CN109888105B - Passivated perovskite solar cell and preparation method thereof - Google Patents

Passivated perovskite solar cell and preparation method thereof Download PDF

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CN109888105B
CN109888105B CN201910169155.0A CN201910169155A CN109888105B CN 109888105 B CN109888105 B CN 109888105B CN 201910169155 A CN201910169155 A CN 201910169155A CN 109888105 B CN109888105 B CN 109888105B
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perovskite
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transport layer
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conductive glass
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CN109888105A (en
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刘治科
钱芳
袁世豪
蔡园
韩玉
赵欢
刘生忠
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Shaanxi Normal University
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Abstract

The invention discloses a passivated perovskite solar cell and a preparation method thereof. The perovskite solar cell optimizes perovskite absorption, so that an anti-solvent tris (pentafluorobenzene) borane is contained in a perovskite absorption layer as an additive. On one hand, the addition of fluorine ions can change the crystallinity and defect states of the perovskite thin film to form a high-quality perovskite thin film with large grain size; the antisolvent tris (pentafluorobenzene) borane can improve the surface appearance of perovskite and has passivation effect at grain boundary; on the other hand, fluorine ions can improve the hydrophobicity of the perovskite thin film, inhibit the phase transition of perovskite, better protect perovskite from being damaged by water, further improve the air stability and light stability of the cell and obtain a high-efficiency perovskite solar cell.

Description

Passivated perovskite solar cell and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of thin film solar energy, and particularly relates to a passivated perovskite solar cell and a preparation method thereof.
[ background ] A method for producing a semiconductor device
With the increasing demand for energy in the development of human society and the decreasing of traditional fossil energy and environmental pollution, it is a great challenge to find a renewable new energy to replace the traditional fossil energy, so that solar cells with the advantages of being renewable, clean and pollution-free are more and more emphasized by people. Solar energy, as a renewable energy source, is one of the important ways to meet the increasing energy needs worldwide. An effective method for converting solar energy into electrical energy is to prepare a solar cell based on the photovoltaic effect, and research and development of a high-efficiency and low-cost solar cell is a technical basis for realizing solar photovoltaic power generation application.
FA x MA (1-x) PbX 3 Solar cells of materials (X represents a halogen element) have attracted considerable attention in the field of photovoltaic research in recent years. According to reports, the efficiency of the perovskite solar cell is improved continuously, and from the efficiency of the perovskite solar cell in 2009 to the certified efficiency of 22.7% in 2017 and further to the newly certified efficiency of 23.7%, the breakthrough of the highest efficiency among the efficiencies is the formamidine-based perovskite solar cell, but the perovskite solar cell with the composition has poor stability under the conditions of light, oxygen, heat, water and the like.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provides a passivated perovskite solar cell and a preparation method thereof; according to the method, the tris (pentafluorobenzene) borane is introduced into the perovskite solar cell as an additive, so that the quality of the perovskite thin film can be effectively improved, the decomposition and phase change of the thin film are inhibited, and the efficiency and the stability of the perovskite solar cell are improved.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a passivated perovskite solar cell comprises the following steps:
step 1, cleaning conductive glass to prepare a conductive glass substrate;
step 2, preparing an electron transport layer on the conductive glass substrate;
step 3, preparing a perovskite absorption layer on the electron transport layer by spin coating a perovskite precursor solution, wherein the perovskite precursor solution is FA with the concentration of 0.8-1.4M 0.85 MA 0.15 PbI 3 Wherein FA is NH 2 CHNH 2 + MA is CH 3 NH 3 + (ii) a Annealing after the spin coating is finished to obtain a perovskite absorption layer;
step 4, preparing a hole transport layer on the perovskite absorption layer;
and 5, preparing a metal electrode on the hole transport layer.
The invention is further improved in that:
preferably, in step 3, the spin coating process of preparing the perovskite absorption layer by spin coating the perovskite precursor solution on the electron transport layer is divided into two stages: in the first stage, the perovskite precursor solution is spin-coated on the electron transport layer at the rotating speed of 500-1500 rpm/s, and the spin-coating time is 5-20 s; in the second stage, the perovskite precursor solution is spin-coated on the electron transport layer at the rotating speed of 2000-5000 rpm/s, 100-300 uL of tris (pentafluorobenzene) borane solution is dropwise added during the spin-coating for 10-20 s, and the spin-coating time in the second stage is 30-50 s in total.
Preferably, in step 3, the preparation process of the perovskite precursor solution is as follows: weighing formamidine-based iodine powder and methylamine-based iodine powder according to a molar ratio of 0.85 to 0.15, uniformly mixing to form a mixture A, mixing the mixture A with lead iodide according to a molar ratio of 1; the volume ratio of the dimethyl formamide to the dimethyl sulfoxide in the mixed solution of the dimethyl formamide and the dimethyl sulfoxide is (4-8): 1.
preferably, in step 3, the tris (pentafluorobenzene) borane solution is prepared by adding a chlorobenzene solvent to tris (pentafluorobenzene) borane powder and stirring at room temperature for more than 6 hours to obtain a tris (pentafluorobenzene) borane solution with a concentration of 0.625-5 mg/mL.
Preferably, in step 3, the annealing temperature after the spin coating is 100 to 200 ℃, and the annealing time is 5 to 30min.
Preferably, in the step 1, the conductive glass is sequentially ultrasonically cleaned in acetone, isopropanol and ethanol for 5-30 min, and is dried by blowing with nitrogen gas to obtain the cleaned conductive glass substrate, wherein the conductive glass is indium tin oxide conductive glass or fluorine-doped tin oxide conductive glass.
Preferably, in step 2, the electron transport layer is prepared on the conductive glass substrate by a hydrothermal deposition method, the deposition temperature is 70 ℃, and the material of the electron transport layer is TiO 2 。
Preferably, in step 4, a Spiro-OMeTAD hole transport layer is prepared on the perovskite absorption layer by a spin coating method, the spin coating speed is 1000-2000 rpm/s, and the spin coating time is 40-60 s.
Preferably, in step 5, a metal electrode is formed on the hole transport layer by a vapor deposition method, the metal electrode has a thickness of 80 to 100nm, and the metal electrode is a gold electrode.
The passivated perovskite solar cell prepared by any preparation method comprises a conductive glass substrate, an electron transport layer, a perovskite absorption layer, a hole transport layer and a metal electrode from bottom to top in sequence, wherein the perovskite absorption layer is FA doped with tris (pentafluorobenzene) borane 0.85 MA 0.15 PbI 3 Wherein FA is NH 2 CHNH 2 + MA is CH 3 NH 3 + 。
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a passivated perovskite solar cell. Compared with the existing solar cell, the perovskite solar cell has the advantages that the light absorption in the visible light range is obviously enhanced, so that more photon-generated carriers can be generated, the defects of the thin film are reduced after the perovskite layer is passivated, the non-radiative recombination of the cell is reduced, and the current density of the cell is increased. The perovskite solar cell optimizes the perovskite absorption layer, so that the perovskite absorption layer contains an anti-solvent tris (pentafluorobenzene) borane as an additive. On one hand, the crystallinity and defect state of the perovskite film can be changed by adding fluorine ions to form a high-quality perovskite film with large grain size, and the antisolvent tris (pentafluorobenzene) borane can improve the surface appearance of the perovskite and has a passivation effect at grain boundaries; on the other hand, fluorine ions can improve the hydrophobicity of the perovskite thin film and inhibit the phase change of the perovskite, so that the perovskite can be better protected from being damaged by water, the air stability and the light stability of the battery are further improved, and the high-efficiency perovskite solar battery is obtained; the quality of the perovskite thin film can be effectively improved, the decomposition and the phase change of the thin film can be effectively inhibited, and the efficiency and the stability of the perovskite solar cell can be further improved by taking the tris (pentafluorobenzene) borane as an additive in the perovskite absorption layer; has important practical value and guiding significance for the industrialization of the perovskite battery.
The invention also discloses a preparation method of the passivated perovskite solar cell, which is characterized in that in the process of preparing the perovskite absorption layer by a spin-coating method, the prepared anti-solvent is dripped, so that tris (pentafluorobenzene) borane is added in the absorption layer of the perovskite film as an additive, and the passivated perovskite absorption layer film is further prepared, and the dripping time and the dripping amount of the tris (pentafluorobenzene) borane solution are strictly controlled, so that the main components in the perovskite absorption layer are ensured, and the tris (pentafluorobenzene) borane is added to play a role in passivation; the method has the advantages of simple operation, good repeatability and easy preparation.
[ description of the drawings ]
FIG. 1 is a schematic structural diagram of a perovskite solar cell with a tris (pentafluorobenzene) borane additive prepared in accordance with the present invention;
wherein: 1 is transparent conductive glass; 2 is an electron transport layer; 3 is a perovskite absorption layer containing a tris (pentafluorobenzene) borane additive; 4 is a hole transport layer; and 5, a metal electrode.
Fig. 2 is a graph comparing the performance of the perovskite cell with tris (pentafluorobenzene) borane added and the perovskite solar cell without tris (pentafluorobenzene) borane added in example 1 of the present invention;
FIG. 3 is a graph comparing the humidity stability of the perovskite cell containing tris (pentafluorobenzene) borane of example 1 with conventional perovskite cells;
fig. 4, panels (a) and (b), are surface topography maps of perovskite absorber layers, SEM images of films without and with tris (pentafluorobenzene) borane addition, respectively;
wherein, the figure (a) is that no tris (pentafluorobenzene) borane is added; the figure (b) shows the addition of tris (pentafluorobenzene) borane.
[ detailed description ] embodiments
The invention is further described in detail with reference to the accompanying drawings and specific embodiments, and discloses a passivated perovskite solar cell and a preparation method thereof, wherein the perovskite solar cell sequentially comprises from bottom to top: the electron hole-transporting layer comprises a transparent conductive glass substrate 1, an electron transporting layer 2, a perovskite absorbing layer 3 containing a tris (pentafluorobenzene) borane additive, a hole transporting layer 4 and a metal electrode 5, wherein the perovskite absorbing layer 3 containing the tris (pentafluorobenzene) borane additive is a perovskite absorbing layer added with the tris (pentafluorobenzene) borane additive; the preparation process of the perovskite solar cell comprises the following steps:
step 1, cleaning a conductive glass substrate
Ultrasonically cleaning conductive glass in acetone, isopropanol and ethanol for 5-30 min, and drying with nitrogen to obtain a cleaned conductive glass substrate; the conductive glass is Indium Tin Oxide (ITO) conductive glass or fluorine-doped tin oxide (FTO) conductive glass.
Step 2, preparing an electron transport layer on the cleaned conductive glass substrate
Preparing an electron transport layer on a conductive glass substrate by a hydrothermal deposition method, wherein the deposition temperature is 70 ℃, and TiO is selected as the material of the electron transport layer 2 。
Step 3, preparing an antisolvent solution
Adding chlorobenzene solvent into the tris (pentafluorobenzene) borane powder, and stirring for more than 6 hours at room temperature on a stirring table to obtain a tris (pentafluorobenzene) borane solution with the concentration of 0.625-5 mg/mL for later use as an anti-solvent solution.
Step 4, preparing perovskite precursor solution
Formamidino iodide (NH) was weighed at a molar ratio of 0.85 2 CHNH 2 I) And methylamine group iodine (CH) 3 NH 3 I) Powder, mixed to form a mixture A, and then the mixture A and lead iodide (PbI) are mixed according to a molar ratio of 1 2 ) Uniformly mixing to obtain a mixture B, and adding the mixture B into the mixture B according to the volume ratio of (4-8): 1, and stirring the mixed solution of dimethyl formamide (DMF) and dimethyl sulfoxide (DMSO) on a stirring table at room temperature for more than 6 hours to obtain a solution with a component of FA 0.85 MA 0.15 PbI 3 And the concentration is 0.8-1.4M.
And 5, when the perovskite precursor solution is spin-coated on the electron transport layer, the spin-coating method is divided into two stages: the rotating speed of the first stage is 500-1500 rpm/s, and the spin coating time is 5-20 s; the rotation speed of the second stage is 2000-5000 rpm/s, the spin-coating time is 30-50 s, and 100-300 uL of chlorobenzene solution containing the trifluorobenzene borane prepared in the step 2 is dripped when the second stage is in spin-coating for 10-20 s; and (3) annealing treatment after spin coating, wherein the annealing temperature is 100-200 ℃, and the annealing time is 5-30 min, so that the perovskite absorption layer is prepared.
And 6, preparing a hole transport layer, and preparing the hole transport layer on the perovskite absorption layer by a spin coating method, wherein the hole transport layer is made of Spiro-OMeTAD, the spin coating speed is 1000-2000 rpm/s, and the spin coating time is 40-60 s.
Step 7, finally, evaporating a gold electrode with the thickness of 80-100 nm on the hole transport layer to obtain the perovskite solar cell;
comparative example
Step 1, sequentially ultrasonically cleaning a cut FTO conductive glass substrate in acetone, isopropanol and ethanol for 5min respectively, and drying the FTO conductive glass substrate by nitrogen to obtain a cleaned conductive glass substrate;
step 2, depositing a layer of TiO on the etched FTO surface at 70 ℃ by adopting a hydrothermal heat preservation deposition method 2 Making an electron transport material;
step 3, weighing NH according to the molar ratio of 0.85 2 CHNH 2 I and CH 3 NH 3 I powder, mixing to form a mixture A, and mixing the mixture A and PbI according to a molar ratio of 1 2 Mixing, adding the mixture in a volume ratio of 6:1 in DMF and DMSO, and stirring for 7h at room temperature on a stirring table to obtain the composition FA 0.85 MA 0.15 PbI 3 Perovskite precursor solution with the concentration of 1.2M.
And 4, spin-coating the perovskite absorption layer on the electronic layer by a solution spin-coating method, wherein the spin-coating method comprises two stages: the rotating speed of the first stage is 1000rpm/s, and the spin coating time is 10s; the rotation speed of the second stage is 4000rpm/s, and the spin coating time is 40s; and (3) annealing treatment after spin coating, wherein the annealing temperature is 150 ℃, and the annealing time is 15min, so that the perovskite absorption layer is prepared.
And 6, spin-coating a Spiro-OMeTAD solution with the concentration of 90mg/mL on the perovskite layer as a hole transport layer by adopting a solution spin-coating method, wherein the spin-coating speed is 1500rpm/s, and the spin-coating time is 50s.
Step 7, evaporating a gold film with the thickness of 80nm on the hole transport layer Spiro-OMeTAD, wherein the area of the cell is 0.09cm 2 And obtaining the perovskite solar cell.
Example 1
Step 1, sequentially ultrasonically cleaning a cut FTO conductive glass substrate in acetone, isopropanol and ethanol for 5min respectively, and drying the FTO conductive glass substrate by nitrogen to obtain a cleaned conductive glass substrate;
step 2, depositing a layer of TiO on the etched FTO surface at 70 ℃ by adopting a hydrothermal heat preservation deposition method 2 Making an electron transport material;
step 3, weighing tris (pentafluorobenzene) borane powder, adding a chlorobenzene solvent to prepare a tris (pentafluorobenzene) borane solution with the concentration of 1.25mg/mL, and stirring on a stirring table for 7 hours to obtain a tris (pentafluorobenzene) borane solution;
step 4, weighing NH according to a molar ratio of 0.85 2 CHNH 2 I and CH 3 NH 3 I powder, mixing to form a mixture A, and mixing the mixture A with PbI according to a molar ratio of 1 2 Mixing, adding the mixture in a volume ratio of 6:1 as solvent, and stirring for 7h at room temperature on a stirring table to obtain the composition FA 0.85 MA 0.15 PbI 3 Perovskite precursor solution with the concentration of 1.2M.
Step 5, spin-coating the perovskite absorption layer on the electronic layer by a solution spin-coating method, wherein the rotating speed of the first stage is 1000rpm/s, and the spin-coating time is 10s; the rotation speed of the second stage is 4000rpm/s, the spin coating time is 40s, and 200uL of chlorobenzene solution containing the trifluorobenzene borane prepared in the step 2 is dripped in 15s in the second stage; and (3) annealing treatment is carried out after spin coating, the annealing temperature is 150 ℃, and the annealing time is 15min, so that the perovskite absorption layer is prepared.
And 6, spin-coating a Spiro-OMeTAD solution with the concentration of 90mg/mL on the perovskite layer as a hole transport layer by adopting a solution spin-coating method, wherein the spin-coating speed is 1500rpm/s, and the spin-coating time is 50s.
Step 7, evaporating a gold film with the thickness of 80nm on the hole transport layer Spiro-OMeTAD, wherein the area of the cell is 0.09cm 2 And obtaining the perovskite solar cell.
The perovskite solar cell containing the tris (pentafluorobenzene) borane additive prepared in the present example, as shown in fig. 1, includes a conductive glass substrate 1, an electron transport layer 2, a perovskite absorption layer 3 containing the tris (pentafluorobenzene) borane additive, a hole transport layer 4 and a gold electrode 5, which are sequentially stacked and assembled; as can be seen from fig. 2, the efficiencies of the solar cell prepared in this example and the solar cell of the comparative example were tested by heating the spin-coated perovskite layer on a hot stage at 150 ℃ for 30min, and as can be seen from the figure, the efficiency of the solar cell of the comparative example was 19.55%, the efficiency (PCE) of the solar cell prepared in this example was 21.60%, and the efficiency was improved by 10.5% compared to the comparative sample; the open voltage of the solar cell in the comparative example was 1.09V, whereas the open voltage (V) of the solar cell prepared in this example was oc ) 1.12V, the open pressure is improved by 2.75 percent compared with a comparative sample; the current density of the solar cell in the comparative example was 24.02mA/cm 2 And the current density (J) of the solar cell prepared in this example sc ) Is 24.69mA/cm 2 Compared with a comparative sample, the current density is improved by 2.79%; the fill factor of the solar cell in the comparative example was 74.91%, while the Fill Factor (FF) of the solar cell prepared in this example was 78.22%, which was a 4.42% increase over the comparative sample; as can be seen from fig. 3, the performance of the perovskite solar cell is significantly improved. After the battery is placed for 720h under the condition that the air humidity is 40% and the battery is not packaged, the efficiency can be kept at 75% of the original efficiency. However, the efficiency of the conventional perovskite cell without the tris (pentafluorobenzene) borane additive dropped to 55% of the original efficiency when the cell was not packaged at 40% air humidity. As can be seen from fig. 4, the bright point on the perovskite surface disappears (i.e., no δ phase appears) after the addition of tris (pentafluorobenzene) borane, and the hydrophobic property of the thin film is significantly improved, relative to the perovskite cell prepared in the comparative example.
Example 2
Step 1, sequentially ultrasonically cleaning a cut ITO conductive glass substrate in acetone, isopropanol and ethanol for 10min respectively, and drying the substrate by using nitrogen to obtain the cleaned conductive glass substrate;
step 2, adoptDepositing a layer of TiO on the etched FTO surface at 70 ℃ by a hydrothermal heat preservation deposition method 2 Making an electron transport material;
step 3, weighing the tris (pentafluorobenzene) borane powder, adding a chlorobenzene solvent to prepare a tris (pentafluorobenzene) borane solution with the concentration of 0.625mg/mL, and stirring on a stirring table for 8 hours to obtain a tris (pentafluorobenzene) borane solution;
step 4, weighing NH according to the molar ratio of 0.85 2 CHNH 2 I and CH 3 NH 3 I powder, mixing to form a mixture A, and mixing the mixture A and PbI according to a molar ratio of 1 2 Mixing, adding 8:1, taking a mixed solution of DMF and DMSO as a solvent, and stirring for 8 hours at room temperature on a stirring table to obtain a solution with a component of FA 0.85 MA 0.15 PbI 3 Perovskite precursor solution with the concentration of 1.1M.
Step 5, spin-coating the perovskite absorption layer on the electronic layer through a solution spin-coating method, wherein the rotation speed of the first stage is 1500rpm/s, and the spin-coating time is 5s; the rotation speed of the second stage is 5000rpm/s, the spin coating time is 30s, and 300uL of chlorobenzene solution containing the tris (pentafluorobenzene) borane prepared in the step 2 is dripped in the second stage at 20s; and (3) annealing treatment is carried out after spin coating, the annealing temperature is 200 ℃, and the annealing time is 5min, so that the perovskite absorption layer is prepared.
And 6, spin-coating a Spiro-OMeTAD solution with the concentration of 90mg/mL on the perovskite layer as a hole transport layer by adopting a solution spin-coating method, wherein the spin-coating speed is 2000rpm/s, and the spin-coating time is 40s.
Step 7, evaporating a gold film with the thickness of 100nm on the hole transport layer Spiro-OMeTAD, wherein the area of the cell is 0.09cm 2 And obtaining the perovskite solar cell.
Example 3
Step 1, sequentially ultrasonically cleaning a cut FTO conductive glass substrate in acetone, isopropanol and ethanol for 15min respectively, and drying the FTO conductive glass substrate by nitrogen to obtain a cleaned conductive glass substrate;
step 2, depositing a layer of TiO on the etched FTO surface at 70 ℃ by adopting a hydrothermal heat preservation deposition method 2 Making an electron transport material;
step 3, weighing the tris (pentafluorobenzene) borane powder, adding a chlorobenzene solvent to prepare a tris (pentafluorobenzene) borane solution with the concentration of 1.875mg/mL, and stirring on a stirring table for 8 hours to obtain a tris (pentafluorobenzene) borane solution;
step 4, weighing NH according to the molar ratio of 0.85 2 CHNH 2 I and CH 3 NH 3 I powder, mixing to form a mixture A, and mixing the mixture A with PbI according to a molar ratio of 1 2 Mixing, adding the mixture in a volume ratio of 4:1 as solvent, and stirring for 8h at room temperature on a stirring table to obtain the composition FA 0.85 MA 0.15 PbI 3 And perovskite precursor solution with the concentration of 0.8M.
Step 5, spin-coating the perovskite absorption layer on the electronic layer by a solution spin-coating method, wherein the rotating speed of the first stage is 600rpm/s, and the spin-coating time is 15s; the rotation speed of the second stage is 3000rpm/s, the spin coating time is 35s, and 120uL of chlorobenzene solution containing the trifluorobenzene borane prepared in the step 2 is dripped in the second stage at 18s; and (3) annealing treatment after spin coating, wherein the annealing temperature is 100 ℃, and the annealing time is 30min, so that the perovskite absorption layer is prepared.
And step 6, spin-coating a Spiro-OMeTAD solution with the concentration of 90mg/mL on the perovskite layer as a hole transport layer by adopting a solution spin-coating method, wherein the spin-coating speed is 1800rpm/s, and the spin-coating time is 40s.
Step 7, evaporating a gold film with the thickness of 80nm on the hole transport layer Spiro-OMeTAD, wherein the area of the cell is 0.09cm 2 And obtaining the perovskite solar cell.
Example 4
Step 1, sequentially ultrasonically cleaning a cut ITO conductive glass substrate in acetone, isopropanol and ethanol for 20min respectively, and drying the ITO conductive glass substrate by nitrogen to obtain a cleaned conductive glass substrate;
step 2, depositing a layer of TiO on the etched FTO surface at 70 ℃ by adopting a hydrothermal heat preservation deposition method 2 Making an electron transport material;
step 3, weighing tris (pentafluorobenzene) borane powder, adding a chlorobenzene solvent to prepare a tris (pentafluorobenzene) borane solution with the concentration of 2.5mg/mL, and stirring on a stirring table for 7 hours to obtain a tris (pentafluorobenzene) borane solution;
step 4, pressWeighing NH according to the molar ratio of 0.85 2 CHNH 2 I and CH 3 NH 3 I powder, mixing to form a mixture A, and mixing the mixture A with PbI according to a molar ratio of 1 2 Mixing, adding the mixture in a volume ratio of 5:1 as solvent, and stirring for 7h at room temperature on a stirring table to obtain the composition FA 0.85 MA 0.15 PbI 3 Perovskite precursor solution with the concentration of 1.4M.
Step 5, spin-coating the perovskite absorption layer on the electronic layer through a solution spin-coating method, wherein the rotation speed of the first stage is 1200rpm/s, and the spin-coating time is 18s; the rotation speed of the second stage is 2500rpm/s, the spin coating time is 45s, and 250uL of chlorobenzene solution containing the tris (pentafluorobenzene) borane prepared in the step 2 is dripped in 12s in the second stage; and (3) annealing treatment after spin coating, wherein the annealing temperature is 120 ℃, and the annealing time is 20min, so that the perovskite absorption layer is prepared.
And 6, spin-coating a Spiro-OMeTAD solution with the concentration of 90mg/mL on the perovskite layer as a hole transport layer by adopting a solution spin-coating method, wherein the spin-coating speed is 1200rpm/s, and the spin-coating time is 45s.
Step 7, evaporating a gold film with the thickness of 80nm on the hole transport layer Spiro-OMeTAD, wherein the area of the cell is 0.09cm 2 And obtaining the perovskite solar cell.
Example 5
Step 1, sequentially ultrasonically cleaning a cut FTO conductive glass substrate in acetone, isopropanol and ethanol for 25min respectively, and drying the FTO conductive glass substrate by nitrogen to obtain a cleaned conductive glass substrate;
step 2, depositing a layer of TiO on the etched FTO surface at 70 ℃ by adopting a hydrothermal heat preservation deposition method 2 Making an electron transport material;
step 3, weighing the tris (pentafluorobenzene) borane powder, adding a chlorobenzene solvent to prepare a tris (pentafluorobenzene) borane solution with the concentration of 5mg/mL, and stirring on a stirring table for 6 hours to obtain a tris (pentafluorobenzene) borane solution;
step 4, weighing NH according to the molar ratio of 0.85 2 CHNH 2 I and CH 3 NH 3 I powder, mixing to form a mixture A, and mixing the mixture A with PbI according to a molar ratio of 1 2 Mixing and addingThe product ratio is 4:1 as solvent, and stirring for 6h at room temperature on a stirring table to obtain the composition FA 0.85 MA 0.15 PbI 3 Perovskite precursor solution with concentration of 1.2M.
Step 5, spin-coating the perovskite absorption layer on the electronic layer through a solution spin-coating method, wherein the rotation speed of the first stage is 800rpm/s, and the spin-coating time is 8s; the rotation speed of the second stage is 3500rpm/s, the spin coating time is 40s, and 180uL of chlorobenzene solution containing the tris (pentafluorobenzene) borane prepared in the step 2 is dripped in 14s at the second stage; and (3) annealing treatment after spin coating, wherein the annealing temperature is 160 ℃, and the annealing time is 25min, so that the perovskite absorption layer is prepared.
And 6, spin-coating a Spiro-OMeTAD solution with the concentration of 90mg/mL on the perovskite layer as a hole transport layer by adopting a solution spin-coating method, wherein the spin-coating speed is 1400rpm/s, and the spin-coating time is 55s.
Step 7, evaporating a gold film with the thickness of 90nm on the hole transport layer Spiro-OMeTAD, wherein the area of the cell is 0.09cm 2 And obtaining the perovskite solar cell.
Example 6
Step 1, sequentially ultrasonically cleaning a cut FTO conductive glass substrate in acetone, isopropanol and ethanol for 30min respectively, and drying the FTO conductive glass substrate by nitrogen to obtain a cleaned conductive glass substrate;
step 2, depositing a layer of TiO on the etched FTO surface at 70 ℃ by adopting a hydrothermal heat preservation deposition method 2 Making an electron transport material;
step 3, weighing tris (pentafluorobenzene) borane powder, adding a chlorobenzene solvent to prepare a tris (pentafluorobenzene) borane solution with the concentration of 1.25mg/mL, and stirring on a stirring table for 6 hours to obtain a tris (pentafluorobenzene) borane solution;
step 4, weighing NH according to the molar ratio of 0.85 2 CHNH 2 I and CH 3 NH 3 I powder, mixing to form a mixture A, and mixing the mixture A and PbI according to a molar ratio of 1 2 Mixing, adding the mixture in a volume ratio of 7:1, and stirring the mixture for 6 hours at room temperature on a stirring table to obtain a solution with a component of FA 0.85 MA 0.15 PbI 3 Perovskite precursor solution with concentration of 0.9M。
Step 5, spin-coating the perovskite absorption layer on the electronic layer through a solution spin-coating method, wherein the rotation speed of the first stage is 500rpm/s, and the spin-coating time is 20s; the rotation speed of the second stage is 2000rpm/s, the spin coating time is 50s, and 100uL of chlorobenzene solution containing the trifluorobenzene borane prepared in the step 2 is dripped in the second stage at 10s; and (3) annealing treatment after spin coating, wherein the annealing temperature is 180 ℃, and the annealing time is 10min, so that the perovskite absorption layer is prepared.
And 6, spin-coating a Spiro-OMeTAD solution with the concentration of 90mg/mL on the perovskite layer as a hole transport layer by adopting a solution spin-coating method, wherein the spin-coating speed is 1000rpm/s, and the spin-coating time is 60s.
Step 7, evaporating a gold film with the thickness of 90nm on the hole transport layer Spiro-OMeTAD, wherein the area of the cell is 0.09cm 2 And obtaining the perovskite solar cell.
The results of the performance tests of the above examples are shown in the following table, and it can be seen that the cell performance, cell open voltage, current density, fill factor and cell efficiency of the cell prepared by the method of the present invention are superior to those of the solar cell of the comparative example to which no boron tris (pentafluorobenzene) is added.
Table 1 results of cell performance tests for examples 1-5
Figure GDA0004041947300000121
Figure GDA0004041947300000131
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A preparation method of a passivated perovskite solar cell is characterized by comprising the following steps:
step 1, cleaning conductive glass to prepare a conductive glass substrate (1);
step 2, preparing an electron transport layer (2) on the conductive glass substrate (1);
step 3, preparing a perovskite absorption layer (3) on the electron transport layer by spin coating a perovskite precursor solution, wherein the perovskite precursor solution is FA with the concentration of 0.8-1.4M 0.85 MA 0.15 PbI 3 Wherein FA is NH 2 CHNH 2 + MA is CH 3 NH 3 + (ii) a Annealing after the spin coating is finished to obtain a perovskite absorption layer (3);
the spin coating process for preparing the perovskite absorption layer (3) by spin coating the perovskite precursor solution on the electron transport layer (2) is divided into two stages: in the first stage, the perovskite precursor solution is spin-coated on the electron transport layer at the rotating speed of 500-1500 rpm/s, and the spin-coating time is 5-20 s; in the second stage, the perovskite precursor solution is spin-coated on the electron transport layer at the rotating speed of 2000-5000 rpm/s, 100-300 uL of tris (pentafluorobenzene) borane solution is dropwise added in the second stage when 10-20 s of spin-coating is carried out, and the spin-coating time of the second stage is 30-50 s in total;
step 4, preparing a hole transport layer (4) on the perovskite absorption layer (3);
and 5, preparing a metal electrode (5) on the hole transport layer (4).
2. A method according to claim 1, wherein in step 3, the perovskite precursor solution is prepared by: weighing formamidine-based iodine powder and methylamine-based iodine powder according to a molar ratio of 0.85 to 0.15, uniformly mixing to form a mixture A, mixing the mixture A with lead iodide according to a molar ratio of 1; the volume ratio of the dimethyl formamide to the dimethyl sulfoxide in the mixed solution of the dimethyl formamide and the dimethyl sulfoxide is (4-8): 1.
3. a method according to claim 1, wherein in step 3, the tris (pentafluorobenzene) borane solution is prepared by adding chlorobenzene solvent to tris (pentafluorobenzene) borane powder and stirring at room temperature for more than 6 hours to obtain a tris (pentafluorobenzene) borane solution with a concentration of 0.625-5 mg/mL.
4. The method for preparing a passivated perovskite solar cell according to claim 1, wherein in step 3, the annealing temperature after the spin coating is 100-200 ℃ and the annealing time is 5-30 min.
5. The preparation method of the passivated perovskite solar cell according to claim 1, characterized in that in step 1, the conductive glass is sequentially cleaned in acetone, isopropanol and ethanol for 5-30 min by ultrasonic wave, and dried by blowing with nitrogen gas to obtain the cleaned conductive glass substrate (1), wherein the conductive glass is indium tin oxide conductive glass or fluorine-doped tin oxide conductive glass.
6. A method for preparing a passivated perovskite solar cell according to claim 1, characterized in that in step 2, the electron transport layer (2) is prepared on the conductive glass substrate (1) by hydrothermal deposition, the deposition temperature is 70 ℃, the material of the electron transport layer (2) is TiO 2 。
7. A method of fabricating a passivated perovskite solar cell according to claim 1, characterized in that in step 4, a Spiro-OMeTAD hole transporting layer is fabricated on the perovskite absorption layer (3) by spin coating, the spin coating speed is 1000-2000 rpm/s and the spin coating time is 40-60 s.
8. A method according to claim 1, wherein in step 5, a metal electrode (5) is formed on the hole transport layer (4) by evaporation, wherein the metal electrode has a thickness of 80-100 nm and is a gold electrode.
9. A composition prepared by the method of any one of claims 1 to 8The passivated perovskite solar cell prepared by the preparation method is characterized by sequentially comprising a conductive glass substrate (1), an electron transport layer (2), a perovskite absorption layer (3), a hole transport layer (4) and a metal electrode (5) from bottom to top, wherein the perovskite absorption layer (3) is FA doped with tris (pentafluorobenzene) borane 0.85 MA 0.15 PbI 3 Wherein FA is NH 2 CHNH 2 + MA is CH 3 NH 3 + 。
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