CN115802770A - Method for efficiently passivating lead iodide-rich wide-band-gap perovskite by using pure-chlorine two-dimensional perovskite and solar cell thereof - Google Patents
Method for efficiently passivating lead iodide-rich wide-band-gap perovskite by using pure-chlorine two-dimensional perovskite and solar cell thereof Download PDFInfo
- Publication number
- CN115802770A CN115802770A CN202211487944.7A CN202211487944A CN115802770A CN 115802770 A CN115802770 A CN 115802770A CN 202211487944 A CN202211487944 A CN 202211487944A CN 115802770 A CN115802770 A CN 115802770A
- Authority
- CN
- China
- Prior art keywords
- perovskite
- dimensional
- perovskites
- lead
- iodide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
Landscapes
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a method for efficiently passivating lead iodide-rich wide-bandgap perovskite by using pure chlorine two-dimensional perovskite and a solar cell thereof. According to the invention, the chlorinated organic amine salt is screened, and a specific means is adopted to carry out in-situ reaction on the surface of the three-dimensional perovskite active layer to generate pure chlorine two-dimensional perovskite, so that the surface defects of the three-dimensional perovskite are passivated efficiently, and the nonradiative recombination of current carriers is inhibited, thereby improving the open-circuit voltage and the filling factor of the perovskite solar cell. The invention can improve the photoelectric conversion efficiency and stability of the semitransparent wide band gap perovskite solar cell on the premise of ensuring low cell preparation cost and simple and convenient method, and can be applied to the preparation of perovskite/perovskite or perovskite/silicon tandem solar cells.
Description
Technical Field
The invention relates to the field of chemical and solar cell new materials, in particular to a passivation method of a perovskite solar cell.
Background
Perovskite solar cells have achieved unprecedented development over the last few years, with a certified Photovoltaic Conversion Efficiency (PCE) that has risen dramatically from 3.8% in 2009 to 25.7% at present, but the efficiency of single junction perovskite solar cells is limited by the shokrill-quinetise (S-Q) limit. Theoretical studies indicate that constructing a stacked structure to reduce thermalization losses is one of the effective strategies to break through the S-Q limit of single junctions. At present, the PCE of the perovskite/silicon laminated solar cell reaches 31.3%, so that the technology has a good application prospect in the future photovoltaic market. However, the PCE of perovskite/silicon tandem solar cells is still well below the theoretical limit above 40%. The performance of wide bandgap perovskite solar cells greatly limits the overall performance of tandem solar cells compared to the industrially mature silicon-based cells. The large open circuit voltage loss due to high defect density and interface level mismatch is among the main reasons.
Therefore, it is a key to put this type of solar cell into practical use to explore a method for preparing a highly efficient and stable wide bandgap perovskite solar cell by a simple method. The formation of 2D/3D heterojunctions on the surface of perovskites by bulky amine salts has proven to be one of the effective ways to passivate perovskites, but the insight into how bulky cations in two-dimensional perovskites affect the defect density of perovskites is crucial for designing more effective surface passivation strategies to further improve the performance of such cells.
Disclosure of Invention
The invention aims to provide a method for efficiently passivating lead iodide-rich wide-bandgap perovskite by using pure chlorine two-dimensional perovskite and a solar cell thereof.
In order to achieve the purpose, one of the technical schemes adopted by the invention is as follows:
a method for high-efficiency passivation of lead iodide-rich wide-bandgap perovskite by using pure chlorine two-dimensional perovskite comprises the following preparation steps:
firstly, spin-coating a tin dioxide electron transport layer with the thickness of 25-50 nm on a substrate, and annealing for 14-16 min at 148-152 ℃ in air;
secondly, transferring the substrate treated in the first step into an inert atmosphere, and preparing a lead iodide-rich wide-band-gap three-dimensional perovskite layer by adopting a two-step spin coating method;
thirdly, dynamically dripping isopropanol solution of benzyl ammonium chloride (PMACl) on the surface of the three-dimensional perovskite layer prepared in the second step at the rotating speed of 3500-4500 rpm, annealing at 98-102 ℃ for 4-6 min, and forming pure chlorine two-dimensional Perovskite (PMA) on the surface of the three-dimensional perovskite layer 2 PbCl 4 ；
Fourthly, spin coating a hole transport layer on the product of the third step, and evaporating MoO x And the buffer layer is used for sputtering a transparent electrode, and then a metal grid electrode is evaporated to form the semitransparent wide band gap perovskite solar cell.
Preferably, the second step is as follows: firstly, rotating a lead source solution at the rotating speed of 1500-2500 rpm for 28-32 s to spin-coat the lead source solution on a substrate treated in the first step, and annealing at the temperature of 68-72 ℃ for 55 s-1 min; after the formed film is cooled to room temperature, standing the organic amine salt solution for 18-22 s, rotating at 1500-2000 rpm for 28-32 s to spin-coat the film, and quickly transferring the film into air with the relative humidity of 30-40% to anneal at 148-152 ℃ for 14-16 min to form the final lead iodide-rich wide-band gap three-dimensional perovskite layer.
Preferably, the lead source solution comprises lead iodide, lead bromide and cesium iodide, wherein the formula ratio of the solvents of the lead iodide, the lead bromide, the cesium iodide and the lead source solution is 0.85-0.95M: 0.085-0.095M: 0.8-1.2 mL.
Preferably, the solvent of the lead source solution is a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide.
Preferably, the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 8-10: 1.
Preferably, the organic amine salt solution comprises formamidine hydroiodide, methyl amine chloride and methyl amine iodide, wherein the formula ratio of the solvents of the formamidine hydroiodide, the methyl amine chloride, the methyl amine iodide and the organic amine salt solution is 0.35-0.4M: 0.35-0.45M: 0.14-0.16M: 0.8-1.2 mL.
Preferably, the solvent of the organic amine salt solution is isopropanol.
Preferably, in the third step, the concentration of the isopropyl alcohol solution of benzyl ammonium chloride is 2 to 4mg/mL.
Preferably, the substrate is conductive glass.
Preferably, the metal mesh electrode is a gold or silver metal mesh electrode.
The second technical scheme adopted by the invention is as follows:
a perovskite solar cell prepared according to the above method.
Compared with phenethyl amine chloride (PEACl) with one more alkyl chain than the side chain or 1-naphthylmethyl amine chloride (NMACl) with one more benzene ring, the PMA molecule selected by the invention is PMA + Has a very low two-dimensional perovskite formation energy, and - weaker hydrogen bond interaction and no pi-pi interaction between single crystals can enable the PMACl to form two-dimensional pure chlorine (PMA) with good distribution on the surface of the lead iodide-rich perovskite 2 PbCl 4 Perovskite.
The equipment, reagents, processes, parameters and the like related to the invention are conventional equipment, reagents, processes, parameters and the like except for special description, and no embodiment is needed.
All ranges recited herein include all point values within the range.
In the present invention, the "room temperature", i.e., the normal ambient temperature, may be 10 to 30 ℃.
Compared with the background technology, the technical scheme has the following advantages:
the invention adopts in-situ reaction on the surface of lead-calcium-titanium-rich iodide ore, and two-dimensional pure chlorine (PMA) is generated in situ on the surface of perovskite by screening specific amine chloride salt PMACl with crystal structure molecules having no pi-pi strong interaction force and suitable halide hydrogen bond strength 2 PbCl 4 The perovskite has good distribution, can efficiently passivate the surface defects of the perovskite and inhibit the non-radiative recombination of carriers so as to promote calciumOpen circuit voltage and fill factor of the titanium ore solar cell. The preparation method is simple, the preparation cost is low, and the generated two-dimensional perovskite is beneficial to improving the stability of the device. The semitransparent wide band gap solar cell prepared by the method has higher photoelectric conversion efficiency and good stability, and is suitable for being used as a top cell of a perovskite/perovskite or perovskite/silicon laminated solar cell.
Drawings
FIG. 1 is a scanning electron micrograph of a blank sample and a PMACl, PEACl, NMACl passivated perovskite surface according to an example of the present invention; wherein, a is a blank sample, b is PMACl, c is PEACl, d is NMACl, and e and f are transient and steady fluorescence maps of different passivation conditions respectively.
FIG. 2 is a graph illustrating the optimal J-V curve and stability of a device prepared according to an embodiment of the present invention, wherein: a is an optimal J-V curve of a device prepared under different passivation conditions under standard sunlight; b is the stability of the device (stored in air at-25 ℃ C. At-10% relative humidity).
FIG. 3 is used to illustrate the principle of passivating the perovskite surface by PMACl, PEACl, NMACl in an embodiment of the present invention.
Fig. 4 is used to illustrate that the photoelectric conversion efficiency of the perovskite surface passivated by PMACl in the embodiment of the present invention is improved compared with that of the blank group.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example (b):
the method for efficiently passivating the lead iodide-rich wide-bandgap perovskite by the pure-chlorine two-dimensional perovskite comprises the following preparation steps:
firstly, spin-coating a tin dioxide electron transport layer with the thickness of 25-50 nm on conductive glass, and annealing for 15min at 150 ℃ in air;
and secondly, transferring the conductive glass into an inert atmosphere glove box, and preparing a lead iodide-rich wide-band-gap three-dimensional perovskite layer by adopting a two-step spin coating method: first, a lead source solution (lead iodide: lead bromide: cesium iodide = 0.9M: 0.09M in 1mL of a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide (v/v = 9/1)) was rotated at 30s at a rotation speed of 2000rpm, and annealed at 70 ℃ for 1min; after the film is cooled to room temperature, a salt solution (formamidine hydroiodide: methyl amine chloride: methyl amine iodide = 0.37M: 0.4M: 0.15M dissolved in 1mL of isopropanol) is stood for 20s, then is rotated at the rotating speed of 1700rpm for 30s, and is rapidly transferred into air with the relative humidity of 30-40% to be annealed at 150 ℃ for 15min, so that a final lead iodide-rich wide-bandgap three-dimensional perovskite layer is formed;
thirdly, dynamically dripping isopropanol solution of PMACl, PEACl or NMACl associated with the large-volume cation structure on the surface of the three-dimensional perovskite layer prepared in the second step at the rotating speed of 4000rpm, and annealing at 100 ℃ for 5min to respectively form two-dimensional pure chlorine (PMA) 2 PbCl 4 Two dimensional hybrid (PEA) 2 PbI x Cl 4-x Or a non-two dimensional NMAI salt;
fourthly, spin coating a hole transport layer and evaporating MoO x And sputtering an indium tin oxide transparent electrode on the buffer layer, and then evaporating a silver metal grid electrode to form the semitransparent wide-band gap perovskite solar cell.
Since PMA + The middle N has weak hydrogen bond interaction with halogen ions and no strong pi-pi interaction in a two-dimensional crystal structure, and the generated two-dimensional pure chlorine (PMA) 2 PbCl 4 The distribution on the surface of the perovskite is good, and the non-radiative recombination of carriers is well inhibited (shown in figure 1). The cell was rated at AM 1.5G (100 mW. Cm) -2 ) Test in standard sunlight, short-circuit Current Density (J) SC ) Is 19.87mA/cm 2 Open circuit voltage (V) OC ) At 1.23V, the Fill Factor (FF) was 76.31%, and the optimum photoelectric conversion efficiency reached 18.60% (a in fig. 2 and table 1). And PEA + Medium N to PMA + Has strong electronegativity, strong hydrogen bond interaction with halogen and strong pi-pi interaction in a two-dimensional crystal structure, is easy to aggregate, so that two-dimensional hybridization (PEA) is formed 2 PbI x Cl 4-x The passivation ability is weak, in AM 1.5G (100 mW. Cm) -2 ) The photoelectric conversion efficiency is only 18.42 percent when tested under standard sunlight. Because the formation energy of the NMA-based two-dimensional perovskite is high, the non-two-dimensional NMAI salt formed on the surface of the perovskite by ion exchange is relatively messySequence, weaker passivation, in AM 1.5G (100 mW. Cm) -2 ) The photoelectric conversion efficiency is only 18.12 percent when tested under standard sunlight. The invention indirectly regulates and controls the anion composition of the lead iodide-rich perovskite interface by regulating and controlling the structure of the large-volume cations. Stability is another important parameter for evaluating device performance. To characterize the long-term stability of the devices, the present examples were stored in a dark environment in air (-10% relative humidity, 25 ℃) for 50 days, and the efficiency of the devices was monitored (b in fig. 2). The PCE of the blank device dropped to 73% of the initial PCE, while the PCEs of the perovskite thin film devices passivated based on PMACl, PEACl and NMACl maintained 94%, 90% and 84% of the initial PCE, respectively. The great improvement of the stability of the PMACl passivated perovskite thin film device can be caused by the formation of a pure Cl-2D phase, so that the defect density of the device is reduced, and the moisture resistance of the device is improved. TABLE 1 photovoltaic parameters for optimal devices for different passivation conditions
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, and all equivalent variations and modifications made within the scope of the present invention and the content of the description should be included in the scope of the present invention.
Claims (10)
1. A method for passivating lead iodide-rich wide-bandgap perovskite by using pure chlorine two-dimensional perovskite is characterized by comprising the following steps: the method comprises the following steps:
firstly, spin-coating a tin dioxide electron transport layer with the thickness of 25-50 nm on a substrate, and annealing for 14-16 min at 148-152 ℃ in air;
secondly, transferring the substrate treated in the first step into an inert atmosphere, and preparing a lead iodide-rich wide-band-gap three-dimensional perovskite layer by adopting a two-step spin coating method;
thirdly, dripping the isopropanol solution of benzyl ammonium chloride on the surface of the three-dimensional perovskite layer prepared in the second step at the rotating speed of 3500-4500 rpm, annealing at the temperature of 98-102 ℃ for 4-6 min, and forming pure chlorine dioxide on the surface of the three-dimensional perovskite layerVitamin Perovskite (PMA) 2 PbCl 4 ；
Fourthly, spin coating a hole transport layer on the product of the third step, and evaporating MoO x And sputtering a transparent electrode on the buffer layer, and evaporating an upper metal grid electrode to obtain the semitransparent wide band gap perovskite solar cell.
2. The method for passivating lead iodide-rich wide band gap perovskites by pure chlorine two-dimensional perovskites as claimed in claim 1, wherein: the second step includes: firstly, rotating a lead source solution at the rotating speed of 1500-2500 rpm for 28-32 s to spin-coat the lead source solution on a substrate treated in the first step, and annealing at the temperature of 68-72 ℃ for 55 s-1 min; after the formed film is cooled to room temperature, standing the organic amine salt solution for 18-22 s, rotating at 1500-2000 rpm for 28-32 s to spin-coat the film, and annealing in air with relative humidity of 30-40% at 148-152 ℃ for 14-16 min to form the lead iodide-rich wide band gap three-dimensional perovskite layer.
3. The method for passivating lead iodide-rich wide band gap perovskites by pure chlorine two-dimensional perovskites as claimed in claim 2, wherein: the lead source solution comprises lead iodide, lead bromide and cesium iodide, wherein the formula ratio of the lead iodide, the lead bromide, the cesium iodide and the lead source solution is 0.85-0.95M to 0.085-0.095M to 0.8-1.2 mL.
4. The method for passivating lead iodide-rich wide bandgap perovskite by pure chlorine two-dimensional perovskite according to claim 3, wherein: the solvent of the lead source solution is a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide with the volume ratio of 8-10: 1.
5. The method for passivating lead iodide-rich wide band gap perovskites by pure chlorine two-dimensional perovskites as claimed in claim 2, wherein: the organic amine salt solution comprises formamidine hydroiodide, methyl amine chloride and methyl amine iodide, wherein the formula ratio of the solvents of the formamidine hydroiodide, the methyl amine chloride, the methyl amine iodide and the organic amine salt solution is 0.35-0.4M: 0.35-0.45M: 0.14-0.16M: 0.8-1.2 mL.
6. The method for passivating lead iodide-rich wide band gap perovskites by pure chlorine two-dimensional perovskites as claimed in claim 5, wherein: the solvent of the organic amine salt solution is isopropanol.
7. The method for passivating lead iodide-rich wide band gap perovskites by pure chlorine two-dimensional perovskites as claimed in claim 1, wherein: in the third step, the concentration of the isopropanol solution of benzyl ammonium chloride is 2-4 mg/mL.
8. The method for passivating lead iodide-rich wide band gap perovskites by pure chlorine two-dimensional perovskites as claimed in claim 1, wherein: the substrate is conductive glass.
9. The method for passivating lead iodide-rich wide band gap perovskites by pure chlorine two-dimensional perovskites as claimed in claim 1, wherein: the metal grid electrode is a gold or silver metal grid electrode.
10. A perovskite solar cell prepared according to the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211487944.7A CN115802770A (en) | 2022-11-25 | 2022-11-25 | Method for efficiently passivating lead iodide-rich wide-band-gap perovskite by using pure-chlorine two-dimensional perovskite and solar cell thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211487944.7A CN115802770A (en) | 2022-11-25 | 2022-11-25 | Method for efficiently passivating lead iodide-rich wide-band-gap perovskite by using pure-chlorine two-dimensional perovskite and solar cell thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115802770A true CN115802770A (en) | 2023-03-14 |
Family
ID=85441350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211487944.7A Pending CN115802770A (en) | 2022-11-25 | 2022-11-25 | Method for efficiently passivating lead iodide-rich wide-band-gap perovskite by using pure-chlorine two-dimensional perovskite and solar cell thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115802770A (en) |
-
2022
- 2022-11-25 CN CN202211487944.7A patent/CN115802770A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gao et al. | Recent progresses on defect passivation toward efficient perovskite solar cells | |
| Wang et al. | Suppressed recombination for monolithic inorganic perovskite/silicon tandem solar cells with an approximate efficiency of 23% | |
| Song et al. | Recent advances in electrolytes for quantum dot-sensitized solar cells | |
| CN108389967B (en) | Light absorption layer material of solar cell, wide-band-gap perovskite solar cell and preparation method thereof | |
| Xu et al. | Optimizing solution-processed C60 electron transport layer in planar perovskite solar cells by interfacial modification with solid-state ionic-liquids | |
| Cho et al. | Phenylethylammonium-formamidinium-methylammonium quasi-2D/3D tin wide-bandgap perovskite solar cell with improved efficiency and stability | |
| CN111628080A (en) | Perovskite solar cell and preparation method of perovskite absorption layer | |
| Xia et al. | Interfacial passivation of wide-bandgap perovskite solar cells and tandem solar cells | |
| Ye et al. | Preparation of hysteresis-free flexible perovskite solar cells via interfacial modification | |
| Wang et al. | Advances in perovskite solar cells: film morphology control and interface engineering | |
| CN115347121A (en) | Perovskite solar cell based on DDS surface modification | |
| Li et al. | Selection of functional spacer cations for efficient 2D/3D perovskite solar cells | |
| Ahn et al. | Monolithic all-perovskite tandem solar cells: recent progress and challenges | |
| Marimuthu et al. | Two-dimensional hybrid perovskite solar cells: a review | |
| CN114883493A (en) | Solar cell based on three-dimensional/two-dimensional perovskite and preparation method thereof | |
| CN113972323A (en) | Sodium thiocyanate-doped efficient and stable perovskite solar cell and preparation method thereof | |
| Marchant et al. | Perovskite/silicon tandem solar cells–compositions for improved stability and power conversion efficiency | |
| Chen et al. | Efficient and stable perovskite solar cells doped by cesium acetate | |
| Huang et al. | Enhancement of CsPbI3 perovskite solar cells with dual functional passivator 4-Fluoro-3-phenoxybenzaldehyde | |
| Zhang et al. | Organic compound passivation for perovskite solar cells with improving stability and photoelectric performance | |
| Mateen et al. | Engineering the intermediate adduct phase to control the crystallization of perovskites for efficient and stable perovskite solar cells | |
| CN115942842A (en) | Perovskite solar cell and preparation method thereof | |
| CN115802770A (en) | Method for efficiently passivating lead iodide-rich wide-band-gap perovskite by using pure-chlorine two-dimensional perovskite and solar cell thereof | |
| Hu et al. | π-Conjugated zwitterion for dual-interfacial modification in high-performance perovskite solar cells | |
| Huang et al. | Additive-assisted defect passivation of perovskite with metformin hydrochloride: toward high-performance pin perovskite solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |