CN113644199A - Perovskite solar cell with phytic acid dipotassium complexed with tin dioxide and preparation method thereof - Google Patents

Perovskite solar cell with phytic acid dipotassium complexed with tin dioxide and preparation method thereof Download PDF

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CN113644199A
CN113644199A CN202110858504.7A CN202110858504A CN113644199A CN 113644199 A CN113644199 A CN 113644199A CN 202110858504 A CN202110858504 A CN 202110858504A CN 113644199 A CN113644199 A CN 113644199A
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tin dioxide
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苏海军
刘聪聪
翟鹏
郭敏
张军
刘林
傅恒志
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Northwestern Polytechnical University
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Abstract

A stannic oxide electron transport layer with excellent electronic performance is obtained by a dipotassium phytate complex stannic oxide colloidal solution with a plurality of functional groups, so that the defect of a stannic oxide electron transport layer/perovskite layer interface is obviously reduced, and the electronic performance of the stannic oxide electron transport layer is improved; the in-plane growth of perovskite crystal grains is promoted by potassium ions in the dipotassium phytate, so that the average crystal grain size of the perovskite is increased from 350nm to 900 nm. Therefore, the photoelectric conversion efficiency of the perovskite solar cell taking tin dioxide complexed with dipotassium phytate as an electron transport layer reaches 21.61%, and 19.52% of the photoelectric conversion efficiency of the perovskite solar cell taking tin dioxide as an electron transport layer is improved to 10.7%, so that the application range of the perovskite solar cell is expanded, and the sustainable development of flexible and clean energy is promoted.

Description

Perovskite solar cell with phytic acid dipotassium complexed with tin dioxide and preparation method thereof
Technical Field
The invention relates to the field of perovskite solar cells, in particular to a perovskite solar cell taking dipotassium phytate complexed tin dioxide as an electron transport layer and a preparation method thereof.
Background
The solar energy has the advantages of inexhaustibility, convenience in collection and greenness and cleanness, so that the solar energy becomes the new energy with the greatest development potential. The solar cell directly converts solar energy into electric energy, has the advantages of environmental protection, safety, reliability and the like, and is one of the hot fields of the current domestic and foreign researches. Currently, the most widely used silicon-based solar cells have long-term development restricted due to high cost and complex processes. Based on this, researchers favor a novel third-generation solar cell with low cost, low energy consumption and abundant raw materials. Since 2009, in a few years, the energy conversion efficiency of organic-inorganic hybrid perovskite solar cells is improved from the initial 3.8% to 25.5%, which is mainly attributed to the advantages of perovskite materials such as high light absorption rate, bipolar transmission, long carrier life, adjustable band gap, and the like.
The organic-inorganic hybrid perovskite solar cell consists of an electron transport layer, a perovskite layer, a hole transport layer and a counter electrodeAnd (4) forming. As an important component of perovskite solar cells, the electron transport layer plays a key role in photoelectron extraction transport and hole blocking. At present, tin dioxide is generally selected as an electron transport layer, and compared with a titanium dioxide electron transport layer, the tin dioxide electron transport layer has the advantages of wider optical band gap (3.8eV), higher electron mobility, low-temperature preparation and the like. However, the interface defects and incomplete energy level matching of the tin dioxide electron transport layer and the perovskite layer lead to poor electronic performance, and further improvement of the efficiency of the tin dioxide-based perovskite solar cell is restricted. In order to reduce the interface defect between the tin dioxide electron transport layer and the perovskite layer and improve the electronic performance of the tin dioxide electron transport layer, it is necessary to modify the tin dioxide electron transport layer. The use of organic substances with strong complexation to modify the tin dioxide electron transport layer has been widely studied by researchers. Wherein Liu Sheng faithful subject group modifies tin dioxide by using ethylenediaminetetraacetic acid (EDTA) with strong complexation ability to obtain 21.60% photoelectric conversion efficiency (see the documents Dong Yang, Ruixia Yang, Kai Wang, Congcong Wu, Xuejie Zhu, Jiangshan Feng, Xiaodong Ren, Guojia Fang, Shashank Prya, Shengzhong (Frank) Liu, High affinity plant-type perivskite solar cell with negligent SnO complex2Comm,2018, 9, 3239). However, the complexing agents used in the above reports have a certain toxicity, which causes environmental pollution, and have a limited effect of passivating the defects at the tin dioxide/perovskite layer interface. Therefore, there is a strong need for a complexing agent that is non-toxic and that effectively adheres to tin dioxide to passivate the tin dioxide/perovskite layer for interface defects and to achieve a high quality tin dioxide electron transport layer.
Disclosure of Invention
In order to solve the problems that an organic complexing agent in the prior art is toxic and has limited passivation effect on interface defects, the invention provides a perovskite solar cell taking dipotassium phytate complexed tin dioxide as an electron transport layer and a preparation method thereof.
The invention provides a perovskite solar cell with phytic acid dipotassium complex tin dioxide as an electron transport layer, which comprises a substrate glass,The FTO conductive substrate, the electron transport layer, the perovskite layer, the hole transport layer and the silver counter electrode; the FTO conductive substrate is prepared on the upper surface of the base glass. The electron transport layer is prepared on the upper surface of the FTO conductive substrate. The perovskite layer is prepared on the upper surface of the electron transport layer. The hole transport layer is prepared on the upper surface of the perovskite layer. The silver counter electrode is positioned on the upper surface of the hole transport layer. The electron transport layer is prepared by complexing tin dioxide with dipotassium phytate, and the silver counter electrode is formed by evaporating silver on the upper surface of the hole transport layer. The electron transport layer is phytic acid dipotassium complex tin dioxide; the perovskite layer is MAxFA1-xPbBryI3-yA perovskite; the hole transport layer is 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]-9, 9' -spirobifluorene. The thickness of the electron transport layer is 55-60 nm, the thickness of the perovskite layer is 500-506 nm, the thickness of the hole transport layer is 200-205 nm, and the area of the silver counter electrode is 0.055-0.059 cm2。
The perovskite solar cell is prepared by the specific process:
step 1, pretreating an FTO conductive substrate:
step 2, preparing the dipotassium phytate complexing tin dioxide colloid precursor solution:
dissolving 3.7-15 mmol of dipotassium phytate in 1ml of deionized water to form a uniform and transparent dipotassium phytate aqueous solution.
And adding deionized water into a commercially available tin dioxide colloid aqueous solution, and stirring for 2 hours at normal temperature by using a magnetic stirrer to obtain a tin dioxide colloid diluted aqueous solution. The volume ratio of the deionized water to the tin dioxide colloid aqueous solution is 3: 1.
And mixing the dipotassium phytate aqueous solution with the obtained tin dioxide colloid diluted aqueous solution according to the volume ratio of 1:1, and stirring for 2 hours at 70 ℃ to obtain the dipotassium phytate complex tin dioxide colloid precursor solution.
Step 3, preparing the phytic acid dipotassium complex tin dioxide electron transport layer:
preparing a phytic acid dipotassium complex tin dioxide electron transport layer on the pretreated FTO conductive substrate:
dripping 40 mu l of the colloidal precursor of the phytic acid dipotassium complexing tin dioxide on the upper surface of the pretreated FTO conductive substrate; spin coating the phytic acid dipotassium complex tin dioxide precursor liquid dripped on the upper surface of the FTO conductive substrate; the rotating speed of the spin coater is 3000-3600 r/min, and the spin coating time is 30 s. Placing the FTO conductive substrate subjected to spin coating on a heating table for annealing treatment; the annealing temperature is 150-180 ℃, and the annealing time is 30-60 min. And cooling to room temperature at normal temperature, and then cleaning the FTO conductive substrate for 15min by ozone. And forming a 55-60 nm thick phytic acid dipotassium complex tin dioxide electron transport layer on the upper surface of the FTO conductive substrate.
Step 4, preparing a perovskite layer:
the perovskite layer is MAxFA1-xPbBryI3-yThe perovskite layer is prepared by a two-step spin coating method. The method comprises the following steps:
firstly, dripping a lead iodide mixed solution on the upper surface of the phytic acid dipotassium complex tin dioxide electronic transmission layer, and carrying out spin coating on the lead iodide mixed solution on the upper surface of the phytic acid dipotassium complex tin dioxide electronic transmission layer by using a spin coater to obtain a lead iodide thin film; the rotating speed of a spin coater is 5000r/min during spin coating, and the spin coating time is 20 s.
Secondly, spin-coating the MA on the upper surface of the obtained lead iodide filmxFA1-xBryI1-yA solution; the rotating speed of a spin coater is 4000r/min during spin coating, the spin coating time is 30s, and the MA is formedxFA1-xPbBryI3-yA perovskite thin film.
In a third step, the preparation is carried out with MAxFA1-xPbBryI3-yPlacing the FTO conductive substrate of the perovskite thin film on a heating table for annealing at 100 ℃ for 1h to form MA with the thickness of 500-506 nmxFA1-xPbBryI3-yA perovskite layer.
When the lead iodide mixed solution is prepared, dissolving 1.5mmol of lead iodide in 1ml of mixed solvent of dimethyl formamide and dimethyl sulfoxide, and stirring for 2 hours at 70 ℃ to obtain a lead iodide mixed solution; the volume ratio of dimethylformamide to dimethyl sulfoxide in the mixed solvent is 9: 1.
Preparation of said MAxFA1-xBryI1-yWhen in solution, the methyl ammonium iodide, formamidine ammonium iodide and methyl ammonium bromide are mixed according to the weight ratio of 7: 2: 1, stirring for 10min to obtain MA with concentration of 70mg/mlxFA1-xBryI1-yAnd (3) solution. The total mass of the methyl ammonium iodide, the formamidine ammonium iodide and the methyl ammonium bromide is 70mg, and the dosage of the diisopropanol solution is 1 ml.
Step 5, preparing a hole transport layer:
the hole transport layer is 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino ] -9, 9 ' -spirocyclic bifluorene.
2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]Dropping the (E) -9, 9' -spirocyclic dibenzofluorene chlorobenzene solution to the MA obtainedxFA1-xPbBryI3-yAn upper surface of the perovskite layer; for the MAxFA1-xPbBryI3-y2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino group on the upper surface of perovskite layer]Spin coating of a solution of-9, 9' -spirocyclic dibenzofluorene chlorobenzene. When in spin coating, the rotating speed of a spin coater is 4000r/min, the spin coating time is 30s, and 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino is obtained]-a film of 9, 9' -spirobifluorene. Then preparing the 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]Drying the FTO conductive substrate of the-9, 9 ' -spirobifluorene film in a drying oven at normal temperature for 8 hours to obtain 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino with the thickness of 200-205 nm]-9, 9' -spirocyclic bifluorene hole transport layer.
When the 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino ] -9, 9 ' -spirocyclic difluorene chlorobenzene solution is prepared, 340mg of lithium bistrifluoromethanesulfonate imide is dissolved in 1ml of acetonitrile solution and is uniformly stirred, so that lithium bistrifluoromethanesulfonate imide acetonitrile mixed solution is obtained.
90mg of 2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino ] -9, 9 '-spirobifluorene, 30. mu.l of a lithium acetonitrile bistrifluoromethanesulfonamide mixture and 18.3. mu.l of 4-tert-butylpyridine were sequentially added to 1ml of chlorobenzene, and the mixture was sealed and stirred at normal temperature in the dark for 12 hours to obtain a 2, 2, 7, 7' -tetrakis [ N, N '-bis (4-methoxyphenyl) amino ] -9, 9' -spirobifluorene chlorobenzene solution.
Step 6, silver plating of the counter electrode:
preparing the compound with 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]Placing an FTO conductive substrate of the-9, 9' -spirobifluorene hole transport layer in a high vacuum thermal evaporation coating machine, and evaporating a silver electrode on the surface of the hole transport layer by adopting a conventional thermal evaporation process, wherein the evaporation rate is 0.3 nm/s. The area of the silver counter electrode is 0.055-0.059 cm2。
Thus, the perovskite solar cell with the dipotassium phytate complexed tin dioxide as the electron transport layer is obtained.
The dipotassium phytate is a phytate containing 6 phosphate groups, and can be adhered to a metal surface through complexation of lone pair electrons of oxygen in the phosphate groups and metal ions.
The perovskite solar cell of the phytic acid dipotassium complex tin dioxide comprises substrate glass and an FTO conductive substrate on the substrate glass, wherein a phytic acid dipotassium complex tin dioxide electronic transmission layer and MA are sequentially arranged from bottom to top on the FTO conductive substrate layerxFA1-xPbBryI3-yPerovskite layer, 2, 7, 7 '-tetrakis [ N, N' -di (4-methoxyphenyl) amino]-9, 9' -spirocyclic bifluorene hole transport layer, silver counter electrode layer. Wherein the thickness of the phytic acid dipotassium complex tin dioxide electron transport layer is 55-60 nm; MA (MA)xFA1-xPbBryI3-yThe thickness of the perovskite layer is 500-506 nm; 2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino]The thickness of the-9, 9' -spirocyclic bifluorene hole transport layer is 200-205 nm; the area of the silver counter electrode is 0.055-0.059 cm2。
In the prior art, the used complexing agent has certain toxicity, can cause environmental pollution, and has limited passivation effect on the interface defects of the stannic oxide/perovskite layer. Therefore, there is a strong need for a complexing agent that is non-toxic and that effectively adheres to tin dioxide to passivate the tin dioxide/perovskite layer for interface defects and to achieve a high quality tin dioxide electron transport layer.
The invention provides a perovskite solar cell which is simple in modification strategy, high in photoelectric conversion efficiency and wide in application range and a preparation method thereof. The method adopts the nontoxic dipotassium phytate complexing tin dioxide precursor liquid to prepare the dipotassium phytate complexing tin dioxide electron transport layer, obviously reduces the interface defects of the tin dioxide electron transport layer/perovskite layer, and improves the electron performance of the tin dioxide electron transport layer. Thereby expanding the application range of the perovskite solar cell and promoting the sustainable development of flexible and clean energy. Based on the method, the phytic acid dipotassium with a plurality of functional groups is added, so that an effective multifunctional strategy complexing tin dioxide colloid precursor solution is provided, and the tin dioxide electronic transmission layer with excellent electronic performance is obtained. Research results show that the dipotassium phytate can reduce the conduction band of a tin dioxide electron transport layer from-3.68 eV to-3.93 eV, is more matched with the conduction band of a perovskite layer, and realizes efficient charge extraction and transmission, so that the conductivity of the tin dioxide is improved to 2 times of the original conductivity. In addition, potassium ions in dipotassium phytate promote in-plane growth of perovskite grains, increasing the average grain size of the perovskite from 350nm to 900 nm. Therefore, the photoelectric conversion efficiency of the perovskite solar cell based on the dipotassium phytate complex tin dioxide as the electron transport layer reaches 21.61 percent, and is improved by 10.7 percent compared with that of the tin dioxide-based perovskite solar cell.
Compared with the prior art, the preparation method of the perovskite solar cell based on the phytic acid dipotassium complex tin dioxide as the electron transport layer, provided by the invention, has the following main beneficial effects:
firstly, the introduction of natural nontoxic organic molecule dipotassium phytate with strong complexing ability obviously reduces the interface defect of tin dioxide/perovskite, adjusts the energy level of tin dioxide to be more matched with a perovskite layer, thereby enhancing the extraction and transmission efficiency of charges; as shown in figure 1b, the surface of the tin dioxide electron transport layer complexed by the dipotassium phytate is more compact and uniform. Secondly, as shown in fig. 2, 1 in the figure is a current-voltage linear curve of the tin dioxide electron transport layer prepared by the prior art; 2 is the current-voltage linear curve of the tin dioxide electron transport layer complexed by the dipotassium phytate. As can be seen from the figure, the slope of the current-voltage line of the tin dioxide electron transport layer complexed with dipotassium phytate is higher than that of the tin dioxide electron transport layer prepared in the prior art, which means that the electrical conductivity of the tin dioxide electron transport layer is significantly increased by the complexation of dipotassium phytate.
Meanwhile, as shown in fig. 3a and 3b, the perovskite layer prepared based on the dipotassium phytate complex tin dioxide has a significantly increased grain size compared to the tin dioxide electron transport layer, thereby improving the quality of the perovskite thin film.
As shown in FIG. 4, the limiting voltage (V) based on trap filling in the current-voltage response diagram (measured by the space-charge-limited-current method) of the perovskite layer prepared on the phytic dipotassium complex tin dioxide electron transport layer was compared with that of the perovskite layer prepared on the tin dioxide electron transport layerTFL) The obvious reduction shows that the complexation of the dipotassium phytate obviously reduces the defect state density of the perovskite layer.
In addition, the dipotassium phytate complexed tin dioxide is used as an electron transport layer, so that the photoelectric conversion efficiency of the perovskite solar cell is remarkably improved, and as shown in fig. 5, the addition of the dipotassium phytate improves the optimal photoelectric conversion efficiency of the perovskite solar cell by 10.7%, namely from 19.52% to 21.61%. The method has the advantages of simple process and low cost, is beneficial to improving the photoelectric property of the perovskite solar cell, provides a new method for developing the perovskite solar cell with high efficiency and low cost, and has good commercial application prospect. As shown in fig. 2, the difference between the process parameters and the ratio in the prior art and the present invention is as follows: in the prior art, a tin dioxide colloid aqueous solution is used, and 40 mu l of the tin dioxide colloid aqueous solution is dropwise added to the upper surface of the pretreated FTO conductive substrate; and spin-coating the tin dioxide colloid aqueous solution dropwise added on the upper surface of the FTO conductive substrate by using a spin coater, wherein the rotation speed of the spin coater is 2500r/min, and the spin-coating time is 30 s. Placing the FTO conductive substrate subjected to spin coating on a heating table for annealing treatment; the annealing temperature is 150 ℃, and the annealing time is 30 min. In the invention, a dipotassium phytate aqueous solution with the concentration of 3.7-15 mmol/ml and a tin dioxide colloid diluted aqueous solution are mixed according to the volume ratio of 1:1, and the mixture is stirred for 2 hours at 70 ℃ to prepare the dipotassium phytate complex tin dioxide colloid precursor solution. Dripping 40 mu l of the phytic acid dipotassium complex tin dioxide precursor on the upper surface of the pretreated FTO conductive substrate; spin-coating the phytic acid dipotassium complex tin dioxide precursor liquid dripped on the upper surface of the FTO conductive substrate by using a spin coater; the rotating speed of the spin coater is 3000-3600 r/min, and the spin coating time is 30 s. Placing the FTO conductive substrate subjected to spin coating on a heating table for annealing treatment; the annealing temperature is 150-180 ℃, and the annealing time is 30-60 min. As shown in table 4, compared with the prior art, the photoelectric conversion efficiency of the perovskite solar cell prepared by examples 1 to 5 based on the tin dioxide electron transport layer complexed with dipotassium phytate is significantly improved, wherein the photoelectric conversion efficiency of the perovskite solar cell prepared by example 2 is the highest.
Drawings
FIG. 1a is a scanning electron microscope topography of a tin dioxide electron transport layer prepared based on the prior art; FIG. 1b is a scanning electron microscope topography of a dipotassium phytate complexed tin dioxide electron transport layer;
fig. 2 is a current-voltage linear relationship diagram of a tin dioxide electron transport layer prepared by the prior art and a tin dioxide electron transport layer complexed with dipotassium phytate.
Fig. 3a is a scanning electron microscope topography of a perovskite layer prepared on a tin dioxide electron transport layer prepared based on the prior art, and fig. 3b is a scanning electron microscope topography of a perovskite layer prepared on a tin dioxide electron transport layer based on dipotassium phytate complexation.
FIG. 4 is a current-voltage response graph; wherein 3 is a current-voltage response curve measured by a space charge current limiting method based on a perovskite layer prepared by the prior art, and 4 is a current-voltage response curve measured by a space charge current limiting method based on a perovskite layer prepared by a dipotassium phytate-complexed tin dioxide electron transport layer.
Fig. 5 is a graph of the short circuit current and open circuit voltage of the perovskite solar cell of the tin dioxide electron transport layer prepared in the prior art and the short circuit current and open circuit voltage of the perovskite solar cell of the dipotassium phytate complex tin dioxide electron transport layer measured under 1.5G sunlight.
Fig. 6 is a structural diagram of a perovskite solar cell prepared according to the present invention.
FIG. 7 is a flow chart of the present invention.
In the figure: 1. a current-voltage linear relation diagram of a tin dioxide electron transport layer prepared by the prior art; 2. a current-voltage linear relation graph of the phytic acid dipotassium complexed tin dioxide electron transport layer prepared in the example 2; 3. the limiting voltage V based on the trap filling of the perovskite layer prepared on the tin dioxide electron transport layer is measured in the curve 3 for the current-voltage response curve measured by the space charge current limiting method based on the perovskite layer prepared in the prior artTFL0.37 eV; 4. the current-voltage response curve measured for the space charge current-limiting method of the perovskite layer prepared on the basis of the dipotassium phytate-complexed tin dioxide electron transport layer prepared in example 2, and the limit voltage V of the trap filling measured in said curve 4 on the basis of the perovskite layer prepared on the dipotassium phytate-complexed tin dioxide electron transport layerTFL0.25 eV; 5. the photoelectric conversion efficiency of the perovskite solar cell prepared by taking tin dioxide as an electron transport layer is prepared by the prior art; 6. the photoelectric conversion efficiency of the perovskite solar cell prepared by using the dipotassium phytate complex tin dioxide prepared in the example 1 as an electron transport layer; 7. the photoelectric conversion efficiency of the perovskite solar cell prepared by using the dipotassium phytate complex tin dioxide as the electron transport layer in the embodiment 2 is high; 8. the photoelectric conversion efficiency of the perovskite solar cell prepared by using the dipotassium phytate complex tin dioxide prepared in the embodiment 3 as an electron transport layer; 9. the photoelectric conversion efficiency of the perovskite solar cell prepared by using the dipotassium phytate complex tin dioxide prepared in the embodiment 4 as an electron transport layer; 10. perovskite prepared by using dipotassium phytate complex tin dioxide prepared in example 5 as electron transport layerPhotoelectric conversion efficiency of solar cells.
Detailed Description
The invention relates to a perovskite solar cell taking dipotassium phytate complexed tin dioxide as an electron transport layer and a preparation method thereof, and the technical scheme of the perovskite solar cell is described in detail through 4 specific embodiments.
The perovskite solar cell with tin dioxide as an electron transport layer is in the prior art and comprises substrate glass 11, an FTO conductive substrate 12, an electron transport layer 13, a perovskite layer 14, a hole transport layer 15 and a silver counter electrode 16; the FTO conductive substrate is prepared on the upper surface of the base glass. The electron transport layer is prepared on the upper surface of the FTO conductive substrate. The perovskite layer is prepared on the upper surface of the electron transport layer. The hole transport layer is prepared on the upper surface of the perovskite layer. The silver counter electrode is positioned on the upper surface of the hole transport layer. The electron transport layer is prepared by complexing tin dioxide with dipotassium phytate, and the silver counter electrode is formed by evaporating silver on the hole transport layer.
The thickness of the electron transport layer is 55-60 nm, the thickness of the perovskite layer is 500-506 nm, the thickness of the hole transport layer is 200-205 nm, and the area of the silver counter electrode is 0.055-0.059 cm2。
TABLE 1 structural parameters of the examples
Figure BDA0003184962940000081
The preparation method of the perovskite solar cell with the dipotassium phytate complexed tin dioxide as the electron transport layer comprises the following specific steps:
step 1, pretreating an FTO conductive substrate:
and sequentially ultrasonically cleaning the FTO conductive substrate for 15min by using acetone, ethanol and deionized water respectively. Blowing the glass by nitrogen flow, and then washing the glass by ultraviolet ozone for 15 min. A clean FTO conductive substrate is obtained.
Step 2, preparing the dipotassium phytate complexing tin dioxide colloid precursor solution:
dissolving 3.7-15 mmol of dipotassium phytate in 1ml of deionized water to form a uniform and transparent dipotassium phytate aqueous solution.
And adding deionized water into a commercially available tin dioxide colloid aqueous solution, and stirring for 2 hours at normal temperature by using a magnetic stirrer to obtain a tin dioxide colloid diluted aqueous solution. The volume ratio of the deionized water to the tin dioxide colloid aqueous solution is 3: 1.
And mixing the dipotassium phytate aqueous solution with the obtained tin dioxide colloid diluted aqueous solution according to the volume ratio of 1:1, and stirring for 2 hours at 70 ℃ to obtain the dipotassium phytate complex tin dioxide colloid precursor solution.
Step 3, preparing the phytic acid dipotassium complex tin dioxide electron transport layer:
preparing a phytic acid dipotassium complex tin dioxide electron transport layer on a pretreated FTO conductive substrate:
dripping 40 mu l of the colloidal precursor of the phytic acid dipotassium complexing tin dioxide on the upper surface of the pretreated FTO conductive substrate; spin-coating the phytic acid dipotassium complex tin dioxide precursor liquid dripped on the upper surface of the FTO conductive substrate by using a spin coater; the rotating speed of the spin coater is 3000-3600 r/min, and the spin coating time is 30 s. Placing the FTO conductive substrate subjected to spin coating on a heating table for annealing treatment; the annealing temperature is 150-180 ℃, and the annealing time is 30-60 min. And cooling to room temperature at normal temperature, and then cleaning the FTO conductive substrate for 15min by ozone. And forming a phytic acid dipotassium complex tin dioxide electron transport layer on the upper surface of the FTO conductive substrate. The thickness of the phytic acid dipotassium complex tin dioxide electron transport layer is 55-60 nm.
Step 4, preparing a perovskite layer:
the perovskite layer is MAxFA1-xPbBryI3-yThe perovskite layer is prepared by a two-step spin coating method.
Dissolving lead iodide in a mixed solvent of dimethylformamide and dimethyl sulfoxide, stirring for 2h at 70 ℃, wherein the volume ratio of dimethylformamide to dimethyl sulfoxide in the mixed solvent is 9:1, and dissolving 1.5mmol of lead iodide in 1ml of the mixed solvent to form a lead iodide mixed solution.
Mixing methyl ammonium iodide, formamidine ammonium iodide and methyl ammonium bromide according to the weight ratio of 7: 2: 1 is dissolved in a diisopropylalcohol solution and stirred for 10min to form MA with a concentration of 70mg/mlxFA1-xBryI1-yAnd (3) solution. The total mass of the methyl ammonium iodide, the formamidine ammonium iodide and the methyl ammonium bromide is 70mg, and the volume of the diisopropanol solution is 1 ml.
When preparing a perovskite layer:
firstly, dripping the lead iodide mixed solution on the upper surface of the phytic acid dipotassium complex tin dioxide electronic transmission layer, and carrying out spin coating on the lead iodide mixed solution on the upper surface of the phytic acid dipotassium complex tin dioxide electronic transmission layer by using a spin coater to obtain a lead iodide thin film; the rotating speed of a spin coater is 5000r/min during spin coating, and the spin coating time is 20 s.
Secondly, spin-coating the MA on the surface of the prepared lead iodide filmxFA1-xBryI1-yA solution; the rotating speed of a spin coater is 4000r/min during spin coating, the spin coating time is 30s, and the MA is formedxFA1-xPbBryI3-yA perovskite thin film.
Preparing said with MAxFA1-xPbBryI3-yPlacing the FTO conductive substrate of the perovskite thin film on a heating table for annealing at 100 ℃ for 1h to form MA with the thickness of 500-506 nmxFA1-xPbBryI3-yA perovskite layer.
Step 5, preparing a hole transport layer:
the hole transport layer is 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino ] -9, 9 ' -spirocyclic bifluorene.
Dissolving 340mg of lithium bistrifluoromethanesulfonate imide in 1ml of acetonitrile solution, and uniformly stirring to obtain a lithium bistrifluoromethanesulfonate imide acetonitrile mixed solution.
90mg of 2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino ] -9, 9 '-spirobifluorene, 30. mu.l of a lithium acetonitrile bistrifluoromethanesulfonamide mixture and 18.3. mu.l of 4-tert-butylpyridine were sequentially added to 1ml of chlorobenzene, and the mixture was sealed and stirred at normal temperature in the dark for 12 hours to obtain a 2, 2, 7, 7' -tetrakis [ N, N '-bis (4-methoxyphenyl) amino ] -9, 9' -spirobifluorene chlorobenzene solution.
The obtained 2, 2, 7, 7 '-tetrakis [ N, N' -di (4-methoxyphenyl) amino](iii) dropping a solution of (9, 9' -spirocyclic) bifluorenylchlorobenzene onto said MAxFA1-xPbBryI3-yAn upper surface of the perovskite layer; using spin coater to spin the MAxFA1-xPbBryI3-y2, 2, 7, 7 '-tetrakis [ N, N' -di (4-methoxyphenyl) amino group on the upper surface of perovskite layer]Spin coating of a solution of-9, 9' -spirocyclic dibenzofluorene chlorobenzene. When in spin coating, the rotating speed of a spin coater is 4000r/min, the spin coating time is 30s, and 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino is obtained]-a film of 9, 9 ' -spirobifluorene which will be prepared with 2, 2, 7, 7 ' -tetrakis [ N, N ' -bis (4-methoxyphenyl) amino]Drying the FTO conductive substrate of the-9, 9 ' -spirobifluorene film for 8 hours at normal temperature in a drying oven to obtain 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino with the thickness of 200-205 nm]-9, 9' -spirocyclic bifluorene hole transport layer.
Step 6, silver plating of the counter electrode:
preparing the compound with 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]Placing an FTO conductive substrate of the-9, 9' -spirobifluorene hole transport layer in a high vacuum thermal evaporation coating machine, and evaporating a silver electrode on the surface of the hole transport layer by adopting a conventional thermal evaporation process, wherein the evaporation rate is 0.3 nm/s. The area of the silver counter electrode is 0.055-0.059 cm2。
Thus, the perovskite solar cell with the dipotassium phytate complexed tin dioxide as the electron transport layer is obtained.
The photoelectric property of the optimum perovskite solar cell prepared by the invention is shown as a curve 7 in figure 5, the optimum open-circuit voltage of the perovskite solar cell of the phytic acid dipotassium complex tin dioxide electron transport layer reaches 1.11V, and the short-circuit current reaches 23.56mA/cm2The filling factor reaches 82.50%, and the photoelectric conversion efficiency reaches 21.61%, which shows that the photoelectric conversion material has excellent photoelectric performance. The optimum open-circuit voltage of the perovskite solar cell of the stannic oxide electron transport layer is 1.09V, and the short-circuit current is 23.15mA/cm2The fill factor was 77.61%, and the photoelectric conversion efficiency reached 19.52%, as shown by curve 5 in fig. 5.
The specific processes of the embodiments of the present invention are the same. The process parameters in the examples are shown in Table 2.
TABLE 2
Figure BDA0003184962940000101
Figure BDA0003184962940000111
Table 3 the process parameters and ratios of the prior art are different from those of the present invention:
Figure BDA0003184962940000112
compared with the prior art, the invention introduces the dipotassium phytate and changes the process parameters when preparing the electron transport layer.
TABLE 4 comparison of opto-electrical properties of the invention with those of the prior art
Examples Open circuit voltage (V) Short circuit current (mA/cm)2) Filling factor (%) Photoelectric conversion efficiency (%)
Prior Art 1.09 23.15 77.61 19.52
Example 1 1.14 23.36 78.91 20.96
Example 2 1.11 23.56 82.50 21.61
Example 3 1.09 23.75 81.84 21.11
Example 4 1.10 24.22 77.57 20.65
Example 5 1.09 23.75 77.58 20.01

Claims (10)

1. The perovskite solar cell with the stannic oxide complexed by dipotassium phytate and the preparation method thereof, wherein the stannic oxide is used as the perovskite solar cell with the stannic oxide complexed by dipotassium phytate of an electron transport layer, and the preparation method thereof comprises substrate glass, an FTO conducting layer, the electron transport layer, a perovskite layer, a hole transport layer and a silver counter electrode; the FTO conductive layer is prepared on the upper surface of the substrate glass; the electron transmission layer is prepared on the upper surface of the FTO conductive layer; the perovskite layer is prepared on the upper surface of the electron transport layer; the hole transport layer is prepared on the upper surface of the perovskite layer; the silver counter electrode is positioned on the upper surface of the hole transport layer; the electron transport layer is prepared by complexing tin dioxide with dipotassium phytate, and the silver counter electrode is formed by evaporating silver on the upper surface of the hole transport layer; the preparation method is characterized in that the electron transport layer is formed by complexing tin dioxide with dipotassium phytate; the perovskite layer is MAxFA1-xPbBryI3-yA perovskite; the hole transport layer is 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]-9, 9' -spirobifluorene.
2. The perovskite solar cell of claim 1, wherein the thickness of the electron transport layer is 55 to 60nm, the thickness of the perovskite layer is 500 to 506nm, the thickness of the hole transport layer is 200 to 205nm, and the area of the silver counter electrode is 0.055 to 0.059cm2。
3. The method for preparing the perovskite solar cell of the dipotassium phytate complex tin dioxide of claim 1 is characterized by comprising the following specific steps:
step 1, pretreating an FTO conductive substrate:
step 2, preparing the dipotassium phytate complexing tin dioxide colloid precursor solution:
step 3, preparing the phytic acid dipotassium complex tin dioxide electron transport layer:
preparing a phytic acid dipotassium complex tin dioxide electron transport layer on the pretreated FTO conductive substrate:
dripping 40 mu l of the colloidal precursor of the phytic acid dipotassium complexing tin dioxide on the upper surface of the pretreated FTO conductive substrate; spin coating the phytic acid dipotassium complex tin dioxide precursor liquid dripped on the upper surface of the FTO conductive substrate; cooling to room temperature at normal temperature, and cleaning the FTO conductive substrate for 15min by ozone; forming a 55-60 nm thick phytic acid dipotassium complex tin dioxide electron transport layer on the upper surface of the FTO conductive substrate;
step 4, preparing a perovskite layer:
the perovskite layer is an MAXFA1-xPbBryI3-y perovskite layer and is prepared by a two-step spin coating method; the method comprises the following steps:
firstly, dripping a lead iodide mixed solution on the upper surface of the phytic acid dipotassium complex tin dioxide electronic transmission layer, and carrying out spin coating on the lead iodide mixed solution on the upper surface of the phytic acid dipotassium complex tin dioxide electronic transmission layer by using a spin coater to obtain a lead iodide thin film;
secondly, spin-coating the MAxFA1-xBryI1-y solution on the upper surface of the obtained lead iodide film; forming a MAXFA1-xPbBryI3-y perovskite thin film;
in a third step, the preparation is carried out with MAxFA1-xPbBryI3-yPlacing the FTO conductive substrate of the perovskite thin film on a heating table for annealing at 100 ℃ for 1h to form MA with the thickness of 500-506 nmxFA1-xPbBryI3-yA perovskite layer;
step 5, preparing a hole transport layer:
the hole transport layer is 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]-9, 9' -spirobifluorene; 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]Dropping the (E) -9, 9' -spirocyclic dibenzofluorene chlorobenzene solution to the MA obtainedxFA1- xPbBryI3-yAn upper surface of the perovskite layer; for the MAxFA1-xPbBryI3-y2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino group on the upper surface of perovskite layer]Spin coating of-9, 9 '-spirocyclic dibenzofuran chlorobenzene solution to obtain 2, 2, 7, 7' -tetra[ N, N' -bis (4-methoxyphenyl) amino group]-thin films of 9, 9' -spirobifluorene; then preparing the 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]Drying the FTO conductive substrate of the-9, 9 ' -spirobifluorene film in a drying oven at normal temperature for 8 hours to obtain 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino with the thickness of 200-205 nm]-a 9, 9' -spirocyclic bifluorene hole transport layer;
step 6, silver plating of the counter electrode:
preparing the compound with 2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]Placing an FTO conductive substrate of a 9, 9' -spirobifluorene hole transport layer in a high vacuum thermal evaporation coating machine, and evaporating a silver electrode on the surface of the hole transport layer by adopting a conventional thermal evaporation process, wherein the evaporation rate is 0.3 nm/s; the area of the silver counter electrode is 0.055-0.059 cm2；
Thus, the perovskite solar cell with the dipotassium phytate complexed tin dioxide as the electron transport layer is obtained.
4. The method for preparing the phytic dipotassium tin dioxide perovskite solar cell according to claim 3, wherein when preparing the phytic dipotassium tin dioxide colloid precursor solution in the step 2, 3.7-15 mmol of phytic dipotassium is dissolved in 1ml of deionized water to form a uniform and transparent phytic dipotassium water solution; adding deionized water into the tin dioxide colloid aqueous solution, and stirring for 2h at normal temperature by using a magnetic stirrer to obtain a tin dioxide colloid diluted aqueous solution; the volume ratio of the deionized water to the tin dioxide colloid aqueous solution is 3: 1; and mixing the dipotassium phytate aqueous solution with the obtained tin dioxide colloid diluted aqueous solution according to the volume ratio of 1:1, and stirring for 2 hours at 70 ℃ to obtain the dipotassium phytate complex tin dioxide colloid precursor solution.
5. The method for preparing the perovskite solar cell of the dipotassium phytate complex tin dioxide as claimed in claim 3, wherein in the step 3, when the dipotassium phytate complex tin dioxide precursor solution is spin-coated, the rotation speed of the spin coater is 3000-3600 r/min, and the spin-coating time is 30 s; placing the FTO conductive substrate subjected to spin coating on a heating table for annealing treatment; the annealing temperature is 150-180 ℃, and the annealing time is 30-60 min.
6. The method for preparing the perovskitic acid dipotassium complex tin dioxide perovskite solar cell according to claim 3, wherein in the step 4, when the lead iodide mixed solution is spin-coated, the rotation speed of a spin coater is 5000r/min, and the spin-coating time is 20 s; in spin coating the MAxFA1-xIyBr1-yWhen the solution is prepared, the rotation speed of a spin coater is 4000r/min, and the spin coating time is 30 s.
7. The method for preparing the perovskitic solar cell of the phytic dipotassium complex tin dioxide as claimed in claim 3, wherein the lead iodide mixed solution is prepared by dissolving 1.5mmol of lead iodide in 1ml of a mixed solvent of dimethylformamide and dimethyl sulfoxide and stirring at 70 ℃ for 2 hours to obtain a lead iodide mixed solution; the volume ratio of dimethylformamide to dimethyl sulfoxide in the mixed solvent is 9: 1.
8. The method of preparing the perovskitic solar cell of dipotassium phytate complex tin dioxide as claimed in claim 3, wherein said MA is preparedxFA1-xBryI1-yWhen in solution, the methyl ammonium iodide, formamidine ammonium iodide and methyl ammonium bromide are mixed according to the weight ratio of 7: 2: 1, stirring for 10min to obtain MA with concentration of 70mg/mlxFA1-xBryI1-yA solution; the total mass of the methyl ammonium iodide, the formamidine ammonium iodide and the methyl ammonium bromide is 70mg, and the dosage of the diisopropanol solution is 1 ml.
9. The method for preparing the perovskites solar cell of the phytic acid dipotassium complex tin dioxide as claimed in claim 3, wherein when preparing the 2, 2, 7, 7 ' -tetrakis [ N, N ' -bis (4-methoxyphenyl) amino ] -9, 9 ' -spirocyclic bifluorene chlorobenzene solution in the step 5, 340mg of lithium bistrifluoromethane sulfenamide is dissolved in 1ml of acetonitrile solution and is uniformly stirred to obtain a lithium bistrifluoromethane sulfenamide acetonitrile mixed solution;
90mg of 2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino ] -9, 9 '-spirobifluorene, 30. mu.l of a lithium acetonitrile bistrifluoromethanesulfonamide mixture and 18.3. mu.l of 4-tert-butylpyridine were sequentially added to 1ml of chlorobenzene, and the mixture was sealed and stirred at normal temperature in the dark for 12 hours to obtain a 2, 2, 7, 7' -tetrakis [ N, N '-bis (4-methoxyphenyl) amino ] -9, 9' -spirobifluorene chlorobenzene solution.
10. The method for preparing the perovskitic solar cell of the phytic acid dipotassium complex tin dioxide according to claim 3, wherein in the step 5, when the 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino ] -9, 9 ' -spiro bifluorene chlorobenzene solution is spin-coated, the rotation speed of a spin coater is 4000r/min, and the spin-coating time is 30 s.
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