Nanofabrication is continuously searching for new methodologies to fabricate 3D nanostructures with 3D control over their chemical composition. A new approach for heterostructure nanorod array fabrication through spatially controlled–growth of multiple metal oxides within block copolymer (BCP) templates is presented. Selective growth of metal oxides within the cylindrical polymer domains of polystyrene‐block‐poly methyl methacrylate is performed using sequential infiltration synthesis (SIS). Tuning the diffusion of trimethyl aluminum and diethyl zinc organometallic precursors in the BCP film directs the growth of AlOx and ZnO to different locations within the cylindrical BCP domains, in a single SIS process. BCP removal yields an AlOx‐ZnO heterostructure nanorods array, as corroborated by 3D characterization with scanning transmission electron microscopy (STEM) tomography and a combination of STEM and energy‐dispersive X‐ray spectroscopy tomography. The strategy presented here will open up new routes for complex 3D nanostructure fabrication.

Continuous thin films of Pt on A-plane 1 1 2 0 À Á sapphire substrates were dewetted to characterize the morphological evolution and dewetting kinetics at 800°C using an oxygen partial pressure of 10 À20 atm. Hole growth was studied, focusing on partially dewetted samples. Four different low-index orientation relationships were found between the Pt and sapphire substrate by electron backscattered diffraction combined with transmission electron diffraction patterns. Abnormal grains adjacent to the holes with a small deviation from one of the low-index orientation relationships were observed. The difference in the heights of the abnormal grains adjacent to the holes (rim-height) is influenced by the initial position of the hole, and the existence of grains with a low-energy interface orientation relationship, and not only by diffusivity rates dictated by surface orientation as described in existing edge-retraction models. The existence of low-index orientation relationships is seen as the driving force for abnormal grain growth in the vicinity of the holes, and is a dominant factor in controlling the dewetting rate of thin metal films on oxide surfaces.

Lead-free double perovskites are studied as an optional replacement to lead halide perovskites in optoelectronic applications. Recently, double-perovskite materials in which two divalent lead cations are replaced with an Ag + and a trivalent cation have been demonstrated. The presence of a reactive silver cation and observations of metallic silver nanodecorations raised concerns regarding the stability and applicability of these materials. To better understand the nucleation and crystal growth of lead-free double perovskites, we explore the origin and role that metallic silver nanoparticles (NPs) play in the Ag-based Pb-free double-perovskite nanocrystal (NC) systems such as Cs 2 AgInCl 6 , Cs 2 AgSbCl 6 , Cs 2 AgBiCl 6 , and Cs 2 AgBiBr 6 . With major focus on Cs 2 AgInCl 6 NCs, we show evidence supporting growth of the NCs through heterogeneous nucleation on preexisting metallic silver seeds. The silver seeds nucleate prior to injection of halide through reduction of the Ag + ion by the aminic ligand. The presence of preexisting silver NPs is supported by a localized surface plasmon resonance (LSPR). The injection of halide precursor into the reaction mixture step initiates a fast nucleation and growth of the perovskite NC on the silver seed. The change in the dielectric medium at the interface of the silver NP results in a quantifiable red shift of the LSPR peak. In addition, we demonstrate charge transfer from the perovskite to the silver NP through photoinduced electrochemical Ostwald ripening of the silver NPs via UV irradiation. The ripened perovskite–metal hybrid nanocrystal exhibits modified optical properties in the form of quenched emission and enhanced plasmonic absorption. Future development of Ag-based double-perovskite NC applications depends on the ability to control Ag + reduction at all synthetic stages. This understanding is critical for delivering stability and functionality for silver-based lead-free perovskite nanocrystals.

The optical and structural properties of a new kind of InAs/InGaAlAs/InP quantum dot (QD)-like objects grown by molecular beam epitaxy have been investigated. These nanostructures were found to have significantly more symmetrical shapes compared to the commonly obtained dash-like geometries typical of this material system. The enhanced symmetry has been achieved due to the use of an As2 source and the consequent shorter migration length of the indium atoms. Structural studies based on a combination of scanning transmission electron microscopy (STEM) and atom probe tomography (APT) provided detailed information on both the structure and composition distribution within an individual nanostructure. However, it was not possible to determine the lateral aspect ratio from STEM or APT. To verify the in-plane geometry, electronic structure calculations, including the energy levels and transition oscillator strength for the QDs have been performed using an eight-band k·p model a nd realistic system parameters. The results of calculations were compared to measured polarization-resolved photoluminescence data. On the basis of measured degree of linear polarization of the surface emission, the in-plane shape of the QDs has been assessed proving a substantial increase in lateral symmetry. This results in quantum-dot rather than quantum-dash like properties, consistent with expectations based on the growth conditions and the structural data

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