CN117222238A - High-efficiency stable solar cell with pure-phase two-dimensional/three-dimensional tin-based perovskite thin film and preparation method thereof - Google Patents
High-efficiency stable solar cell with pure-phase two-dimensional/three-dimensional tin-based perovskite thin film and preparation method thereof Download PDFInfo
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- LTALGLGRMHWWKA-UHFFFAOYSA-N ethane-1,2-diamine;hydroiodide Chemical class [I-].NCC[NH3+] LTALGLGRMHWWKA-UHFFFAOYSA-N 0.000 claims description 5
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- Photovoltaic Devices (AREA)
Abstract
The invention provides a solar cell with a pure-phase two-dimensional/three-dimensional tin-based perovskite film and a preparation method thereof. The solar cell comprises a conductive substrate, a hole transmission layer, a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer, an electron transmission layer, a barrier layer and a metal counter electrode layer which are sequentially arranged from bottom to top. The invention prepares the pure phase DFPD with high orientation and lattice matching by utilizing the strong coupling effect of 4, 4-difluoropiperidine ions with high electropositive ion ends and tin-iodine components and adopting a one-step solution process 2 SnI 4 /FASnI 3 A perovskite thin film; robust 2D-DFPD at thin film grain boundaries 2 SnI 4 Perovskite can stabilize 3D-FASnI 3 The edge lattice of the crystal grain suppresses the generation of defects and improves the stability of the film; and a perovskite solar cell device with a trans-structure is further constructed, and the photovoltaic performance and stability of the obtained tin-based perovskite solar cell device are effectively improved.
Description
Technical Field
The invention relates to a high-efficiency stable solar cell with a pure-phase two-dimensional/three-dimensional tin-based perovskite film and a preparation method thereof, and belongs to the technical field of perovskite material synthesis and solar cells.
Background
At present, a halide perovskite solar cell becomes a research hot spot in the photovoltaic field due to excellent photoelectric performance and low cost, but the toxicity of water-soluble lead ions to the environment and human bodies restricts the industrialized development of the halide perovskite solar cell. Development of an environment-friendly tin-based perovskite material is an important measure for realizing the green perovskite photovoltaic industry. However, tin-based perovskite has problems of Sn (II) being easily oxidized, poor structural stability, and low device performance, as compared to lead-based perovskite.
The dimensional modulation strategy can improve the intrinsic and environmental stability of tin-based perovskite films, but most organic ion spacers will partition the three-dimensional perovskite into metastable quasi-two-dimensional perovskites of various n values, reducing the light absorption capacity of the film and limiting carrier transport. Chinese patent document CN113437222a discloses a lead-free tin-based perovskite thin film, a lead-free tin-based perovskite solar cell and a method for preparing the same, the method for preparing the lead-free tin-based perovskite thin film comprises the following steps: 1) Dissolving iodized salt of chiral amine, formamidine iodine, stannous iodide and stannous fluoride in a polar organic solvent, and stirring to prepare lead-free tin-based perovskite precursor liquid; 2) On the ITO transparent conductive glass on which the hole transport layer is deposited, a lead-free tin-based perovskite precursor solution is configured by the step 1) to deposit a tin-based perovskite film; 3) And (3) adopting a gradient annealing mode to obtain the lead-free tin-based perovskite film with the two-dimensional/three-dimensional plane heterojunction structure, wherein the lower layer is of a two-dimensional structure, and the upper layer is of a three-dimensional structure. However, in the preparation of the invention, the two-dimensional perovskite is positioned at the bottom of the film to block charge transmission, so that the photovoltaic performance of the film is poor. Chinese patent document CN114583061a discloses a three-dimensional lead-free tin-based perovskite thin film and a method for preparing a solar cell, and the stability of the tin-based perovskite solar cell is improved by formamide iodide; mixing formamide iodized salt, formamidine iodized salt, stannous iodide and stannous fluoride, and then dissolving the mixture in a polar organic solvent to obtain a precursor solution; and spin-coating the precursor solution on a perovskite substrate, and annealing to obtain the tin-based perovskite film. However, the solar cell prepared by the method has low open-circuit voltage and poor photovoltaic performance.
Therefore, how to regulate and control the components and distribution of two-dimensional phases and three-dimensional phases in the tin-based perovskite film, construct a thermodynamically stable pure-phase two-dimensional/three-dimensional perovskite film, and realize the preparation of the tin-based perovskite solar cell with excellent photovoltaic performance and stability, and deserve further exploration.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a solar cell with a pure-phase two-dimensional/three-dimensional tin-based perovskite film and a preparation method thereof. The invention prepares the pure phase DFPD with high orientation and lattice matching by utilizing the strong coupling effect of 4, 4-difluoropiperidine ions with high electropositive ion ends and tin-iodine components and adopting a one-step solution process 2 SnI 4 /FASnI 3 A perovskite thin film; robust 2D-DFPD at thin film grain boundaries 2 SnI 4 Perovskite can stabilize 3D-FASnI 3 The edge lattice of the crystal grain suppresses the generation of defects and improves the stability of the film; and a trans-structure (conductive substrate/hole transport layer/pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer/electron transport layer/barrier layer/metal counter electrode layer) perovskite solar cell device is further constructed, and the photovoltaic performance and stability of the obtained tin-based perovskite solar cell device are effectively improved.
The technical scheme of the invention is as follows:
a high-efficiency stable solar cell with pure-phase two-dimensional/three-dimensional tin-based perovskite film comprises a conductive substrate, a hole transport layer and a pure-phase two-dimensional/three-dimensional tin-based perovskite film layer (namely pure-phase DFPD) 2 SnI 4 /FASnI 3 Perovskite light absorption layer), electron transport layer, barrier layer, metal counter electrode layer;
the preparation method of the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer comprises the following steps:
(1) Stannous iodide (SnI) 2 ) Formamidine hydroiodate (FAI), stannous fluoride (SnF) 2 ) Germanium iodide (GeI) 2 ) Ethylenediamine hydroiodides (EDAI) 2 ) Dissolving in solvent, adding tin particles, stirring, reacting, and filtering to obtain FASnI 3 A precursor solution;
(2) Stannous iodide (SnI) 2 ) And 4, 4-difluoropiperidineDissolving hydriodide (DFPDI) in solvent, adding tin particles, stirring for reaction, and filtering to obtain DFPD 2 SnI 4 A precursor solution;
(3) DFPD is to 2 SnI 4 Precursor solution and fasnl 3 And uniformly mixing the precursor solution, spin-coating on the hole transport layer, and then annealing to obtain the pure-phase two-dimensional/three-dimensional tin-based perovskite film layer.
According to the invention, the thickness of the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer is preferably 250-300 nanometers.
According to a preferred embodiment of the present invention, in step (1), stannous iodide (SnI 2 ) Formamidine hydroiodate (FAI), stannous fluoride (SnF) 2 ) Germanium iodide (GeI) 2 ) Ethylenediamine hydroiodides (EDAI) 2 ) The molar ratio of (3) is 1:1:0.05-0.15:0.04-0.06:0.007-0.015.
According to the present invention, preferably, in the step (1), the solvent is a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF); wherein the volume ratio of dimethyl sulfoxide (DMSO) to N, N-Dimethylformamide (DMF) is 1:3-5.
According to a preferred embodiment of the present invention, in step (1), stannous iodide (SnI 2 ) The molar ratio of the solvent to the solvent is 0.8 to 1.2mol/L.
According to a preferred embodiment of the invention, in step (1), the tin particles and stannous iodide (SnI 2 ) The mass ratio of (2) is 1:1-3. The step of shaking is also included after the tin shot is added, preferably shaking for 1-3 minutes.
According to the invention, in the step (1), the stirring reaction temperature is 40-50 ℃ and the stirring reaction time is 2-4 hours.
According to a preferred embodiment of the present invention, in step (1), the filtration is carried out using a filter membrane having a pore size of 0.22. Mu.m.
According to a preferred embodiment of the present invention, in step (2), stannous iodide (SnI 2 ) And 4, 4-difluoropiperidine hydroiodidate (DFPDI) in a molar ratio of 1:2.
According to the present invention, preferably, in the step (2), the solvent is a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF); wherein the volume ratio of dimethyl sulfoxide (DMSO) to N, N-Dimethylformamide (DMF) is 1:3-5.
According to a preferred embodiment of the present invention, in step (2), stannous iodide (SnI 2 ) The molar ratio of the solvent to the solvent is 0.4 to 0.6mol/L.
According to a preferred embodiment of the invention, in step (2), the tin particles and stannous iodide (SnI 2 ) The mass ratio of (2) is 1:1-3. The step of shaking is also included after the tin shot is added, preferably shaking for 1-3 minutes.
According to the invention, in the step (2), the stirring reaction temperature is 40-50 ℃ and the stirring reaction time is 2-4 hours.
According to a preferred embodiment of the present invention, in step (2), the filtration is carried out using a filter membrane having a pore size of 0.22. Mu.m.
According to a preferred embodiment of the present invention, in step (3), the DFPD is 2 SnI 4 Precursor solution and fasnl 3 The volume ratio of the precursor solution is 1:5-50.
According to the preferred embodiment of the present invention, in step (3), spin coating process parameters: spin coating rotation speed is 4000-6000 rpm, and the duration is 30-60 seconds; in the spin coating process, anti-solvent chlorobenzene is dripped, and perovskite is extracted in time. Preferably, during spin coating for 5-20 seconds, dropwise adding an anti-solvent chlorobenzene; the volume ratio of chlorobenzene to spin-coating liquid is 1-4:1. The antisolvent is used for making the perovskite film more compact and flat.
According to the invention, in the step (3), the annealing temperature is 80-120 ℃ and the duration is 6-16 minutes.
According to the invention, the preparation of the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer is preferably carried out in a protective gas atmosphere; preferably, the shielding gas is nitrogen.
According to the present invention, the conductive substrate, the hole transport layer, the electron transport layer, the barrier layer and the metal counter electrode layer are all as in the prior art.
According to a preferred embodiment of the present invention, the conductive substrate is an Indium Tin Oxide (ITO) transparent conductive substrate.
According to the invention, the hole transport layer is preferably poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) with a thickness of 30-40 nm.
According to the present inventionPreferably, the electron transport layer is fullerene C 60 The thickness is 20-40 nanometers.
According to a preferred embodiment of the invention, the barrier layer is Bathocuproine (BCP) with a thickness of 4-8 nm.
According to the invention, the metal counter electrode layer is preferably silver (Ag) with a thickness of 90-130 nm.
The preparation method of the solar cell with the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film comprises the following steps:
(1) Pretreatment of a conductive substrate;
(2) Preparing a hole transport layer on a conductive substrate;
(3) Preparing a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer on the hole transport layer;
(4) Sequentially depositing an electron transport layer and a barrier layer on the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer;
(5) A metal counter electrode layer is prepared on the barrier layer.
According to the invention, steps (1), (2), (4), (5) can be prepared using prior art techniques.
According to the present invention, preferably, in the step (1), the pretreatment method of the conductive substrate includes the steps of: and sequentially placing the conductive substrate in ultrapure water, acetone and ethanol solvent for ultrasonic cleaning, then purging with nitrogen flow, and carrying out ultraviolet ozone treatment after the conductive substrate is dried. Preferably, the ultrasonic cleaning time period of each solvent is 10-30 minutes. The ultraviolet ozone treatment time is 10-30 minutes.
According to a preferred embodiment of the present invention, in the step (2), the method for preparing a hole transport layer on a conductive substrate includes the steps of: an aqueous solution of a hole transporting material is spin coated onto a conductive substrate and then annealed. Preferably, the spin coating rotating speed is 3500-5500 r/min, and the spin coating time is 25-50 seconds; the annealing treatment temperature is 140-160 ℃ and the duration is 30-50 minutes.
According to a preferred embodiment of the present invention, in step (4), the vacuum is lower than 5×10 -5 Under Pa, sequentially depositing an electron transport layer and a barrier layer on the pure-phase two-dimensional/three-dimensional tin-based perovskite film layer by a physical vapor deposition method (thermal evaporation)An interlayer; the deposition rate of the electron transport layer isThe deposition rate of the barrier layer is +.>Preferably, the deposition rates of the electron transport layer and the barrier layer are +.>And->
According to a preferred embodiment of the present invention, in step (5), the vacuum is lower than 5 x 10 -5 Preparing a metal counter electrode layer by a physical vapor deposition method (thermal evaporation) under Pa; the deposition rate of the metal counter electrode layer isPreferably, the deposition rate of the metal counter electrode layer is +.>
The invention has the technical characteristics and beneficial effects that:
1. the invention adopts a one-step solution process to successfully prepare the pure-phase two-dimensional/three-dimensional tin-based perovskite film, realizes reasonable distribution of two-dimensional phases and three-dimensional phases, simplifies the preparation process and reduces the process cost.
2. The invention utilizes the strong coupling effect of 4, 4-difluoropiperidine ions with high electropositive ion ends and tin iodine components to regulate and control the components and distribution of two-dimensional phases and three-dimensional phases in the tin-based perovskite film, and induces pure-phase and thermodynamically stable DFPD 2 SnI 4 /FASnI 3 And (3) forming a perovskite thin film. 2D-DFPD in the present invention 2 SnI 4 The perovskite precursor regulates film crystallization, induces the preferential orientation of the (h 0 0) crystal face of the film, and forms the DFPD with high orientation and good lattice matching degree 2 SnI 4 /FASnI 3 A perovskite thin film; as shown in FIG. 1, highly stable 2D-DFPD 2 SnI 4 Perovskite is distributed at the grain boundary of the film to stabilize 3D-FASnI 3 Grain edges, inhibit defect generation and improve the environmental stability of the film.
3. In the preparation method of the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer, DFPD 2 SnI 4 The usage amount of the precursor is proper, if the usage amount is excessive, the holes of the prepared perovskite film are increased, the leakage current is increased, and the photovoltaic performance of the solar cell is reduced; if the usage amount is too small, the performance improvement effect on the solar cell is not obvious. In the preparation of the pure-phase two-dimensional/three-dimensional tin-based perovskite film layer, the dosage of the antisolvent used in the spin coating process and the time point of adding the antisolvent dropwise are important, if not proper, the pure-phase DFPD which is compact and flat cannot be obtained 2 SnI 4 /FASnI 3 Perovskite thin films.
4. Pure phase DFPD of the invention 2 SnI 4 /FASnI 3 The perovskite film has reduced trap recombination and improved interface transmission properties, and has better light absorption capacity and carrier transmission performance. Further constructing a perovskite solar cell device, and effectively improving the photovoltaic performance and stability of the obtained tin-based perovskite solar cell device; the photoelectric conversion efficiency of 13.34% is realized, and the storage stability is obviously improved.
Drawings
FIG. 1 is a schematic diagram of the formation mechanism and structure of a pure phase two-dimensional/three-dimensional tin-based perovskite thin film layer of the invention.
Fig. 2 is a schematic structural view of a solar cell prepared in example 1 of the present invention.
FIG. 3 is a scanning electron microscope topography of a pure phase two-dimensional/three-dimensional tin-based perovskite thin film layer as prepared by example 1 (b) and comparative example 1 (a) of the invention.
Fig. 4 is a current density-voltage curve of the solar cell prepared in example 1 (b) and comparative example 1 (a) of the present invention.
FIG. 5 is an X-ray photoelectron spectrum of a pure phase two-dimensional/three-dimensional tin-based perovskite thin film layer as prepared by example 1 (b) and comparative example 1 (a) of the invention.
Fig. 6 is a storage stability test chart of the solar cells prepared in example 1 and comparative example 1 of the present invention.
Fig. 7 is a graph for testing the working stability of the solar cells prepared in example 1 and comparative example 1 of the present invention.
Detailed Description
The invention is further illustrated by, but not limited to, the following specific examples.
The raw materials used in the examples are all conventional raw materials and are commercially available unless otherwise specified; the methods used in the examples, unless otherwise specified, are all prior art.
Example 1
A preparation method of a solar cell with a pure-phase two-dimensional/three-dimensional tin-based perovskite film with high efficiency and stability comprises the following steps:
step (1): the conductive surface of the ITO transparent conductive glass is partially etched, and the etching method comprises the following steps: dropwise adding diluted hydrochloric acid with the concentration of 2mol/L to the surface of ITO glass covered with half area zinc powder at room temperature, and completing etching after reacting for 5 min; the etched ITO conductive glass is sequentially placed in ultrapure water, acetone and ethanol solvents for ultrasonic cleaning for 20 minutes, then dried by nitrogen flow, and treated in an ultraviolet ozone cleaning machine for 25 minutes to obtain an Indium Tin Oxide (ITO) transparent conductive substrate (ITO substrate, surface resistivity resistance 10ohm/sq, and overall thickness of 1.1 mm).
Step (2): and (3) placing the Indium Tin Oxide (ITO) transparent conductive substrate obtained in the step (1) on a spin coater, dropwise adding 80 microliters of PEDOT/PSS aqueous solution, and adopting a one-step spin coating method combined with an annealing process to prepare the PEDOT/PSS hole transport layer with the thickness of 40 nanometers. Technological parameters: spin rate of spin machine 4500 rpm for 30 seconds, followed by annealing on a 160 ℃ hot plate for 30 minutes.
Step (3): stannous iodide (SnI) 2 ) Formamidine hydroiodate (FAI), stannous fluoride (SnF) 2 ) Germanium iodide (GeI) 2 ) And ethylenediamine hydroiodic acid salt (EDAI 2 ) (molar ratio 1:1:0.1:0.05:0.01) in dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF)The volume ratio of the co-solvent (dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) is 1:4, stannous iodide (SnI) 2 ) To a volume ratio of 1mol/L of the solvent, tin particles (tin particles and stannous iodide (SnI) 2 ) Adding a magnet, oscillating for 2 minutes by using an oscillator, placing the mixture on a hot plate at 45 ℃ for stirring for 3 hours, and filtering by using a needle tube and a polytetrafluoroethylene filter head with the aperture of 0.22 micrometers to obtain FASnI 3 Precursor solution. All the above processes are carried out under the protection of nitrogen.
Step (4): stannous iodide (SnI) 2 ) And 4, 4-difluoropiperidine hydroiodide (DFPDI) (molar ratio 1:2) in a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF) (volume ratio of dimethyl sulfoxide (DMSO) to N, N-Dimethylformamide (DMF) is 1:4, stannous iodide (SnI) 2 ) Molar amount of (2) and volume ratio of solvent of 0.5 mol/L); adding tin particles (tin particles and stannous iodide (SnI) 2 ) Adding a magnet, oscillating for 2 minutes by using an oscillator, placing the mixture on a hot plate at 45 ℃ for stirring for 3 hours, and filtering by using a needle tube and a polytetrafluoroethylene filter head with the aperture of 0.22 micrometers to obtain the DFPD 2 SnI 4 Precursor solution. All the above processes are carried out under the protection of nitrogen.
Step (5): DFPD is to 2 SnI 4 Precursor solution and fasnl 3 Precursor solution mixing, DFPD 2 SnI 4 Precursor solution and fasnl 3 The volume ratio of the precursor solution is 1:16.7, and the precursor solution is vibrated for 2 minutes by using a vibrator to be uniformly mixed. Dropwise adding the precursor solution on the PEDOT/PSS hole transport layer prepared in the step (2) by using a liquid-transferring gun, spin-coating, and dropwise adding an antisolvent in the spin-coating process, wherein the method comprises the following steps of: the rotation speed is 5000 revolutions per minute, the operation is carried out for 50 seconds, and chlorobenzene anti-solvent is dripped in the 10 th second operation (the volume ratio of chlorobenzene to precursor solution is 2.4:1). After spin coating, the substrate is placed on a hot plate at 100 ℃ for annealing for 10 minutes to obtain a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer (namely pure-phase DFPD) with the thickness of 260 nanometers 2 SnI 4 /FASnI 3 Perovskite light absorbing layer). All the above processes are carried out under the protection of nitrogen.
Step (6): in a high vacuum environment of the thermal evaporation apparatus (vacuum degree lower than 5×10 -5 Under Pa), sequentially depositing C on the pure-phase two-dimensional/three-dimensional tin-based perovskite film layer obtained in the step (5) by using a physical vapor deposition process 60 An electron transport layer (25 nm in thickness) and a BCP barrier layer (5 nm in thickness); c (C) 60 The deposition rate of the electron transport layer isThe deposition rate of the BCP barrier layer is +.>
Step (7): in a high vacuum environment of the thermal evaporation apparatus (vacuum degree lower than 5×10 -5 Pa) on the BCP barrier layer obtained in step (6) by using a physical vapor deposition process toA silver electrode layer with the thickness of 120 nanometers is deposited at a rate to obtain the solar cell with the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film, and the structure schematic diagram is shown in figure 2.
The formation mechanism and structure of the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer prepared in the step (5) of the embodiment are schematically shown in FIG. 1, and it can be seen from the graph that DFPD is in solution + Strong coupling between ions and Sn-I components induces 2D-DFPD 2 SnI 4 Preferential formation of precursors to achieve lattice matching and pure phase DFPD by one-step solution process 2 SnI 4 /FASnI 3 Constructing a perovskite thin film; in addition, 2D-DFPD distributed at grain boundaries 2 SnI 4 Perovskite (organic spacer layer contains intermolecular strong hydrogen bonding), and DFPD is enhanced 2 SnI 4 /FASnI 3 Intrinsic and environmental stability of perovskite thin films.
The morphology diagram of the scanning electron microscope of the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer prepared in the step (5) of the embodiment is shown in fig. 3 b. From the figure, pure phase DFPD 2 SnI 4 /FASnI 3 PerovskiteGrain size compared with simple FASnI 3 Slightly reduced.
The X-ray photoelectron spectrum of the pure phase two-dimensional/three-dimensional tin-based perovskite thin film layer prepared in step (5) of this example is shown in FIG. 5b, the lower part is unaged, the upper part is aged in air at room temperature for 0.5 hours, and compared with comparative example 1, the pure phase DFPD before and after aging 2 SnI 4 /FASnI 3 Perovskite thin films have less Sn (IV), indicating that the formation of a pure phase two-dimensional/three-dimensional structure improves the oxidation resistance stability of the thin film.
The current density-voltage curve of the tin-based perovskite solar cell prepared in this example is shown in fig. 4 b. Pure phase DFPD 2 SnI 4 /FASnI 3 Perovskite solar cells have a higher open circuit voltage (0.806V), short circuit current density (23.24 mA/cm 2 ) And a fill factor (71.23%), the photoelectric conversion efficiency reached 13.34%, which is higher than 11.63% in comparative example 1.
The tin-based perovskite solar cell (not encapsulated) prepared in this example was subjected to storage stability testing in a nitrogen glove box. The testing process comprises the following steps: the unpackaged tin-based perovskite solar cell was subjected to photovoltaic performance testing after storage for a certain period of time in a nitrogen glove box (water content below 0.01ppm, oxygen content below 0.5 ppm). The test results are shown in fig. 6. From the figure, pure phase DFPD 2 SnI 4 /FASnI 3 After 1000 hours, the efficiency decay of the perovskite solar cell is about 8%, which indicates that the formation of a pure-phase two-dimensional/three-dimensional structure improves the stability of the solar cell.
The tin-based perovskite solar cell prepared in this example (packaged with ultraviolet-curable adhesive custom-made glass sheets) was subjected to a job stability test under 1 sunlight. The testing process comprises the following steps: the packaged tin-based perovskite solar cell was subjected to a maximum power point tracking test under continuous irradiation of a solar simulator (AM 1.5G) of a xenon lamp light source. The test results are shown in FIG. 7, which shows that the pure phase DFPD 2 SnI 4 /FASnI 3 After the perovskite solar cell works for 200 hours, the performance retention rate is higher than 90%, which indicates that the formation of a pure-phase two-dimensional/three-dimensional structure improves the working stability of the solar cell。
Example 2
A method for preparing a solar cell with a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film with high efficiency and stability, which is as described in example 1, except that:
step (5): DFPD is to 2 SnI 4 Precursor solution and fasnl 3 Precursor solution mixing, DFPD 2 SnI 4 Precursor solution and fasnl 3 The volume ratio of the precursor solution is 1:50, and the precursor solution is vibrated for 2 minutes by using a vibrator to be uniformly mixed. Dropwise adding the precursor solution on the PEDOT/PSS hole transport layer prepared in the step (2) by using a liquid-transferring gun, spin-coating, and dropwise adding an antisolvent in the spin-coating process, wherein the method comprises the following steps of: the rotation speed is 5000 revolutions per minute, the operation is carried out for 50 seconds, and chlorobenzene anti-solvent is dripped in the 10 th second operation (the volume ratio of chlorobenzene to precursor solution is 2.4:1). After spin coating, the substrate is placed on a hot plate at 100 ℃ for annealing for 10 minutes to obtain a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer (namely pure-phase DFPD) with the thickness of 260 nanometers 2 SnI 4 /FASnI 3 Perovskite light absorbing layer). All the above processes are carried out under the protection of nitrogen.
Other steps and conditions were consistent with example 1.
The photoelectric conversion efficiency of the tin-based perovskite solar cell prepared in the example was 12.47%, the open circuit voltage was 0.784V and the short circuit current density was 22.68mA/cm 2 The fill factor was 70.12%.
Example 3
A method for preparing a solar cell with a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film with high efficiency and stability, which is as described in example 1, except that:
step (5): DFPD is to 2 SnI 4 Precursor solution and fasnl 3 Precursor solution mixing, DFPD 2 SnI 4 Precursor solution and fasnl 3 The volume ratio of the precursor solution is 1:8.3, and the precursor solution is vibrated for 2 minutes by using a vibrator to be uniformly mixed. Dripping the precursor solution on the PEDOT-PSS hole transmission layer prepared in the step (2) by using a liquid-transfering gun, spin-coating, and dripping an antisolvent in the spin-coating process, wherein the spin-coating process is specific: the rotation speed is 5000 revolutions per minute, the operation is carried out for 50 seconds, and chlorobenzene anti-solvent is dripped in the 10 th second operation (the volume ratio of chlorobenzene to precursor solution is 2.4:1). After spin coating, the substrate is placed on a hot plate at 100 ℃ for annealing for 10 minutes to obtain a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer (namely pure-phase DFPD) with the thickness of 260 nanometers 2 SnI 4 /FASnI 3 Perovskite light absorbing layer). All the above processes are carried out under the protection of nitrogen.
Other steps and conditions were consistent with example 1.
The photoelectric conversion efficiency of the tin-based perovskite solar cell prepared in this example was 11.98%, the open circuit voltage was 0.796V and the short circuit current density was 21.55mA/cm 2 The fill factor was 69.85%.
Comparative example 1
The preparation method of the three-dimensional tin-based perovskite thin film solar cell comprises the following steps:
steps (1) - (3) are the same as in example 1;
step (4): using a pipette to carry out FASnI obtained in the step (3) 3 And (3) dropwise adding the precursor solution on the PEDOT/PSS hole transport layer prepared in the step (2), performing spin coating, and dropwise adding an antisolvent in the spin coating process, wherein the specific spin coating process comprises the following steps of: the rotation speed is 5000 revolutions per minute, the operation is carried out for 50 seconds, and chlorobenzene anti-solvent is dripped in the 10 th second operation (the volume ratio of chlorobenzene to precursor solution is 2.4:1). And after spin coating is finished, placing the substrate on a hot plate at 100 ℃ for annealing for 10 minutes to obtain the three-dimensional tin-based perovskite thin film layer with the thickness of 260 nanometers. All the above processes are carried out under the protection of nitrogen.
Step (5): in a high vacuum environment of the thermal evaporation apparatus (vacuum degree lower than 5×10 -5 Under Pa), sequentially depositing C on the three-dimensional tin-based perovskite film layer obtained in the step (4) by using a physical vapor deposition process 60 An electron transport layer (25 nm in thickness) and a BCP barrier layer (5 nm in thickness); c (C) 60 The deposition rate of the electron transport layer isThe deposition rate of the BCP barrier layer is +.>
Step (6): in a high vacuum environment of the thermal evaporation apparatus (vacuum degree lower than 5×10 -5 Pa) using a physical vapor deposition process on the BCP barrier layer obtained in step (5) toAnd depositing a silver electrode layer with the thickness of 120 nanometers at a rate to obtain the solar cell of the three-dimensional tin-based perovskite film.
FASnI prepared in this comparative example 3 The scanning electron microscope topography of the perovskite thin film is shown in fig. 3 (a).
FASnI prepared in this comparative example 3 The X-ray photoelectron spectrum of the perovskite film is shown in FIG. 5a, the lower part is unaged, and the upper part is aged for 0.5 hours in air at room temperature. As compared with example 1, FASnI before and after aging 3 The perovskite thin films all have more Sn (IV) content, which shows that the oxidation resistance is poor, and shows that the pure phase DFPD 2 SnI 4 /FASnI 3 The perovskite thin film has improved oxidation resistance.
FASnI prepared in this comparative example 3 As shown in FIG. 4 (a), the photoelectric conversion efficiency of the perovskite solar cell was 11.63% (open circuit voltage was 0.752V, short circuit current density was 22.16 mA/cm) 2 The packing factor was 69.80%) which is significantly lower than the pure phase DFPD prepared in example 1 of the present invention 2 SnI 4 /FASnI 3 Perovskite solar cell, illustrating pure phase DFPD 2 SnI 4 /FASnI 3 The structure enhances the photovoltaic performance of the tin-based solar cell.
FASnI prepared in this comparative example 3 Perovskite solar cells (not encapsulated) were subjected to storage stability testing in a nitrogen glove box. The testing process comprises the following steps: the unpackaged tin-based perovskite solar cell was subjected to photovoltaic performance testing after storage for a certain period of time in a nitrogen glove box (water content below 0.01ppm, oxygen content below 0.5 ppm). The test results are shown in fig. 6. From the figure, the comparative example solar cell was 1000 hours oldAfter that, the efficiency attenuation is about 18%, and the photovoltaic performance attenuation is higher than that of pure phase DFPD 2 SnI 4 /FASnI 3 8% of perovskite solar cell.
FASnI prepared in this comparative example 3 Perovskite solar cells (packaged with ultraviolet cured adhesive custom glass sheets) were tested for operational stability under 1 sunlight. The testing process comprises the following steps: the packaged tin-based perovskite solar cell was subjected to a maximum power point tracking test under continuous irradiation of a solar simulator (AM 1.5G) of a xenon lamp light source. The test results are shown in fig. 7. From the figure, pure phase DFPD 2 SnI 4 /FASnI 3 After the perovskite solar cell works for 100 hours, the performance retention rate is about 82 percent, and the working stability is obviously lower than that of pure phase DFPD 2 SnI 4 /FASnI 3 Perovskite solar cell.
Comparative example 2
A method for preparing a solar cell with a pure phase two-dimensional/three-dimensional tin-based perovskite thin film, as described in example 1, except that:
in the spin coating process of step (5), chlorobenzene antisolvent (the volume ratio of chlorobenzene to precursor solution is 2.4:1) is added dropwise during 20 seconds of operation.
Other steps and conditions were consistent with example 1.
In this comparative example, since the dropping time of the antisolvent was too late, dense and flat pure phase DFPD could not be obtained 2 SnI 4 /FASnI 3 Perovskite thin films.
Comparative example 3
A method for preparing a solar cell with a pure phase two-dimensional/three-dimensional tin-based perovskite thin film, as described in example 1, except that:
in the spin coating process of the step (5), chlorobenzene anti-solvent (the volume ratio of chlorobenzene to precursor solution is 6:1) is added dropwise during 10 seconds of operation.
Other steps and conditions were consistent with example 1.
In this comparative example, since the amount of the antisolvent is too large, a dense and flat pure phase DFPD could not be obtained 2 SnI 4 /FASnI 3 Perovskite thin films.
Claims (10)
1. The solar cell is characterized by comprising a conductive substrate, a hole transmission layer, a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer, an electron transmission layer, a barrier layer and a metal counter electrode layer which are sequentially arranged from bottom to top;
the preparation method of the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer comprises the following steps:
(1) Stannous iodide (SnI) 2 ) Formamidine hydroiodate (FAI), stannous fluoride (SnF) 2 ) Germanium iodide (GeI) 2 ) Ethylenediamine hydroiodides (EDAI) 2 ) Dissolving in solvent, adding tin particles, stirring, reacting, and filtering to obtain FASnI 3 A precursor solution;
(2) Stannous iodide (SnI) 2 ) Dissolving 4, 4-difluoropiperidine hydroiodic acid salt (DFPDI) in solvent, adding tin particles, stirring for reaction, and filtering to obtain DFPD 2 SnI 4 A precursor solution;
(3) DFPD is to 2 SnI 4 Precursor solution and fasnl 3 And uniformly mixing the precursor solution, spin-coating on the hole transport layer, and then annealing to obtain the pure-phase two-dimensional/three-dimensional tin-based perovskite film layer.
2. The solar cell with a pure phase two-dimensional/three-dimensional tin-based perovskite thin film according to claim 1, wherein the thickness of the pure phase two-dimensional/three-dimensional tin-based perovskite thin film layer is 250-300 nanometers.
3. The high efficiency stable solar cell having a pure phase two-dimensional/three-dimensional tin-based perovskite thin film according to claim 1, wherein in step (1) comprising one or more of the following conditions:
i. stannous iodide (SnI) 2 ) Formamidine hydroiodate (FAI), stannous fluoride (SnF) 2 ) Germanium iodide (GeI) 2 ) Ethylenediamine hydroiodides (EDAI) 2 ) The molar ratio of (3) is 1:1:0.05-0.15:0.04-0.06:0.007-0.015;
ii. The solvent is a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF); wherein, the volume ratio of dimethyl sulfoxide (DMSO) to N, N-Dimethylformamide (DMF) is 1:3-5;
iii, stannous iodide (SnI) 2 ) The molar ratio of the solvent to the solvent is 0.8-1.2mol/L;
iv, tin particles and stannous iodide (SnI 2 ) The mass ratio of (2) is 1:1-3; the step of shaking is also included after the tin particles are added, and the shaking is preferably carried out for 1-3 minutes;
v, stirring and reacting at 40-50 ℃ for 2-4 hours;
vi, filtering by using a filter membrane with a pore size of 0.22 micrometers.
4. The high efficiency stable solar cell having a pure phase two-dimensional/three-dimensional tin-based perovskite thin film according to claim 1, wherein in step (2) comprising one or more of the following conditions:
i. stannous iodide (SnI) 2 ) And 4, 4-difluoropiperidine hydroiodidate (DFPDI) in a molar ratio of 1:2;
ii. The solvent is a mixed solvent of dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF); wherein, the volume ratio of dimethyl sulfoxide (DMSO) to N, N-Dimethylformamide (DMF) is 1:3-5;
iii, stannous iodide (SnI) 2 ) The molar ratio of the solvent to the solvent is 0.4-0.6mol/L;
iv, tin particles and stannous iodide (SnI 2 ) The mass ratio of (2) is 1:1-3; the step of shaking is also included after the tin particles are added, and the shaking is preferably carried out for 1-3 minutes;
v, stirring and reacting at 40-50 ℃ for 2-4 hours;
vi, filtering by using a filter membrane with a pore size of 0.22 micrometers.
5. The high efficiency stable solar cell having a pure phase two-dimensional/three-dimensional tin-based perovskite thin film according to claim 1 wherein in step (3), DFPD 2 SnI 4 Precursor solution and fasnl 3 The volume ratio of the precursor solution is 1:5-50.
6. The high efficiency stable solar cell having a pure phase two-dimensional/three-dimensional tin-based perovskite thin film according to claim 1, wherein in step (3) comprising one or more of the following conditions:
i. spin coating process parameters: spin coating rotation speed is 4000-6000 rpm, and the duration is 30-60 seconds; in the spin coating process, dropwise adding anti-solvent chlorobenzene; preferably, during spin coating for 5-20 seconds, dropwise adding an anti-solvent chlorobenzene; the volume ratio of chlorobenzene to spin-coating liquid is 1-4:1;
ii. The annealing temperature is 80-120 ℃ and the duration is 6-16 minutes.
7. The efficient and stable solar cell with the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film according to claim 1, wherein the preparation of the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer is performed in a protective gas atmosphere; preferably, the shielding gas is nitrogen.
8. The high efficiency stable solar cell having a pure phase two-dimensional/three-dimensional tin-based perovskite thin film according to claim 1, comprising one or more of the following conditions:
i. the conductive substrate is an Indium Tin Oxide (ITO) transparent conductive substrate;
ii. The hole transport layer is poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) with the thickness of 30-40 nanometers;
iii, the electron transport layer is fullerene C 60 The thickness is 20-40 nanometers;
iv, the barrier layer is Bathocuproine (BCP) with the thickness of 4-8 nanometers;
v, the metal counter electrode layer is silver (Ag) with the thickness of 90-130 nanometers.
9. The method for preparing a solar cell with a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film according to any one of claims 1 to 8, comprising the steps of:
(1) Pretreatment of a conductive substrate;
(2) Preparing a hole transport layer on a conductive substrate;
(3) Preparing a pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer on the hole transport layer;
(4) Sequentially depositing an electron transport layer and a barrier layer on the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer;
(5) A metal counter electrode layer is prepared on the barrier layer.
10. The method of preparing a highly efficient and stable solar cell with a pure phase two-dimensional/three-dimensional tin-based perovskite thin film according to claim 9, characterized by comprising one or more of the following conditions:
i. in the step (1), the pretreatment method of the conductive substrate comprises the following steps: sequentially placing the conductive substrate in ultrapure water, acetone and ethanol solvent for ultrasonic cleaning, then purging with nitrogen flow, and carrying out ultraviolet ozone treatment after the conductive substrate is dried; preferably, the ultrasonic cleaning time of each solvent is 10-30 minutes; the ultraviolet ozone treatment time is 10-30 minutes;
ii. In step (2), the method for preparing a hole transport layer on a conductive substrate includes the steps of: spin-coating an aqueous solution of a hole transport material on a conductive substrate, and then annealing; preferably, the spin coating rotating speed is 3500-5500 r/min, and the spin coating time is 25-50 seconds; the annealing treatment temperature is 140-160 ℃ and the duration is 30-50 minutes;
iii, in step (4), the vacuum degree is lower than 5×10 -5 Under Pa, sequentially depositing an electron transport layer and a barrier layer on the pure-phase two-dimensional/three-dimensional tin-based perovskite thin film layer by a physical vapor deposition method (thermal evaporation); the deposition rate of the electron transport layer isThe deposition rate of the barrier layer is +.>Preferably, the deposition rates of the electron transport layer and the barrier layer are +.>And->
iv, in step (5), the vacuum degree is lower than 5×10 -5 Preparing a metal counter electrode layer by a physical vapor deposition method (thermal evaporation) under Pa; the deposition rate of the metal counter electrode layer isPreferably, the deposition rate of the metal counter electrode layer is +.>
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