CN113097386B - Composite electron transport layer with efficient charge extraction and application thereof in perovskite solar cell - Google Patents
Composite electron transport layer with efficient charge extraction and application thereof in perovskite solar cell Download PDFInfo
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Abstract
The invention disclosesA composite electron transport layer with efficient charge extraction and application thereof in a perovskite solar cell are provided, and mainly the modification of the electron transport layer is realized. Firstly, preparing TiO with the thickness of 20-25nm by spin coating 2 A dense layer; secondly, further spin coating TiO 2 Preparation of TiO from slurry 2 A mesoporous layer; again, it will be at TiO 2 SnO is spin-coated on the mesoporous layer 2 And (4) nano particles, so as to complete the preparation of the composite electron transport layer. The composite electron transport layer with efficient charge extraction can improve charge extraction, reduce charge recombination and reduce perovskite material degradation, thereby obtaining a high-performance perovskite solar cell.
Description
Technical Field
The invention relates to a composite electron transport layer with efficient charge extraction and application thereof in a perovskite solar cell, and belongs to the technical field of photovoltaics.
Background
Solar energy is one of the most representative green energy sources at present, and is inexhaustible. Therefore, solar energy is receiving wide attention from countries all over the world, and development and utilization of solar energy are gradually expanding to more application fields. The perovskite solar cell is a novel photovoltaic device with a wide application prospect, and is widely concerned in the fields of scientific research and industry, and the perovskite material has the advantages of adjustable band gap, long carrier diffusion length, high defect tolerance, long carrier service life and the like, so that the performance of the perovskite solar cell is greatly improved in a short period.
In perovskite solar cells, an electron transport layer plays an essential role in transporting electrons, blocking holes, and the like. More common electron transport layers include TiO 2 ZnO, etc. Wherein, tiO 2 By virtue of its good stabilityThe prepared perovskite type solar cell has good performance and a proper energy band structure, and can be widely applied to perovskite cells. For example, nanjing aerospace university discloses a TiO for perovskite solar cells 2 An electron transport layer and a preparation method (application number: CN 201711076827.0). However, tiO 2 The catalyst has a strong catalytic action on the perovskite material under the irradiation of ultraviolet light, and can cause the degradation and decomposition of the perovskite material; at the same time, tiO 2 And perovskite charge mobility mismatch (y. Wang et al, ACS applied. Materials, etc.)&Interfaces.2020,12, 31659-31666). ZnO has a higher TiO content 2 Two orders of magnitude charge mobility and band placement are also suitable. For example, hubei university discloses a preparation method of an inorganic perovskite cell with ZnO as an electron transport layer (application number: CN 201811559303.1). However, znO and perovskite also accelerate decomposition of the perovskite material when in direct contact, resulting in poor device stability (R.H. Chen et al, journal of the American Chemical society.2019,141, 541-547). Therefore, there is a need to explore the preparation of electron transport layers with efficient charge extraction to build high performance perovskite solar cells.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a composite electron transport layer with efficient charge extraction and its application in perovskite solar cells. The composite electron transport layer can improve charge extraction, reduce charge recombination and reduce perovskite material degradation, thereby obtaining a high-performance perovskite solar cell.
The composite electron transport layer with high-efficiency charge extraction is formed on TiO 2 Surface spin coating TiO of compact layer 2 Mesoporous layer and SnO 2 And (4) obtaining the composite electron transport layer after the nanoparticles are formed.
In the composite electron transport layer, tiO 2 Dense layer (c-TiO) 2 ) Has a thickness of 20-25nm and is made of TiO 2 Mesoporous layer (m-TiO) 2 ) Has a thickness of 100-300nm and SnO 2 Nanoparticles (NP-SnO) 2 ) Has a size of 4-5nm.
The preparation method of the composite electron transport layer with efficient charge extraction comprises the following steps:
step 1: cleaning of conductive substrates
Cutting the conductive substrate according to required size, sequentially and continuously cleaning the etched substrate with detergent solution, deionized water, acetone, ethanol and isopropanol for 10-20min, and using N 2 And (4) airflow drying. Densifying TiO by spin coating 2 Previously, the cleaned substrates were subjected to UV ozone treatment for 15-25min for storage.
Step 2: preparation of the dense layer
Placing the conductive substrate cleaned in the step 1 in a spin coater, sucking the dense layer precursor solution by a liquid transfer gun and dropping the solution on the substrate, and forming TiO (acetylacetone) with the thickness of 20-25nm by spin-coating and diluting (sequentially spin-coating at the rotating speed of 300-600rpm for 5-10s and at the rotating speed of 1000-4000rpm for 10-50 s) with the diisopropoxybiacetylacetonate titanium (acetylacetone) with the thickness of 0.1-0.2 μm in n-butyl alcohol 2 Thin layer, heat treating on a hot plate at 120-150 deg.C for 5-15min, and annealing at 400-500 deg.C in air for 20-40min to obtain TiO 2 A dense layer;
and step 3: preparation of mesoporous layer
Preparing the obtained TiO in step 2 by adopting a spin coating process 2 Spinning Tu Jie pore layer slurry on the dense layer to obtain mesoporous TiO with the thickness of 100-300nm 2 Coating at 3500-4500rpm, sintering at 400-500 deg.C for 20-40min in air to obtain FTO/c-TiO 2 /m-TiO 2 Subjecting the substrate to ultraviolet ozone treatment for 15-30min to obtain TiO 2 A mesoporous layer;
and 4, step 4: snO 2 Preparation of nanoparticles
0.2-0.6mL of SnO with the concentration of 10-20wt% 2 Diluting the colloidal dispersion in 3-5mL of ultrapure water, and rotating at 2000-4000rpm to obtain FTO/c-TiO in step 3 2 /m-TiO 2 Spin-coating on the substrate for 20-40s, annealing at 100-200 deg.C for 20-40min to form composite electron transport layer FTO/c-TiO 2 /m-TiO 2 +NP-SnO 2 And carrying out ultraviolet ozone treatment for 15-30min.
The invention relates to an application of a composite electron transport layer with efficient charge extraction, which is used as an electron transport layer to prepare perovskite solar energy electricityAnd (4) a pool. The perovskite solar cell has the following device structure: conductive substrate/TiO 2 Dense layer/TiO 2 Mesoporous layer + SnO 2 Nanoparticles/perovskite layer/hole transport layer/metal electrode.
The method specifically comprises the following steps:
and 5: preparation of perovskite layer
At ambient temperature, 400-500mgPbI 2 150-200mg MAI and 60-80mg DMSO (molar ratio 1: 1) were dissolved in 500-700mg DMF and the mixture solution was stirred for 1h under a glove box nitrogen atmosphere. In particular, 40-60 μ L of perovskite precursor solution is added dropwise to the FTO/c-TiO 2 Or FTO/c-TiO 2 /m-TiO 2 Followed by spin coating at 3000-5000rpm for 20-30s, wherein a drop (60-120 μ L) of ethyl acetate as an anti-solvent is added dropwise onto the spinning substrate after 6-8 s. The coating film is heat treated on a hot plate at 100-120 ℃ for 6-12min. During drying at 100-120 ℃, the color of the film changed from light yellow to dark brown, indicating the formation of a perovskite film.
Step 6: preparation of hole transport layer
Casting 1-1.2mL of a chlorobenzene solution containing 70-75mg of spiro-OMeTAD, 28-30. Mu.L of tert-butyl pyridine and 17-18. Mu.L of lithium bis (trifluoromethylstyryl) imide dissolved in acetonitrile (0.5-0.6 g/mL) onto the perovskite surface and spinning at 2000-4000rpm for 25-30s to form a hole transport layer, and placing the sample in dark air for 12-24h;
and 7: evaporation of electrodes
Placing the sample prepared in the step 6 in a thermal evaporation device, evaporating a metal electrode to finally finish the preparation of the perovskite solar cell with high charge extraction capacity, wherein the device structure is a conductive substrate/c-TiO 2 /m-TiO 2 +NP-SnO 2 Perovskite layer/hole transport layer/metal electrode.
In the step 1, the conductive substrate is FTO, ITO or AZO conductive glass.
In step 5, the perovskite film is MAPbI 3 、FAPbI 3 、(Cs,MA,FA)PbI 3 And the like perovskite thin films.
In step 6, the hole transport layer is made of Spiro-OMeTAD or P3HT.
In step 7, the metal electrode is a gold or silver electrode.
Compared with the prior art, the invention has the beneficial effects that:
1. the composite electron transport layer can enhance charge extraction and reduce charge recombination.
2. The surface of the composite electron transport layer prepared by the method is smoother, and the compact and uniform high-quality perovskite thin film can be obtained.
3. SnO in the present invention 2 The nano-particles separate TiO 2 With perovskite absorption layer, tiO reduction 2 Photocatalytic effect on perovskite materials.
4. The composite electron transport layer can improve the electron mobility, and has good application prospect in the aspects of constructing the composite electron transport layer with efficient charge extraction and the perovskite solar cell thereof.
Drawings
Fig. 1 is a structural diagram of a composite electron transport layer with efficient charge extraction and its perovskite solar cell. Wherein, 1 is a metal electrode; 2 is a hole transport layer; 3 is a perovskite layer; 4 is SnO 2 A nanoparticle; 5 is TiO 2 A mesoporous layer; 6 is TiO 2 A dense layer; and 7 is conductive glass.
FIG. 2 is the TiO produced 2 Atomic Force Microscopy (AFM) image of the dense layer with a roughness of 8.84nm.
FIG. 3 is the TiO prepared 2 Dense layer plus SnO 2 AFM imaging of nanoparticles with roughness of 8.71nm; comparison of FIG. 2 shows that the addition of SnO 2 After the nanoparticles, the roughness decreased, indicating the introduction of SnO 2 After the nano particles are formed, the surface appearance of the electron transmission layer is improved.
FIG. 4 is an X-ray diffraction (XRD) pattern. It can be seen that SnO is introduced 2 After the nanoparticles, it can be seen that the perovskite crystallization is good.
FIG. 5 is a graph of photocurrent density-voltage (J-V) curves of perovskite solar cells based on composite electron transport layers prepared by the method of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following specific embodiments and accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1:
1. cleaning of conductive substrates
Cutting the conductive substrate according to required size, sequentially and continuously cleaning the etched substrate with detergent solution, deionized water, acetone, ethanol and isopropanol for 15min, and cleaning with N 2 And (4) airflow drying. Densifying TiO by spin coating 2 Before, the cleaned substrate is subjected to ultraviolet ozone treatment for 20min and stored for standby;
2、TiO 2 preparation of the dense layer
Placing the cleaned conductive substrate in a spin coater, sucking a certain amount of dense layer precursor solution by a liquid-transferring gun, dropping the solution on the substrate, and forming TiO with thickness of 20-25nm by spin-coating and diluting (spin-coating at 500rpm for 5s and spin-coating at 2000rpm for 30s in turn) 0.15 μm diisopropoxybis-acetylacetone titanium (acetylacetonate) in n-butanol 2 A thin layer, followed by heat treatment on a hot plate at 135 ℃ for 10min and annealing in air at 500 ℃ for 30min;
3、TiO 2 preparation of mesoporous layer
Adopting spin coating process to spin Tu Jie pore layer slurry on the prepared film sample, under the condition of mesoporous structure, 200nm thick mesoporous TiO 2 Layer by spin coating of commercially available TiO 2 The slurry (Dyesol 18 NR-T) was further deposited on dense TiO 2 On the layer of the TiO 2 Diluting the slurry at a weight ratio of 1: 10 in anhydrous ethanol at a rotation speed of 4000rpm for 30s, sintering in air at 500 deg.C for 30min, and mixing the obtained FTO/c-TiO 2 Layer of m-TiO 2 The substrate was further subjected to uv ozone treatment for 20min;
4、SnO 2 preparation of nanoparticles
0.5mLSnO 2 Colloidal dispersion (15 wt%) was diluted in 3-5mL of ultrapure water and then spun at 3000rpm at FTO/c-TiO 2 /m-TiO 2 The substrate was spin coated for 30s and then annealed at 150 ℃ for 30min. Formation of FTO/c-TiO 2 /m-TiO 2 +NP-SnO 2 Subjecting to ultraviolet ozone treatment for 20min;
5. preparation of perovskite layer
At ambient temperature, 461mgPbI 2 159mg MAI and 78mg DMSO (molar ratio 1: 1) were dissolved in 600mg DMF, and the mixture solution was stirred in a glove box under nitrogen for 1h. In particular, 50. Mu.L of perovskite precursor solution was added dropwise to the FTO/c-TiO 2 Or FTO/c-TiO 2 /m-TiO 2 Followed by spin coating at 4000rpm for 25s, where after 7s a drop (100 μ L) of the anti-solvent ethyl acetate is added dropwise to the spinning substrate. The coated film was heat treated on a hot plate at 105 ℃ for 10min. During drying at 105 ℃, the color of the film changed from light yellow to dark brown, indicating the formation of a perovskite film;
6. preparation of hole transport layer
1mL of a chlorobenzene solution containing 72.3mg of spiro-OMeTAD, 28.8. Mu.L of tert-butylpyridine and 17.5. Mu.L of lithium bis (trifluoromethylstyryl) imide salt dissolved in acetonitrile (0.52 g/mL) was cast onto the perovskite surface and rotated at 3000rpm for 30s to form an HTL layer, and the obtained sample was left overnight in dark air before thermal evaporation of the silver electrode was performed to complete the fabrication of the printed circuit board;
7. evaporation of electrodes
And placing the prepared sample in a thermal evaporation device, evaporating the metal electrode, and finally completing the preparation of the perovskite solar cell with different electron transport layer structures. The device structure is conductive substrate/c-TiO 2 Perovskite layer/hole transport layer/metal electrode, conductive substrate/c-TiO 2 /m-TiO 2 Perovskite layer/hole transport layer/metal electrode and conductive substrate/c-TiO 2 /m-TiO 2 +NP-SnO 2 Perovskite layer/hole transport layer/metal electrode.
TABLE 1 Effect of different electron transport layer structures on perovskite cell Performance
It can be seen from table 1 that different electron transport layer structures have a significant effect on the performance of the perovskite cell.
Example 2:
1. cleaning of conductive substrates
Cutting the conductive substrate according to required size, sequentially and continuously cleaning the etched substrate with detergent solution, deionized water, acetone, ethanol and isopropanol for 15min, and using N 2 And (4) airflow drying. Densifying TiO by spin coating 2 Before, the cleaned substrate is subjected to ultraviolet ozone treatment for 20min and stored for standby;
2、TiO 2 preparation of the dense layer
Placing the cleaned conductive substrate in a spin coater, sucking a certain amount of dense layer precursor solution by a liquid-transferring gun, dropping the solution on the substrate, and forming TiO with thickness of 20-25nm by spin-coating and diluting (spin-coating at 500rpm for 5s and spin-coating at 2000rpm for 30s in turn) 0.15 μm diisopropoxybis-acetylacetone titanium (acetylacetonate) in n-butanol 2 A thin layer, followed by heat treatment on a hot plate at 135 ℃ for 10min and annealing in air at 500 ℃ for 30min;
3、TiO 2 preparation of mesoporous layer
Adopting spin coating process to spin Tu Jie pore layer slurry on the prepared film sample, under the condition of mesoporous structure, 200nm thick mesoporous TiO 2 Layer by spin coating of commercially available TiO 2 The slurry (Dyesol 18 NR-T) was further deposited on dense TiO 2 On the layer of the TiO 2 Diluting the slurry in anhydrous ethanol at a rotation speed of 4000rpm for 30s in a weight ratio of 1: 8, 1: 10 and 1: 12 in sequence, sintering the slurry in air at 500 ℃ for 30min, and mixing the obtained FTO/c-TiO 2 /m-TiO 2 The substrate was further subjected to uv ozone treatment for 20min;
4、SnO 2 preparation of nanoparticles
0.5mLSnO 2 Colloidal dispersion (15 wt%) was diluted in 3-5mL of ultrapure water and then spun at 3000rpm in FTO/c-TiO 2 /m-TiO 2 The substrate was spin coated for 30s and then annealed at 150 ℃ for 30min. Formation of FTO/c-TiO 2 /m-TiO 2 +NP-SnO 2 Subjecting to ultraviolet ozone treatment for 20min;
5. preparation of perovskite layer
At ambient temperature, 461mgPbI 2 159mgMAI and 78mgDMSO (molar ratio 1: 1) were dissolved in 600mgDMF, and the mixture solution was stirred for 1h under a glove box nitrogen atmosphere. In particular, 50. Mu.L of perovskite precursor solution was added dropwise to the FTO/c-TiO 2 Or FTO/c-TiO 2 /m-TiO 2 Followed by spin coating at 4000rpm for 25s, where after 7s a drop (100 μ L) of the anti-solvent ethyl acetate is added dropwise to the spinning substrate. The coated film was heat treated on a hot plate at 105 ℃ for 10min. During drying at 105 ℃, the color of the film changed from light yellow to dark brown, indicating the formation of a perovskite film;
6. preparation of hole transport layer
1mL of a chlorobenzene solution containing 72.3mg of spiro-OMeTAD, 28.8. Mu.L of tert-butylpyridine and 17.5. Mu.L of lithium bis (trifluoromethylstyryl) imide salt dissolved in acetonitrile (0.52 g/mL) was cast onto the perovskite surface and rotated at 3000rpm for 30s to form an HTL layer, and the obtained sample was left overnight in dark air before thermal evaporation of the silver electrode was performed to complete the fabrication of the printed circuit board;
7. evaporation of electrodes
Placing the prepared sample in a thermal evaporation device, evaporating a metal electrode to finally finish the preparation of the perovskite solar cell with high charge extraction capability, wherein the device structure is a conductive substrate/c-TiO 2 /m-TiO 2 +NP-SnO 2 Perovskite layer/hole transport layer/metal electrode.
TABLE 2 preparation of mesoporous layers TiO 2 Solar cell performance impact of different weight ratios of paste
It can be seen from Table 2 that TiO is present in the preparation of the mesoporous layer 2 Different weight ratios of the slurry have obvious influence on the performance of the solar cell in absolute ethyl alcohol.
Example 3:
1. cleaning of conductive substrates
Cutting the conductive substrate according to required size, sequentially and continuously cleaning the etched substrate with detergent solution, deionized water, acetone, ethanol and isopropanol for 15min, and using N 2 And (4) airflow drying. Densifying TiO by spin coating 2 Before, the cleaned substrate is subjected to ultraviolet ozone treatment for 20min and stored for standby;
2、TiO 2 preparation of the dense layer
Placing the cleaned conductive substrate in a spin coater, sucking a certain amount of dense layer precursor solution by a liquid-transferring gun, dropping the solution on the substrate, and forming TiO with thickness of 20-25nm by spin-coating and diluting (spin-coating at 500rpm for 5s and spin-coating at 2000rpm for 30s in turn) 0.15 μm diisopropoxybis-acetylacetone titanium (acetylacetonate) in n-butanol 2 A thin layer, followed by heat treatment on a hot plate at 135 ℃ for 10min and annealing in air at 500 ℃ for 30min;
3、TiO 2 preparation of mesoporous layer
Adopting spin coating process to spin Tu Jie pore layer slurry on the prepared film sample, under the condition of mesoporous structure, 200nm thick mesoporous TiO 2 Layer by spin coating of commercially available TiO 2 The slurry (Dyesol 18 NR-T) was further deposited on dense TiO 2 On the layer of the TiO 2 Diluting the slurry at a weight ratio of 1: 10 in anhydrous ethanol at a rotation speed of 4000rpm for 30s, sintering in air at 500 ℃ for 30min, and mixing the obtained FTO/c-TiO 2 /m-TiO 2 The substrate was further subjected to uv ozone treatment for 20min;
4、SnO 2 preparation of nanoparticles
0.5mLSnO 2 Colloidal dispersion (15 wt%) was diluted in 3-5mL of ultrapure water and then spun at 3000rpm in FTO/c-TiO 2 /m-TiO 2 The substrate was spin coated for 30s and then annealed at 150 ℃ for 30min. Formation of FTO/c-TiO 2 /m-TiO 2 +NP-SnO 2 Subjecting to ultraviolet ozone treatment for 20min;
5. preparation of perovskite layer
461mgPbI at ambient temperature 2 159mgMAI and 78mgDMSO (molar ratio 1: 1) were dissolved in 600mgDMF, and the mixture solution was stirred for 1h under a glove box nitrogen atmosphere. In particular, 50. Mu.L of perovskite precursor solution was added dropwise to the FTO/c-TiO 2 Or FTO/c-TiO 2 /m-TiO 2 Followed by spin coating at 4000rpm for 25s, where after 7s a drop (100 μ L) of the anti-solvent ethyl acetate is added dropwise to the spinning substrate. The coating film is heat-treated on hot plates of 95 deg.C, 105 deg.C and 115 deg.C for 10min. During drying at 105 ℃, the color of the film changed from light yellow to dark brown, indicating the formation of a perovskite film;
6. preparation of hole transport layer
1mL of a chlorobenzene solution containing 72.3mg of spiro-OMeTAD, 28.8. Mu.L of tert-butyl pyridine and 17.5. Mu.L of lithium bis (trifluoromethylstyryl) imide dissolved in acetonitrile (0.52 g/mL) was cast onto the perovskite surface and rotated at 3000rpm for 30s to form an HTL layer, and the obtained sample was left overnight in a dark air before thermal evaporation of the silver electrode was performed to complete the manufacture of the printed circuit board;
7. evaporation of electrodes
Placing the prepared sample in a thermal evaporation device, evaporating a metal electrode to finally finish the preparation of the perovskite solar cell with high charge extraction capability, wherein the device structure is a conductive substrate/c-TiO 2 /m-TiO 2 +NP-SnO 2 Perovskite layer/hole transport layer/metal electrode.
TABLE 3 influence of different annealing temperatures on solar cell performance during perovskite thin film preparation
It can be seen from table 3 that different annealing temperatures during the perovskite thin film preparation process have significant effects on the solar cell performance.
Example 4:
1. cleaning of conductive substrates
Cutting the conductive substrate according to required size, sequentially and continuously cleaning the etched substrate with detergent solution, deionized water, acetone, ethanol and isopropanol for 15min, and using N 2 And (4) airflow drying. Densifying TiO by spin coating 2 Before, the cleaned substrate is subjected to ultraviolet ozone treatment for 20min and stored for standby;
2、TiO 2 preparation of the dense layer
Placing the cleaned conductive substrate in a spin coater, sucking a certain amount of dense layer precursor solution by a liquid-transferring gun, dropping the solution on the substrate, and forming TiO with thickness of 20-25nm by spin-coating and diluting (spin-coating at 500rpm for 5s and spin-coating at 2000rpm for 30s in turn) 0.15 μm diisopropoxybis-acetylacetone titanium (acetylacetonate) in n-butanol 2 A thin layer, followed by heat treatment on a hot plate at 135 ℃ for 10min and annealing in air at 500 ℃ for 30min;
3、TiO 2 preparation of mesoporous layer
Adopting spin coating process to spin Tu Jie pore layer slurry on the prepared film sample, under the condition of mesoporous structure, 200nm thick mesoporous TiO 2 Layer by spin coating of commercially available TiO 2 The slurry (Dyesol 18 NR-T) was further deposited on dense TiO 2 On the layer of the TiO 2 Diluting the slurry at a weight ratio of 1: 10 in anhydrous ethanol at a rotation speed of 4000rpm for 30s, sintering in air at 500 deg.C for 30min, and mixing the obtained FTO/c-TiO 2 layer/m-TiO 2 The substrate was further subjected to ultraviolet ozone treatment for 20min;
4、SnO 2 preparation of nanoparticles
0.5mLSnO 2 Colloidal dispersions (10 wt%, 15wt% and 20wt% in this order) were diluted in 3-5mL of ultrapure water and then spun at 3000rpm in FTO/c-TiO 2 /m-TiO 2 The substrate was spin coated for 30s and then annealed at 150 ℃ for 30min. Formation of FTO/c-TiO 2 /m-TiO 2 +NP-SnO 2 Subjecting to ultraviolet ozone treatment for 20min;
5. preparation of perovskite layer
461mgPbI at ambient temperature 2 159mg MAI and 78mg DMSO (molar ratio 1: 1) were dissolved in 600mg DMF and the mixture solution was stirred in a glove box under nitrogen for 1h. In particular, 50. Mu.L of perovskite precursor solution was added dropwise to the FTO/c-TiO 2 Or FTO/c-TiO 2 /m-TiO 2 Followed by spin coating at 4000rpm for 25s, where after 7s a drop (100 μ L) of the anti-solvent ethyl acetate is added dropwise to the spinning substrate. The coated film was heat treated on a hot plate at 105 ℃ for 10min. During drying at 105 ℃, the color of the film changed from light yellow to dark brown, indicating the formation of a perovskite film;
6. preparation of hole transport layer
1mL of a chlorobenzene solution containing 72.3mg of spiro-OMeTAD, 28.8. Mu.L of tert-butylpyridine and 17.5. Mu.L of lithium bis (trifluoromethylstyryl) imide salt dissolved in acetonitrile (0.52 g/mL) was cast onto the perovskite surface and rotated at 3000rpm for 30s to form an HTL layer, and the obtained sample was left overnight in dark air before thermal evaporation of the silver electrode was performed to complete the fabrication of the printed circuit board;
7. evaporation of electrodes
Placing the prepared sample in a thermal evaporation device, evaporating a metal electrode to finally finish the preparation of the perovskite solar cell with high charge extraction capability, wherein the device structure is a conductive substrate/c-TiO 2 /m-TiO 2 +NP-SnO 2 Perovskite layer/hole transport layer/metal electrode.
TABLE 4 different SnO 2 The mass percentage of the colloidal dispersion liquid affects the performance of the perovskite battery
From Table 4, it can be seen that different SnO 2 The mass percentage of the colloidal dispersion has obvious influence on the performance of the perovskite battery.
Claims (6)
1. A composite electron transport layer with efficient charge extraction, characterized by:
the composite electron transport layer is made of TiO 2 Sequentially spin-coating TiO on the surface of the compact layer 2 Mesoporous layers and SnO 2 A composite electron transport layer obtained after nanoparticles;
in the composite electron transport layer, tiO 2 The thickness of the compact layer is 20-25nm 2 The thickness of the mesoporous layer is 100-300nm 2 The size of the nano particles is 4-5nm;
the composite electron transport layer with efficient charge extraction is prepared by a method comprising the following steps:
step 1: cleaning of conductive substrates
Cutting the conductive substrate according to the required size, sequentially and continuously cleaning the etched substrate with a detergent solution, deionized water, acetone, ethanol and isopropanol, and using N 2 Drying by airflow; densifying TiO by spin coating 2 Before, the cleaned substrate is subjected to ultraviolet ozone treatment for 15-25min and stored for later use;
step 2: preparation of the dense layer
Placing the conductive substrate cleaned in the step 1 in a glue homogenizing machine, sucking the dense layer precursor solution by a liquid-transferring gun and dropping the solution on the substrate, and forming TiO with the thickness of 20-25nm by spin-coating 0.1-0.2 mu m of diisopropoxy bis-acetylacetonato titanium diluted in n-butyl alcohol 2 Thin layer, heat treating on hot plate at 120-150 deg.C for 5-15min, and annealing in air to obtain TiO 2 A dense layer;
and step 3: preparation of mesoporous layer
Preparing the obtained TiO in the step 2 by adopting a spin coating process 2 Spinning Tu Jie pore layer slurry on the dense layer to obtain mesoporous TiO with the thickness of 100-300nm 2 Coating the layer at 3500-4500rpm, sintering in air, and mixing the obtained FTO/c-TiO 2 /m-TiO 2 Subjecting the substrate to ultraviolet ozone treatment for 15-30min to obtain TiO 2 A mesoporous layer;
and 4, step 4: snO 2 Preparation of nanoparticles
0.2-0.6mL of SnO with the concentration of 10-20wt% 2 Diluting colloidal dispersion in 3-5mLIn pure water, and then in step 3 at 2000-4000rpm to obtain FTO/c-TiO 2 /m-TiO 2 Spin-coating on the substrate for 20-40s, annealing to obtain composite electron transport layer FTO/c-TiO 2 /m-TiO 2 +NP-SnO 2 And carrying out ultraviolet ozone treatment for 15-30min.
2. The composite electron transport layer with efficient charge extraction of claim 1, wherein:
in the step 2, the annealing temperature is 400-500 ℃, and the annealing time is 20-40min.
3. The composite electron transport layer with efficient charge extraction of claim 1, wherein:
in the step 3, the sintering temperature is 400-500 ℃, and the sintering time is 20-40min.
4. The composite electron transport layer with efficient charge extraction of claim 1, wherein:
in the step 4, the annealing temperature is 100-200 ℃, and the annealing time is 20-40min.
5. Use of a composite electron transport layer with efficient charge extraction according to claim 1, 2,3 or 4, characterized in that: the perovskite solar cell is prepared by taking the perovskite solar cell as an electron transport layer.
6. Use according to claim 5, characterized in that:
the perovskite solar cell has the following device structure: conductive substrate/TiO 2 Dense layer/TiO 2 Mesoporous layer + SnO 2 Nanoparticles/perovskite layer/hole transport layer/metal electrode.
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