solar cell |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008063390A (en) * | 2006-09-05 | 2008-03-21 | Gunma Univ | Dye for dye-sensitized solar battery, photoelectric transfer element using the dye, and dye-sensitized solar battery |
| CN101694813A (en) * | 2009-09-30 | 2010-04-14 | 中国科学院等离子体物理研究所 | Liquid crystal electrolyte solution for dye-sensitized nano film solar battery |
| CN102603542A (en) * | 2012-03-02 | 2012-07-25 | 河北联合大学 | Saccharide-modified triphenylamine organic hole transport material for all-solid-state quantum dot dye-sensitized solar cell |
Non-Patent Citations (3)
| Title |
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| KENJI KAKIAGE,YOHEI AOYAMA,ET AL: "A novel alkoxysilyl azobenzene dye photosensitizer with alkylamino group for dye sensitized solar cells", 《ORIGINAL PAPER》 * |
| 丘龙斌，孙雪梅，ET AL: "取向碳纳米管/高分子新型复合材料的制备及应用", 《化学学报》 * |
| 刘剑，田晶晶，ET AL: "偶氮共轭聚合物光电特性研究进展", 《高分子通报》 * |
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