CN105470398B - Organic thin film solar cell based on tri compound cathode buffer layer and preparation method thereof - Google Patents
Organic thin film solar cell based on tri compound cathode buffer layer and preparation method thereof Download PDFInfo
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- CN105470398B CN105470398B CN201510833373.1A CN201510833373A CN105470398B CN 105470398 B CN105470398 B CN 105470398B CN 201510833373 A CN201510833373 A CN 201510833373A CN 105470398 B CN105470398 B CN 105470398B
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- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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Abstract
The invention discloses a kind of organic thin film solar cell based on tri compound cathode buffer layer and preparation method thereof, belong to organic semiconductor thin-film area of solar cell.Organic solar batteries provided by the invention use reciprocal form structure, are followed successively by substrate, transparent conductive cathode ITO, tri compound cathode buffer layer, photoactive layer, anode buffer layer, metal anode from top to bottom；The tri compound cathode buffer layer is that a certain proportion of alcohol-soluble copolymer and graphene oxide are mixed in zinc oxide.By mixing specific alcohol-soluble copolymer, electric transmission is reduced in active layer to transparent conductive cathode ITO potential barrier, reduces the contact resistance of cathode buffer layer and both active layers interface；And by mixing graphene oxide, add the electron mobility of cathode buffer layer.So as to improve the carrier transport efficiency of organic thin film solar cell and density of photocurrent, the series resistance of battery is reduced, improves the photoelectric transformation efficiency of device.
Description
Technical field
The invention belongs to organic polymer photovoltaic device or organic semiconductor thin-film area of solar cell, and in particular to one
Organic thin film solar cell of the kind based on tri compound cathode buffer layer.
Background technology
With the increase year by year of global energy requirements amount, the effective of regenerative resource is asked using as urgently to be resolved hurrily
Topic.Most of energy used in the world at present comes from the exploitation of fossil fuel, including oil, natural gas and coal etc..
However, these resources are limited.Accounting for the solar energy of earth gross energy more than 99% has inexhaustible, no dirt
The characteristics of dye, thus one of new energy developed and utilized as scientists from all over the world.At present, according to the light of composition solar cell
The difference of the material character of active layer, active layer material can be divided into inorganic semiconductor material and organic semiconducting materials.With
Inorganic semiconductor material is compared, and organic solar batteries not only have identical highest theoretical energy conversion efficiency, but also have
Have light weight, can water-laid film, specific character can be processed into flexible device is easily made, can even realize that all plastic etc. is notable
Advantage, oneself is through turning into one of focus researched and developed both at home and abroad at present.
However, compared with the large-scale production of inorganic solar cell, organic solar batteries are imitated due to its opto-electronic conversion
Rate is also relatively low, and its is practical also to need time.It is to improve organic photovoltaic cell photoelectricity to turn to prepare suitable cathode buffer layer
Change the effective ways of efficiency.Currently, by using reciprocal form structure, and using metal oxide such as ZnO, TiO2Equistability is stronger
Oxide be obviously improved as cathode buffer layer, the efficiency and stability of organic solar batteries.But due to
Energy level matches not enough between these oxide-coated cathode cushions and photoactive layer so that larger contact gesture therebetween be present
Build.Due to the presence of this contact berrier, the transmission for causing electronics is obstructed with separating, and causes device to possess larger interface and connect
Get an electric shock resistance and larger Carrier recombination probability, all by serious constraint device efficiency.And due to metal oxide such as ZnO, TiO2
Electron mobility Deng material is relatively low so that electronics produces compound when being diffused into electrode from active bed boundary, and be diffused into negative electrode
Electronics it is also less.
Therefore it is the key for improving organic solar batteries photoelectric transformation efficiency that how research, which optimizes and modify cushion,
It is the emphasis and difficult point of this current area research.
The content of the invention
Problem to be solved by this invention is：How a kind of transoid organic thin film solar cell and its preparation side are provided
Method, it is therefore an objective to by introducing a kind of organic thin film solar cell of tri compound cathode buffer layer, to realize：(1) device is reduced
Contact berrier between part cathode buffer layer and photoactive layer；(2) improve cathode buffer layer film morphology, reduce the series electrical of device
Resistance；(3) electron mobility is improved, improves shorted devices current density.
The technical scheme is that：
A kind of organic thin film solar cell based on tri compound cathode buffer layer, the solar cell use transoid knot
Structure, it is followed successively by from top to bottom：Substrate, transparent conductive cathode ITO, tri compound cathode buffer layer, photoactive layer, anode buffer layer
And metal anode；The tri compound cathode buffer layer is by zinc oxide, graphene oxide and alcohol-soluble copolymer is compound forms, and three
The mass ratio of person is：Zinc oxide 30%~40%, %~40% of alcohol-soluble copolymer 30, the % of the % of graphene oxide 20~40, ternary
Composite cathode buffer layer thickness scope is 20~40 nm.
Preferably, the alcohol-soluble copolymer is Poly (9,9-bis (3`- (N, N-dimethyl)-propyl-2,7-
fluorene)-alt-2,7-(9,9-dioctylfluorene))(PFN)。
Preferably, mixed solution system of the photoactive layer by electron donor material PTB7 and electron acceptor material PCBM
Standby to form, thickness range is 80~100 nm；PTB7 and PCBM mass percent is 1 in the mixed solution:2~2:1.
Preferably, the anode buffer layer material is MoO3, thickness range is 5~20 nm.
Preferably, the metal anode material is the one or more in Ag, Al or Cu, thickness range is 100~200
nm。
Preferably, the backing material is glass or transparent polymer, the transparent polymer material is polyethylene, gathered
Methyl methacrylate, makrolon, polyurethanes, polyimides, the one or more of vinyl chloride-vinyl acetate resin or polyacrylic acid.
A kind of preparation method of the organic thin film solar cell based on tri compound cathode buffer layer, device fabrication process
Comprise the following steps：
1) substrate being made up of transparent substrates and transparent conductive cathode ITO is cleaned, dried up after cleaning with nitrogen；
2) in transparent conductive cathode ITO surfaces rotary coating, printing or spraying incorporation zinc oxide, alcohol-soluble copolymer and oxygen
The compound of graphite alkene, and the film formed is toasted, tri compound cathode buffer layer is prepared；
3) using spin coating or spraying or self assembly or inkjet printing or silk-screen printing on tri compound cathode buffer layer
Mode prepares PTB7:PCBM photoactive layers；
4) anode buffer layer MoO is deposited on active layer3；
5) the evaporation metal anode on anode buffer layer.
Preferably, the zinc oxide, alcohol-soluble copolymer and graphene oxide compound are prepared in the following ways：Institute
State burnett's solution to be made for zinc acetate precursor solution is annealed, concentration is 0.1~1 g/ml；The alcohol-soluble copolymer
In PFN solution, solvent is the mixed solution of methanol and glacial acetic acid, and its volume ratio composition is the % of methanol 99, glacial acetic acid 1 %, described
Concentration of the PFN in mixed solution is 0.2~5 mg/ml；The graphene oxide be graphene oxide aqueous dispersions prepare and
Into concentration is 1~5 mg/ml.
The advantage of the invention is that：
1st, by introducing water alcohol solubility copolymer, the contact gesture between cathode buffer layer and photoactive layer is significantly reduced
Build, so as to improve carrier transport efficiency.
2nd, by introducing the graphene oxide of high electron mobility, the series resistance of device is significantly reduced, is reduced
Electronics cathode buffer layer/photoactive layer interface recombination probability and electric transmission to negative electrode quantity.
3rd, Ohmic contact is formd in cathode buffer layer/photoactive layer interface, so as to improve the transmission speed of electronics,
Increase the short-circuit current density of device.
Brief description of the drawings
Fig. 1 is a kind of structure based on tri compound cathode buffer layer organic thin film solar cell involved in the present invention
Schematic diagram, it is followed successively by from top to bottom：Substrate（1）；Transparent conductive cathode ITO（2）；Tri compound cathode buffer layer（3）；Photolytic activity
Layer（4）；5 anode buffer layers（5）；Metal anode（6）.
Embodiment：
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.
Embodiment 1：
The substrate that transparent substrates 1 and transparent conductive cathode ITO 2 is made up of of the surface roughness less than 1 nm is carried out
Cleaning, is dried up after cleaning with nitrogen；In the surface rotary coatings of transparent conductive cathode ITO 2 by zinc oxide, alcohol-soluble copolymer, oxygen
The tri compound cathode buffer layer 3 (5000 rpm, 40 s, 15 nm) of graphite alkene composition, its mass ratio composition is zinc oxide
30 %, the % of alcohol-soluble copolymer 30, graphene oxide 40%, and the film formed is toasted (200 DEG C, 60 min)；
PTB7 is prepared using spin coating on tri compound cathode buffer layer 3:PCBM(1:1.5,10 mg/ml) photoactive layer 4 (1200
Rpm, 40 s), dries two hours under nitrogen atmosphere；Anode is prepared in the surface of photoactive layer 4 evaporation MoO3 (15 nm) to delay
Rush layer 5；Evaporation metal anode 6Ag (100 nm) on anode buffer layer 5.Under standard test condition：AM 1.5, 100 mW/
Cm2, measures open-circuit voltage (VOC)=0.70 V of device, short circuit current (JSC)=12.41 mA/cm2, and fill factor, curve factor (FF)=
0.61, photoelectric transformation efficiency (PCE)=5.20 %.
Embodiment 2：
The substrate that transparent substrates 1 and transparent conductive cathode ITO 2 is made up of of the surface roughness less than 1 nm is carried out
Cleaning, is dried up after cleaning with nitrogen；In the surface rotary coatings of transparent conductive cathode ITO 2 by zinc oxide, alcohol-soluble copolymer, oxygen
The tri compound cathode buffer layer 3 (5000 rpm, 40 s, 15 nm) of graphite alkene composition, its mass ratio composition is zinc oxide
40 %, the % of alcohol-soluble copolymer 40, graphene oxide 20%, and the film formed is toasted (200 DEG C, 60 min)；
PTB7 is prepared using spin coating on tri compound cathode buffer layer 3:PCBM(1:1.5,10 mg/ml) photoactive layer 4 (1200
Rpm, 40s), two hours are dried under nitrogen atmosphere；Anode buffer is prepared in the surface of photoactive layer 4 evaporation MoO3 (15 nm)
Layer 6；Evaporation metal anode 6Ag (100 nm) on anode buffer layer 5.Under standard test condition：AM 1.5, 100 mW/
Cm2, measures open-circuit voltage (VOC)=0.72 V of device, short circuit current (JSC)=13.51 mA/cm2, and fill factor, curve factor (FF)=
0.62, photoelectric transformation efficiency (PCE)=6.02 %.
Embodiment 3：
The substrate that transparent substrates 1 and transparent conductive cathode ITO 2 is made up of of the surface roughness less than 1 nm is carried out
Cleaning, is dried up after cleaning with nitrogen；In the surface rotary coatings of transparent conductive cathode ITO 2 by zinc oxide, alcohol-soluble copolymer, oxygen
The tri compound cathode buffer layer 3 (5000 rpm, 40 s, 15 nm) of graphite alkene composition, its mass ratio composition is zinc oxide
30 %, the % of alcohol-soluble copolymer 40, graphene oxide 30%, and the film formed is toasted (200 DEG C, 60 min)；
PTB7 is prepared using spin coating on tri compound cathode buffer layer 3:PCBM(1:1.5,10 mg/ml) photoactive layer 4 (1200
Rpm, 40 s), dries two hours under nitrogen atmosphere；Anode is prepared in the surface of photoactive layer 4 evaporation MoO3 (15 nm) to delay
Rush layer 5；Evaporation metal anode 6Ag (100 nm) on anode buffer layer 5.Under standard test condition：AM 1.5, 100 mW/
Cm2, measures open-circuit voltage (VOC)=0.71 V of device, short circuit current (JSC)=13.1 mA/cm2, and fill factor, curve factor (FF)=
0.55, photoelectric transformation efficiency (PCE)=5.12 %.
Embodiment 4：
The substrate that transparent substrates 1 and transparent conductive cathode ITO 2 is made up of of the surface roughness less than 1 nm is carried out
Cleaning, is dried up after cleaning with nitrogen；In the surface rotary coatings of transparent conductive cathode ITO 2 by zinc oxide, alcohol-soluble copolymer, oxygen
The tri compound cathode buffer layer 3 (5000 rpm, 40 s, 15 nm) of graphite alkene composition, its mass ratio composition is zinc oxide
40 %, the % of alcohol-soluble copolymer 30, graphene oxide 30%, and the film formed is toasted (200 DEG C, 60 min)；
PTB7 is prepared using spin coating on tri compound cathode buffer layer 3:PCBM(1:1.5,10 mg/ml) photoactive layer 4 (1200
Rpm, 40 s), dries two hours under nitrogen atmosphere；Anode is prepared in the surface of photoactive layer 4 evaporation MoO3 (15 nm) to delay
Rush layer 5；Evaporation metal anode 6Ag (100 nm) on anode buffer layer 5.Under standard test condition：AM 1.5, 100 mW/
Cm2, measures open-circuit voltage (VOC)=0.73 V of device, short circuit current (JSC)=12.54 mA/cm2, and fill factor, curve factor (FF)=
0.58, photoelectric transformation efficiency (PCE)=5.30 %.
Embodiment 5：
The substrate that transparent substrates 1 and transparent conductive cathode ITO 2 is made up of of the surface roughness less than 1 nm is carried out
Cleaning, is dried up after cleaning with nitrogen；In the surface rotary coatings of transparent conductive cathode ITO 2 by zinc oxide, alcohol-soluble copolymer, oxygen
The tri compound cathode buffer layer 3 (5000 rpm, 40 s, 15 nm) of graphite alkene composition, its mass ratio composition is zinc oxide
35 %, the % of alcohol-soluble copolymer 35, graphene oxide 30%, and the film formed is toasted (200 DEG C, 60 min)；
PTB7 is prepared using spin coating on tri compound cathode buffer layer 3:PCBM(1:1.5,10 mg/ml) photoactive layer 4 (1200
Rpm, 40s), two hours are dried under nitrogen atmosphere；Anode buffer is prepared in the surface of photoactive layer 4 evaporation MoO3 (15 nm)
Layer 5；Evaporation metal anode 6Ag (100 nm) on anode buffer layer 5.Under standard test condition：AM 1.5, 100 mW/
Cm2, measures open-circuit voltage (VOC)=0.70 V of device, short circuit current (JSC)=12.11 mA/cm2, and fill factor, curve factor (FF)=
0.60, photoelectric transformation efficiency (PCE)=4.36 %.
Embodiment 6：
The substrate that transparent substrates 1 and transparent conductive cathode ITO 2 is made up of of the surface roughness less than 1 nm is carried out
Cleaning, is dried up after cleaning with nitrogen；In the surface rotary coatings of transparent conductive cathode ITO 2 by zinc oxide, alcohol-soluble copolymer, oxygen
The tri compound cathode buffer layer 3 (5000 rpm, 40 s, 15 nm) of graphite alkene composition, its mass ratio composition is zinc oxide
35 %, the % of alcohol-soluble copolymer 40, graphene oxide 25%, and the film formed is toasted (200 DEG C, 60 min)；
PTB7 is prepared using spin coating on tri compound cathode buffer layer 3:PCBM(1:1.5,10 mg/ml) photoactive layer 4 (1200
Rpm, 40 s), dries two hours under nitrogen atmosphere；Anode is prepared in the surface of photoactive layer 4 evaporation MoO3 (15 nm) to delay
Rush layer 5；Evaporation metal anode 6Ag (100 nm) on anode buffer layer 5.Under standard test condition：AM 1.5, 100 mW/
Cm2, measures open-circuit voltage (VOC)=0.73 V of device, short circuit current (JSC)=12.81 mA/cm2, and fill factor, curve factor (FF)=
0.63, photoelectric transformation efficiency (PCE)=5.89 %.
Embodiment 7：
The substrate that transparent substrates 1 and transparent conductive cathode ITO 2 is made up of of the surface roughness less than 1 nm is carried out
Cleaning, is dried up after cleaning with nitrogen；In the surface rotary coatings of transparent conductive cathode ITO 2 by zinc oxide, alcohol-soluble copolymer, oxygen
The tri compound cathode buffer layer 3 (5000 rpm, 40 s, 15 nm) of graphite alkene composition, its mass ratio composition is zinc oxide
40 %, the % of alcohol-soluble copolymer 35, the % of graphene oxide 25, and the film formed toasted (200 DEG C, 60
min)；PTB7 is prepared using spin coating on tri compound cathode buffer layer 3:PCBM(1:1.5,10 mg/ml) photoactive layer 4
(1200 rpm, 40 s), dries two hours under nitrogen atmosphere；Prepared in the surface of photoactive layer 4 evaporation MoO3 (15 nm)
Anode buffer layer 5；Evaporation metal anode 6Ag (100 nm) on anode buffer layer 5.Under standard test condition：AM 1.5,
100 mW/cm2, measure open-circuit voltage (VOC)=0.72 V of device, short circuit current (JSC)=13.54 mA/cm2, fill factor, curve factor
(FF)=0.62, photoelectric transformation efficiency (PCE)=6.04 %.
The present invention is illustrated by above-described embodiment, but it is to be understood that, above-described embodiment is only intended to
Citing and the purpose of explanation, and be not intended to limit the invention in described scope of embodiments.In addition people in the art
Member can also make more kinds of it is understood that the invention is not limited in above-described embodiment according to the teachings of the present invention
Variants and modifications, these variants and modifications are all fallen within scope of the present invention.Protection scope of the present invention by
The appended claims and its equivalent scope are defined.
Claims (8)
- A kind of 1. organic thin film solar cell based on tri compound cathode buffer layer, it is characterised in that the solar cell Using reciprocal form structure, it is followed successively by from top to bottom：Substrate, transparent conductive cathode ITO, tri compound cathode buffer layer, photoactive layer, Anode buffer layer and metal anode；The tri compound cathode buffer layer is by zinc oxide, graphene oxide and alcohol-soluble copolymer Compound composition, mass ratio of the three in material solution are：Zinc oxide 30%~40%, %~40% of alcohol-soluble copolymer 30, The % of the % of graphene oxide 20~40, tri compound cathode buffer layer thickness range is 20~40 nm.
- 2. a kind of organic thin film solar cell based on tri compound cathode buffer layer according to claim 1, it is special Sign is, the alcohol-soluble copolymer be Poly (9,9-bis (3`- (N, N-dimethyl)-propyl-2,7-fluorene)- alt-2,7-(9,9-dioctylfluorene))(PFN)。
- 3. a kind of organic thin film solar cell based on tri compound cathode buffer layer according to claim 1, it is special Sign is that the photoactive layer is prepared by electron donor material PTB7 and electron acceptor material PCBM mixed solution, thick Degree scope is 80~100 nm；PTB7 and PCBM mass percent is 1 in the mixed solution:2~2:1.
- 4. a kind of organic thin film solar cell based on tri compound cathode buffer layer according to claim 1, it is special Sign is that the anode buffer layer material is MoO3, thickness range is 5~20 nm.
- 5. a kind of organic thin film solar cell based on tri compound cathode buffer layer according to claim 1, it is special Sign is that the metal anode material is the one or more in Ag, Al or Cu, and thickness range is 100~200 nm.
- 6. a kind of organic thin film solar cell based on tri compound cathode buffer layer according to claim 1, it is special Sign is that the backing material is glass or transparent polymer, and the transparent polymer material is polyethylene, polymethylacrylic acid Methyl esters, makrolon, polyurethanes, polyimides, the one or more of vinyl chloride-vinyl acetate resin or polyacrylic acid.
- A kind of 7. electricity of the organic thin film solar based on tri compound cathode buffer layer according to claim any one of 1-6 The preparation method in pond, it is characterised in that comprise the following steps：(1) substrate being made up of transparent substrates and transparent conductive cathode ITO is cleaned, dried up after cleaning with nitrogen；(2) in transparent conductive cathode ITO surfaces rotary coating, printing or spraying incorporation zinc oxide, alcohol-soluble copolymer and oxidation The compound of graphene, and the film formed is toasted, tri compound cathode buffer layer is prepared；(3) on tri compound cathode buffer layer by the way of spin coating or spraying or self assembly or inkjet printing or silk-screen printing Prepare PTB7:PCBM photoactive layers；(4) anode buffer layer MoO is deposited on active layer3；(5) the evaporation metal anode on anode buffer layer.
- 8. the preparation side of the organic thin film solar cell according to claim 7 based on tri compound cathode buffer layer Method, it is characterised in that zinc oxide, alcohol-soluble copolymer and graphene oxide compound are prepared in the following ways：The oxidation Zinc solution is made for zinc acetate precursor solution is annealed, and concentration is 0.1~1 g/ml；The alcohol-soluble copolymer p FN solution In, solvent is the mixed solution of methanol and glacial acetic acid, and its volume ratio composition is the % of methanol 99, and glacial acetic acid 1 %, the PFN are mixed The concentration closed in solution is 0.2~5 mg/ml；The graphene oxide is that graphene oxide aqueous dispersions are prepared, concentration For 1~5 mg/ml.
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| CN106784331B (en) * | 2017-01-12 | 2018-10-09 | 吉林大学 | A kind of lamination cathode buffer layer organic polymer solar cell and preparation method thereof |
| CN106601916B (en) * | 2017-01-24 | 2018-11-27 | 吉林大学 | Organic solar batteries and preparation method thereof based on hetero-junctions cathode buffer layer |
| CN109233440A (en) * | 2017-05-03 | 2019-01-18 | 上海幂方电子科技有限公司 | A kind of buffer layer ink preparing organic semiconductor device for solwution method |
| CN109390475A (en) * | 2017-08-02 | 2019-02-26 | Tcl集团股份有限公司 | A kind of QLED device |
| CN110459684B (en) * | 2019-08-26 | 2021-03-09 | 电子科技大学 | Organic solar cell preparation method based on double-solvent sol-gel ZnO cathode buffer layer |
| KR102329624B1 (en) * | 2020-04-24 | 2021-11-22 | 부경대학교 산학협력단 | Polymer solar cell having cathode buffer layer including acid derivative modified conjugate polymer electrolyte |
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