Highly Stable Luminous "snakes" from CsPbX3 Perovskite Nanocrystals Anchored on Amine-Coated Silica Nanowires

CsPbX3 (X = Cl, Br, and I) perovskite nanocrystals (NCs) are known for their exceptional optoelectronic properties, yet the material's instability toward polar solvents, heat, or UV irradiation greatly limits its further applications. Herein, an efficient in situ growing strategy has been developed to give highly stable perovskite NC composites (abbreviated CsPbX3@CA-SiO2) by anchoring CsPbX3 NCs onto silica nanowires (NWs), which effectively depresses the optical degradation of their photoluminescence (PL) and enhances stability. The preparation of surface-functionalized serpentine silica NWs is realized by a sol-gel process involving hydrolysis of a mixture of tetraethyl orthosilicate (TEOS), 3-aminopropyltriethoxysilane (APTES), and trimethoxy(octadecyl)silane (TMODS) in a water/oil emulsion. The serpentine NWs are formed via an anisotropic growth with lengths up to 8 μm. The free amino groups are employed as surface ligands for growing perovskite NCs, yielding distributed monodisperse NCs (∼8 nm) around the NW matrix. The emission wavelength is tunable by simple variation of the halide compositions (CsPbX3, X = Cl, Br, or I), and the composites demonstrate a high photoluminescence quantum yield (PLQY 32-69%). Additionally, we have demonstrated the composites CsPbX3@CA-SiO2 can be self-woven to form a porous 3D hierarchical NWs membrane, giving rise to a superhydrophobic surface with hierarchical micro/nano structural features. The resulting composites exhibit high stability toward water, heat, and UV irradiation. This work elucidates an effective strategy to incorporate perovskite nanocrystals onto functional matrices as multifunctional stable light sources

High Open Circuit Voltage Solar Cells based on bright mixed-halide CsPbBrI2 Perovskite Nanocrystals Synthesized in Ambient Air Conditions

Lead halide perovskite nanocrystals (NCs) are currently emerging as one of the most interesting solution processed semiconductors since they possess high photoluminescence quantum yield (PLQY), and colour tunability through anion exchange reactions or quantum confinement. Here, we show efficient solar cells based on mixed halide (CsPbBrI2) NCs obtained via anion exchange reactions in ambient conditions. We performed anion exchange reactions in concentrated NC solutions with I-, thus inducing a PL red-shift up to 676 nm, and obtaining a high PLQY in film (65%). Solar cell devices operating in the wavelength range 350-660 nm were fabricated in air with two different deposition methods. The solar cells display a photo-conversion efficiency of 5.3% and open circuit voltage (Voc) up to 1.31V, among the highest reported for perovskite based solar cells with band gap below 2eV, clearly demonstrating the potential of this material.Peer ReviewedPostprint (author's final draft

Mechanical Properties of APbX3 (A=Cs or CH3NH3; X=I or Br) Perovskite Single Crystals

The remarkable optoelectronic, and especially photovoltaic performance of hybrid-organic-inorganic perovskite (HOIP) materials drives efforts to connect materials properties to this performance. From nano-indentation experiments on solution-grown single crystals we obtain elastic modulus and nano-hardness values of APbX3 (A = Cs, CH3NH3 and X = I, Br). The Youngs moduli are about 14, 19.5 and 16 GPa, for CH3NH3PbI3, CH3NH3PbBr3 and CsPbBr3, respectively, lending credence to theoretically calculated values. We discuss possible relevance of our results to suggested self-healing, ion diffusion and ease of manufacturing. Using our results, together with literature data on elastic moduli, we classified HOIPs amongst relevant materials groups, based on their elasto-mechanical properties.Comment: 20 pages (including 4 pages of Supporting Information after the references), 3 figures (+3 in the Supporting Information), 2 tables (+1 in the Supporting Information

Photoluminescence Blinking beyond Quantum-Confinement: Spatiotemporally Correlated Intermittency over Entire Micron Sized Perovskite Polycrystalline Disks

Abrupt fluorescence intermittency or blinking is long recognized to be characteristic of single nano-emitters. Extended quantum-confined nanostructures also undergo spatially heterogeneous blinking, however, there is no such precedence in dimensionally unconfined (bulk) materials. Here, we report multi-level blinking of entire individual organo-lead bromide perovskite micro-crystals (volume 0.1-3 micron-cuble) under ambient conditions. Extremely high spatiotemporal correlation (>0.9) in intra-crystal emission intensity fluctuations signifies effective communication amongst photogenerated carriers at distal locations (up to ~4 microns) within each crystal. Fused polycrystalline grains also exhibit this intriguing phenomenon, which is rationalized by correlated and efficient migration of carriers to a few transient non-radiative traps, the nature and population of which determine blinking propensity. Observation of spatiotemporally correlated emission intermittency in bulk semiconductor crystals opens up the possibility to design novel devices involving long range (mesoscopic) electronic communication.Comment: 6 pages, 3 figures, supporting information included, Title of manuscript slightly different from accepted article to elaborate on the main result

Size-Dependent Lattice Structure and Confinement Properties in CsPbI₃ Perovskite Nanocrystals: Negative Surface Energy for Stabilization

CsPbI₃ nanocrystals with narrow size distributions were prepared to study the size-dependent properties. The nanocrystals adopt the perovskite (over the nonperovskite orthorhombic) structure with improved stability over thin-film materials. Among the perovskite phases (cubic α, tetragonal β, and orthorhombic γ), the samples are characterized by the γ phase, rather than α, but may have a size-dependent average tilting between adjacent octahedra. Size-dependent lattice constants systematically vary 3% across the size range, with unit cell volume increasing linearly with the inverse of size to 2.1% for the smallest size. We estimate the surface energy to be from −3.0 to −5.1 eV nm⁻² for ligated CsPbI₃ nanocrystals. Moreover, the size-dependent bandgap is best described using a nonparabolic intermediate confinement model. We experimentally determine the bulk bandgap, effective mass, and exciton binding energy, concluding with variations from the bulk α-phase values. This provides a robust route to understanding γ-phase properties of CsPbI₃