Functional CsPbI3 perovskite phases are not stable at ambient conditions and spontaneously convert to a non-perovskite δ phase, limiting their applications as solar cell materials. We demonstrate the preservation of a black CsPbI3 perovskite structure to room temperature by subjecting the δ phase to pressures of 0.1 – 0.6 GPa followed by heating and rapid cooling. Synchrotron X-ray diffraction and Raman spectroscopy indicate that this perovskite phase is consistent with orthorhombic γ-CsPbI3. Once formed, γ-CsPbI3 could be then retained after releasing pressure to ambient conditions and shows substantial stability at 35% relative humidity. First-principles density functional theory calculations indicate that compression directs the out-of-phase and in-phase tilt between the [PbI6]4− octahedra which in turn tune the energy difference between δ- and γ-CsPbI3, leading to the preservation of γ-CsPbI3. Here, we present a high-pressure strategy for manipulating the (meta)stability of halide perovskites for the synthesis of desirable phases with enhanced materials functionality.
Lanthanide-doped nanoparticles are an emerging class of optical sensors, exhibiting sharp emission peaks, high signal-to-noise ratio, photostability, and a ratiometric color response to stress. The same centrosymmetric crystal field environment that allows for high mechanosensitivity in the cubic-phase (α), however, contributes to low upconversion quantum yield (UCQY). In this work, we engineer brighter mechanosensitive upconverters using a core-shell geometry. Sub-25 nm α-NaYF:Yb,Er cores are shelled with an optically inert surface passivation layer of ∼4.5 nm thickness. Using different shell materials, including NaGdF, NaYF, and NaLuF, we study how compressive to tensile strain influences the nanoparticles' imaging and sensing properties. All core-shell nanoparticles exhibit enhanced UCQY, up to 0.14% at 150 W/cm, which rivals the efficiency of unshelled hexagonal-phase (β) nanoparticles. Additionally, strain at the core-shell interface can tune mechanosensitivity. In particular, the compressive Gd shell results in the largest color response from yellow-green to orange or, quantitatively, a change in the red to green ratio of 12.2 ± 1.2% per GPa. For all samples, the ratiometric readouts are consistent over three pressure cycles from ambient to 5 GPa. Therefore, heteroepitaxial shelling significantly improves signal brightness without compromising the core's mechano-sensing capabilities and further, promotes core-shell cubic-phase nanoparticles as upcoming in vivo and in situ optical sensors.
Gold-copper alloys have rich forms. Here we report an atomically resolved [Au52Cu72(p-MBT)55]+Cl− nanoalloy (p-MBT = SPh-p-CH3). This nanoalloy exhibits unusual structural patterns. First, two Cu atoms are located in the inner 7-atom decahedral kernel (M7, M = Au/Cu). The M7 kernel is then enclosed by a second shell of homogold (Au47), giving rise to a two-shelled M54 (i.e. Au52Cu2) full decahedron. A comparison of the non-truncated M54 decahedron with the truncated homogold Au49 kernel in similar-sized gold nanoparticles provides for the first time an explanation for Marks decahedron truncation. Second, a Cu70(SR)55 exterior cage resembling a 3D Penrose tiling protects the M54 decahedral kernel. Compared to the discrete staple motifs in gold:thiolate nanoparticles, the Cu-thiolate surface of Au52Cu72 forms an extended cage. The Cu-SR Penrose tiling retains the M54 kernel’s high symmetry (D5h). Third, interparticle interactions in the assembly are closely related to the symmetry of the particle, and a “quadruple-gear-like” interlocking pattern is observed.
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