Revealing the Role of Tin(IV) Halides in the Anisotropic Growth of CsPbX3 Perovskite Nanoplates.

CsPbX3 perovskite nanoplates (PNPLs) were formed in a synthesis driven by SnX4 (X=Cl, Br, I) salts. The role played by these hard Lewis acids in directing PNPL formation is addressed. Sn4+ disturbs the acid-base equilibrium of the system, increasing the protonation rate of oleylamine and inducing anisotropic growth of nanocrystals. Sn4+ cations influence the reaction dynamics owing to complexation with oleylamine molecules. By monitoring the photoluminescence excitation and photoluminescence (PL) spectra of the PNPLs grown at different temperatures, the influence of the thickness on their optical properties is mapped. Time-resolved and spectrally resolved PL for colloidal dispersions with different optical densities reveals that the dependence of the overall PL lifetime on the emission wavelength do not originate from energy transfer between PNPLs but from the contribution of PNPLs with distinct thickness, indicating that thicker PNPLs exhibit longer PL lifetimes.

Effect of dimensionality on the optical absorption properties of CsPbI3 perovskite nanocrystals.

The bandgaps of CsPbI3 perovskite nanocrystals are measured by absorption spectroscopy at cryogenic temperatures. Anomalous bandgap shifts are observed in CsPbI3 nanocubes and nanoplatelets, which are modeled accurately by bandgap renormalization due to lattice vibrational modes. We find that decreasing dimensionality of the CsPbI3 lattice in nanoplatelets greatly reduces electron-phonon coupling, and dominant out-of-plane quantum confinement results in a homogeneously broadened absorption line shape down to cryogenic temperatures. An absorption tail forms at low-temperatures in CsPbI3 nanocubes, which we attribute to shallow defect states positioned near the valence band edge.

Exploring Au Droplet Motion in Nanowire Growth: A Simple Route toward Asymmetric GaP Morphologies.

Here we show a new nanowire growth procedure, exploring the thermally activated motion of Au droplets on III-V surfaces. We show that by setting a single growth parameter we can activate the crawling motion of Au droplets in vacuum and locally modify surface composition in order to enhance vapor-solid (VS) growth along oxide-free areas on the trail of the metal particle. Asymmetric VS growth rates are comparable in magnitude to the vapor-liquid-solid growth, producing unconventional wurtzite GaP morphologies, which shows negligible defect density as well as optical signal in the green spectral region. Finally, we demonstrate that this effect can also be explored in different substrate compositions and orientations with the final shape finely tuned by group III flow and nanoparticle size. This distinct morphology for wurtzite GaP nanomaterials can be interesting for the design of nanophotonics devices.

Unveiling nanometer scale extinction and scattering phenomena through combined electron energy loss spectroscopy and cathodoluminescence measurements.

Plasmon modes of the exact same individual gold nanoprisms are investigated through combined nanometer-resolved electron energy-loss spectroscopy (EELS) and cathodoluminescence (CL) measurements. We show that CL only probes the radiative modes, in contrast to EELS, which additionally reveals dark modes. The combination of both techniques on the same particles thus provides complementary information and also demonstrates that although the radiative modes give rise to very similar spatial distributions when probed by EELS or CL, their resonant energies appear to be different. We trace this phenomenon back to plasmon dissipation, which affects in different ways the plasmon signatures probed by these techniques. Our experiments are in agreement with electromagnetic numerical simulations and can be further interpreted within the framework of a quasistatic analytical model. We therefore demonstrate that CL and EELS are closely related to optical scattering and extinction, respectively, with the addition of nanometer spatial resolution.

2D Phase Formation on 3D Perovskite: Insights from Molecular Stiffness.

Several studies have demonstrated that low-dimensional structures (e.g., two-dimensional (2D)) associated with three-dimensional (3D) perovskite films enhance the efficiency and stability of perovskite solar cells. Here, we aim to track the formation sites of the 2D phase on top of the 3D perovskite and to establish correlations between molecular stiffness and steric hindrance of the organic cations and their influence on the formation and crystallization of 2D/3D. Using cathodoluminescence combined with a scanning electron microscopy technique, we verified that the formation of the 2D phase occurs preferentially on the grain boundaries of the 3D perovskite. This helps explain some passivation mechanisms conferred by the 2D phase on 3D perovskite films. Furthermore, by employing in situ grazing-incidence wide-angle X-ray scattering, we monitored the formation and crystallization of the 2D/3D perovskite using three cations with varying molecular stiffness. In this series of molecules, the formation and crystallization of the 2D phase are found to be dependent on both steric hindrance around the ammonium group and molecular stiffness. Finally, we employed a 2D/3D perovskite heterointerface in a solar cell. The presence of the 2D phase, particularly those formed from flexible cations, resulted in a maximum power conversion efficiency of 21.5%. This study provides insight into critical aspects related to how bulky organic cations' stiffness and steric hindrance influence the formation, crystallization, and distribution of 2D perovskite phases.

High-resolution scanning transmission electron microscopy (HRSTEM) techniques: high-resolution imaging and spectroscopy side by side.

This work presents an overview of high-resolution scanning transmission electron microscopy (HRSTEM) techniques and exemplifies the novel quantitative characterization possibilities that have emerged from recent advances in these methods. The synergistic combination of atomic resolution imaging and spectroscopy provided by HRSTEM is highlighted as a unique feature that can provide a comprehensive analytical description of material properties at the nanoscale. State-of-the-art high-angle annular dark field and annular bright field examples are depicted as well as the use of X-ray energy-dispersive spectroscopy and electron energy-loss spectroscopy for probing samples properties at the atomic scale. In addition, promising techniques such as cathodoluminescence, confocal HRSTEM, and diffraction mapping are introduced. The presented examples and results indicate that HRSTEM-related techniques are fundamental tools for comprehensive assessment of properties at the atomic scale.

Toward Engineering Intrinsic Line Widths and Line Broadening in Perovskite Nanoplatelets.

Perovskite nanoplatelets possess extremely narrow absorption and emission line widths, which are crucial characteristics for many optical applications. However, their underlying intrinsic and extrinsic line-broadening mechanisms are poorly understood. Here, we apply multidimensional coherent spectroscopy to determine the homogeneous line broadening of colloidal perovskite nanoplatelet ensembles. We demonstrate a dependence of not only their intrinsic line widths but also of various broadening mechanisms on platelet geometry. We find that decreasing nanoplatelet thickness by a single monolayer results in a 2-fold reduction of the inhomogeneous line width and a 3-fold reduction of the intrinsic homogeneous line width to the sub-millielectronvolts regime. In addition, our measurements suggest homogeneously broadened exciton resonances in two-layer (but not necessarily three-layer) nanoplatelets at room-temperature.

Multidimensional coherent spectroscopy reveals triplet state coherences in cesium lead-halide perovskite nanocrystals.

Advances in optoelectronics require materials with novel and engineered characteristics. A class of materials that has garnered tremendous interest is metal-halide perovskites, stimulated by meteoric increases in photovoltaic efficiencies of perovskite solar cells. In addition, recent advances have applied perovskite nanocrystals (NCs) in light-emitting devices. It was found recently that, for cesium lead-halide perovskite NCs, their unusually efficient light emission may be due to a unique excitonic fine structure composed of three bright triplet states that minimally interact with a proximal dark singlet state. To study this fine structure without isolating single NCs, we use multidimensional coherent spectroscopy at cryogenic temperatures to reveal coherences involving triplet states of a CsPbI3 NC ensemble. Picosecond time scale dephasing times are measured for both triplet and inter-triplet coherences, from which we infer a unique exciton fine structure level ordering composed of a dark state energetically positioned within the bright triplet manifold.

Effective killing of bacteria under blue-light irradiation promoted by green synthesized silver nanoparticles loaded on reduced graphene oxide sheets.

Graphene oxide (GO) materials loaded with silver nanoparticles (AgNPs) have drawn considerable attention due to their capacity to efficiently inactivate bacteria though a multifaceted mechanism of action, as well as for presenting a synergetic effect against bacteria when compared to the activity of AgNPs and GO alone. In this investigation, we present an inexpensive and environmentally-friendly method for synthesizing reduced GO sheets coated with silver nanoparticles (AgNPs/r-GO) using a coffee extract solution as a green reducing agent. The physical and chemical properties of the produced materials were extensively characterized by scanning electron microscopy (SEM), field-emission gun transmission electron microscopy (FEG-TEM), ultraviolet and visible absorption (UV-Vis), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-optical emission spectroscopy (ICP-OES) and ion release determination. The results demonstrated that AgNPs/r-GO composites were successfully produced, revealing the formation of micrometer-sized r-GO sheets decorated by AgNPs of approximately 70 nm diameter. Finally, bactericidal and photobactericidal effects of the AgNPs/r-GO composites were tested against Staphylococcus aureus, in which the results showed that the composites presented antimicrobial and photoantimicrobial activities. Moreover, our results demonstrated for the first time, to our knowledge, that an efficient process of bacterial inactivation can be achieved by using AgNPs/r-GO composites under blue light irradiation as a result of three different bacterial killing processes: (i) chemical effect promoted by Ag+ ion release from AgNPs; (ii) photocatalytic activity induced by AgNPs/r-GO composites, enhancing the bacterial photoinactivation due to the excited-Plasmons of the AgNPs when anchored on r-GO; and (iii) photodynamic effect produced by bacterial endogenous photosensitizers under blue-light irradiation. In summary, the present findings demonstrated that AgNPs/r-GO can be obtained by a non-toxic procedure with great potential for biomedical-related applications.

Photocatalytic hydrogen production of Co(OH)2 nanoparticle-coated α-Fe2O3 nanorings.

The production of hydrogen from water using only a catalyst and solar energy is one of the most challenging and promising outlets for the generation of clean and renewable energy. Semiconductor photocatalysts for solar hydrogen production by water photolysis must employ stable, non-toxic, abundant and inexpensive visible-light absorbers capable of harvesting light photons with adequate potential to reduce water. Here, we show that α-Fe2O3 can meet these requirements by means of using hydrothermally prepared nanorings. These iron oxide nanoring photocatalysts proved capable of producing hydrogen efficiently without application of an external bias. In addition, Co(OH)2 nanoparticles were shown to be efficient co-catalysts on the nanoring surface by improving the efficiency of hydrogen generation. Both nanoparticle-coated and uncoated nanorings displayed superior photocatalytic activity for hydrogen evolution when compared with TiO2 nanoparticles, showing themselves to be promising materials for water-splitting using only solar light.

Imaging and quantifying the morphology of an organic-inorganic nanoparticle at the sub-nanometre level.

The development of hybrid organic-inorganic nanoparticles is of interest for applications such as drug delivery, DNA and protein recognition, and medical diagnostics. However, the characterization of such nanoparticles remains a significant challenge due to the heterogeneous nature of these particles. Here, we report the direct visualization and quantification of the organic and inorganic components of a lipid-coated silica particle that contains a smaller semiconductor quantum dot. High-angle annular dark-field scanning transmission electron microscopy combined with electron energy loss spectroscopy was used to determine the thickness and chemical signature of molecular coating layers, the element atomic ratios, and the exact positions of different elements in single nanoparticles. Moreover, the lipid ratio and lipid phase segregation were also quantified.