CN108511607A - TiO2The preparation method of cookies shape microballoon and the method for preparing perovskite solar cell - Google Patents
TiO2The preparation method of cookies shape microballoon and the method for preparing perovskite solar cell Download PDFInfo
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Abstract
The invention discloses TiO2The preparation method of cookies shape microballoon and the method for preparing perovskite solar cell, TiO2Microballoon is dropwise addition positive four butyl ester of metatitanic acid after acetonitrile, isopropanol, acetylacetone,2,4-pentanedione mixing, and tetrabutylammonium hydroxide precipitates centrifuge washing and drying, then obtain TiO through high annealing as controlling agent in 160 DEG C of 200 DEG C of heating 12h 20h2Microsphere powder.Gained powder and P25 are prepared by mixing into slurry, are spin-coated on the mesoporous layer on the FTO for having been coated with compacted zone and as perovskite solar cell.In TiO2Priority spin coating MAPbI on film3With Spiro OMeTAD, layer of Au is finally deposited.The TiO of the high-specific surface area2Microballoon uses one step hydro thermal method, and preparation process is simple, of low cost；Prepared TiO2Film shows excellent electric conductivity and the sink effect to visible light, while being applied and obtaining excellent electricity conversion in perovskite solar cell, and possibility is provided to prepare large area, low cost, efficient perovskite solar cell.
Description
Technical field
The invention belongs to area of solar cell, specially TiO2The preparation method of cookies shape microballoon and prepare perovskite
The method of solar cell.
Background technology
Nano material as perovskite solar cell (PSC) mesoporous layer need to meet following feature：One, translucency
It is good, more incident lights are can pass through, light loss is reduced；Two, conduction level position can match with light absorbent energy level, subtract
Small exciton energy loss；Three, excellent electron transport performance effectively inhibits the compound of electronics and hole；Four, big porosity and
Specific surface area is conducive to enhance reflection of the incident light in inside battery, improves device light capture ability.It is commonly used for PSC at this stage
Mesoporous layer material has TiO2, ZnO, NiOx and ZrO2, wherein application it is most common be Cheap highly effective TiO2Particle.Compare it
Its several TiO2Array structure (nano wire, nanometer rods and nanotube), mesoporous TiO2Nanometer spherical structure has the specific surface of bigger
Product, this feature can effectively make mesoporous layer and extinction material layer be in close contact the electronic selection contact area to form bigger, effectively
Improve the short-circuit current density (J of PSCsc) and open-circuit voltage (Voc).In addition, it has been reported that TiO2Nanometer spherical at perforated membrane have
Help the growth of perovskite big crystal grain thereon.
The TiO of document report2Preparation method of granules mainly has：(1)TiCl4Vapour phase oxidation process passes through TiCl4And O2900
It is reacted at DEG C -1400 DEG C, generates nano-TiO2Particle, then captured, realize gas solid separation；(2) it is atomized Hydrolyze method, using titanium
Alkoxide is presoma, so that it is atomized into droplet using means such as ultrasonic electrostatics, hydrolyzes to obtain titania powder through the short time；
(3) heat plasma method, the ion of a large amount of high activities is attached in the presence of the high-temperature plasma stream being made of hydrogen or nitrogen
Presoma surface experience melting gas, last nucleating growth, then rapid cooling, obtain titanium dioxide granule；(4) sol-gal process,
Titanate is added in alcohol and is stirred continuously to form colloidal sol, hydrolysis then occurs with water, loses alcohol process through dehydration, then dried
Dry calcining and grinding obtains titania powder；(5) hydrothermal synthesis method, by the pressure and temperature of control solution by titanium source in high pressure
Hydrolysis in kettle；(6) alkaloids are added in titanium salt solution and form Ti (OH) by liquid phase deposition4, washing and drying is refiltered,
Different crystal forms titanium dioxide is obtained finally by calcining.
Different synthetic methods respectively have advantage and disadvantage, the advantage of wherein heat plasma method to be that the high grain size of work purity is small, but very
Hardly possible realizes large-scale production；For sol-gel method, the low particle simple for process of required temperature is small and good dispersion, but
It is that cost is higher, is limited by instrument and equipment larger.
For PSC components, meso-hole structure is the classical architecture of PSC.The structure of battery can be divided into：Working electrode
(FTO, tin oxide fluorine doped), electronic barrier layer (EBL), electron transfer layer, active layer, hole transmission layer (HTM) and metal are to electricity
This six most of composition of pole.Meso-hole structure is derived from DSSC, main to be that its essence is by conductor oxidate a little
Nanometer framework frame transmits light induced electron.At present it is reported that the stable PSC overwhelming majority is all based on mesoporous nano knot in the world
Structure.Be commonly used for the mesoporous layer materials of PSC at this stage has TiO2、ZnO、NiOxAnd ZrO2, wherein using more generally cheap and
And efficient TiO2 materials.Studies have shown that mesoporous TiO2Membrane structure has the specific surface area of bigger, shows can have by test
Effect improves the short-circuit current density (Jsc) and open-circuit voltage (Voc) of PSC.It has been reported that TiO2Nanometer spherical at porous structure
Help the growth of perovskite big crystal grain thereon.
Light-absorption layer in PSC is frequently with a kind of three-dimensional perovskite material, structure ABX3.Under normal circumstances, A is methylamine
Cation (CH3NH3+) or carbonamidine cation (HC (NH2)2+), B is lead (Pb2+) or tin ion (Sn2+), X is halide ion.
The photoelectric properties of PSC are mainly determined by the pattern of perovskite thin film and purity, therefore the quality of film technique is efficient to obtaining
PSC has prodigious decisive role.Solution technology of preparing is divided into a step spin coating cladding process and two step order sedimentations.One step spin coating
Cladding process is by lead halide (PbX2, X=I, Br, Cl) and it is obtained with molten (DMF) to N,N-dimethylformamide of iodine methylamine (MAI)
Precursor liquid, then precursor liquid is spin-coated in substrate by suitable spin coating proceeding parameter, it forms a film after high annealing.This method behaviour
It is extremely simple to make method, but extremely stringent to membrance casting condition, the concentration of solution, the environment of glove box and when annealing in thermal station
Between and temperature can all directly affect the pattern of film.Two step order sedimentations byWhat seminar proposed.The method is first
PbI is grown on substrate2FTO is put into MAI solution by seed layer later, and MAI ions can incorporate rapidly PbI2It is middle to form three
The MAPbI of dimension3.Same two-step method also has some disadvantages of itself, when the thickness of the perovskite of synthesis is more than 200nm, MAI from
Son is difficult to enter into PbI2In, lead to not obtain pure MAPbI3, this is but also the performance of battery is greatly reduced.
Invention content
To overcome the shortcomings of the above method, the present invention relates to a kind of TiO of high-specific surface area2The preparation method of microballoon.It should
Method prepares a kind of titanium dioxide microballoon sphere with special appearance, if as the mesoporous layer of perovskite solar cell,
High-specific surface area can greatly enhance the absorption to visible light, effectively improve the short-circuit current density (J of PSCsc) and open-circuit voltage
(Voc).Its operating procedure is simple, and experimental cost is cheap, and preparation process uses green reagent, almost without byproduct, environmental pollution
It is few；In addition, prepared TiO2Micron ball size distribution is uniform, and crystallinity is good, can be efficiently applied to mesoporous perovskite too
Positive energy battery, has a good application prospect.Specific technical solution is：
TiO2The preparation method of cookies shape microballoon, includes the following steps：
(1) liner of polytetrafluoroethylene (PTFE) reaction vessel is successively using cleaning agent, deionized water, acetone, four kinds of absolute ethyl alcohol
Liquid ultrasonic cleans, each liquid handling 1 time, 20 minutes every time, dry drying after cleaning；
(2) a variety of organic solvents are added in reaction vessel, then positive four butyl ester of metatitanic acid is slowly added dropwise as mixed solvent, mix
The volume ratio of bonding solvent and positive four butyl ester of metatitanic acid is 50ml：2ml is stirred simultaneously；
Mixed solvent includes at least two in acetonitrile, isopropanol, acetylacetone,2,4-pentanedione, water, methanol, benzaldehyde, diethylene glycol (DEG), ethyl alcohol
Kind.
Preferably, it is 3 that the mixed solvent in the step (2), which includes volume ratio,：1：1 acetonitrile, isopropanol, levulinic
Ketone.
(3) tetrabutylammonium hydroxide aqueous solution is slowly added dropwise in acquired solution into step (2) as controlling agent, stirring is equal
It is even；The volume ratio of tetrabutylammonium hydroxide aqueous solution and positive four butyl ester of metatitanic acid is 0.1ml-0.5ml：2ml；
(4) reaction vessel is sealed, heating temperature is increased to 160 DEG C -200 DEG C, reacts 12h-20h；
(5) it by the product natural cooling obtained by step (4), is centrifuged, rate 5000rmp/min, centrifuges 5 points
Clock, taking precipitate and with being dried for standby after deionized water and absolute ethyl alcohol successively washing four times；
(6) being deposited in Muffle furnace after washing in step (5) is made annealing treatment, obtains that there is monodispersity
TiO2Cookies microballoon.
Preferably, the middle annealing conditions in the step (6) are to rise to 140 DEG C in 10min by room temperature, keep the temperature 2min；
It heats up again, 350 DEG C is risen in 10min, after keeping the temperature 5min, be warming up to 510 DEG C again in 15min, dropped naturally after keeping the temperature 30min
It to 120 DEG C, and keeps the temperature, it is spare to take out cooled to room temperature.
The present invention also provides a kind of perovskite solar cells, including TiO2Mesoporous layer, the TiO2Mesoporous layer is by right
It is required that 1 to 4 any one of them TiO2Cookies shape microballoon is made.
Specifically, further including fluorine doped tin oxide transparent conducting glass as substrate, in thickness 380nm, FTO substrate
The TiO stated2Mesoporous layer；TiO2Mesoporous layer includes electron transfer layer, perovskite active layer, hole transmission layer successively；The TiO2
Cookies shape microballoon is mixed with P25 titania nanoparticles is used as electron transfer layer, thickness 500nm, MAPbI3As calcium
Titanium ore active layer, thickness 500nm, Spiro-OMeTAD are as hole transmission layer, thickness 200nm, have on hole transmission layer
Gold electrode, golden thickness are 60nm.
The preparation method of the perovskite solar cell, includes the following steps：
(1) in FTO substrates, TiO is formed2Mesoporous layer film；
(a) substrate is cleaned, FTO is chosen and is successively ultrasonically treated by cleaning agent, deionized water, acetone, isopropanol, every time
20min, each solvent are handled 1 time, then handle 15min through UV ozone；
(b) TiO is prepared2Compacted zone：Titanium source solution and absolute ethyl alcohol are with 1:10 volume ratio mixing, stirring 5min to solution
It is transparent；The FTO handled well in (a) is placed on spin coating instrument objective table, 150 μ l mixed solutions are covered into full FTO tables with dropper
Face, spin-coated instrument spin coating form uniform and transparent film after handling 20s with 3500rmp/min；After spin coating instrument stops, it will moistening
Film be immediately placed on and toast 15min on 100 DEG C of warm table after, be placed in box-annealing furnace gradient increased temperature and anneal to 500 DEG C；
(c) spin coating TiO2Mesoporous layer：Prepare the TiO of high-specific surface area2The titania slurry of cookies shape microballoon；bl-
TiO2/ FTO substrates reserve electrode with Kapton Tape, slurry and ethyl alcohol by volume 1：5 are diluted；It is pipetted with liquid-transfering gun
FTO substrates are covered with rear spin coating and handle 20s with 3500rmp/min by the slurry that 100 μ l have diluted；Above-mentioned film is placed into thermal station
100 DEG C of bakings；Adhesive tape is removed, and substrate is placed in gradient increased temperature in batch-type furnace and is annealed to 500 DEG C；
(2) MAPbI is prepared3Perovskite thin film
By the PbI of 1.1064g2It is dissolved in the MAI of 0.3816g in the DMSO mixed liquors of the DMF and 0.44g of 1.5112g, 70
It is filtered after DEG C heating stirring 30min；In the TiO prepared2Perovskite is prepared with the rotating speed spin coating of 3000rmp/min on mesoporous layer
Film, while using chlorobenzene as anti-solvent；After placing in air until becoming dark brown, sample is placed on to 100 DEG C of heating
10min is heated on platform；
(3) hole transmission layer is prepared
The Spiro-OMeTAD of 72.3mg is dissolved in the chlorobenzene of 1.1g, the TBP of 28.8ul, stirring are added thereto
15min；The cobalt salt of the lithium salts and 30mg that take 52mg is dissolved in the acetonitrile of 76mg respectively, takes the lithium salt solution of 17.5ul respectively later
Be added thereto with the cobalt salt solution of 29ul, stir 30min after filter, on the perovskite thin film sample prepared with
The rotating speed spin coating 20s of 4000rmp/min is to prepare hole transmission layer；
(4) it prepares to electrode
Then, gold electrode is deposited on the hole transport layer, obtains TiO2Mesoporous layer perovskite solar cell.
The technique effect that the present invention has has：
(1) one step hydro thermal method synthesizes a kind of TiO of high-specific surface area2Cookies microballoon, preparation process is easy to operate, safely may be used
It leans on, it is of low cost, while environmental pollution is few.
(2) TiO that the present invention obtains2With good crystallinity, anti-reflection property, electric conductivity, and with high light scattering.
The present invention uses fluorine doped tin oxide transparent conducting glass (FTO) for substrate, and the direct accumulation of EBL is formed fine and close on FTO substrates
Layer.Then by the TiO of preparation2Cookies ball is made into slurry for rotary coating with P25 and is used as electron transfer layer, assembling efficient on compacted zone
The plane perovskite solar cell of rate.Prepared TiO2Film shows excellent electric conductivity and is imitated to the absorption of visible light
Answer, while being applied and obtaining excellent electricity conversion in perovskite solar cell, for prepare large area, it is low at
Originally, efficient perovskite solar cell provides possibility.Compared with the mesoporous perovskite solar cells of traditional P25, this hair
Bright obtained TiO2The short circuit current of the mesoporous perovskite solar cell of microballoon is obviously improved, and open-circuit voltage also has by a small margin
It is promoted, the photoelectric conversion efficiencies of small-area devices can 16% or more.
Description of the drawings
Fig. 1 is the structural schematic diagram of the perovskite solar cell of the present invention；
Fig. 2 is the TiO of the present invention2The surface topography SEM figures of mesoporous layer；
Fig. 3 is the TiO of embodiment2The XRD diagram of powder and P25 comparisons；
Fig. 4 (a) is the TiO of embodiment2The transmitted spectrum of mesoporous layer；
Fig. 4 (b) is the TiO of embodiment2The absorption spectrum of perovskite on mesoporous layer；
Fig. 4 (c) is the TiO of embodiment2Mesoporous layer perovskite battery J-V curves；
Fig. 4 (d) is the different TiO of embodiment2Mesoporous layer perovskite battery IPCE curves.
Specific implementation mode
Below by embodiment it will be better understood that the present invention.
TiO2The preparation of cookies shape microballoon
Include the following steps：
Step (1) polytetrafluoroethylene (PTFE) reaction vessel liner is successively by cleaning agent, deionized water, acetone, absolute ethyl alcohol point
Ultrasonic cleaning is not handled, each 20min, the dry drying after respectively handling 1 time of each liquid；
Step (2) volume ratio 3：1：1 acetonitrile, isopropanol, acetylacetone,2,4-pentanedione are sequentially added as solvent in reaction vessel
In courage, positive four butyl ester of metatitanic acid is slowly dropped in reaction vessel liner, the volume ratio of mixed solvent and positive four butyl ester of metatitanic acid is
50ml：2ml makes it stir；
0.3ml is slowly added dropwise into step (2) for step (3) tetrabutylammonium hydroxide aqueous solution in gained mixed solution is made
Agent in order to control, uniform stirring；
Step (4) seals polytetrafluoroethylene (PTFE) reaction vessel liner tinning, is put into baking oven, at 160 DEG C -200 DEG C, reaction
12h-20h；
Step (5) by obtained by step (4) product cool down, 5000r/min centrifuge 5min, take precipitation and with deionized water with
Absolute ethyl alcohol is dried for standby after successively washing four times；
Product in step (5) is put into Muffle furnace and makes annealing treatment by step (6), obtains monodispersed TiO2It is micro-
Ball.Annealing conditions are to rise to 140 DEG C in 10min by room temperature, keep the temperature 2min；It heats up again, 350 DEG C is risen in 10min, heat preservation
After 5min, it is warming up to 510 DEG C again in 15min, is down to 120 DEG C naturally after keeping the temperature 30min, and keep the temperature.
Prepare TiO2Mesoporous perovskite solar cell
As shown in Figure 1, TiO2The structure of mesoporous perovskite solar cell is FTO substrates/TiO2Hole blocking layer/TiO2
Electron transfer layer/MAPbI3Perovskite active layer/Spiro-OMeTAD hole transmission layers/Au electrode layers.Wherein electrically conducting transparent glass
The thickness of glass (FTO) substrate is 380nm；
The TiO on FTO electrode layers2The thickness on barrier layer is 100nm；
In TiO2TiO on barrier layer2The thickness of mesoporous layer is 500nm；
In TiO2MAPbI on electron transfer layer3The thickness of perovskite active layer is 500nm；
In MAPbI3The thickness of Spiro-OMeTAD hole transmission layers on perovskite active layer is 200nm；
The thickness of gold electrode on Spiro-OMeTAD hole transmission layers is 60nm, small areas perovskite solar energy
The area of battery is 0.06cm2, the area of large area perovskite solar cell is 1cm2。
The present invention prepares plane perovskite solar cell, and structure is FTO substrates/TiO2Barrier layer/TiO2Electron-transport
Layer/MAPbI3Perovskite active layer/Spiro-OMeTAD hole transmission layers/Au electrodes, electrode area 0.06cm2。
Step is：
1, in FTO substrates, large area TiO is formed2Mesoporous layer.
(a) substrate is cleaned
Choose 1.1mm, length and width be 2cm × 2cm square structure FTO, successively pass through cleaning agent, deionized water, acetone,
Isopropanol is ultrasonically treated, each 30min, each solvent respectively processing 1 time, then through the 15min processing of UV ozone room；
(b) TiO is prepared2Compacted zone：Titanium source solution and absolute ethyl alcohol are with 1:10 volume ratio mixing, stirring 5min to solution
It is transparent.The FTO handled well before is placed on the objective table of spin coating instrument, 150 μ l mixed solutions are covered into full FTO tables with dropper
Face, spin-coated instrument spin coating (3500rmp/min, 20s) form uniform and transparent film afterwards.After spin coating instrument stops, by moistening
Film is immediately placed on 100 DEG C of warm table after heating 15min, removes preset adhesive tape, sample is placed in box-annealing furnace terraced
Degree is warming up to 500 DEG C of annealing.
(C) spin coating TiO2Mesoporous layer：Prepare TiO2Cookies microsphere slurries.bl-TiO2/ FTO substrate Kapton Tapes are pre-
Electrode, slurry is stayed to press 1 with ethyl alcohol：5 volume ratios are diluted.FTO substrates are covered with by the slurry after taking 100 μ l dilutions with liquid-transfering gun
And after spin coating (3500rmp/min, 20s) uniformly, it is positioned over 100 DEG C of thermal station heating.Adhesive tape is removed, sample is placed in batch-type furnace
Gradient increased temperature is annealed to 500 DEG C.
2, MAPbI is prepared3Perovskite thin film
By the PbI of 1.1064g2DMSO (the volume ratios 4 of the DMF and 0.44g of 1.5112g are dissolved in the MAI of 0.3816g:
1) it in, is filtered after 70 DEG C of heating stirring 30min.In the TiO prepared2With the rotating speed spin coating of 3000rmp/min on mesoporous layer
Perovskite thin film, time 40s are prepared, while using chlorobenzene as anti-solvent；It, will after placing in air until becoming dark brown
Sample is placed in 100 DEG C of thermal station and heats 10min, prepares the calcium titanium ore bed that thickness is 400nm~500nm.
3, hole transmission layer is prepared
The Spiro-OMeTAD of 72.3mg is dissolved in the chlorobenzene of 1.1g, the TBP of 28.8 μ l is added thereto, is stirred
15min；The cobalt salt of the lithium salts and 30mg that take 52mg is dissolved in the acetonitrile of 76mg respectively, takes the lithium salt solution of 17.5 μ l respectively later
It is added thereto, is filtered after stirring 30min, with the rotating speed spin coating 20s systems of 4000rmp/min on sample with the cobalt salt solution of 29 μ l
The hole transmission layer of standby 200nm.
4,10-4Under the vacuum of Pa, the Au electrodes of thermal evaporation 60nm obtain TiO2The group of mesoporous perovskite solar cell
Dress.
Film characterization and device detection
By preparation-obtained TiO2Film carries out analytical table using transmission spectrum, X-ray diffraction, electronic scanner microscope
Sign.As shown in Fig. 2, Fig. 3, Fig. 4 a, Fig. 4 b.
The instrument that X-ray diffraction (XRD) analysis uses is D8Advance, and determination condition is 0.001 °/step.Electron scanning
Microscope is carried out under the voltage of 15KV.
Assembled plane perovskite solar cell is subjected to photoelectric properties test.The photoelectricity as shown in figure Fig. 4 c, Fig. 4 d
The measurement of stream-photovoltage (J-V) curve is that the 236 source measuring unit of Keithley controlled in a computer carries out.Device characteristics
Change is carried out in the environment illuminated under AM1.5G, with 100mW cm-2Xenon lamp based on solar simulator
(Newport Co.,LTD.).The intensity of the light of each wavelength and the monocrystalline Silicon photrouics of standard are calibrated.
Claims (7)
1.TiO2The preparation method of cookies shape microballoon, which is characterized in that include the following steps：
(1) liner of polytetrafluoroethylene (PTFE) reaction vessel is successively using four kinds of cleaning agent, deionized water, acetone, absolute ethyl alcohol liquid
It is cleaned by ultrasonic, each liquid handling 1 time, 20 minutes every time, dry drying after cleaning；
(2) a variety of organic solvents are added in reaction vessel, then positive four butyl ester of metatitanic acid is slowly added dropwise as mixed solvent, and mixing is molten
The volume ratio of agent and positive four butyl ester of metatitanic acid is 50ml：2ml is stirred simultaneously；
(3) tetrabutylammonium hydroxide aqueous solution is slowly added dropwise as controlling agent in acquired solution into step (2), stirs evenly；
The volume ratio of tetrabutylammonium hydroxide aqueous solution and positive four butyl ester of metatitanic acid is 0.1ml-0.5ml：2ml；
(4) reaction vessel is sealed, heating temperature is increased to 160 DEG C -200 DEG C, reacts 12h-20h；
(5) it by the product natural cooling obtained by step (4), is centrifuged, rate 5000rmp/min, centrifuges 5 minutes, take
Sediment and with being dried for standby after deionized water and absolute ethyl alcohol successively washing four times；
(6) being deposited in Muffle furnace after washing in step (5) is made annealing treatment, obtains the TiO with monodispersity2It is bent
Strange microballoon.
2. the TiO of high-specific surface area according to claim 12The preparation method of cookies shape microballoon, which is characterized in that described
Mixed solvent in step (2) include in acetonitrile, isopropanol, acetylacetone,2,4-pentanedione, water, methanol, benzaldehyde, diethylene glycol (DEG), ethyl alcohol extremely
It is two kinds few.
3. the TiO of high-specific surface area according to claim 22The preparation method of cookies shape microballoon, which is characterized in that described
Mixed solvent in step (2) includes that volume ratio is 3：1：1 acetonitrile, isopropanol, acetylacetone,2,4-pentanedione.
4. the TiO of high-specific surface area according to claim 12The preparation method of cookies shape microballoon, which is characterized in that described
Middle annealing conditions in step (6) are to rise to 140 DEG C in 10min by room temperature, keep the temperature 2min；It heats up, is risen in 10min again
It 350 DEG C, after keeping the temperature 5min, is warming up to 510 DEG C again in 15min, is down to 120 DEG C naturally after keeping the temperature 30min, takes out natural cooling
It is spare to room temperature.
5. perovskite solar cell, which is characterized in that including TiO2Mesoporous layer, the TiO2Mesoporous layer by claim 1 to
4 any one of them TiO2Cookies shape microballoon is made.
6. perovskite solar cell according to claim 5, which is characterized in that further include fluorine doped tin oxide electrically conducting transparent
Glass has the TiO as substrate in thickness 380nm, FTO substrate2Mesoporous layer；TiO2Mesoporous layer includes that electronics passes successively
Defeated layer, perovskite active layer, hole transmission layer；The TiO2Cookies shape microballoon mixes work with P25 titania nanoparticles
For electron transfer layer, thickness 500nm, MAPbI3As perovskite active layer, thickness 500nm, Spiro-OMeTAD work
For hole transmission layer, thickness 200nm, it is 60nm to have gold electrode, golden thickness on hole transmission layer.
7. the preparation method of perovskite solar cell according to claim 6, which is characterized in that include the following steps：
(1) in FTO substrates, TiO is formed2Mesoporous layer film；
(a) substrate is cleaned, FTO is chosen and is successively ultrasonically treated by cleaning agent, deionized water, acetone, isopropanol, each 20min,
Each solvent is handled 1 time, then handles 15min through UV ozone；
(b) TiO is prepared2Compacted zone：Titanium source solution and absolute ethyl alcohol are with 1:10 volume ratio mixing, stirring 5min are transparent to solution；
The FTO handled well in (a) is placed on spin coating instrument objective table, 150 μ l mixed solutions are covered into the full surfaces FTO, warp with dropper
The spin coating of spin coating instrument forms uniform and transparent film after handling 20s with 3500rmp/min；After spin coating instrument stops, by the thin of moistening
Film is immediately placed on 100 DEG C of warm table after baking 15min, is placed in gradient increased temperature in box-annealing furnace and is annealed to 500 DEG C；
(c) spin coating TiO2Mesoporous layer：Prepare the TiO of high-specific surface area2The titania slurry of cookies shape microballoon；bl-TiO2/FTO
Substrate reserves electrode with Kapton Tape, slurry and ethyl alcohol by volume 1：5 are diluted；It is dilute that 100 μ l are pipetted with liquid-transfering gun
FTO substrates are covered with rear spin coating and handle 20s with 3500rmp/min by the slurry released；Above-mentioned film is placed into 100 DEG C of bakings of thermal station
It is roasting；Adhesive tape is removed, and substrate is placed in gradient increased temperature in batch-type furnace and is annealed to 500 DEG C；
(2) MAPbI is prepared3Perovskite thin film
By the PbI of 1.1064g2It is dissolved in the MAI of 0.3816g in the DMSO mixed liquors of the DMF and 0.44g of 1.5112g, 70 DEG C add
It is filtered after thermal agitation 30min；In the TiO prepared2It is thin that perovskite prepared with the rotating speed spin coating of 3000rmp/min on mesoporous layer
Film, while using chlorobenzene as anti-solvent；After placing in air until becoming dark brown, sample is placed on to 100 DEG C of warm table
Upper heating 10min；
(3) hole transmission layer is prepared
The Spiro-OMeTAD of 72.3mg is dissolved in the chlorobenzene of 1.1g, the TBP of 28.8ul is added thereto, stirs 15min；It takes
The lithium salts of 52mg and the cobalt salt of 30mg be dissolved in the acetonitrile of 76mg respectively, takes the lithium salt solution and 29ul of 17.5ul respectively later
Cobalt salt solution is added thereto, and is filtered after stirring 30min, with 4000rmp/min's on the perovskite thin film sample prepared
Rotating speed spin coating 20s is to prepare hole transmission layer；
(4) it prepares to electrode
Then, gold electrode is deposited on the hole transport layer, obtains TiO2Mesoporous layer perovskite solar cell.
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| CN113087012A (en) * | 2019-12-23 | 2021-07-09 | 有研工程技术研究院有限公司 | TiO of perovskite solar cell2Preparation method of electron transport layer |
| RU2756135C1 (en) * | 2021-02-12 | 2021-09-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "ДАГЕСТАНСКИЙ ГОСУДАРСТВЕННЫЙ УНИВЕРСИТЕТ" | Technology for creating a magnetically controlled memristor based on titanium dioxide nanotubes |
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