CN110518128B - ACI type two-dimensional perovskite solar cell and preparation method thereof - Google Patents
ACI type two-dimensional perovskite solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ACI type two-dimensional perovskite solar cell and a preparation method thereof, wherein a perovskite absorption layer of the solar cell is C (NH) 2 ) 3 I、CH 3 NH 3 I and PbI 2 Is added with CH during the preparation process 3 NH 3 Cl is used as an additive, compared with the prior two-dimensional perovskite device, CH 3 NH 3 The addition of the Cl additive greatly improves the crystallization quality of the perovskite thin film, increases the grain size, reduces the carrier recombination loss caused by defects at grain boundaries, prolongs the service life of carriers, increases the effective gradient distribution of different n values, improves the charge transmission efficiency, and finally directly determines the improvement of the photoelectric conversion efficiency of the perovskite battery device, improves the series-parallel resistance of the device, and finally obtains 18.48% of photoelectric conversion efficiency. Its excellent photovoltaic properties and device efficiency will help drive perovskite solar cells towards commercial applications.
Description
[ field of technology ]
The invention belongs to the technical field of solar photovoltaic, and particularly relates to an ACI type two-dimensional perovskite solar cell and a preparation method thereof.
[ background Art ]
In recent years, organic-inorganic hybrid perovskite solar cells have received a great deal of attention for their excellent photoelectric properties, and the photoelectric conversion efficiency has been rapidly increased from 3.8% in 2009 to 25.2% at present. However, the conventional three-dimensional perovskite light and heat stability restricts the industrialization of photovoltaic devices. Compared with a three-dimensional perovskite solar cell, the two-dimensional perovskite solar cell has better stability, wherein Alternating Cationic (ACI) two-dimensional metal halide perovskite materials have great potential in the photovoltaic field, however, factors such as low carrier mobility, irregular crystal orientation, higher film defect state density and the like of a two-dimensional perovskite film in the solar cell still cause low device efficiency, and the industrialization process of the solar cell is severely restricted.
[ invention ]
The invention aims to overcome the defects of the prior art and provide an ACI type two-dimensional perovskite solar cell and a preparation method thereof; the technical problems of low carrier mobility, irregular crystal orientation and higher film defect state density of the ACI type two-dimensional perovskite solar cell are solved.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
an ACI type two-dimensional perovskite solar cell comprises an FTO substrate, an electron transport layer, a perovskite absorption layer, a hole transport layer and a metal electrode which are sequentially stacked from bottom to top; the perovskite absorption layer is (GA) (MA) n Pb n I 3n+1 (n=3), wherein GA is C (NH 2 ) 3 + MAI is CH 3 NH 3 + The method comprises the steps of carrying out a first treatment on the surface of the CH is added in the preparation process of the perovskite absorption layer 3 NH 3 Cl as an additive.
The invention further improves that:
preferably, the ACI-type two-dimensional perovskite solar cell has a maximum photoelectric conversion efficiency of 18.5%.
The preparation method of the ACI type two-dimensional perovskite solar cell comprises the following steps:
and 5, preparing a metal electrode on the hole transport layer.
Preferably, in step 3, the concentration of the solute in the perovskite precursor solution is 1.1 to 1.3M.
Preferably, in step 3, pbI in the solute 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The molar ratio of Cl is: 3:1:3: (0-0.74).
Preferably, in step 3, the volume ratio of DMSO to DMF in the solvent is (1-10): (1-10).
Preferably, in the step 3, the spin coating is divided into two stages, wherein the rotating speed of the first stage is 100-1000rpm, and the spin coating time is 1-10s; the second stage rotating speed is 1000-4000rpm, and the spin coating time is 10-60s; and (3) when the spin coating in the second stage is finished and the residual time is 10-30 seconds, 100-300 mu L of chlorobenzene is dripped on the surface of the perovskite, the obtained perovskite film is annealed at the annealing temperature of 100-150 ℃ for 10-60 minutes, and the perovskite absorption layer is prepared on the electron transport layer.
Preferably, in step 2, the electron transport layer is prepared by: tiCl is added to the mixture 4 Dripping into ice water to obtain electron transport layer precursor liquid; immersing FTO substrate in electron transport layer precursor solution, reacting in dry environment, and taking out the substrate with TiO 2 After annealing treatment, preparing TiO on the FTO substrate 2 The thin film serves as an electron transport layer.
Preferably, in step 4, the hole transport layer is prepared by spin-coating a Spiro-ome tad solution on the perovskite absorption layer, wherein the Spiro-ome tad solution is prepared from a chlorobenzene solution, a Li-TFSI solution and a tBP solution of Spiro-ome tad according to a volume ratio of 1mL: (10-40) μl: (10-50) mu L.
Preferably, in step 5, a metal electrode is deposited on the hole transport layer by thermal evaporation, wherein the metal electrode is Au, ag or Cu.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses an ACI type two-dimensional perovskite solar cell, wherein a perovskite absorption layer of the solar cell is C (NH) 2 ) 3 I、CH 3 NH 3 I and PbI 2 Is added with CH during the preparation process 3 NH 3 Cl is used as an additive, compared with the prior two-dimensional perovskite device, CH 3 NH 3 The addition of the Cl additive can reduce the crystallization rate, is favorable for the gradient formation process of the crystallization process, reduces the crystallization rate, prolongs the crystallization time, thereby forming the gradient distribution of Quantum Wells (QWs) in the perovskite film, has better thickness distribution in the film, and adopts the method based on the Density Functional Theory (DFT) for calculation (GA) (MA) n Pb n I 3n+1 (n=1, 2, 3 …) crystal formation energy (Δh), as the n value decreases (as in fig. 10, the lower the n value, the lower the Δh value, the corresponding n=3, 2 and 1, Δh values gradually decrease, from-0.004 to-0.356 eV), the lower the crystal formation energy is more stable, so that the lower n value preferentially forms, the higher n value gradually forms over time, and finally forms a bulk phase, increasing the effective gradient distribution of different n values, improving the charge transfer efficiency, greatly improving the crystal quality of the perovskite thin film, increasing the grain size, reducing the defects of the formed thin film, reducing the carrier recombination loss caused by the defects at the grain boundary, and increasing the carrier lifetime; and finally, the improvement of the photoelectric conversion efficiency of the perovskite battery device is directly determined, the series-parallel resistance of the device is improved, and the photoelectric conversion efficiency of 18.48% is finally obtained. Its excellent photovoltaic properties and device efficiency will help drive perovskite solar cells towards commercial applications.
The invention also discloses a preparation method of the ACI type two-dimensional perovskite solar cell, compared with the traditional perovskite preparation method, the preparation method prepares a perovskite film with high quality and large crystal grain by a solution method so as to greatly improve the efficiency of the solar cell, optimizes the component proportion in a perovskite precursor liquid, selects mixed solvents of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and uses MACl (CH 3 NH 3 Cl) as an additive to prepare ACI type two-dimensional perovskite precursor liquidAdding CH into the liquid 3 NH 3 Cl additives such that during formation of the perovskite absorber layer CH 3 NH 3 The Cl additive can improve the crystallization quality of the perovskite thin film.
Further, pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 The molar ratio of I to 3:3:1, and finally (GA) (MA) was prepared n Pb n I 3n+1 Perovskite absorber layer in the form of (n=3).
[ description of the drawings ]
FIG. 1 is a graph comparing the photoelectric conversion efficiency of perovskite solar cell prepared according to example 1 of the present invention containing additive MACl and example 6 without additive MACl (0 mg/mL).
FIG. 2 is a graph comparing the external quantum efficiency of perovskite solar cell prepared according to example 1 of the invention containing additive MACl with example 6 without additive MACl (0 mg/mL).
FIG. 3 (a) is a graph showing the comparison of the surface Scanning Electron Microscope (SEM) of a perovskite absorber layer prepared according to example 1 of the present invention containing additive MACl and example 6 without additive MACl (0 mg/mL); FIG. 3 (b) is a cross-sectional scanning electron microscope image of a perovskite solar cell prepared by the method described in the example of the invention and a conventional additive-free MACl (0 mg/mL);
FIG. 4 (a) is a graph showing the statistical distribution of the efficiency of 0.37mol/mL (10 mg/mL) at various temperatures in example 1 of the present invention; FIG. 4 (b) is a statistical distribution of the efficiency of MACl additives at 150 ℃.
FIG. 5 is a graph showing the ultraviolet absorption of perovskite thin films prepared in example 5 to example 8 according to the present invention.
FIG. 6 is a graph showing steady-state fluorescence contrast of perovskite thin films prepared in example 5 to example 8 according to the present invention.
FIG. 7 is a graph showing the comparison of the lifetime of perovskite thin films prepared in example 5 to example 8 in the present invention.
Fig. 8 (a) is a graph showing TA spectra at t=1ps of the ACI films prepared in examples 5 to 8 as a function of bottom photoexcitation; (b) The graph shows the half-width of the high n-value phase bleaching of the ACI films prepared in examples 5-8.
Fig. 9 is a graph of bulk ultra-fast Transient Absorption (TA) kinetics for bottom excitation with films of varying concentrations.
Fig. 10 is a theoretical calculation of energy of formation for different values of n.
Fig. 11 is an ACI film XRD pattern of the preparation of example 5-example 8.
[ detailed description ] of the invention
The invention is further described in detail below with reference to the accompanying drawings and specific examples, and discloses an ACI type two-dimensional perovskite solar cell and a preparation method thereof. The preparation method of the perovskite solar cell comprises the following steps:
(1) Preparing perovskite precursor liquid: mixing lead iodide (PbI) at a molar ratio of 3:1:3 (0-0.74) 2 ) Guanidine hydroiodidate C (NH) 2 ) 3 I. Methyl ammonium iodide (CH) 3 NH 3 I) And methylamine Chloride (CH) 3 NH 3 Cl) (MACl) is taken as a solute, the solute is dissolved in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF), and the volume ratio of the DMSO to the DMF is (1-10): (1-10) preparing a mixed solution with a concentration of 1.1-1.3M; the mixed solution is stirred for more than 6 hours at 60 ℃, and then filtered by a polytetrafluoroethylene filter membrane with the pore diameter of 0.45 mu m to obtain clear perovskite precursor liquid for standby.
(2) Cleaning the FTO glass substrate: selecting fluorine doped SnO 2 (FTO) transparent conductive glass (2.5 x 2.5cm 2 ) Respectively using acetone, isopropanol, ethanol and ultrapure water for ultrasonic cleaning for 30min, and then using a nitrogen gun to blow-dry ultraviolet ozone for treatment for 10-15 min for standby, so as to prepare the FTO substrate.
(3) Preparation of compact TiO 2 Electron transport layer
Preparation of the transport layer: tiCl is added to the mixture 4 The solution is TiCl in volume ratio 4 :H 2 O=0.0225:1 is added dropwise into a mixture of ice and water, the reaction temperature in the dilution process is guaranteed to be 0 ℃ all the time, an electron transport layer precursor liquid is prepared, and the diluted precursor liquid is poured into a culture dish to submerge FTO glass; then placing the culture dish in an electrothermal blowing drying box for reaction at the constant temperature of 70 ℃ for 50-60 minutes, taking out, and then using water and waterWashing with ethanol, annealing at 180-200 deg.c for 20-30 min, and ultraviolet ozone treatment for 5-10 min to obtain compact TiO 2 A thin film, which serves as an electron transport layer for the device.
(4) Preparation of perovskite absorber layer
Transferring 60-70 mu L and 1.1-1.3M perovskite precursor liquid to uniformly coat the TiO 2 A film; the spin coating process comprises two working sections of 100-1000rpm,1-10s and 1000-4000rpm,10-60s respectively; when 10 to 30 seconds is left from the end of spin coating, 100 to 300 mu l of chlorobenzene is dripped on the surface of perovskite, and then the prepared perovskite film is annealed at the annealing temperature of 100 to 150 ℃ for 10 to 60 minutes, and the TiO is prepared 2 Preparing a perovskite absorption layer on the film; the perovskite is absorbed into a structure (GA) (MA) n Pb n I 3n+1 (n=3), wherein GAI is C (NH 2 ) 3 + MAI is CH 3 NH 3 + 。
(5) Preparation of a Spiro-OMeTAD hole transport layer
Adding (10-40) mu L of a pre-prepared bis (trifluoromethanesulfonyl) imide lithium solution (Li-TFSI solution) (520 mg/mL) and (10-50) mu L of a tert-butylpyridine solution (tBP) solution into a chlorobenzene solution with the volume of 1mL and the concentration of 90mg/mL of Spiro-OMeTAD, stirring at normal temperature and in a dark place for 5-6 h, and filtering with a polytetrafluoroethylene filtering membrane with the pore diameter of 0.45 mu m to obtain Spiro-OMeTAD solution; and (3) cooling the annealed perovskite film to room temperature, spin-coating the Spiro-OMeTAD solution on the perovskite substrate at 5000rpm for 30s to obtain a hole transport layer, drying and storing for 5-6 hours in a dark place, and obtaining the Spiro-OMeTAD hole transport layer on the perovskite absorption layer.
(6) Metal electrode evaporation: FTO substrate/TiO 2 The electron transport layer/perovskite absorption layer/Spiro-OMeTAD hole transport layer device is transferred into an evaporation cabin, a metal electrode with the thickness of 100-120 nm is evaporated on the Spiro-OMeTAD hole transport layer by using a thermal evaporation method, and the effective area of a battery of a mask is 0.09cm 2 The metal electrode is made of Au, cu or Ag.
Testing photoelectric conversion efficiency of a battery device: at the room temperature of the glass fiber reinforced plastic composite material,a model 2400 solar simulator from Keithley was used at an intensity of 100mW/cm 2 The battery efficiency test is carried out under the condition of (AM 1.5G), the scanning speed is 0.3-0.4V/s, the delay time is 10-50ms, and the scanning step width is 0.01-0.02V.
The perovskite solar cell is prepared through the preparation process, and the device has the structure of an FTO substrate and TiO in sequence 2 Electron transport layer, perovskite absorption layer, spiro-ome tad and Au electrode. The perovskite film preparation with high quality and large crystal grains is realized by controlling the solvent ratio in the perovskite precursor liquid, which is beneficial to further improving the performance of perovskite battery devices.
The perovskite battery of the present invention is further described below with reference to examples:
example 1
(1) Preparing perovskite precursor liquid: pbI was mixed in a molar ratio of 3:1:3:0.37 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 Cl is taken as solute, DMSO and DMF are mixed according to the volume ratio of 1:10 to be taken as solvent, and the perovskite precursor solution with the concentration of 1.2M is prepared, wherein CH in the solute 3 NH 3 The concentration of Cl in the perovskite precursor solution was 10mg/mL.
(2) Cleaning an FTO glass substrate, and selecting a glass substrate with an area of 2.5cm to 2.5cm 2 The FTO conductive glass is used as a substrate, acetone, isopropanol, ethanol and ultrapure water are respectively used for ultrasonic cleaning for 30min, then a nitrogen gun is used for blow-drying, and ultraviolet ozone treatment is carried out for 15 min for standby, so that the FTO substrate is prepared.
(3) Preparation of compact TiO 2 Electron transport layer
TiCl is added to the mixture 4 The solution is TiCl in volume ratio 4 :H 2 O=0.0225:1 is added dropwise into an ice-water mixture, the reaction temperature in the dilution process is guaranteed to be 0 ℃ all the time, and diluted precursor liquid is poured into a culture dish to submerge FTO glass; placing the culture dish in an electrothermal blowing drying oven, reacting at 70deg.C for 60min, taking out, washing with water and ethanol, annealing at 200deg.C for 30min, and treating with ultraviolet ozone for 10 min to obtain compact TiO 2 Thin film as electron of deviceA transport layer.
(4) Preparation of perovskite absorber layer
Removing 70 μl of 1.2M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections, namely 500rpm,3s and 4000rpm,60s respectively; after 300. Mu.L of chlorobenzene was dropped on the perovskite surface after 15s from the end of spin coating, the prepared perovskite thin film was annealed at 150℃for 15 minutes.
(5) Preparation of a Spiro-OMeTAD hole transport layer
Adding 22 mu L of a pre-prepared Li-TFSI solution (520 mg/mL) and 36 mu L of tBP solution into a chlorobenzene solution with the volume of 1mL and the concentration of 90mg/mL of Spiro-OMeTAD, stirring for 6 hours at normal temperature and in a dark place, and filtering by a polytetrafluoroethylene filtering membrane with the pore diameter of 0.45 mu m to obtain Spiro-OMeTAD solution; and (3) cooling the annealed perovskite film to room temperature, spin-coating the Spiro-OMeTAD solution on the perovskite substrate at 5000rpm for 30s, and drying and storing for 8 hours in a dark place to obtain the Spiro-OMeTAD hole transport layer.
(6) Au electrode evaporation: FTO substrate/TiO 2 The device of the electron transport layer/perovskite absorption layer/Spiro-OMeTAD hole transport layer is transferred into an evaporation cabin, an Au electrode with the thickness of 80nm is evaporated by using a thermal evaporation method, and the effective area of a battery of a mask is 0.09cm 2 。
The photoelectric conversion efficiency of the perovskite solar cell prepared by the embodiment is 18.48%; the photoelectric conversion efficiency pair of the perovskite solar cell prepared in this example and example 6 is shown in fig. 1; from the figure it can be seen that an ACI perovskite solar cell with MACl addition can produce 18.48% PCE (PCE) from 10mg/mL additive max ) (Table 1), V oc 1.14V, J sc 22.26mA cm -2 FF is 72.67%. Whereas the efficiency of example 6 (0 mg/mL) was 15.78%, V oc Is 1.14v1.10v, J sc 20.90mA cm -2 FF was 67.20%.
As can be seen from FIG. 2, the External Quantum Efficiency (EQE) spectrum shows that the optimized device has higher intensity at-510-670 nm and-720-770 nm relative to example 6 (0 mg/mL), where photocurrents are respectivelyPhotons absorbed from low n QWs (n=1-4) and high n QWs or three-dimensional bulk phases. This result shows that the charge extraction layer in the optimized cell has better extraction effect on the charges generated by low n and high n QWs or 3D bodies than the original device, resulting in integration J sc Increasing from 20.25 to 21.17mA cm -2
From FIG. 3, it can be seen that the morphology of the perovskite film after optimization is smoother and the grain size is larger than that of the comparative sample (0 mg/mL).
Example 2
In the step (4), the annealing conditions of the perovskite thin film are as follows: slowly heating from 40 ℃ to 100 ℃, and finally annealing at 100 ℃ for 10 minutes; the other steps were the same as in example 1.
Example 3
In the step (4), the annealing conditions of the perovskite thin film are as follows: the temperature is 100 ℃ and the time is 10 minutes; the other steps were the same as in example 1.
Example 4
In the step (4), the annealing conditions of the perovskite thin film are as follows: annealing for 10 minutes at 120 ℃; the other steps were the same as in example 1.
Example 5
In the step (4), the annealing conditions of the perovskite thin film are as follows: annealing for 10 minutes at 150 ℃; the other steps were the same as in example 1.
Example 6
In step (1), the solute PbI in the perovskite precursor solution 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The molar ratio of Cl is 3:1:3:0; the remaining steps and parameters were the same as in example 5.
Example 7
In step (1), the solute PbI in the perovskite precursor solution 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The molar ratio of Cl is 3:1:3:0.185, wherein CH 3 NH 3 The concentration of Cl in the perovskite precursor liquid is 5mg/mL; the remaining steps and parameters were the same as in example 5.
Example 8
In step (1), the solute PbI in the perovskite precursor solution 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The molar ratio of Cl is 3:1:3:0.74, wherein CH 3 NH 3 The concentration of Cl in the perovskite precursor solution is 20mg/mL; the remaining steps and parameters were the same as in example 5.
The highest photoelectric conversion efficiencies of examples 1 to 8 are shown in table 1 below:
table 1 examples 1-8 highest photoelectric conversion efficiency of perovskite solar cell under different parameter conditions
As can be seen from the above table, the comparison of examples 5 to 8 and examples 1 to 4 and the graph (a) in fig. 4 shows that the increase of the annealing temperature is advantageous for the improvement of the photoelectric conversion efficiency under the condition that other parameters are not changed, because: the temperature is increased, so that MACl can be removed; as can be seen from the graph (b) in FIG. 4, in the comparative examples 5 to 8, in the case of inconvenience of other parameters, the photoelectric conversion efficiency was highest when the concentration of MACl was 10 mg/mL; when the concentration of MACl is 20mg/mL, the photoelectric conversion efficiency is lowered, and the analysis is because: at MACl levels exceeding 10mg/mL, both (006) and (008) faces appear (FIG. 11), and the blue shift in PL indicates increased defects, both of which are detrimental to charge collection and transport.
From FIG. 5, ACI perovskite (GA) (MA) at various addition concentrations are given n Pb n I 3n+1 (<n>=3) uv-vis absorption spectrum of the film. It can be seen that all films exhibited a similar behavior to MAPbI 3 The band edge absorption locations where the bodies are similar indicate the presence of the body phase. The absorption strength of the ACI film is slightly reduced within the range of 660-740 nm.
From fig. 6 it can be seen that the Photoluminescence (PL) spectrum shows dominant emission in the bulk phase, with additional shoulders in n=2 and 3 QWs. As the additive concentration increased, the emission intensities of n=2 and 3QWs increased, indicating that the concentrations of n=2 and n=3 QWs were higher in the ACI film. As the additive concentration increased from 0 to 5mg/mL, 10mg/mL and 20mg/mL, the emission peak positions of the bulk phases varied between 760-754 nm, 754nm and 766nm, respectively. When small amounts (. Ltoreq.10 mg/mL) of additive were added, the blue shift of the body emission was attributed to defect reduction, and when the additive content was greater than (10 mg/mL), the red shift indicated defect increase.
As can be seen from FIG. 7, the TRPL life was the longest at 10mg/mL, indicating the least defects. …
From fig. 8, it can be seen that (a) TA spectrum at t=1ps for ACI films of different additive concentrations varies with bottom photoexcitation and (b) peak width at half of high n-value phase bleaching for ACI films of different additive concentrations.
From FIG. 9, it can be seen that the bottom-excited bulk TA kinetics of films containing different concentrations are more efficient at transferring charge at 10mg/mL.
Example 9
In the step (1), the concentration of the perovskite precursor solution is 1.1M, and the specific process of the step (4) is as follows: removing 70 μl of 1.1M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections of 100rpm,10s and 1000rpm,50s respectively; when 30s is left from the end of spin coating, 300 mu L of chlorobenzene is dripped on the surface of the perovskite, and then the prepared perovskite film is annealed under the annealing condition of annealing at 150 ℃ for 50 minutes; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1mL, 10. Mu.L, and 10. Mu.L.
The remaining steps were the same as in example 1.
Example 10
In step (1), pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The mixing mole ratio of Cl is 3:1:3:0.2, the volume ratio of DMSO and DMF is 1:5, the concentration of perovskite precursor solution is 1.3M, and the specific process of the step (4) is as follows: removing 70 μl of 1.3M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections of 1000rpm,1s and 2000rpm,20s respectively; when 10s remains from the end of spin coating, 100 mu L of chlorobenzene is dripped on the surface of the perovskite, and then the prepared perovskite film is annealed under the annealing condition of annealing at 150 ℃ for 60 minutes; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1mL, 40. Mu.L, and 50. Mu.L.
The remaining steps were the same as in example 1.
Example 11
In step (1), pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The mixing mole ratio of Cl is 3:1:3:0.3, the volume ratio of DMSO and DMF is 1:7, the concentration of perovskite precursor solution is 1.1M, and the specific process of the step (4) is as follows: removing 70 μl of 1.1M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections, 300rpm,8s and 3000rpm,30s respectively; when 15s is left from the end of spin coating, 150 mu L of chlorobenzene is dripped on the surface of the perovskite, and then the prepared perovskite film is annealed for 20 minutes at 140 ℃; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1mL, 15. Mu.L, 25. Mu.L.
The remaining steps were the same as in example 1.
Example 12
In step (1), pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The mixing mole ratio of Cl is 3:1:3:0.4, the volume ratio of DMSO and DMF is 1:2, the concentration of perovskite precursor solution is 1.3M, and the specific process of the step (4) is as follows: removing 70 μl of 1.3M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections, namely 800rpm,2s and 3000rpm,10s; when 25s remains from the end of spin coating, dropwise adding 250 mu L of chlorobenzene on the surface of the perovskite, and then annealing the prepared perovskite film for 30 minutes at 130 ℃; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1mL, 30. Mu.L, and 20. Mu.L.
The remaining steps were the same as in example 1.
Example 13
In step (1), pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The mixing mole ratio of Cl is 3:1:3:0.5, the volume ratio of DMSO and DMF is 10:1, the concentration of perovskite precursor solution is 1.25M, and the specific process of the step (4) is as follows: removing 70 μl of 1.25M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections of 200rpm,7s and 1500rpm,45s respectively; when 20s is left from the end of spin coating, 200 mu L of chlorobenzene is dripped on the surface of the perovskite, and then the prepared perovskite film is annealed under the annealing condition of annealing at 100 ℃ for 60 minutes; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1mL, 20. Mu.L, 30. Mu.L.
The remaining steps were the same as in example 1.
Example 14
In step (1), pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The mixing mole ratio of Cl is 3:1:3:0.6, the volume ratio of DMSO and DMF is 1:5, the concentration of perovskite precursor solution is 1.3M, and the specific process of the step (4) is as follows: removing 70 μl of 1.3M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections of 400rpm,6s and 2500rpm,50s respectively; when 22s is left from the end of spin coating, 220 mu L of chlorobenzene is dripped on the surface of the perovskite, and then the prepared perovskite film is annealed under the annealing condition of annealing at 120 ℃ for 50 minutes; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1 mL/35. Mu.L/15. Mu.L.
The remaining steps were the same as in example 1.
Example 15
In step (1), pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The mixing mole ratio of Cl is 3:1:3:0.7, the volume ratio of DMSO to DMF is 1:8, and the concentration of the perovskite precursor solution is1.15M, the specific process of the step (4) is as follows: removing 70 μl of 1.15M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections, namely 600rpm,4s and 3500rpm,40s; when 24 seconds remain from the end of spin coating, 240 mu L of chlorobenzene is dripped on the surface of the perovskite, and then the prepared perovskite film is annealed under the annealing condition of annealing at 110 ℃ for 45 minutes; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1mL, 25. Mu.L, 40. Mu.L.
The remaining steps were the same as in example 1.
Example 16
In step (1), pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The mixing mole ratio of Cl is 3:1:3:0.74, the volume ratio of DMSO and DMF is 10:3, the concentration of perovskite precursor solution is 1.12M, and the specific process of the step (4) is as follows: removing 70 μl of 1.12M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections of 700rpm,3s and 1200rpm,55s respectively; when 26s is left from the end of spin coating, 200 mu L of chlorobenzene is dripped on the surface of the perovskite, and then the prepared perovskite film is annealed under the annealing condition of annealing at 120 ℃ for 40 minutes; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1 mL/15. Mu.L/35. Mu.L.
The remaining steps were the same as in example 1.
Example 17
In step (1), pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The mixing mole ratio of Cl is 3:1:3:0.55, the volume ratio of DMSO and DMF is 10:6, the concentration of perovskite precursor solution is 1.16M, and the specific process of the step (4) is as follows: removing 70 μl of 1.16M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections, namely 900rpm,2s and 2800rpm,25s; when 13s is left from the end of spin coating, 120 mu L of chlorobenzene is dripped on the surface of the perovskite, and then the prepared perovskite film is annealed under the annealing condition of annealing at 130 DEG CFire for 30 minutes; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1mL, 20. Mu.L, 45. Mu.L.
The remaining steps were the same as in example 1.
Example 18
In step (1), pbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The mixing mole ratio of Cl is 3:1:3:0.35, the volume ratio of DMSO and DMF is 10:10, the concentration of perovskite precursor solution is 1.22M, and the specific process of the step (4) is as follows: removing 70 μl of 1.22M perovskite precursor solution, and uniformly coating on TiO 2 A film; the spin coating process comprises two working sections, namely 500rpm,5s and 3400rpm,15s; when 18s is left from the end of spin coating, 160 mu L of chlorobenzene is dripped on the surface of the perovskite, and then the prepared perovskite film is annealed for 12 minutes at 140 ℃; in step (5), the volume ratio of the chlorobenzene solution of Spiro-OMeTAD, the Li-TFSI solution and tBp was 1 mL/35. Mu.L/40. Mu.L.
The remaining steps were the same as in example 1.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. The preparation method of the ACI type two-dimensional perovskite solar cell is characterized by comprising the following steps of:
step 1, cleaning an FTO glass substrate to obtain an FTO substrate;
step 2, preparing an electron transport layer on the FTO substrate;
step 3, spin-coating the perovskite precursor liquid on the electron transport layer to prepare a perovskite absorption layer; the solute of the perovskite precursor liquid is PbI 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 A mixture of Cl, a solvent being a mixture of DMSO and DMF; pbI in solute 2 、C(NH 2 ) 3 I、CH 3 NH 3 I and CH 3 NH 3 The molar ratio of Cl is: 3:1:3: (0-0.74); the concentration of the solute in the perovskite precursor liquid is 1.1-1.3M; the perovskite absorption layer is (GA) (MA) n Pb n I 3n+1 (n=3), wherein GA is C (NH 2 ) 3 + MAI is CH 3 NH 3 + The method comprises the steps of carrying out a first treatment on the surface of the Wherein CH is 3 NH 3 Cl as an additive;
step 4, preparing a hole transport layer on the perovskite absorption layer;
and 5, preparing a metal electrode on the hole transport layer.
2. The preparation method of the ACI-type two-dimensional perovskite solar cell according to claim 1, wherein in the step 3, the volume ratio of DMSO and DMF in a solvent is (1-10): (1-10).
3. The preparation method of the ACI type two-dimensional perovskite solar cell according to claim 1, wherein in the step 3, a spin coating method is divided into two stages, the rotation speed of the first stage is 100-1000rpm, and the spin coating time is 1-10s; the second stage rotating speed is 1000-4000rpm, and the spin coating time is 10-60s; and (3) dropwise adding 100-300 mL of chlorobenzene on the surface of the perovskite after the spin coating in the second stage is finished for 10-30 s, and carrying out annealing treatment on the obtained perovskite film at the annealing temperature of 100-150 ℃ for 10-60 min to prepare the perovskite absorption layer on the electron transport layer.
4. The method for preparing an ACI-type two-dimensional perovskite solar cell according to claim 1, wherein in the step 2, the preparation process of the electron transport layer is as follows: tiCl is added to the mixture 4 Dripping into ice water to obtain electron transport layer precursor liquid; immersing FTO substrate in electron transport layer precursor solution, reacting in dry environment, and taking out the substrate with TiO 2 After annealing treatment, preparing TiO on the FTO substrate 2 The thin film serves as an electron transport layer.
5. The preparation method of the ACI-type two-dimensional perovskite solar cell according to claim 1, wherein in the step 4, a hole transport layer is prepared by spin-coating a Spiro-ome tad solution on a perovskite absorption layer, wherein the Spiro-ome tad solution is prepared from a chlorobenzene solution of Spiro-ome tad, a Li-TFSI solution and a tBP solution according to a volume ratio of 1mL: (10-40) μl: (10-50) mu L.
6. The method for producing an ACI-type two-dimensional perovskite solar cell according to any one of claims 1 to 5, wherein in step 5, a metal electrode, which is Au, ag or Cu, is vapor-deposited on the hole transport layer by a thermal vapor deposition method.
7. An ACI-type two-dimensional perovskite solar cell manufactured by the manufacturing method according to claim 1, characterized by comprising an FTO substrate, an electron transport layer, a perovskite absorption layer, a hole transport layer and a metal electrode which are stacked in this order from bottom to top; the perovskite absorption layer is (GA) (MA) n Pb n I 3n+1 (n=3), wherein GA is C (NH 2 ) 3 + MAI is CH 3 NH 3 + The method comprises the steps of carrying out a first treatment on the surface of the CH is added in the preparation process of the perovskite absorption layer 3 NH 3 Cl as an additive.
8. An ACI-type two-dimensional perovskite solar cell according to claim 7, wherein the highest photoelectric conversion efficiency of the ACI-type two-dimensional perovskite solar cell is 18.5%.
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