CN110379927A - A kind of organic photovoltaic cell and preparation method thereof - Google Patents
A kind of organic photovoltaic cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of organic photovoltaic cells and preparation method thereof while guaranteeing open-circuit voltage with higher-energy transfer efficiency.The organic photovoltaic cell includes photoactive layer, which includes electron donor and non-fullerene electron acceptor, and electron donor PCE-10, non-fullerene electron acceptor is IEICO-4F and IT-M.The present invention uses the third component as photoactive layer IT-M more broader than original receptor component band gap.On the one hand, the addition of IT-M enhances light absorption in a certain range while guaranteeing the light absorption range of 300-1000nm；On the other hand, IT-M has proper energy level, can make up for it in duel cell to band gap difference between receptor it is excessive caused by open-circuit voltage it is too low；Open-circuit voltage is increased while guaranteeing that organic photovoltaic cell short-circuit current density improves to realize, significantly improves energy conversion efficiency.
Description
Technical field
The present invention relates to photovoltaic cell technical fields, more particularly, to a kind of organic photovoltaic cell and preparation method thereof.
Background technique
The photoactive layer of traditional organic photovoltaic cell is a kind of by electron donor and a kind of binary that electron acceptor forms
Blend film (binary organic photovoltaic cell).But since organic electron donor and electron acceptor have discrete energy level knot
Structure limits battery to the absorption of sunlight so that binary blend film is difficult to obtain wide and strong spectral absorption range, short
Road current density can not be with inorganic solar cell (such as monocrystalline silicon and polysilicon sun electricity with continuous energy level structure (energy band)
Pond) it compares favourably.For this purpose, people add the third group complementary with original binary blend film absorption in binary organic photovoltaic cell
Point, the photoelectric respone spectrum of the ternary organic photovoltaic cell made is widened, or originally absorbs the absorbing ability of weak spectral coverage
Enhancing, so that short-circuit current density increases, energy conversion efficiency (PCE) also has a certain upgrade.
Therefore, constructing ternary battery is to improve that organic photovoltaic cell PCE is simple and effective method.But current ternary
Battery to the improvement degree of photovoltaic performance also than relatively limited, especially in the improvement of open-circuit voltage.Reason for that is have
The active layer pattern of machine solar cell, including nanoscale phase separation structure and through the charge transmission channel etc. of entire active layer,
Its photovoltaic performance is played a crucial role.Third component is added in binary blend film, be easy to cause original good shape
The destruction of looks, influences the generation and transmission of photogenerated charge, to limit the promotion amplitude of battery short circuit current density and efficiency.
On the other hand, in order to widen light absorption range, researcher can attempt the material that narrow band gap is added in duel cell, for example,
Near-infrared has the material absorbed by force.But it finds in an experiment, while short circuit current obtains significant increase, due to narrow band gap material
Material can will certainly make the open-circuit voltage of battery too low along with the raising of HOMO energy level or the reduction of lumo energy.If root
According to existing design principle selection low bandgap material to adjust, having, which greatly may only will continue to, reduces open-circuit voltage, or even meeting
Short circuit current is impacted.It is therefore desirable to provide one kind to have higher-energy conversion while guaranteeing open-circuit voltage
The organic photovoltaic cell of efficiency.
Summary of the invention
The technical problem to be solved by the present invention is to how provide one kind to have higher energy while guaranteeing open-circuit voltage
Measure the organic photovoltaic cell and preparation method thereof of transfer efficiency.
According to the first aspect of the invention, the present invention provides a kind of organic photovoltaic cell, according to an embodiment of the invention,
The organic photovoltaic cell includes photoactive layer, which includes electron donor and non-fullerene electron acceptor, electron donor
For PCE-10, non-fullerene electron acceptor is IEICO-4F and IT-M.
Wherein, shown in the structural formula of PCE-10 such as formula (I):
N >=10, R1For
Shown in the structural formula of IEICO-4F such as formula (II):
R is C6H13；
Shown in the structural formula of IT-M such as formula (III):
According to an embodiment of the invention, the weight ratio of electron donor and non-fullerene electron acceptor is 1.5:(1-2.25).
According to an embodiment of the invention, the weight of IT-M accounts for the 5-20% of the weight of non-fullerene electron acceptor.
According to an embodiment of the invention, the organic photovoltaic cell includes the substrate layer, cathode layer, electron-transport set gradually
Layer, photoactive layer, hole transmission layer, anode layer.
According to an embodiment of the invention, photoactive layer with a thickness of 50-300nm.
The photoactive layer of the preparation method of above-mentioned organic photovoltaic cell, organic photovoltaic cell is made by following steps:
Electron donor, non-fullerene electron acceptor, solvent and solvent additive is taken to be prepared into photoactive layer solution, coating system
Film.
The solvent additive added in photoactive layer solution is big in solvent by possessing different rate of volatilizations from solvent
After amount volatilization, the relative quantity of solvent additive is quicklyd increase, and the solubility comparison of electron donor and electron acceptor changes, from
And the pattern of formation is remolded, so that the energy conversion efficiency of battery is improved.The solvent addition added in the present invention
Agent can be at least one of aromatic additives, non-aromatic additive.Its non-limiting example can be 1,8- pungent two
Mercaptan (ODT), 1,8- diiodo-octane (DIO), 1- chloronaphthalene (1-CN) and diphenyl ether (DPE).
According to an embodiment of the invention, solvent additive is selected from least one of 1- chloronaphthalene, 1,8- diiodo-octane.
According to an embodiment of the invention, the volume of solvent additive is the 0.5-4% of the volume of photoactive layer solution.
According to an embodiment of the invention, further including annealing, annealing temperature is 80-100 DEG C, annealing time 5-
40min。
Annealing can effectively remove remaining additive, be more clear the interface of receptor, not only increase battery
Performance, also improve its thermal stability.
The beneficial effects of the present invention are:
PCE-10:IEICO-4F is a kind of representative non-fullerene material system, body in organic photovoltaic cell
Tying up to has huge application potential in solar cell, but in order to further enhance its energy conversion efficiency, existing method is past
Keep its open-circuit voltage too low in turn toward low bandgap material can be added, and this programme is using IT-M more broader than original receptor component band gap
Third component as photoactive layer.On the one hand, the addition of IT-M enhances while guaranteeing the light absorption range of 300-1000nm
Light absorption in a certain range；On the other hand, IT-M have proper energy level, can make up for it in duel cell to by
Open-circuit voltage is too low caused by band gap difference is excessive between body；Guarantee organic photovoltaic cell short-circuit current density to realize
Open-circuit voltage is increased while raising, significantly improves energy conversion efficiency.Compared with the laminated cell of ternary material, greatly
Process flow is simplified, the success rate of preparation is improved.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the organic photovoltaic cell of one embodiment of the present of invention.
Fig. 2 is the energy level signal of the electron donor and non-fowler electron acceptor of the photoactive layer of one embodiment of the present of invention
Figure.
Fig. 3 is the current -voltage curve figure of the organic photovoltaic cell comparative experiments of another embodiment of the invention.
Specific embodiment
It is carried out below with reference to technical effect of the embodiment to design of the invention, specific structure and generation clear, complete
Ground description, to be completely understood by the purpose of the present invention, feature and effect.Obviously, described embodiment is of the invention one
Section Example, rather than whole embodiments, based on the embodiment of the present invention, those skilled in the art are not paying creativeness
Other embodiments obtained, belong to the scope of protection of the invention under the premise of labour.
Embodiment 1
Fig. 1 is the structural schematic diagram of the organic photovoltaic cell of one embodiment of the present of invention, as shown in Figure 1, the battery is
Inverted structure, from top to bottom respectively substrate layer 1, cathode layer 2, electron transfer layer 3, photoactive layer 4, hole transmission layer 5, anode
Layer 6.In the present embodiment, substrate layer 1 is glass, and cathode layer 2 is tin indium oxide semiconductor, and electron transfer layer 3 is ZnO material, light
Active layer 4 is PCE-10:IEICO-4F:IT-M, and hole transmission layer 5 is MoO3, anode layer 6 is Al.
The organic photovoltaic cell the preparation method is as follows:
(1) it successively uses acetone, deionized water, dehydrated alcohol to be cleaned by ultrasonic the ito glass purchased, is placed in 80 DEG C of baking ovens and dries
It does spare.Before starting experiment, ito glass is placed in plasma processor and handles 30s, it is then that the zinc acetate prepared is molten
Liquid is spin-coated on ITO, 200 DEG C of annealing 1h, its complete hydrolysis is made to produce zinc oxide film.
(2) by polymer-electronics donor material PCE-10 and non-fullerene electron acceptor material IEICO-4F, IT-M claim in
It in clean vial, is transferred in nitrogen glove box, adds chlorobenzene and 1% chloronaphthalene is dissolved into certain density photoactive layer solution
(the weight accounting of IT-M is 5% in receptor).In nitrogen glove box, one layer of active layer material (its PCE- of spin coating in ZnO layer
10, IEICO-4F, IT-M ratio are (1:1.425:0.075).It is 1 × 10 in vacuum degree-4In the vacuum coating equipment of mbar, vapor deposition
Molybdenum trioxide and aluminium electrode.
The final structure that obtains is ITO/ZnO/PCE-10:IEICO-4F:IT-M/MoO3The inversion photovoltaic device of/Al.It is all
Preparation process carries out in the glove box for providing nitrogen inert atmosphere.
Fig. 2 is the energy level schematic diagram of the electron donor of photoactive layer and non-fowler electron acceptor in the present invention.Such as Fig. 2 institute
Show, in the present embodiment on the basis of the system of PCE-10:IEICO-4F, using IT-M conduct more broader than original receptor component band gap
The third component of photoactive layer.The addition of IT-M enhances while guaranteeing the light absorption range of 300-1000nm in a certain range
Interior light absorption；In addition, IT-M has proper energy level, can make up for it in duel cell to band gap difference mistake between receptor
Open-circuit voltage is too low caused by big；It is increased while guaranteeing that organic photovoltaic cell short-circuit current density improves to realize
Open-circuit voltage significantly improves energy conversion efficiency.
Embodiment 2
A kind of organic photovoltaic cell, the difference from embodiment 1 is that, it is different to the ratio of acceptor material in photoactive layer,
It is specific the preparation method is as follows:
(1) it successively uses acetone, deionized water, dehydrated alcohol to be cleaned by ultrasonic the ito glass purchased, is placed in 80 DEG C of baking ovens and dries
It does spare.Before starting experiment, ito glass is placed in plasma processor and handles 30s, it is then that the zinc acetate prepared is molten
Liquid is spin-coated on ITO, 200 DEG C of annealing 1h, its complete hydrolysis is made to produce zinc oxide film.
(2) by polymer-electronics donor material PCE-10 and non-fullerene electron acceptor material IEICO-4F, IT-M claim in
It in clean vial, is transferred in nitrogen glove box, adds chlorobenzene and 1% chloronaphthalene is dissolved into certain density active layer solution
(the weight accounting of IT-M is 8% in receptor).In nitrogen glove box, one layer of active layer material (its PCE- of spin coating in ZnO layer
10, IEICO-4F, IT-M ratio are (1:1.38:0.12).It is 1 × 10 in vacuum degree-4In the vacuum coating equipment of mbar, vapor deposition three
Molybdenum oxide and aluminium electrode.
The final structure that obtains is ITO/ZnO/PCE-10:IEICO-4F:IT-M/MoO3The inversion photovoltaic device of/Al.It is all
Preparation process carries out in the glove box for providing nitrogen inert atmosphere.
Embodiment 3
A kind of organic photovoltaic cell, the difference from embodiment 1 is that, it is different to the ratio of acceptor material in photoactive layer,
It is specific the preparation method is as follows:
(1) it successively uses acetone, deionized water, dehydrated alcohol to be cleaned by ultrasonic the ito glass purchased, is placed in 80 DEG C of baking ovens and dries
It does spare.Before starting experiment, ito glass is placed in plasma processor and handles 30s, it is then that the zinc acetate prepared is molten
Liquid is spin-coated on ITO, 200 DEG C of annealing 1h, its complete hydrolysis is made to produce zinc oxide film.
(2) by polymer-electronics donor material PCE-10 and non-fullerene electron acceptor material IEICO-4F, IT-M claim in
It in clean vial, is transferred in nitrogen glove box, adds chlorobenzene and 1% chloronaphthalene is dissolved into certain density active layer solution
(the weight accounting of IT-M is 10% in receptor).In nitrogen glove box, one layer of active layer material (its of spin coating in ZnO layer
PCE-10, IEICO-4F, IT-M ratio are (1:1.35:0.15).It is 1 × 10 in vacuum degree-4In the vacuum coating equipment of mbar, steam
Plate molybdenum trioxide and aluminium electrode.
The final structure that obtains is ITO/ZnO/PCE-10:IEICO-4F:IT-M/MoO3The inversion photovoltaic device of/Al.It is all
Preparation process carries out in the glove box for providing nitrogen inert atmosphere.
Embodiment 4
A kind of organic photovoltaic cell, the difference from embodiment 1 is that, it is different to the ratio of acceptor material in photoactive layer,
It is specific the preparation method is as follows:
(1) it successively uses acetone, deionized water, dehydrated alcohol to be cleaned by ultrasonic the ito glass purchased, is placed in 80 DEG C of baking ovens and dries
It does spare.Before starting experiment, ito glass is placed in plasma processor and handles 30s, it is then that the zinc acetate prepared is molten
Liquid is spin-coated on ITO, 200 DEG C of annealing 1h, its complete hydrolysis is made to produce zinc oxide film.
(2) by polymer-electronics donor material PCE-10 and non-fullerene electron acceptor material IEICO-4F, IT-M claim in
It in clean vial, is transferred in nitrogen glove box, adds chlorobenzene and 1% chloronaphthalene is dissolved into certain density active layer solution
(the weight accounting of IT-M is 20% in receptor).In nitrogen glove box, one layer of active layer material (its of spin coating in ZnO layer
PCE-10, IEICO-4F, IT-M ratio are (1:1.2:0.3).It is 1 × 10 in vacuum degree-4In the vacuum coating equipment of mbar, vapor deposition
Molybdenum trioxide and aluminium electrode.
The final structure that obtains is ITO/ZnO/PCE-10:IEICO-4F:IT-M/MoO3The inversion photovoltaic device of/Al.It is all
Preparation process carries out in the glove box for providing nitrogen inert atmosphere.
Embodiment 5
Comparative experiments
Comparative example 1: the difference with embodiment 1 is only that photoactive layer material uses PCE-10 and IEICO-4F, weight
Than for 1:1.5.
Organic photovoltaic cell made from embodiment 1-4 and comparative example 1 is chosen respectively, under a standard solar irradiation
(100Mw/cm2, AM1.5 spectrum), its I-E characteristic is measured by Keithley2400 Current Voltage source, as a result such as Fig. 3
It is shown.Fig. 3 is the current -voltage curve figure of the organic photovoltaic cell comparative experiments of another embodiment of the invention.Such as Fig. 3 institute
Show, is 0.5-0.6mA/cm with current density2It is embodiment 4, embodiment 1, embodiment 2, reality respectively from top to bottom for section
Apply the current -voltage curve of example 3 and comparative example 1.The parameter such as table 1 of each organic photovoltaic cell is obtained according to the curve:
1. organic photovoltaic cell contrast and experiment of table
| Short-circuit current density (mA/cm2) | Open-circuit voltage (V) | Fill factor (%) | Transfer efficiency (%) | |
| Embodiment 1 | 23.33 | 0.709 | 60.79 | 10.06 |
| Embodiment 2 | 24.34 | 0.74 | 57.00 | 10.36 |
| Embodiment 3 | 24.88 | 0.74 | 58.62 | 10.79 |
| Embodiment 4 | 23.40 | 0.74 | 56.00 | 9.7 |
| Comparative example 1 | 22.38 | 0.709 | 60.38 | 9.59 |
It can be seen that compared with comparative example 1 from above-mentioned experimental result, embodiment 1 is effectively promoting energy conversion efficiency
On the basis of, it can guarantee that open-circuit voltage is unlikely to too low；And embodiment 2-4 then further can increase simultaneously open-circuit voltage simultaneously
And effectively promoted energy conversion efficiency, compared with the prior art in cause open-circuit voltage mistake while promoting energy conversion efficiency
Low is a huge promotion.
It is to be illustrated to presently preferred embodiments of the present invention, but the present invention is not limited to the embodiment above,
Those skilled in the art can also make various equivalent deformation or replacement on the premise of without prejudice to spirit of the invention, this
Equivalent deformation or replacement are all included in the scope defined by the claims of the present application a bit.
Claims (9)
1. a kind of organic photovoltaic cell, which is characterized in that including photoactive layer, the photoactive layer includes electron donor and non-lipid
Alkene electron acceptor is strangled, the electron donor is PCE-10, and the non-fullerene electron acceptor is IEICO-4F and IT-M.
2. organic photovoltaic cell according to claim 1, which is characterized in that the electron donor and the non-fullerene electricity
The weight ratio of sub- receptor is 1.5:(1-2.25).
3. organic photovoltaic cell according to claim 2, which is characterized in that the weight of the IT-M accounts for the non-fullerene
The 5-20% of the weight of electron acceptor.
4. organic photovoltaic cell according to claim 1, which is characterized in that including set gradually substrate layer, cathode layer,
Electron transfer layer, the photoactive layer, hole transmission layer, anode layer.
5. organic photovoltaic cell according to claim 1-4, which is characterized in that the photoactive layer with a thickness of
50-300nm。
6. the preparation method of the described in any item organic photovoltaic cells of claim 1-5, which is characterized in that the photoactive layer is logical
Following steps are crossed to be made:
Electron donor, non-fullerene electron acceptor, solvent and solvent additive is taken to be prepared into photoactive layer solution, coating film.
7. the preparation method of organic photovoltaic cell according to claim 6, which is characterized in that the solvent additive is selected from
At least one of 1- chloronaphthalene, 1,8- diiodo-octane.
8. the preparation method of organic photovoltaic cell according to claim 6, which is characterized in that the body of the solvent additive
Product is the 0.5-4% of the volume of the photoactive layer solution.
9. the preparation method of organic photovoltaic cell according to claim 6, which is characterized in that further include annealing, move back
Fiery temperature is 80-100 DEG C, annealing time 5-40min.
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