CN116284513B - Perovskite film doping and defect passivation method - Google Patents
Perovskite film doping and defect passivation method Download PDFInfo
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- CN116284513B CN116284513B CN202310267159.9A CN202310267159A CN116284513B CN 116284513 B CN116284513 B CN 116284513B CN 202310267159 A CN202310267159 A CN 202310267159A CN 116284513 B CN116284513 B CN 116284513B
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- alkali metal
- conversion material
- photoelectric conversion
- polymer
- perovskite
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Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及光电材料及器件技术领域，进一步涉及碱金属功能化聚合物材料的制备，具体公开一种碱金属功能化聚合物，所述聚合物是由碱金属盐和含有酸性基团的高分子有机化合物在有机溶液中通过酸碱中和反应获得；碱该金属功能化聚合物可用于修饰光电转换材料，进一步的调控观点材料薄膜的结晶过程，显著提高功率转换效率，同时提高了操作稳定性并将环境影响降至最低。The present invention relates to the technical field of optoelectronic materials and devices, and further to the preparation of alkali metal functionalized polymer materials. Specifically, an alkali metal functionalized polymer is disclosed. The polymer is obtained by acid-base neutralization reaction of an alkali metal salt and a high molecular organic compound containing an acidic group in an organic solution. The alkali metal functionalized polymer can be used to modify a photoelectric conversion material, further regulate the crystallization process of a photoelectric material film, significantly improve power conversion efficiency, and at the same time improve operational stability and minimize environmental impact.
Description
Technical Field
The invention relates to the technical field of photoelectric materials and devices, and further relates to preparation of an alkali metal polymer material, in particular to preparation and application of a photoelectric conversion material capable of being modified.
Background
Solar energy generated by nuclear fusion is the most main natural energy form on the earth, is a recognized environment-friendly clean energy, has the advantages of wide distribution, large reserve, no pollution and the like, provides energy necessary for photosynthesis of plants, can provide power support for other green energy sources such as water energy, wind energy and the like in the nature, and is one of the most promising new energy sources at present. The solar cell device can convert the inexhaustible energy source of solar energy into the electric energy which is essential in the modern society and is visible everywhere. Solar cell devices have recently been the focus of attention of researchers as a new solar application technology. The research on the development of solar cell technology is getting more and more vigorous, photovoltaic devices in the field of solar cells are rapidly developed, and the optimal energy conversion efficiency is continuously refreshed.
Currently, various solar cells have been derived, and research on solar cell devices has been generally progressed in three stages according to their materials and manufacturing techniques. The first generation solar cell represented by silicon base mainly comprises monocrystalline silicon, polycrystalline silicon and amorphous silicon, and the silicon base solar cell has a plurality of excellent characteristics, such as higher photoelectric conversion efficiency, larger absorption spectrum range, green, safe and reliable raw materials and the like; nevertheless, the silicon-based solar cell still has a not-to-be-ignored defect, such as the need of high-purity silicon material in the manufacturing process, complicated manufacturing process, high cost, environmental pollution to a certain extent, etc., which are the bottleneck that hinders the further development of the silicon-based solar cell.
Thin film solar cells, typified by cadmium telluride (CdTe), copper indium gallium selenide (CIS or CIGS), gallium arsenide (GaAs) and other multi-element inorganic compounds, are the second stage in the solar cell development history. Compared with the traditional silicon solar cell, the thin film solar cell greatly reduces the consumption of raw materials, improves the yield, has a shorter spectrum absorption range and ideal band gap (1.45 eV), reduces the recombination of carriers at the grain boundary, and improves the collection efficiency of photo-generated carriers. However, the highest efficiency of the current thin film solar cell can reach 30%, but the cost is always high, and the reserves of part of elements on the earth are limited and toxic, so that serious pollution to the environment is easy to cause, and the thin film solar cell cannot become the main development direction of the solar cell technology.
The third generation solar cells currently mainstream are mainly represented by organic solar cells, quantum dot solar cells, dye sensitized solar cells and perovskite solar cells. Organic solar cells are one of the main flows of new generation solar cell technology, and have great progress in recent decades due to the advantages of light weight, low cost, flexible translucency, wide material sources, simple preparation process, easy large-scale commercial production and the like; nevertheless, the conversion efficiency is still low compared to polysilicon and monocrystalline silicon solar cells. The quantum dot solar cell uses quantum dots as photosensitization materials, and has high theoretical energy conversion efficiency and low preparation cost; the energy conversion efficiency of the current quantum dot solar cell is already more than 14%, but still has a large difference from the ideal performance. The dye sensitized solar cell mainly comprises photosensitive dye and nano ferric oxide, and has the advantages of relatively low material acquisition and input cost, simple preparation technology, large commercial development potential, green and harmless raw materials and preparation technology and the like; however, there is a great development space in terms of durability, high efficiency, stability, etc., and these problems restrict the application process of the dye-sensitized solar cell. The perovskite material has excellent photoelectric characteristics such as direct band gap, adjustable forbidden band width, lower carrier recombination rate, higher carrier migration length and the like, so that the perovskite solar cell is the solar photovoltaic device which is the most attention at present, and the energy conversion efficiency reaches more than 25%. Of course, perovskite solar cells also have some problems to be optimized, such as to improve the stability of the device, and the inclusion of soluble heavy metal lead (Pb) in the material.
In the production process, the perovskite thin film with flatness, high coverage rate and few holes is prepared as a basis for realizing a device with high photoelectric conversion efficiency, the quality of the perovskite thin film is a key parameter affecting the photovoltaic performance of the device, and the defects of the perovskite thin film, particularly the interface and the Grain Boundary (GBs) of the perovskite thin film, are not beneficial to the photovoltaic performance and the stability of the perovskite solar cell. When the perovskite light absorption layer in the perovskite solar cell is prepared by a solution method, the nucleation and the crystal growth process are difficult to control because the preparation process involves a complex crystal growth process, so that the crystal quality is poor or the crystal is easy to generate defects, which is usually caused by metal elements which are not normally coordinated. Surface engineering has been widely used to reduce defects at perovskite thin film interfaces, which act as carrier recombination centers, greatly limiting the open circuit voltage (V OC) of organic-inorganic lead halide perovskite solar cells. At the same time, these defects promote rapid penetration and ion migration of water molecules in the perovskite layer, accelerating the degradation of the device in the surrounding environment.
Up to now, various passivation materials have been widely used in perovskite solar cells to suppress defect formation or reduce defect density by molecular interactions with under-coordinated metal cations or halide anions. In particular, passivation of perovskite surface interfaces is considered as an effective means of suppressing non-radiative recombination losses while increasing photovoltage. For example, crown ethers are used to alter the surface properties of perovskite thin films, passivating defects. It is reported that the multifunctional passivating agent 2, 5-thiophenedicarboxylic acid can effectively target interface defects and improve the operation stability of the organic-inorganic lead halide perovskite solar cell. Studies have also found that phenethyl iodinated amines (PEAI) and other amine analogues are effective in reducing defects and inhibiting non-radiative recombination and continuously improving performance. More recently, halides such as quaternary ammonium halides, diammonium iodide, potassium halides, and iodopentafluorobenzenes have been used to deactivate dangling bonds in perovskite layers by exploiting the related intermolecular interactions; at present, the research of improving the performance of a polymer solar cell by alkali metal salt doping is reported, acetic acid and cesium acetate are used as doping agents, the concentration of the alkali metal salt is controlled, and the influence of different doping concentrations on experimental results is explored; experimental results show that the alkali metal salt doped ZnO electron transport layer has an improvement effect on the electrical property of the polymer solar cell device; meanwhile, the defect states in and on the surface of the ZnO film modified by alkali metal salt are reduced, more convenient conditions are provided for carrier transmission, the light absorption capacity of the active layer is improved to a certain extent, more excitons are generated, and the enhancement effect on the light current is remarkable.
Disclosure of Invention
Based on the defects of perovskite thin film interfaces and Grain Boundaries (GBs) which are unfavorable for the photovoltaic performance and stability of perovskite solar cells, the multifunctional alkali metal polymer is adopted to regulate the crystallization process of the FAPbI 3 perovskite thin film in the research, so that the Power Conversion Efficiency (PCE) is remarkably improved, the operation stability is improved, and the environmental influence is minimized. Based on this study, the present invention has been completed.
In a first aspect, the invention provides an alkali metal polymer, which is obtained by an acid-base neutralization reaction of an alkali metal salt and a high molecular organic compound containing an acidic group in an organic solution, wherein the structural formula of the alkali metal polymer is shown as i:
wherein R1, R2, r3=c, H, O, S, N, CH 2,CF2; n=10-100000000.
Further, the alkali metal is selected from one or more of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr).
Still further, the alkali metal salt is selected from the group consisting of carbonates, bicarbonates, alkali metal nitrates, alkali metal sulfates, and the like, formed from the alkali metal.
Still further, the alkali metal salt is preferably a carbonate and/or bicarbonate.
In one embodiment, the alkali metal carbonate is selected from one or more of K 2CO3、Rb2CO3 and Cs 2CO3, and the like.
Further, the acidic group refers to a carboxylic acid group (-COOH).
Further, the polymer compound containing an acidic group is selected from polymer compounds containing a carboxylic acid group or a mixture thereof;
further, the polymer compound of the acidic group is preferably: polyacrylic acid (PAA)
Further, all organic solutions refer to solvents for synthesizing organic or inorganic alkali metal polymers, which are selected from one or more of toluene, n-hexane, chloroform, iodobenzene, chlorobenzene, o-dichlorobenzene, anisole, ethyl acetate, methyl acetate, sec-butanol, acetonitrile.
In a second aspect, the present invention provides an alkali metal polymer modified photoelectric conversion material.
Further, the modification is to spin-coat an organic solution containing an alkali metal polymer on the surface of the photoelectric conversion material to participate in improving the crystallization process of the photoelectric material.
Further, the photoelectric conversion material is selected from one or more of FAPbI 3、MAPbI3、CsPbI3、(FAPbI3)1-x(MAPbBr3)x;
In one embodiment, the photoelectric conversion material is preferably a perovskite thin film (FAPbI 3).
In a third aspect, the present invention provides a photovoltaic device made from an alkali metal polymer modified photovoltaic conversion material.
Further, the optoelectronic device includes a laminated substrate, a metal anode, a hole collection layer, a hole transport layer, a light absorption layer, an electron transport layer, and a conductive base.
Further, the light absorbing layer is made of an alkali metal polymer modified photoelectric conversion material.
Further, the photoelectric conversion material is selected from one or more of FAPbI 3、MAPbI3、CsPbI3、(FAPbI3)1-x(MAPbBr3)x.
In one embodiment, the photovoltaic device produced is a perovskite solar cell.
In a fourth aspect, the present invention provides a process for the preparation of an alkali metal polymer, the process comprising the steps of:
s1, mixing a high molecular compound containing an acid group and an alkali metal salt in an organic solvent;
S2, stirring the mixed solution to synthesize the alkali metal salt polymer.
S3, filtering the solution to obtain an alkali metal salt polymer.
Further, the organic solvent is preferably chlorobenzene, o-dichlorobenzene, toluene, anisole, ethyl acetate or the like.
Further, the polymer compound of an acidic group and the alkali metal salt are represented by 1:1-3 moles mixing in proportion.
In a fifth aspect, the present invention provides a method for producing a photovoltaic device produced from an alkali metal polymer-modified photovoltaic material, the method comprising the steps of:
s01, preparing an etched, clean and dry substrate material, and spin-coating or soaking the substrate material in a mesoporous layer-by-layer solution to finish a compact layer and a mesoporous layer to form a mesoporous substrate;
S02, preparing a precursor solution of the photoelectric conversion material, and spin-coating the precursor solution of the photoelectric conversion material on a mesoporous substrate by using a one-step solution method to prepare a photoelectric conversion material film;
s03, after spin coating is completed, dripping an organic solution of an alkali metal polymer on the film prepared in the S02, and annealing to obtain a film of the photoelectric conversion material modified by the alkali metal polymer;
S04, preparing a hole transport layer precursor solution, coating the solution on the alkali metal polymer modified photoelectric conversion material film, and depositing a gold electrode through thermal evaporation to finish device manufacturing.
Further, the substrate material is preferably FTO, ITO flexible substrate, or the like.
Further, the mesoporous layer solution is selected from one or more of TiO 2、SnO2 and NiOx, PTAA, SAM, preferably mesoporous TiO 2 slurry.
Further, the precursor solution of the photoelectric conversion material as described in S02 includes Dimethylformamide (DMF), dimethylsulfoxide (DMSO), 1, 4-butyrolactone, DMA, methylamine, acetonitrile, and the like.
Further, the precursor solution is subjected to a one-step spin coating method, and the spin coating speed is 1000-6000rpm; the spin coating time is 10-30 seconds.
Further, the hole transport layer precursor as described in S04 is preferably a spiro-ome tad solution.
In a sixth aspect, the present invention provides the use of an alkali metal polymer in a solar cell.
Further, the solar cell is selected from one or more of FAPbI 3、MAPbI3、CsPbI3、(FAPbI3)1-x(MAPbBr3)x.
Drawings
FIG. 1 Process for synthesizing alkali Metal polyacrylic acid
FIG. 2, panel a, is the molecular structure of PAA and PAA-Rb polymers. Figure b schematic of perovskite film preparation by modification of antisolvents. Figure c is the XRD pattern of the perovskite film. Surface SEM images and cross-sectional SEM (upper right hand corner of the figure) of perovskite thin films of the experimental control group (panel d), PAA treated group (panel e) and Rb-PAA treated group (panel f) were scaled to 0.5 μm. XPS nuclear energy spectra of Pb 4f (panel g) and Rb 3d (panel h). FIG. i is a TOF-SIMS depth profile of Rb-PAA treated perovskite solar cell.
FIG. 3 is a schematic representation of the preparation of alkali metal polyacrylic acid passivated perovskite thin films.
Figure 4 is a graph of statistics of photovoltaic parameters for different alkali metal polyacrylates.
Figure 5. Optimization of performance at different concentrations.
Fig. 6. Small angle XRD of perovskite thin films at 0.8 °.
FIG. 7 XPS nuclear energy spectrum of oxygen
FIG. 8 effect of Rb-PAA treatment on optical and electrical properties of perovskite thin films. (a) ultraviolet-visible and PL spectra. (b) Time Resolved Photoluminescence (TRPL) spectra. An ultraviolet electron spectroscopy (UPS) spectrum in the secondary electron cutoff (c) and valence band (d) regions for the control and treated perovskite thin film. Kelvin Probe Force Microscopy (KPFM) images of control (e), PAA treatment (f) and Rb-PAA treatment (g). (h) graph corresponding surface potential. 2e-g.
FIG. 9 Atomic Force Microscope (AFM) images of control, PAA and Rb-PAA samples
Fig. 10 photovoltaic device performance. (a) Photovoltaic index of undoped Rb-PAA (control), doped PAA, device after treatment with Rb-PAA (target). (b) The champion target PSC measured J-V curves in both the reverse and forward scan modes. (c) EQE spectrum (left axis) and integrated Jsc (right axis) of champion target PSC. (d) Stable V OC of the layered structure glass/FTO/compact-TiO 2/meso-TiO 2/perovskite/interfacial layer/HTL and quasi-fermi level splitting Δef/q.
FIG. 11 comparison of optimal efficiency for control, PAA and Rb-PAA samples
Fig. 12 device stability and environmental impact. (a) Stability of the control and target PSCs without encapsulation under 1 sun simulated illumination in ambient air. (b) Stability of the unpackaged control and target PSCs on hot plates at about 65 ℃ in dry air. (c) lead leakage test schematic. (d) Lead leakage was evaluated when the solar cell was immersed in water, and the concentration of lead in water was determined by inductively coupled plasma emission spectroscopy (ICP-OES) measurement.
Fig. 13. Stability of control, PAA and target PSCs in ambient air at 1 sun simulates illumination for 160 hours.
Detailed Description
Alkali metal: the metal elements of group IA of the periodic Table include six kinds of metal elements including lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr), the first five kinds of metal elements exist in nature, and francium can only be produced by nuclear reaction. Alkali metal is a very metallic element, and simple substance is also typical metal, and has strong electric conductivity and thermal conductivity. The simple substance of alkali metal has high reactivity and exists only as salts in natural state.
Band gap: the band gap is the difference in energy between the lowest point of the conduction band and the highest point of the valence band; also known as the energy gap. The larger the band gap, the more difficult it is for electrons to be excited from the valence band to the conduction band, the lower the intrinsic carrier concentration and thus the lower the conductivity.
The microstructure of the perovskite crystal is a three-dimensional framework formed by mutually connecting octahedral arrays through vertexes, wherein metal cations are positioned in a body center, halogen anions are positioned in a face center, and organic or inorganic cations are positioned in gaps of the octahedron to form coordination with peripheral 12 ions. As a material capable of generating electricity and emitting light, the perovskite has the characteristics of low preparation cost, high fluorescence quantum efficiency, high color purity, adjustable color and the like.
Organic-inorganic lead halide Perovskite Solar Cells (PSCs) are receiving widespread attention for their low cost fabrication, flexibility and high efficiency. The Power Conversion Efficiency (PCE) of PSCs rapidly increased from 3.8% to an authentication value of 25.7% over decades. Although FAPbI 3 -based PSCs hold promise in the next generation photovoltaic field, they still suffer from poor operational stability and potential negative environmental impact due to the ease of degradation under ambient conditions, as well as toxic lead components.
EXAMPLE 1 Synthesis of alkali Polymer
An alkali metal polyacrylic acid compound was synthesized by mixing polyacrylic acid (PAA) and alkali metal carbonate (K 2CO3、Rb2CO3 and Cs 2CO3) in a molar ratio of 1:1.5 in 1mL of anhydrous chlorobenzene and uniformly stirring at room temperature. The amount of acrylic acid (PAA) was 0.01mg/mL.
Example 2 perovskite solar cell preparation
(1) Fluorine doped tin oxide glass Substrates (FTOs) were etched using zinc powder and concentrated hydrochloric acid (1M).
(2) The etched FTO was washed in ultrasonic waves sequentially with 2% commercial detergent (Hellmanex) aqueous solution, ethanol and acetone for 15 minutes, rinsed with deionized water, and then the FTO substrate was dried using compressed air.
(3) Diisopropyl di (acetylacetonate) titanate with the content of 75% is diluted by ethanol with the volume ratio of 1:9, acetylacetone with the volume ratio of 4% is added, and finally the titanium dioxide electron transport layer precursor solution is prepared.
(4) After the dried FTO substrate was treated with uv ozone for 15 minutes, a precursor solution of titanium diisopropoxybis (acetylacetonate) was deposited onto the cleaned FTO substrate by spray pyrolysis using oxygen as a carrier gas at 450 ℃.
(5) After the titanium dioxide electron transport layer was cooled to room temperature, the substrate was subjected to ultraviolet ozone treatment for 15 minutes, and mesoporous TiO2 (mp-TiO 2) solution (weight ratio to ethanol: 1:6) was previously dispersed with ethanol, and the mesoporous TiO 2(mp-TiO2 solution was spin-coated onto the dense layer TiO 2 at a rotation speed of 4000rpm, to obtain a mesoporous layer having a thickness of 100 to 150 nm. The mesoporous TiO 2 film was gradually heated to 450 ℃ for sintering, held at this temperature for 30 minutes, and cooled to room temperature.
(6) Before use, the mesoporous TiO 2 film was treated with 0.1M Li-TFSI acetonitrile solution, spun at 3000rpm for 20 seconds, and then sintered at 450℃for 30 minutes.
(7) After cooling the above mesoporous film to 150 ℃, the substrate was transferred into a dry air glove box (relative humidity < 15%) to deposit a perovskite film.
(8) Perovskite precursor solutions were prepared by mixing powders of lead iodide (1.51M, alfaAesar), formamidine iodide (1.47M, greatcell) and methylamine bromide (0.045M, greatcell), lead bromide (0.045M, TCI) and methylamine chloride (0.6M, sigmaAldrich) and dissolving in a mixed solution of DMF and DMSO (mixing ratio 4:1).
(9) The perovskite precursor solution was spin coated onto a mesoporous TiO 2 (mp-TiO 2) substrate. The precursor solution was spin coated in a two-step spin coating process at 1000rpm for 10 seconds and then 6000 rpm for 25 seconds. 10s, 200-300. Mu.l of chlorobenzene solution with or without alkali metal functionalized polymer was dropped on the perovskite film before the end of the second spin-coating step. The film was then annealed in a heated station at 150 ℃ for 10 minutes to finally obtain a perovskite film.
(10) A hole transport layer precursor solution was prepared by adding 40mM Li-TFSI (99.95%, sigma-Aldrich) and 270mM tBP (96%, sigma-Aldrich) additives to a solution of spiro-OMeTAD at a concentration of 75mM, and the solution was spin-coated dynamically on a perovskite film at a speed of 3000rpm for 30s. Device fabrication was then completed by thermal evaporation deposition of gold electrodes (-70 nm).
Example 3 analysis of results
(1) Synthesis of alkali metal polymers
Alkali metal salt polyacrylic acid (PAA) complexes were synthesized by mixing PAA organic polymer with alkali metal carbonate in Chlorobenzene (CB), as shown in fig. 1 and 2a. The synthesized alkali metal functionalized PAA complex solution was used as an antisolvent for preparing perovskite thin films (fig. 3). Unless otherwise indicated, the present invention uses (FAPbI 3)0.97(MAPbBr3)0.03, FAPbI 3 component perovskite-based to prepare solar cell devices.
As shown by the photovoltaic performance of the solar cell (as shown in fig. 4-5), the process conditions (i.e., concentration and alkali cation) are optimized; the best condition is an Rb-PAA complex concentration of 0.1mg/mL for further investigation (expressed as Rb-PAB).
(2) Analysis of crystallinity and structural characteristics of perovskite thin films by X-ray diffraction at different incident angles
As shown in fig. 2c and 6, both the control and target films showed well crystallized photosensitive alpha phase of the 3D perovskite with two peaks at 14.2 ° and 28.4 °, belonging to (110) and (220), respectively, indicating that all films had good crystallinity. The small signal of PbI 2 appears at 12.7 ° of the control film at the small angle X-ray diffraction (SAXS) of the perovskite film at 0.8 ° (see fig. 6), which is well known for the prepared perovskite formulation; excess PbI 2. In contrast, the signal of excess PbI 2 was sharply suppressed in the PAA and Rb-PAA treated films, especially in the latter films; as shown in fig. 2d-f, the morphology of the perovskite surface was analyzed by Scanning Electron Microscope (SEM) top view images. All control and treated perovskite films had similar dense structures with grain sizes in the hundreds of nanometers with no observable pinholes. Meanwhile, the grain size (1.44 μm) of the Rb-PAA treated perovskite film was slightly larger than that of the PAA treated film (1.14 μm) and the control film (1.02 μm), resulting in reduction of grain boundaries and defects.
(3) The surface composition of the perovskite thin film was studied by X-ray photoelectron spectroscopy (XPS).
The XPS spectrum in the Pb4f range (FIG. 2 g) shows two signals in the control film, binding energies of 138.5 and 143.3eV, respectively, attributable to Pb4f 7/2 and Pb4f 5/2, and two small main peaks at 136.6 and 141.6eV, due to the presence of metallic lead (PbO). The signal of metal Pb disappeared in Rb-PAA treated films, indicating that polyacrylic acid was able to bind to Pb 2+ ions responsible for the formation of the undercooked Pb metal, which was evidenced by a slight shift of peak position to low binding energy. This would greatly benefit the operational stability of the PSC because of the presence of elemental lead. XPS spectra of the Rb3d level range in the treated films showed two 109.9 and 111.5eV signals assigned to Rb3d 3/2 and 3d5/2 levels, respectively (FIG. 2 h), whereas no signal was observed in the control perovskite film. This result demonstrates that Rb + has successfully transferred to the target perovskite thin film. Furthermore, the presence of an O1s energy level peak at 533.1eV indicates the presence of polyacrylic acid at the top surface of the target film (fig. 7). It is deduced that PAA is mainly distributed on the top surface of the perovskite thin film because long chain structures create large-sized regions with steric hindrance. With the benefit of this, PAA acts as a passivating agent at the film surface between the perovskite and HTL by coordinating c=o with the undercrown Pb 2+ ions, thereby reducing the trapping state of the top surface.
(4) Distribution of Rb + in perovskite blocks
In the synthesis of Rb-PAA complexes, rb 2CO3 reacts with PAA (polyacrylic acid) as a simple acid-base neutralization reaction, and Rb-PAA is an ionic compound, i.e. intermolecular bond. The Rb + ion and-COO-groups are soft ionic bonds rather than solid covalent bonds. At this point, the Rb + ion is much easier to separate from the Rb-PAA complex, especially in chlorobenzene solutions, even in the wet perovskite films produced. During the anti-solvent drop process, chlorobenzene can carry DMF and DMSO away from the wet perovskite film, and Rb-PAA complex will be uniformly distributed in the perovskite film bulk. Due to the large molecular size domains of sterically hindered PAA polymers, the PAA polymers redistribute during annealing and are mainly present at the film surface, while the easily separated Rb + ions will be mainly retained in the bulk of the perovskite film.
To further investigate the distribution of Rb + in the perovskite bulk, the depth profile was measured using time of flight secondary ion mass spectrometry (TOF-SIMS) to investigate the ion distribution in the target perovskite thin film (fig. 2 i). The Rb+ ions were predominantly present in the bulk perovskite, indicating that Rb + ions were successfully incorporated into the perovskite from the Rb-PAA complex. More interestingly, PAA predominantly occupies the surface of the perovskite at the beginning of sputtering, indicated by a strong-COO-signal (inset in fig. 2 i), which enables the Rb-PAA complex to act as a synergistic passivation through easy separation of PAA polymer and Rb + ions. Meanwhile, rb + ions, pb 2+ and I - ions are uniformly distributed, and further doping rubidium ions can obtain a more uniform passivation effect. (5) optical and electronic properties of perovskite thin films.
As shown in fig. 8a, the ultraviolet-visible (UV-Vis) absorption spectra show that the positions of the absorption edges are all around 800nm, and have good light absorption ranges, indicating that Rb-PAA and PAA treatments do not change the optical properties (i.e., optical band gap) of the perovskite thin film. This result further shows that the incorporation of PAA has no effect on the crystallization of the perovskite and that Rb + is not incorporated into the lattice to form Rb-based perovskite, resulting in the formation of a narrower bandgap perovskite structure. Photoluminescence (PL) spectra showed that the emission intensity of Rb-PAA treated films was about 2 times higher than that of PAA alone or untreated films, indicating that doping Rb + can effectively reduce defect density, thereby minimizing non-radiative recombination. Since Rb + is far smaller than the radii of FA, MA and Cs and proved not to be incorporated into bulk perovskite by occupying the a cation sites, it was determined that it passivated grain boundary defects by Rb + -rich phases.
(6) Carrier transport and recombination studies of perovskite layer
The carrier transport and recombination of the perovskite layer was studied by Time Resolved Photoluminescence (TRPL) measurements, the recombination in TRPL being mainly first order trap assisted recombination from the TRPL spectrum shown in fig. 8 b. The fit life of the perovskite thin film increases dramatically from 470ns to 1059ns due to Rb + and PAA passivation effects (table 1). The longer the carrier lifetime, the lower the non-radiative recombination rate associated with reduced trap states in the perovskite film, resulting in higher Voc of the PSC. The enhanced PL intensity and significantly prolonged charge carrier lifetime of perovskite thin films with Rb + are due to reduced defects. In addition, perovskite thin films with Rb + have longer carrier lifetimes, which is also consistent with micron-sized grains with fewer grain boundaries, which serve as recombination centers and carrier traps.
Table 1 shows the TRPL results of the exponential fit.
The effect of Rb-PAA treatment on the energy level of the perovskite film was studied by ultraviolet electron spectroscopy (UPS) characterization, as shown in FIGS. 8c-d, with no significant change in VBM and CBM values for all samples, indicating that Rb-PAA treatment did not change the electronic structure of the perovskite film.
In addition to these structural changes, kelvin Probe Force Microscopy (KPFM) also showed that the electronic structure of the treated perovskite film surface was different from the control sample. As shown in fig. 8e-h and fig. 9, the target Rb-PAA doped perovskite thin film had a higher and more uniform surface with a more uniform surface potential distribution ranging from + 5mV, while others showed similar ranges of + 10 mV. This suggests that the number of grain boundaries in the perovskite layer is reduced after Rb-PAA treatment, thus reducing defect density and carrier recombination.
(7) PSC photovoltaic performance and stability study
To investigate the photovoltaic properties of the corresponding PSC, a widely used conventional device structure was employed here, namely FTO/dense layer (TiO 2, -50 nm)/mesoporous layer (TiO 2, -150 nm)/(FAPbI 3) 0.97 (MAPbBr 3) 0.03 perovskite layer (650 nm)/hole transport layer (Spiro-OMeTAD, -150 nm)/Au (80 nm). The Rb-PAA treated target device was compared to devices without any passivation and PAA passivation, where both PAA and Rb + were dissolved in CB as anti-solvent. As shown in fig. 10a and 11, this base functionalized polymer passivation strategy significantly improved the performance of PSCs compared to the control. The improvement in the overall performance of the device is mainly due to the improvement in the open circuit voltage (Voc) and the Fill Factor (FF). After addition of Rb-PAA, voc increased from 1.10.+ -. 0.02V to 1.170.+ -. 0.005V and FF increased from 76.9.+ -. 1.2% to 80.9.+ -. 1%. These improvements significantly increase the Power Conversion Efficiency (PCE) (average) from 21.2±1.1% to 23.6±0.5%. Further reduces the content of MAPbBr3 in the FAPbI 3-based perovskite from 3mol% to 1.5mol%, thereby obviously improving the photovoltaic performance of the target device. As shown in FIG. 10b, the champion Rb-PAA polymer processing device had a reverse scan PCE of 24.93%, voc of 1.185V, jsc of 25.42mA/cm 2, FF of 82.8%, PCE 24.69%, for forward scan, voc of 1.178V, jsc of 25.49mA/cm 2, FF of 82.2% and stability efficiency of 24.74%. The External Quantum Efficiency (EQE) of the device was measured (fig. 10 c) and the integrated current closely matched the Jsc value obtained from the J-V curve.
The above results indicate that by incorporating the base functionalized polymer into the bulk and the surface of the FAPbI 3 -based perovskite film, the interfacial non-radiative recombination process is inhibited (fig. 10 d).
To explore this further, quasi-fermi level splitting (Δe F) was calculated by measuring the photoluminescence quantum yield (PLQY). As shown in fig. 9, the PLQY of the target device was about 16 times higher than the control sample. The interfacial layer results in a significant reduction of interfacial recombination at the perovskite/HTL interface and grain boundaries, which means improved defect chemistry. From PLQY, ΔE F can be calculated by the following equation:
ΔEF＝qVOC,rad+kBTln(PLQY)
Where q is the fundamental charge, V OC,rad is the radiative limit of V OC, k B is the boltzmann constant, and T is the device temperature (25 ℃). The ΔE F/q of the differently treated films is shown in FIG. 10 d. The control film showed a ΔE F of 1.131meV, while the Rb-PAA passivated target film showed a 51meV ΔE F increase. Since Δe F/q is the theoretical maximum V OC,rad of PSC with this layered structure, a quasi-steady state V OC,rad was measured, i.e. stable after two minutes of exposure to 1 sun simulated illumination. V OC,rad after Rb-PAA passivation increased 67mV to 1.165mV from 1.098V compared to control samples, consistent with the trend seen in the ΔE F measurement; the offsets between stable V OC,rad and ΔE F/q are 34mV and 17mV, respectively, corresponding to the control and target devices.
As to the MPP operation stability of PSC under 1 solar light intensity irradiation under dry air flow, as shown in fig. 12 a. After 500 hours of operation, the Rb-PAA passivated PSC retained 83% of its initial efficiency, while the non Rb-PAA polymer treated PSC had an efficiency of 30%.
To investigate whether the improvement in stability is primarily from the synergistic passivation of PAA polymers or Rb-PAA complexes, the operation stability test of PAA treated PSCs was also compared under the same measurement conditions as before. As shown in FIG. 12a, the PAA-treated PSC showed better stability than the control device, but was still lower than the Rb-PAA-treated PSC. Thus, we conclude that the enhanced operational stability of Rb-PAA treated PSC is due to the synergistic passivation of PAA and Rb +.
To further test the thermal stability, the Rb-PAA passivated and non Rb-PAA passivated PSCs were aged at 65℃under ambient conditions of RH (relative humidity) of 30%, the results are shown in FIG. 12 b. It was observed that after 600 hours, PSCs passivated with Rb-PAA were reduced by less than 10%, compared to about 20% for the control samples. The enhanced environmental and operational stability can be attributed to the lower defect concentration at the interface between the hole transport material and the perovskite absorber layer, and the lower impurities on the surface and inside (including excess PbI 2 and non-perovskite polymorphs) FAPbI 3, caused in large part by the injection of Rb +.
From the above, it can be seen that high thermal stability can be attributed to the rigidity of ligands containing carbonyl and hydrogen bond donors, thereby maintaining passivation of various cationic and anionic defects through coordination and hydrogen bonding. The strong binding of the ligand on the surface results in suppressed interfacial recombination and migration of the halide into the Hole Transport Layer (HTL); furthermore, PAA polymers have the potential to inhibit lead leakage due to interactions between c=o bonds and lead. This was explored by immersing the solar cell in water and quantifying the lead content (fig. 12c, d), the presence of PAA polymers can mitigate the detrimental effects of lead on the environment. This has been shown by the optimal concentration of PAA used in solar cell fabrication, which is quite low, and increasing this content may further suppress the effect of lead on the environment.
In summary, the present invention uses a solution of a synthetic Rb-PAA complex to control the formation of FAPbI 3 -rich perovskite crystals and defects. Electro-optic characterization shows that PAA polymers can not only act as carriers for alkali ions, but also passivate surface defects through their multiple c=o functionalities. The Rb-PAA treated perovskite thin film exhibits less non-radiative charge carrier recombination, i.e., lower defect density, and significantly improved charge extraction from the perovskite thin film to the HTL. An increase of 60mV in V OC was observed for Rb-PAA treated devices compared to control samples. The results show that the best performing device produced a high PCE of 24.93% with improved operational stability. The Rb-PAA treated PSC retained over 83% of initial efficiency after 500 hours of continuous operation under standard simulated solar intensity illumination and over 90% of initial efficiency (20% RH) after 600 hours of aging on a hot plate at about 65 ℃ in dry air (see fig. 13). Meanwhile, lead leakage is also inhibited due to the strong interaction between PAA and Pb 2+, which is critical for commercialization of PSC. This work provides a simple and efficient method to manufacture perovskite photovoltaic cells with excellent performance and operational stability.
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