CN109545979A - The organic photovoltaic cell of metallic transparent electrode and preparation method and composition - Google Patents
The organic photovoltaic cell of metallic transparent electrode and preparation method and composition Download PDFInfo
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- CN109545979A CN109545979A CN201811219314.5A CN201811219314A CN109545979A CN 109545979 A CN109545979 A CN 109545979A CN 201811219314 A CN201811219314 A CN 201811219314A CN 109545979 A CN109545979 A CN 109545979A
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- H—ELECTRICITY
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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Abstract
The invention discloses metallic transparent electrode and the organic photovoltaic cells of preparation method and composition.Metallic transparent electrode is made of ultrathin Al film, ultra-thin Ag film and Ag grid；And cathode buffer layer of successively arranging on metallic transparent electrode, active layer, anode buffer layer and back electrode constitute organic photovoltaic cell.Metallic transparent electrode of the present invention solves the problems, such as that adhesion is poor between ultra-thin Ag film and substrate, improves the surface topography of ultra-thin Ag film, improves its optically and electrically performance.Ag grid result can be further improved the electric conductivity of metallic transparent electrode simultaneously.Gained metallic transparent electrode can replace traditional tin indium oxide (ITO) electrode, prepare high performance organic photovoltaic cell device.
Description
Technical field
The present invention relates to area of solar cell, and in particular to a kind of metallic transparent electrode and preparation method and composition have
Machine solar cell.
Technical background
The most popular transparent electrode material of organic photovoltaic cell is tin indium oxide (ITO) at present.ITO has good
Optically and electrically performance, however since the price of raw material indium rises steadily, the preparation cost of ITO increases.In addition, ITO's is soft
Toughness is poor, and electric conductivity declines to a great extent after bending.These disadvantages limit ITO in large area flexible solar cell device
Using.In order to find replace ITO electrode material, scientists develop conducting polymer, carbon nanotube, graphene film,
The materials such as metal nanometer line, super thin metal film are as transparent electrode.Metallic film due to it is conductive it is high, stability is high,
The features such as ductility is good becomes the material of the substitution ITO of most future.
With other metal phase ratios, Ag conductive good (conductivity is up to 1.62 μ Ω cm), stability are high, ductility is good
The advantages that (being only second to Au) is the preferred material for preparing metallic transparent electrode.Meanwhile the optical resonance formed between Ag-Ag electrode
Microcavity effect is conducive to enhance the capture to incident light, obtains higher photoelectric current.However, the electric conductivity and transmission of Ag film
The thickness of rate and film is closely related, and transmitance can be reduced with film thickness index.Meet requirement on devices to obtain
Light transmission rate, the thickness of Ag film are generally very thin.However the initial stage due to metallic atom in film forming tends to island growth
Mode, can not form continuous, smooth Ag film when causing thickness too thin, sheet resistance is larger.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of metallic transparent electrode and preparation method and composition
Organic photovoltaic cell.
The technical scheme is that
One, a kind of metallic transparent electrode:
The metallic transparent electrode is made of ultrathin Al film, ultra-thin Ag film and Ag grid.
The ultrathin Al film with a thickness of 1-5nm.
The ultra-thin Ag film with a thickness of 5-20nm.
The Ag grid with a thickness of 5-30nm, the inscribed circle diameter of the Ag grid is 50-200 μm, line width 5-
20μm。
Two, a kind of organic photovoltaic cell:
Including substrate, metallic transparent electrode, cathode buffer layer, photoactive layer, anode buffer layer, back electrode, the metal
Transparent electrode is made of ultrathin Al film, ultra-thin Ag film and Ag grid.
The ultrathin Al film with a thickness of 1-5nm.
The ultra-thin Ag film with a thickness of 5-20nm.
The Ag grid with a thickness of 5-30nm, the size (diameter) of Ag grid is 50-200 μm, and line width is 5-20 μm.
The substrate material is glass or polyester film；The cathode cushioning layer material is ZnO；The photoactive layer is
PTB7-Th and PC71The hybrid films of BM；The anode buffer layer material is MoO3；The back electrode material is Ag.
Beneficial effect
On the one hand the metallic transparent electrode that the present invention designs can be enhanced between ultra-thin Ag film and substrate by ultrathin Al film
Adhesion, improve the pattern of ultra-thin Ag film, improve its transmitance and electric conductivity.On the other hand, by ultra-thin Ag film preparation
Ag network forms ultra-thin Ag film/Ag grid combination electrode, can be further improved the electric conductivity of metallic transparent electrode.Cause
This, compared to traditional ITO electrode, which not only has preferable electric conductivity and flexibility, while can benefit
The optical microcavity effect generated with Ag film, the optical field distribution in adjusting means improve the utilization rate of light, and obtaining high performance has
Machine solar cell device.
Detailed description of the invention
Fig. 1 is organic photovoltaic cell device architecture schematic diagram of the invention.
Fig. 2 is the organic photovoltaic cell device I-V curve graph of the embodiment of the present invention 7.
Specific embodiment
Below with reference to specific example, invention is further described in detail.
As shown in Figure 1, metallic transparent electrode of the invention is made of ultrathin Al film, ultra-thin Ag film and Ag grid.
Preferred ultrathin Al film with a thickness of 1-5nm.
Preferred ultra-thin Ag film with a thickness of 5-20nm.
Preferred Ag grid with a thickness of 5-30nm, the size (diameter) of Ag grid is 50-200 μm, and line width is 5-20 μm.
Organic photovoltaic cell of the invention includes including substrate, metallic transparent electrode, cathode buffer layer, photoactive layer, sun
Pole buffer layer, back electrode, metallic transparent electrode are made of ultrathin Al film, ultra-thin Ag film and Ag grid.
Preferred ultrathin Al film with a thickness of 1-5nm.
Preferred ultra-thin Ag film with a thickness of 5-20nm.
Preferred Ag grid with a thickness of 5-30nm, the inscribed circle diameter of the Ag grid is 50-200 μm, and line width is
5-20μm。
Preferred substrate material is glass or polyester film；Preferred cathode cushioning layer material is ZnO；Preferred photolytic activity
Layer is PTB7-Th and PC71The hybrid films of BM；Preferred anode buffer layer material is MoO3；Preferred back electrode material is Ag.
The embodiment of the present invention is as follows:
Embodiment 1:
Glass substrate is successively cleaned by ultrasonic with detergent, isopropanol, ethyl alcohol, acetone, with being dried with nitrogen after cleaning；
The ultra-thin Ag film of the ultrathin Al film of one layer of 5nm and 5nm on glass substrate surface successively vacuum evaporation；Then thickness is prepared on it
Degree is 30nm, and inscribed circle diameter is 50 μm, and the Ag grid that line width is 5 μm forms metallic transparent electrode.
The ZnO cathode buffer layer of spin coating 30nm on transparent metal electrode surface, and film will be formed by and annealed,
Annealing temperature is 150 DEG C, and annealing time is 10 minutes；Then spin coating PTB7-Th and PC71The mixed solution of BM, PTB7-Th with
PC71The mass ratio of BM is 1:1.5, obtains the PTB7-Th and PC that a layer thickness is 90nm71The hybrid films (active layer) of BM；Then
On active layer in vacuum evaporation one layer of 8nm thickness MoO3(anode buffer layer)；Finally, in anode modification layer in vacuum evaporation
The Ag of one layer of 100nm thickness is as anode, to obtain organic photovoltaic cell as shown in Figure 1, photoelectric conversion efficiency is
5.4%.
Embodiment 2:
Glass substrate is successively cleaned by ultrasonic with detergent, isopropanol, ethyl alcohol, acetone, with being dried with nitrogen after cleaning；
The ultra-thin Ag film of the ultrathin Al film of one layer of 2nm and 10nm on glass substrate surface successively vacuum evaporation；Then it prepares on it
With a thickness of 20nm, diameter is 50 μm, and the Ag grid that line width is 5 μm forms metallic transparent electrode.
The ZnO cathode buffer layer of spin coating 30nm on transparent metal electrode surface, and film will be formed by and annealed,
Annealing temperature is 150 DEG C, and annealing time is 10 minutes；Then spin coating PTB7-Th and PC71The mixed solution of BM, PTB7-Th with
PC71The mass ratio of BM is 1:1.5, obtains the PTB7-Th and PC that a layer thickness is 90nm71The hybrid films (active layer) of BM；Then
On active layer in vacuum evaporation one layer of 8nm thickness MoO3(anode buffer layer)；Finally, in anode modification layer in vacuum evaporation
The Ag of one layer of 100nm thickness is as anode, to obtain organic photovoltaic cell as shown in Figure 1, photoelectric conversion efficiency is
6.9%.
Embodiment 3:
Glass substrate is successively cleaned by ultrasonic with detergent, isopropanol, ethyl alcohol, acetone, with being dried with nitrogen after cleaning；
The ultra-thin Ag film of the ultrathin Al film of one layer of 1nm and 20nm on glass substrate surface successively vacuum evaporation；Then it prepares on it
With a thickness of 5nm, inscribed circle diameter is 50 μm, and the Ag grid that line width is 5 μm forms metallic transparent electrode.
The ZnO cathode buffer layer of spin coating 30nm on transparent metal electrode surface, and film will be formed by and annealed,
Annealing temperature is 150 DEG C, and annealing time is 10 minutes；Then spin coating PTB7-Th and PC71The mixed solution of BM, PTB7-Th with
PC71The mass ratio of BM is 1:1.5, obtains the PTB7-Th and PC that a layer thickness is 90nm71The hybrid films (active layer) of BM；Then
On active layer in vacuum evaporation one layer of 8nm thickness MoO3(anode buffer layer)；Finally, in anode modification layer in vacuum evaporation
The Ag of one layer of 100nm thickness is as anode, so that organic photovoltaic cell as shown in Figure 1 is obtained, photoelectric conversion efficiency 6.7%
Embodiment 4:
Glass substrate is successively cleaned by ultrasonic with detergent, isopropanol, ethyl alcohol, acetone, with being dried with nitrogen after cleaning；
The ultra-thin Ag film of the ultrathin Al film of one layer of 1nm and 5nm on glass substrate surface successively vacuum evaporation；Then thickness is prepared on it
Degree is 30nm, and inscribed circle diameter is 50 μm, and the Ag grid that line width is 5 μm forms metallic transparent electrode.
The ZnO cathode buffer layer of spin coating 30nm on transparent metal electrode surface, and film will be formed by and annealed,
Annealing temperature is 150 DEG C, and annealing time is 10 minutes；Then spin coating PTB7-Th and PC71The mixed solution of BM, PTB7-Th with
PC71The mass ratio of BM is 1:1.5, obtains the PTB7-Th and PC that a layer thickness is 90nm71The hybrid films (active layer) of BM；Then
On active layer in vacuum evaporation one layer of 8nm thickness MoO3(anode buffer layer)；Finally, in anode modification layer in vacuum evaporation
The Ag of one layer of 100nm thickness is as anode, to obtain organic photovoltaic cell as shown in Figure 1, photoelectric conversion efficiency is
6.2%.
Embodiment 5:
Glass substrate is successively cleaned by ultrasonic with detergent, isopropanol, ethyl alcohol, acetone, with being dried with nitrogen after cleaning；
The ultra-thin Ag film of the ultrathin Al film of one layer of 1nm and 10nm on glass substrate surface successively vacuum evaporation；Then it prepares on it
With a thickness of 20nm, inscribed circle diameter is 200 μm, and the Ag grid that line width is 20 μm forms metallic transparent electrode.
The ZnO cathode buffer layer of spin coating 30nm on transparent metal electrode surface, and film will be formed by and annealed,
Annealing temperature is 150 DEG C, and annealing time is 10 minutes；Then spin coating PTB7-Th and PC71The mixed solution of BM, PTB7-Th with
PC71The mass ratio of BM is 1:1.5, obtains the PTB7-Th and PC that a layer thickness is 90nm71The hybrid films (active layer) of BM；Then
On active layer in vacuum evaporation one layer of 8nm thickness MoO3(anode buffer layer)；Finally, in anode modification layer in vacuum evaporation
The Ag of one layer of 100nm thickness is as anode, to obtain organic photovoltaic cell as shown in Figure 1, photoelectric conversion efficiency is
5.1%.
Embodiment 6:
Glass substrate is successively cleaned by ultrasonic with detergent, isopropanol, ethyl alcohol, acetone, with being dried with nitrogen after cleaning；
The ultra-thin Ag film of the ultrathin Al film of one layer of 1nm and 10nm on glass substrate surface successively vacuum evaporation；Then it prepares on it
With a thickness of 20nm, inscribed circle diameter is 100 μm, and the Ag grid that line width is 10 μm forms metallic transparent electrode.
The ZnO cathode buffer layer of spin coating 30nm on transparent metal electrode surface, and film will be formed by and annealed,
Annealing temperature is 150 DEG C, and annealing time is 10 minutes；Then spin coating PTB7-Th and PC71The mixed solution of BM, PTB7-Th with
PC71The mass ratio of BM is 1:1.5, obtains the PTB7-Th and PC that a layer thickness is 90nm71The hybrid films (active layer) of BM；Then
On active layer in vacuum evaporation one layer of 8nm thickness MoO3(anode buffer layer)；Finally, in anode modification layer in vacuum evaporation
The Ag of one layer of 100nm thickness is as anode, to obtain organic photovoltaic cell as shown in Figure 1, photoelectric conversion efficiency is
6.6%.
Embodiment 7:
Glass substrate is successively cleaned by ultrasonic with detergent, isopropanol, ethyl alcohol, acetone, with being dried with nitrogen after cleaning；
The ultra-thin Ag film of the ultrathin Al film of one layer of 1nm and 10nm on glass substrate surface successively vacuum evaporation；Then it prepares on it
With a thickness of 20nm, inscribed circle diameter is 50 μm, and the Ag grid that line width is 5 μm forms metallic transparent electrode.
The ZnO cathode buffer layer of spin coating 30nm on transparent metal electrode surface, and film will be formed by and annealed,
Annealing temperature is 150 DEG C, and annealing time is 10 minutes；Then spin coating PTB7-Th and PC71The mixed solution of BM, PTB7-Th with
PC71The mass ratio of BM is 1:1.5, obtains the PTB7-Th and PC that a layer thickness is 90nm71The hybrid films (active layer) of BM；Then
On active layer in vacuum evaporation one layer of 8nm thickness MoO3(anode buffer layer)；Finally, in anode modification layer in vacuum evaporation
The Ag of one layer of 100nm thickness is as anode, to obtain organic photovoltaic cell as shown in Figure 1, photoelectric conversion efficiency is
7.3%.
The above embodiment of the present invention is only example to illustrate the invention, and is not to implementation of the invention
The restriction of mode.For those of ordinary skill in the art, other can also be made not on the basis of the above description
With the variation and variation of form, all embodiments can not be exhaustive here.It is all to belong to technical solution of the present invention
Changes and variations that derived from are still in the scope of protection of the present invention.
Claims (7)
1. metallic transparent electrode, it is characterised in that: the metallic transparent electrode successively includes ultrathin Al film, ultra-thin Ag from top to bottom
Film and Ag grid；The ultrathin Al film with a thickness of 1-5nm；The ultra-thin Ag film with a thickness of 5-20nm；The Ag grid
With a thickness of 5-30nm, the inscribed circle diameter of the Ag grid is 50-200 μm, and line width is 5-20 μm.
2. the preparation method of metallic transparent electrode according to claim 1, it is characterised in that: this method specifically: to glass
Substrate is successively cleaned by ultrasonic with detergent, isopropanol, ethyl alcohol, acetone, with being dried with nitrogen after cleaning；In glass substrate surface
Successively in vacuum evaporation the ultrathin Al film of one layer of 1-5nm and 5-20nm ultra-thin Ag film；Then thickness is prepared on ultra-thin Ag film
For 5-30nm, diameter is 50-200 μm, and the Ag grid that line width is 5-20 μm forms metallic transparent electrode.
3. according to claim 1 metallic transparent electrode constitute organic photovoltaic cell, including substrate, metallic transparent electrode,
Cathode buffer layer, photoactive layer, anode buffer layer, back electrode.
4. the organic photovoltaic cell that metallic transparent electrode according to claim 3 is constituted, it is characterised in that: the substrate material
For glass or polyester film.
5. the organic photovoltaic cell that metallic transparent electrode according to claim 3 is constituted, it is characterised in that: the cathode buffering
Layer material is ZnO.
6. the organic photovoltaic cell that metallic transparent electrode according to claim 3 is constituted, it is characterised in that: the photoactive layer
For PTB7-Th and PC71The hybrid films of BM.
7. the organic photovoltaic cell that metallic transparent electrode according to claim 3 is constituted, it is characterised in that: the anode buffer
Layer material is MoO3；The back electrode material is Ag.
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| CN110828671A (en) * | 2019-11-30 | 2020-02-21 | 华南理工大学 | Organic solar cell with organic-inorganic cathode modification layer material and preparation method thereof |
| CN111326659A (en) * | 2020-02-24 | 2020-06-23 | 杭州电子科技大学 | Metal transparent electrode and organic solar cell |
| CN113258005A (en) * | 2021-04-16 | 2021-08-13 | 杭州电子科技大学 | Organic solar cell formed by composite electrode and preparation method |
| CN114586162A (en) * | 2019-10-23 | 2022-06-03 | 株式会社日本显示器 | Semiconductor device with a plurality of transistors |
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