- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
Enhanced Stability of Perovskite Solar Cells Incorporating Dopant‐Free Crystalline Spiro‐OMeTAD Layers by Vacuum Sublimation
摘要： The main handicap still hindering the eventual exploitation of organometal halide perovskite-based solar cells is their poor stability under prolonged illumination, ambient conditions, and increased temperatures. This article shows for the first time the vacuum processing of the most widely used solid-state hole conductor (SSHC), i.e., the Spiro-OMeTAD [2,2′,7,7′-tetrakis (N,N-di-p-methoxyphenyl-amine) 9,9′-spirobifluorene], and how its dopant-free crystalline formation unprecedently improves perovskite solar cell (PSC) stability under continuous illumination by about two orders of magnitude with respect to the solution-processed reference and after annealing in air up to 200 °C. It is demonstrated that the control over the temperature of the samples during the vacuum deposition enhances the crystallinity of the SSHC, obtaining a preferential orientation along the π–π stacking direction. These results may represent a milestone toward the full vacuum processing of hybrid organic halide PSCs as well as light-emitting diodes, with promising impacts on the development of durable devices. The microstructure, purity, and crystallinity of the vacuum sublimated Spiro-OMeTAD layers are fully elucidated by applying an unparalleled set of complementary characterization techniques, including scanning electron microscopy, X-ray diffraction, grazing-incidence small-angle X-ray scattering and grazing-incidence wide-angle X-ray scattering, X-ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy.
关键词： perovskite solar cells,organometal halide perovskites,stability,vacuum deposition,solid state hole conductors,Spiro-OMeTAD
更新于2025-09-11 14:15:04
-
Atomic Structure and Electrical Activity of Grain Boundaries and Ruddlesden-Popper Faults in Cesium Lead Bromide Perovskite
摘要： To evaluate the role of planar defects in lead-halide perovskites—cheap, versatile semiconducting materials—it is critical to examine their structure, including defects, at the atomic scale and develop a detailed understanding of their impact on electronic properties. In this study, postsynthesis nanocrystal fusion, aberration-corrected scanning transmission electron microscopy, and first-principles calculations are combined to study the nature of different planar defects formed in CsPbBr3 nanocrystals. Two types of prevalent planar defects from atomic resolution imaging are observed: previously unreported Br-rich [001](210)∑5 grain boundaries (GBs) and Ruddlesden–Popper (RP) planar faults. The first-principles calculations reveal that neither of these planar faults induce deep defect levels, but their Br-deficient counterparts do. It is found that the ∑5 GB repels electrons and attracts holes, similar to an n–p–n junction, and the RP planar defects repel both electrons and holes, similar to a semiconductor–insulator–semiconductor junction. Finally, the potential applications of these findings and their implications to understand the planar defects in organic–inorganic lead-halide perovskites that have led to solar cells with extremely high photoconversion efficiencies are discussed.
关键词： Ruddlesden–Popper faults,lead-halide perovskites,scanning transmission electron microscopy,density-functional theory,grain boundaries
更新于2025-09-10 09:29:36
-
Conducting Bridge Resistive Switching Behaviors in Cubic MAPbI <sub/>3</sub> , Orthorhombic RbPbI <sub/>3</sub> , and Their Mixtures
摘要： Recently, halide perovskites (HPs), which exhibit resistive switching (RS) behaviors, are proposed as a promising candidate for next-generation memory because of their low power consumption, low cost, and mechanical flexibility. However, HP-based memories have crucial problems related to short endurance and vague switching mechanism. Here, the RS behaviors of switchable methylammonium lead iodide (MAPbI3) and nonswitchable rubidium lead iodide (RbPbI3) mixtures are reported and it is elucidated on the source of the switching phenomena. By controlling the ratio of rubidium iodide (RbI)/methylammonium iodide (MAI), five compositions of the mixture of RbPbI3 and MAPbI3 (Rb1?xMAxPbI3, x = 0, 0.31, 0.52, 0.71, and 1) films are fabricated. The mixtures of cubic MAPbI3 and orthorhombic RbPbI3 films exhibit excellent performances in Ag/polymethyl methacrylate/Rb1?xMAxPbI3/Pt cells, with endurance of 103 cycles, a high on/off ratio of 106, and an operation speed of 640 μs. Plausible explanations for the switching mechanism are provided based on Ag bridges by using the combination of conductive atomic force microscopy and energy dispersive X-ray spectroscopy. It is suggested nonswitchable RbPbI3 contributes to the endurance enhancement by restraining the growth of Ag bridges. The unique approaches provide a new strategy to overcome the bottleneck of the HP-based RS memories for next-generation computing.
关键词： halide perovskites,rubidium,conducting bridges,endurance,resistive switching
更新于2025-09-10 09:29:36
-
Electronic Traps and Phase Segregation in Lead Mixed-Halide Perovskite
摘要： An understanding of the factors driving halide segregation in lead mixed-halide perovskites is required for their implementation in tandem solar cells with existing silicon technology. Here we report that the halide segregation dynamics observed in the photoluminescence from CH3NH3Pb(Br0.5I0.5)3 is strongly influenced by the atmospheric environment, and that encapsulation of films with a layer of poly(methyl methacrylate) allows for halide segregation dynamics to be fully reversible and repeatable. We further establish an empirical model directly linking the amount of halide segregation observed in the photoluminescence to the fraction of charge-carriers recombining through trap-mediated channels, and the photon flux absorbed. From such quantitative analysis we show that under pulsed illumination, the frequency of the modulation alone has no influence on the segregation dynamics. Additionally, we extrapolate that working CH3NH3Pb(Br0.5I0.5)3 perovskite cells would require a reduction of the trap-related charge-carrier recombination rate to (cid:46) 105 s?1 in order for halide segregation to be sufficiently suppressed.
关键词： photoluminescence,lead mixed-halide perovskites,halide segregation,charge-carrier dynamics,trap-mediated recombination
更新于2025-09-09 09:28:46
-
Excess charge-carrier induced instability of hybrid perovskites
摘要： Identifying the origin of intrinsic instability for organic–inorganic halide perovskites (OIHPs) is crucial for their application in electronic devices, including solar cells, photodetectors, radiation detectors, and light-emitting diodes, as their efficiencies or sensitivities have already been demonstrated to be competitive with commercial available devices. Here we show that free charges in OIHPs, whether generated by incident light or by current-injection from electrodes, can reduce their stability, while efficient charge extraction effectively stabilizes the perovskite materials. The excess of both holes and electrons reduce the activation energy for ion migration within OIHPs, accelerating the degradation of OIHPs, while the excess holes and electrons facilitate the migration of cations or anions, respectively. OIHP solar cells capable of efficient charge-carrier extraction show improved light stability under regular operation conditions compared to an open-circuit condition where the photo-generated charges are confined in the perovskite layers.
关键词： charge-carrier extraction,ion migration,organic–inorganic halide perovskites,stability,solar cells
更新于2025-09-09 09:28:46
-
Controlling the Phase Segregation in Mixed Halide Perovskite through Nanocrystal Size
摘要： Mixed halide perovskites are one of the promising candidates in developing solar cells and LEDs, among others applications due to their tunable optical properties. Nonetheless, photoinduced phase segregation, by forming segregated Br-rich and I-rich domains, limits the overall applicability. We tracked the phase segregation with increasing crystalline sizes of CsPbBr3-xIx and their photoluminescence under continuous-wave laser irradiation (405 nm, 10 mW cm-2), and observed the occurrence of the phase segregation from the threshold size of 46 ± 7 nm. This results have an outstanding agreement with the diffusion length (45.8 nm) calculated also experimentally from the emission lifetime, segregation rates. Furthermore, through Kelvin probe forced microscopy, we confirmed the correlation between the phase segregation and the reversible halide ion migration among grain center/boundaries. These results open a way to achieve segregation-free mixed halide perovskites and improve their performances in optoelectronic devices.
关键词： nanocrystal size,photoluminescence,phase segregation,Kelvin probe force microscopy,Mixed halide perovskites
更新于2025-09-09 09:28:46
-
Lead‐Free Semiconductors: Soft Chemistry, Dimensionality Control, and Manganese‐Doping of Germanium Halide Perovskites
摘要： Lead halide perovskites have drawn enormous interest due to their exceptional photovoltaic and optoelectronic properties. However, the toxic heavy metal lead is harmful to humans and the environment resulting in a need for strategies to replace this toxic element. Herein, we report a facile aqueous synthesis of CsGeX3 (X = I, Br) perovskite nanocrystals with size control achieved by varying the cysteammonium halide ligand concentration. We observe a variety of morphologies including pyramidal, hexagonal, and spheroidal. CsGeX3 nanocrystals undergo a lattice expansion due to partial replacement of Cs+ with larger cysteNH3+ cations into the lattice. We successfully dope Mn2+ into the CsGeX3 lattice for the first time with incorporation up to 29% in bulk and 16% in nano samples. XRD peak shifts and EPR hyperfine splitting strongly indicate that Mn2+ is doped into the lattice. Our results introduce a new member to the lead-free halide perovskite family and set the fundamental stage for their use in optoelectronic devices.
关键词： Germanium Halide Perovskites,Manganese(II) Doping,Perovskite Phases,Lead Substitution,Perovskite Nanocrystals
更新于2025-09-09 09:28:46
-
Effect of Environmental Humidity in the Electrical Properties of Lead Halide Perovskites
摘要： In large quantities, water is detrimental to lead halide perovskite solar cells, mainly because of the decomposition of the perovskite layer. On the contrary, the presence of small quantities of water has been observed to play a key role in the crystallization of the perovskite and in the performance of the corresponding devices. However, it is still under debate the exact role of water during the operation of perovskite solar cells. In this paper, impedance spectroscopy is used to analyze the changes produced by environmental humidity in the electronic properties of methylammonium lead triiodide perovskite. Our results show that water absorbed from environmental humidity induces a huge increase in the capacitance of this material. This capacitance can reach values as large as the accumulation capacitance found in devices based in perovskite, which is the responsible of the characteristic large hysteresis observed between forward and reverse J-V curves. In parallel to this outstanding rise of the capacitance, water absorption produces a significant rise of the conductivity, in agreement with previous reports in the literature. Activation energy of 0.52 eV is found for electronic transport, a value in line with activation energy of ionic transport found in literature, what suggests ambipolar diffusion as the transport mechanism that links these two phenomena.
关键词： impedance spectroscopy,environmental humidity,electrical properties,lead halide perovskites,capacitance,conductivity
更新于2025-09-09 09:28:46
-
Switching excitonic recombination and carrier trapping in cesium lead halide perovskites by air
摘要： All-inorganic cesium lead halide perovskites have been emerging as the promising semiconductor materials for next-generation optoelectronics. However, the fundamental question of how the environmental atmosphere affects their photophysical properties, which is closely related to the practical applications, remains elusive. Here, we report the dynamic switching between radiative exciton recombination and non-radiative carrier trapping in CsPbBr3 by controlling the atmospheric conditions. Specifically, we show that the photoluminescence (PL) intensity from the CsPbBr3 crystals can be boosted by ~ 60 times by changing the surrounding from vacuum to air. Based on the comprehensive optical characterization, near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) as well as density functional theory (DFT) calculations, we unravel that the physisorption of oxygen molecules, which repairs the trap states by passivating the PL-quenching bromine vacancies, is accountable for the enhanced PL in air. These results are helpful for better understanding the optical properties of all-inorganic perovskites.
关键词： trap states,bromine vacancies,oxygen physisorption,photoluminescence,all-inorganic cesium lead halide perovskites
更新于2025-09-09 09:28:46
-
Geometry Distortion and Small Polaron Binding Energy Changes with Ionic Substitution in Halide Perovskites
摘要： Halide perovskites have demonstrated remarkable performance in optoelectronic applications. Despite extraordinary progress, questions remain about device stability. We report an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies of several experimentally relevant halide perovskites using isolated clusters. Local lattice symmetry, electronic structure, and electron-phonon coupling are interrelated in polaron formation in these materials. To illustrate this, first principles calculations are performed on (MA/Cs/FA)Pb(I/Br)3 and MASnI3. Across the materials studied, electron small polaron formation is manifested by Jahn-Teller like distortions in the central octahedron, with apical PbI bonds expanding significantly more than the equatorial bonds. In contrast, hole polarons cause the central octahedron to uniformly contract. This difference in manifestation of electron and hole polaron formation can be a tool to determine what is taking place in individual systems to systematically control performance. Other trends as the anion and cations are changed, are established for optimization in specific optoelectronic applications.
关键词： optoelectronic applications,reorganization energies,Jahn-Teller distortions,charge density,Halide perovskites,small polaron formation,electronic structure
更新于2025-09-09 09:28:46