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Cations with suitable sizes to occupy an interstitial site of perovskite crystals have been widely used to inhibit ion migration and promote the performance and stability of perovskite optoelectronics. However, such interstitial doping inevitably leads to lattice microstrain that impairs the long-range ordering and stability of the crystals, causing a sacrificial trade-off. Here, we unravel the evident influence of the valence states of the interstitial cations on their efficacy to suppress the ion migration. Incorporation of a trivalent neodymium cation (Nd3+) effectively mitigates the ion migration in the perovskite lattice with a reduced dosage (0.08%) compared to a widely used monovalent cation dopant (Na+, 0.45%). The photovoltaic performances and operational stability of the prototypical perovskite solar cells are enhanced with a trace amount of Nd3+ doping while minimizing the sacrificial trade-off.
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Waterborne fluoropolymer emulsions were synthesized using the one-step semi-continuous seed emulsion polymerization of chlorotrifluoroethylene (CTFE), vinyl acetate (VAc), n-butyl acrylate (BA), Veova 10, and acrylic acid (AA). The main physical parameters of the polymer emulsions were tested and analyzed. Characteristics of the polymer films such as thermal stability, glass transition temperature, film-forming properties, and IR spectrum were studied. Meanwhile, the weatherability of fluoride coatings formulated by the waterborne fluoropolymer and other coatings were evaluated by the quick ultraviolet (QUV) accelerated weathering test, and the results showed that the fluoropolymer with more than 12% fluoride content possessed outstanding weather resistance. Moreover, scale-up and industrial-scale experiments of waterborne fluoropolymer emulsions were also performed and investigated.
Assuntos
Acrilatos/química , Clorofluorcarbonetos/química , Ácidos Decanoicos/química , Polímeros de Fluorcarboneto/síntese química , Compostos de Vinila/química , Calorimetria , Emulsões/química , Polimerização , Espectroscopia de Infravermelho com Transformada de Fourier , Tempo (Meteorologia)RESUMO
Perovskite solar cells (PSCs) have led to distinguished achievements and become one of the state-of-the-art photovoltaic technologies. Undoubtedly, reliable preparation of large area high-quality perovskite (PVK) films with uniform optoelectronic properties has become a critical and challenging task to transition PSCs from lab to market. Here, methyldiphenylphosphine oxide (MDPPO) is employed as an additive in a PVK precursor solution to promote uniform conductivity and carrier transport of PVK films. More important, to check its compatibility with the upscaling process, the MDPPO additive strategy was further applied to doctor-blade large-area PVK films. As a result, benefit from the favorable role of MDPPO additive, the power conversion efficiencies (PCEs) of small-area PSCs reach 23.85% with superb open circuit voltage (Voc) of 1.15 V and fill factor of 81.21%, while an impressive PCE of 19.22% was achieved for the large-area PSC minimodules with active area of 61.48 cm2. Remarkably, the MDPPO modified device exhibits significantly improved operational stability, maintaining an initial efficiency of 68% even after 750 h under continuous 1-sun illumination. Our achievements will provide profound insight and further guidance for the scale-up process of PSCs from lab to large-scale modules.
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Sn-doped lead halide perovskites (LHPs) have attracted considerable attention for their lower bandgap and lower toxicity. While it is well-established that Sn doping easily introduces a lot of structural defects into LHP films, the extent to which these defects impact carrier dynamics has yet to be fully elucidated. Herein, we take Sn-doped MAPbBr3 films as an example to explore the influence of Sn doping on their carrier dynamics. The results show that Sn doping can simultaneously introduce many fillable electron traps and unfillable hole traps, consequently instigating an ultrafast carrier capture process. This further elicits long-lived internal charge separation between band edge and trap states or between two kinds of trap states, thereby enabling these carriers to persist for up to â¼2.6 µs. Our findings suggest that Sn doping potentially serves as an effective strategy to prolong the carrier lifetime in LHPs, which could pave the way for potential applications within Sn-based perovskites.
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Interface modification and bulk doping are two major strategies to improve the photovoltaic performance of perovskite solar cells (PSCs). Dipolar molecules are highly favored due to their unique dipolarity. This review discusses the basic concepts and characteristics of dipoles. In addition, the role of dipoles in PSCs and the corresponding conventional characterization methods for dipoles are introduced. Then, we systematically summarize the latest progress in achieving efficient and stable PSCs in dipole materials at several key interfaces. Finally, we look forward to the future application directions of dipole molecules in PSCs, aiming at providing deep insight and inspiration for developing efficient and stable PSCs.
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Perovskite solar cells (PSCs) are usually modified and passivated to improve their performance and stability. The interface modification and bulk doping are the two basic strategies. Fluorine (F)-containing materials are highly favored because of their unique hydrophobicity and coordination ability. This review discusses the basic characteristics of F, and the basic principles of improving the photovoltaic performance and stability of PSC devices using F-containing materials. We systematically summarized the latest progress in the application of F-containing materials to achieve efficient and stable PSCs on several key interface layers. It is believed that this work will afford significant understanding and inspirations toward the future application directions of F-containing materials in PSCs, and provide profound insights for the development of efficient and stable PSCs.
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Defect passivation through Lewis acid-base chemistry has recently attracted significant interest because of its proven ability to improve the power conversion efficiency (PCE) and stability of perovskite solar cells (PSCs). However, tedious trial-and-error procedures are commonly used for the selection of Lewis molecules due to their abundant variety. Herein, two typical Lewis base molecules, the M molecule containing only carbonyl groups and the 3M molecule containing both carbonyl and carboxyl groups, are proposed to passivate the Pb-based defects and mitigate their negative impacts on PSC performance. The results indicated that much stronger coordination bonds can be formed between the 3M molecule and uncoordinated Pb2+ than with the M molecule. Because of the benefit from the synergetic co-passivation effect of carbonyl and carboxyl groups, an impressive maximum PCE of 24.07% was achieved via 3M modification. More importantly, the modified devices demonstrated remarkably improved operational stability.
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Interfacial passivation engineering plays a crucial role in the explosive development of perovskite solar cells (PSCs). However, previous studies on passivation layers mainly focused on the defect-passivation mechanism rather than the interfacial charge transport efficiency. Here, by precisely tuning the interplanar spacing of the ammonium iodide passivation layer, we elucidate the promoting effect of the reduced interplanar spacing of the passivation layer on the photogenerated hole tunneling efficiency at the interface of the hole transport layer and perovskite. Compared with the commonly used phenethylammonium iodide passivation layer with a wider interplanar spacing, 2-chlorobenzylammonium iodide with a narrower interplanar spacing can help break through the thickness limitation of the passivation layer, thus showing a better comprehensive passivation effect. Therefore, we demonstrate photovoltaic devices with an enhanced fill factor (FF) and open-circuit voltage (VOC), which yield a high power conversion efficiency (PCE) of up to 23.1%. We thus identify an efficient scheme to achieve optimal passivation conditions for high-performance PSCs.
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Semitransparent organic photovoltaics (OPVs) have drawn significant attention for their promising potential in the field of building integrated photovoltaics such as energy-generating greenhouses. However, the conflict between the need to attain satisfying average visible transmittances for greenhouse applications and the need to maintain high power conversion efficiencies is limiting the commercialization of semitransparent OPVs. A major manifestation of this issue is the undermining of charge carrier extraction efficiency when opaque, visible-light-absorbing electrodes are substituted with semitransparent ones. Here, we incorporated a dual-function p-type compatible interlayer to modify the interface of the hole-transporting layer and the ultrathin electrode of the semitransparent devices. We find that the p-type interlayer not only enhances the charge carrier extraction of the electrode but also increases the light transmittance in the wavelength range of 400-450 nm, which covers most of the photosynthetic absorption spectrum. The modified semitransparent devices reach a power conversion efficiency of 13.7% and an average visible transmittance of 22.2%.
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Silver-doped zinc oxide (Ag:ZnO) nanostructures were prepared by a facile and efficient wet oxidation method. This method included two steps: metallic Zn thin films mixed with Ag atoms were prepared by magnetron sputtering as the precursors, and then the precursors were oxidized in an O(2) atmosphere with water vapour present to form Ag:ZnO nanostructures. By controlling the oxidation conditions, pure ZnO and Ag:ZnO nanobelts/nanowires with a thickness of â¼ 20 nm and length of up to several tens of microns were synthesized. Scanning electron microscopy, transmission electron microscopy, cathodoluminescence and low temperature photoluminescence (PL) measurements were adopted to characterize the microstructure and optical properties of the prepared samples. The results indicated that Ag doping during magnetron sputtering was a feasible method to tune the optical properties of ZnO nanostructures. For the Ag:ZnO nanostructures, the intensity of ultraviolet emission was increased up to three times compared with the pure ones. The detailed PL intensity variation with the increasing temperature is also discussed based on the ionization energy of acceptor in ZnO induced by Ag dopants.
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A simple two-steps method has been successfully developed to synthesize ZnO nanotubes. The alkaline etching process was investigated in detail using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The formation of ZnO nanotube structures was due to the preferential dissolution of the defect-rich top (polar) faces. Cathodoluminescence (CL) was performed on both top and side surfaces of the ZnO tubes. Only the near-band-edge UV emission was observed, implying that the as-grown ZnO nanotubes have a very low concentration of defects. This CL result also provides evidence for explanation of ZnO tubular structure growth.
Assuntos
Medições Luminescentes/métodos , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Óxido de Zinco/química , Eletrodos , Medições Luminescentes/instrumentação , Substâncias Macromoleculares/química , Teste de Materiais , Microesferas , Conformação Molecular , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
PbSe films deposited by chemical bath deposition (CBD) technology were sensitized in various atmospheres to distinguish the role of iodine and oxygen in the sensitization process. No infrared (IR) photo response was observed in samples sensitized in pure oxygen, showing the O element cannot trigger the infrared response of PbSe. However, a high detectivity of 1 × 1010 was achieved in the sample sensitized in a N2/I2 atmosphere, which demonstrates iodine is a key element for inducing an IR response. The role of iodine was analyzed from the morphological evolution, phase composition transformation and resistance change during the sensitization process. The XRD and FESEM results show a PbI2 3D network forming around the PbSe grains in the sensitization process, playing the role of photo-generated electron transporting channels, which is key to inducing the IR response of PbSe detectors. The 3D network conducting model can explain well the charge separation mechanism of PbSe IR photoconductive detection.
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In perovskite solar cells (PSCs), the hole-transport layer (HTL) plays an essential role in effective charge transport and extraction from the photoexcited perovskite, thus being significant for overall power conversion efficiency (PCE) and operational stability. So far, spiro-MeOTAD has been the most widely used HTL despite its inherent drawbacks, such as highly hygroscopic nature, poor conductivity, and mismatched energy-level alignment with the perovskite active layer. Here, a spiro-MeOTAD-based composite HTL modified by microwave method-synthesized carbon quantum dots (CQDs) was proposed and demonstrated as a promising HTL candidate for high-performance PSCs. The results demonstrated that the CQDs/spiro-MeOTAD composite HTL possesses several appealing characteristics for PSC applications, such as suitable energy levels for hole extraction, passivated interfacial trap states, and reduced recombination losses. Consequently, as compared to the control one using an unmodified spiro-MeOTAD HTL, (FAPbI3)0.95(MAPbBr3)0.05-based planar PSCs with composite HTL exhibit notably enhanced PCE and operational stability. Remarkably, an encouraging PCE of 20.41% was achieved for the champion device, and much improved operational stability was also demonstrated under continuous AM1.5 illumination with maximum power point (MPP) tracking conditions.
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Understanding the photoinduced carrier dynamics in Cs2AgBiBr6 double perovskites is essential for their application in optoelectronic devices. Herein, we report an investigation on the temperature-dependent carrier dynamics in a Cs2AgBiBr6 single crystal (SC). The time-resolved photoluminescence (TRPL) measurement indicates that the majority of carriers (>99%) decay through a fast trapping process at room temperature, and as the temperature decreases to 123 K, the population of carriers with a slow fundamental decay kinetics rises to â¼50%. We show that the carrier diffusion coefficient (theoretical diffusion length) varies from 0.020 ± 0.003 cm2 s-1 (0.70 µm) at 298 K to 0.11 ± 0.010 cm2 s-1 (2.44 µm) at 123 K. However, in spite of the long diffusion length, the population of carriers that can perform long-distance transport is restricted by the trap state, which is likely a key reason limiting the performance of Cs2AgBiBr6 optoelectronic devices.
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ZnSe microspheres with various Ag and Mn doping levels were prepared by the hydrothermal method using Zn(NO3)2·6H2O and Na2SeO3 as precursors and N2H4·H2O as the reducing agent. The effects of Ag and Mn doping on the phase composition, morphology, and optical and electrical properties of the final products were systematically investigated. A remarkable change in morphology from microspheres with a cubic sphalerite structure to rodlike structure was observed by Ag doping, while the pristine structure was nearly unchanged via Mn doping. Moreover, the band gap of ZnSe microspheres could be tunable in a broad range via controlling the Ag and Mn doping concentration, and ZnSe with high electrical properties could be obtained by doping with an appropriate concentration. The first-principle plane-wave method was carried out to explain the above mentioned experimental results.
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The overall performance of perovskite solar cells (PSCs) depends particularly on the chemical composition and crystalline quality of the perovskite light harvester. Here, the well-crystallized mixed-cation lead mixed-halide perovskite films with the optimized composition of FA0.85MA0.15Pb(I0.8Br0.2)3 were achieved by antisolvent-assisted single-step spin-coating in ambient conditions. The resulting PSCs with the well-crystallized FA0.85MA0.15Pb(I0.8Br0.2)3 exhibit impressive power conversion efficiency (PCE) over 20% under standard AM 1.5 illumination with excellent reproducibility. Remarkably, no perceivable degradation in PCE was detected from the PSCs stored in ambient conditions without any encapsulation after 7000 h (nearly 300 days), which was among the best shelf stability ever reported for PSCs. The superior performance was mainly attributed to the improved structural quality of the FA0.85MA0.15Pb(I0.8Br0.2)3 layer with reduced grain boundaries, reduced trap-state density, and prolonged carrier lifetime, as well as the better intrinsic stability of the mixed perovskite with an optimized composition.
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Vanadium dioxide (VO2) thermochromic thin films with various thicknesses were grown on quartz glass substrates by radio frequency (RF)-plasma assisted oxide molecular beam epitaxy (O-MBE). The crystal structure, morphology and chemical stoichiometry were investigated systemically by X-ray diffraction (XRD), atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analyses. An excellent reversible metal-to-insulator transition (MIT) characteristics accompanied by an abrupt change in both electrical resistivity and optical infrared (IR) transmittance was observed from the optimized sample. Remarkably, the transition temperature (TMIT) deduced from the resistivity-temperature curve was reasonably consistent with that obtained from the temperature-dependent IR transmittance. Based on Raman measurement and XPS analyses, the observations were interpreted in terms of residual stresses and chemical stoichiometry. This achievement will be of great benefit for practical application of VO2-based smart windows.