CN109888112B - Method for preparing efficient and stable perovskite solar cell by using cerium oxide - Google Patents

Method for preparing efficient and stable perovskite solar cell by using cerium oxide Download PDF

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CN109888112B
CN109888112B CN201910156638.7A CN201910156638A CN109888112B CN 109888112 B CN109888112 B CN 109888112B CN 201910156638 A CN201910156638 A CN 201910156638A CN 109888112 B CN109888112 B CN 109888112B
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electron transport
cerium oxide
transport material
precursor solution
solar cell
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CN109888112A (en
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曹靖
蒙蕤谦
冯晓霞
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Lanzhou University
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Abstract

The invention belongs to the field of perovskite solar cell preparation, and particularly relates to a method for preparing a high-efficiency stable perovskite solar cell by using cerium oxide; the method is mainly characterized by comprising the following steps: firstly, preparing a precursor solution of an electron transport material; secondly, mixing and preparing a precursor solution of the electron transport material doped with cerium oxide; thirdly, FTO spin coating of an electron transport material precursor solution; fourthly, assembling the battery by the FTO and various processes; the beneficial effects are as follows: the cerium oxide is introduced into the electron transport material, so that the minimum conduction band of the electron transport material is improved, the interface stability between the perovskite and the electron transport material is improved, and the extraction and the transmission of charges are facilitated. By introducing the cerium oxide, the efficiency and the stability are greatly improved, and the ultraviolet light stability of the battery is mainly improved.

Description

Method for preparing efficient and stable perovskite solar cell by using cerium oxide
Technical Field
The invention belongs to the field of perovskite solar cell preparation, and particularly relates to a method for preparing a high-efficiency stable perovskite solar cell by using cerium oxide.
Background
As an important component in the perovskite solar cell structure, electron transport materials play an important role in charge extraction and transport. Commonly used electron transport materials are titanium dioxide, zinc oxide and tin oxide. However, the common electron transport materials and perovskite materials have general chemical compatibility, poor energy level matching, poor ultraviolet stability and the like. The Photoelectric Conversion Efficiency (PCE) of Perovskite Solar Cells (PSCs) is rapidly increased from 3.8% in 2009 to more than 23%, and the perovskite solar cells have great development potential. Further improvements in efficiency and stability are of paramount importance to the development of batteries. A large number of researches prove that the Electron Transport Materials (ETMs) and the perovskites have important influence on PCE and stability due to poor energy level matching, severe interface charge recombination and the like. Therefore, the selection of proper ETM is of great significance to the preparation of efficient and stable PSCs.
Among the commonly used electron transport materials, ZnO, TiO2And SnO2Have received a wide range of attention. Wherein, the ZnO surface shows alkalinity, thereby leading MAPbI to be under the condition of slightly high temperature3The proton of the medium MA + is easily abstracted by ZnO, thereby leading toThe perovskite structure is destroyed. TiO 22Under the condition of illumination, the decomposition of perovskite is catalyzed. SnO2Is much lower than the perovskite. Taking ZnO as an example, there is poor interface stability between ZnO and the perovskite interface, which in turn leads to severe degradation of the perovskite during heat treatment. In addition, the minimum Conduction Band (CBM) of ZnO is much lower than that of perovskites, further forming a serious interfacial barrier. Meanwhile, ZnO as an n-type semiconductor shows higher photocatalytic activity under ultraviolet irradiation, thereby causing decomposition of perovskite. TiO 22And SnO2There are also corresponding disadvantages, especially in respect of uv stability. In order to overcome the above defects, researchers have passivated surface defects using methods such as interface modification. However, to further improve the PCE and stability of the battery, it is also necessary to achieve synergistic effects of enhanced chemical compatibility, energy level matching, and excellent uv stability of the electron transport material and the perovskite interface.
Disclosure of Invention
In view of the defects and the problems in the prior art, the invention provides a method for preparing a high-efficiency stable perovskite solar cell by using cerium oxide, which is characterized by specifically comprising the following steps:
s1, dissolving soluble zinc salt in 2-methoxyethanol, adding ethanolamine, heating and dissolving to prepare a precursor solution of the ZnO electron transport material;
s2, adding cerium acetate into the precursor solution of the ZnO electron transport material, and heating and dissolving to form a precursor solution of the zinc oxide electron transport material doped with cerium oxide;
s3, spin-coating the zinc oxide electron transport material precursor solution doped with cerium oxide on FTO, and annealing at 550 ℃ for 30min to obtain a compact electron transport layer;
s4, sequentially carrying out TiCl on the electron transport layer containing the cerium oxide4Solution treatment, TiO2And coating the slurry, coating the perovskite precursor and vacuum plating gold to finish the assembly of the battery.
The electron transport materials in S1, S2, S3 and S4 are ZnO and TiO2Or SnO2，TiO2Electronic transmission materialDissolving a precursor solution of the material in isopropanol by using tetraisopropyl titanate, and heating and dissolving to obtain the material; SnO2The precursor solution of the electron transport material is obtained by dissolving stannous chloride dihydrate in ethanol and heating for dissolving.
Preferably, cerium acetate is added to the precursor solution of the ZnO electron transport material at a ratio of 3 mol% in S2.
Preferably, the heating temperature of the zinc oxide and cerium oxide doped electron transport material is 85 ℃.
In S3, the precursor solution of the cerium oxide-doped zinc oxide electron transport material is coated by a spin coater, where the operating parameters of the spin coater are 2800rpm for 30S.
The invention has the beneficial effects that: the cerium oxide is introduced into the electron transport material, so that the minimum conduction band of the electron transport material is improved, the interface stability between the perovskite and the electron transport material is improved, and the extraction and the transmission of charges are facilitated. By introducing the cerium oxide, the efficiency and the stability are greatly improved, and the ultraviolet light stability of the battery is mainly improved. Meanwhile, the cerium oxide doped electron transport layer also has the following advantages: 1) CeOx is one of the most abundant rare earth oxides on earth, which means that it has the potential for low-cost mass production. 2) CeOx has good chemical stability and high electron mobility. 3) CeOx has the capability of converting ultraviolet light into visible light, and has the advantage of improving the stability of the ultraviolet light of the cell.
Drawings
FIG. 1 is an energy level diagram for fabricating a solar cell;
FIG. 2 is an XPS spectrum of cerium doped with cerium oxide (powder) in zinc oxide;
FIG. 3 is an XPS spectrum of the zinc element doped with cerium oxide (powder) in zinc oxide;
FIG. 4 is an XRD spectrum of cerium oxide (powder) doped zinc oxide;
FIG. 5 is a graph comparing cell efficiencies before and after doping ZnO with 3 mol% CeOx;
FIG. 6 is a graph of cell efficiency versus time at a particular humidity;
FIG. 7 is a graph of cell efficiency as a function of time at a heating temperature of 85 deg.C;
FIG. 8 is a graph of cell efficiency as a function of time under UV light illumination.
Detailed Description
Example 1
The invention is further described with reference to the following examples and drawings:
the invention provides a method for preparing a high-efficiency stable perovskite solar cell by using cerium oxide, which is characterized in that the cerium oxide is doped into an electron transport material (ZnO, TiO)2、SnO2And the like), the unique 4f electronic structure of the rare earth oxide and the property of converting ultraviolet light into visible light are utilized, so that the stability of the cell, particularly the stability of the ultraviolet light, is improved while higher photoelectric conversion efficiency is realized.
The following steps take ZnO electron transport materials as an example.
Step 1, preparation of an electron transport material precursor solution: soluble zinc salts such as zinc acetate dihydrate (169mg, 0.77mmol) were dissolved in 2.5mL 2-methoxyethanol, 60uL ethanolamine was added and dissolved by heating.
Step 2, preparing a precursor solution of cerium oxide doped zinc oxide: adding cerium acetate (7.33mg, 0.23mmol) into the zinc oxide precursor solution, and heating and dissolving at 85 ℃ to obtain the cerium oxide doped zinc oxide precursor solution. As shown in fig. 5 and 6, the cell efficiency was maximized at a doping ratio of 3 mol% CeOx in ZnO and at a temperature of 85 ℃. As shown in FIG. 1, the ETM of ZnO/CeOx was successfully constructed by directly doping CeOx into a precursor solution of zinc oxide. Fig. 2, 3 and 4 are XPS spectra of cerium element doped with cerium oxide (powder) in zinc oxide, XPS spectra of zinc element doped with cerium oxide (powder) in zinc oxide, and XRD spectra of cerium oxide doped with zinc oxide (powder), respectively. As can be seen from fig. 2, the cerium oxide is prepared in which the valence states of cerium are a mixture of trivalent and tetravalent states. As can be seen from fig. 3, the solution contains zinc. From fig. 4, it is confirmed that the electron transport material in which zinc oxide and cerium oxide are mixed is successfully prepared.
Step 3, preparing the battery: the preparation of the battery is divided into the following steps:
s1, etching the FTO glass by using zinc powder and 2mol/L hydrochloric acid, and then ultrasonically washing the substrate by using acetone, deionized water and ethanol in sequence.
And S2, spin-coating the precursor solution of cerium oxide doped zinc oxide on FTO, and rotating at 2800rpm for 30S by using a spin coater.
S3, annealing at 550 ℃ for 30min to obtain a compact electron transport layer. After cooling to room temperature, the substrate containing the dense layer was placed in 40mM TiCl at 75 deg.C4The solution was boiled for 15 minutes, taken out and dried.
S4, mixing TiO2An isopropanol solution (mass ratio 1: 7) of the slurry (Dyesol DSL 18NR-T) was spin-coated on the substrate at 5000rpm for 25s and annealed at 550 ℃ for 30min to obtain a mesoporous layer.
S5, dissolving 461mg of lead iodide and 159mg of iodomethylamine in 600uLDMF and 70uLDMSO, and spin-coating the obtained perovskite precursor on a substrate at 4000rpm for 25S.
S6, 0.5mL of diethyl ether was added dropwise to the solution by an anti-solvent method, followed by annealing at 70 ℃ for 1min and at 100 ℃ for 2min to form a perovskite layer.
S7, spin coating the hole transport material on the perovskite at 4000rpm for 25S. Wherein the hole transport material comprises the following components: Spiro-OMeTAD was dissolved in chlorobenzene (72mg/1mL) and the additive contained 17.5uL of Li-TFSI/acetonitrile (520mg/1mL) and 28.8uL of TBP.
S8, at 2X 10-7And (5) evaporating 80nm of gold under the Torr vacuum condition to finish the assembly of the battery.
The invention leads the minimum conduction band of the electron transport material to be increased by introducing CeOx, thereby promoting the charge injection and transfer of the perovskite to the ETM. Meanwhile, the modified ETM has better film forming property, and the growth of the perovskite film is further regulated. Furthermore, the contact between ETM and perovskite is more stable. Based on the above effects, the optimized PSCs achieved PCEs as high as 19.5%.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (4)

1. A method for preparing a high-efficiency stable perovskite solar cell by using cerium oxide is characterized by specifically comprising the following steps:
s1, dissolving soluble zinc salt in 2-methoxyethanol, adding ethanolamine, heating and dissolving to prepare a precursor solution of the ZnO electron transport material;
s2, adding cerium acetate into the precursor solution of the ZnO electron transport material, and heating and dissolving to form a precursor solution of the zinc oxide electron transport material doped with cerium oxide;
s3, spin-coating the zinc oxide electron transport material precursor solution doped with cerium oxide on FTO, and annealing at 550 ℃ for 30min to obtain a compact electron transport layer;
s4, sequentially carrying out TiCl on the electron transport layer containing the cerium oxide4Solution treatment, TiO2And coating the slurry, coating the perovskite precursor and vacuum plating gold to finish the assembly of the battery.
2. The method for preparing the high-efficiency stable perovskite solar cell by using the cerium oxide as claimed in claim 1, wherein the method comprises the following steps: and adding the cerium acetate in the S2 into a precursor solution of the ZnO electron transport material in a proportion of 3 mol%.
3. The method for preparing the high-efficiency stable perovskite solar cell by using the cerium oxide as claimed in claim 2, wherein the method comprises the following steps: the heating temperature in S2 was 85 ℃.
4. The method for preparing the high-efficiency stable perovskite solar cell by using the cerium oxide as claimed in claim 1, wherein the method comprises the following steps: and coating the precursor solution of the cerium oxide doped zinc oxide electron transport material in the S3 by using a spin coater, wherein the working parameters of the spin coater are 2800rpm for 30S.
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CN103456888A (en) * 2013-09-26 2013-12-18 天津理工大学 Hybrid solar cell with Cs mingling with ZnO as electron transfer layer
CN108447993A (en) * 2018-03-19 2018-08-24 吉林大学 A kind of optical interval layer inversion polymer solar battery
US20180315939A1 (en) * 2017-04-28 2018-11-01 Research & Business Foundation Sungkyunkwan University Fabrication method of a large area perovskite solar cell
CN109301069A (en) * 2018-10-30 2019-02-01 深圳清华大学研究院 Solar cell and preparation method thereof

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CN103456888A (en) * 2013-09-26 2013-12-18 天津理工大学 Hybrid solar cell with Cs mingling with ZnO as electron transfer layer
US20180315939A1 (en) * 2017-04-28 2018-11-01 Research & Business Foundation Sungkyunkwan University Fabrication method of a large area perovskite solar cell
CN108447993A (en) * 2018-03-19 2018-08-24 吉林大学 A kind of optical interval layer inversion polymer solar battery
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