CN103258961A - Application of fullerene derivative with double hydrophobic groups in solar cell - Google Patents
Application of fullerene derivative with double hydrophobic groups in solar cell Download PDFInfo
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- CN103258961A CN103258961A CN201210572385XA CN201210572385A CN103258961A CN 103258961 A CN103258961 A CN 103258961A CN 201210572385X A CN201210572385X A CN 201210572385XA CN 201210572385 A CN201210572385 A CN 201210572385A CN 103258961 A CN103258961 A CN 103258961A
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 125000001165 hydrophobic group Chemical group 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 229920000620 organic polymer Polymers 0.000 claims abstract description 10
- 238000004528 spin coating Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 230000004888 barrier function Effects 0.000 claims abstract description 8
- 238000003672 processing method Methods 0.000 claims abstract description 8
- 230000005540 biological transmission Effects 0.000 claims abstract description 6
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 6
- 229910003472 fullerene Inorganic materials 0.000 claims description 51
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 45
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000012876 topography Methods 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 230000003993 interaction Effects 0.000 claims description 6
- 229930192474 thiophene Natural products 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 230000021615 conjugation Effects 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000012958 reprocessing Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- RVCKCEDKBVEEHL-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzyl alcohol Chemical compound OCC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl RVCKCEDKBVEEHL-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 235000009161 Espostoa lanata Nutrition 0.000 description 2
- 240000001624 Espostoa lanata Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- -1 C 60Fullerene compound Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000746 body region Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 230000001394 metastastic effect Effects 0.000 description 1
- 206010061289 metastatic neoplasm Diseases 0.000 description 1
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical class COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Images
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses an application of fullerene derivatives with double hydrophobic groups in solar cells, which comprises the following steps: step 1) arranging an electron barrier layer on clean conductive glass; step 2) preparing a mixed solution of a donor material and an acceptor material by using a conjugated polymer or a conjugated organic micromolecule as the donor material and a fullerene derivative with a double-hydrophobic group as the acceptor material, and arranging an active layer film on the electron blocking layer at room temperature by using a processing method of solution spin coating; and 3) arranging a layer of electrode on the active layer film to obtain the organic polymer heterojunction solar cell. The invention can obtain the solar cell active layer with an ideal structure of long-range order, nano-scale phase separation and continuous transmission channels, greatly improves the photoelectric conversion efficiency, simplifies the preparation process of the device and eliminates the risks of easy oxidation and degradation of the device in the post-treatment.
Description
Technical field
The invention belongs to the photovoltaic material field, be specifically related to have the application of fullerene derivate in solar cell of two hydrophobic groups.
Background technology
Solar energy becomes the focus of various countries scientific circles research as inexhaustible, nexhaustible reproducible green energy resource.Wherein, the solar cell that solar energy is converted to electric energy becomes one of research topic the most popular in the world today.Organic solar batteries (OSCs) is a kind of good very promising selection that obtains cleaning solar energy capable of circulation.Compare with inorganic semiconductor, organic material has a lot of advantages: raw material sources are extensive, and handling ease, but large tracts of land film forming are carried out physical modification easily, low price, characteristics such as technology is simple.Therefore be expected to mass preparation low cost, frivolous, the solar cell that can curl, can use flexibly.The organic photoelectric pond early stage of development is that the active layer with one-component is clipped in the middle of the electrode with different work functions, but this form makes energy conversion efficiency very low because charge generation seldom shifts with unbalanced electric charge.1995, people's reported first such as Yu by gathering (2-methoxyl group-5-(2-ethyl hexyl oxy)-1,4-phenylene ethylene) (MEH-PPV) prepare the bulk heterojunction solar cell (Bulk-Heterojunction BHJ) of active layer with fullerene derivate PCBM blend, this work has proposed the concept of bulk heterojunction solar cell first.By this method, absorption region in the active layer is from the distance of having only several nanometers for the acceptor material interface, and this has just improved quantum efficiency greatly, and two tracks have been created in the formation of this co-continuous network, shifting the hole to body region respectively, at acceptor zone metastatic electron.But because the unformed state of polymer donor material ubiquity, poorly soluble and with acceptor material (for example, characteristics such as compatibility is relatively poor PCBM), in the blend active layer that obtains by solution spin coating processing method, there is large scale state of aggregation (not having continuous electronics, hole transport passage) in majority, seriously is separated etc. and is unfavorable for the surface topography of exciton dissociation, transmission.And effective exciton diffusion length only is the 10-20 nanometer in the blend active layer, exciton is just fallen for body and acceptor in no show at the interface by cancellation, even the exciton that separates also can occur owing to the isolated island structure of large scale state of aggregation and can't be transferred to corresponding electrode, finally also can be fallen by cancellation.At giving acceptor material blend active layer surface topography ubiquity the problems referred to above at present, existing main improvement method has: (1) selects different solvents, for example different boiling, mixed solvent, additive etc. according to solvent evaporates kinetic effect factor; (2) device carries out reprocessing, as physical methods such as solvent annealing, thermal annealings; (3) by active layer material is carried out molecular structure alteration, improve and give acceptor material dissolubility and compatibility between the two.These methods have extraordinary effect for obtaining the desirable active layer pattern that long-range order, intermolecular tightly packed, homogeneous, nanoscale be separated, and can greatly improve mobility and the solar cell device efficient of active layer.Yet because the physical property difference (as dissolubility, compatibility, phase transition temperature, crystallinity etc.) that different active layer material possesses, carry out pattern optimization by selecting the means of different solvents and reprocessing in the said method, exist optimal conditions complexity, narrow application range, pattern to be difficult to shortcomings such as control, the method of thermal annealing also can cause the aging acceleration of device, reduce the life-span of device, and be not suitable for broad area device, especially the preparation of flexible device.Method by molecular structure alteration then can cause loaded down with trivial details building-up process because of the modification criterion that does not have to determine, thereby increases preparation cost and the cycle of material.Owing to be difficult to find the method that a kind of technology is simple, applied widely, controllability is high that the active layer surface topography is controlled, though having caused in recent years, a large amount of novel solar battery materials are in the news, device efficiency also has steady lifting, but the report present situation seldom of real high-photoelectric transformation efficiency.Therefore develop a kind of solution spin coating of passing through, do not carry out reprocessings such as thermal annealing, and the method for the control of more efficiently active layer surface topography and optimization, the matter of utmost importance that organic polymer bulk heterojunction solar cell develops will be become.The two hydrophobicity fullerene derivates synthetic by above method can substitute PCBM effectively, become fullerene acceptor material of new generation.
Summary of the invention
For addressing the above problem, the purpose of this invention is to provide the application of fullerene derivate in solar cell with two hydrophobic groups, replace PCBM, be applied in the bulk heterojunction solar cell.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
Have the application of fullerene derivate in solar cell of two hydrophobic groups, may further comprise the steps:
Step 1) arranges an electronic barrier layer at the electro-conductive glass of cleaning;
Step 2) be donor material with conjugated polymer or conjugation organic molecule, with fullerene derivate with two hydrophobic groups as acceptor material, the mixed solution of preparation donor material and acceptor material utilizes under the processing method room temperature of solution spin coating and at electronic barrier layer one active layer film is set;
Step 3) arranges one deck electrode at the active layer film, namely obtains the organic polymer heterojunction solar battery.
Further, described fullerene derivate comprises the methylene fullerene hydrophobic group and the tri-alkoxy benzene hydrophobic group that is connected by the flexible spacer group that benzene replaces, the fullerene [6 that while replaces at methylene, 6] fluorine that carries out diverse location and number on the phenyl replaces, and its structural formula is as follows:
Further, described fullerene derivate is unbodied, can not form large scale and assemble, and has excellent thermal stability.
Further, described fullerene derivate has good dissolubility owing to introduce the end alkyl chain in organic solvent.
Further, the tri-alkoxy benzene of described fullerene derivate end group can have good interaction with donor material, can induce poly-3 hexyl thiophene P3HT crystallizations, and the degree of crystallinity of P3HT is improved, and conjugacy strengthens, and forms to be similar to annealing back P3HT/[6.6]-C
60The fibrous ordered lamellar structure of P3HT among the-phenylbutyric acid methyl esters PCBM can obtain the bulk heterojunction active layer surface topography with co-continuous transmission channel of long-range order.
Further, introduce after the fluorine atom, can strengthen the interaction between described fullerene derivate, form orderly molecular structure, improve light abstraction width, improve short circuit current.
Further, donor material is selected from step 2): P3HT, poly-((5-(5,6--, two octyloxies-4-thiophene-benzo [c] [1,2,5] thiadiazoles-7-thiophene-9-octyl group-9H-carbazole) or polythiophene be [3,4-b] thiophene benzo two thiophene also for 2-.
Further, step 2) in the mixed solution of donor material and acceptor material, the mass ratio of donor material and acceptor material is 1: 0.5～1: 6 described in, and the concentration of the mixed solution of described donor material and acceptor material is 5～40 mg/ml.
Further, step 2) in the processing method of solution spin coating, rotating speed is 600 ~ 4000rpm described in, and the thickness of described active layer film is 100 ~ 200 nanometers.
Further, electrode described in the step 3) is magnesium/silver, calcium/aluminium or lithium fluoride/aluminium electrode.
The invention has the beneficial effects as follows:
1, the fullerene derivate that contains two hydrophobic groups that the present invention adopts is with respect to PCBM, because the introducing of long oxyalkyl chain has better dissolubility;
2, the fullerene derivate that contains two hydrophobic groups that the present invention adopts is unbodied with respect to PCBM, can not form big gathering in the film forming procedure, thereby can improve interfacial area effectively, improve the life-span of photoproduction exciton, improve the quantity of charge carrier, therefore improved the efficient of organic solar batteries;
3, the fullerene derivate that contains two hydrophobic groups that the present invention adopts can be induced the P3HT crystallization effectively, improves the degree of crystallinity of P3HT, causes short circuit current significantly to raise under unannealed condition, thereby has improved solar battery efficiency greatly;
4, after the present invention adopts the fullerene derivate and P3HT blend that contain two hydrophobic groups, under the situation of any reprocessing, can obtain that long-range order, nanoscale are separated, the ideal structure solar cell active layer of transmission channel continuously, improve electricity conversion greatly and simplified the technology that device prepares, eliminated the risk of device easily oxidation, degraded in reprocessing.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.The specific embodiment of the present invention is provided in detail by following examples and accompanying drawing thereof.
Description of drawings
Fig. 1 is P3HT/PCBB-C
8 1HNMR collection of illustrative plates, wherein [6.6]-C
60-phenylbutyric acid-3,4,5-three octyloxy benzyl esters are abbreviated as PCBB-C
8
Fig. 2 is P3HT/PCBB-C
8, the film after P3HT/PCBM and the P3HT/PCBM annealing the UV, visible light collection of illustrative plates;
Fig. 3 is P3HT/PCBB-C
8The heterojunction solar battery current-voltage curve of active layer;
Fig. 4 is P3HT/ PCBB-C
8The heterojunction solar battery external quantum efficiency curve of active layer.
Embodiment
Below with reference to the accompanying drawings and in conjunction with the embodiments, describe the present invention in detail.
A kind of preparation method who contains the fullerene derivate of two hydrophobic groups specifically may further comprise the steps:
(1) 3,4,5-trihydroxybenzoic acid methyl esters and alkyl halide are reacted under weakly alkaline environment, obtain 3,4,5-tri-alkoxy methyl benzoate, described alkyl halide is that carbon chain lengths is single halogenated hydrocarbons that replaces of 4～20;
(2) in anhydrous tetrahydrofuran solution, with lithium aluminium hydride reduction (LiAlH
4) reduction 3,4,5-tri-alkoxy benzoic acid obtains 3,4,5-tri-alkoxy phenmethylol;
(3) press literature method PCBM processed, PCBM hydrolysis under acetic acid/hydrochloric acid effect obtains [6.6]-C
60-phenylbutyric acid (PCBA).
(4) with [6.6]-C
60-phenylbutyric acid (PCBA) and 3,4, the reaction of 5-tri-alkoxy phenmethylol, with N, N-lutidines (DMAP), p-methyl benzenesulfonic acid (PTSA), N, N-diisopropylamide (DIPC) is catalyst, esterification takes place obtain end product, is and contains C
60Fullerene compound.
In the technique scheme, described halogenated hydrocarbons is that alkyl chain is the even number of 4-20.
Have the application of fullerene derivate in solar cell of two hydrophobic groups, may further comprise the steps:
Step 1) arranges an electronic barrier layer at the electro-conductive glass of cleaning;
Step 2) be donor material with conjugated polymer or conjugation organic molecule, with fullerene derivate with two hydrophobic groups as acceptor material, the mixed solution of preparation donor material and acceptor material utilizes under the processing method room temperature of solution spin coating and at electronic barrier layer one active layer film is set;
Step 3) arranges one deck electrode at the active layer film, namely obtains the organic polymer heterojunction solar battery.
Further, described fullerene derivate comprises the methylene fullerene hydrophobic group and the tri-alkoxy benzene hydrophobic group that is connected by the flexible spacer group that benzene replaces, the fullerene [6 that while replaces at methylene, 6] fluorine that carries out diverse location and number on the phenyl replaces, and its structural formula is as follows:
Further, described fullerene derivate is unbodied, can not form large scale and assemble, and has excellent thermal stability.
Further, described fullerene derivate has good dissolubility owing to introduce the end alkyl chain in organic solvent.
Further, the tri-alkoxy benzene of described fullerene derivate end group can have good interaction with donor material, can induce poly-3 hexyl thiophenes (P3HT) crystallization, and the degree of crystallinity of P3HT is improved, and conjugacy strengthens, and forms to be similar to annealing back P3HT/[6.6]-C
60The fibrous ordered lamellar structure of P3HT in the-phenylbutyric acid methyl esters (PCBM) can obtain the bulk heterojunction active layer surface topography with co-continuous transmission channel of long-range order.
Further, introduce after the fluorine atom, can strengthen the interaction between described fullerene derivate, form orderly molecular structure, improve light abstraction width, improve short circuit current.
Further, donor material is selected from step 2): P3HT, poly-((5-(5,6--, two octyloxies-4-thiophene-benzo [c] [1,2,5] thiadiazoles-7-thiophene-9-octyl group-9H-carbazole) or polythiophene be [3,4-b] thiophene benzo two thiophene also for 2-.
Further, step 2) in the mixed solution of donor material and acceptor material, the mass ratio of donor material and acceptor material is 1: 0.5～1: 6 described in, and the concentration of the mixed solution of described donor material and acceptor material is 5～40 mg/ml.
Further, step 2) in the processing method of solution spin coating, rotating speed is 600 ~ 4000rpm described in, and the thickness of described active layer film is 100 ~ 200 nanometers.
Further, electrode described in the step 3) is magnesium/silver, calcium/aluminium or lithium fluoride/aluminium electrode.
Embodiment one:
(1) with the quartz glass plate chloroform, acetone, the wiping of isopropyl alcohol cotton balls were put in the baking oven 100 ℃ of heat dryings 25 minutes then, removed isopropyl alcohol.
(2) under the room temperature condition, with conjugated polymer P3HT and PCBB-C
8, PC
60BM is dissolved in the solution that is mixed with 10 mg/ml in its good solvent chlorobenzene (CB) respectively, stirs under the mixing speed of 200 ~ 1200rpm 6 ~ 10 hours, fully dissolve to guarantee conjugated polymer, in room temperature with the P3HT/PCBB-C for preparing
8Chlorobenzene solution is with the rotating speed of 1100rpm, and the P3HT/PCBM chlorobenzene solution is spin-coated on the quartz glass plate with the rotating speed of 800rpm.
(3) wherein a slice P3HT/PCBM that step (2) is prepared is transferred in the glove box, with 145 ℃ annealing temperature 10 minutes, namely prepares the film that absorbs (Uv-vis absorption) test for UV, visible light on hot platform.
Fig. 1 is P3HT/PCBB-C
8 1The HNMR collection of illustrative plates.
Referring to shown in Figure 2, P3HT/PCBB-C
8Under unannealed condition, than P3HT/PCBM tangible red shift is arranged, the resonance absorption band also broadens, and P3HT/PCBB-C is described
8In P3HT degree of crystallinity be significantly improved, conjugacy strengthens, and has formed the structure of long-range order.
Embodiment two: with PCBB-C
8Be acceptor material, be equivalent to replace PCBM.
(1) with the ito glass chloroform, acetone, the wiping of isopropyl alcohol cotton balls, then with rotating speed 3000rpm spin coating, obtaining a layer thickness is the PEDOT:PSS layer of 40 nanometers, with as electronic barrier layer, is put on the hot platform 125 ℃ of heat dryings then 25 minutes, removes moisture.
(2) according to the step (2) of embodiment one with P3HT/PCBB-C
8Be dissolved in the chlorobenzene solution with P3HT/PCBM, be mixed with 10 mg/ml solution. again with the P3HT/PCBB-C for preparing
8Chlorobenzene solution is with the rotating speed of 1100rpm, and the P3HT/PCBM chlorobenzene solution is spin-coated on the ito glass sheet of having modified with the rotating speed of 800rpm, obtains the active layer that thickness is about 150 nanometers.
(3) wherein a slice P3HT/PCBM that step (2) is prepared is transferred in the glove box on hot platform with 145 ℃ annealing temperature 10 minutes.
(4) last, treat that solvent volatilizees fully after, method evaporation one layer thickness by vacuum evaporation is the lithium fluoride of 0.8 nanometer and the aluminium electrode of 100 nanometers, namely prepares the organic polymer heterojunction solar battery.P3HT/PCBB-C
8Current-voltage curve as shown in Figure 3, the external quantum efficiency curve is as shown in Figure 4.
Organic polymer heterojunction solar battery performance in the comparing embodiment two gets table 1.
Table 1: utilize PCBB-C respectively
8With PCBM be that relatively (light intensity is 100mW/cm for the organic polymer heterojunction solar battery performance of acceptor material
2Measure under the AM 1.5 white light conditions)
| Active layer | J sc(mA/cm 2) | Voc(V) | FF | PCE(%) |
| P3HT/PCBM | 1.99 | 0.70 | 0.34 | 0.47 |
| P3HT/PCBM-annealing | 8.81 | 0.55 | 0.62 | 2.98 |
| P3HT/PCBB-C8 | 8.42 | 0.56 | 0.49 | 2.32 |
Table 1
As shown in Table 1: use method of the present invention prepared with PCBB-C
8Be the organic polymer heterojunction solar battery of acceptor material, do not passing through under the condition of any reprocessing that its energy conversion efficiency has reached 2.32%, short circuit current is 8.42mA/cm
2, be that acceptor material has obtained to increase substantially according to device efficiency and the short circuit current that the same terms prepares than adopting PCBM, approach by the reprocessed device efficiency of annealing, in detail relatively see Table 1.Studies show that: the fullerene derivate that application the present invention contains two hydrophobic groups is that the prepared organic polymer heterojunction solar battery of acceptor material not only can make exciton separate for the acceptor material interface fully, and can obtain effective collection, with respect to being that the device for preparing under the acceptor material condition of the same race has obtained significant raising with PCBM, approach the device efficiency by the annealing reprocessing at the device photoelectric transformation efficiency that does not obtain by any reprocessing.Therefore, utilize method of the present invention not only can prepare the high performance polymer solar cell, and simplify the technology of device preparation greatly.
The above only for the preferred embodiment of invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. have the application of fullerene derivate in solar cell of two hydrophobic groups, it is characterized in that, may further comprise the steps:
Step 1) arranges an electronic barrier layer at the electro-conductive glass of cleaning;
Step 2) be donor material with conjugated polymer or conjugation organic molecule, with fullerene derivate with two hydrophobic groups as acceptor material, the mixed solution of preparation donor material and acceptor material utilizes under the processing method room temperature of solution spin coating and at electronic barrier layer one active layer film is set;
Step 3) arranges one deck electrode at the active layer film, namely obtains the organic polymer heterojunction solar battery.
2. the application of fullerene derivate in solar cell with two hydrophobic groups according to claim 1, it is characterized in that: described fullerene derivate comprises the methylene fullerene hydrophobic group and the tri-alkoxy benzene hydrophobic group that is connected by the flexible spacer group that benzene replaces, the fullerene [6 that while replaces at methylene, 6] fluorine that carries out diverse location and number on the phenyl replaces its structural formula such as figure below:
3. the application of fullerene derivate in solar cell with two hydrophobic groups according to claim 1, it is characterized in that: described fullerene derivate is unbodied, can not form large scale and assemble, and has excellent thermal stability.
4. the application of fullerene derivate in solar cell with two hydrophobic groups according to claim 1 is characterized in that: described fullerene derivate has good dissolubility owing to introduce the end alkyl chain in organic solvent.
5. the application of fullerene derivate in solar cell with two hydrophobic groups according to claim 1, it is characterized in that: the tri-alkoxy benzene of described fullerene derivate end group can have good interaction with donor material, can induce poly-3 hexyl thiophenes (P3HT) crystallization, the degree of crystallinity of P3HT is improved, conjugacy strengthens, and forms to be similar to annealing back P3HT/[6.6]-C
60The fibrous ordered lamellar structure of P3HT in the-phenylbutyric acid methyl esters (PCBM) can obtain the bulk heterojunction active layer surface topography with co-continuous transmission channel of long-range order.
6. the application of fullerene derivate in solar cell with two hydrophobic groups according to claim 1, it is characterized in that: introduce after the fluorine atom, can strengthen the interaction between described fullerene derivate, form orderly molecular structure, improve light abstraction width, improve short circuit current.
7. the application of fullerene derivate in solar cell with two hydrophobic groups according to claim 1, it is characterized in that: step 2) described in donor material be selected from: P3HT, poly-((5-(5 for 2-, 6--two octyloxies-4-thiophene-benzo [c] [1,2, thiadiazoles-7-thiophene-9-octyl group-9H-carbazole) or polythiophene [3,4-b] thiophene benzo two thiophene also 5].
8. the application of fullerene derivate in solar cell with two hydrophobic groups according to claim 1, it is characterized in that: step 2) described in the mixed solution of donor material and acceptor material, the mass ratio of donor material and acceptor material is 1: 0.5～1: 6, and the concentration of the mixed solution of described donor material and acceptor material is 5～40 mg/ml.
9. the application of fullerene derivate in solar cell with two hydrophobic groups according to claim 1, it is characterized in that: step 2) described in the processing method of solution spin coating, rotating speed is 600 ~ 4000rpm, and the thickness of described active layer film is 100 ~ 200 nanometers.
10. the application of fullerene derivate in solar cell with two hydrophobic groups according to claim 1, it is characterized in that: electrode described in the step 3) is magnesium/silver, calcium/aluminium or lithium fluoride/aluminium electrode.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910045A (en) * | 2015-06-30 | 2015-09-16 | 苏州大学 | Triad fullerene derivative and preparation method and application thereof |
| CN104910045B (en) * | 2015-06-30 | 2017-08-01 | 苏州大学 | Triad fullerene derivate and preparation method and application |
| CN105153182A (en) * | 2015-09-29 | 2015-12-16 | 苏州大学 | A5-alkyl-2, 3-dihydrobenzofuran-C60fullerene double adduct, its prepn. method and use |
| CN106800511A (en) * | 2016-12-14 | 2017-06-06 | 中节能万润股份有限公司 | A kind of fullerene derivate and its application in perovskite solar cell |
| CN106800511B (en) * | 2016-12-14 | 2020-01-31 | 中节能万润股份有限公司 | fullerene derivatives and application thereof in perovskite solar cell |
| CN111384245A (en) * | 2018-12-27 | 2020-07-07 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
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