Phase Segregation and Photothermal Remixing of Mixed-Halide Lead Perovskites.
Ontology highlight
ABSTRACT:
SUBMITTER: Vicente JR
PROVIDER: S-EPMC8409127 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Mixed halide perovskites are one of the promising candidates in developing solar cells and light-emitting diodes (LEDs), among other applications, because of their tunable optical properties. Nonetheless, photoinduced phase segregation, by formation of segregated Br-rich and I-rich domains, limits the overall applicability. We tracked the phase segregation with increasing crystalline size of CsPbBr3-x I x 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. These results have an outstanding agreement with the diffusion length (45.8 nm) calculated also experimentally from the emission lifetime and segregation rates. Furthermore, through Kelvin probe force microscopy, we confirmed the correlation between the phase segregation and the reversible halide ion migration among grain centers and boundaries. These results open a way to achieve segregation-free mixed halide perovskites and improve their performances in optoelectronic devices.
| S-EPMC6333216 | biostudies-literature
Project description:Mixed-halide perovskites can undergo a photoinduced phase segregation. Even though many reports have claimed that such a phase segregation process is reversible, what happens after phase segregation and its impact on the performance of perovskite-based devices are still open questions. Here, the phase transformation of MAPb(I1- x Brx )3 after phase segregation and probe an irreversible phase reconstruction of MAPbBr3 is investigated. The photoluminescence imaging microscopy technique is introduced to in situ record the whole process. It is proposed that the type-I band alignment of segregated I-rich and Br-rich domains can enhance the emission of the I-rich domains by suppressing the nonradiative recombination channels. At the same time, the charge injection from Br-rich to I-rich domains drives the expulsion of iodide from the lattice, and thus triggers the reconstruction of MAPbBr3 . The work highlights the significance of ion movements in mixed-halide perovskites and provides new perspectives to understand the property evolution.
| S-EPMC8844510 | biostudies-literature
Project description:Mixed halide perovskites can provide optimal bandgaps for tandem solar cells which are key to improved cost-efficiencies, but can still suffer from detrimental illumination-induced phase segregation. Here we employ optical-pump terahertz-probe spectroscopy to investigate the impact of halide segregation on the charge-carrier dynamics and transport properties of mixed halide perovskite films. We reveal that, surprisingly, halide segregation results in negligible impact to the THz charge-carrier mobilities, and that charge carriers within the I-rich phase are not strongly localised. We further demonstrate enhanced lattice anharmonicity in the segregated I-rich domains, which is likely to support ionic migration. These phonon anharmonicity effects also serve as evidence of a remarkably fast, picosecond charge funnelling into the narrow-bandgap I-rich domains. Our analysis demonstrates how minimal structural transformations during phase segregation have a dramatic effect on the charge-carrier dynamics as a result of charge funnelling. We suggest that because such enhanced recombination is radiative, performance losses may be mitigated by deployment of careful light management strategies in solar cells.
| S-EPMC8630172 | biostudies-literature
Project description:The bandgap tunability of mixed-halide perovskites makes them promising candidates for light-emitting diodes and tandem solar cells. However, illuminating mixed-halide perovskites results in the formation of segregated phases enriched in a single halide. This segregation occurs through ion migration, which is also observed in single-halide compositions, and whose control is thus essential to enhance the lifetime and stability. Using pressure-dependent transient absorption spectroscopy, we find that the formation rates of both iodide- and bromide-rich phases in MAPb(Br x I1-x )3 reduce by 2 orders of magnitude on increasing the pressure to 0.3 GPa. We explain this reduction from a compression-induced increase of the activation energy for halide migration, which is supported by first-principle calculations. A similar mechanism occurs when the unit cell volume is reduced by incorporating a smaller cation. These findings reveal that stability with respect to halide segregation can be achieved either physically through compressive stress or chemically through compositional engineering.
| S-EPMC7552080 | biostudies-literature
Project description:Mixed-halide perovskites offer bandgap tunability essential for multijunction solar cells; however, a detrimental halide segregation under light is often observed. Here we combine simultaneous in situ photoluminescence and X-ray diffraction measurements to demonstrate clear differences in compositional and optoelectronic changes associated with halide segregation in MAPb(Br0.5I0.5)3 and FA0.83Cs0.17Pb(Br0.4I0.6)3 films. We report evidence for low-barrier ionic pathways in MAPb(Br0.5I0.5)3, which allow for the rearrangement of halide ions in localized volumes of perovskite without significant compositional changes to the bulk material. In contrast, FA0.83Cs0.17Pb(Br0.4I0.6)3 lacks such low-barrier ionic pathways and is, consequently, more stable against halide segregation. However, under prolonged illumination, it exhibits a considerable ionic rearrangement throughout the bulk material, which may be triggered by an initial demixing of A-site cations, altering the composition of the bulk perovskite and reducing its stability against halide segregation. Our work elucidates links between composition, ionic pathways, and halide segregation, and it facilitates the future engineering of phase-stable mixed-halide perovskites.
| S-EPMC7888268 | biostudies-literature
Project description:Lead halide perovskites are extensively investigated as efficient solution-processable materials for photovoltaic applications. The greatest stability and performance of these compounds are achieved by mixing different ions at all three sites of the APbX3 structure. Despite the extensive use of mixed lead halide perovskites in photovoltaic devices, a detailed and systematic understanding of the mixing-induced effects on the structural and dynamic aspects of these materials is still lacking. The goal of this review is to summarize the current state of knowledge on mixing effects on the structural phase transitions, crystal symmetry, cation and lattice dynamics, and phase diagrams of three- and low-dimensional lead halide perovskites. This review analyzes different mixing recipes and ingredients providing a comprehensive picture of mixing effects and their relation to the attractive properties of these materials.
| S-EPMC10941198 | biostudies-literature
Project description:Near-infrared light-emitting diodes (NIR-LEDs) are widely used in various applications such as night-vision devices, optical communication, biological imaging and optical diagnosis. The current solution-processed high-efficiency perovskite NIR-LEDs are typically based on CsPbI3 and FAPbI3 with emission peaks being limited in the range of 700-800 nm. NIR-LEDs with longer emission wavelengths near to 900 nm can be prepared by replacing Pb with Sn. However, Sn-based perovskite LEDs usually exhibit a low efficiency owing to the high concentration of Sn-related defects and the rapid oxidation of Sn2+ to Sn4+, which further induces the device degradation. These problems can be solved by rationally adjusting the ratio between Pb content with Sn. Mixed Sn-Pb halide perovskites with a smaller bandgap and superior stability than pure Sn-based perovskites are promising candidates for manufacturing next-generation NIR emitters. In this study, we systematically investigated the optical properties of a family of hybrid Sn and Pb iodide compounds. The emission spectra of the mixed Sn-Pb halide perovskites were tuned by changing the Sn:Pb ratio. Consequently, the peak emission wavelength red-shifted from 710 nm to longer than 950 nm. The absorption and photoluminescence emission properties associated with different compositions were compared, and the results demonstrated the potential of MA- and FA-based mixed Sn-Pb halide perovskites for preparing low-cost and efficient NIR-LEDs. In addition, we clarified the influence of cations on the bandgap bowing effect and electronic properties of mixed Sn-Pb halide perovskites.
| S-EPMC9194474 | biostudies-literature
Project description:Direct piezoelectric force microscopy (DPFM) is employed to examine whether or not lead halide perovskites exhibit ferroelectricity. Compared to conventional piezoelectric force microscopy, DPFM is a novel technique capable of measuring piezoelectricity directly. This fact is fundamental to be able to examine the existence of ferroelectricity in lead halide perovskites, an issue that has been under debate for several years. DPFM is used to detect the current signals, i.e. changes in the charge distribution under the influence of the scan direction and applied force of the atomic force microscope (AFM) tip in contact mode. For comparison, (i) we use DPFM on lead halide perovskites and well-known ferroelectric materials (i.e. periodically poled lithium niobate and lead zirconate titanate); and (ii) we conduct parallel experiments on MAPbI3 films of different grain sizes, film thicknesses, substrates, and textures using DPFM as well as piezoelectric force microscopy (PFM) and electrostatic force microscopy (EFM). In contrast to previous work that claimed there were ferroelectric domains in MAPbI3 perovskite films, our work shows that the studied perovskite films Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3 and MAPbI3 are ferroelectricity-free. The observed current profiles of lead halide perovskites possibly originate from ion migration that happens under an applied electrical bias and in strained samples under mechanical stress. This work provides a deeper understanding of the fundamental physical properties of the organic-inorganic lead halide perovskites and solves a longstanding dispute about their non-ferroelectric character: an issue of high relevance for optoelectronic and photovoltaic applications.
| S-EPMC8522734 | biostudies-literature
Project description:Sustained stimulated emission under continuous-wave (CW) excitation is a prerequisite for new semiconductor materials being developed for laser gain media. Although hybrid organic-inorganic lead-halide perovskites have attracted much attention as optical gain media, the demonstration of room-temperature CW lasing has still not been realized. Here, we present a critical step towards this goal by demonstrating CW amplified spontaneous emission (ASE) in a phase-stable perovskite at temperatures up to 120 K. The phase-stable perovskite maintains its room-temperature phase while undergoing cryogenic cooling and can potentially support CW lasing also at higher temperatures. We find the threshold level for CW ASE to be 387 W cm-2 at 80 K. These results indicate that easily-fabricated single-phase perovskite thin films can sustain CW stimulated emission, potential at higher temperatures as well, by further optimization of the material quality in order to extend the carrier lifetimes.
| S-EPMC6395683 | biostudies-literature
Project description:Lead halide perovskites show marked defect tolerance responsible for their excellent optoelectronic properties. These properties might be explained by the formation of large polarons, but how they are formed and whether organic cations are essential remain open questions. We provide a direct time domain view of large polaron formation in single-crystal lead bromide perovskites CH3NH3PbBr3 and CsPbBr3. We found that large polaron forms predominantly from the deformation of the PbBr3- frameworks, irrespective of the cation type. The difference lies in the polaron formation time, which, in CH3NH3PbBr3 (0.3 ps), is less than half of that in CsPbBr3 (0.7 ps). First-principles calculations confirm large polaron formation, identify the Pb-Br-Pb deformation modes as responsible, and explain quantitatively the rate difference between CH3NH3PbBr3 and CsPbBr3. The findings reveal the general advantage of the soft [PbX3]- sublattice in charge carrier protection and suggest that there is likely no mechanistic limitations in using all-inorganic or mixed-cation lead halide perovskites to overcome instability problems and to tune the balance between charge carrier protection and mobility.
| S-EPMC5553817 | biostudies-other