CN108832002B - Perovskite solar cell based on PVA (polyvinyl alcohol) modified hole transport layer - Google Patents
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Abstract
The invention relates to a perovskite solar cell based on a PVA (polyvinyl alcohol) modified hole transport layer, which comprises a lower transparent electrode layer and an upper electrode layer, wherein five functional layers are clamped between the lower transparent electrode layer and the upper electrode layer, the five functional layers are a hole transport layer, a PVA interface modified layer, a perovskite active layer, an electron transport layer and a buffer layer from bottom to top, and the hole transport layer, the PVA interface modified layer, the perovskite active layer and the electron transport layer are all prepared into films by a low-temperature solution method. According to the invention, the film is prepared by adopting a low-temperature solution method, the process conditions are reasonably controlled, and the PVA modification layer is added between the PEDOT, PSS layer and the perovskite layer, so that the surface wettability of the perovskite is effectively improved, the hole transmission efficiency is improved, the perovskite film is continuously and uniformly prepared, the quality of the perovskite absorption layer is improved, and the prepared perovskite solar cell has high photoelectric conversion efficiency and good stability.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a perovskite solar cell based on a PVA modified hole transport layer and a preparation method thereof.
Background
Along with the increasing development of heavy industry, the frequency of non-renewable resources such as coal, petroleum and the like is urgent, the energy problem increasingly becomes the bottleneck of the development of the international socioeconomic industry, and in addition, the environmental problem is more serious due to the improper use of the non-renewable resources, so that the human survival is greatly threatened; solar energy and other environment-friendly renewable resources are increasingly paid attention to human beings, and the solar cell is an important way for solving the problems of energy exhaustion and environmental pollution in human society.
A solar cell is a device for directly converting light energy into electric energy through a photoelectric effect or a photochemical effect, is also called a solar chip or a photovoltaic cell, and is a photovoltaic semiconductor sheet for directly generating electricity by using sunlight. However, the thickness of the perovskite thin-film solar cell is usually about several hundred nanometers due to the limitations of the thin-film thickness, the material characteristics and the preparation process, so that the absorption of visible light by the perovskite thin-film solar cell is limited to a certain extent, and the improvement of the current density of the perovskite thin-film solar cell is limited.
Disclosure of Invention
In order to solve the problems, the invention provides a perovskite solar cell based on a PVA modified hole transport layer, wherein a PVA modified layer is introduced between an active layer and a hole transport layer of the traditional perovskite solar cell, and aims to improve the surface wettability of PEDOT (Poly vinyl acetate)/PSS (Poly styrene), obtain a continuous and uniform perovskite thin film, improve the light absorption capacity of the perovskite active layer and improve the photoelectric conversion efficiency of the perovskite solar cell.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the invention relates to a perovskite solar cell based on a PVA (polyvinyl alcohol) modified hole transport layer, which comprises a lower transparent electrode layer and an upper electrode layer, wherein five functional layers are clamped between the lower transparent electrode layer and the upper electrode layer, the five functional layers are a hole transport layer, a PVA interface modified layer, a perovskite active layer, an electron transport layer and a buffer layer from bottom to top, and the hole transport layer, the PVA interface modified layer, the perovskite active layer and the electron transport layer are all prepared into films by a low-temperature solution method.
The invention is further improved in that: the lower transparent electrode layer comprises fluorine-doped tin oxide, indium-doped tin oxide, silver nanowires, carbon nanotubes or graphene.
The invention is further improved in that: PSS, and the thickness of the hole transport layer is 30 to 40 nanometers.
The invention is further improved in that: the interface modification layer is PVA, the thickness of the interface modification layer is 2-10 nanometers, the interface modification layer is continuously spin-coated for 15 seconds at 900rpm and 25 seconds at 4000rpm, and the interface modification layer is annealed for 10 minutes to form a film at 100 ℃ in a glove box environment.
The invention is further improved in that: the perovskite active layer is CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbIx Br3-x、CH3NH3PbIxCl3-xAccording to different solution preparation modes, x is between 1 and 3, and the thickness of the perovskite active layer is 300 to 600 nanometers.
The invention is further improved in that: the electron transport layer comprises a PC60BM、PC70BM, ICBA and fullerene derivatives, the thickness of the electron transport layer is 30 nm to 120 nm.
The invention is further improved in that: the buffer layer is bcp, and the thickness of the buffer layer is 10 nanometers.
The invention is further improved in that: the low temperature is between room temperature and 130 ℃.
The invention is further improved in that: the solution processes include spin coating, doctor blading, ink jet printing, roll-to-roll printing techniques.
The invention is further improved in that: the upper electrode layer includes aluminum, silver, gold, ITO, carbon nanotubes, or graphene.
The invention has the beneficial effects that: according to the invention, the film is prepared by adopting a low-temperature solution method, the process conditions are reasonably controlled, and the PVA modification layer is added between the PEDOT, PSS layer and the perovskite layer, so that the surface wettability of the perovskite is effectively improved, the hole transmission efficiency is improved, the perovskite film is continuously and uniformly prepared, the quality of the perovskite absorption layer is improved, and the prepared perovskite solar cell has high photoelectric conversion efficiency and good stability.
According to the perovskite solar cell based on the PVA modified PEDOT and PSS, the thin PVA film is added between the hole transport layer and the perovskite active layer of the perovskite solar cell, the surface wettability of the PEDOT and PSS can be improved by the PVA, the continuous and uniform perovskite film is easy to form, the photoelectric conversion efficiency of the perovskite solar cell is improved from 8.25 to 10.31 and is improved by 24.96%, and the perovskite solar cell based on the PVA modified PSS is prepared by a solution technology at a low temperature, is good in repeatability and low in cost, and has a wide application prospect.
Drawings
Fig. 1 is a schematic structural view of a solar cell of the present invention.
FIG. 2 is a graph showing the voltammetric characteristics of solar cells prepared with different concentrations of PVA according to the present invention.
Detailed Description
For the purpose of enhancing the understanding of the present invention, the present invention will be described in further detail with reference to the accompanying drawings and examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention.
As shown in figures 1-2, the invention is a perovskite solar cell based on a PVA modified hole transport layer, which comprises a lower transparent electrode layer and an upper electrode layer, wherein five functional layers are clamped between the lower transparent electrode layer and the upper electrode layer, the five functional layers are a hole transport layer, a PVA interface modification layer, a perovskite active layer, an electron transport layer and a buffer layer from bottom to top in sequence, the hole transport layer, the PVA interface modification layer, the perovskite active layer and the electron transport layer are all prepared into films by a low-temperature solution method,
wherein: the upper electrode layer comprises aluminum, silver, gold, ITO, carbon nanotubes or graphene; the lower transparent electrode layer comprises fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), silver nanowires, carbon nanotubes or graphene; PSS, wherein the thickness of the hole transport layer is 30 to 40 nanometers; the interface modification layer is PVA, the thickness of the interface modification layer is 2-10 nanometers, the interface modification layer is continuously spin-coated for 15 seconds at 900rpm and 25 seconds at 4000rpm, annealing is carried out for 10 minutes to form a film at 100 ℃ in a glove box environment, and the perovskite active layer is CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbIx Br3-x、CH3NH3PbIxCl3-xAccording to different solution configuration modes, x is between 1 and 3, and the thickness of the perovskite active layer is 300 nanometers to 600 nanometersRice; the electron transport layer comprises a PC60BM、PC70BM, ICBA and fullerene derivatives, wherein the thickness of the electron transport layer is 30 to 120 nanometers; the buffer layer is bcp, and the thickness of the buffer layer is 10 nanometers; the low temperature is between room temperature and 130 ℃, wherein the room temperature is about 20 ℃; the solution processes include spin coating, doctor blading, ink jet printing, roll-to-roll printing techniques.
Example one
The preparation of the device is carried out according to the structural schematic diagram of the solar cell shown in figure 1, and the preparation method comprises the following steps:
washing commercial ITO twice in washing liquid, deionized water, acetone and ethanol respectively, wherein each washing time is 15 minutes, then drying by nitrogen, and treating by plasma for 4 minutes;
spin-coating the cleaned and plasma-treated ITO glass on a spin coater at 4000rpm for 30 seconds to prepare a hole transport layer PEDOT, wherein PSS is annealed on a hot table at 130 ℃ for 20 minutes;
dissolving PVA in deionized water at the concentration of 0.25mg/ml, heating and stirring at 95 ℃ to fully disperse the PVA, carrying out two-step continuous spin coating of 15s at 900rpm and 25s at 4000rpm, and annealing for 10 minutes at 100 ℃ in a glove box environment;
mixing lead iodide with methylamine lead iodide according to a molar ratio of 1: 1, preparing a solution with the concentration of 1.4mmol/ml, wherein the molar ratio of the solvent is 3: 7, heating the mixed solution of DMSO and GBL at 70 ℃ for 4 hours, fully dissolving, then spin-coating the perovskite precursor solution on a PVA modification layer for 15s at 900rpm and 25s at 4000rpm, dropwise adding an anti-solvent toluene at the second step for 15s, and then annealing for 10 minutes at 100 ℃ on a hot bench;
spin-coating PCBM chlorobenzene solution of 20mg/ml onto the perovskite film at 2000 rpm as a hole transport layer, and annealing at 70 deg.C for 10 min;
transferring the spin-coated four-layer functional layer film sample into a vacuum evaporation instrument with the vacuum degree of less than 4 multiplied by 10-4Pa, evaporating 100nm silver as an upper electrode.
Example two
The preparation of the device is carried out according to the structural schematic diagram of the solar cell shown in figure 1, and the preparation method comprises the following steps:
washing commercial ITO twice in washing liquid, deionized water, acetone and ethanol respectively, wherein each washing time is 15 minutes, then drying by nitrogen, and treating by plasma for 4 minutes;
spin-coating the cleaned and plasma-treated ITO glass on a spin coater at 4000rpm for 30 seconds to prepare a hole transport layer PEDOT, wherein PSS is annealed on a hot table at 130 ℃ for 20 minutes;
dissolving PVA in deionized water at the concentration of 0.5mg/ml, heating and stirring at 95 ℃ to fully disperse the PVA, carrying out two-step continuous spin coating of 15s at 900rpm and 25s at 4000rpm, and annealing for 10 minutes at 100 ℃ in a glove box environment;
mixing lead iodide with methylamine lead iodide according to a molar ratio of 1: 1, preparing a solution with the concentration of 1.4mmol/ml, wherein the molar ratio of the solvent is 3: 7, heating the mixed solution of DMSO and GBL at 70 ℃ for 4 hours, fully dissolving, then spin-coating the perovskite precursor solution on a PVA modification layer for 15s at 900rpm and 25s at 4000rpm, dropwise adding an anti-solvent toluene at the second step for 15s, and then annealing for 10 minutes at 100 ℃ on a hot bench;
spin-coating PCBM chlorobenzene solution of 20mg/ml onto the perovskite film at 2000 rpm as a hole transport layer, and annealing at 70 deg.C for 10 min;
transferring the spin-coated four-layer functional layer film sample into a vacuum evaporation instrument with the vacuum degree of less than 4 multiplied by 10-4Pa, evaporating 100nm silver as an upper electrode.
EXAMPLE III
The preparation of the device is carried out according to the structural schematic diagram of the solar cell shown in figure 1, and the preparation method comprises the following steps:
washing commercial ITO twice in washing liquid, deionized water, acetone and ethanol respectively, wherein each washing time is 15 minutes, then drying by nitrogen, and treating by plasma for 4 minutes;
spin-coating the cleaned and plasma-treated ITO glass on a spin coater at 4000rpm for 30 seconds to prepare a hole transport layer PEDOT, wherein PSS is annealed on a hot table at 130 ℃ for 20 minutes;
dissolving PVA in deionized water at the concentration of 0.75mg/ml, heating and stirring at 95 ℃ to fully disperse the PVA, carrying out two-step continuous spin coating of 15s at 900rpm and 25s at 4000rpm, and annealing for 10 minutes at 100 ℃ in a glove box environment;
mixing lead iodide with methylamine lead iodide according to a molar ratio of 1: 1, preparing a solution with the concentration of 1.4mmol/ml, wherein the molar ratio of the solvent is 3: 7, heating the mixed solution of DMSO and GBL at 70 ℃ for 4 hours, fully dissolving, then spin-coating the perovskite precursor solution on a PVA modification layer for 15s at 900rpm and 25s at 4000rpm, dropwise adding an anti-solvent toluene at the second step for 15s, and then annealing for 10 minutes at 100 ℃ on a hot bench;
spin-coating PCBM chlorobenzene solution of 20mg/ml onto the perovskite film at 2000 rpm as a hole transport layer, and annealing at 70 deg.C for 10 min;
transferring the spin-coated four-layer functional layer film sample into a vacuum evaporation instrument with the vacuum degree of less than 4 multiplied by 10-4Pa, evaporating 100nm silver as an upper electrode.
Example four
The preparation of the device is carried out according to the structural schematic diagram of the solar cell shown in figure 1, and the preparation method comprises the following steps:
washing commercial ITO twice in washing liquid, deionized water, acetone and ethanol respectively, wherein each washing time is 15 minutes, then drying by nitrogen, and treating by plasma for 4 minutes;
spin-coating the cleaned and plasma-treated ITO glass on a spin coater at 4000rpm for 30 seconds to prepare a hole transport layer PEDOT, wherein PSS is annealed on a hot table at 130 ℃ for 20 minutes;
dissolving PVA in deionized water at the concentration of 1mg/ml, heating and stirring at 95 ℃ to fully disperse the PVA, carrying out two-step continuous spin coating at 900rpm for 15s and 4000rpm for 25s, and annealing for 10 minutes at 100 ℃ in a glove box environment;
mixing lead iodide with methylamine lead iodide according to a molar ratio of 1: 1, preparing a solution with the concentration of 1.4mmol/ml, wherein the molar ratio of the solvent is 3: 7, heating the mixed solution of DMSO and GBL at 70 ℃ for 4 hours, fully dissolving, then spin-coating the perovskite precursor solution on a PVA modification layer for 15s at 900rpm and 25s at 4000rpm, dropwise adding an anti-solvent toluene at the second step for 15s, and then annealing for 10 minutes at 100 ℃ on a hot bench;
spin-coating PCBM chlorobenzene solution of 20mg/ml onto the perovskite film at 2000 rpm as a hole transport layer, and annealing at 70 deg.C for 10 min;
transferring the spin-coated four-layer functional layer film sample into a vacuum evaporation instrument with the vacuum degree of less than 4 multiplied by 10-4Pa, evaporating 100nm silver as an upper electrode.
The experimental effect is as follows: the performance test of the solar cell is carried out, the current-voltage characteristic curve is shown in figure 2, the specific performance of the device is shown in table 1,
TABLE 1
Wherein comparative sample Voc =0.91, Jsc =11.40, FF =78.78, PCE = 8.25; when the PVA concentration of the modification layer is 0.75mg/ml, Voc =0.99, Jsc =14.27, FF =72.54, and PCE =10.31, it can be seen that the optimal concentration of PVA solvent is 0.75 mg/ml.
Claims (9)
1. A perovskite solar cell based on PVA modification hole transport layer comprises a lower transparent electrode layer and an upper electrode layer, and is characterized in that: five functional layers are sandwiched between the lower transparent electrode layer and the upper electrode layer, the five functional layers are sequentially a hole transport layer, a PVA interface modification layer, a perovskite active layer, an electron transport layer and a buffer layer from bottom to top, the hole transport layer, the PVA interface modification layer, the perovskite active layer and the electron transport layer are all prepared into a film by a low-temperature solution method, the hole transport layer is PEDOT, PSS, the interface modification layer is PVA with the thickness of 2-10 nanometers, the film is formed by two-step continuous spin coating of 15s at 900rpm and 25s at 4000rpm, and the film is formed by annealing for 10 minutes at 100 ℃ in a glove box environment.
2. The perovskite solar cell based on the PVA modified hole transport layer as claimed in claim 1, wherein: the lower transparent electrode layer comprises fluorine-doped tin oxide, indium-doped tin oxide, silver nanowires, carbon nanotubes or graphene.
3. The perovskite solar cell based on the PVA modified hole transport layer as claimed in claim 1, wherein: the hole transport layer has a thickness of 30 nm to 40 nm.
4. The perovskite solar cell based on the PVA modified hole transport layer as claimed in claim 1, wherein: the perovskite active layer is CH3NH3PbI3、CH3NH3PbBr3、CH3NH3PbCl3、CH3NH3PbIx Br3-x、CH3NH3PbIxCl3-xThe thickness of the perovskite active layer is 300 nanometers to 600 nanometers, and x is between 1 and 3, but not including 3.
5. The perovskite solar cell based on the PVA modified hole transport layer as claimed in claim 1, wherein: the electron transport layer comprises a PC60BM or PC70BM or ICBA, the thickness of the electron transport layer is 30 nm to 120 nm.
6. The perovskite solar cell based on the PVA modified hole transport layer as claimed in claim 1, wherein: the buffer layer is bcp, and the thickness of the buffer layer is 10 nanometers.
7. The perovskite solar cell based on the PVA modified hole transport layer as claimed in claim 1, wherein: the low temperature is between room temperature and 130 ℃.
8. The perovskite solar cell based on the PVA modified hole transport layer as claimed in claim 1, wherein: the solution process is a spin or doctor-blade coating or ink-jet printing or roll-to-roll printing technique.
9. The perovskite solar cell based on the PVA modified hole transport layer as claimed in claim 1, wherein: the upper electrode layer includes aluminum, silver, gold, ITO, carbon nanotubes, or graphene.
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