Zhiya Dang

Colloidal Synthesis of Quantum Confined Single Crystal CsPbBr3 Nanosheets with Lateral Size Control up to the Micrometer Range

We report the nontemplated colloidal synthesis of single crystal CsPbBr3 perovskite nanosheets with lateral sizes up to a few micrometers and with thickness of just a few unit cells (i.e., below 5 nm), hence in the strong quantum confinement regime, by introducing short ligands (octanoic acid and octylamine) in the synthesis together with longer ones (oleic acid and oleylamine). The lateral size is tunable by varying the ratio of shorter ligands over longer ligands, while the thickness is mainly unaffected by this parameter and stays practically constant at 3 nm in all the syntheses conducted at short-to-long ligands volumetric ratio below 0.67. Beyond this ratio, control over the thickness is lost and a multimodal thickness distribution is observed.

Three-dimensional silicon micromachining

A process for fabricating arbitrary-shaped, two- and three-dimensional silicon and porous silicon components has been developed, based on high-energy ion irradiation, such as 250 keV to 1 MeV protons and helium. Irradiation alters the hole current flow during subsequent electrochemical anodization, allowing the anodization rate to be slowed or stopped for low/high fluences. For moderate fluences the anodization rate is selectively stopped only at depths corresponding to the high defect density at the end of ion range, allowing true three-dimensional silicon machining. The use of this process in fields including optics, photonics, holography and nanoscale depth machining is reviewed.

Colloidal Synthesis of Strongly Fluorescent CsPbBr3 Nanowires with Width Tunable down to the Quantum Confinement Regime

We report the colloidal synthesis of strongly fluorescent CsPbBr3 perovskite nanowires (NWs) with rectangular section and with tuneable width, from 20 nm (exhibiting no quantum confinement, hence emitting in the green) down to around 3 nm (in the strong quan-tum-confinement regime, emitting in the blue), by introducing in the synthesis a short acid (octanoic acid or hexanoic acid) together with alkyl amines (octylamine and oleylamine). Temperatures below 70 {\deg}C promoted the formation of monodisperse, few unit cell thick NWs that were free from byproducts. The photoluminescence quantum yield of the NW samples went from 12% for non-confined NWs emitting at 524 nm to a maximum of 77% for the 5 nm diameter NWs emitting at 497 nm, down to 30% for the thinnest NWs (diameter ~ 3nm), in the latter sample most likely due to aggregation occurring in solution.

In Situ Transmission Electron Microscopy Study of Electron Beam-Induced Transformations in Colloidal Cesium Lead Halide Perovskite Nanocrystals

An increasing number of studies have recently reported the rapid degradation of hybrid and all-inorganic lead halide perovskite nanocrystals under electron beam irradiation in the transmission electron microscope, with the formation of nanometer size, high contrast particles. The nature of these nanoparticles and the involved transformations in the perovskite nanocrystals are still a matter of debate. Herein, we have studied the effects of high energy (80/200 keV) electron irradiation on colloidal cesium lead bromide (CsPbBr3) nanocrystals with different shapes and sizes, especially 3 nm thick nanosheets, a morphology that facilitated the analysis of the various ongoing processes. Our results show that the CsPbBr3 nanocrystals undergo a radiolysis process, with electron stimulated desorption of a fraction of bromine atoms and the reduction of a fraction of Pb2+ ions to Pb0. Subsequently Pb0 atoms diffuse and aggregate, giving rise to the high contrast particles, as previously reported by various groups. The diffusion is facilitated by both high temperature and electron beam irradiation. The early stage Pb nanoparticles are epitaxially bound to the parent CsPbBr3 lattice, and evolve into nonepitaxially bound Pb crystals upon further irradiation, leading to local amorphization and consequent dismantling of the CsPbBr3 lattice. The comparison among CsPbBr3 nanocrystals with various shapes and sizes evidences that the damage is particularly pronounced at the corners and edges of the surface, due to a lower diffusion barrier for Pb0 on the surface than inside the crystal and the presence of a larger fraction of under-coordinated atoms.

Fluorescence Concentric Triangles: A Case of Chemical Heterogeneity in WS2 Atomic Monolayer

We report a novel optical property in WS2 monolayer. The monolayer naturally exhibits beautiful in-plane periodical and lateral homojunctions by way of alternate dark and bright band in the fluorescence images of these monolayers. The interface between different fluorescence species within the sample is distinct and sharp. This gives rise to intriguing concentric triangular fluorescence patterns in the monolayer. The novel optical property of this special WS2 monolayer is facilitated by chemical heterogeneity. The photoluminescence of the bright band is dominated by emissions from trion and biexciton while the emission from defect-bound exciton dominates the photoluminescence at the dark band. The discovery of such concentric fluorescence patterns represents a potentially new form of optoelectronic or photonic functionality.

Changing the Dimensionality of Cesium Lead Bromide Nanocrystals by Reversible Postsynthesis Transformations with Amines

by Reversible Postsynthesis Transformations with Amines Francisco Palazon,† Guilherme Almeida,†,§ Quinten A. Akkerman,†,§ Luca De Trizio,† Zhiya Dang,† Mirko Prato,‡ and Liberato Manna*,† †Nanochemistry Department and ‡Materials Characterization Facility, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy Dipartimento di Chimica e Chimica Industriale, Universita ̀ degli Studi di Genova, Via Dodecaneso, 31, 16146 Genova, Italy

Fluorescent Alloy CsPbxMn1–xI3 Perovskite Nanocrystals with High Structural and Optical Stability

CsPbI3 nanocrystals are still limited in their use because of their phase instability as they degrade into the yellow nonemitting δ-CsPbI3 phase within a few days. We show that alloyed CsPbxMn1–xI3 nanocrystals have essentially the same optical features and crystal structure as the parent α-CsPbI3 system, but they are stable in films and in solution for periods over a month. The stabilization stems from a small decrease in the lattice parameters slightly increasing the Goldsmith tolerance factor, combined with an increase in the cohesive energy. Finally, hybrid density functional calculations confirm that the Mn2+ levels fall within the conduction band, thus not strongly altering the optical properties.

Fabrication of large-area ultra-thin single crystal silicon membranes

Perfectly, crystalline, 55 nm thick silicon membranes have been fabricated over several square millimeters and used to observe transmission ion channeling patterns showing the early evolution of the axially channeled beam angular distribution for small tilts away from the [011] axis. The reduced multiple scattering through such thin layers allows fine angular structure produced by the highly non-equilibrium transverse momentum distribution of the channeled beam during its initial propagation in the crystal to be resolved. The membrane crystallinity and flatness were measured by using proton channeling measurements and the surface roughness of 0.4 nm using atomic force microscopy.

Silicon-based photonic crystals fabricated using proton beam writing combined with electrochemical etching method

A method for fabrication of three-dimensional (3D) silicon nanostructures based on selective formation of porous silicon using ion beam irradiation of bulk p-type silicon followed by electrochemical etching is shown. It opens a route towards the fabrication of two-dimensional (2D) and 3D silicon-based photonic crystals with high flexibility and industrial compatibility. In this work, we present the fabrication of 2D photonic lattice and photonic slab structures and propose a process for the fabrication of 3D woodpile photonic crystals based on this approach. Simulated results of photonic band structures for the fabricated 2D photonic crystals show the presence of TE or TM gap in mid-infrared range.

Defect enhanced funneling of diffusion current in silicon

We report a current transport mechanism observed during electrochemical anodization of ion irradiated p-type silicon, in which a hole diffusion current is highly funneled along the gradient of modified doping profile towards the maximum ion induced defect density, dominating the total current flowing and hence the anodization behaviour. This study is characterized within the context of electrochemical anodization but relevant to other fields where any residual defect density may result in similar effects, which may adversely affect performance, such as in wafer gettering or satellite-based microelectronics. Increased photoluminescence intensity from localized buried regions of porous silicon is also shown.