CN113571643B - Novel perovskite solar cell with organic hole transport layer and preparation method thereof - Google Patents

Novel perovskite solar cell with organic hole transport layer and preparation method thereof Download PDF

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CN113571643B
CN113571643B CN202110660545.5A CN202110660545A CN113571643B CN 113571643 B CN113571643 B CN 113571643B CN 202110660545 A CN202110660545 A CN 202110660545A CN 113571643 B CN113571643 B CN 113571643B
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transport layer
perovskite
hole transport
solar cell
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CN113571643A (en
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陈晓红
李炳生
王月飞
龙碧宇
宋仁静
何楠楠
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East China Normal University
Northeast Normal University
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Northeast Normal University
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    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

The invention relates to a novel perovskite solar cell with an organic hole transport layer and a preparation method thereof, wherein the basic structure of the perovskite solar cell 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 sequentially arranged from bottom to top; the hole transport material provided by the invention has good hole transport performance and good solubility, and can be dissolved in a green solvent to obtain a good film morphology and 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 air for 500 hours. The novel thought provided by the invention has wide application prospect in the field of photoelectric devices, in particular to perovskite solar cells.

Description

Novel perovskite solar cell with organic hole transport layer and preparation method thereof
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
Since eleven years after 2009, perovskite solar cells developed rapidly due to their excellent advantages. The perovskite battery is simple to prepare and high in conversion efficiency, becomes an ideal light absorption material of a new generation of photovoltaic devices, and has good commercialization prospect and great market value. Since the perovskite invention, conversion efficiency has been continually broken through. At present, the photoelectric conversion efficiency is more than 25%, and the use cost of the solar cell can be greatly reduced. The hole transport layers of the perovskite solar cell at present are mostly PEDOT: PSS, spiro and nickel oxide, the organic hole transport layers such as PEDOT: PSS and Spiro are expensive and unstable, and the perovskite solar cell prepared from the material has excellent stability and extremely strong ultraviolet irradiation resistance in experiments by using a single-crystal polypyrrole (PPY) polymer as the hole transport layer. The present invention provides a new idea for solving such problems.
The perovskite solar cell mainly comprises a transparent conductive layer, a hole transmission layer, a perovskite light absorption layer, an electron transmission layer and an electrode, and a modification layer is added between the hole transmission layer and the perovskite light absorption layer in some cases, so that energy level potential barriers and surface defects are reduced, and the efficiency is improved. At present, the choice of materials for the hole transport layer is not very large, and the prior art has not proposed a new idea for providing a hole transport layer with a single crystalline polypyrrole (PPY) polymer as the hole transport layer.
Disclosure of Invention
The invention designs a novel perovskite solar cell with an organic hole transport layer and a preparation method thereof, and solves the technical problems that the perovskite solar cell in the prior art has poor ultraviolet irradiation resistance and stability in outdoor operation, and the planar perovskite solar cell has high cost.
In order to solve the technical problems, the invention adopts the following scheme:
a novel perovskite solar cell with an organic hole transport layer 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 absorbing layer is ABX 3 Organic-inorganic hybrid perovskite material with structure, wherein A is CH 3 NH 3 + (methylamine), NH 2 CH=NH 2 (formamidine), cs + One or more of B is Pb 2+ 、Sn 2+ One or two of X is Cl - 、Br - 、I - One or more of the following.
Preferably, the electron transport layer is ZnO and SnO 2 、TiO 2 Or PCBM.
Preferably, the metal back electrode adopts silver-aluminum alloy with the thickness of 70-120nm.
In the invention, the solar cell module can be selected from other organic solar cell modules. In the present invention, the modification layer in the perovskite solar cell may be omitted or added. And the modification layer adopts PEAI.
The preparation method of the novel perovskite solar cell with the organic hole transport layer comprises the following steps:
step 1: cleaning and drying the conductive substrate, and then performing 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;
step 3: spin-coating a perovskite precursor solution on the organic hole transport layer, then adding a chlorobenzene solvent for continuous spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a perovskite light absorption layer;
step 4: spin-coating a chlorobenzene solution of PCBM on the perovskite light absorption layer to form an electron transport layer;
step 5: and evaporating a 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, characterized in that: the solar cell comprises a transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a monocrystalline polypyrrole (PPY) polymer hole 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 absorbing layer is ABX 3 Organic-inorganic hybrid perovskite material with structure, wherein A is CH 3 NH 3 + (methylamine), NH 2 CH=NH 2 (formamidine), cs + One or more of B is Pb 2+ 、Sn 2+ One or two of X is Cl - 、Br - 、I - One or more of the following. The perovskite absorption layer adopts CH 3 NH 3 PbI 3
Preferably, the electron transport layer is ZnO and SnO 2 、TiO 2 Or PCBM.
Preferably, the metal back electrode adopts silver-aluminum alloy with the thickness of 70-120nm.
The preparation method of the novel perovskite solar cell with the organic hole transport layer comprises the following steps: step 1: cleaning and drying an FTO conductive glass substrate, and then performing ultraviolet cleaning treatment to obtain a pretreated substrate; step 2: selectively coating PCBM films on the pretreated substrate to form an organic electronic transmission layer; step 3: spin-coating a perovskite precursor solution on the organic electronic transmission layer, then adding a chlorobenzene solvent for continuous spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer; step 4: covering a hole transport layer PPY monocrystalline film on the light absorption layer to form a hole transport layer; step 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 duration of the perovskite battery in the air, so that the stability is good.
(2) The hole transport material provided by the invention has good hole transport performance and good solubility, and can be dissolved in a green solvent to obtain a good film morphology and has adjustable photoelectric performance.
(3) The novel monocrystalline polypyrrole (PPY) polymer material provided by the invention can prove that the monocrystalline material can be applied to an organic solar cell, has good hole mobility and photostability, and can inhibit the recombination of photo-generated electrons and photo-generated holes.
(4) Experiments prove that the hole transport material provided by the invention can obviously improve the ultraviolet irradiation resistance of the solar cell, and can maintain stable cell performance after being placed in air for 500 hours.
(5) The novel thought provided by the invention has wide application prospect in the field of photoelectric devices, in particular to perovskite solar cells.
Drawings
Fig. 1: the cross-sectional structure of the novel perovskite solar cell example 1 is schematically shown;
fig. 2: the front structure schematic diagram of the perovskite solar cell is shown;
fig. 3: the cross-sectional structure of the novel perovskite solar cell embodiment 2 is schematically shown;
fig. 4: the I-V curve of the initial cell in example 1 of the present invention;
fig. 5: the I-V curve of the battery after two weeks in the indoor environment in example 1 of the present invention;
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 present invention.
Reference numerals illustrate:
1-a metal back electrode; 2-PCBM; a 3-perovskite absorber layer; 4-PPY single crystal film; 5-FTO conductive glass.
Detailed Description
The invention is further described with reference to fig. 1 to 7:
as shown in fig. 1, an encapsulated perovskite solar cell comprising: a metal back electrode 1, PCBM2, a perovskite absorption layer 3, a PPY single crystal film 4 and FTO conductive glass 5. The invention is not limited to the inverted structure, but is also applicable to the normal structure.
A method of making an encapsulated perovskite solar cell comprising the steps of;
step 1: cleaning and drying the conductive glass substrate, and then performing 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; step 3: spin-coating a perovskite precursor solution on the organic hole transport layer, then adding a chlorobenzene solvent for continuous spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer; step 4: spin-coating a chlorobenzene solution of PCBM on the light absorption layer to form an electron transport layer; step 5: and evaporating a 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, wherein the acid can be hydrochloric acid, sulfuric acid, phosphoric acid or organic acid, and deionized water is used as a solvent. Next, ammonium persulfate was weighed and dissolved in the above acid solution as the oxidizing agent for the reaction. Simultaneously, a small amount of pyrrole monomer is taken by a liquid-transferring gun, chloroform is selected as a solvent, and the mixture is stirred uniformly for later use. And (3) putting the prepared monomer and the oxidant into a refrigerator for refrigeration, taking out and mixing after 1h, and forming an interface after mixing due to the different densities of the two solutions, wherein a polypyrrole film is formed at the interface.
The perovskite solar cell provided by the invention can have stable filling factor and photoelectric conversion efficiency after being tested, has certain ultraviolet resistance, and can stably exist in air for a plurality of weeks by being compared with other perovskite solar cells, so that the monocrystalline polypyrrole (PPY) polymer material has certain water-oxygen resistance, and the invention proves that the monocrystalline polypyrrole (PPY) polymer can be used as a hole transport material and can provide a new idea for the later monocrystalline material as the hole transport material.
Example 1:
the perovskite solar cell shown in fig. 1 is manufactured by the following specific steps:
in inverted MAPbI 3 Perovskite solar cell modules are examples. Wherein the perovskite solar cell component comprises an FTO layer (transparent conductive layer), a hole transport layer (PPY) and a MAPbI 3 Perovskite 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 front of the battery component is provided with a transparent conductive layer, FTO conductive glass 5 is selected, a PPY single crystal film 4 is arranged on the FTO conductive glass 5, a perovskite absorption layer 3 is arranged on the PPY single crystal film 4, an electron transmission layer PCBM2 is arranged on the perovskite absorption layer 3, a metal back electrode 1 is arranged on the electron transmission layer (PCBM) 2, and the metal back electrode 1 is made of silver-aluminum alloy.
Step 1: cleaning and drying the FTO conductive glass 5 substrate, and then performing 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;
step 3: spin-coating a perovskite precursor solution on the organic hole transport layer, then adding a chlorobenzene solvent for continuous spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer;
step 4: spin-coating a chlorobenzene solution of PCBM on the light absorption layer to form an electron transport layer;
step 5: and evaporating a 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, durability test of the battery, which was placed in an indoor environment for two weeks at an ambient humidity of 60%, a temperature of 25 ℃, the battery performance was as shown in the following table:
Voc V Jsc FF Efficiency
0.804 7.31 46.5 2.74
table 1: initial battery efficiency
Voc V Jsc FF Efficiency
0.78 6.7 47 2.5
Table 2: battery performance in two weeks in indoor environment
Referring to fig. 5 and table 2, it can be concluded from the above figures that using PPY single crystal film as the hole transport layer of perovskite can increase the stability of the battery and can increase its durability in practical use environments.
Referring to tables 3 to 4 and fig. 6 to 7, the battery was tested for uv resistance, and after continuous irradiation under a uv lamp for one hour, the battery performance was tested as follows:
Voc V Jsc FF Efficiency
0.65 6.74 34 1.5
table 3: initial battery efficiency
Voc V Jsc FF Efficiency
0.57 11.3 38 2.5
Table 4: cell efficiency one hour after UV irradiation
From the above data, it can be proved that the efficiency of the solar cell is not reduced and reversely increased under ultraviolet irradiation, which indicates that the perovskite solar cell taking the single crystal polypyrrole (PPY) polymer material as the hole transport layer has strong ultraviolet light resistance, and the efficiency can be steadily increased under ultraviolet irradiation, so that the material has great application potential.
Example 2:
the present embodiment utilizes CsPbI 2 Br perovskite layer replacement MAPbI in example 1 3 Perovskite layer, and adopt the structure of putting in front, battery structure is: the front of the battery component is provided with a transparent conductive layer, FTO conductive glass 5 is selected as the transparent conductive layer, an electron transmission layer PCBM2 is arranged on the transparent conductive layer, a perovskite absorption layer 3 is arranged on the electron transmission layer PCBM2, a hole transmission layer PPY monocrystalline film 4 is arranged on the perovskite absorption layer 3, and a metal back electrode 1 is arranged on the hole transmission layer PPY monocrystalline film 4 and is made of silver-aluminum alloy. The battery 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 performing ultraviolet cleaning treatment to obtain a pretreated substrate;
step 2: selectively coating PCBM films on the pretreated substrate to form an organic electronic transmission layer;
step 3: spin-coating a perovskite precursor solution on the organic electronic transmission layer, then adding a chlorobenzene solvent for continuous spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer;
step 4: covering a hole transport layer PPY monocrystalline film on the light absorption layer to form a hole transport layer;
step 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 durability test and the anti-ultraviolet test prove that the perovskite solar cell has stable filling factor and photoelectric conversion efficiency, has strong anti-ultraviolet capability, can exist stably in the air for a plurality of weeks through comparison with other perovskite solar cells, and shows 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 perovskite solar cell with an organic hole transport layer, and the prepared solar cell device structure comprises the following steps: 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, is prepared by an organic chemical synthesis method, is dissolved in an organic solvent, is then spin-coated on a conductive glass substrate, and has the advantages of simple synthesis step, low cost and no toxicity, greatly reduces the cost of the perovskite solar cell, provides a new idea for the material selection of the hole transport layer of the organic solar cell, and simultaneously, the prepared perovskite cell has excellent stability and extremely strong ultraviolet irradiation resistance. The material can also be applied to other organic solar cells.
The invention has been described above by way of example with reference to the accompanying drawings, it is clear that the implementation of the invention is not limited to the above-described manner, but it is within the scope of the invention to apply the inventive concept and technical solution to other situations as long as various improvements made by the inventive concept and technical solution are adopted or without any improvement.

Claims (4)

1. A novel organic hole transport layer perovskite solar cell, characterized in that: the solar cell 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 in sequence; the transparent conductive substrate is made of FTO, ITO or AZO; the perovskite light absorption layer is ABX 3 Organic-inorganic hybrid perovskite material with structure, wherein A is CH 3 NH 3 + (methylamine), NH 2 CH=NH 2 + (formamidine), cs + One or more of B is Pb 2+ 、Sn 2+ One or two of X is Cl - 、Br - 、I - One or more of the following; the electron transport layer is ZnO and SnO 2 、TiO 2 Or PCBM; monocrystalline polypyrrole (PPY) polymeric materials have resistance to water and oxygen.
2. A method of making the novel organic hole transport layer perovskite solar cell of claim 1 comprising the steps of:
step 1: cleaning and drying the conductive substrate, and then performing ultraviolet cleaning treatment to obtain a pretreated substrate;
step 2: depositing a monocrystalline polypyrrole polymer on the pretreated substrate obtained in the step 1 to form a monocrystalline polypyrrole (PPY) polymer hole transport layer; monocrystalline polypyrrole (PPY) polymeric materials have resistance to water and oxygen;
step 3: spin-coating a perovskite precursor solution on the organic hole transport layer, then adding a chlorobenzene solvent for continuous spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a perovskite light absorption layer;
step 4: spin-coating a chlorobenzene solution of PCBM on the perovskite light absorption layer to form an electron transport layer;
step 5: and evaporating a metal electrode material onto the electron transport layer through thermal evaporation under vacuum to obtain the perovskite solar cell.
3. A novel organic hole transport layer perovskite solar cell, characterized in that: the solar cell comprises a transparent conductive substrate, an electron transport layer, a perovskite light absorption layer, a monocrystalline polypyrrole (PPY) polymer hole transport layer and a metal back electrode layer from bottom to top in sequence; the transparent conductive substrate is made of FTO, ITO or AZO; the perovskite light absorption layer is ABX 3 Organic-inorganic hybrid perovskite material with structure, wherein A is CH 3 NH 3 + (methylamine), NH 2 CH=NH 2 + (formamidine), cs + One or more of B is Pb 2+ 、Sn 2+ One or two of X is Cl - 、Br - 、I - One or more of the following; the electron transport layer is ZnO and SnO 2 、TiO 2 Or PCBM; monocrystalline polypyrrole (PPY) polymeric materials have resistance to water and oxygen.
4. A method of making the novel organic hole transport layer perovskite solar cell of claim 3 comprising the steps of:
step 1: cleaning and drying an FTO conductive glass (5) substrate, and then performing ultraviolet cleaning treatment to obtain a pretreated substrate;
step 2: selectively coating PCBM films on the pretreated substrate to form an organic electronic transmission layer;
step 3: spin-coating a perovskite precursor solution on the organic electronic transmission layer, then adding a chlorobenzene solvent for continuous spin-coating, and annealing at 100 ℃ to obtain a perovskite crystal film, namely a light absorption layer;
step 4: covering a hole transport layer polypyrrole monocrystal film on the light absorption layer to form a monocrystal polypyrrole polymer hole transport layer;
step 5: and evaporating a metal electrode material onto the monocrystalline polypyrrole polymer hole transport layer by thermal evaporation under vacuum to obtain the perovskite solar cell.
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