CN107369768B - A kind of preparation method of the perovskite solar battery based on new Organic leadP source - Google Patents
A kind of preparation method of the perovskite solar battery based on new Organic leadP source Download PDFInfo
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H10K71/10—Deposition of organic active material
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Abstract
The invention discloses a kind of preparation methods of perovskite solar battery based on new Organic leadP source, belong to area of solar cell.The present invention has synthesized CH by solwution method with methylpyridinium iodide ammonium using lead formate3NH3PbI3Light absorbing layer of the film as solar battery, the present invention are lower for the purity requirement in lead source, relatively easily obtain and low in cost；Tests prove that photoelectric conversion efficiency is higher, and optimum efficiency is up to 18.4% with perovskite solar battery made from preparation process of the present invention.The present invention has the advantage that low energy consumption, prepared by low cost, high efficiency and easy large area compared with prior art, is conducive to accelerate the commercialized paces of perovskite solar cell, promotes perovskite solar cell large-scale production.
Description
Technical field
The invention belongs to technical field of solar batteries, and in particular to a kind of perovskite solar energy based on new Organic leadP source
The preparation method of battery.
Background technique
Now using fossil energies such as petroleum, coal, natural gases as the non-regeneration energy of representative, since reserves are limited, open
It sends out at high cost and be easy to cause the factors such as environmental pollution in use, it is renewable for cleaning not to be able to satisfy people more
The demand of the energy.Compare fossil energy, solar energy is because its storage capacity is abundant, the environmentally protective and advantages such as cheap are known as not
Carry out the most potential new energy instead of fossil energy.And it can satisfy environmental energy sustainable development using solar energy generation technology
The demand of exhibition becomes the research hotspot of this field.
Solar battery basic functional principle is to absorb sunlight photon using organic or inorganic semiconductor light-sensitive material
Energy form light induced electron, the photoelectric conversion of solar energy is realized by the displacement of light induced electron.It is sent out from solar battery
Since exhibition, it successively experienced first generation crystal silicon solar energy battery, second generation thin-film solar cells and currently studied
The novel battery of third generation new material new technology, such as dye-sensitized cell, quantum dot cell, organic solar batteries and calcium
Titanium ore solar battery (Perovskite solar cell, PSC).Metal-halide perovskite is through Science Explorations as crystal
Material, then in solar battery and fast-developing as the contenders for leading photovoltaic technology.Day in 2009 undergraduate course
Scholar has found a kind of metal-halide Ca-Ti ore type light absorbent --- CH3NH3PbI3, forbidden bandwidth 1.55eV, this
Characteristic makes it have good development prospect in photovoltaic art.
Currently, CH3NH3PbI3Primary synthetic methods be using lead source and ammonium salt.Common lead source includes: inorganic lead source
Lead iodide (PbI2) and Organic leadP source lead acetate ((CH3COO)2Pb) etc..However, above two lead source needs higher purity
Can be prepared high performance perovskite solar cell light absorption layer, and high-purity require to also mean that it is relatively high
Cost.On the other hand, PbI2Fusing point be about 402 DEG C, anhydrous (CH3COO)2The fusing point of Pb is about 280 DEG C.It is above two common
The fusing point in lead source is above the fusing point of ammonium salt, such as prepares large area perovskite solar battery according to vacuum vapor deposition, then
It is excessively high to will lead to energy consumption.CH is prepared in the prior art3NH3PbI3Lead source used in material becomes limitation perovskite solar battery and produces
Therefore the main resistance of industryization development needs a kind of method that can be overcome the shortage of prior art.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides one kind prepares perovskite solar energy based on new Organic leadP source
The method of cell light absorption layer solves existing lead source and prepares energy consumption present in perovskite solar cell light absorption layer and cost
Excessively high problem is conducive to the industrialization of perovskite solar battery.
To achieve the goals above, the invention provides the following technical scheme:
A kind of preparation method of the perovskite solar battery based on new Organic leadP source is included in transparent conducting glass deposition
The step of electron transfer layer, the step of then depositing perovskite absorbed layer on the electron transport layer, then in the perovskite
On absorbed layer the step of deposition of hole transport layer, finally on the hole transport layer deposit metal electrodes layer the step of；It is special
The step of sign is, deposits perovskite absorbed layer on the electron transport layer are as follows:
Step A: lead formate and methylpyridinium iodide ammonium are dissolved in organic reagent and are stirred, is filtered after mixing
Processing, preparation obtain perovskite precursor solution；
Step B: by perovskite precursor solution made from step A using spin coating proceeding in the electron-transport layer surface shape
At film；
Step C: the sample that spin coating is obtained makes annealing treatment, and obtains CH3NH3PbI3Film.
Further, the purity of lead formate is not less than 90% in the present invention.
Further, in the present invention in perovskite precursor solution the molar ratio of lead formate and methylpyridinium iodide ammonium 1:
In 2.5~1: 3.5 ranges.Further, organic solvent is preferably N,N-Dimethylformamide (DMF) and diformazan in the present invention
The mixed system that base sulfoxide (DMSO) is formed, specifically, the percent by volume 80~95% of DMF, DMSO in the mixed system
Percent by volume be 5~20%.
Further, in the present invention spin coating operation technological parameter are as follows: 2500~5000rpm of revolving speed, spin-coating time 20s
~60s.Further, spin coating operation starts the substrate table for uniformly brushing rotation after 15s using nitrogen in step B in the present invention
Face, until spin coating process terminates.
Further, making annealing treatment temperature range in step C of the present invention is 100~120 DEG C, the time 10~30 minutes.
Further, CH is made in the present invention3NH3PbI3Film with a thickness of 300nm~500nm.
Compared with prior art, the beneficial effects of the present invention are:
The present invention uses lead formate (Pb (HCOO)2) and methylpyridinium iodide ammonium (CH3NH3I high quality) is synthesized by solwution method
CH3NH3PbI3Light absorbing layer of the film as solar battery, solwution method is easy to operate controllable, the advantage with low energy consumption；This
The lead source that uses is invented as low-purity lead formate, easy acquisition and low in cost, can overcome current lead source because of high-purity caused by
High-cost disadvantage；It will be based on CH made from the method for the present invention3NH3PbI3Film applies in perovskite solar battery, test
It proves, photoelectric conversion efficiency is higher, and optimum efficiency is up to 18.4% at present.To sum up, the present invention provides a kind of high efficiency, low
The method that cost, low energy consumption prepare perovskite solar battery helps speed up the commercialization paces of perovskite solar battery,
Promote the large-scale production of perovskite solar battery.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of perovskite solar cell, wherein 1 is metal electrode layer, and 2 be hole transmission layer, and 3 are
Perovskite light absorbing layer, 4 be mesoporous layer, and 5 be electron transfer layer, and 6 be transparent conducting glass.
Fig. 2 is the X-ray diffractogram that perovskite light absorption layer material is made in the embodiment of the present invention 1.
Fig. 3 is the scanning electron microscope (SEM) photograph that perovskite light absorption layer material is made in embodiment 1.
Fig. 4 is the current density voltage curve figure that perovskite solar cell is made in embodiment 1.
Fig. 5 is the current density voltage curve figure that perovskite solar cell is made in embodiment 2.
Fig. 6 is the scanning electron microscope (SEM) photograph of perovskite light absorbing layer made from embodiment 3.
Fig. 7 is the current density voltage curve figure that embodiment 3 prepares perovskite solar cell.
Specific embodiment
The principle of the present invention and characteristic are described in detail with Figure of description combined with specific embodiments below:
A kind of method that the gist of the invention is to provide low cost, low energy consumption prepares efficient perovskite solar battery,
The present invention uses new Organic leadP source --- lead formate, by mixing lead formate with methylpyridinium iodide ammonium through suitable filming technology
Perovskite precursor thin-film, then annealed processing are formed, following chemical reaction occurs for whole process:
Pb(HCOO)2+3CH3NH3I→CH3NH3PbI3+2CH3NH3(HCOO)↑
Be conducive to chemically react through this heat treatment, byproduct of reaction CH3NH3(HCOO) reactant is left for gas heating
System, while further promoting lead formate and being reacted with methylpyridinium iodide ammonium.
As shown in Figure 1, the present invention provides the structural schematic diagram of existing traditional perovskite solar cell, sunlight is led from transparent
Electric glass 6 enters, and after perovskite light absorbing layer 3 absorbs the photon energy higher than forbidden bandwidth, electronics transits to conduction band by valence band,
And then produce electron hole pair；Hole in valence band is transferred in metal electrode layer 1 by hole transmission layer 2, in conduction band
The electron injection being excited is to electron transfer layer 5, and bracket of the intermediary hole layer 4 as battery, then electron-transport reaches transparent
Conductive layer in electro-conductive glass 6；In this course, light anode of the conductive layer in transparent conducting glass 6 as battery, metal
Hole is not only transmitted to photocathode from perovskite, is also prevented from simultaneously by photocathode of the electrode layer 1 as battery, hole transmission layer 2
Electron-transport is to photocathode, and correspondingly, electronics is not only transmitted in light anode by electron transfer layer 5 from perovskite light absorbing layer,
Hole transport is also prevented to light anode simultaneously.
Embodiment 1:
The preparation method of perovskite solar battery, specifically comprises the following steps:
Step 1: cleaning substrate:
The present embodiment selects FTO electro-conductive glass as substrate, that is, Fluorin doped stannic oxide (SnO2: F), the present invention couple
In substrate material selection with no restrictions, can be any suitable substrate material；
FTO electro-conductive glass is tentatively cleaned using abluent and nanosponges first, is then rushed using deionized water
It washes for several times, the substrate after flushing is successively used into acetone, ethyl alcohol, deionized water as solvent and is ultrasonically treated, it will be through ultrasound
Treated, and FTO electro-conductive glass use is dried with nitrogen, and then reuses the key of oxygen plasma treatment enhancing substrate material surface
Resultant force and adhesive force；
Step 2: prepare electron transfer layer:
The present embodiment selects TiO2Film does not do the selection of electron transport layer materials as electron transfer layer, the present invention
Limitation, can be any suitable electron transport layer materials；
Weigh butyl titanate be dissolved in ethyl alcohol prepare obtain butyl titanate ethanol solution as preparation TiO2Film
Precursor solution, the percent by volume of butyl titanate is 10% in precursor solution；Precursor solution is revolved by spin coating
Coating is deposited on to be handled in obtained FTO Conducting Glass through step 1, and then under conditions of temperature is 480 DEG C, high temperature is burnt
Knot 30 minutes is to get arriving TiO2Dense film；
Step 3: preparing mesoporous layer；
The present embodiment selects TiO2It is nanocrystalline be used as mesoporous layer, the present invention for mesoporous layer material selection with no restrictions,
It can be any suitable mesoporous layer material；
Fine and close TiO is made in step 22Spin coating TiO on film2It is nanocrystalline to form mesoporous layer, the TiO2Nanocrystalline crystalline substance
Grain partial size is about 25nm, and aperture is 20~50nm, and the thickness of mesoporous layer is about 100nm~200nm；
Step 3: preparation CH3NH3PbI3Light absorbing layer；
(1) weighs the lead formate of 0.001mol and the methylpyridinium iodide of 0.003mol using electronic balance in glove box
The two is dissolved in the in the mixed solvent that dimethyl sulfoxide and N,N-Dimethylformamide are formed, is sufficiently stirred and makes it dissolve by ammonium,
Then perovskite precursor solution is obtained by filtration treatment；Solvent main function is to dissolve in the present invention, it is contemplated that does not draw
Enter impurity, the preferred dimethyl sulfoxide of the present embodiment and N,N-Dimethylformamide mixing are used as solvent, and those skilled in the art can select
With any suitable solvent, the present invention is to this and with no restrictions；
(2), which takes precursor solution made from 80 μ L steps (1) and is added dropwise, is made mesoporous layer surface in step 3, opens
Spin coating instrument, adjusting revolving speed are 3000rpm, uniformly brush the substrate surface of rotation using nitrogen after spin coating 15 seconds, at the uniform velocity to it
Spin coating instrument is closed after spin coating 40 seconds；
(3) sample obtained through step (2) processing is placed on warm table by, and adjusting heating platen temperature is 100 DEG C, annealing
Processing 30 minutes, i.e. acquisition CH3NH3PbI3Light absorbing layer；
By CH made from step (3)3NH3PbI3Film is characterized to obtain result figure as shown in Figure 2 through X-ray diffractometer,
It can clearly be seen that CH from Fig. 23NH3PbI3(110), (220) diffraction maximum；
By CH made from step (3)3NH3PbI3Film scanning electron microscope is characterized to obtain result as shown in Figure 3
Figure, apparent big crystal grain, multiple little crystal grains and little crystal grain wrap up crystal boundary in film as can be seen from Figure 3；
Step 5: preparing hole transmission layer；
The present embodiment selects 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes, double trifluoros
The laminated film that sulfonyl methane imine lithium and 4- tert .-butylpyridine are formed is as hole transmission layer, and the present invention is for hole transport
The selection of layer material with no restrictions, can be any suitable hole transport layer material；
Weigh 80mg2,2', two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, the 20 bis- trifluoros of μ L
Sulfonyl methane imine lithium acetonitrile solution and 28 μ L 4- tert .-butylpyridines, above-mentioned three is dissolved in chlorobenzene and forms mixed solution
System, in which: the concentration of double trifluoromethanesulfonimide lithiums is 500mg/mL in double trifluoromethanesulfonimide lithium acetonitrile solutions,
It measures mixed solution system described in 70 μ L and is spin-coated on step 4 and CH is made3NH3PbI3Hole transmission layer is formed on film；
Step 6: preparing metal electrode layer；
Metal electrode layer of the present invention can be any suitable materials such as Au, Ag, Cu, and its thickness is about 100nm, this reality
It applies example and the metal Au that 100nm thickness is deposited on hole transmission layer is made as metal electrode layer, through hot pressing in step 5 using vapour deposition method
The preparation of perovskite solar battery is completed after processing.
Analysis test:
Solar battery avoid light place made from the present embodiment is subjected to analysis test afterwards for a period of time, calcium is made in this implementation
The effective active area of titanium ore solar battery is 0.09 square centimeter, places it in standard analog sunlight AM1.5, and 30% is empty
Air humidity degree is tested under conditions of 25 DEG C of temperature；It is illustrated in figure 4 the Current density-voltage of the present embodiment perovskite solar cell
Curve obtains its photovoltaic performance parameter according to this current density voltage curve are as follows: short-circuit current density 22.1mA/cm2, open
Road voltage 1.084V, fill factor 0.77, transfer efficiency 18.4%.
Embodiment 2:
It is adjusted according to preparation flow described in embodiment 1 and preparation and the calcium that effective active area is 1 square centimeter is prepared
Solar battery avoid light place made from the present embodiment is carried out analysis test, by it by titanium ore solar battery afterwards for a period of time
It is placed in standard analog sunlight AM1.5,30% air humidity is tested under conditions of 25 DEG C of temperature；It is illustrated in figure 5 the present embodiment
The current density voltage curve of perovskite solar cell obtains the present embodiment solar-electricity according to this current density voltage curve
The photovoltaic performance parameter in pond are as follows: short-circuit current density 18.7mA/cm2, open-circuit voltage 1.099V, fill factor 0.51, conversion
Efficiency 10.5%.
Embodiment 3:
The preparation method of perovskite solar battery, specifically comprises the following steps:
Step 1: cleaning substrate:
The present embodiment selects FTO electro-conductive glass as substrate, that is, Fluorin doped stannic oxide (SnO2: F), the present invention couple
In substrate material selection with no restrictions, can be any suitable substrate material；
FTO electro-conductive glass is tentatively cleaned using abluent and nanosponges first, is then rushed using deionized water
It washes for several times, the substrate after flushing is successively used into acetone, ethyl alcohol, deionized water as solvent and is ultrasonically treated, it will be through ultrasound
Treated, and FTO electro-conductive glass use is dried with nitrogen, and then reuses the key of oxygen plasma treatment enhancing substrate material surface
Resultant force and adhesive force；
Step 2: prepare electron transfer layer:
The present embodiment selects TiO2Film does not do the selection of electron transport layer materials as electron transfer layer, the present invention
Limitation, can be any suitable electron transport layer materials；
Weigh butyl titanate be dissolved in ethyl alcohol prepare obtain butyl titanate ethanol solution as preparation TiO2Film
Precursor solution, the percent by volume of butyl titanate is 10% in precursor solution；Precursor solution is revolved by spin coating
Coating is deposited on to be handled in obtained FTO Conducting Glass through step 1, and then under conditions of temperature is 480 DEG C, high temperature is burnt
Knot 30 minutes is to get arriving TiO2Dense film；
Step 3: preparing mesoporous layer；
The present embodiment selects TiO2It is nanocrystalline be used as mesoporous layer, the present invention for mesoporous layer material selection with no restrictions,
It can be any suitable mesoporous layer material；
Fine and close TiO is made in step 22Spin coating TiO on film2It is nanocrystalline to form mesoporous layer, the TiO2Nanocrystalline crystalline substance
Grain partial size is about 25nm, and aperture is 20~50nm, and the thickness of mesoporous layer is about 100nm~200nm；
Step 3: preparation CH3NH3PbI3Light absorbing layer；
(1) weighs the lead formate of 0.001mol and the methylpyridinium iodide of 0.003mol using electronic balance in glove box
The two is dissolved in N,N-Dimethylformamide solvent by ammonium, is then added 80mg ammonium chloride, is sufficiently stirred and makes it dissolve, so
Perovskite precursor solution is obtained by filtration treatment afterwards；Solvent main function is to dissolve in the present invention, it is contemplated that does not introduce
Impurity, the preferred N,N-Dimethylformamide solvent of the present embodiment, those skilled in the art can select any suitable solvent, the present invention
To this and with no restrictions；
(2), which takes precursor solution made from 80 μ L steps (1) and is added dropwise, is made mesoporous layer surface in step 3, opens
Spin coating instrument, adjusting revolving speed are 3000rpm, use the lining for uniformly brushing rotation in vertical direction with nitrogen gun after starting spin coating 15 seconds
Spin coating instrument is closed at bottom after its at the uniform velocity spin coating 40 seconds；
(3) sample obtained through step (2) processing is placed on warm table by, and adjusting heating platen temperature is 100 DEG C, annealing
50 μ L DMF solutions are added in annealing process and carry out ambient anneal processing, obtain after the completion of annealing for processing 30 minutes
Obtain CH3NH3PbI3Light absorbing layer；
By CH made from step (3)3NH3PbI3Film scanning electron microscope is characterized to obtain result as shown in Figure 6
Figure, crystal boundary understands, obviously in film as can be seen from Figure 6, and no little crystal grain wraps up crystal boundary；
Step 5: preparing hole transmission layer；
The present embodiment selects 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes, double trifluoros
The laminated film that sulfonyl methane imine lithium and 4- tert .-butylpyridine are formed is as hole transmission layer, and the present invention is for hole transport
The selection of layer material with no restrictions, can be any suitable hole transport layer material；
Weigh 80mg2,2', two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, the 20 bis- trifluoros of μ L
Sulfonyl methane imine lithium acetonitrile solution and 28 μ L 4- tert .-butylpyridines, above-mentioned three is dissolved in chlorobenzene and forms mixed solution
System, in which: the concentration of double trifluoromethanesulfonimide lithiums is 500mg/mL in double trifluoromethanesulfonimide lithium acetonitrile solutions,
It measures mixed solution system described in 70 μ L and is spin-coated on step 4 and CH is made3NH3PbI3Hole transmission layer is formed on film；
Step 6: preparing metal electrode layer；
Metal electrode layer of the present invention can be any suitable materials such as Au, Ag, Cu, and its thickness is about 100nm, this reality
It applies example and the metal Au that 100nm thickness is deposited on hole transmission layer is made as metal electrode layer, through hot pressing in step 5 using vapour deposition method
The preparation of perovskite solar battery is completed after processing.
Analysis test:
Solar battery avoid light place made from the present embodiment is subjected to analysis test afterwards for a period of time, calcium is made in this implementation
The effective active area of titanium ore solar battery is 0.09 square centimeter, places it in standard analog sunlight AM1.5, and 30% is empty
Air humidity degree is tested under conditions of 25 DEG C of temperature；It is illustrated in figure 7 the Current density-voltage of the present embodiment perovskite solar cell
Curve obtains the photovoltaic performance parameter of the present embodiment solar battery according to this current density voltage curve are as follows: short circuit current is close
Degree is 22.58mA/cm2, open-circuit voltage 0.926V, fill factor 0.68, transfer efficiency 14.2%.
Embodiment 4:
The preparation method of perovskite solar battery, specifically comprises the following steps:
Step 1: cleaning substrate:
The present embodiment selects FTO electro-conductive glass as substrate, that is, Fluorin doped stannic oxide (SnO2: F), the present invention couple
In substrate material selection with no restrictions, can be any suitable substrate material；
FTO electro-conductive glass is tentatively cleaned using abluent and nanosponges first, is then rushed using deionized water
It washes for several times, the substrate after flushing is successively used into acetone, ethyl alcohol, deionized water as solvent and is ultrasonically treated, it will be through ultrasound
Treated, and FTO electro-conductive glass use is dried with nitrogen, and then reuses the key of oxygen plasma treatment enhancing substrate material surface
Resultant force and adhesive force；
Step 2: prepare electron transfer layer:
The present embodiment selects TiO2Film does not do the selection of electron transport layer materials as electron transfer layer, the present invention
Limitation, can be any suitable electron transport layer materials；
Weigh butyl titanate be dissolved in ethyl alcohol prepare obtain butyl titanate ethanol solution as preparation TiO2Film
Precursor solution, the percent by volume of butyl titanate is 10% in precursor solution；Precursor solution is revolved by spin coating
Coating is deposited on to be handled in obtained FTO Conducting Glass through step 1, and then under conditions of temperature is 480 DEG C, high temperature is burnt
Knot 30 minutes is to get arriving TiO2Dense film；
Step 3: preparing mesoporous layer；
The present embodiment selects TiO2It is nanocrystalline be used as mesoporous layer, the present invention for mesoporous layer material selection with no restrictions,
It can be any suitable mesoporous layer material；
Fine and close TiO is made in step 22Spin coating TiO on film2It is nanocrystalline to form mesoporous layer, the TiO2Nanocrystalline crystalline substance
Grain partial size is about 25nm, and aperture is 20~50nm, and the thickness of mesoporous layer is about 100nm~200nm；
Step 3: preparation CH3NH3PbI3Light absorbing layer；
(1) weighs the lead formate of 0.001mol and the methylpyridinium iodide of 0.0025mol using electronic balance in glove box
The two is dissolved in the in the mixed solvent that dimethyl sulfoxide and N,N-Dimethylformamide are formed, is sufficiently stirred and makes it dissolve by ammonium,
Then perovskite precursor solution is obtained by filtration treatment；Solvent main function is to dissolve in the present invention, it is contemplated that does not draw
Enter impurity, the preferred dimethyl sulfoxide of the present embodiment and N,N-Dimethylformamide mixing are used as solvent, and those skilled in the art can select
With any suitable solvent, the present invention is to this and with no restrictions；
(2), which takes precursor solution made from 80 μ L steps (1) and is added dropwise, is made mesoporous layer surface in step 3, opens
Spin coating instrument, adjusting revolving speed are 4500rpm, use the lining for uniformly brushing rotation in vertical direction with nitrogen gun after starting spin coating 15 seconds
Spin coating instrument is closed at bottom after its at the uniform velocity spin coating 20 seconds；
(3) sample obtained through step (2) processing is placed on warm table by, and adjusting heating platen temperature is 120 DEG C, annealing
50 μ L DMF solutions are added in annealing process and carry out ambient anneal processing, obtain after the completion of annealing for processing 20 minutes
Obtain CH3NH3PbI3Light absorbing layer；
Step 5: preparing hole transmission layer；
The present embodiment selects 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes, double trifluoros
The laminated film that sulfonyl methane imine lithium and 4- tert .-butylpyridine are formed is as hole transmission layer, and the present invention is for hole transport
The selection of layer material with no restrictions, can be any suitable hole transport layer material；
Weigh 80mg2,2', two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, the 20 bis- trifluoros of μ L
Sulfonyl methane imine lithium acetonitrile solution and 28 μ L 4- tert .-butylpyridines, above-mentioned three is dissolved in chlorobenzene and forms mixed solution
System, in which: the concentration of double trifluoromethanesulfonimide lithiums is 500mg/mL in double trifluoromethanesulfonimide lithium acetonitrile solutions,
It measures mixed solution system described in 70 μ L and is spin-coated on step 4 and CH is made3NH3PbI3Hole transmission layer is formed on film；
Step 6: preparing metal electrode layer；
Metal electrode layer of the present invention can be any suitable materials such as Au, Ag, Cu, and its thickness is about 100nm, this reality
It applies example and the metal Au that 100nm thickness is deposited on hole transmission layer is made as metal electrode layer, through hot pressing in step 5 using vapour deposition method
The preparation of perovskite solar battery is completed after processing.
Embodiment 5:
The preparation method of perovskite solar battery, specifically comprises the following steps:
Step 1: cleaning substrate:
The present embodiment selects FTO electro-conductive glass as substrate, that is, Fluorin doped stannic oxide (SnO2: F), the present invention couple
In substrate material selection with no restrictions, can be any suitable substrate material；
FTO electro-conductive glass is tentatively cleaned using abluent and nanosponges first, is then rushed using deionized water
It washes for several times, the substrate after flushing is successively used into acetone, ethyl alcohol, deionized water as solvent and is ultrasonically treated, it will be through ultrasound
Treated, and FTO electro-conductive glass use is dried with nitrogen, and then reuses the key of oxygen plasma treatment enhancing substrate material surface
Resultant force and adhesive force；
Step 2: prepare electron transfer layer:
The present embodiment selects TiO2Film does not do the selection of electron transport layer materials as electron transfer layer, the present invention
Limitation, can be any suitable electron transport layer materials；
Weigh butyl titanate be dissolved in ethyl alcohol prepare obtain butyl titanate ethanol solution as preparation TiO2Film
Precursor solution, the percent by volume of butyl titanate is 10% in precursor solution；Precursor solution is revolved by spin coating
Coating is deposited on to be handled in obtained FTO Conducting Glass through step 1, and then under conditions of temperature is 480 DEG C, high temperature is burnt
Knot 30 minutes is to get arriving TiO2Dense film；
Step 3: preparing mesoporous layer；
The present embodiment selects TiO2It is nanocrystalline be used as mesoporous layer, the present invention for mesoporous layer material selection with no restrictions,
It can be any suitable mesoporous layer material；
Fine and close TiO is made in step 22Spin coating TiO on film2It is nanocrystalline to form mesoporous layer, the TiO2Nanocrystalline crystalline substance
Grain partial size is about 25nm, and aperture is 20~50nm, and the thickness of mesoporous layer is about 100nm~200nm；
Step 3: preparation CH3NH3PbI3Light absorbing layer；
(1) weighs the lead formate of 0.001mol and the methylpyridinium iodide of 0.0035mol using electronic balance in glove box
The two is dissolved in N,N-Dimethylformamide solvent, is sufficiently stirred and makes it dissolve by ammonium, then obtains calcium by filtration treatment
Titanium ore precursor solution；Solvent main function is to dissolve in the present invention, it is contemplated that does not introduce impurity, the preferred nitrogen nitrogen of the present embodiment
Solvent dimethylformamide, those skilled in the art can select any suitable solvent, and the present invention is to this and with no restrictions；
(2), which takes precursor solution made from 80 μ L steps (1) and is added dropwise, is made mesoporous layer surface in step 3, opens
Spin coating instrument, adjusting revolving speed are 2500rpm, use the lining for uniformly brushing rotation in vertical direction with nitrogen gun after starting spin coating 15 seconds
Spin coating instrument is closed at bottom after its at the uniform velocity spin coating 60 seconds；
(3) sample obtained through step (2) processing is placed on warm table by, and adjusting heating platen temperature is 110 DEG C, annealing
Processing 15 minutes, annealing obtain CH after the completion3NH3PbI3Light absorbing layer；
Step 5: preparing hole transmission layer；
The present embodiment selects 2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, two fluorenes, double trifluoros
The laminated film that sulfonyl methane imine lithium and 4- tert .-butylpyridine are formed is as hole transmission layer, and the present invention is for hole transport
The selection of layer material with no restrictions, can be any suitable hole transport layer material；
Weigh 80mg2,2', two fluorenes of 7,7'- tetra- [N, N- bis- (4- methoxyphenyl) amino] -9,9'- spiral shell, the 20 bis- trifluoros of μ L
Sulfonyl methane imine lithium acetonitrile solution and 28 μ L 4- tert .-butylpyridines, above-mentioned three is dissolved in chlorobenzene and forms mixed solution
System, in which: the concentration of double trifluoromethanesulfonimide lithiums is 500mg/mL in double trifluoromethanesulfonimide lithium acetonitrile solutions,
It measures mixed solution system described in 70 μ L and is spin-coated on step 4 and CH is made3NH3PbI3Hole transmission layer is formed on film；
Step 6: preparing metal electrode layer；
Metal electrode layer of the present invention can be any suitable materials such as Au, Ag, Cu, and its thickness is about 100nm, this reality
It applies example and the metal Au that 100nm thickness is deposited on hole transmission layer is made as metal electrode layer, through hot pressing in step 5 using vapour deposition method
The preparation of perovskite solar battery is completed after processing.
Claims (6)
1. a kind of preparation method of the perovskite solar battery based on new Organic leadP source, comprising: deposited in transparent conducting glass
The step of electron transfer layer, the step of then depositing perovskite light absorbing layer on the electron transport layer, then in the calcium titanium
On mine light absorbing layer the step of deposition of hole transport layer, finally on the hole transport layer deposit metal electrodes layer the step of；
It is characterized in that, the step of depositing perovskite light absorbing layer on the electron transport layer are as follows:
Step A: being dissolved in lead formate and methylpyridinium iodide ammonium in organic reagent and be stirred, wherein lead formate and methylpyridinium iodide ammonium
Molar ratio in 1: 2.5~1: 3.5 ranges；It is filtered processing after mixing, preparation obtains perovskite precursor solution；
Step B: perovskite precursor solution made from step A is formed in the electron-transport layer surface using spin coating proceeding thin
Film；
Step C: the sample that spin coating is obtained makes annealing treatment, and obtains CH3NH3PbI3Film.
2. a kind of preparation method of perovskite solar battery based on new Organic leadP source according to claim 1, special
Sign is that the purity of the lead formate is not less than 90%.
3. a kind of preparation method of perovskite solar battery based on new Organic leadP source according to claim 1, special
Sign is that the organic solvent is the mixed system that DMF and DMSO is formed, specifically, the volume hundred of DMF in the mixed system
Divide ratio 80~95%, the percent by volume of DMSO is 5~20%.
4. a kind of preparation method of perovskite solar battery based on new Organic leadP source according to claim 1, special
Sign is, the technological parameter of spin coating operation in the step B are as follows: revolving speed is 2500~5000rpm, and spin-coating time is 20~60
Second.
5. a kind of preparation method of perovskite solar battery based on new Organic leadP source according to claim 1, special
Sign is that the treatment temperature made annealing treatment in the step C is 100 DEG C, and the processing time is 10~30 minutes.
6. a kind of preparation method of perovskite solar battery based on new Organic leadP source according to claim 1, special
Sign is, the CH3NH3PbI3Film with a thickness of 300nm~500nm.
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