This work has developed conditions for the synthesis of AgPO cubes, rhombic dodecahedra, {100}-truncated rhombic dodecahedra, tetrahedra, and tetrapods by tuning the amount of NHNO, NaOH, AgNO, and KHPO solutions added. Use of a minimal amount of AgNO solution can form much smaller rhombic dodecahedra and tetrahedra. Submicrometer-sized AgPO cubes and rhombic dodecahedra with sizes larger than 300 nm do not exhibit the optical size effect, but ∼290 nm rhombic dodecahedra show a smaller band gap value than larger cubes, and tetrahedra show the most blue-shifted absorption edge. The optical facet effect is present in AgPO crystals. AgPO cubes are more photocatalytically active than rhombic dodecahedra toward photodegradation of methyl orange, but tetrahedra are inactive, showing clear presence of photocatalytic facet effects. Electron paramagnetic resonance results confirm much higher production of hydroxyl radicals from photoirradiated AgPO cubes than from rhombic dodecahedra, while tetrahedra yield essentially no radicals. A modified band diagram showing different degrees of band edge bending can explain these observations. All these AgPO crystals show poor electrical conductivity properties, but the {110} faces are slightly more conductive than the {100} faces. As a result, current rectifying I-V curves have been obtained, demonstrating that facet-dependent electrical properties are broadly observable in many semiconductor materials. This work reveals again that facet-dependent optical, photocatalytic, and electrical conductivity properties are intrinsic semiconductor properties.

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By breaking intrinsic Si (100) and (111) wafers to expose sharp {111} and {112} facets, electrical conductivity measurements on single and different silicon crystal faces were performed through contacts with two tungsten probes. While Si {100} and {110} faces are barely conductive at low applied voltages, as expected, the Si {112} surface is highly conductive and Si {111} surface also shows good conductivity. Asymmetrical I-V curves have been recorded for the {111}/{112}, {111}/{110}, and {112}/{110} facet combinations because of different degrees of conduction band bending at these crystal surfaces presenting different barrier heights to current flow. In particular, the {111}/{110} and {112}/{110} facet combinations give I-V curves resembling those of p-n junctions, suggesting a novel field effect transistor design is possible capitalizing on the pronounced facet-dependent electrical conductivity properties of silicon.

Two-dimensional-on-three-dimensional (2D/3D) halide perovskite heterostructures have been extensively utilized in optoelectronic devices. However, the labile nature of halide perovskites makes it difficult to form such heterostructures with well-defined compositions, orientations, and interfaces, which inhibits understanding of the carrier transfer properties across these heterostructures. Here, we report solution growth of both horizontally and vertically aligned 2D perovskite (PEA)2PbBr4 (PEA = phenylethylammonium) microplates onto 3D CsPbBr3 single crystal thin films, with well-defined heterojunctions. Time-resolved photoluminescence (TRPL) transients of the heterostructures exhibit the monomolecular and bimolecular dynamics expected from exciton annihilation, dissociation, and recombination, as well as evidence for carrier transfer in these heterostructures. Two kinetic models based on Type-I and Type-II band alignments at the interface of horizontal 2D/3D heterostructures are applied to reveal a shift in balance between carrier transfer and recombination: Type-I band alignment better describes the behaviors of heterostructures with thin 2D perovskite microplates but Type-II band alignment better describes those with thick 2D microplates (>150 nm). TRPL of vertically aligned 2D microplates is dominated by directly excited PL and is independent of the height above the 3D film. Electrical measurements reveal current rectification behaviors in both heterostructures with vertical heterostructures showing better electrical transport. As the first systematic study on comparing models of 2D/3D perovskite heterostructures with controlled orientations and compositions, this work provides insights on the charge transfer mechanisms in these perovskite heterostructures and guidelines for designing better optoelectronic devices.

Electrical conductivity measurements show that the {100} faces of a perfect SrTiO3 cube are insulating, but the {110} faces of a SrTiO3 truncated rhombic dodecahedron are considerably more conductive. Interestingly, compared to electrodes touching the proximal {110} faces, adjacent {110} face contacts give notably higher current. Unexpectedly, while the {110} faces of a truncated rhombic dodecahedron remain much more conductive than its {100} faces, the adjacent conductive {110} facets may cause the poorly conductive {100} facets to become more conductive through slight current leakage to the adjacent conductive faces. Consistent with previous insulating behavior observed for a {110}-bound Cu2O rhombic dodecahedron, the {110} faces of a Cu2O rhombicuboctahedral microcrystal remain insulating. Thus, the influence of adjacent conductive facet may be avoided using sharper electrodes. Still, the adjacent facet effect may always be present even with the use of sharp electrodes. Current-rectifying asymmetric I–V curves were recorded with electrodes contacting the {100} and {110} faces of a SrTiO3 truncated rhombic dodecahedron. The electrical facet effects can be understood with different degrees of band bending at these crystal surfaces and thus different barrier heights to charge carrier transport across these surfaces. Finally, high-resolution transmission electron microscopy (HR-TEM) images over the surfaces of SrTiO3 truncated rhombic dodecahedra and cubes were taken, showing notable shifts in atomic positions within the few layers of surface lattice planes relative to the atomic positions of the interior lattice, suggesting that the lattice deviations within the thin surface layer as predicted by density functional theory (DFT) calculations may be visually observable.