CN113571643A - Novel organic hole transport layer perovskite solar cell and preparation method thereof - Google Patents
Novel organic hole transport layer perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a novel organic hole transport layer perovskite solar cell and a preparation method thereof, wherein the basic structure comprises a transparent conductive substrate, a monocrystalline polypyrrole (PPY) polymer hole transport layer, a perovskite light absorption layer, an electron transport layer and a metal back electrode layer which are arranged from bottom to top in sequence; the hole transport material provided by the invention has good hole transport performance and excellent solubility, some hole transport materials can be dissolved and processed even in a green solvent, a good film appearance can be obtained, and the hole transport material has adjustable photoelectric performance, and the perovskite solar cell prepared from the material has extremely strong ultraviolet irradiation resistance, and can maintain stable cell performance after being placed in the air for 500 hours. The new idea provided by the invention has wide application prospect in the field of photoelectric devices, in particular perovskite solar cells.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a perovskite solar cell based on a monocrystalline polypyrrole (PPY) polymer hole transport layer and a preparation method thereof.
Background
In eleven years after 2009, perovskite solar cells are distinguished by their outstanding advantages and are rapidly developed. The perovskite cell is simple to prepare and high in conversion efficiency, so that the perovskite cell becomes an ideal light absorption material of a new-generation photovoltaic device, and has good commercial prospect and great market value. Since the perovskite invention, the conversion efficiency is continuously broken through. At present, the photoelectric conversion efficiency of more than 25 percent is obtained, and the use cost of the solar cell can be greatly reduced. At present, most of hole transport layers of perovskite solar cells are PEDOT, PSS, Spiro and nickel oxide, organic hole transport layers such as PEDOT, PSS and Spiro are expensive and unstable, the invention provides that single-crystal polypyrrole (PPY) polymers are used as the hole transport layers, and perovskite cells prepared from the materials show excellent stability and have extremely strong ultraviolet irradiation resistance in experiments. The present invention provides a new idea for solving such problems.
The perovskite solar cell mainly comprises a transparent conducting layer, a hole transport layer, a perovskite light absorption layer, an electron transport layer and an electrode, and a modification layer is added between the hole transport layer and the perovskite light absorption layer sometimes, so that the energy level barrier and the surface defects are reduced, and the efficiency is improved. At present, the material selection of the hole transport layer is not very much, and the prior art has not proposed that a single-crystal polypyrrole (PPY) polymer is used as the hole transport layer to provide a new idea for the material selection of the hole transport layer.
Disclosure of Invention
The invention designs a novel organic hole transport layer perovskite solar cell and a preparation method thereof, and solves the technical problems that in the prior art, the perovskite solar cell is poor in ultraviolet irradiation resistance and stability of outdoor work, and the cost of a planar perovskite solar cell is high.
In order to solve the technical problems, the invention adopts the following scheme:
the novel organic hole transport layer perovskite solar cell sequentially comprises a transparent conductive substrate, a monocrystalline polypyrrole (PPY) polymer hole transport layer, a perovskite light absorption layer, an electron transport layer and a metal back electrode layer from bottom to top.
Preferably, the transparent conductive substrate is made of FTO, ITO or AZO.
Preferably, the perovskite light absorption layer is ABX3Organic-inorganic hybrid perovskite material with structure of type A, wherein A is CH3NH3 +(methylamine), NH2CH=NH2(formamidine), Cs+B is Pb2+、Sn2+One or two of them, X is Cl-、Br-、I-One or more of (a).
Preferably, the electron transport layer is ZnO or SnO2、TiO2Or a PCBM.
Preferably, the metal back electrode is made of silver-aluminum alloy with the thickness of 70-120 nm.
In the invention, other organic solar cell modules can be selected as the solar cell module. In the present invention, the modification layer in the perovskite solar cell may be omitted or added. The modification layer adopts PEAI.
A preparation method of a novel organic hole transport layer perovskite solar cell comprises the following steps:
step 1: cleaning and drying the conductive substrate, and then carrying out ultraviolet cleaning treatment to obtain a pretreated substrate;
step 2: depositing PPY single crystal polymer on the pretreated substrate obtained in the step (1) to form a single crystal polypyrrole (PPY) polymer hole transport layer;
and step 3: spin-coating a perovskite precursor solution on the organic hole transport layer, adding a chlorobenzene solvent, continuing spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a perovskite light absorption layer;
and 4, step 4: spin-coating a chlorobenzene solution of PCBM on the perovskite light absorption layer to form an electron transmission layer;
and 5: and evaporating the metal electrode material onto the electron transport layer through thermal evaporation under vacuum to obtain the perovskite solar cell.
A novel organic hole transport layer perovskite solar cell is characterized in that: the solar cell sequentially comprises a transparent conductive substrate, an electron transmission layer, a perovskite light absorption layer, a monocrystalline polypyrrole (PPY) polymer hole transmission layer and a metal back electrode layer from bottom to top.
Preferably, the transparent conductive substrate is made of FTO, ITO or AZO.
Preferably, the perovskite light absorption layer is ABX3Organic-inorganic hybrid perovskite material with structure of type A, wherein A is CH3NH3 +(methylamine), NH2CH=NH2(formamidine), Cs+B is Pb2+、Sn2+One or two of them, X is Cl-、Br-、I-One or more of (a). The perovskite absorption layer adopts CH3NH3PbI3。
Preferably, the electron transport layer is ZnO or SnO2、TiO2Or a PCBM.
Preferably, the metal back electrode is made of silver-aluminum alloy with the thickness of 70-120 nm.
A preparation method of a novel organic hole transport layer perovskite solar cell comprises the following steps: step 1: cleaning and drying the FTO conductive glass substrate, and then carrying out ultraviolet cleaning treatment to obtain a pretreated substrate; step 2: selectively coating a PCBM film on the pretreated substrate to form an organic electron transport layer; and step 3: spin-coating a perovskite precursor solution on the organic electron transport layer, adding a chlorobenzene solvent, continuing spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer; and 4, step 4: covering a hole transport layer PPY single crystal film on the light absorption layer to form a hole transport layer; and 5: and evaporating a metal electrode material onto the PPY hole transport layer through thermal evaporation under vacuum to obtain the perovskite solar cell.
Compared with the prior art, the invention has the following technical effects:
(1) the battery provided by the invention can effectively block the influence of water and oxygen on the perovskite battery, and the used hole transport layer can prolong the effective time of the perovskite battery in the air and has good stability.
(2) The hole transport material provided by the invention has good hole transport performance and excellent solubility, some hole transport materials can be dissolved and processed even in a green solvent, and a good film appearance and adjustable photoelectric performance can be obtained.
(3) The novel single crystal polypyrrole (PPY) polymer material provided by the invention can prove that the single crystal material can be suitable for organic solar cells, has good hole mobility and light stability, and can inhibit the recombination of photogenerated electrons and photogenerated holes.
(4) Experiments prove that the hole transport material provided by the invention can obviously improve the ultraviolet radiation resistance of the solar cell, and can maintain stable cell performance after being placed in the air for 500 hours.
(5) The new idea provided by the invention has wide application prospect in the field of photoelectric devices, in particular perovskite solar cells.
Drawings
FIG. 1: the cross-sectional structure of the novel perovskite solar cell of the invention is shown in the figure 1;
FIG. 2: the front structure of the perovskite solar cell is shown schematically;
FIG. 3: the cross-sectional structure of the novel perovskite solar cell of the invention in the embodiment 2 is shown schematically;
FIG. 4: the I-V curve of the initial cell in example 1 of the present invention;
FIG. 5: in embodiment 1 of the present invention, the I-V curve of the battery after two weeks in an indoor environment is shown;
FIG. 6: the I-V curve of the initial cell in example 1 of the present invention;
FIG. 7: I-V curve of the cell after 1 hour of uv in example 1 of the invention.
Description of reference numerals:
1-a metal back electrode; 2-PCBM; 3-perovskite absorption layer; 4-PPY single crystal film; 5-FTO conductive glass.
Detailed Description
The invention is further described below with reference to fig. 1 to 7:
as shown in fig. 1, an encapsulated perovskite solar cell, as shown in fig. 1, comprises: metal back electrode 1, PCBM2, perovskite absorbing layer 3, PPY single crystal membrane 4 and FTO conductive glass 5. The present invention is not limited to the inverted configuration but can be applied to the forward configuration.
A method of making an encapsulated perovskite solar cell, comprising the steps of;
step 1: cleaning and drying the conductive glass substrate, and then carrying out ultraviolet cleaning treatment to obtain a pretreated substrate; step 2: depositing PPY single crystal polymer on the pretreated substrate to form an organic hole transport layer; and step 3: spin-coating a perovskite precursor solution on the organic hole transport layer, adding a chlorobenzene solvent, continuing spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer; and 4, step 4: spin-coating a chlorobenzene solution of PCBM on the light absorption layer to form an electron transport layer; and 5: and evaporating the metal electrode material onto the electron transport layer through thermal evaporation under vacuum to obtain the perovskite solar cell.
The preparation of the PPY single crystal polymer in the step 2 comprises the following steps: an acid solution is first prepared, where the acid may be hydrochloric acid, sulfuric acid, phosphoric acid, or an organic acid, using deionized water as the solvent. Secondly, ammonium persulfate is weighed and dissolved in the acid solution to serve as an oxidant for reaction. Meanwhile, a small amount of pyrrole monomer is taken by using a liquid-transfering gun, chloroform is selected as a solvent, and the mixture is uniformly stirred for standby. And (3) putting the prepared monomer and the oxidant into a refrigerator for refrigeration, taking out and mixing after 1h, wherein an interface is formed after mixing due to different densities of the two solutions, and a polypyrrole film is generated at the interface.
The perovskite solar cell disclosed by the invention can have stable filling factors and photoelectric conversion efficiency after being tested, and has certain ultraviolet resistance, and compared with other perovskite solar cells, the perovskite solar cell disclosed by the invention can exist stably for a plurality of weeks in the air, so that the single crystal polypyrrole (PPY) polymer material has certain anti-water-oxygen capacity.
Example 1:
the perovskite solar cell as shown in FIG. 1 is manufactured by the following specific steps:
with inverted MAPbI3Perovskite solar cell modules are an example. Wherein, the perovskite solar cell component comprises an FTO layer (transparent conductive layer), a hole transport layer (PPY), a MAPbI3Perovskite layer, electron transport layer (PCBM), metal back electrode.
The embodiment relates to a novel perovskite solar cell, which comprises a metal back electrode 1, PCBM2, a perovskite absorption layer 3, a PPY single crystal film 4 and FTO conductive glass 5 from top to bottom as shown in figure 2. The positive FTO conductive glass 5 that chooses for use of transparent conducting layer of battery pack, the last PPY single crystal membrane 4 that sets up of FTO conductive glass 5 sets up the perovskite absorbed layer 3 on PPY single crystal membrane 4, sets up electron transport layer PCBM2 on perovskite absorbed layer 3, sets up metal back electrode 1 on electron transport layer (PCBM) 2, and the material of metal back electrode 1 is silver-aluminum alloy.
Step 1: cleaning and drying the FTO conductive glass 5 substrate, and then carrying out ultraviolet cleaning treatment to obtain a pretreated substrate;
step 2: depositing PPY single crystal polymer on the pretreated substrate to form an organic hole transport layer;
and step 3: spin-coating a perovskite precursor solution on the organic hole transport layer, adding a chlorobenzene solvent, continuing spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer;
and 4, step 4: spin-coating a chlorobenzene solution of PCBM on the light absorption layer to form an electron transport layer;
and 5: and evaporating the metal electrode material onto the electron transport layer through thermal evaporation under vacuum to obtain the perovskite solar cell.
Referring to fig. 4 and table 1, the durability test of the cell, placed in an indoor environment for two weeks, at an ambient humidity of 60%, a temperature of 25 ℃, the cell performance is shown in the following table:
| Voc V | Jsc | FF | Efficiency |
| 0.804 | 7.31 | 46.5 | 2.74 |
table 1: initial cell efficiency
| Voc V | Jsc | FF | Efficiency |
| 0.78 | 6.7 | 47 | 2.5 |
Table 2: cell performance in indoor environment for two weeks
Referring to fig. 5 and table 2, it can be concluded from the above figures that the use of a PPY single crystal film as a hole transport layer of perovskite can increase the stability of the battery, and can increase the durability thereof in an actual use environment.
Referring to tables 3-4 and FIGS. 6-7, the UV resistance of the cells was tested by irradiating the cells under a UV lamp for one hour, and then testing the cell performance as follows:
| Voc V | Jsc | FF | Efficiency |
| 0.65 | 6.74 | 34 | 1.5 |
table 3: initial cell efficiency
| Voc V | Jsc | FF | Efficiency |
| 0.57 | 11.3 | 38 | 2.5 |
Table 4: cell efficiency one hour after UV irradiation
The data prove that the efficiency of the solar cell does not decrease and inversely increase under ultraviolet irradiation, which shows that the perovskite solar cell using the single crystal polypyrrole (PPY) polymer material as the hole transport layer not only has strong ultraviolet light resistance, but also has steadily increased efficiency under the irradiation of ultraviolet light, and is enough to show that the material has great application potential.
Example 2:
this example utilizes CsPbI2Replacement of MAPbI in Br perovskite layer in example 13The perovskite layer, and adopt and just put the structure, the battery structure is: the positive FTO conductive glass 5 that chooses for use of battery pack is transparent conducting layer, sets up electron transport layer PCBM2 on the transparent conducting layer, sets up perovskite absorbed layer 3 on electron transport layer PCBM2, sets up hole transport layer PPY single crystal membrane 4 on perovskite absorbed layer 3, sets up metal back electrode 1 on hole transport layer PPY single crystal membrane 4, and its material is silver-aluminum alloy. The cell structure of example 2 is shown in fig. 3, and the specific implementation steps are as follows:
step 1: cleaning and drying the FTO conductive glass 5 substrate, and then carrying out ultraviolet cleaning treatment to obtain a pretreated substrate;
step 2: selectively coating a PCBM film on the pretreated substrate to form an organic electron transport layer;
and step 3: spin-coating a perovskite precursor solution on the organic electron transport layer, adding a chlorobenzene solvent, continuing spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer;
and 4, step 4: covering a hole transport layer PPY single crystal film on the light absorption layer to form a hole transport layer;
and 5: and evaporating a metal electrode material onto the PPY hole transport layer through thermal evaporation under vacuum to obtain the perovskite solar cell.
The perovskite solar cell has stable filling factor and photoelectric conversion efficiency and strong ultraviolet resistance, and compared with other perovskite solar cells, the perovskite solar cell can stably exist in the air for a plurality of weeks, so that the single crystal polypyrrole (PPY) polymer material has certain water-oxygen resistance and ultraviolet irradiation resistance.
The invention provides a preparation method of a novel organic hole transport layer perovskite solar cell, and the structure of a prepared solar cell device comprises the following steps from bottom to top: the device comprises a substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer and a metal back electrode. The hole transport layer is a single-crystal polypyrrole film, the hole transport layer is prepared by an organic chemical synthesis method, the single-crystal polypyrrole film is dissolved in an organic solvent, and then the single-crystal polypyrrole film is spin-coated on the conductive glass substrate. The material can also be applied to other organic solar cells.
The invention is described above with reference to the accompanying drawings, it is obvious that the implementation of the invention is not limited in the above manner, and it is within the scope of the invention to adopt various modifications of the inventive method concept and solution, or to apply the inventive concept and solution directly to other applications without modification.
Claims (10)
1. A novel organic hole transport layer perovskite solar cell is characterized in that: the solar cell sequentially comprises a transparent conductive substrate, a monocrystalline polypyrrole (PPY) polymer hole transport layer, a perovskite light absorption layer, an electron transport layer and a metal back electrode layer from bottom to top.
2. The novel organic hole transport layer perovskite solar cell of claim 1, wherein: the transparent conductive substrate is made of FTO, ITO or AZO.
3. The novel organic hole transport layer perovskite solar cell of claim 1, wherein: the perovskite light absorption layer is ABX3Organic-inorganic hybrid perovskite material with structure of type A, wherein A is CH3NH3 +(methylamine), NH2CH=NH2(formamidine), Cs+B is Pb2+、Sn2+One or two of them, X is Cl-、Br-、I-One or more of (a).
4. The novel organic hole transport layer perovskite solar cell of claim 1, wherein: the electron transport layer is ZnO or SnO2、TiO2Or PCBM, or the metal back electrode adopts silver-aluminum alloy with the thickness of 70-120 nm.
5. A preparation method of a novel organic hole transport layer perovskite solar cell comprises the following steps:
step 1: cleaning and drying the conductive substrate, and then carrying out ultraviolet cleaning treatment to obtain a pretreated substrate;
step 2: depositing PPY single crystal polymer on the pretreated substrate obtained in the step (1) to form a single crystal polypyrrole (PPY) polymer hole transport layer;
and step 3: spin-coating a perovskite precursor solution on the organic hole transport layer, adding a chlorobenzene solvent, continuing spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a perovskite light absorption layer;
and 4, step 4: spin-coating a chlorobenzene solution of PCBM on the perovskite light absorption layer to form an electron transmission layer;
and 5: and evaporating the metal electrode material onto the electron transport layer through thermal evaporation under vacuum to obtain the perovskite solar cell.
6. A novel organic hole transport layer perovskite solar cell is characterized in that: the solar cell sequentially comprises a transparent conductive substrate, an electron transmission layer, a perovskite light absorption layer, a monocrystalline polypyrrole (PPY) polymer hole transmission layer and a metal back electrode layer from bottom to top.
7. The novel organic hole transport layer perovskite solar cell of claim 6, wherein: the transparent conductive substrate is made of FTO, ITO or AZO.
8. The novel organic hole transport layer perovskite solar cell of claim 6, wherein: the perovskite light absorption layer is ABX3Organic-inorganic hybrid perovskite material with structure of type A, wherein A is CH3NH3 +(methylamine), NH2CH=NH2(formamidine), Cs+B is Pb2+、Sn2+One or two of them, X is Cl-、Br-、I-One or more of (a).
9. The novel organic hole transport layer perovskite solar cell of claim 6, wherein: the electron transport layer is ZnO or SnO2、TiO2Or PCBM, or the metal back electrode adopts silver-aluminum alloy with the thickness of 70-120 nm.
10. A preparation method of a novel organic hole transport layer perovskite solar cell comprises the following steps:
step 1: cleaning and drying the FTO conductive glass (5) substrate, and then carrying out ultraviolet cleaning treatment to obtain a pretreated substrate;
step 2: selectively coating a PCBM film on the pretreated substrate to form an organic electron transport layer;
and step 3: spin-coating a perovskite precursor solution on the organic electron transport layer, adding a chlorobenzene solvent, continuing spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer;
and 4, step 4: covering a hole transport layer PPY single crystal film on the light absorption layer to form a hole transport layer;
and 5: and evaporating a metal electrode material onto the PPY hole transport layer through thermal evaporation under vacuum to obtain the perovskite solar cell.
Priority Applications (1)
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