CN113707814B - Low-temperature preparation method of tin dioxide core-shell structure nanocrystalline and application of tin dioxide core-shell structure nanocrystalline in perovskite solar cell - Google Patents
Low-temperature preparation method of tin dioxide core-shell structure nanocrystalline and application of tin dioxide core-shell structure nanocrystalline in perovskite solar cell Download PDFInfo
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Abstract
The invention provides a tin dioxide core-shell structure nanocrystalline and a low-temperature preparation method, and a perovskite solar cell prepared from the core-shell structure nanocrystalline.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to preparation of tin dioxide core-shell structure nanocrystals and application of the tin dioxide core-shell structure nanocrystals as electron transport materials in perovskite solar cells.
Background
Currently, titanium dioxide (TiO 2 ) Is the most widely used electron transport layer material in high-efficiency formal perovskite solar cell devices. However, tiO 2 High temperature sintering is generally required in the preparation process to obtain higher crystallization quality and electron mobility, and TiO 2 Has stronger ultraviolet light catalytic activity and has adverse effect on the stability of the whole perovskite solar cell device. Thus, it is necessary to develop an electron transport material that can be produced at low temperature, has high electron mobility, and does not have photocatalytic activity.
Tin dioxide (SnO) 2 ) Does not need high temperature treatment in the preparation process and has weaker propertyIs very suitable for preparing the high-efficiency stable formal perovskite solar cell device. Nonetheless, snO 2 The electron transport material still has the problems of low film electron mobility, high surface defect state density, multiple carrier recombination sites and the like.
Disclosure of Invention
Based on the technical background, the inventor performs keen approach, and researches and discovers that: the tin dioxide nanocrystalline with the surface coating layer, namely the tin dioxide nanocrystalline with the core-shell structure, can be obtained by simple coating on the surface of the tin dioxide nanocrystalline, can improve the conductivity, the carrier density and the carrier mobility of the tin dioxide by coating, and can reduce the defect state density of the tin dioxide.
The first aspect of the invention provides a tin dioxide core-shell structure nanocrystal, which comprises a tin dioxide nanocrystal and a coating layer coated on the surface of the tin dioxide.
The second aspect of the invention provides a preparation method of the tin dioxide core-shell structure nanocrystalline according to the first aspect of the invention, which comprises the following steps:
step 1, preparing a coating layer precursor solution;
and step 2, mixing tin dioxide with the coating precursor solution, and reacting to obtain the tin dioxide core-shell structure nanocrystalline.
The third aspect of the invention provides a perovskite solar cell, which comprises the tin dioxide core-shell structure nanocrystalline according to the first aspect of the invention and the tin dioxide core-shell structure nanocrystalline prepared by the preparation method according to the second aspect of the invention.
A fourth aspect of the present invention is to provide a method for manufacturing a perovskite solar cell according to the third aspect of the present invention, the method comprising the steps of:
step a, forming an electron transport layer on a substrate;
step b, forming a perovskite layer on the electron transport layer;
step c, forming a hole transport layer on the perovskite layer;
and d, forming an electrode on the hole transport layer.
The tin dioxide core-shell structure nanocrystalline and the preparation method thereof and the application of the tin dioxide core-shell structure nanocrystalline as an electron transport material in perovskite solar cells have the following advantages:
(1) The tin dioxide core-shell structure nanocrystalline has the advantages of high conductivity, high carrier density, high carrier mobility, low defect state density and the like;
(2) The tin dioxide core-shell structure nanocrystalline disclosed by the invention is applied to a rigid perovskite solar cell, and has excellent photoelectric conversion efficiency;
(3) The tin dioxide core-shell structure nanocrystalline disclosed by the invention is applied to a flexible perovskite solar cell, and has higher photoelectric conversion efficiency.
Drawings
Fig. 1 shows a schematic structural view of a perovskite solar cell according to a preferred embodiment of the invention;
FIG. 2a shows a transmission electron micrograph of tin dioxide nanocrystals used in the comparative example of the present invention;
fig. 2b shows a transmission electron microscope photograph of the nano-crystal with the tin dioxide core-shell structure prepared in the embodiment 1 of the present invention;
FIG. 3 shows the current-voltage curves in conductivity tests for inventive example 1 and comparative example 1;
fig. 4 shows current-voltage curves measured under one solar simulation of perovskite solar cell prepared as example 5 and comparative example 1 according to the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
The first aspect of the invention provides a tin dioxide core-shell structure nanocrystal, which comprises a tin dioxide nanocrystal and a coating layer coated on the surface of the tin dioxide.
The coating layer is selected from one or more of neodymium trioxide, niobium pentoxide, rubidium oxide, cobalt oxide, manganese dioxide, zinc oxide, titanium dioxide and vanadium pentoxide, preferably one or more of neodymium trioxide, niobium pentoxide, cobalt oxide, titanium dioxide and manganese dioxide, more preferably niobium pentoxide.
The inventor finds that the coating layer is coated on the surface of the tin dioxide to improve the performance of the tin dioxide, in particular to a core-shell structure nanocrystal prepared by coating niobium pentoxide on the surface of the tin dioxide, compared with the tin dioxide, the core-shell structure nanocrystal has higher conductivity, carrier density, carrier mobility and lower defect state density, can be applied to perovskite solar cells, can effectively improve the photoelectric conversion efficiency of the perovskite solar cells, and has good application prospects in the solar cells.
In the present invention, the molar ratio of the metal element of the coating layer to the tin element in the tin dioxide is (0.4 to 1.5): 1, preferably (0.5 to 1.2): 1, more preferably (0.7 to 1.0): 1.
experiments show that when the molar ratio of tin element in the tin dioxide to metal element in the coating layer is in the range, the thickness of the coating layer coated on the surface of the tin dioxide is uniform, the thickness is proper, and the conductivity of the obtained core-shell structure nanocrystalline is higher.
The tin dioxide core-shell structure nanocrystalline has the advantages of high conductivity, high carrier density, high carrier mobility, low defect state density and the like, and the conductivity is 1.2 multiplied by 10 -2 ～1.25×10 -2 mS·cm -1 。
The second aspect of the invention provides a preparation method of the tin dioxide core-shell structure nanocrystalline according to the first aspect of the invention, which comprises the following steps:
step 1, preparing a coating layer precursor solution;
and step 2, mixing tin dioxide with the coating precursor solution, and reacting to obtain the tin dioxide core-shell structure nanocrystalline.
This step is specifically described and illustrated below.
And step 1, preparing a coating layer precursor solution.
In the present invention, the coating precursor solution is prepared from a coating agent selected from one or more of an oxide, chloride, hydroxide and carbonate of neodymium, niobium, rubidium, cobalt, manganese, zinc, titanium or vanadium, preferably from one or more of an oxide and chloride of neodymium, niobium, cobalt, titanium or manganese, more preferably niobium pentachloride, and a solvent.
The coating agent is dissolved in a solvent which is an alcohol, carbon tetrachloride or dilute hydrochloric acid, preferably dilute hydrochloric acid, to inhibit too rapid a hydrolysis process of the coating agent.
After dissolution in the solvent, it is then dissolved in water, preferably ice water, to prevent rapid hydrolysis of the coating agent at room temperature. The mixing means is preferably stirring mixing.
The concentration of the coating precursor solution is 4 to 6mg/mL, preferably 5 to 5.3mg/mL.
And step 2, mixing tin dioxide with the coating precursor solution, and reacting to obtain the tin dioxide core-shell structure nanocrystalline.
Before mixing the tin dioxide with the coating precursor solution, preferably the tin dioxide is dissolved in ethanol to prepare a dispersion, and then mixed with the coating precursor solution.
The tin dioxide is dissolved in the ethanol and then mixed with the coating layer precursor solution, so that the thickness of the coating agent coated on the surface of the tin dioxide is more uniform, and the prepared tin dioxide core-shell structure nanocrystalline has more uniform grain diameter and is more beneficial to the improvement of electrical property.
The mass concentration of the dispersion is 7 to 20mg/mL, preferably 10 to 17mg/mL, more preferably 12 to 15mg/mL.
The mass ratio of the coating agent to the tin dioxide is (0.8-3): 1, preferably (1-2.5): 1, more preferably the mass ratio is (1.5 to 2): 1.
experiments show that when the mass ratio of the tin dioxide to the coating agent is in the range, the prepared tin dioxide core-shell structure nanocrystalline has higher conductivity, higher carrier density, higher carrier mobility and lower defect state density.
The mixing mode is mechanical stirring, transparent solution is formed after complete dissolution, and the mixed solution is heated.
The heating temperature is 50 to 90 ℃, preferably 60 to 80 ℃, more preferably 70 ℃. Mechanical stirring is continuously carried out in the heating process.
The heating time is 10 to 120 minutes, preferably 20 to 90 minutes, more preferably 30 to 60 minutes.
The inventor finds that the heating temperature and the heating time can influence the performance of the prepared tin dioxide core-shell structure nanocrystalline, and the performance of the prepared perovskite solar cell is influenced, and experiments show that the prepared tin dioxide core-shell structure nanocrystalline is applied to the perovskite solar cell along with the extension of the heating time, the photoelectric conversion efficiency of the solar cell tends to be increased firstly and then reduced, and when the heating temperature is 50-90 ℃ and the heating time is 30-120 min, the performance of the tin dioxide core-shell structure nanocrystalline is the best, and the photoelectric conversion efficiency of the tin dioxide core-shell structure nanocrystalline applied to the perovskite solar cell is the best.
After the reaction is completed, the solid product is obtained by centrifugation at 2000 to 5000rpm, preferably 3000 to 4000rpm, more preferably 3500rpm.
The centrifugation time is 1 to 10 minutes, preferably 3 to 7 minutes, more preferably 5 minutes.
After centrifugation, washing is carried out, wherein the detergent is preferably ethanol, the washing mode is preferably centrifugal washing, and the washing times are preferably 3 times.
The centrifugal speed is 2000 to 5000rpm, preferably 3000 to 4000rpm, more preferably 3500rpm.
The centrifugation time is 1 to 10 minutes, preferably 3 to 7 minutes, more preferably 5 minutes.
A third aspect of the present invention is to provide a perovskite solar cell comprising the tin dioxide core-shell structure nanocrystal of the first aspect of the present invention and the tin dioxide core-shell structure nanocrystal prepared by the preparation method of the second aspect of the present invention.
The perovskite solar cell comprises a transparent conductive substrate, and an electron transport layer, a perovskite layer, a hole transport layer and an electrode which are sequentially deposited on the transparent conductive substrate.
The existing perovskite solar cell can be represented by a sandwich structure, which is sequentially a transparent conductive substrate/electron transport layer/perovskite layer/hole transport layer/electrode, or a substrate/hole transport layer/perovskite layer/electron transport layer/electrode, wherein the former is generally called a formal structure in which an electron transport layer is firstly formed on the substrate, and the latter is called a trans structure in which a hole transport layer is firstly formed on the substrate. The perovskite solar cell of the present invention has a formal structure.
In the present invention, the transparent conductive substrate is derived from commercially available products. The transparent conductive substrate includes a substrate and a transparent conductive film deposited on a surface thereof.
The substrate is selected from one of a rigid glass substrate, a flexible PEN (polyethylene naphthalate), a flexible PET (polyethylene terephthalate) substrate.
The transparent conductive film is one of Indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), indium Zinc Oxide (IZO), boron doped zinc oxide (BZO), aluminum doped zinc oxide (AZO), and zinc gallium oxide (GZO), preferably one of ITO, FTO, and IZO, more preferably ITO.
According to a preferred embodiment of the present invention, the electron transport layer is a tin dioxide core-shell structure nanocrystal according to the first aspect of the present invention or a tin dioxide core-shell structure nanocrystal prepared by the preparation method according to the second aspect of the present invention.
The thickness of the electron transport layer is 10 to 80nm, preferably 20 to 50nm, more preferably 20 to 40nm.
The perovskite layer is formed of a perovskite material, preferably an organic-inorganic hybrid perovskite or an all-inorganic perovskite, such as Cs + 、MA + 、FA + The perovskite material forms a perovskite layer on the electron transport layer by a solution method or a vacuum auxiliary method.
The thickness of the perovskite layer is 300-1000 nm, preferably 400-900 nm, more preferably 500-800 nm, and the thickness range can realize effective utilization of sunlight, is too thin, easily causes insufficient light absorption, is too thick, is difficult to obtain a high-quality film, and finally has low photoelectric conversion efficiency.
The thickness of the hole transport layer is 10 to 100nm, preferably 20 to 80nm, more preferably 30 to 70nm.
In the present invention, the electrode is preferably a gold electrode, and the thickness of the electrode is 60 to 120nm, preferably 70 to 100nm, and more preferably 80nm.
The inventors have found through experiments that the solar cell is operated with light entering from one side of the substrate, and in order to ensure excellent charge collecting capability, the electrode is preferably a gold electrode in the present invention.
The photoelectric conversion efficiency of the perovskite solar cell is 23.04% -24.01%.
A fourth aspect of the present invention is to provide a method for manufacturing a perovskite solar cell according to the third aspect of the present invention, the method comprising the steps of:
step a, forming an electron transport layer on a transparent conductive substrate;
step b, forming a perovskite layer on the electron transport layer;
step c, forming a hole transport layer on the perovskite layer;
and d, forming an electrode on the hole transport layer.
This step is specifically described and illustrated below.
And a step a, forming an electron transport layer on the transparent conductive substrate.
According to the present invention, the transparent conductive substrate includes a substrate and a transparent conductive film deposited on a surface thereof.
The substrate is selected from one of a rigid glass substrate, a flexible PEN (polyethylene naphthalate), a flexible PET (polyethylene terephthalate) substrate.
The transparent conductive film is selected from one of Indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), indium Zinc Oxide (IZO), boron doped zinc oxide (BZO), aluminum doped zinc oxide (AZO) and zinc gallium oxide (GZO), preferably one of ITO, FTO and IZO, more preferably ITO.
The electron transport layer is prepared from the tin dioxide core-shell structure nanocrystalline according to the first aspect of the present invention or the tin dioxide core-shell structure nanocrystalline prepared by the preparation method according to the second aspect of the present invention.
The tin dioxide core-shell structure nanocrystalline is dispersed into a solvent to form a precursor solution, wherein the dispersion mode is preferably ultrasonic dispersion, and the ultrasonic dispersion time is 30 min-2 h, preferably 45-90 min, and more preferably 60min.
Before the precursor solution is applied to the substrate, the substrate is preferably subjected to a pretreatment, preferably a plasma treatment or an ultraviolet ozone treatment, more preferably an oxygen plasma treatment.
The substrate is subjected to plasma treatment, so that the cleanliness of the substrate surface can be improved, the wettability of the solution on the substrate surface is facilitated, the high-quality electron transport layer film is ensured to be obtained, the phenomenon of internal short circuit of the solar cell caused by incomplete coverage is prevented, and the performance of the solar cell is improved.
However, the time of the plasma treatment is not too long, the non-conductive area of the substrate is increased and the conductive performance of the substrate is reduced due to the too long time of the plasma treatment, and the time of the plasma treatment is 10-20 min, preferably 15min.
The coating mode is preferably spin coating, and more preferably spin coating is performed by placing the substrate on a spin coating apparatus and dropping the prepared precursor solution onto the substrate.
The spin coating is followed by annealing at a temperature of 100 to 200 c, preferably 120 to 170 c, more preferably 150 c for rigid substrates and more preferably 120 c for flexible substrates such as PEN, PET, etc.
The annealing time is 10 to 60 minutes, preferably 20 to 45 minutes, more preferably 30 minutes.
The crystallinity of the electron transport layer can be affected by the annealing temperature and the annealing time, the higher the annealing temperature and the longer the annealing time, the more and more fully crystallized the electron transport layer, the larger and larger the crystal grains, and the higher the crystallinity, but the higher the post-treatment temperature can reduce the stability of the solar cell. Particularly for flexible substrates such as PEN, PET and the like, the substrate is curled and deformed due to the excessively high temperature, so that the deposition of each subsequent functional layer is seriously affected, and the device cannot work.
The thickness of the electron transport layer is 10 to 80nm, preferably 20 to 50nm, more preferably 20 to 40nm.
And b, forming a perovskite layer on the electron transport layer.
In the invention, the perovskite layer is prepared in two steps, namely, a lead iodide film is obtained by spin coating on an electron transport layer, and then the perovskite layer is obtained by spin coating on the lead iodide film.
According to a preferred embodiment of the present invention, spin coating is preferably performed by dissolving lead iodide in a solvent to obtain a lead iodide solution, and then dropping the solution onto the electron transport layer.
The solvent is preferably a mixed solvent of N, N-dimethylformamide and dimethyl sulfoxide, lead iodide has good solubility in the mixed solvent, and the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is preferably (5-15): 1, more preferably (8 to 11): 1, e.g., 9:1.
The concentration of the lead iodide solution is 0.5-0.8 g/mL, preferably 0.65-0.7 g/mL.
In the present invention, the spin-coating speed is 1000 to 2000rpm, and the obtained film is more uniform, preferably 1200 to 1700rpm, and more preferably 1500rpm.
The spin coating time is 30 to 60 seconds, preferably 35 to 45 seconds, more preferably 30 seconds.
The spin coating is followed by an annealing treatment at a temperature of 50 to 100 ℃, preferably 60 to 80 ℃, more preferably 70 ℃.
The annealing time is 5 to 60s, preferably 10 to 30s, more preferably 15s.
The thickness of the lead iodide thin film is 150 to 500nm, preferably 200 to 450nm, more preferably 250 to 400nm.
Formamidine iodine (FAI), methyl Ammonium Iodide (MAI) and methylamine hydrochloride (MACl) are preferably dissolved and mixed in isopropanol to obtain a mixed solution.
The FAI concentration in the mixed solution is 0.07 to 0.12g/mL, preferably 0.09g/mL.
The MAI concentration in the mixed solution is 0.005-0.007 g/mL by mass, preferably 0.0064g/mL by mass.
The MACI in the mixed solution has a mass concentration of 0.007 to 0.01g/mL, preferably 0.009g/mL.
The mixed solution is dripped on a lead iodide film and then spin-coated, wherein the spin-coating rotating speed is 1000-3000 rpm, preferably 2000rpm; the spin-coating time is 20 to 60s, preferably 40s.
The spin coating is followed by an annealing treatment in which the annealing atmosphere is preferably air, more preferably air having a relative humidity of 30%, and air having a humidity of 30% has an accelerating effect on the crystallization process of the perovskite thin film.
The annealing temperature is 100 to 200 ℃, preferably 120 to 170 ℃, more preferably 150 ℃ for rigid substrates, and more preferably 120 ℃ for flexible substrates.
The annealing time is 5 to 30 minutes, preferably 10 to 20 minutes, more preferably 15 minutes.
Similar to the electron transport layer, the annealing temperature and the annealing time can influence the crystallinity of the perovskite layer, and the perovskite layer obtained through the annealing temperature and the annealing time has good crystallinity, and the obtained solar cell has good photoelectric conversion efficiency.
The thickness of the perovskite layer is 300-1000 nm, preferably 400-900 nm, more preferably 500-800 nm, so that the effective utilization of sunlight can be realized, insufficient light absorption is easily caused by over-thinness, the current density is too small and too thick, a high-quality film is difficult to obtain, and good photoelectric conversion efficiency is still not obtained.
And c, forming a hole transport layer on the perovskite layer.
2,2', 7' -tetrabromo-9, 9' -spirodi, tris (4-iodobenzene) amine (spiro-OMeTAD) was dissolved in chlorobenzene, and then tert-butylpyridine, bis (trifluoromethanesulfonyl) imide lithium acetonitrile solution and tris [ 4-tert-butyl-2- (1H-pyrazol-1-yl) pyridine ] cobalt tris (1, 1-trifluoro-N- [ (trifluoromethyl) sulfonyl ] methane sulfonamide salt) acetonitrile solution were added thereto to obtain a spiro-OMeTAD solution.
The mass concentration of the spiro-OMeTAD in the spiro-OMeTAD solution is 0.07-0.15 g/mL, and the mass concentration is preferably 0.09-0.105 g/mL.
The mass concentration of the lithium bis (trifluoromethanesulfonyl) imide acetonitrile solution is 500-550 mg/mL, preferably 520mg/mL.
The mass concentration of the tris [ 4-tertiary butyl-2- (1H-pyrazol-1-yl) pyridine ] cobalt tris (1, 1-trifluoro-N- [ (trifluoromethyl) sulfonyl ] methane sulfonamide salt) acetonitrile solution is 250-350 mg/mL, preferably 300mg/mL.
The volume ratio of the tert-butylpyridine, the lithium bis (trifluoromethanesulfonyl) imide acetonitrile solution, the tris [ 4-tert-butyl-2- (1H-pyrazol-1-yl) pyridine ] cobalt tris (1, 1-trifluoro-N- [ (trifluoromethyl) sulfonyl ] methane sulfonamide salt) acetonitrile solution and the chlorobenzene is (0.03-0.05): (0.02-0.03): (0.04-0.05): 1, preferably the volume ratio is (0.04-0.045): (0.024 to 0.027): (0.045-0.05): 1.
The spin-OMeTAD solution is applied dropwise to the perovskite layer for spin coating at 4000 to 5000rpm, preferably 4500rpm.
The spin-coating time is 15 to 45s, preferably 30s.
The thickness of the hole transport layer is 10 to 150nm, preferably 20 to 120nm, more preferably 30 to 110nm.
The thickness of the hole transport layer is related to the thickness of the hole transport material, and the thicknesses of the corresponding hole transport layers are different for different hole materials, which is related to the photoelectric performance of the material, and the inventors found that the perovskite solar cell obtained has higher photoelectric conversion efficiency when the thickness of the hole transport material is in the above range.
And d, forming an electrode on the hole transport layer.
In the present invention, the electrode is preferably a gold electrode.
The electrode is preferably formed on the hole transport layer by a pyrolysis method, a CVD method, or a vacuum evaporation method, and more preferably formed on the hole transport layer by a vacuum evaporation method.
The thickness of the electrode is 60 to 120nm, preferably 70 to 100nm, more preferably 80nm.
The invention has the beneficial effects that:
(1) The preparation method of the tin dioxide core-shell structure nanocrystalline is simple, and has good photoelectric conversion efficiency when being applied to perovskite solar cells;
(2) The tin dioxide core-shell structure nanocrystalline has the advantages of high conductivity, high carrier density, high carrier mobility, low defect state density and the like, and the conductivity can reach 1.23 multiplied by 10 -2 mS·cm -1 ；
(3) The perovskite solar cell provided by the invention has the advantages of simple preparation method and good photoelectric conversion efficiency, and the photoelectric conversion efficiency is 23.04% -24.01%, and is up to 24.01%.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
0.54g of NbCl 5 Placing in a small bottle, placing in an ice water bath, slowly dripping 3mL of hydrochloric acid to form a clear solution, slowly adding the clear solution into 100mL of ice water, and continuously stirring until ice blocks are completely dissolved to form NbCl 5 A solution;
8mL of the NbCl is taken 5 Adding the solution into flask, adding magneton, stirring, collecting 2mL with concentration of 13mg/mLSnO 2 Dropwise adding nanocrystalline ethanol dispersion into NbCl 5 In the solution, the flask is closed;
and (3) after the solution is stirred and dispersed completely to form a transparent solution, placing the flask in an oil bath kettle, continuously heating and stirring at 70 ℃ for 40min, centrifuging the completely reacted solution at 3500rpm for 5min to obtain a solid sample, and continuously repeatedly centrifuging the solid sample at 3500rpm for 5min with ethanol for three times to obtain tin dioxide core-shell structure nanocrystals, wherein the quantitative analysis result of X-ray photoelectron spectroscopy shows that the molar ratio of niobium element in the coating layer to tin element in the core layer tin dioxide is 0.87:1.
Example 2
The preparation of the tin dioxide core-shell structured nanocrystals was performed in a similar manner to that of example 1, except that: heating and stirring for 30min at 70deg.C.
Example 3
The preparation of the tin dioxide core-shell structured nanocrystals was performed in a similar manner to that of example 1, except that: stirring was continued for 50min at 70 ℃.
Example 4
The preparation of the tin dioxide core-shell structured nanocrystals was performed in a similar manner to that of example 1, except that: stirring was continued for 60min at 70 ℃.
Example 5
Dispersing the tin dioxide core-shell structure nanocrystalline obtained in the example 1 into 10mL of ethanol to form a precursor solution, placing the precursor solution in an ultrasonic instrument for ultrasonic dispersion for 1h, treating an ITO transparent conductive substrate (the transmittance of 93% in Hunan city of China) with oxygen plasma for 15min, placing the treated ITO transparent conductive substrate on a spin coating instrument, dripping the precursor solution onto the ITO transparent conductive substrate to prepare a film by spin coating, and then annealing at 150 ℃ for 30min to obtain a tin dioxide core-shell structure nanocrystalline electron transport layer film with the thickness of 30nm;
dissolving 0.6915g of lead iodide in a mixed solvent of 0.9mLN, N-dimethylformamide and 0.1mL of dimethyl sulfoxide, stirring until the lead iodide is completely dissolved, then dropwise adding the solution onto a tin dioxide core-shell structure nanocrystalline electron transport layer film, spin-coating the solution at 1500rpm for 30s, annealing the solution at 70 ℃ for 15s to obtain a lead iodide film, dissolving 0.09g of formamidine iodine (FAI), 0.0064g of Methyl Ammonium Iodide (MAI) and 0.009g of methylamine hydrochloride (MACl) in 1mL of isopropanol, dropwise adding the solution onto the lead iodide film after the dissolution is complete, spin-coating the solution at 2000rpm for 40s, transferring the solution into air with 30% humidity and annealing the solution at 150 ℃ for 15min to obtain a perovskite light absorption layer film, wherein the thickness of a perovskite layer is 750nm;
0.1012g of 2,2', 7' -tetrabromo-9, 9' -spirodi-, tris (4-iodobenzene) amine (spiroo-OMeTAD) was weighed and dissolved in 1mL of chlorobenzene, 42. Mu.L of t-butylpyridine, 26. Mu.L of 520mg/mL of lithium bis (trifluoromethanesulfonyl) imide acetonitrile solution and 45. Mu.L of 300mg/mL of tris [ 4-t-butyl-2- (1H-pyrazol-1-yl) pyridine ] cobalt tris (1, 1-trifluoro-N- [ (trifluoromethyl) sulfonyl ] methane sulfonamide salt) acetonitrile solution were added, and after the solution was sufficiently stirred and dissolved, 20. Mu.L of spiroo-OMeTAD solution was added dropwise to the perovskite film, and spin coating was performed at 4500rpm for 30 seconds, whereby the spiroo-OMeTAD hole transport layer was prepared, the thickness of the hole transport layer was 100nm.
The electrode is a gold electrode, and the hole transport layer is evaporated by a vacuum evaporation method to 80nm. Obtaining the perovskite solar cell.
Example 6
The perovskite solar cell was prepared in a similar manner to example 5, except that: the tin dioxide core-shell structured nanocrystal obtained in example 2 was dispersed in 10mL of ethanol to form a precursor solution.
Example 7
The perovskite solar cell was prepared in a similar manner to example 5, except that: the tin dioxide core-shell structure nanocrystal prepared in example 3 was dispersed in 10mL of ethanol to form a precursor solution.
Example 8
The perovskite solar cell was prepared in a similar manner to example 5, except that: the tin dioxide core-shell structure nanocrystal prepared in example 4 was dispersed in 10mL of ethanol to form a precursor solution.
Comparative example
The perovskite solar cell was prepared in a similar manner to example 5, except that: snO is prepared 2 Dispersing the nanocrystalline into 10mL of ethanol to form a precursor solution, placing the precursor solution into an ultrasonic instrument for ultrasonic dispersion for 1h, treating an ITO conductive substrate (93% in Hunan city of China) with oxygen plasma for 15min, placing the treated ITO conductive substrate on a spin coating instrument, dripping the precursor solution onto the ITO conductive substrate to spin coat, preparing a film, and annealing at 150 ℃ for 30min to obtain SnO 2 An electron transport layer film.
Experimental example
Experimental example 1 photoelectric conversion efficiency test
The perovskite solar cells produced in examples 5 to 8 and comparative example were subjected to a current-voltage curve test under one sunlight using a solar simulator (Enlite ch, SSF 5-3A) for Taiwan light-band, as shown in FIG. 4, and the test results are shown in Table 1.
TABLE 1
For solar cells, open circuit voltage, short circuit current, fill factor and conversion efficiency are the 4 most important parameters, where the photoelectric conversion efficiency is the ratio of maximum output power to solar radiation from the sun to ground. I.e. the greater the conversion efficiency, the more light energy is converted to electrical energy under the same solar radiation, while the product of the other 3 parameters is proportional to the efficiency.
As can be seen from Table 1, each photovoltaic parameter of the perovskite solar cell prepared by using the tin dioxide core-shell structure nanocrystals prepared in examples 1 to 4 of the present application is higher than that of the comparative example only using SnO 2 Perovskite solar cell prepared by nanocrystalline benefits from tin dioxide core-shell structure nanocrystalline obtained after niobium pentoxide cladding and initial SnO 2 Compared with the nanocrystalline, the perovskite thin film has the advantages of high conductivity, high carrier density, high carrier mobility, low defect state density, more matching with the energy level of the perovskite thin film, and higher crystallization quality of the perovskite thin film prepared on the tin dioxide core-shell structure nanocrystalline, so that the interface contact between an electron transport layer and the perovskite layer is improved, the extraction and the transmission of electrons are promoted, and the aggregation and the recombination of the carriers are inhibited.
The perovskite solar cell based on the tin dioxide core-shell structure nanocrystalline can obtain the photoelectric conversion efficiency as high as 24.01%, and the perovskite solar cell based on the tin dioxide nanocrystalline can only obtain the photoelectric conversion efficiency of 22.28%, which shows that the improvement of the photoelectric conversion efficiency is facilitated after the niobium pentoxide is coated.
Experimental example 2TEM test
The core-shell structured nanocrystal of tin dioxide obtained in example 1 and tin dioxide used in comparative example were subjected to transmission electron microscopy, and the test results are shown in fig. 2b and 2a, respectively.
As can be seen from fig. 2a and fig. 2b, the crystallinity of the tin dioxide core-shell structure nanocrystal prepared in example 1 and the crystallinity of the tin dioxide adopted in comparative example 1 are both higher, and it can be seen that niobium pentoxide is uniformly coated on the surface of the tin dioxide.
Experimental example 3 conductivity test
The tin dioxide core-shell structure nanocrystals prepared in example 1 and the tin dioxide of comparative example 1 were used as electron transport layers (ETM), respectively, to prepare device structures ITO/ETM/Au shown in the inset in fig. 3, and the current-voltage curves were tested using electrochemical workstation equipment, as shown in fig. 3.
As can be seen from FIG. 3, the direct current conductivity of the tin dioxide core-shell structured nanocrystalline film is 1.23×10 -2 mS·cm -1 The direct current conductivity of the tin dioxide nanocrystalline film is 1.02X10 -2 mS·cm -1 The niobium pentoxide coating is favorable for improving the conductivity.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (11)
1. The tin dioxide core-shell structure nanocrystalline is characterized by comprising tin dioxide nanocrystalline and a coating layer coated on the surface of the tin dioxide;
the coating layer is niobium pentoxide.
2. The tin dioxide core-shell structured nanocrystal of claim 1, wherein,
the molar ratio of the metal element of the coating layer to the tin element in the tin dioxide is (0.4-1.5): 1.
3. A method for preparing the tin dioxide core-shell structure nanocrystalline according to claim 1 or 2, characterized in that the preparation method comprises:
step 1, preparing a coating layer precursor solution by a coating agent and a solvent;
and step 2, mixing tin dioxide with the coating precursor solution, and reacting to obtain the tin dioxide core-shell structure nanocrystalline.
4. A process according to claim 3, wherein in step 1,
the coating agent is niobium chloride.
5. The method according to claim 3 or 4, wherein in step 1,
the coating agent is niobium pentachloride.
6. A process according to claim 3, wherein in step 2,
before mixing tin dioxide with the coating precursor solution, dissolving the tin dioxide in ethanol to prepare dispersion liquid, and then mixing the dispersion liquid with the coating precursor solution.
7. A process according to claim 3, wherein in step 2,
the mass ratio of the coating agent to the tin dioxide is (0.8-3): 1.
8. A process according to claim 3, wherein in step 2,
the mixed solution is heated at 50-90 ℃ for 10-120 min.
9. A perovskite solar cell, characterized in that the perovskite solar cell comprises the tin dioxide core-shell structured nanocrystal of claim 1 or 2.
10. The perovskite solar cell as claimed in claim 9, wherein,
the perovskite solar cell comprises a transparent conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer and an electrode, wherein the electron transport layer, the perovskite layer, the hole transport layer and the electrode are sequentially deposited on the transparent conductive substrate;
the tin dioxide core-shell structure nanocrystalline is an electron transmission layer of the solar cell.
11. A method of preparing a perovskite solar cell according to claim 9 or 10, characterized in that the preparation method comprises the steps of:
step a, forming an electron transport layer on a transparent conductive substrate;
step b, forming a perovskite layer on the electron transport layer;
step c, forming a hole transport layer on the perovskite layer;
and d, forming an electrode on the hole transport layer.
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