CN108511607B - TiO2Preparation method of cookie-shaped microspheres and method for preparing perovskite solar cell - Google Patents
TiO2Preparation method of cookie-shaped microspheres and method for preparing perovskite solar cell Download PDFInfo
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Abstract
The invention discloses TiO2Preparation method of cookie-like microspheres, preparation method of perovskite solar cell and TiO2Mixing the microsphere with acetonitrile, isopropanol and acetylacetone, dripping tetrabutyl titanate and tetrabutylammonium hydroxide as control agents, heating at 160-200 deg.C for 12-20 h, precipitating, centrifuging, washing, drying, and annealing at high temperature to obtain TiO2And (3) microsphere powder. The obtained powder is mixed with P25 to prepare slurry, and the slurry is spin-coated on FTO coated with a dense layer and used as a mesoporous layer of the perovskite solar cell. In TiO2The MAPbI is spin-coated on the film in sequence3And Spiro-OMeTAD, and finally evaporating a layer of Au. The TiO with high specific surface area2The microspheres adopt a one-step hydrothermal method, the preparation process is simple, and the cost is low; prepared TiO2The film shows excellent conductivity and absorption effect on visible light, and meanwhile, the film is applied to the perovskite solar cell to obtain excellent photoelectric conversion efficiency, so that the possibility is provided for preparing the perovskite solar cell with large area, low cost and high efficiency.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to TiO2A method for preparing cookie-like microspheres and a method for preparing perovskite solar cells.
Background
The nano-material used as the mesoporous layer of the Perovskite Solar Cell (PSC) needs to satisfy the following characteristics: the light transmission is good, more incident light can be transmitted, and the light loss is reduced; the energy level position of a conduction band of the organic light-emitting diode can be matched with the energy level of a light-absorbing material, so that the energy loss of excitons is reduced; thirdly, the compound of electrons and holes is effectively inhibited due to excellent electron transport performance; and fourthly, the porosity and the specific surface area are large, so that the reflection of incident light in the battery is enhanced, and the light capture capability of the device is improved. TiO is commonly used as a PSC mesoporous layer material at present2ZnO, NiOx and ZrO2, wherein the most common application is cheap and efficient TiO2And (3) granules. Compared with other TiO2Array structure (nanowire, nanorod and nanotube), mesoporous TiO2The nanosphere structure has larger specific surface area, and the characteristic can effectively ensure that the mesoporous layer and the light absorbing material layer are in close contact to form larger electron selective contact area, thereby effectively improving the short-circuit current density (J) of the PSCsc) And open circuit voltage (V)oc). In addition, there is a report of TiO2The porous membrane formed of nanospheres facilitates the growth of large grains of perovskite thereon.
Reported in literature TiO2The preparation method of the particles mainly comprises the following steps: (1) TiCl (titanium dioxide)4Gas phase oxidation by TiCl4And O2Reacting at 900-1400 ℃ to generate nano TiO2The particles are captured to realize gas-solid separation; (2) the atomization hydrolysis method adopts titanium alkoxide as a precursor, atomizes the titanium alkoxide into small drops by means of ultrasonic static electricity and the like, and hydrolyzes the small drops for a short time to obtain titanium dioxide powder; (3) the thermal plasma method, a large amount of high-activity ions existing in the high-temperature plasma flow consisting of hydrogen or nitrogen are attached to the surface of a precursor body to undergo molten gas, finally, nucleation growth is carried out, and then rapid cooling is carried out to obtain titanium dioxide particles; (4) adding titanate into alcohol, continuously stirring to form sol, then carrying out hydrolysis reaction with water, and drying, calcining and grinding to obtain titanium dioxide powder through the process of losing alcohol; (5) a hydrothermal synthesis method, wherein the titanium source is hydrolyzed in an autoclave by controlling the pressure and the temperature of the solution; (6) liquid phase deposition method, adding alkali substance into titanium salt solution to form Ti (OH)4And filtering, washing and drying, and finally calcining to obtain titanium dioxide with different crystal forms.
Different synthesis methods have advantages and disadvantages, wherein the thermal plasma method has the advantages of high purity, small particle size, and difficulty in realizing large-scale production; for the sol-gel method, the required temperature is low, the process is simple, the particles are small, the dispersity is good, but the cost is high, and the limitation of instruments and equipment is large.
For PSC components, mesoporous structures are the classical structures of PSCs. The structure of the battery can be divided into: the working electrode (FTO,tin oxide doped with fluorine), an Electron Blocking Layer (EBL), an electron transport layer, an active layer, a hole transport layer (HTM) and a metal counter electrode. The mesoporous structure is derived from DSSCs, which have the main advantage of transporting photogenerated electrons by its very nature via a semiconductor oxide nanostructural framework. It is reported that the internationally stable PSC is mostly based on a nano mesoporous structure. TiO is commonly used as a PSC mesoporous layer material at present2、ZnO、NiOxAnd ZrO2Among them, the cheap and efficient TiO2 material is used. Research shows that the mesoporous TiO2The thin film structure has a larger specific surface area, and tests show that the short circuit current density (Jsc) and the open circuit voltage (Voc) of the PSC can be effectively improved. Reported to be TiO2The porous structure formed by the nanospheres facilitates the growth of large perovskite grains on the nanospheres.
The light absorption layer in PSC is usually made of a three-dimensional perovskite material with the structure of ABX3. Typically, A is a methylamine Cation (CH)3NH3(+) or formamidine cation (HC (NH)2)2(+) and B is lead (Pb)2(+) or tin ion (Sn)2And (+) and X is halogen ion. The photoelectric property of PSC is mainly determined by the morphology and purity of perovskite thin film, so the quality of film forming technology is very decisive for obtaining high-efficiency PSC. The solution preparation technology is divided into a one-step spin coating method and a two-step sequential deposition method. The one-step spin coating method is to coat lead halide (PbX)2Dissolving X ═ I, Br, Cl) and iodomethylamine (MAI) in N, N-Dimethylformamide (DMF) to obtain a precursor solution, spin-coating the precursor solution on a substrate by proper spin-coating process parameters, and forming a film after high-temperature annealing. The method is simple in operation method, but the film forming conditions are extremely strict, and the concentration of the solution, the environment of the glove box and the annealing time and temperature on the hot bench directly influence the morphology of the film. A two-step sequential deposition process consisting of
The subject group is proposed. The method firstly grows PbI on a substrate2Seed layer, and then putting FTO into MAI solution, MAI ion can be rapidly fused into PbI2Middle shapeMAPbI in three-dimension3. Also, the two-step process has its own drawbacks, as MAI ions are difficult to access PbI when the thickness of the synthesized perovskite exceeds 200nm2In this way, pure MAPbI cannot be obtained3This also causes the performance of the battery to be greatly degraded.
Disclosure of Invention
In order to overcome the defects of the method, the invention relates to TiO with high specific surface area2A method for preparing microspheres. The titanium dioxide microspheres with special morphology prepared by the method have high specific surface area and can greatly enhance the absorption of visible light and effectively improve the short-circuit current density (J) of PSC (Pre-stressed ceramic) if being used as a mesoporous layer of a perovskite solar cellsc) And open circuit voltage (V)oc). The operation steps are simple, the experiment cost is low, a green reagent is used in the preparation process, almost no by-product is generated, and the environmental pollution is less; in addition, the TiO so produced2The microspheres have uniform size distribution and good crystallinity, can be effectively applied to mesoporous perovskite solar cells, and have good application prospect. The specific technical scheme is as follows:
TiO2the preparation method of the cookie-like microspheres comprises the following steps:
(1) ultrasonically cleaning an inner container of a polytetrafluoroethylene reaction container by adopting four liquids of a cleaning agent, deionized water, acetone and absolute ethyl alcohol in sequence, treating each liquid for 1 time and 20 minutes each time, and drying after cleaning;
(2) adding a plurality of organic solvents serving as mixed solvents into a reaction container, and slowly dropwise adding tetrabutyl titanate, wherein the volume ratio of the mixed solvents to the tetrabutyl titanate is 50 ml: 2ml, and simultaneously fully and uniformly stirring;
the mixed solvent comprises at least two of acetonitrile, isopropanol, acetylacetone, water, methanol, benzaldehyde, diethylene glycol and ethanol.
Preferably, the mixed solvent in the step (2) comprises a solvent mixture of 3: 1:1 acetonitrile, isopropanol, acetylacetone.
(3) Slowly dropwise adding tetrabutyl ammonium hydroxide aqueous solution serving as a control agent into the solution obtained in the step (2), and uniformly stirring; the volume ratio of the tetrabutylammonium hydroxide aqueous solution to the tetrabutyl titanate is 0.1ml-0.5 ml: 2 ml;
(4) sealing the reaction vessel, heating to 160-200 ℃, and reacting for 12-20 h;
(5) naturally cooling the product obtained in the step (4), carrying out centrifugal separation at the speed of 5000rmp/min for 5 minutes, taking the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for four times in sequence, and drying the precipitate for later use;
(6) annealing the precipitate washed in the step (5) in a muffle furnace to obtain the TiO with monodispersity2Cookie micro-spheres.
Preferably, the medium annealing condition in the step (6) is that the temperature is increased to 140 ℃ from room temperature within 10min, and the temperature is kept for 2 min; heating again to 350 deg.C within 10min, maintaining the temperature for 5min, heating to 510 deg.C within 15min, maintaining the temperature for 30min, naturally cooling to 120 deg.C, maintaining the temperature, taking out, and naturally cooling to room temperature for use.
The invention also provides a perovskite solar cell comprising TiO2Mesoporous layer of said TiO2The mesoporous layer is prepared by the above-mentioned preparation method2Cookie-like microspheres.
Specifically, the fluorine-doped tin oxide transparent conductive glass is used as a substrate, the thickness is 380nm, and the TiO is arranged on an FTO substrate2A mesoporous layer; TiO22The mesoporous layer comprises an electron transport layer, and the FTO substrate further comprises a perovskite active layer and a hole transport layer; the TiO is2The cookie-like microspheres are mixed with P25 titanium dioxide nanoparticles to form an electron transport layer with the thickness of 500nm and MAPbI3The perovskite active layer is 500nm thick, the Spiro-OMeTAD is a hole transport layer, the thickness is 200nm, a gold electrode is arranged on the hole transport layer, and the thickness of gold is 60 nm.
The preparation method of the perovskite solar cell comprises the following steps:
(1) forming TiO on FTO substrate2A mesoporous layer film;
(a) cleaning a substrate, selecting FTO, sequentially carrying out ultrasonic treatment on the FTO by using a cleaning agent, deionized water, acetone and isopropanol, treating each solvent for 1 time for 20min each time, and then carrying out ultraviolet ozone treatment for 15 min;
(b) preparation of TiO2A dense layer: mixing the titanium source solution and absolute ethyl alcohol in a volume ratio of 1:10, and stirring for 5min until the solution is transparent; placing the FTO treated in the step (a) on a stage of a spin coater, covering the surface of the FTO with 150 mu l of mixed solution by using a dropper, and carrying out spin coating by using the spin coater for 3500rmp/min for 20s to form a uniform and transparent film; after the spin coater is stopped, immediately placing the wet film on a heating table at 100 ℃ for baking for 15min, and then placing the film in a box-type annealing furnace for annealing at 500 ℃ by gradient heating;
(c) spin coating TiO2A mesoporous layer: preparation of TiO with high specific surface area2A slurry of titanium dioxide in cookie-like microspheres; bl-TiO2The electrode is reserved on the FTO substrate by using a polyimide adhesive tape, and the volume ratio of the slurry to ethanol is 1: 5, diluting; transferring 100 mul of diluted slurry by using a liquid transfer gun, coating the FTO substrate with the slurry, and processing the FTO substrate for 20s at 3500rmp/min in a spin coating manner; baking the film at 100 ℃ on a hot table; removing the adhesive tape, and placing the substrate in a box furnace to perform gradient heating to 500 ℃ for annealing;
(2) preparation of MAPbI3Perovskite thin film
1.1064g of PbI2And 0.3816g of MAI in 1.5112g of DMF and 0.44g of DMSO, stirring the mixture at 70 ℃ for 30min and filtering the mixture; in the prepared TiO2Preparing a perovskite film on the mesoporous layer by spin coating at a rotating speed of 3000rmp/min, and simultaneously using chlorobenzene as an anti-solvent; placing in air until it turns brown, heating the sample on a heating table at 100 deg.C for 10 min;
(3) preparation of hole transport layer
72.3mg of Spiro-OMeTAD was dissolved in 1.1g of chlorobenzene, 28.8ul of TBP was added thereto, and stirred for 15 min; respectively dissolving 52mg of lithium salt and 30mg of cobalt salt in 76mg of acetonitrile, respectively adding 17.5ul of lithium salt solution and 29ul of cobalt salt solution, stirring for 30min, filtering, and spin-coating on the prepared perovskite film sample at the rotating speed of 4000rmp/min for 20s to prepare a hole transport layer;
(4) preparation of counter electrode
Subsequently, a gold electrode was evaporated on the hole transport layer to obtainTiO2A mesoporous layer perovskite solar cell.
The invention has the technical effects that:
(1) one-step hydrothermal method for synthesizing TiO with high specific surface area2The cookie microspheres have the advantages of simple preparation process operation, safety, reliability, low cost and little environmental pollution.
(2) TiO obtained by the invention2Has good crystallinity, permeability, conductivity and high light scattering property. The invention adopts fluorine-doped tin oxide transparent conductive glass (FTO) as a substrate, and EBL is directly deposited on the FTO substrate to form a compact layer. Then the prepared TiO is mixed2The cookie balls and the P25 are prepared into slurry to be spin-coated on the compact layer to serve as an electron transport layer, and the high-efficiency planar perovskite solar cell is assembled. Prepared TiO2The film shows excellent conductivity and absorption effect on visible light, and meanwhile, the film is applied to the perovskite solar cell to obtain excellent photoelectric conversion efficiency, so that the possibility is provided for preparing the perovskite solar cell with large area, low cost and high efficiency. Compared with the traditional P25 mesoporous perovskite solar cell, the TiO prepared by the method provided by the invention2The short-circuit current of the microsphere mesoporous perovskite solar cell is remarkably improved, the open-circuit voltage is also improved to a small extent, and the photoelectric conversion efficiency of a small-area device can be more than 16%.
Drawings
FIG. 1 is a schematic structural view of a perovskite solar cell of the present invention;
FIG. 2 shows TiO of the present invention2SEM image of the surface appearance of the mesoporous layer;
FIG. 3 shows TiO of examples2XRD pattern of powder compared to P25;
FIG. 4(a) shows TiO of an example2A transmission spectrum of the mesoporous layer;
FIG. 4(b) shows TiO of examples2Absorption spectra of perovskites on the mesoporous layer;
FIG. 4(c) shows TiO of examples2A J-V curve of the mesoporous layer perovskite cell;
FIG. 4(d) shows different TiO examples2A mesoporous layer perovskite cell IPCE curve.
Detailed Description
The invention will be better understood by the following examples.
TiO2Preparation of cookie-like microspheres
The method comprises the following steps:
carrying out ultrasonic cleaning treatment on the inner container of the polytetrafluoroethylene reaction container sequentially by using a cleaning agent, deionized water, acetone and absolute ethyl alcohol, wherein each time is 20min, and drying each liquid after each liquid is treated for 1 time;
step (2) using a volume ratio of 3: 1:1, taking acetonitrile, isopropanol and acetylacetone as solvents, sequentially adding the solvents into a reaction container liner, slowly dripping tetrabutyl titanate into the reaction container liner, wherein the volume ratio of the mixed solvent to the tetrabutyl titanate is 50 ml: 2ml of the mixture is fully and evenly stirred;
step (3) slowly dripping 0.3ml of tetrabutyl ammonium hydroxide aqueous solution serving as a control agent into the mixed solution obtained in the step (2), and uniformly stirring;
step (4), canning and sealing the inner container of the polytetrafluoroethylene reaction container, putting the container into an oven, and reacting for 12-20 h at 160-200 ℃;
step (5) cooling the product obtained in the step (4), centrifuging for 5min at 5000r/min, taking the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for four times in sequence, and drying for later use;
step (6) annealing the product obtained in the step (5) in a muffle furnace to obtain monodisperse TiO2And (3) microspheres. The annealing condition is that the temperature is increased to 140 ℃ from room temperature within 10min, and the temperature is kept for 2 min; heating again to 350 deg.C within 10min, maintaining the temperature for 5min, heating to 510 deg.C within 15min, maintaining the temperature for 30min, naturally cooling to 120 deg.C, and maintaining the temperature.
Preparation of TiO2Mesoporous perovskite solar cell
As shown in FIG. 1, TiO2The mesoporous perovskite solar cell has the structure of FTO substrate/TiO2Hole blocking layer/TiO2Electron transport layer/MAPbI3Perovskite active layer/Spiro-OMeTAD hole transport layer/Au electrode layer. Wherein the transparent conductive glass (FTO) substrate has a thickness of 380 nm;
TiO on FTO electrode layer2The thickness of the barrier layer is 100 nm;
in TiO2TiO on barrier layer2The thickness of the mesoporous layer is 500 nm;
in TiO2MAPbI on electron transport layer3The thickness of the perovskite active layer is 500 nm;
in MAPbI3The thickness of the Spiro-OMeTAD hole transport layer on the perovskite active layer is 200 nm;
the thickness of the gold electrode on the Spiro-OMeTAD hole transport layer was 60nm, wherein the area of the small-area perovskite solar cell was 0.06cm2The area of the large-area perovskite solar cell is 1cm2。
The planar perovskite solar cell prepared by the invention has the structure of FTO substrate/TiO2Barrier/TiO2Electron transport layer/MAPbI3Perovskite active layer/spiral-OMeTAD hole transport layer/Au electrode with electrode area of 0.06cm2。
The method comprises the following steps:
1. forming large area TiO on FTO substrate2A mesoporous layer.
(a) Cleaning a substrate
Selecting FTO with 1.1mm and 2cm × 2cm length and width, subjecting to ultrasonic treatment with cleaning agent, deionized water, acetone and isopropanol for 30min each time, treating each solvent for 1 time, and treating in ultraviolet ozone chamber for 15 min;
(b) preparation of TiO2A dense layer: mixing the titanium source solution and absolute ethyl alcohol in a volume ratio of 1:10, and stirring for 5min until the solution is transparent. The FTO which is pretreated is placed on a stage of a spin coater, 150 mu l of mixed solution is used for covering the surface of the FTO by a dropper, and a uniform and transparent thin film is formed after the FTO is spin-coated by the spin coater (3500rmp/min, 20 s). And after the spin coater is stopped, immediately placing the wet film on a heating table at 100 ℃ for heating for 15min, removing the preset adhesive tape, and placing the sample in a box type annealing furnace for annealing at 500 ℃ in a gradient manner.
(C) Spin coating TiO2A mesoporous layer: preparation of TiO2Cookie microsphere slurry. bl-TiO2/FTReserving electrodes on an O substrate by using a polyimide adhesive tape, and mixing the slurry and ethanol according to the ratio of 1: 5 volume ratio for dilution. Using a pipette, 100. mu.l of the diluted slurry was applied to an FTO substrate, and the FTO substrate was spread and spin-coated (3500rmp/min, 20 seconds) uniformly, and then heated on a 100 ℃ hot plate. Removing the adhesive tape, placing the sample in a box type furnace, and annealing at 500 ℃ in a gradient manner.
2. Preparation of MAPbI3Perovskite thin film
1.1064g of PbI2And 0.3816g of MAI were dissolved in 1.5112g of DMF and 0.44g of DMSO (volume ratio: 4:1), stirred at 70 ℃ for 30min and filtered. In the prepared TiO2Preparing a perovskite thin film on the mesoporous layer by spin coating at a rotating speed of 3000rmp/min for 40s, and simultaneously using chlorobenzene as an anti-solvent; after being placed in the air until the color of the sample becomes brown, the sample is placed on a hot stage at 100 ℃ and heated for 10min, and a perovskite layer with the thickness of 400 nm-500 nm is prepared.
3. Preparation of hole transport layer
72.3mg of Spiro-OMeTAD was dissolved in 1.1g of chlorobenzene, 28.8. mu.l of TBP was added thereto, and stirred for 15 min; 52mg of lithium salt and 30mg of cobalt salt were dissolved in 76mg of acetonitrile, and 17.5. mu.l of lithium salt solution and 29. mu.l of cobalt salt solution were added thereto, followed by stirring for 30min, filtration, and spin-coating on the sample at 4000rmp/min for 20s to prepare a 200nm hole transport layer.
4. At 10-4Carrying out thermal evaporation on a 60nm Au electrode under the vacuum of Pa to obtain TiO2And (3) assembling the mesoporous perovskite solar cell.
Thin film characterization and device testing
The prepared TiO is2The film is analyzed and characterized by using a transmission spectrum, X-ray diffraction and an electron scanning microscope. As shown in fig. 2, 3, 4a, 4 b.
The instrument used for X-ray diffraction (XRD) analysis was D8 Advance, and the measurement conditions were 0.001 °/step. The scanning electron microscope was carried out at a voltage of 15 KV.
And carrying out photoelectric performance test on the assembled planar perovskite solar cell. The measurement of the photocurrent-photovoltage (J-V) curves shown in FIGS. 4c and 4d is under a computer controlGishy 236 source measurement unit. Device characterization was performed in an ambient atmosphere under illumination AM 1.5G at 100mW cm-2A xenon lamp-based solar simulator (Newport co., LTD.). The intensity of each wavelength of light is calibrated to a standard single crystal silicon photovoltaic cell.
Claims (5)
1.TiO2The preparation method of the cookie-like microspheres is characterized by comprising the following steps:
(1) ultrasonically cleaning an inner container of a polytetrafluoroethylene reaction container by adopting four liquids of a cleaning agent, deionized water, acetone and absolute ethyl alcohol in sequence, treating each liquid for 1 time and 20 minutes each time, and drying after cleaning;
(2) a plurality of organic solvents are used as mixed solvents, and the mixed solvents comprise 3: 1:1, adding acetonitrile, isopropanol and acetylacetone into a reaction container, and slowly dropwise adding tetrabutyl titanate, wherein the volume ratio of the mixed solvent to the tetrabutyl titanate is 50 ml: 2ml, and simultaneously fully and uniformly stirring;
(3) slowly dropwise adding tetrabutyl ammonium hydroxide aqueous solution serving as a control agent into the solution obtained in the step (2), and uniformly stirring; the volume ratio of the tetrabutylammonium hydroxide aqueous solution to the tetrabutyl titanate is 0.1ml-0.5 ml: 2 ml;
(4) sealing the reaction vessel, heating to 160-200 ℃, and reacting for 12-20 h;
(5) naturally cooling the product obtained in the step (4), carrying out centrifugal separation at the speed of 5000rmp/min for 5 minutes, taking the precipitate, washing the precipitate with deionized water and absolute ethyl alcohol for four times in sequence, and drying the precipitate for later use;
(6) annealing the precipitate washed in the step (5) in a muffle furnace to obtain the TiO with monodispersity2Cookie micro-spheres.
2. The TiO of claim 12The preparation method of the cookie-like microspheres is characterized in that the annealing condition in the step (6) is that the temperature is raised to 140 ℃ from room temperature within 10min, and the temperature is kept for 2 min; heating again to 350 deg.C within 10min, maintaining the temperature for 5min, heating again to 510 deg.C within 15min, and maintaining the temperatureNaturally cooling to 120 deg.C after 30min, taking out, and naturally cooling to room temperature for use.
3. Perovskite solar cell, characterized in that it comprises TiO2Mesoporous layer of said TiO2TiO produced by the production method according to claim 1 or 2, as a mesoporous layer2Cookie-like microspheres.
4. The perovskite solar cell according to claim 3, further comprising a fluorine-doped tin oxide transparent conductive glass as a substrate having a thickness of 380nm, and said TiO on the FTO substrate2A mesoporous layer; TiO22The mesoporous layer comprises an electron transport layer, and the FTO substrate further comprises a perovskite active layer and a hole transport layer; the TiO is2The cookie-like microspheres are mixed with P25 titanium dioxide nanoparticles to form an electron transport layer with the thickness of 500nm and MAPbI3The perovskite active layer is 500nm thick, the Spiro-OMeTAD is a hole transport layer, the thickness is 200nm, a gold electrode is arranged on the hole transport layer, and the thickness of gold is 60 nm.
5. The method of fabricating a perovskite solar cell according to claim 4, comprising the steps of:
(1) forming TiO on FTO substrate2A mesoporous layer film;
(a) cleaning a substrate, selecting FTO, sequentially carrying out ultrasonic treatment on the FTO by using a cleaning agent, deionized water, acetone and isopropanol, treating each solvent for 1 time for 20min each time, and then carrying out ultraviolet ozone treatment for 15 min;
(b) preparation of TiO2A dense layer: mixing the titanium source solution and absolute ethyl alcohol in a volume ratio of 1:10, and stirring for 5min until the solution is transparent; placing the FTO treated in the step (a) on a stage of a spin coater, covering 150 mu l of mixed solution on the surface of the FTO by using a dropper, and carrying out spin coating on the FTO by using the spin coater for 3500rmp/min for 20s to form a uniform and transparent film; after the spin coater is stopped, immediately placing the wet film on a heating table at 100 ℃ for baking for 15min, and then placing the film in a box-type annealing furnace for annealing at 500 ℃ by gradient heating;
(c) spin coating TiO2A mesoporous layer: preparation of TiO with high specific surface area2A slurry of titanium dioxide in cookie-like microspheres; bl-TiO2The electrode is reserved on the FTO substrate by using a polyimide adhesive tape, and the volume ratio of the slurry to ethanol is 1: 5, diluting; transferring 100 mul of diluted slurry by using a liquid transfer gun, coating the FTO substrate with the slurry, and processing the FTO substrate for 20s at 3500rmp/min in a spin coating manner; baking the film at 100 ℃ on a hot table; removing the adhesive tape, and placing the substrate in a box furnace to perform gradient heating to 500 ℃ for annealing;
(2) preparation of MAPbI3Perovskite thin film
1.1064g of PbI2And 0.3816g of MAI in 1.5112g of DMF and 0.44g of DMSO, stirring the mixture at 70 ℃ for 30min and filtering the mixture; in the prepared TiO2Preparing a perovskite film on the mesoporous layer by spin coating at a rotating speed of 3000rmp/min, and simultaneously using chlorobenzene as an anti-solvent; placing in air until it turns brown, heating the sample on a heating table at 100 deg.C for 10 min;
(3) preparation of hole transport layer
72.3mg of Spiro-OMeTAD was dissolved in 1.1g of chlorobenzene, 28.8ul of TBP was added thereto, and stirred for 15 min; respectively dissolving 52mg of lithium salt and 30mg of cobalt salt in 76mg of acetonitrile, respectively adding 17.5ul of lithium salt solution and 29ul of cobalt salt solution, stirring for 30min, filtering, and spin-coating on the prepared perovskite film sample at the rotating speed of 4000rmp/min for 20s to prepare a hole transport layer;
(4) preparation of counter electrode
Subsequently, a gold electrode was evaporated on the hole transport layer to obtain TiO2A mesoporous layer perovskite solar cell.
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| CN201810312071.3A CN108511607B (en) | 2018-04-09 | 2018-04-09 | TiO2Preparation method of cookie-shaped microspheres and method for preparing perovskite solar cell |
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