CN105070833A - Organic solar cell device and preparation method thereof - Google Patents

Organic solar cell device and preparation method thereof Download PDF

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CN105070833A
CN105070833A CN201510416905.1A CN201510416905A CN105070833A CN 105070833 A CN105070833 A CN 105070833A CN 201510416905 A CN201510416905 A CN 201510416905A CN 105070833 A CN105070833 A CN 105070833A
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organic solar
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solar batteries
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CN105070833B (en
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许博为
侯剑辉
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Institute of Chemistry CAS
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • 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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    • 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

Abstract

The invention discloses an organic solar cell device and a preparation method thereof. The organic solar cell device comprises the components of an anode electrode layer, an anode interface modifying layer, a light active layer, a cathode interface modifying layer and a cathode electrode layer. The anode interface modifying layer and the cathode interface modifying layer are made of the same material which is a polymer that is represented by a formula I. In the formula I, A is a random material selected from sulfonic acid group, sodium sulfonate group, potassium sulfonate group, lithium sulfonate group, ammonium sulfonate group, sulphonylamino, carboxylic acid group, carboxylic acid ester group, sodium carboxylate group, potassium carboxylate group, lithium carboxylate group, ammonium carboxylate group and amide; R is an alkyl with 1-12 carbon atoms; Ar is a random member selected from the following unsubstituted or substituted group: single-ring arylene, double-ring arylene, three-ring arylene, arylene with more rings, single-ring heteroarylidene, double-ring heteroarylidene, three-ring heteroarylidene, heteroarylidene with more rings, and a group which is composed of 2-6 arylenes which are connected through single bonds; wherein n is selected from 2-500. The organic solar cell device and the preparation method have advantages of simplifying an optimization process and a manufacture process for the material of the interface modifying layers, and reducing the synthesis cost of the material.

Description

A kind of organic solar batteries device and preparation method thereof
Technical field
The present invention relates to a kind of organic solar batteries device and preparation method thereof, particularly relate to a kind of polymer solar cell device and preparation method thereof.
Background technology
Solar energy is a kind of green non-pollution, inexhaustible clean energy resource.Development and utilization solar energy solves the most promising means of energy crisis.Compare inorganic silicon wafer solar cell material, polymer solar battery is a kind of all solid state solar cell of film, and have quality light, cost is low, and compatible flexible substrates and easily large area such as to prepare at the advantage.In recent years, the bulk heterojunction solar cell based on conjugated polymer becomes new study hotspot, and through the development of short more than ten years, its highest energy conversion efficiency has reached 10%, shows very bright Commercial Prospect.Organic solar batteries mainly comprises five parts: anode, anodic interface decorative layer, photoelectric active layer, embellishing cathode interface layer and negative electrode.Wherein, interface-modifying layer, as the bridge between connecting electrode and active layer, has very important meaning to the extraction of electric charge and collection.Research shows, these electrode modification layers can effectively regulate electrode work content, improves the ohmic contact between electrode and active layer, has vital effect to charge-trapping and device energy conversion efficiency.
Therefore, in OPV device, the innovation of the development of novel interfacial layer material and interface structure design, can produce the raising of essence to the photoelectric properties of device.Such as, PEDOT:PSS and MoO 3deng classical anodic interface decorative material, be widely used in organic solar batteries research, the energy conversion efficiency of photovoltaic device is significantly increased.On the other hand, by the innovation of device structure design and boundary layer preparation method aspect, often can play Simplified flowsheet simultaneously and improve the effect of device performance.Compare traditional spin coating PEDOT method and prepare decorative layer, the people such as Heeger by prepare self assembled monolayer film method modify ITO electrode, obtain based on PTB7:PC 71the OPV device energy conversion efficiency of BM brings up to 8.2% by 7.3%.The method not only makes device performance get a promotion, and also simplify the difficulty of materials synthesis aspect, reduces preparation cost (ChoiH; Adv.Mater.2014).Meanwhile, in order to improve the performance of photoelectric device each side, researchers also utilize various means modified metal negative electrode.The Wu Hongbin of South China Science & Engineering University uses the polyfluorene derivative PFN of amido replacement as metallic cathode decorative layer, and collocation PEDOT:PSS is as ito anode modifying interface material simultaneously, at PTB7/PC 71in the device of BM, energy conversion efficiency brings up to 8.4%, for delivering the peak efficiency (Adv.Mater.2011,23,4636 – 4643) of polymer solar battery bibliographical information at that time.
Be not difficult to find, the innovation each time of interface structure can bring the breakthrough of OPV device performance aspect, and therefore, the interface-modifying layer of design and development new structure has important Research Significance.But, although the research and development of the anode of present stage and embellishing cathode interface material is all very fast, but in device structure design, but still there is very large problem: anodic interface decorative layer and embellishing cathode interface layer material need to screen respectively from the very large different materials of level structure difference, and by constantly test and optimization, best bi-material arrange in pairs or groups the most at last in same device, makes device reach an optimized condition of work.This experimental technique not only makes the preparation process of device become very complicated, and, when the two kinds of interface-modifying layer match materials degree chosen are not high time, greatly can reduce the operating efficiency of device, even cause device not work.
Summary of the invention
The object of this invention is to provide a kind of organic solar batteries device and preparation method thereof, anodic interface decorative layer in this organic solar batteries device and embellishing cathode interface layer all use conjugated polymer of the same race, enormously simplify optimizing process and the preparation technology of modifying interface layer material, and reduce the synthesis cost of material, and energy conversion efficiency can reach more than 7.9%.
Organic solar batteries device provided by the invention, it comprises the anode electrode layer, anodic interface decorative layer, photoactive layer, embellishing cathode interface layer and the negative electrode layer that connect successively, prepare described anodic interface decorative layer identical with the material of described embellishing cathode interface layer, and be polymer shown in formula I;
In formula I, A be selected from sulfonic group, sodium sulfonate group, potassium sulfonate base, Sulfonic Lithium base, sulfonic acid ammonium, sulfoamido, carboxylic acid group, carboxylic acid ester groups, carboxylic acid sodium base, carboxylic acid potassium base, carboxylic acid lithium base, carboxylic acid ammonium and amide groups any one; R is selected from the alkyl that carbon number is 1 ~ 12; Ar be selected from the following radicals not replacing or replace any one: monocycle arlydene, dicyclo arlydene, three rings and with the arlydene of pressed on ring, monocycle heteroarylidene, dicyclo heteroarylidene, three rings and with the heteroarylidene of pressed on ring, the group that formed by singly linked 2 ~ 6 arlydene; The repetitive number of n representation polymer is the natural number between 2 ~ 500.
In above-mentioned organic solar batteries device, in formula I, R can be selected from propyl group or butyl.
In above-mentioned organic solar batteries device, in formula I, Ar can be following 1) or 2):
1) unsubstituted have independently selected from 1 ~ 6 heteroatomic monocycle of nitrogen, sulphur and selenium, dicyclo or three ring heteroarylidenes; What replace has 1 ~ 6 the heteroatomic monocycle, dicyclo or the three ring heteroarylidenes that are independently selected from nitrogen, sulphur and selenium, and wherein, Ar is optionally substituted to form ethylene two oxy together by two adjacent carbon atoms on phenyl, alkyl replacement or Ar group;
2) the monocycle heteroarylidene containing 1 ~ 4 nitrogen-atoms.
In some case study on implementation, formula I can be polymer shown in following formula I-1 or formula I-2:
In formula I-1 and formula I-2, M can be selected from hydrogen, sodium, potassium, lithium, ammonium and amido any one; Ar can be selected from any one of the following radicals not replacing or replace: monocycle arlydene, dicyclo arlydene, three rings and with the arlydene of pressed on ring, monocycle heteroarylidene, dicyclo heteroarylidene, three rings and with the heteroarylidene of pressed on ring, the group that formed by singly linked 2 ~ 6 arlydene; The repetitive number of n representation polymer, can be the natural number between 2 ~ 500.
In formula I-1 and formula I-2, preferably, Ar can be having of not replacing or replace independently selected from 1 ~ 6 heteroatomic monocycle of nitrogen, sulphur and selenium, dicyclo or three ring heteroarylidenes, wherein, Ar is optionally substituted to form ethylene two oxy together by two adjacent carbon atoms on phenyl, alkyl replacement or Ar group.More preferably, Ar is the monocycle heteroarylidene containing 1 ~ 4 nitrogen-atoms.
In some case study on implementation, formula I can be polymer shown in following formula I-3 or formula I-4:
In formula I-3 and formula I-4, M be selected from hydrogen, sodium, potassium, lithium, ammonium and amido any one, Ar is selected from the group not replacing or replace: monocycle arlydene, dicyclo arlydene, three rings and with the arlydene of pressed on ring, monocycle heteroarylidene, dicyclo heteroarylidene, three rings and with the heteroarylidene of pressed on ring, the group that formed by singly linked 2 ~ 6 arlydene; The repetitive number of n representation polymer is the natural number between 2 ~ 500.
In formula I-3 and formula I-4, preferably, Ar can be selected from having of not replacing or replace independently selected from 1 ~ 6 heteroatomic monocycle of nitrogen, sulphur and selenium, dicyclo or three ring heteroarylidenes, wherein, Ar is optionally substituted to form ethylene two oxy together by two adjacent carbon atoms on phenyl, alkyl replacement or Ar group.More preferably, Ar can be the monocycle heteroarylidene containing 1 ~ 4 nitrogen-atoms.
In above-mentioned organic solar batteries device, polymer shown in formula I specifically can be selected from following formula I-a (PFS-PF), formula I-b (PFS-Th), formula I-c (PFS-biTh), formula I-d (PFCA-PF) and formula I-e (PFCA-biTh) any one:
Wherein, the repetitive number of n representation polymer is the natural number between 2 ~ 500.
The preparation method of polymer shown in above-mentioned formula I, comprises the steps: that shown in formula II, compound shown in compound and formula III is under the effect of catalyst, can obtain polymer shown in formula I through polymerization; Described catalyst is tetrakis triphenylphosphine palladium, two (dibenzalacetone) palladium or bi triphenyl phosphorus palladium chloride;
In formula II and formula III, the definition cotype I of A, R and Ar; The Y that X in formula III relies in formula II selects;
In formula II, Y be selected from boric acid base group, borate group, zinc halide group, magnesium halide group and trialkyltin groups any one, and in formula III, X is selected from any one in I, Br and Cl;
In formula II, Y be selected from I, Br and Cl any one, and in formula III, X is selected from any one in boric acid base group, borate group, zinc halide group and trialkyltin groups.
Wherein, described boric acid base group is selected from and includes but not limited to: 1,3,2-dioxaborinate-2-base, 4,4,5,5-tetramethyl-1,2,3-dioxaborolanes-2-bases and 5,5-dimethyl-1,3,2-dioxaborinate-2-base; Described magnesium halide group is selected from and includes but not limited to: magnesium chloride, magnesium bromide and magnesium iodide; The preferred zinc chloride of described zinc halide group or zinc bromide; Described trialkyltin groups is selected from and includes but not limited to: tin trimethyl, tin triethyl and tributyl tin.
Definition and name: unless otherwise noted, otherwise the present invention is not limited to specific raw material, reagent or reaction condition, but can change.Term used herein " alkyl " refers to branching or nonbranched saturated alkyl, and it is usually but not necessarily containing 1 to 30 carbon atom, as methyl, ethyl, n-pro-pyl, isopropyl, n-octyl, iso-octyl, decyl etc.; And cycloalkyl, as cyclopenta, cyclohexyl etc.
" arlydene " has its usual implication.Term used herein " heteroarylidene " refers to the aromatic ring with 5 or 6 atoms containing one or more " hetero-atom " (atom namely except carbon atom, as nitrogen, oxygen, sulphur, silicon, selenium, phosphorus).Term used herein " containing N heteroarylidene " refers to wherein the heteroarylidene that as defined above one or more " hetero-atom " is nitrogen." connection " ring is connected by singly-bound.
As the term " replacement " in " arlydene of replacement ", " heteroarylidene of replacement " etc. refer to be bonded to carbon or at least one hydrogen atom heteroatomic the part that replaces by one or more non-hydrogen substituent, such substituting group can include but not limited to the functional group of alkyl or aryl and halogen, hydroxyl, alkylthio, alkoxyl, aryloxy group, alkyl-carbonyl, acyloxy, nitro, itrile group etc.
In above-mentioned organic solar batteries device, the thickness of described anodic interface decorative layer can be 0 ~ 30nm, but is not 0, specifically can be 7nm; The thickness of described embellishing cathode interface layer can be 0 ~ 20nm, but is not 0, specifically can be 2nm.Described anodic interface decorative layer and described embellishing cathode interface layer specifically can by the films (solvent evaporates) formed after the solution spin coating of polymer shown in formula I.
In above-mentioned organic solar batteries device, described anode can be ITO conductive substrates or FTO conductive substrates; Described negative electrode can be prepared by any one in calcium, magnesium, barium, aluminium, silver, gold, copper, nickel, zinc, titanium, manganese, iron, platinum and molybdenum;
Described photoactive layer is photolytic activity to the composite membrane (mass ratio is 1:1.5) of body and photolytic activity acceptor; Described photoactive layer to body can be polythiofuran derivative, polypara-phenylene vinylene derivative, containing benzo [1,2-b:4,5-b '] two thiophene units polymer or containing and the polymer of pyrroledione unit, specifically can be P3HT, PBDT-TS1, PTB7 or PDPP-3T; Described photoactive layer acceptor can be fullerene and derivative thereof, specifically can be fullerene, [6,6]-phenyl C61 methyl butyrate, [6,6]-phenyl C71 methyl butyrate, containing the two addition fullerene derivative (ICBA) of indenes fullerene or indenes; The composite membrane forming described photoactive layer includes but not limited to: P3HT/PC 60bM, P3HT/PC 71bM, P3HT/ICBA, PBDT-TS1/PC 60bM, PBDT-TS1/PC 71bM, PBDT-TS1/ICBA, PTB7/PC 60bM, PTB7/PC 71bM, PTB7/ICBA, PDPP-3T/PC 60bM, PDPP-3T/PC 71bM, PDPP-3T/ICBA, PBT-1/PC 60bM, PBT-1/PC 71bM and PBT-1/ICBA etc., wherein, P3HT, PBDT-TS1, PTB7, PDPP-3T, PBT-1, PC 60bM, PC 71the structural formula of BM and ICBA is as follows:
Invention further provides the preparation method of above-mentioned organic solar batteries device, comprise the steps:
(1) solution of polymer shown in spin-coating I on anode electrode layer, prepares anodic interface decorative layer;
(2) on anodic interface decorative layer, photoactive layer is prepared;
(3) shown in the formula I that spin coating is identical with step (1) on photoactive layer, the solution of polymer, prepares embellishing cathode interface layer;
(4) on embellishing cathode interface layer, plate negative electrode layer, obtain described organic solar batteries device.
In the preparation method of above-mentioned organic solar batteries device, in step (1) and step (3), shown in described formula I, the concentration of the solution of polymer can be 0 ~ 20mg/mL, but is not 0, specifically can be 0.5 ~ 15mg/mL, 0.5mg/mL or 15mg/mL; Solvent can be any one in methyl alcohol, ethanol, isopropyl alcohol, acetone, oxolane, acetonitrile, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO) and DMF.
In the preparation method of above-mentioned organic solar batteries device, in step (1) and step (3), the rotating speed of described spin coating can be 500 ~ 10000rpm, specifically can be 1000 ~ 3000rpm, 1000rpm or 3000rpm.
In the preparation method of above-mentioned organic solar batteries device, described anode electrode layer is ITO conductive substrates or FTO conductive substrates; Described negative electrode layer is prepared by any one in calcium, magnesium, barium, aluminium, silver, gold, copper, nickel, zinc, titanium, manganese, iron, platinum and molybdenum; Described photoactive layer is photoactive layer to the composite membrane of body and photoactive layer acceptor; Described photoactive layer to body be polythiofuran derivative, polypara-phenylene vinylene derivative, containing benzo [1,2-b:4,5-b '] two thiophene units polymer or containing and the polymer of pyrroledione unit, specifically can be P3HT, PBDT-TS1, PTB7 or PDPP-3T; Described photoactive layer acceptor is fullerene and derivative thereof, specifically can be fullerene, [6,6]-phenyl C61 methyl butyrate, [6,6]-phenyl C71 methyl butyrate, containing the two addition fullerene derivative (ICBA) of indenes fullerene or indenes; The composite membrane forming described photoactive layer includes but not limited to: P3HT/PC 60bM, P3HT/PC 71bM, P3HT/ICBA, PBDT-TS1/PC 60bM, PBDT-TS1/PC 71bM, PBDT-TS1/ICBA, PTB7/PC 60bM, PTB7/PC 71bM, PTB7/ICBA, PDPP-3T/PC 60bM, PDPP-3T/PC 71bM, PDPP-3T/ICBA, PBT-1/PC 60bM, PBT-1/PC 71bM and PBT-1/ICBA etc.
The present invention has following beneficial effect:
In organic solar batteries device of the present invention, the anode interface layer used and cathode interface layer material can be commaterial (shown in formula I polymer), therefore, the preparation method of organic solar batteries device of the present invention, not only simplify optimizing process and the preparation technology of modifying interface layer material, and reduce the synthesis cost of material, preparation method is simple, thickness easily controls, and is applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the synthetic route of conjugated polymer PFS-PF.
Fig. 2 is the synthetic route of conjugated polymer PFS-Th.
Fig. 3 is the synthetic route of conjugated polymer PFS-biTh.
Fig. 4 is the synthetic route of conjugated polymer PFCA-PF.
Fig. 5 is the synthetic route of conjugated polymer PFCA-biTh.
Fig. 6 is the abosrption spectrogram of the conjugated polymer PFCA-biTh prepared.
Fig. 7 is the cyclic voltammetry curve of conjugated polymer PFCA-biTh.
Fig. 8 is the structural representation of organic solar batteries device of the present invention, and its Anodic is ito glass, and the first boundary layer represents anodic interface decorative layer, and second interface layer represents embellishing cathode interface layer.
Fig. 9 is the current-voltage curve of organic solar batteries device prepared by embodiment 1.
Figure 10 is the current-voltage curve of organic solar batteries device prepared by embodiment 2.
Figure 11 is the current-voltage curve of organic solar batteries device prepared by embodiment 3.
Figure 12 is the current-voltage curve of organic solar batteries device prepared by embodiment 4.
Figure 13 is the current-voltage curve of organic solar batteries device prepared by embodiment 5.
Figure 14 is the current-voltage curve of organic solar batteries device prepared by embodiment 6.
Figure 15 is the current-voltage curve of organic solar batteries device prepared by embodiment 7.
Embodiment
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation method of the conjugated polymer adopted in following embodiment is as follows:
(1) conjugated polymer PFS-PF is prepared:
Prepare conjugated polymer PFS-PF in accordance with the following steps, synthetic route as shown in Figure 1:
0.6122g9 is added, 9 '-propyl sulfonic acid sodium base-2,7-dibromo fluorenes, 0.6425g9,9 '-dioctyl-2,7-pinacol borate fluorenes, 25mgPd (PPh in 50mL bottle with two necks 3) 4, 2mLNa 2cO 3(2M) and 20mLDMF.Under argon atmospher, 95 DEG C are reacted 48 hours.After reaction terminates, system is poured in 1M hydrochloric acid and is stirred half an hour, separates out a large amount of solid.The solid obtained is dissolved in DMF, ether sedimentation, three times repeatedly.Finally obtain faint yellow fluffy solid 0.35g, productive rate 44%.Calculated value [C 48h 62o 6s 2]: C, 72.14; H, 7.82.Found:C, 66.19; H, 7.74.
(2) conjugated polymer PFS-Th is prepared
Prepare conjugated polymer PFS-Th in accordance with the following steps, synthetic route as shown in Figure 2:
0.3061g9 is added, 9 '-propyl sulfonic acid sodium base-2,7-dibromo fluorenes, the two tin of 0.2048g thiophene, 20mgPd (PPh in 50mL bottle with two necks 3) 4and 5mLDMF.Under argon atmospher, 95 DEG C are reacted 48 hours.After reaction terminates, system is poured in 1M hydrochloric acid and is stirred half an hour, separates out a large amount of solid.The solid obtained is dissolved in DMF, ether sedimentation, three times repeatedly.Finally obtain yellow green fluffy solid 0.076g, productive rate 31%.Calculated value [C 23h 24o 6s 3]: C, 56.08; H, 4.91. actual measured value C, 55.28; H, 6.32.
(3) conjugated polymer PFS-biTh is prepared
Prepare conjugated polymer PFS-biTh in accordance with the following steps, synthetic route as shown in Figure 3:
0.3061g9 is added, 9 '-propyl sulfonic acid sodium base-2,7-dibromo fluorenes, 0.2459g5,5 '-bis-tin trimethyl bithiophene, 20mgPd (PPh in 50mL bottle with two necks 3) 4, 10mLDMF.Under argon atmospher, 95 DEG C are reacted 48 hours.After reaction terminates, system is poured in the hydrochloric acid of 1M and is stirred half an hour, filters and obtains yellow orange solid.The solid obtained is dissolved in DMF, sedimentation in instillation ether.Solid sedimentation obtained is dissolved in DMF again, ether sedimentation, three times repeatedly.Finally obtain yellow fluffy solid 0.09g, productive rate 31%.Calculated value [C 27h 26o 6s 6]: C, 56.42; H, 4.56. actual measured value C, 56.01; H, 5.30.
(4) conjugated polymer PFCA-PF is prepared
Prepare conjugated polymer PFCA-PF in accordance with the following steps, synthetic route as shown in Figure 4:
0.1489g9 is added, 9 '-propyl group carboxylic acid group-2,7-dibromo fluorenes, 0.1476g9,9 '-dioctyl-2,7-pinacol borate fluorenes, 15mgPd (PPh in 50mL bottle with two necks 3) 4, 2mLNa 2cO 3(2M) and 6mLDMF.Under argon atmospher, 95 DEG C are reacted 48 hours.After reaction terminates, system is poured in 1M hydrochloric acid and is stirred half an hour, separates out a large amount of solid.The solid obtained is dissolved in DMF, ether sedimentation, three times repeatedly.Finally obtain yellow green fluffy solid 0.10g, productive rate 48%.Calculated value [C 50h 62o 4]: C, 82.60; H, 8.60.Found:C, 80.43; H, 8.12.
(5) conjugated polymer PFCA-biTh is prepared
Prepare conjugated polymer PFCA-biTh in accordance with the following steps, synthetic route as shown in Figure 5:
0.1489g9 is added, 9 '-propyl group carboxylic acid group-2,7-dibromo fluorenes, 0.1927g5,5 '-bis-tin trimethyl bithiophene, 15mgPd (PPh in 50mL bottle with two necks 3) 4, 7mLDMF.Under argon atmospher, 95 DEG C are reacted 48 hours.After reaction terminates, system is dissolved in DMF, sedimentation in instillation ether.Solid sedimentation obtained is dissolved in DMF again, ether sedimentation, three times repeatedly.Finally obtain yellow fluffy solid 0.07g, productive rate 43%.Calculated value [C 29h 26o 4s 2]: C, 69.30; H, 5.21. actual measured value C, 69.44; H, 5.68.
The absorption spectrum that polymer thing PFCA-biTh records under methyl alcohol and membrane stage is shown in Fig. 6, the optical band gap use experience formula (E of polymer g=1240/ λ absorb initial, wherein the absworption peak of PFCA-biTh in methyl alcohol is 436 nanometers, and the absorption maximum of film is in 460 nanometers, and ABSORPTION EDGE is in 495 nanometers, and optical band gap is 2.50eV.
The HOMO energy level of polymer is measured according to the method for Li Yongfang (Synth.Met.1999,99,243).By being dissolved in 1mL methyl alcohol at obtained polymer P FCA-biTh (1.0mg), then drip this solution to work electrode as on platinized platinum; Use 0.1mol/LBu 4nPF 6acetonitrile solution as electrolyte; Using platinum filament as to electrode; Filamentary silver is as reference electrode.Use electrochemical cyclic voltammetry to measure to carry out in this system.Repeat identical program to determine HOMO, the lumo energy of other polymer of the present invention.The cyclic voltammetric data of polymer P FCA-biTh prepared by the present embodiment are shown in shown in Fig. 7, and HOMO and lumo energy are respectively-5.15eV and-2.77eV.
Embodiment 1, prepare organic solar batteries device (comparative example)
Be the blended blended active layer solution being dissolved in dichloro-benzenes and preparing 15g/L of 1:1.5 with weight ratio by PBDT-TS1 and PCBM.Transparent ITO-substrate prepares polymer photovoltaics.Conventional anode modification layer PEDOT:PSS is spin-coated on ITO surface modify, the thickness using DektakXT film thickness gauge test PEDOT:PSS layer is 30nm.Then above-mentioned blended active layer solution spin coating thin layer, thickness is 100nm.Then the PFN methanol solution of spin coating 0.5mg/mL under the rotating speed of 3000rpm, obtains embellishing cathode interface layer.Finally, about 10 -4under the pressure of Pa, the thin layer of evaporation 80nm aluminium, obtains the polymer solar cell device of conventional structure, and its structural representation is as shown in Figure 8, lower same.
At filling N 2glove box in use AAA level solar simulator AM1.5G (100mW/cm 2) intensity under test.Described solar simulator uses the silion cell of Newport company of U.S. certification to correct.Current density voltage curve after test is shown in Fig. 9.Wherein open circuit voltage is 0.79V, and short circuit current is 16.5mA/cm 2, fill factor, curve factor is 64.5%, and energy conversion efficiency is 8.4%.
Embodiment 2, prepare organic solar batteries device (PFS-PF makes embellishing cathode interface layer)
Be the blended blended active layer solution being dissolved in dichloro-benzenes and preparing 15g/L of 1:1.5 with weight ratio by PBDT-TS1 and PCBM.Transparent ITO-substrate prepares polymer photovoltaics.Conventional anode modification layer PEDOT:PSS is spin-coated on ITO surface modify, the thickness using DektakXT film thickness gauge test PEDOT:PSS layer is 30nm.Then above-mentioned blended active layer solution spin coating thin layer, thickness is 100nm.Then the PFS-PF methanol solution of spin coating 0.5mg/mL under the rotating speed of 3000rpm, obtain embellishing cathode interface layer, thickness is 2nm.Finally, about 10 -4the thin layer of evaporation 80nm aluminium under the pressure of Pa, obtains the polymer solar cell device that PFS-PF makes embellishing cathode interface layer.
At filling N 2glove box in use AAA level solar simulator AM1.5G (100mW/cm 2) intensity under test.Described solar simulator uses the silion cell of Newport company of U.S. certification to correct.Current density voltage curve after test is shown in Figure 10.Wherein open circuit voltage is 0.79V, and short circuit current is 17.6mA/cm 2, fill factor, curve factor is 65.0%, and energy conversion efficiency is 9.1%.
Embodiment 3, prepare organic solar batteries device (PFS-biTh makes anodic interface decorative layer)
Be the blended blended active layer solution being dissolved in dichloro-benzenes and preparing 15g/L of 1:1.5 with weight ratio by PBDT-TS1 and PCBM.Transparent ITO-substrate prepares polymer photovoltaics.With the rotating speed of 1000rpm, the PFS-biTh methanol solution of 15mg/mL is spin-coated on ITO surface to modify, the thickness using DektakXT film thickness gauge test PFS-biTh layer is 7nm.Then above-mentioned blended active layer solution spin coating thin layer, thickness is 100nm.Then the PFN methanol solution of spin coating 0.5mg/mL under the rotating speed of 3000rpm, obtains embellishing cathode interface layer.Finally, about 10 -4the thin layer of evaporation 80nm aluminium under the pressure of Pa, obtains the polymer solar cell device that PFS-biTh makes anodic interface decorative layer.
At filling N 2glove box in use AAA level solar simulator AM1.5G (100mW/cm 2) intensity under test.Described solar simulator uses the silion cell of Newport company of U.S. certification to correct.Current density voltage curve after test is shown in Figure 11.Wherein open circuit voltage is 0.78V, and short circuit current is 16.4mA/cm 2, fill factor, curve factor is 66.5%, and energy conversion efficiency is 8.6%.
Embodiment 4, prepare organic solar batteries device (PFS-biTh makes anodic interface decorative layer)
Be the blended blended active layer solution being dissolved in dichloro-benzenes and preparing 15g/L of 1:1.5 with weight ratio by PTB7 and PCBM.Transparent ITO-substrate prepares polymer photovoltaics.With the rotating speed of 1000rpm, the PFS-biTh methanol solution of 15mg/mL is spin-coated on ITO surface to modify, the thickness using DektakXT film thickness gauge test PFS-biTh layer is 7nm.Then above-mentioned blended active layer solution spin coating thin layer, thickness is 100nm.Then, about 10 -4the thin layer of evaporation 80nm aluminium under the pressure of Pa, obtains the polymer solar cell device that PFS-biTh makes anodic interface decorative layer.
At filling N 2glove box in use AAA level solar simulator AM1.5G (100mW/cm 2) intensity under test.Described solar simulator uses the silion cell of Newport company of U.S. certification to correct.Current density voltage curve after test is shown in Figure 12.Wherein open circuit voltage is 0.68V, and short circuit current is 14.1mA/cm 2, fill factor, curve factor is 60.7%, and energy conversion efficiency is 5.8%.
Embodiment 5, prepare organic solar batteries device (PFS-biTh makes embellishing cathode interface layer)
Be the blended blended active layer solution being dissolved in dichloro-benzenes and preparing 15g/L of 1:1.5 with weight ratio by PBDT-TS1 and PCBM.Transparent ITO-substrate prepares polymer photovoltaics.Conventional anode modification layer PEDOT:PSS is spin-coated on ITO surface modify, the thickness using DektakXT film thickness gauge test PEDOT:PSS layer is 30nm.Then above-mentioned blended active layer solution spin coating thin layer, thickness is 100nm.Then the PFS-biTh methanol solution of spin coating 0.5mg/mL under the rotating speed of 3000rpm, obtain embellishing cathode interface layer, thickness is 2nm.Finally, about 10 -4the thin layer of evaporation 80nm aluminium under the pressure of Pa, obtains the polymer solar cell device that PFS-biTh makes embellishing cathode interface layer.
At filling N 2glove box in use AAA level solar simulator AM1.5G (100mW/cm 2) intensity under test.Described solar simulator uses the silion cell of Newport company of U.S. certification to correct.Current density voltage curve after test is shown in Figure 13.Wherein open circuit voltage is 0.78V, and short circuit current is 16.0mA/cm 2, fill factor, curve factor is 61.5%, and energy conversion efficiency is 7.7%.
Embodiment 6, prepare organic solar batteries device (PFS-biTh makes embellishing cathode interface layer)
Be the blended blended active layer solution being dissolved in dichloro-benzenes and preparing 15g/L of 1:1.5 with weight ratio by PTB7 and PCBM.Transparent ITO-substrate prepares polymer photovoltaics.Conventional anode modification layer PEDOT:PSS is spin-coated on ITO surface modify, the thickness using DektakXT film thickness gauge test PEDOT:PSS layer is 30nm.Then above-mentioned blended active layer solution spin coating thin layer, thickness is 100nm.Then the PFS-biTh methanol solution of spin coating 0.5mg/mL under the rotating speed of 3000rpm, obtain embellishing cathode interface layer, thickness is 2nm.Finally, about 10 -4the thin layer of evaporation 80nm aluminium under the pressure of Pa, obtains the polymer solar cell device that PFS-biTh makes embellishing cathode interface layer.
At filling N 2glove box in use AAA level solar simulator AM1.5G (100mW/cm 2) intensity under test.Described solar simulator uses the silion cell of Newport company of U.S. certification to correct.Current density voltage curve after test is shown in Figure 14.Wherein open circuit voltage is 0.73V, and short circuit current is 14.9mA/cm 2, fill factor, curve factor is 64.3%, and energy conversion efficiency is 7.0%.
Embodiment 7, preparation organic solar batteries device of the present invention (PFS-biTh makes anodic interface decorative layer and embellishing cathode interface layer simultaneously)
Be the blended blended active layer solution being dissolved in dichloro-benzenes and preparing 15g/L of 1:1.5 with weight ratio by PBDT-TS1 and PCBM.Transparent ITO-substrate prepares polymer photovoltaics.With the rotating speed of 1000rpm, the PFS-biTh methanol solution of 15mg/mL is spin-coated on ITO surface to modify, the thickness using DektakXT film thickness gauge test PFS-biTh layer is 7nm.Then above-mentioned blended active layer solution spin coating thin layer, thickness is 100nm.Then the PFS-biTh methanol solution of spin coating 0.5mg/mL under the rotating speed of 3000rpm, obtain embellishing cathode interface layer, thickness is 2nm.Finally, about 10 -4the thin layer of evaporation 80nm aluminium under the pressure of Pa, obtains the polymer solar cell device that PFS-biTh makes anodic interface decorative layer and embellishing cathode interface layer simultaneously.
At filling N 2glove box in use AAA level solar simulator AM1.5G (100mW/cm 2) intensity under test.Described solar simulator uses the silion cell of Newport company of U.S. certification to correct.Current density voltage curve after test is shown in Figure 15.Wherein open circuit voltage is 0.79V, and short circuit current is 16.1mA/cm 2, fill factor, curve factor is 62.3%, and energy conversion efficiency is 7.93%.

Claims (10)

1. an organic solar batteries device, it comprises the anode electrode layer, anodic interface decorative layer, photoactive layer, embellishing cathode interface layer and the negative electrode layer that connect successively, it is characterized in that: prepare described anodic interface decorative layer identical with the material of described embellishing cathode interface layer, and be polymer shown in formula I;
In formula I, A be selected from sulfonic group, sodium sulfonate group, potassium sulfonate base, Sulfonic Lithium base, sulfonic acid ammonium, sulfoamido, carboxylic acid group, carboxylic acid ester groups, carboxylic acid sodium base, carboxylic acid potassium base, carboxylic acid lithium base, carboxylic acid ammonium and amide groups any one; R is selected from the alkyl that carbon number is 1 ~ 12; Ar be selected from the following radicals not replacing or replace any one: monocycle arlydene, dicyclo arlydene, three rings and with the arlydene of pressed on ring, monocycle heteroarylidene, dicyclo heteroarylidene, three rings and with the heteroarylidene of pressed on ring, the group that formed by singly linked 2 ~ 6 arlydene; The repetitive number of n representation polymer is the natural number between 2 ~ 500.
2. organic solar batteries device according to claim 1, it is characterized in that: in formula I, R is selected from propyl group or butyl.
3. organic solar batteries device according to claim 1 and 2, is characterized in that: in formula I, Ar is following 1) or 2):
1) unsubstituted have independently selected from 1 ~ 6 heteroatomic monocycle of nitrogen, sulphur and selenium, dicyclo or three ring heteroarylidenes; What replace has 1 ~ 6 the heteroatomic monocycle, dicyclo or the three ring heteroarylidenes that are independently selected from nitrogen, sulphur and selenium, and wherein, Ar is optionally substituted to form ethylene two oxy together by two adjacent carbon atoms on phenyl, alkyl replacement or Ar group;
2) the monocycle heteroarylidene containing 1 ~ 4 nitrogen-atoms.
4. the organic solar batteries device according to any one of claim 1-3, is characterized in that: polymer shown in formula I be selected from following formula I-a, formula I-b, formula I-c, formula I-d and formula I-e any one:
Wherein, the repetitive number of n representation polymer is the natural number between 2 ~ 500.
5. the organic solar batteries device according to any one of claim 1-4, is characterized in that: the thickness of described anodic interface decorative layer is 0 ~ 30nm, but is not 0; The thickness of described embellishing cathode interface layer is 0 ~ 20nm, but is not 0.
6. the organic solar batteries device according to any one of claim 1-5, is characterized in that: described anode electrode layer is ITO conductive substrates or FTO conductive substrates;
Described negative electrode layer is prepared by any one in calcium, magnesium, barium, aluminium, silver, gold, copper, nickel, zinc, titanium, manganese, iron, platinum and molybdenum;
Described photoactive layer is photoactive layer to the composite membrane of body and photoactive layer acceptor; Described photoactive layer is any one in P3HT, PBDT-TS1, PTB7 and PDPP-3T to body; Described photoactive layer acceptor be fullerene, [6,6]-phenyl C61 methyl butyrate, [6,6]-phenyl C71 methyl butyrate, containing the two addition fullerene derivative of indenes fullerene or indenes.
7. the preparation method of organic solar batteries device according to any one of claim 1-6, comprises the steps:
(1) shown in the formula I on anode electrode layer in spin coating claim 1-4 in arbitrary described organic solar batteries device, the solution of polymer, prepares anodic interface decorative layer;
(2) on anodic interface decorative layer, photoactive layer is prepared;
(3) shown in the formula I that spin coating is identical with step (1) on photoactive layer, the solution of polymer, prepares embellishing cathode interface layer;
(4) on embellishing cathode interface layer, plate negative electrode layer, obtain described organic solar batteries device.
8. the preparation method of organic solar batteries device according to claim 7, is characterized in that: in step (1) and step (3), shown in described formula I, the concentration of the solution of polymer can be 0 ~ 20mg/mL, but is not 0; Solvent is any one in methyl alcohol, ethanol, isopropyl alcohol, acetone, oxolane, acetonitrile, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO) and DMF.
9. the preparation method of the organic solar batteries device according to claim 7 or 8, is characterized in that: in step (1) and step (3), the rotating speed of described spin coating is 500 ~ 10000rpm.
10. the preparation method of the organic solar batteries device according to any one of claim 7-9, is characterized in that: described anode electrode layer is ITO conductive substrates or FTO conductive substrates; Described negative electrode layer is prepared by any one in calcium, magnesium, barium, aluminium, silver, gold, copper, nickel, zinc, titanium, manganese, iron, platinum and molybdenum; Described photoactive layer is photoactive layer to the composite membrane of body and photoactive layer acceptor; Described photoactive layer is any one in P3HT, PBDT-TS1, PTB7 and PDPP-3T to body; Described photoactive layer acceptor be fullerene, [6,6]-phenyl C61 methyl butyrate, [6,6]-phenyl C71 methyl butyrate, containing the two addition fullerene derivative of indenes fullerene or indenes.
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