Wurtzite Gallium Phosphide via Chemical Beam Epitaxy: Impurity-Related Luminescence vs Growth Conditions.

The metastable wurtzite crystal phase in gallium phosphide (WZ GaP) is a relatively new structure with little available information about its emission properties compared to the most stable zinc-blend phase. Here, the effect of growth conditions of WZ GaP nano- and microstructures obtained via chemical beam epitaxy on the optical properties was studied using power- and temperature-dependent photoluminescence (PL). We showed that the PL spectra are dominated by two strong broad emission bands at 1.68 and 1.88 eV and two relatively narrow peaks at 2.04 and 2.09 eV. The broad emissions are associated with the presence of carbon and a small number of extended crystal defects, respectively. For the sharp emissions, two main radiative recombination channels were observed with ionization energies estimated in the range of 50-80 meV and lower than 10 meV. No variation of the low-temperature PL spectra was observed for samples grown at different P precursor flows, while increasing Ga content enhanced the dominant broad emission at around 1.68 eV, suggesting that the group III organometallic precursor is the main source of impurities. Finally, Be-doped samples were grown, and their characteristic optical emission at 2.03 eV was identified. These results contribute to the understanding of impurity-related luminescence in hexagonal GaP, being useful for further crystal growth optimization required for the fabrication of optoelectronic devices.

Photophysical and Photoelectrochemical Properties of CsPbBr3 Films Grown by Electrochemically Assisted Deposition.

Perovskite have had a great impact on the solid-state physics world in the last decade not only achieving great success in photovoltaics but, more recently, also in the implementation of other optoelectronic devices. One of the main obstacles for the adoption of Pb-based perovskite technologies are the high amounts of Pb needed in the conventional preparation methods. Here we present for the first time a detailed analysis of the photophysical and photoelectrochemical properties of CsPbBr3 films directly grown on fluorine-doped tin oxide (FTO) coated glass through a novel technique based in the electrodeposition of PbO2 as CsPbBr3 precursor. This technique allows to save up to 90 % of the Pb used compared to traditional methods and can be scalable compared with the commonly used spin-coating process. The low temperature analysis of their photoluminescence spectra, performed in both steady state and time dependence, revealed a strong interaction between electrons and longitudinal optical (LO) phonons dominant at high temperatures. On the other hand, the electrochemical and photoelectrochemical analysis proves that CsPbBr3 prepared using this new method has state-of-the-art features, showing a p-type behavior under depletion regime. This is also confirmed by photoelectrochemical measurements using p-benzoquinone as target molecule. These results prove that the proposed method can be used to produce excellent CsPbBr3 films, saving much of the lead waste.

Dual magnetic field and temperature optical probes of controlled crystalline phases in lanthanide-doped multi-shell nanoparticles.

The engineering of core@multi-shell nanoparticles containing heterogeneous crystalline phases in different layers constitutes an important strategy for obtaining optical probes. The possibility of obtaining an opto-magnetic core@multi-shell nanoparticle capable of emitting in the visible and near-infrared ranges by upconversion and downshifting processes is highly desirable, especially when its optical responses are dependent on temperature and magnetic field variations. This work proposes the synthesis of hierarchically structured core@multi-shell nanoparticles of heterogeneous crystalline phases: a cubic core containing DyIII ions responsible for magnetic properties and optically active hexagonal shells, where ErIII, YbIII, and NdIII ions were distributed. This system shows at least three excitation energies located at different biological windows, and its emission intensities are sensitive to temperature and external magnetic field variations. The selected crystalline phases of the core@multi-shell nanoparticles obtained in this work is fundamental to the development of multifunctional materials with potential applications as temperature and magnetic field optical probes.

Acoustically Driven Stark Effect in Transition Metal Dichalcogenide Monolayers.

The Stark effect is one of the most efficient mechanisms to manipulate many-body states in nanostructured systems. In mono- and few-layer transition metal dichalcogenides, it has been successfully induced by optical and electric field means. Here, we tune the optical emission energies and dissociate excitonic states in MoSe2 monolayers employing the 220 MHz in-plane piezoelectric field carried by surface acoustic waves. We transfer the monolayers to high dielectric constant piezoelectric substrates, where the neutral exciton binding energy is reduced, allowing us to efficiently quench (above 90%) and red-shift the excitonic optical emissions. A model for the acoustically induced Stark effect yields neutral exciton and trion in-plane polarizabilities of 530 and 630 × 10-5 meV/(kV/cm)2, respectively, which are considerably larger than those reported for monolayers encapsulated in hexagonal boron nitride. Large in-plane polarizabilities are an attractive ingredient to manipulate and modulate multiexciton interactions in two-dimensional semiconductor nanostructures for optoelectronic applications.

Author Correction: Optical Absorption Exhibits Pseudo-Direct Band Gap of Wurtzite Gallium Phosphide.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Optical Absorption Exhibits Pseudo-Direct Band Gap of Wurtzite Gallium Phosphide.

Definitive evidence for the direct band gap predicted for Wurtzite Gallium Phosphide (WZ GaP) nanowires has remained elusive due to the lack of strong band-to-band luminescence in these materials. In order to circumvent this problem, we successfully obtained large volume WZ GaP structures grown by nanoparticle-crawling assisted Vapor-Liquid-Solid method. With these structures, we were able to observe bound exciton recombination at 2.14 eV with FHWM of approximately 1 meV. In addition, we have measured the optical absorption edges using photoluminescence excitation spectroscopy. Our results show a 10 K band gap at 2.19 eV and indicate a weak oscillator strength for the lowest energy band-to-band absorption edge, which is a characteristic feature of a pseudo-direct band gap semiconductor. Furthermore, the valence band splitting energies are estimated as 110 meV and 30 meV for the three highest bands. Electronic band structure calculations using the HSE06 hybrid density functional agree qualitatively with the valence band splitting energies.

Band structure engineering in strain-free GaAs mesoscopic systems.

We investigate the optical properties of strain-free mesoscopic GaAs/Al x Ga1 - x As structures (MGS) coupled to thin GaAs/Al x Ga1 - x As quantum wells (QWs) with varying Al content (x). We demonstrate that quenching the QW emission by controlling the band crossover between AlGaAs (X-point) and GaAs (Γ-point) gives rise to long carrier lifetimes and enhanced optical emission from the MGS. For x = 0.33, QW and MGS show typical type-I band alignment with strong QW photoluminescence emission and much weaker sharp recombination lines from the MGS localized exciton states. For x ≥ 0.50, the QW emission is considerably quenched due to the change from type-I to type-II structure while the MGS emission is enhanced due to carrier injection from the QW. For x ≥ 0.70, we observe PL quenching from the MGS higher energy states also due to the crossover of X and Γ bands, demonstrating spectral filtering of the MGS emission. Time-resolved measurements reveal two recombination processes in the MGS emission dynamics. The fast component depends mainly on the X - Γ mixing of the MGS states and can be increased from 0.3 to 2.5 ns by changing the Al content. The slower component, however, depends on the X - Γ mixing of the QW states and is associated to the carrier injection rate from the QW reservoir into the MGS structure. In this way, the independent tuning of X - Γ mixing in QW and MGS states allows us to manipulate recombination rates in the MGS as well as to make carrier injection and light extraction more efficient.

Dynamic Local Strain in Graphene Generated by Surface Acoustic Waves.

We experimentally demonstrate that the Raman-active optical phonon modes of single-layer graphene can be modulated by the dynamic local strain created by surface acoustic waves (SAWs). In particular, the dynamic strain field of the SAW is shown to induce a Raman scattering intensity variation as large as 15% and a phonon frequency shift of up to 10 cm-1 for the G band, for instance, for an effective hydrostatic strain of 0.24% generated in single-layer graphene atop a LiNbO3 piezoelectric substrate with a SAW resonator operating at a frequency of ∼400 MHz. Thus, we demonstrate that SAWs are powerful tools for modulating the optical and vibrational properties of supported graphene by means of the high-frequency localized deformations tailored by the acoustic transducers, which can also be extended to other 2D systems.

A Luminescent Thermometer Exhibiting Slow Relaxation of the Magnetization: Toward Self-Monitored Building Blocks for Next-Generation Optomagnetic Devices.

The development and integration of Single-Molecule Magnets (SMMs) into molecular electronic devices continue to be an exciting challenge. In such potential devices, heat generation due to the electric current is a critical issue that has to be considered upon device fabrication. To read out accurately the temperature at the submicrometer spatial range, new multifunctional SMMs need to be developed. Herein, we present the first self-calibrated molecular thermometer with SMM properties, which provides an elegant avenue to address these issues. The employment of 2,2'-bipyrimidine and 1,1,1-trifluoroacetylacetonate ligands results in a dinuclear compound, [Dy2(bpm)(tfaa)6], which exhibits slow relaxation of the magnetization along with remarkable photoluminescent properties. This combination allows the gaining of fundamental insight in the electronic properties of the compound and investigation of optomagnetic cross-effects (Zeeman effect). Importantly, spectral variations stemming from two distinct thermal-dependent mechanisms taking place at the molecular level are used to perform luminescence thermometry over the 5-398 K temperature range. Overall, these properties make the proposed system a unique molecular luminescent thermometer bearing SMM properties, which preserves its temperature self-monitoring capability even under applied magnetic fields.

In-place bonded semiconductor membranes as compliant substrates for III-V compound devices.

Overcoming the critical thickness limit in pseudomorphic growth of lattice mismatched heterostructures is a fundamental challenge in heteroepitaxy. On-demand transfer of light-emitting structures to arbitrary host substrates is an important technological method for optoelectronic and photonic device implementation. The use of freestanding membranes as compliant substrates is a promising approach to address both issues. In this work, the feasibility of using released GaAs/InGaAs/GaAs membranes as virtual substrates to thin films of InGaAs alloys is investigated as a function of the indium content in the films. Growth of flat epitaxial films is demonstrated with critical thickness beyond typical values observed for growth on bulk substrates. Optically active structures are also grown on these membranes with a strong photoluminescence signal and a clear red shift for an InAlGaAs/InGaAs/InAlGaAs quantum well. The red shift is ascribed to strain reduction in the quantum well due to the use of a completely relaxed membrane as the substrate. Our results demonstrate that such membranes constitute a virtual substrate that allows further heterostructure strain engineering, which is not possible when using other post-growth methods.

Three-Dimensional Superlattice of PbS Quantum Dots in Flakes.

In the last two decades, many experiments were conducted in self-organization of nanocrystals into two- and three-dimensional (3D) superlattices and the superlattices were synthesized and characterized by different techniques, revealing their unusual properties. Among all characterization techniques, X-ray diffraction (XRD) is the one that has allowed the confirmation of the 3D superlattice formation due to the presence of sharp and intense diffraction peaks. In this work, we study self-organized superlattices of quantum dots of PbS prepared by dropping a monodispersed colloidal solution on a glass substrate at different temperatures. We showed that the intensity of the low-angle XRD peaks depends strongly on the drying time (substrate temperature). We claim that the peaks are originated from the 3D superlattice. Scanning electron microscopy images show that this 3D superlattice (PbS quantum dots) is formed in flake's shape, parallel to the substrate surface and randomly oriented in the perpendicular planes.

Correction to "Three-Dimensional Superlattice of PbS Quantum Dots in Flakes".

[This corrects the article DOI: 10.1021/acsomega.7b01791.].

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.

Size Control of Silver-Core/Silica-Shell Nanoparticles Fabricated by Laser-Ablation-Assisted Chemical Reduction.

Aqueous colloidal silver nanoparticles have substantial potential in biological application as markers and antibacterial agents and in surface-enhanced Raman spectroscopy applications. A simple method of fabrication and encapsulation into an inert shell is of great importance today to make their use ubiquitous. Here we show that colloids of silver-core/silica-shell nanoparticles can be easily fabricated by a laser-ablation-assisted chemical reduction method and their sizes can be tuned in the range of 2.5 to 6.3 nm by simply choosing a proper water-ethanol proportion. The produced silver nanoparticles possess a porous amorphous silica shell that increases the inertness and stability of colloids, which decreases their toxicity compared with those without silica. The presence of a thin 2 to 3 nm silica shell was proved by EDX mapping. The small sizes of nanoparticles achieved by this method were analyzed using optical techniques, and they show typical photoluminescence in the UV-vis range that shifts toward higher energies with decreasing size.

Fabrication and Optical Properties of Strain-free Self-assembled Mesoscopic GaAs Structures.

We use a combined process of Ga-assisted deoxidation and local droplet etching to fabricate unstrained mesoscopic GaAs/AlGaAs structures exhibiting a high shape anisotropy with a length up to 1.2 µm and a width of 150 nm. We demonstrate good controllability over size and morphology of the mesoscopic structures by tuning the growth parameters. Our growth method yields structures, which are coupled to a surrounding quantum well and present unique optical emission features. Microscopic and optical analysis of single structures allows us to demonstrate that single structure emission originates from two different confinement regions, which are spectrally separated and show sharp excitonic lines. Photoluminescence is detected up to room temperature making the structures the ideal candidates for strain-free light emitting/detecting devices.