CN110518128A - A kind of ACI type two dimension perovskite solar cell and preparation method thereof - Google Patents
A kind of ACI type two dimension perovskite solar cell and preparation method thereof Download PDFInfo
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- 239000007788 liquid Substances 0.000 claims description 40
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- 238000000034 method Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- 150000008422 chlorobenzenes Chemical class 0.000 claims description 14
- 230000005540 biological transmission Effects 0.000 claims description 13
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 13
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 8
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- 229910003074 TiCl4 Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
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- 238000010586 diagram Methods 0.000 description 6
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- AJRXEXGVDMEBCT-UHFFFAOYSA-M [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] Chemical compound [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] AJRXEXGVDMEBCT-UHFFFAOYSA-M 0.000 description 1
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- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- 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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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of ACI type two dimension perovskite solar cell and preparation method thereof, the perovskite absorbed layer of the solar cell is C (NH2)3I、CH3NH3I and PbI2Mixture be added to CH during the preparation process3NH3Cl is as additive, compared to previous two-dimentional perovskite device, CH3NH3The addition of Cl additive greatly improves the crystalline quality of perovskite thin film, increase crystallite dimension, reduce the loss of Carrier recombination brought by grain boundaries defect, so that carrier lifetime is increased, the effective gradient distribution for increasing different n values simultaneously, improves charge transfer efficiency, finally directly determines the promotion of the incident photon-to-electron conversion efficiency of perovskite battery device, the series and parallel compensated resistance of device is improved, and is finally obtained 18.48% incident photon-to-electron conversion efficiency.Its excellent photoelectric properties and device efficiency will be helpful to that perovskite solar cell is pushed to move towards business application.
Description
[technical field]
The invention belongs to solar-photovoltaic technology fields, and in particular to a kind of ACI type two dimension perovskite solar cell and its
Preparation method.
[background technique]
In recent years, organic inorganic hybridization perovskite solar cell is received significant attention because of its brilliant photoelectric properties, photoelectricity
Transfer efficiency is rapidly promoted to current 25.2% from 3.8% in 2009.However, conventional three-dimensional perovskite light and thermally stable
Restrict the industrialization of photovoltaic device.Relative to three-dimensional perovskite solar cell, two-dimentional perovskite solar cell has better
Stability, wherein alternating cationic type (ACI) two-dimensional metallic halide perovskite material illustrates huge latent in photovoltaic art
Power, however the carrier mobility of two-dimentional perovskite thin film is low in the battery, crystal orientation is irregular, the film defects density of states compared with
High factor causes its device efficiency still very low, this seriously constrains its industrialization process.
[summary of the invention]
It is an object of the invention to overcome the above-mentioned prior art, a kind of ACI type two dimension perovskite sun electricity is provided
Pond and preparation method thereof；Carrier mobility existing for ACI type two dimension perovskite solar cell is low, crystal for solving for the program
It is orientated irregular, the higher technical problem of the film defects density of states.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
A kind of ACI type two dimension perovskite solar cell, including stack gradually from top to bottom FTO substrate, electron transfer layer,
Perovskite absorbed layer, hole transmission layer and metal electrode；The perovskite absorbed layer is (GA) (MA)nPbnI3n+1(n=3),
Middle GA is C (NH2)3 +, MAI CH3NH3 +；Being added in perovskite absorbed layer preparation process has CH3NH3Cl is as additive.
A further improvement of the present invention is that:
Preferably, the highest photoelectric conversion efficiency of the ACI type two dimension perovskite solar cell is 18.5%.
A kind of preparation method of ACI type two dimension perovskite solar cell, comprising the following steps:
Step 1, FTO substrate of glass is cleaned, FTO substrate is made；
Step 2, electron transfer layer is prepared on FTO substrate；
Step 3, on the electron transport layer by the spin coating of perovskite precursor liquid, perovskite absorbed layer is prepared；The perovskite
The solute of precursor liquid is PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixture of Cl, solvent are the mixture of DMSO and DMF；
Step 4, hole transmission layer is prepared on perovskite absorbed layer；
Step 5, metal electrode is prepared on the hole transport layer.
Preferably, in step 3, the concentration of solute is 1.1~1.3M in the perovskite precursor liquid.
Preferably, in step 3, PbI in solute2、C(NH2)3I、CH3NH3I and CH3NH3The molar ratio of Cl are as follows: 3:1:3:
(0-0.74)。
Preferably, in step 3, the volume ratio of DMSO and DMF is (1~10): (1~10) in solvent.
Preferably, in step 3, the spin-coating method is divided into two stages, and first stage revolving speed is 100-1000rpm, spin coating
Time is 1-10s；Second stage revolving speed is 1000-4000rpm, spin-coating time 10-60s；Terminate to remain in second stage spin coating
Remaining 10~30s when, be added dropwise 100~300 μ L chlorobenzenes on perovskite surface, obtained perovskite thin film is made annealing treatment, is moved back
Fiery temperature is 100~150 DEG C, and annealing time is 10~60min, prepares perovskite absorbed layer on the electron transport layer.
Preferably, in step 2, the preparation process of electron transfer layer are as follows: by TiCl4It instills in ice water, electron-transport is made
Layer precursor liquid；FTO substrate is submerged in electron transfer layer precursor liquid, is taken out after being reacted in dry environment and is attached with TiO2's
FTO substrate prepares TiO on FTO substrate after annealing2Film is as electron transfer layer.
Preferably, in step 4, hole is prepared by the way that Spiro-OMeTAD solution to be spin-coated on perovskite absorbed layer
Transport layer, the Spiro-OMeTAD solution by Spiro-OMeTAD chlorobenzene solution, Li-TFSI solution and tBP solution according to
Volume ratio 1mL:(10-40) μ L:(10-50) μ L configures.
Preferably, in step 5, by hot steaming method evaporation metal electrode on the hole transport layer, the metal electrode be Au,
Ag or Cu.
Compared with prior art, the invention has the following advantages:
The invention discloses a kind of ACI type two dimension perovskite solar cell, the perovskite absorbed layer of the solar cell is C
(NH2)3I、CH3NH3I and PbI2Mixture be added to CH during the preparation process3NH3Cl is as additive, compared to previous
Two-dimentional perovskite device, CH3NH3The addition of Cl additive can reduce crystalline rate, and facilitating crystallization process is the mistake that gradient is formed
Journey, crystalline rate reduce, so that crystallization time extends, to form the gradient distribution of quantum well in perovskite thin film (QWs), In
There is preferable thickness distribution in film, is calculated (GA) (MA) using based on density functional theory (DFT)nPbnI3n+1(n=1,2,
3 ...) Crystallization energy (Δ H), as n value reduces, (such as Figure 10, n value are lower, and Δ H value is lower, corresponding n=3,2 and 1, Δ H
Value gradually decreases, from -0.004 to -0.356eV), the lower Crystallization can be the more stable, therefore lower n value preferentially forms, with
The progress of time, higher n value gradually form, and eventually form body phase, increase the effective gradient distribution of different n values, improve
Charge transfer efficiency greatly improves the crystalline quality of perovskite thin film, increases crystallite dimension, reduces the film to be formed
Defect, reduce Carrier recombination brought by grain boundaries defect loss so that carrier lifetime is increased；It is final direct
The promotion for determining the incident photon-to-electron conversion efficiency of perovskite battery device, improves the series and parallel compensated resistance of device, and is finally obtained
18.48% incident photon-to-electron conversion efficiency.Its excellent photoelectric properties and device efficiency will be helpful to that perovskite solar cell is pushed to walk
To business application.
The invention also discloses a kind of preparation method of ACI type two dimension perovskite solar cell, the preparation method relative to
Traditional perovskite preparation method, the perovskite thin film of high quality big crystal grain is prepared by solwution method, to realize solar cell
The significantly promotion of efficiency optimizes component proportion in perovskite precursor liquid, selects n,N-Dimethylformamide (DMF), dimethyl
Sulfoxide (DMSO) mixed solvent, with the MACl (CH of various concentration3NH3Cl) ACI type two dimension perovskite forerunner is prepared as additive
Liquid joined CH in precursor liquid together3NH3Cl additive, so that in perovskite absorbed layer forming process, CH3NH3Cl addition
Agent is able to ascend the crystalline quality of perovskite thin film.
Further, PbI2、C(NH2)3I、CH3NH3I and molar ratio are 3:3:1, and then configure final (GA) (MA)nPbnI3n+1(n=3) the perovskite absorbed layer of form.
[Detailed description of the invention]
Fig. 1 is that the embodiment of the present invention 1 includes to prepare in additive MACl and embodiment 6 without additive MACl (0mg/mL)
Perovskite solar cell incident photon-to-electron conversion efficiency comparison diagram.
Fig. 2 is that the embodiment of the present invention 1 includes to prepare in additive MACl and embodiment 6 without additive MACl (0mg/mL)
Perovskite solar cell external quantum efficiency comparison diagram.
(a) figure in Fig. 3 is that the embodiment of the present invention 1 includes in additive MACl and embodiment 6 without additive MACl
Perovskite absorbed layer surface Scanning Electron microscope (SEM) comparison diagram of (0mg/mL) preparation；(b) figure in Fig. 3 is the present invention
The perovskite solar cell cross-sectional scans electron microscope of method described in example and tradition without additive MACl (0mg/mL) preparation；
(a) figure in Fig. 4 is to unite containing 0.37mol/mL (10mg/mL) in different temperatures efficiency in the embodiment of the present invention 1
Score Butut；Fig. 4 (b) is at 150 DEG C, the Efficiency Statistics distribution containing various concentration MACl additive.
Fig. 5 is the perovskite thin film UV absorption comparison diagram prepared in embodiment 5- embodiment 8 in the present invention.
Fig. 6 is the perovskite thin film steady-state fluorescence comparison diagram prepared in embodiment 5- embodiment 8 in the present invention.
Fig. 7 is the perovskite thin film life span comparison figure prepared in embodiment 5- embodiment 8 in the present invention.
(a) figure in Fig. 8 is the TA spectrum of the ACI film for preparing in embodiment 5- embodiment 8 in t=1ps with bottom
Light activated variation；(b) figure is the half-peak breadth mutually bleached of high n-value of the ACI film prepared in embodiment 5- embodiment 8.
Fig. 9 is the mutually ultrafast transient absorption of body (TA) dynamic process figure of the film containing various concentration of bottom excitation.
Figure 10 is the theoretical calculation figure that different n values form energy.
Figure 11 is ACI film XRD diagram prepared by embodiment 5- embodiment 8.
[specific embodiment]
The invention will be described in further detail in the following with reference to the drawings and specific embodiments, and the invention discloses a kind of ACI
Type two dimension perovskite solar cell and preparation method thereof.The preparation method of the perovskite solar cell the following steps are included:
(1) preparation of perovskite precursor liquid: lead iodide (PbI is mixed according to molar ratio 3:1:3:(0-0.74)2), guanidine hydrogen iodine
Hydrochlorate C (NH2)3I, methylpyridinium iodide ammonium (CH3NH3) and chlorination methylamine (CH I3NH3Cl) (MACl) is used as solute, and solute is dissolved in
The volume proportion of the in the mixed solvent of dimethyl sulfoxide (DMSO) and n,N-Dimethylformamide (DMF), DMSO and DMF be (1~
10): (1~10), being configured to concentration is 1.1~1.3M mixed solution；Mixed solution is placed at 60 DEG C and is stirred 6 hours or more,
Then it is spare clear perovskite precursor liquid to be obtained by filtration with the Teflon filtration film in 0.45 μm of aperture.
(2) it cleans FTO substrate of glass: choosing the SnO of doping fluorine2(FTO) transparent conducting glass (2.5*2.5cm2), respectively
It is cleaned by ultrasonic 30min using acetone, isopropanol, ethyl alcohol and ultrapure water, then with nitrogen gun drying UV ozone processing 10~15
Minute is stand-by, prepares FTO substrate.
(3) dense form TiO is prepared2Electron transfer layer
The preparation of transport layer: by TiCl4Solution TiCl by volume4:H2O=0.0225:1 is added dropwise to ice and water
In mixture, guarantee that the reaction temperature of dilution is always 0 DEG C, electron transfer layer precursor liquid is made, and will be before after dilution
It drives liquid and pours into culture dish and flood FTO glass；Culture dish is placed on 70 DEG C of isothermal reactions 50 in electric drying oven with forced convection later
It~60 minutes, is rinsed after taking-up with water and ethyl alcohol, carries out annealing 20~30 minutes with 180~200 DEG C later, and using purple
Outer ozone treatment 5~10 minutes obtains fine and close TiO2Film, the electron transfer layer as device.
(4) perovskite absorbed layer is prepared
60~70 μ L are pipetted, 1.1~1.3M's, perovskite precursor liquid is uniformly coated on TiO2On film；Spin coating proceeding packet
Kuo Liangge workshop section, respectively 100-1000rpm, 1-10s and 1000-4000rpm, 10-60s；Terminating also to remain 10 apart from spin coating
When~30s, 100~300 μ l chlorobenzenes are added dropwise on perovskite surface, later carry out the perovskite thin film being prepared at annealing
Reason, annealing temperature are 100~150 DEG C, and annealing time is 10~60 minutes, in TiO2Perovskite absorbed layer is prepared on film；
The structure that perovskite absorbs is (GA) (MA)nPbnI3n+1(n=3), wherein GAI is C (NH2)3 +, MAI CH3NH3 +。
(5) Spiro-OMeTAD hole transmission layer is prepared
It is 1mL in volume, concentration is that (10-40) μ L is added in the chlorobenzene solution of 90mg/mL Spiro-OMeTAD to match in advance
The double trifluoromethanesulfonimide lithium solution (Li-TFSI solution) (520mg/mL) set and (10-50) μ L tert .-butylpyridine are molten
Liquid (tBP) solution, room temperature are protected from light 5~6h of stirring, then with the Teflon filtration film filtering in 0.45 μm of aperture, obtain
Spiro-OMeTAD solution；Perovskite thin film after annealing is down to room temperature, with 5000rpm, the revolving speed of 30s is by Spiro-
OMeTAD solution is spin-coated on perovskite-based bottom, obtains hole transmission layer, is protected from light kept dry 5~6 hours, is absorbed in perovskite
Spiro-OMeTAD hole transmission layer is made on layer.
(6) metal electrode is deposited: by FTO substrate/TiO2Electron transfer layer/perovskite absorbed layer/Spiro-OMeTAD is empty
Cave transmission layer device is transferred in evaporating compartment room, and 100~120nm is deposited on Spiro-OMeTAD hole transmission layer using hot steaming method
Thick metal electrode, the cell active area of mask plate are 0.09cm2, the material of the metal electrode is Au, Cu or Ag.
The test of battery device incident photon-to-electron conversion efficiency: at room temperature, the sun optical mode of 2400 model of Keithley company is used
Quasi- device is 100mW/cm in light intensity2Battery efficiency test is carried out under the conditions of (AM 1.5G), sweep speed is 0.3~0.4V/s,
Delay time is 10-50ms, and the step width of scanning is 0.01~0.02V.
Perovskite solar cell is prepared by above-mentioned preparation process, the structure of device is followed successively by FTO substrate, TiO2Electronics
Transport layer, perovskite absorbed layer, Spiro-OMeTAD and Au electrode.It is real by the solvent burden ratio in control perovskite precursor liquid
The perovskite thin film preparation of existing high quality big crystal grain is conducive to the performance for further promoting perovskite battery device.
Perovskite battery of the invention is described further below with reference to embodiment:
Embodiment 1
(1) preparation of perovskite precursor liquid: according to molar ratio 3:1:3:0.37 mixing PbI2、C(NH2)3I、CH3NH3I and
CH3NH3Cl is as solute, according to volume ratio 1:10 mixing DMSO and DMF as solvent, is configured to the perovskite that concentration is 1.2M
Precursor liquid, wherein CH in solute3NH3Concentration of the Cl in perovskite precursor liquid is 10mg/mL.
(2) FTO substrate of glass is cleaned, the 2.5*2.5cm that area is is chosen2FTO electro-conductive glass as substrate, make respectively
With acetone, isopropanol, ethyl alcohol and ultrapure water be cleaned by ultrasonic 30min, then dried up with nitrogen gun, UV ozone handle 15 minutes to
With preparing FTO substrate.
(3) dense form TiO is prepared2Electron transfer layer
By TiCl4Solution TiCl by volume4:H2O=0.0225:1 is added dropwise in mixture of ice and water, guarantees dilution
The reaction temperature of process is always 0 DEG C, and the precursor liquid after dilution is poured into culture dish and floods FTO glass；It later will culture
Ware be placed in electric drying oven with forced convection 70 DEG C isothermal reaction 60 minutes, rinsed after taking-up with water and ethyl alcohol, later with 200 DEG C
It carries out annealing 30 minutes, and is handled 10 minutes using UV ozone, obtain fine and close TiO2Film, the electronics as device
Transport layer.
(4) perovskite absorbed layer is prepared
The perovskite precursor liquid for pipetting 70 μ L, 1.2M is uniformly coated on TiO2On film；Spin coating proceeding includes two works
Section, respectively 500rpm, 3s and 4000rpm, 60s；When terminating also to remain 15s apart from spin coating, 300 μ L chlorobenzenes are added dropwise in perovskite
On surface, the perovskite thin film being prepared is made annealing treatment later, annealing conditions are to anneal 15 minutes at 150 DEG C.
(5) Spiro-OMeTAD hole transmission layer is prepared
It is 1mL in volume, it is preconfigured that 22 μ L are added in the chlorobenzene solution that concentration is 90mg/mL Spiro-OMeTAD
Li-TFSI solution (520mg/mL) and 36 μ L tBP solution, room temperature is protected from light stirring 6h, then with the polytetrafluoro in 0.45 μm of aperture
The filtering of ethylene filter membrane, obtains Spiro-OMeTAD solution；Perovskite thin film after annealing is down to room temperature, with 5000rpm,
Spiro-OMeTAD solution is spin-coated on perovskite-based bottom by the revolving speed of 30s, is protected from light kept dry 8 hours, and Spiro- is made
OMeTAD hole transmission layer.
(6) Au electrode is deposited: by FTO substrate/TiO2Electron transfer layer/perovskite absorbed layer/hole Spiro-OMeTAD
The device of transport layer is transferred in evaporating compartment room, uses the Au electrode of thermal evaporation vapor deposition 80nm thickness, the battery significant surface of mask plate
Product is 0.09cm2。
The photoelectric conversion efficiency for the perovskite solar cell that the present embodiment is prepared is 18.48%；The embodiment and implementation
The photoelectric conversion efficiency comparison for the perovskite solar cell that example 6 is prepared is as shown in Figure 1；As can be seen from the figure after MACl being added
ACI perovskite solar battery can produce by 10mg/mL additive 18.48% PCE (PCEmax) (table 1), VocFor
1.14V,JscFor 22.26mA cm-2, FF 72.67%.And the efficiency of embodiment 6 (0mg/mL) is 15.78%, VocFor
1.14V1.10V,JscFor 20.90mA cm-2, FF 67.20%.
As can be seen from Figure 2 external quantum efficiency (EQE) spectrum is shown, relative to embodiment 6 (0mg/mL), after optimization
Device is in~510-670nm and the place~720-770nm with higher intensity, wherein photoelectric current is respectively from low n QWs (n
=1-4) and high n QWs or said three-dimensional body phase in the photon that absorbs.This result shows that, charge-extraction layer is right in the battery after optimization
The extraction effect for the charge that low n and high n QWs or 3D body generate is better than initial devices, leads to integrated JscIncrease to from 20.25
21.17mA cm-2
As can be seen from Figure 3 relative to comparative sample (0mg/mL), the perovskite thin film pattern after optimization is more smooth, brilliant
Particle size is bigger.
Embodiment 2
In step (4), the annealing conditions of perovskite thin film are as follows: be slowly warming up to 100 DEG C from 40 DEG C, finally moved back at 100 DEG C
Fire 10 minutes；Other steps are same as Example 1.
Embodiment 3
In step (4), the annealing conditions of perovskite thin film are as follows: temperature is 100 DEG C, and the time is 10 minutes；Other steps with
Embodiment 1 is identical.
Embodiment 4
In step (4), the annealing conditions of perovskite thin film are as follows: temperature is 120 DEG C, is annealed 10 minutes；Other steps and reality
It is identical to apply example 1.
Embodiment 5
In step (4), the annealing conditions of perovskite thin film are as follows: temperature is 150 DEG C, is annealed 10 minutes；Other steps and reality
It is identical to apply example 1.
Embodiment 6
Solute PbI in step (1), in perovskite precursor liquid2、C(NH2)3I、CH3NH3I and CH3NH3The molar ratio of Cl is
3:1:3:0；Remaining step and parameter and embodiment 5 are identical.
Embodiment 7
Solute PbI in step (1), in perovskite precursor liquid2、C(NH2)3I、CH3NH3I and CH3NH3The molar ratio of Cl is
3:1:3:0.185 wherein CH3NH3Concentration of the Cl in perovskite precursor liquid is 5mg/mL；Remaining step and parameter and embodiment 5
It is identical.
Embodiment 8
Solute PbI in step (1), in perovskite precursor liquid2、C(NH2)3I、CH3NH3I and CH3NH3The molar ratio of Cl is
3:1:3:0.74 wherein CH3NH3Concentration of the Cl in perovskite precursor liquid is 20mg/mL；Remaining step and parameter and embodiment 5
It is identical.
The highest photoelectric conversion efficiency of embodiment 1- embodiment 8 is as shown in table 1 below:
The highest photoelectric conversion efficiency of perovskite solar cell under the conditions of 1 embodiment 1-8 different parameters of table
As can be seen from the above table, (a) figure in comparative example 5-8 and embodiment 1-4 and Fig. 4 can be seen that In
In the case that other parameters are constant, the raising of annealing temperature is conducive to the raising of photoelectric conversion efficiency, analyzes reason are as follows: temperature
It increases, conducive to the removal of MACl；Comparative example 5-8, (b) figure in Fig. 4 it can be found that other parameters inconvenience situation
Under, when the concentration of MACl is 10mg/mL, photoelectric conversion efficiency highest；When the concentration of MACl is 20mg/mL, photoelectric conversion
Efficiency reduces, and analyzes reason are as follows: when MACl content is more than 10mg/mL, has (006) and (Figure 11) occurs in (008) face, and PL
Peak blue shift description defect increases, this is all detrimental to charge-trapping and transmission.
Different addition concentration ACI perovskites (GA) (MA) are given from Fig. 5nPbnI3n+1(<n>=3) film it is ultraviolet-
Visible absorption spectra.It can be seen that all films are shown and MAPbI3Belt edge similar in ontology phase absorbs position, shows
There are ontology phases.Within the scope of~660~740nm, the absorption intensity of ACI film is slightly reduced.
As can be seen from Figure 6 luminescence generated by light (PL) spectrum shows leading transmitting in body phase, in n=2 and 3QWs
There is additional acromion.With the increase of addition concentration, the emissive porwer of n=2 and 3QWs are continuously increased, and illustrate the n=in ACI film
The concentration of 2 and n=3QWs is higher.As additive concentration increases to 5mg/mL, 10mg/mL and 20mg/mL, the hair of body phase from 0
Peak position is penetrated to change between 760~754nm, 754nm and 766nm respectively.When adding a small amount of (≤10mg/mL) additive,
The blue shift of body transmitting is attributed to defect reduction, and when additive level is greater than (10mg/mL), red shift, description defect increases.
As can be seen from Figure 7 when 10mg/mL, TRPL longest-lived, description defect is minimum.…
As can be seen from Figure 8 (a) is that TA spectrum of the ACI film of different addition concentration in t=1ps swashs with bottom light
The variation of hair, (b) half-peak breadth that the high n-value of the ACI film of different addition concentration is mutually bleached.
As can be seen from Figure 9 the body phase TA dynamics of the film containing various concentration of bottom excitation, 10mg/mL transfer
Charge it is more efficient.
Embodiment 9
In step (1), perovskite Concentration of precursor solution is 1.1M, the detailed process of step (4) are as follows: 70 μ L are pipetted, 1.1M's
Perovskite precursor liquid is uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 100rpm, 10s with
1000rpm, 50s；When terminating also to remain 30s apart from spin coating, 300 μ L chlorobenzenes are added dropwise on perovskite surface, will be prepared into later
To perovskite thin film made annealing treatment, annealing conditions be 150 DEG C anneal 50 minutes；In step (5), Spiro-OMeTAD
Chlorobenzene solution, Li-TFSI solution and tBp volume ratio be 1mL:10 μ L:10 μ L.
Remaining step is same as Example 1.
Embodiment 10
In step (1), PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixing molar ratio of Cl be 3:1:3:0.2, DMSO and
The volume ratio of DMF is 1:5, and perovskite Concentration of precursor solution is 1.3M, the detailed process of step (4) are as follows: pipette the calcium of 70 μ L, 1.3M
Titanium ore precursor liquid is uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 1000rpm, 1s with
2000rpm, 20s；When terminating also to remain 10s apart from spin coating, 100 μ L chlorobenzenes are added dropwise on perovskite surface, will be prepared into later
To perovskite thin film made annealing treatment, annealing conditions be 150 DEG C anneal 60 minutes；In step (5), Spiro-OMeTAD
Chlorobenzene solution, Li-TFSI solution and tBp volume ratio be 1mL:40 μ L:50 μ L.
Remaining step is same as Example 1.
Embodiment 11
In step (1), PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixing molar ratio of Cl be 3:1:3:0.3, DMSO and
The volume ratio of DMF is 1:7, and perovskite Concentration of precursor solution is 1.1M, the detailed process of step (4) are as follows: pipette the calcium of 70 μ L, 1.1M
Titanium ore precursor liquid is uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 300rpm, 8s with
3000rpm, 30s；When terminating also to remain 15s apart from spin coating, 150 μ L chlorobenzenes are added dropwise on perovskite surface, will be prepared into later
To perovskite thin film made annealing treatment, annealing conditions be 140 DEG C anneal 20 minutes；In step (5), Spiro-OMeTAD
Chlorobenzene solution, Li-TFSI solution and tBp volume ratio be 1mL:15 μ L:25 μ L.
Remaining step is same as Example 1.
Embodiment 12
In step (1), PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixing molar ratio of Cl be 3:1:3:0.4, DMSO and
The volume ratio of DMF is 1:2, and perovskite Concentration of precursor solution is 1.3M, the detailed process of step (4) are as follows: pipette the calcium of 70 μ L, 1.3M
Titanium ore precursor liquid is uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 800rpm, 2s with
3000rpm, 10s；When terminating also to remain 25s apart from spin coating, 250 μ L chlorobenzenes are added dropwise on perovskite surface, will be prepared into later
To perovskite thin film made annealing treatment, annealing conditions be 130 DEG C anneal 30 minutes；In step (5), Spiro-OMeTAD
Chlorobenzene solution, Li-TFSI solution and tBp volume ratio be 1mL:30 μ L:20 μ L.
Remaining step is same as Example 1.
Embodiment 13
In step (1), PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixing molar ratio of Cl be 3:1:3:0.5, DMSO and
The volume ratio of DMF is 10:1, and perovskite Concentration of precursor solution is 1.25M, the detailed process of step (4) are as follows: pipette 70 μ L, 1.25M
Perovskite precursor liquid be uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 200rpm, 7s with
1500rpm, 45s；When terminating also to remain 20s apart from spin coating, 200 μ L chlorobenzenes are added dropwise on perovskite surface, will be prepared into later
To perovskite thin film made annealing treatment, annealing conditions be 100 DEG C anneal 60 minutes；In step (5), Spiro-OMeTAD
Chlorobenzene solution, Li-TFSI solution and tBp volume ratio be 1mL:20 μ L:30 μ L.
Remaining step is same as Example 1.
Embodiment 14
In step (1), PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixing molar ratio of Cl be 3:1:3:0.6, DMSO and
The volume ratio of DMF is 1:5, and perovskite Concentration of precursor solution is 1.3M, the detailed process of step (4) are as follows: pipette the calcium of 70 μ L, 1.3M
Titanium ore precursor liquid is uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 400rpm, 6s with
2500rpm, 50s；When terminating also to remain 22s apart from spin coating, 220 μ L chlorobenzenes are added dropwise on perovskite surface, will be prepared into later
To perovskite thin film made annealing treatment, annealing conditions be 120 DEG C anneal 50 minutes；In step (5), Spiro-OMeTAD
Chlorobenzene solution, Li-TFSI solution and tBp volume ratio be 1mL:35 μ L:15 μ L.
Remaining step is same as Example 1.
Embodiment 15
In step (1), PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixing molar ratio of Cl be 3:1:3:0.7, DMSO and
The volume ratio of DMF is 1:8, and perovskite Concentration of precursor solution is 1.15M, the detailed process of step (4) are as follows: 70 μ L are pipetted, 1.15M's
Perovskite precursor liquid is uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 600rpm, 4s with
3500rpm, 40s；When terminating also to remain 24s apart from spin coating, 240 μ L chlorobenzenes are added dropwise on perovskite surface, will be prepared into later
To perovskite thin film made annealing treatment, annealing conditions be 110 DEG C anneal 45 minutes；In step (5), Spiro-OMeTAD
Chlorobenzene solution, Li-TFSI solution and tBp volume ratio be 1mL:25 μ L:40 μ L.
Remaining step is same as Example 1.
Embodiment 16
In step (1), PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixing molar ratio of Cl is 3:1:3:0.74, DMSO
Volume ratio with DMF is 10:3, and perovskite Concentration of precursor solution is 1.12M, the detailed process of step (4) are as follows: 70 μ L are pipetted,
The perovskite precursor liquid of 1.12M is uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 700rpm,
3s and 1200rpm, 55s；When terminating also to remain 26s apart from spin coating, 200 μ L chlorobenzenes are added dropwise on perovskite surface, it later will system
Standby obtained perovskite thin film is made annealing treatment, and annealing conditions are to anneal 40 minutes at 120 DEG C；In step (5), Spiro-
The volume ratio of the chlorobenzene solution of OMeTAD, Li-TFSI solution and tBp is 1mL:15 μ L:35 μ L.
Remaining step is same as Example 1.
Embodiment 17
In step (1), PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixing molar ratio of Cl is 3:1:3:0.55, DMSO
Volume ratio with DMF is 10:6, and perovskite Concentration of precursor solution is 1.16M, the detailed process of step (4) are as follows: 70 μ L are pipetted,
The perovskite precursor liquid of 1.16M is uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 900rpm,
2s and 2800rpm, 25s；When terminating also to remain 13s apart from spin coating, 120 μ L chlorobenzenes are added dropwise on perovskite surface, it later will system
Standby obtained perovskite thin film is made annealing treatment, and annealing conditions are to anneal 30 minutes at 130 DEG C；In step (5), Spiro-
The volume ratio of the chlorobenzene solution of OMeTAD, Li-TFSI solution and tBp is 1mL:20 μ L:45 μ L.
Remaining step is same as Example 1.
Embodiment 18
In step (1), PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixing molar ratio of Cl is 3:1:3:0.35, DMSO
Volume ratio with DMF is 10:10, and perovskite Concentration of precursor solution is 1.22M, the detailed process of step (4) are as follows: 70 μ L are pipetted,
The perovskite precursor liquid of 1.22M is uniformly coated on TiO2On film；Spin coating proceeding includes Liang Ge workshop section, respectively 500rpm,
5s and 3400rpm, 15s；When terminating also to remain 18s apart from spin coating, 160 μ L chlorobenzenes are added dropwise on perovskite surface, it later will system
Standby obtained perovskite thin film is made annealing treatment, and annealing conditions are to anneal 12 minutes at 140 DEG C；In step (5), Spiro-
The volume ratio of the chlorobenzene solution of OMeTAD, Li-TFSI solution and tBp is 1mL:35 μ L:40 μ L.
Remaining step is same as Example 1.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of ACI type two dimension perovskite solar cell, which is characterized in that including FTO substrate, the electricity stacked gradually from top to bottom
Sub- transport layer, perovskite absorbed layer, hole transmission layer and metal electrode；The perovskite absorbed layer is (GA) (MA)nPbnI3n+1
(n=3), wherein GA is C (NH2)3 +, MAI CH3NH3 +；Being added in perovskite absorbed layer preparation process has CH3NH3Cl, which is used as, to be added
Add agent.
2. a kind of ACI type two dimension perovskite solar cell according to claim 1, which is characterized in that the ACI type two dimension
The highest photoelectric conversion efficiency of perovskite solar cell is 18.5%.
3. a kind of preparation method of ACI type two dimension perovskite solar cell, which comprises the following steps:
Step 1, FTO substrate of glass is cleaned, FTO substrate is made；
Step 2, electron transfer layer is prepared on FTO substrate；
Step 3, on the electron transport layer by the spin coating of perovskite precursor liquid, perovskite absorbed layer is prepared；The perovskite forerunner
The solute of liquid is PbI2、C(NH2)3I、CH3NH3I and CH3NH3The mixture of Cl, solvent are the mixture of DMSO and DMF；
Step 4, hole transmission layer is prepared on perovskite absorbed layer；
Step 5, metal electrode is prepared on the hole transport layer.
4. a kind of preparation method of ACI type two dimension perovskite solar cell according to claim 3, which is characterized in that step
In rapid 3, the concentration of solute is 1.1~1.3M in the perovskite precursor liquid.
5. a kind of preparation method of ACI type two dimension perovskite solar cell according to claim 3, which is characterized in that step
In rapid 3, PbI in solute2、C(NH2)3I、CH3NH3I and CH3NH3The molar ratio of Cl are as follows: 3:1:3:(0-0.74).
6. a kind of preparation method of ACI type two dimension perovskite solar cell according to claim 3, which is characterized in that step
In rapid 3, the volume ratio of DMSO and DMF is (1~10): (1~10) in solvent.
7. a kind of preparation method of ACI type two dimension perovskite solar cell according to claim 3, which is characterized in that step
In rapid 3, the spin-coating method is divided into two stages, and first stage revolving speed is 100-1000rpm, spin-coating time 1-10s；Second-order
Section revolving speed is 1000-4000rpm, spin-coating time 10-60s；When second stage spin coating terminates 10~30s of residue, it is added dropwise 100
~300 μ L chlorobenzenes make annealing treatment obtained perovskite thin film on perovskite surface, and annealing temperature is 100~150 DEG C,
Annealing time is 10~60min, prepares perovskite absorbed layer on the electron transport layer.
8. a kind of preparation method of ACI type two dimension perovskite solar cell according to claim 3, which is characterized in that step
In rapid 2, the preparation process of electron transfer layer are as follows: by TiCl4It instills in ice water, electron transfer layer precursor liquid is made；By FTO substrate
It is submerged in electron transfer layer precursor liquid, is taken out after being reacted in dry environment and be attached with TiO2FTO substrate, after annealing
TiO is prepared on FTO substrate2Film is as electron transfer layer.
9. a kind of preparation method of ACI type two dimension perovskite solar cell according to claim 3, which is characterized in that step
In rapid 4, hole transmission layer is prepared by the way that Spiro-OMeTAD solution to be spin-coated on perovskite absorbed layer, the Spiro-
OMeTAD solution is by the chlorobenzene solution, Li-TFSI solution and tBP solution of Spiro-OMeTAD according to volume ratio 1mL:(10-40) μ
L:(10-50) μ L is configured.
10. according to the preparation method of ACI type two dimension perovskite solar cell described in claim 3-9 any one, feature
It is, in step 5, by hot steaming method, evaporation metal electrode, the metal electrode are Au, Ag or Cu on the hole transport layer.
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| CN112968134A (en) * | 2021-02-03 | 2021-06-15 | 陕西师范大学 | Perovskite solar cell with molten salt auxiliary crystallization and preparation method thereof |
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| CN113380951A (en) * | 2021-05-18 | 2021-09-10 | 泰山学院 | Perovskite solar cell based on green anti-solvent method and preparation method thereof |
| CN114031310A (en) * | 2021-11-08 | 2022-02-11 | 太原理工大学 | Method for regulating growth of gradient phase-change type all-inorganic perovskite thin film by two-dimensional perovskite substrate |
| CN114031310B (en) * | 2021-11-08 | 2023-09-19 | 太原理工大学 | Method for regulating growth gradient phase-change type all-inorganic perovskite film through two-dimensional perovskite substrate |
| LU501865B1 (en) * | 2022-01-21 | 2023-07-24 | Univ Hubei Arts & Science | An efficient inorganic hybrid perovskite ink and its application |
| WO2023234601A1 (en) * | 2022-05-31 | 2023-12-07 | 한화솔루션(주) | Coating agent for forming large-area perovskite thin film and method for forming perovskite thin film using same |
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