CN111211232B - Preparation method of perovskite solar cell with dopamine chelated titanium dioxide - Google Patents
Preparation method of perovskite solar cell with dopamine chelated titanium dioxide Download PDFInfo
- Publication number
- CN111211232B CN111211232B CN202010179012.0A CN202010179012A CN111211232B CN 111211232 B CN111211232 B CN 111211232B CN 202010179012 A CN202010179012 A CN 202010179012A CN 111211232 B CN111211232 B CN 111211232B
- Authority
- CN
- China
- Prior art keywords
- dopamine
- titanium dioxide
- solution
- transport layer
- perovskite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The preparation method of the perovskite solar cell with dopamine-chelated titanium dioxide uses the dopamine-chelated titanium dioxide prepared by an anhydrous sol-gel method as an electron transport layer, reduces the preparation temperature and the defect state density of the titanium dioxide electron transport layer, and improves the electron mobility of the titanium dioxide electron transport layer. The invention has simple process and high photoelectric conversion efficiency, expands the application range of the perovskite solar cell and promotes the sustainable development of flexible and clean energy.
Description
Technical Field
The invention relates to the field of perovskite solar cells, in particular to a preparation method of a perovskite solar cell with dopamine chelated titanium dioxide.
Background
With the development of society, the traditional non-renewable energy is exhausted and pollutes the environment when being used, and solar energy is a key point of human attention as an inexhaustible clean energy. The solar energy has the characteristics of wide coverage, convenient collection and utilization and no pollution, so that the solar energy becomes a new energy with the greatest development potential. The use of solar cells is mainly achieved by photoelectric conversion.
The energy conversion efficiency of a novel third-generation solar cell, namely an organic-inorganic hybrid perovskite solar cell, is improved to 25.2% from the initial 3.8% in a few years, which is mainly attributed to the advantages of high light absorption rate, bipolar transmission, long carrier life, adjustable band gap, low cost, simple preparation process and the like of the perovskite material.
The perovskite solar cell consists of an electron transport layer, a perovskite absorption layer, a hole transport layer and a counter electrode. The electron transport layer is used as an important component of the perovskite solar cell, and plays an important role in photoelectron transport, hole blocking and efficiency improvement. At present, titanium dioxide is generally used as an electron transport layer, and has the advantages of low cost, simple preparation process, proper conduction band and valence band, excellent light transmittance and the like. However, titanium dioxide for anatase phase requires high sintering temperatures above 450 ℃ and is complicated to prepare, which limits its application to flexible substrates. In order to simplify the preparation process of organic-inorganic hybrid perovskite solar cells and improve the photoelectric conversion efficiency of perovskite solar cells, researchers are constantly exploring low-temperature preparation processes of titanium dioxide electron transport layers, such as low-temperature atomic layer deposition, magnetron sputtering, low-temperature chemical bath and other technologies. However, the titanium dioxide electron transport Layer prepared at low temperature has the disadvantages of low conductivity, high defect state density, etc., and in order to improve the electron mobility and reduce the defect state density of the titanium dioxide electron transport Layer, the titanium dioxide electron transport Layer modified with organic substances has received extensive attention from researchers (the documents nafes Ahmad, Xuning Zhang, Shuo Yang, donggang Zhang, Jianqiu Wang, Saud uzafer, Yanxun Li, Yuan Zhang, Sabir Hussain, zhiha Cheng, Anbu kumarian, huqiong Zhou, polypamine/ZnO electron transport layers, carbon transport channels, expression in organic inorganic-organic colloidal fibers, j. matrix. chem. c.2019,7,10795 modified titanium dioxide electron transport layers, especially modified by coating with organic amines, yellow dye transport layers, yellow transport layers, yellow transport layers, yellow layers, ACS appl. mater. interfaces.2018, 10, 30607-. However, the modified layer after the post-treatment in these reports hardly ensures good interface contact between the organic molecule and the electron transport layer, and the introduction of the modified layer undoubtedly makes the preparation process more complicated, and prolongs the experimental period. Therefore, in order to achieve effective interfacial binding of dopamine to the electron transport layer, it is necessary to employ chelation.
Disclosure of Invention
The invention provides a preparation method of a perovskite solar cell with dopamine-chelated titanium dioxide, which aims to overcome the defects that in the prior art, a titanium dioxide electron transport layer is low in conductivity and high in defect state density, or a titanium dioxide electron transport layer is modified by an organic substance, so that the preparation process is complex, and the modified layer after post-treatment is difficult to ensure good interface contact between organic molecules and the electron transport layer.
The specific process of the invention is as follows:
step 1, pretreating an FTO conductive substrate:
step 2, preparing a dopamine chelating titanium dioxide nanocrystal dispersion liquid:
13.6mmol of titanium tetrachloride was added to 5ml of anhydrous ethanol, and mixed with stirring to form a yellow transparent titanium tetrachloride alcoholysis solution.
Adding 2.72-27.2 mmol of 3-dopamine hydrochloride into 30ml of benzyl alcohol, and stirring and mixing to obtain a benzyl alcohol dopamine ligand solution.
Adding the obtained titanium tetrachloride alcoholysis solution into the benzyl alcohol dopamine ligand solution, uniformly stirring at normal temperature, and stirring at 80 ℃ for 4 hours to obtain a dopamine chelating titanium dioxide precursor solution, wherein the molar ratio of the benzyl alcohol dopamine ligand solution to the titanium tetrachloride alcoholysis solution is 0.2-2.
And centrifuging and washing the dopamine chelating titanium dioxide precursor solution to obtain the titanium dioxide nanocrystal with the size of 3 nm.
Dispersing 10mg of the titanium dioxide nanocrystal into 1ml of absolute ethyl alcohol, and uniformly stirring to uniformly disperse the dopamine chelating titanium dioxide nanocrystal in the absolute ethyl alcohol to obtain the dopamine chelating titanium dioxide nanocrystal dispersion liquid.
Step 3, preparing a dopamine chelating titanium dioxide electron transport layer:
preparing a dopamine chelating titanium dioxide electron transport layer on the pretreated FTO conductive substrate;
dripping 60 mu l of dopamine chelated titanium dioxide nanocrystal dispersion liquid onto the upper surface of the pretreated FTO conductive substrate; spin-coating the dopamine chelating titanium dioxide nanocrystal dispersion 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 rpm, 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 dopamine chelating titanium dioxide electron transport layer on the upper surface of the FTO conductive substrate. The thickness of the titanium dioxide electron transport layer is 50-60 nm.
Step 4, preparing a perovskite layer:
the perovskite layer is FAxMA1-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 dopamine chelating titanium dioxide electron transport layer, and spin-coating the lead iodide mixed solution on the upper surface of the dopamine chelating titanium dioxide electron transport layer by using a spin coater to obtain a lead iodide film; the spin coating time is 20s, and the rotation speed of a spin coater is 5000 rpm.
Secondly, spin-coating the FA on the upper surface of the obtained lead iodide filmxMA1-xBryI1-yA solution; the rotation speed of a spin coater is 4000rpm, the spin coating time is 30s, and finally FA is formedxMA1-xPbBryI3-yA perovskite thin film.
Preparing the solution with FAxMA1-xPbBryI3-yPlacing FTO conductive substrate of perovskite film on a heating table, annealing at 100 deg.C for 1h to form FA with thickness of 490nmxMA1-xPbBryI3-yA perovskite absorption layer.
When the lead iodide mixed solution is prepared, dissolving lead iodide in a 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 the dimethyl formamide to the dimethyl sulfoxide in the mixed solvent is 9:1, the amount of the mixed solvent is 1ml, and the addition amount of the lead iodide is 1.5 mmol.
Preparation of the FAxMA1-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 is added into the diisopropyl alcohol solution and stirred for 10min to form FA with the concentration of 60mg/mlxMA1-xBryI1-yAnd (3) solution. The total mass of the methyl ammonium iodide, the formamidine ammonium iodide and the methyl ammonium bromide is 60mg, and the volume 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]Dripping the (E) -9, 9' -spirocyclic dibenzofluorene chlorobenzene solution to the FA obtained in step 4xMA1-xPbBryI3-yAn upper surface of the perovskite absorption layer; align the FA with a spin coaterxMA1-xPbBryI3-y2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino group on the upper surface of the perovskite absorption layer]Spin coating of a solution of-9, 9' -spirocyclic dibenzofluorene chlorobenzene. When spin coating is carried out, the rotating speed of a spin coater is 4000rpm, 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]FTO conductive substrate of-9, 9' -spirobifluorene film in drying ovenDrying at room temperature for 8h to obtain 200nm thick 2, 2, 7, 7 '-tetrakis [ N, N' -di (4-methoxyphenyl) amino]-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, 520mg of lithium bistrifluoromethanesulfonate imide is firstly dissolved in 1ml of acetonitrile solution and is uniformly stirred to obtain lithium bistrifluoromethanesulfonate imide acetonitrile mixed solution.
72.3mg of 2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino ] -9, 9 '-spirobifluorene, 18.6. mu.l of a lithium acetonitrile bistrifluoromethanesulfonamide mixture and 28.6. mu.l of 4-tert-butylpyridine were sequentially added to 1ml of chlorobenzene, and the mixture was sealed and stirred at normal temperature for 12 hours in the dark to obtain a 2, 2, 7, 7' -tetrakis [ N, N '-bis (4-methoxyphenyl) amino ] -9, 9' -spirobifluorene chlorobenzene solution.
Step 6, evaporating a metal counter electrode:
placing the FTO conductive substrate with the 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino ] -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 0.3nm/s, and the silver electrode is a metal counter electrode. The thickness of the metal counter electrode was 80 nm.
Thus, the perovskite solar cell with the dopamine chelated titanium dioxide is obtained.
The invention provides a perovskite solar cell method which is simple in process, high in photoelectric conversion efficiency and wide in application range. The invention uses the dopamine chelating titanium dioxide prepared by the anhydrous sol-gel method as the electron transport layer, reduces the preparation temperature and the defect state density of the titanium dioxide electron transport layer, and improves the electron mobility of the titanium dioxide electron transport layer. Thereby expanding the application range of the perovskite solar cell and promoting the sustainable development of flexible and clean energy.
The perovskite solar cell with dopamine chelated titanium dioxide comprises substrate glass and FTO (fluorine-doped tin oxide) conductor on the substrate glassAn electric layer, which is sequentially provided with a dopamine chelating titanium dioxide electron transport layer and FA from the FTO conductive substrate layer from bottom to topxMA1-xPbBryI3-yPerovskite absorption layer, 2, 7, 7 '-tetrakis [ N, N' -di (4-methoxyphenyl) amino]A 9, 9' -spirocyclic bifluorene hole transport layer and a silver counter electrode layer, wherein the thickness of the dopamine chelating titanium dioxide electron transport layer is 50-60 nm, and FAxMA1-xPbBryI3-yThe light absorbing layer has a thickness of 490nm, and is 2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino group]The thickness of the-9, 9' -spirocyclic bifluorene hole transport layer is 200nm, and the thickness of the silver counter electrode is 80 nm.
Compared with the prior art, the preparation method of the perovskite solar cell based on the dopamine chelated titanium dioxide mainly has the following beneficial effects:
the method has the advantages that the dopamine chelated titanium dioxide is adopted as the electron transport layer, firstly, the electron transport layer is completed under the low-temperature condition, so that the preparation cost of the perovskite solar cell is greatly reduced, the preparation process is simplified, and the method is also suitable for the preparation of the flexible perovskite solar cell; secondly, as shown in fig. 1, the crystal structure of the nanocrystal of dopamine-chelated titanium dioxide is not changed compared to the titanium dioxide nanocrystal; finally, by using dopamine chelated titanium dioxide as an electron transport layer, the photoelectric conversion efficiency of the perovskite solar cell can be improved, and as shown in fig. 3, the maximum efficiency of the perovskite solar cell is improved from 16.74% to 19.45% by adding dopamine. 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.
Description of the drawings:
FIG. 1 (a) is a high power transmission microscope image of titanium dioxide nanocrystals prepared in the prior art dispersed in anhydrous ethanol;
fig. 1 (b) is a high transmission microscope image of the dopamine chelating titanium dioxide nanocrystal dispersed in absolute ethanol in example 1. The same crystal structure is shown in fig. 1 (a) and fig. 1 (b), indicating that chelation of dopamine with titanium dioxide does not alter the crystal structure of titanium dioxide;
FIG. 2 (a) is a high scanning electron microscope image of a titanium dioxide electron transport layer prepared according to the prior art;
fig. 2 (b) is a high-power scanning electron microscope image of the electron transport layer of dopamine chelating titanium dioxide prepared in example 1, and it is obvious that the image (b) in fig. 2 is more dense and uniform than the electron transport layer in the image (a) in fig. 2;
FIG. 3 is a schematic structural diagram of a perovskite solar cell based on dopamine chelating titanium dioxide as an electron transport layer prepared in example 1;
fig. 4 is a graph of the short circuit current and open circuit voltage of a perovskite solar cell having a titania electron transport layer prepared according to the prior art and a perovskite solar cell having a dopamine-chelated titania electron transport layer measured under 1.5G sunlight. Wherein 7 is the photoelectric conversion efficiency of the perovskite solar cell prepared by using titanium dioxide prepared by the prior art as an electron transport layer, and 8 is the photoelectric conversion efficiency of the perovskite solar cell prepared by using the dopamine chelated titanium dioxide prepared in example 1 as an electron transport layer;
FIG. 5 is a schematic view of the present invention;
FIG. 6 is a flow chart of the present invention.
In the figure: 1. a substrate glass; an FTO conductive layer; 3. a dopamine chelating titanium dioxide electron transport layer; 4. a perovskite absorption layer; 5. a hole transport layer; 6. a silver counter electrode; 7. the titanium dioxide is used as the photoelectric conversion efficiency of the perovskite solar cell prepared by the electron transport layer; 8. the photoelectric conversion efficiency of the perovskite solar cell prepared by using the dopamine chelated titanium dioxide as an electron transport layer.
Table 1 shows the process parameters and ratios in the prior art and 4 examples;
table 2 shows the differences between the process parameters and the ratio of the prior art and the present invention;
table 3 comparison of the photovoltaic performance parameters of the present invention with those of the prior art.
Detailed Description
The invention relates to a preparation method of a perovskite solar cell with dopamine chelated titanium dioxide.
The titanium dioxide perovskite solar cell is in the prior art and comprises substrate glass 1, an FTO conducting layer 2, an electron transport layer 3, a perovskite absorption layer 4, a hole transport layer 5 and a silver counter electrode 6; the FTO conductive layer is prepared on the upper surface of the substrate glass. The electron transport layer is prepared on the upper surface of the FTO conductive layer. The perovskite absorption 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 absorption layer. The silver counter electrode is positioned on the upper surface of the hole transport layer. The electron transport layer is prepared by chelating titanium dioxide with dopamine, and the silver counter electrode is formed by evaporating silver on the hole transport layer.
The invention will be described in detail with 4 specific embodiments.
The specific process of the invention is as follows:
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 a dopamine chelating titanium dioxide nanocrystal dispersion liquid:
13.6mmol of titanium tetrachloride was added to 5ml of anhydrous ethanol, and mixed with stirring to form a yellow transparent titanium tetrachloride alcoholysis solution.
Adding 2.72-27.2 mmol of 3-dopamine hydrochloride into 30ml of benzyl alcohol, and stirring and mixing to obtain a benzyl alcohol dopamine ligand mixed solution.
Adding the obtained titanium tetrachloride alcoholysis solution into the benzyl alcohol dopamine ligand solution, uniformly stirring at normal temperature, and stirring at 80 ℃ for 4 hours to obtain a dopamine chelating titanium dioxide precursor solution, wherein the molar ratio of the benzyl alcohol dopamine ligand solution to the titanium tetrachloride alcoholysis solution is 0.2-2.
And centrifuging and washing the dopamine chelating titanium dioxide precursor solution to obtain the dopamine chelating titanium dioxide nanocrystal with the size of 3 nm. Dispersing 10mg of the dopamine chelating titanium dioxide nanocrystal into 1ml of absolute ethyl alcohol, and uniformly stirring to uniformly disperse the dopamine chelating titanium dioxide in the absolute ethyl alcohol to obtain the dopamine chelating titanium dioxide nanocrystal dispersion liquid.
Step 3, preparing a dopamine chelating titanium dioxide electron transport layer:
preparing a dopamine chelating titanium dioxide electron transport layer on the pretreated FTO conductive substrate:
dripping 60 mu l of dopamine chelated titanium dioxide nanocrystal dispersion liquid onto the upper surface of the pretreated FTO conductive substrate; spin-coating the dopamine chelating titanium dioxide nanocrystal dispersion 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 rpm, 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 dopamine chelating titanium dioxide electron transport layer on the upper surface of the FTO conductive substrate. The thickness of the dopamine chelating titanium dioxide electron transport layer is 50-60 nm.
Step 4, preparing a perovskite layer:
the perovskite layer is FAxMA1-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 diisopropyl alcohol solution and stirred for 10min to form FA with a concentration of 60mg/mlxMA1-xBryI1-yAnd (3) solution. The methyl ammonium iodide, formamidine ammonium iodide and formamidineThe total mass of the ammonium bromide is 60mg, and the volume of the diisopropylalcohol solution is 1 ml.
When preparing a perovskite layer:
firstly, dripping the mixed solution of lead iodide on the upper surface of the dopamine chelating titanium dioxide electron transport layer, and spin-coating the mixed solution of lead iodide on the upper surface of the dopamine chelating titanium dioxide electron transport layer by using a spin coater to obtain a lead iodide film; the spin coating time is 20s, and the rotation speed of a spin coater is 5000 rpm.
Secondly, spin-coating the FA on the upper surface of the prepared lead iodide filmxMA1-xBryI1-yA solution; the rotating speed of a spin coater is 4000rpm, the spin coating time is 30s, and FA is formedxMA1-xPbBryI3-yA perovskite thin film.
Preparing the solution with FAxMA1-xPbBryI3-yPlacing FTO conductive substrate of perovskite film on a heating table, annealing at 100 deg.C for 1h to form FA with thickness of 490nmxMA1-xPbBryI3-yA perovskite absorption 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.
520mg of lithium bistrifluoromethanesulfonate imide is dissolved in 1ml of acetonitrile solution and is stirred uniformly to obtain the lithium bistrifluoromethanesulfonate imide acetonitrile mixed solution.
72.3mg of 2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino ] -9, 9 '-spirobifluorene, 18.6. mu.l of a lithium acetonitrile bistrifluoromethanesulfonamide mixture and 28.6. mu.l of 4-tert-butylpyridine were sequentially added to 1ml of chlorobenzene, and the mixture was sealed and stirred at normal temperature for 12 hours in the dark 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 (E) -9, 9' -spirocyclic dibenzofluorene chlorobenzene onto said FAxMA1-xPbBryI3-yAn upper surface of the perovskite absorption layer; align the FA with a spin coaterxMA1-xPbBryI3-y2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino group on the upper surface of the perovskite absorption layer]Spin coating of a solution of-9, 9' -spirocyclic dibenzofluorene chlorobenzene. When spin coating is carried out, the rotating speed of a spin coater is 4000rpm, 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 FTO conductive substrate of-9, 9 ' -spirobifluorene film in a drying oven at normal temperature for 8h to obtain 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino with thickness of 200nm]-9, 9' -spirocyclic bifluorene hole transport layer.
Step 6, evaporating a metal counter electrode:
placing the FTO conductive substrate with the 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino ] -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 0.3nm/s, and the silver electrode is a metal counter electrode. The thickness of the metal counter electrode was 80 nm.
Thus, the perovskite solar cell with dopamine chelating titanium dioxide electrons is obtained.
The photoelectric properties of the invention are shown as 8 in fig. 4, the best open-circuit voltage of the perovskite solar cell with the dopamine chelating titanium dioxide electron transport layer reaches 1.12V, and the short-circuit current reaches 22.51mA cm-2The filling factor reaches 77.33%, and the photoelectric conversion efficiency reaches 19.45%, which shows that the composite material has excellent photoelectric conversion property. The optimum open-circuit voltage of the perovskite solar cell of the titanium dioxide electron transport layer is 1.09V, and the short-circuit current reaches 20.37mAcm-2The fill factor reaches 75.32% and the photoelectric conversion efficiency reaches 16.74%, as shown by 7 in fig. 4.
The specific processes of the embodiments of the present invention are the same. The process parameters and ratios in the examples are shown in Table 1.
TABLE 1
Table 2 the process parameters and ratios of the prior art are different from those of the present invention:
compared with the prior art, the invention introduces 3-dopamine hydrochloride and changes the process parameters when preparing the electron transport layer.
TABLE 3 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 | 20.37 | 75.33 | 16.74 |
| Example 1 | 1.12 | 20.98 | 76.52 | 18.36 |
| Example 2 | 1.12 | 22.51 | 77.33 | 19.45 |
| Example 3 | 1.12 | 22.84 | 75.92 | 19.19 |
| Example 4 | 1.12 | 20.90 | 73.91 | 17.26 |
Claims (4)
1. A preparation method of a perovskite solar cell with dopamine chelated titanium dioxide is characterized by comprising the following specific steps:
step 1, pretreating an FTO conductive substrate:
step 2, preparing a dopamine chelating titanium dioxide nanocrystal dispersion liquid:
adding 13.6mmol of titanium tetrachloride into 5mL of absolute ethanol, stirring and mixing to form a yellow and transparent titanium tetrachloride alcoholysis solution;
adding 6.8-13.6 mmol of 3-dopamine hydrochloride into 30mL of benzyl alcohol, and stirring and mixing to obtain a benzyl alcohol dopamine ligand solution;
adding the obtained titanium tetrachloride alcoholysis solution into the benzyl alcohol dopamine ligand solution, uniformly stirring at normal temperature, and stirring at 80 ℃ for 4 hours to obtain a dopamine chelating titanium dioxide precursor solution, wherein the molar ratio of the benzyl alcohol dopamine ligand mixed solution to the titanium tetrachloride alcoholysis solution is 0.5-1;
centrifuging and washing the dopamine chelating titanium dioxide precursor solution to obtain titanium dioxide nanocrystals with the size of 3 nm;
dispersing 10mg of the titanium dioxide nanocrystal into 1mL of absolute ethyl alcohol, and uniformly stirring to uniformly disperse the dopamine chelating titanium dioxide in the absolute ethyl alcohol to obtain a dopamine chelating titanium dioxide nanocrystal dispersion liquid;
step 3, preparing a dopamine chelating titanium dioxide electron transport layer:
preparing a dopamine chelating titanium dioxide electron transport layer on the pretreated FTO conductive glass substrate;
dripping 60 mu L of dopamine chelated titanium dioxide nanocrystal dispersion liquid onto the upper surface of the pretreated FTO conductive substrate; spin-coating the dopamine chelating titanium dioxide nanocrystal dispersion 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 rpm, 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; cooling to room temperature at normal temperature, and cleaning the FTO conductive substrate for 15min by ozone; forming a dopamine chelating titanium dioxide electron transport layer on the upper surface of the FTO conductive substrate; the thickness of the titanium dioxide electron transport layer is 50-60 nm;
step 4, preparing a perovskite layer:
the perovskite layer is FAxMA1-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 dopamine chelating titanium dioxide electron transport layer, and spin-coating the lead iodide mixed solution on the upper surface of the dopamine chelating titanium dioxide electron transport layer by using a spin coater to obtain a lead iodide film; the rotating speed of a spin coater is 5000rpm during spin coating, and the spin coating time is 20 s;
secondly, coating FA on the upper surface of the obtained lead iodide film in a spin modexMA1-xBryI1-yA solution; the rotation speed of a spin coater is 4000rpm, the spin coating time is 30s, and finally FA is formedxMA1-xPbBryI3-yA perovskite thin film;
preparing the solution with FAxMA1-xPbBryI3-yPlacing FTO conductive substrate of perovskite film on a heating table, annealing at 100 deg.C for 1h to form FA with thickness of 490nmxMA1-xPbBryI3-yA perovskite absorption 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;
2, 2, 7, 7 '-tetra [ N, N' -di (4-methoxyphenyl) amino]Dripping the (E) -9, 9' -spirocyclic dibenzofluorene chlorobenzene solution to the FA obtained in step 4xMA1-xPbBryI3-yAn upper surface of the perovskite absorption layer; align the FA with a spin coaterxMA1-xPbBryI3-y2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino group on the upper surface of the perovskite absorption layer]Spin coating 9, 9' -spiro-dibenzofluorene chlorobenzene solution; when spin coating is carried out, the rotating speed of a spin coater is 4000rpm, 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 FTO conductive substrate of-9, 9 ' -spirobifluorene film in a drying oven for 8h, and drying in the drying oven at normal temperature for 8h to obtain 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino with thickness of 200nm]-a 9, 9' -spirocyclic bifluorene hole transport layer;
step 6, evaporating a metal counter electrode:
placing the FTO conductive substrate with the 2, 2, 7, 7 ' -tetra [ N, N ' -di (4-methoxyphenyl) amino ] -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 0.3nm/s, and the silver electrode is a metal counter electrode; the thickness of the metal counter electrode is 80 nm;
thus, the perovskite solar cell with the dopamine chelated titanium dioxide is obtained.
2. The method for preparing the perovskite solar cell with dopamine-chelated titanium dioxide as claimed in claim 1, wherein, in the step of preparing the lead iodide mixed solution in the step 4, lead iodide is dissolved in a mixed solvent of dimethylformamide and dimethyl sulfoxide, and the mixture is stirred for 2 hours at 70 ℃ to obtain a lead iodide mixed solution; the volume ratio of the dimethyl formamide to the dimethyl sulfoxide in the mixed solvent is 9:1, the mixed solvent amount is 1mL, and the addition amount of the lead iodide is 1.5 mmol.
3. The method of preparing the perovskite solar cell with dopamine chelating titanium dioxide as claimed in claim 1, wherein the FA in the step 4 is preparedxMA1-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 is added into the diisopropyl alcohol solution and stirred for 10min to form FA with the concentration of 60mg/mLxMA1-xBryI1-yA solution; the total mass of the methyl ammonium iodide, the formamidine ammonium iodide and the methyl ammonium bromide is 60mg, and the volume of the diisopropanol solution is 1 mL.
4. The method for preparing the perovskite solar cell with dopamine-chelated titanium dioxide as claimed in claim 1, wherein, in the step of preparing the 2, 2, 7, 7 ' -tetrakis [ N, N ' -bis (4-methoxyphenyl) amino ] -9, 9 ' -spirocyclic dibenzofluorene-chlorobenzene solution in step 5, 520mg of lithium bistrifluoromethanesulfonate imide is firstly dissolved in 1mL of acetonitrile solution and uniformly stirred to obtain lithium bistrifluoromethanesulfonate imide acetonitrile mixed solution;
72.3mg of 2, 2, 7, 7 '-tetrakis [ N, N' -bis (4-methoxyphenyl) amino ] -9, 9 '-spirobifluorene, 18.6. mu.L of a lithium acetonitrile bistrifluoromethanesulfonamide mixture and 28.6. mu.L of 4-tert-butylpyridine were sequentially added to 1mL of chlorobenzene, and the mixture was sealed and stirred at normal temperature for 12 hours in the dark to obtain a 2, 2, 7, 7' -tetrakis [ N, N '-bis (4-methoxyphenyl) amino ] -9, 9' -spirobifluorene chlorobenzene solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010179012.0A CN111211232B (en) | 2020-03-15 | 2020-03-15 | Preparation method of perovskite solar cell with dopamine chelated titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010179012.0A CN111211232B (en) | 2020-03-15 | 2020-03-15 | Preparation method of perovskite solar cell with dopamine chelated titanium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111211232A CN111211232A (en) | 2020-05-29 |
| CN111211232B true CN111211232B (en) | 2022-04-05 |
Family
ID=70788911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010179012.0A Active CN111211232B (en) | 2020-03-15 | 2020-03-15 | Preparation method of perovskite solar cell with dopamine chelated titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111211232B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111682113B (en) * | 2020-06-23 | 2021-09-21 | 西北工业大学 | Pyrocatechol anchoring molecule passivation perovskite solar cell containing long fluorocarbon chain and preparation method thereof |
| CN112713243B (en) * | 2020-12-28 | 2023-05-30 | 华侨大学 | Preparation method of bulk heterojunction perovskite solar cell |
| CN113644199B (en) * | 2021-06-13 | 2022-11-25 | 西北工业大学 | Perovskite solar cell with phytic acid dipotassium complexed with tin dioxide and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107302055A (en) * | 2017-06-15 | 2017-10-27 | 南京工业大学 | A kind of preparation method of perovskite thin film |
| CN107316942A (en) * | 2017-06-07 | 2017-11-03 | 武汉理工大学 | A kind of perovskite solar cell and preparation method thereof |
| KR20190042958A (en) * | 2017-10-17 | 2019-04-25 | 전남대학교산학협력단 | Nanoaggregate for drug delivery and electromagnetic actuation |
| CN110280313A (en) * | 2019-07-11 | 2019-09-27 | 哈尔滨工业大学 | A kind of three-dimensional structure load TiO2-xThe preparation method of material |
| CN110534653A (en) * | 2018-05-23 | 2019-12-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Perovskite thin film and its preparation method and application |
| CN110756055A (en) * | 2019-05-15 | 2020-02-07 | 北京化工大学 | Bipolar membrane and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101773972B1 (en) * | 2016-04-01 | 2017-09-04 | 한국과학기술연구원 | Electron transporting layer for flexible perovskite solar cells and flexible perovskite solar cells including the same |
| CN106449988B (en) * | 2016-11-29 | 2019-04-19 | 宁波大学 | A kind of perovskite solar battery of super-thin electronic transport layer structure |
-
2020
- 2020-03-15 CN CN202010179012.0A patent/CN111211232B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107316942A (en) * | 2017-06-07 | 2017-11-03 | 武汉理工大学 | A kind of perovskite solar cell and preparation method thereof |
| CN107302055A (en) * | 2017-06-15 | 2017-10-27 | 南京工业大学 | A kind of preparation method of perovskite thin film |
| KR20190042958A (en) * | 2017-10-17 | 2019-04-25 | 전남대학교산학협력단 | Nanoaggregate for drug delivery and electromagnetic actuation |
| CN110534653A (en) * | 2018-05-23 | 2019-12-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Perovskite thin film and its preparation method and application |
| CN110756055A (en) * | 2019-05-15 | 2020-02-07 | 北京化工大学 | Bipolar membrane and preparation method thereof |
| CN110280313A (en) * | 2019-07-11 | 2019-09-27 | 哈尔滨工业大学 | A kind of three-dimensional structure load TiO2-xThe preparation method of material |
Non-Patent Citations (3)
| Title |
|---|
| Chemical bath deposited rutile TiO2 compact layer toward efficient planar heterojunction perovskite solar cells;Chao Liang等;《Applied Surface Science》;20160707;第391卷;全文 * |
| Dopamine-crosslinked TiO2 perovskite layer for efficient and photostable perovskite solar cells under full spectral continuous illumination;Yiming Sun等;《Nano Energy》;20190228;第56卷;第4页第1段至第13页第1段，图1-5 * |
| In Situ Interface Engineering of TiO2 Nanocrystals for Fully Ambient-Processed Perovskite Solar Cells;Peng Zhai等;《Sol. RRL》;20181231;第2卷(第9期);第1页第2栏第2段至第6页第2栏倒数第1段，图1-5 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111211232A (en) | 2020-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106025085B (en) | Based on Spiro OMeTAD/CuXPerovskite solar cell of S composite hole transporting layers and preparation method thereof | |
| CN111211232B (en) | Preparation method of perovskite solar cell with dopamine chelated titanium dioxide | |
| CN103456888B (en) | A kind of Cs doping ZnO is the hybrid solar cell of electron transfer layer | |
| CN110246967B (en) | Method for preparing flexible perovskite solar cell at low temperature | |
| CN108878661B (en) | Preparation method of carbon quantum dot modified perovskite solar cell | |
| CN103474574A (en) | Hybrid solar cell with aluminum-doped zinc oxide nanorod as electron transfer layer | |
| CN104362253A (en) | All solid state perovskite microcrystalline silicon composite solar battery and preparation method thereof | |
| CN109216557A (en) | One kind being based on citric acid/SnO2Perovskite solar battery of electron transfer layer and preparation method thereof | |
| CN110335945B (en) | Double-electron-transport-layer inorganic perovskite solar cell and manufacturing method and application thereof | |
| CN111987220A (en) | Perovskite solar cell based on down-conversion layer and preparation method | |
| CN108649124B (en) | High-efficiency inorganic perovskite solar cell and preparation method thereof | |
| CN111525038B (en) | Perovskite solar cell doped with multifunctional additive and preparation method thereof | |
| CN108539026B (en) | Preparation method of perovskite thin film with micron tube array structure | |
| CN101872685B (en) | Solid dye-sensitized nanocrystal/microcrystal silicon composite film solar cell and preparation method thereof | |
| Chen et al. | Optimization of plastic crystal ionic liquid electrolyte for solid-state dye-sensitized solar cell | |
| CN116056469A (en) | Perovskite solar cell based on ionic liquid interface modification | |
| CN114975790A (en) | Ionic liquid modified double-interface perovskite solar cell and preparation method and application thereof | |
| CN110246969B (en) | Preparation method of perovskite solar cell with pyridine modified tin oxide compact layer | |
| CN103972398A (en) | Organic and inorganic hybridization solar cell and manufacturing method of organic and inorganic hybridization solar cell | |
| CN114864822A (en) | Perovskite solar cell and preparation method thereof | |
| CN114583061A (en) | Lead-free tin-based perovskite thin film with three-dimensional structure and preparation method of solar cell thereof | |
| CN108461635B (en) | A kind of method and its application of boron compound surface modification perovskite thin film | |
| Manseki et al. | Current Advances in the Preparation of SnO2 Electron Transport Materials for Perovskite Solar Cells | |
| CN113644199B (en) | Perovskite solar cell with phytic acid dipotassium complexed with tin dioxide and preparation method thereof | |
| Zhang et al. | Optimization of polymer electrolytes for quasi-solidstate dye-sensitized solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |