Imaging the strain evolution of a platinum nanoparticle under electrochemical control.

Surface strain is widely employed in gas phase catalysis and electrocatalysis to control the binding energies of adsorbates on active sites. However, in situ or operando strain measurements are experimentally challenging, especially on nanomaterials. Here we exploit coherent diffraction at the new fourth-generation Extremely Brilliant Source of the European Synchrotron Radiation Facility to map and quantify strain within individual Pt catalyst nanoparticles under electrochemical control. Three-dimensional nanoresolution strain microscopy, together with density functional theory and atomistic simulations, show evidence of heterogeneous and potential-dependent strain distribution between highly coordinated ({100} and {111} facets) and undercoordinated atoms (edges and corners), as well as evidence of strain propagation from the surface to the bulk of the nanoparticle. These dynamic structural relationships directly inform the design of strain-engineered nanocatalysts for energy storage and conversion applications.

Spatially and Time-Resolved Carrier Dynamics in Core-Shell InGaN/GaN Multiple-Quantum Wells on GaN Wire.

Time-resolved cathodoluminescence is a key tool with high temporal and spatial resolution. However, optical spectroscopic information can be also extracted using synchrotron pulses in a hard X-ray nanoprobe, exploiting a phenomenon called X-ray excited optical luminescence. Here, with 20 ps time resolution and 80 nm lateral resolution, we applied this time-resolved X-ray microscopy technique to individual core-shell InGaN/GaN multiple quantum well heterostructures deposited on GaN wires. Our findings suggest that the m-plane related multiple quantum well states govern the carrier dynamics. Likewise, our observations support not only the influence of In incorporation in the recombination rates, but also carrier localization phenomena at the hexagon wire apex. In addition, our experiment calls for further investigations of the spatiotemporal domain on the underlying mechanisms of optoelectronic nanodevices. Its great potential becomes more valuable when time-resolved X-ray excited optical luminescence microscopy is used in operando with other methods, such as X-ray absorption spectroscopy.

A helium mini-cryostat for the nanoprobe beamline ID16B at ESRF: characteristics and performance.

A helium mini-cryostat has been developed for the hard X-ray nanoprobe ID16B of the European Synchrotron to collect X-ray excited optical luminescence and X-ray fluorescence at low temperature (<10 K). The mini-cryostat has been specifically designed to fit within the strong space restrictions and high-demanding mechanical constraints imposed by the beamline to provide vibration-free operation and maximal thermal stability. This paper reports the detailed design, architecture and technical requirements of the mini-cryostat, and presents the first experimental data measured using the cryogenic equipment. The resulting cryo-system features ultimate thermal stability, fast cool-down and ultra-low vibrations. The simultaneous X-ray fluorescence and X-ray excited optical luminescence data acquired from bulk GaN and core/shell InGaN/GaN multi-quantum wells validated the excellent performance of the cryostat with ultimate resolution, stability and sensitivity.

Silane-Induced N-Polarity in Wires Probed by a Synchrotron Nanobeam.

Noncentrosymmetric one-dimensional structures are key driving forces behind advanced nanodevices. Owing to the critical role of silane injection in creating nanosized architectures, it has become a challenge to investigate the induced local lattice polarity in single GaN wires. Thus, if axial and radial structures are well-grown by a silane-mediated approach, an ideal model to study their polar orientations is formed. By combining synchrotron X-ray fluorescence and X-ray excited optical luminescence, we show here experimental evidence of the role of silane to promote the N-polarity, light emission, and elemental incorporation within single wires. In addition, our experiment demonstrates the ability to spatially examine carrier diffusion phenomena without electrical contacts, opening new avenues for further studies with simultaneous optical and elemental sensitivity at the nanoscale.

Thin-Wall GaN/InAlN Multiple Quantum Well Tubes.

Thin-wall tubes composed of nitride semiconductors (III-N compounds) based on GaN/InAlN multiple quantum wells (MQWs) are fabricated by metal-organic vapor-phase epitaxy in a simple and full III-N approach. The synthesis of such MQW-tubes is based on the growth of N-polar c-axis vertical GaN wires surrounded by a core-shell MQW heterostructure followed by in situ selective etching using controlled H2/NH3 annealing at 1010 °C to remove the inner GaN wire part. After this process, well-defined MQW-based tubes having nonpolar m-plane orientation exhibit UV light near 330 nm up to room temperature, consistent with the emission of GaN/InAlN MQWs. Partially etched tubes reveal a quantum-dotlike signature originating from nanosized GaN residuals present inside the tubes. The possibility to fabricate in a simple way thin-wall III-N tubes composed of an embedded MQW-based active region offering controllable optical emission properties constitutes an important step forward to develop new nitride devices such as emitters, detectors or sensors based on tubelike nanostructures.

Flexible Light-Emitting Diodes Based on Vertical Nitride Nanowires.

We demonstrate large area fully flexible blue LEDs based on core/shell InGaN/GaN nanowires grown by MOCVD. The fabrication relies on polymer encapsulation, nanowire lift-off and contacting using silver nanowire transparent electrodes. The LEDs exhibit rectifying behavior with a light-up voltage around 3 V. The devices show no electroluminescence degradation neither under multiple bending down to 3 mm curvature radius nor in time for more than one month storage in ambient conditions without any protecting encapsulation. Fully transparent flexible LEDs with high optical transmittance are also fabricated. Finally, a two-color flexible LED emitting in the green and blue spectral ranges is demonstrated combining two layers of InGaN/GaN nanowires with different In contents.

Correlation of microphotoluminescence spectroscopy, scanning transmission electron microscopy, and atom probe tomography on a single nano-object containing an InGaN/GaN multiquantum well system.

A single nanoscale object containing a set of InGaN/GaN nonpolar multiple-quantum wells has been analyzed by microphotoluminescence spectroscopy (µPL), high-resolution scanning transmission electron microscopy (HR-STEM) and atom probe tomography (APT). The correlated measurements constitute a rich and coherent set of data supporting the interpretation that the observed µPL narrow emission lines, polarized perpendicularly to the crystal c-axis and with energies in the interval 2.9-3.3 eV, are related to exciton states localized in potential minima induced by the irregular 3D In distribution within the quantum well (QW) planes. This novel method opens up interesting perspectives, as it will be possible to apply it on a wide class of quantum confining emitters and nano-objects.

Unveiling Core-Shell Structure Formation in a Ni3Fe Nanoparticle with In Situ Multi-Bragg Coherent Diffraction Imaging.

Solid-state reactions play a key role in materials science. The evolution of the structure of a single 350 nm Ni3Fe nanoparticle, i.e., its morphology (facets) as well as its deformation field, has been followed by applying multireflection Bragg coherent diffraction imaging. Through this approach, we unveiled a demixing process that occurs at high temperatures (600 °C) under an Ar atmosphere. This process leads to the gradual emergence of a highly strained core-shell structure, distinguished by two distinct lattice parameters with a difference of 0.4%. Concurrently, this transformation causes the facets to vanish, ultimately yielding a rounded core-shell nanoparticle. This final structure comprises a Ni3Fe core surrounded by a 40 nm Ni-rich outer shell due to preferential iron oxidation. Providing in situ 3D imaging of the lattice parameters at the nanometer scale while varying the temperature, this study─with the support of atomistic simulations─not only showcases the power of in situ multireflection BCDI but also provides valuable insights into the mechanisms at work during a solid-state reaction characterized by a core-shell transition.

M-plane core-shell InGaN/GaN multiple-quantum-wells on GaN wires for electroluminescent devices.

Nonpolar InGaN/GaN multiple quantum wells (MQWs) grown on the {11-00} sidewalls of c-axis GaN wires have been grown by organometallic vapor phase epitaxy on c-sapphire substrates. The structural properties of single wires are studied in detail by scanning transmission electron microscopy and in a more original way by secondary ion mass spectroscopy to quantify defects, thickness (1-8 nm) and In-composition in the wells (∼16%). The core-shell MQW light emission characteristics (390-420 nm at 5 K) were investigated by cathodo- and photoluminescence demonstrating the absence of the quantum Stark effect as expected due to the nonpolar orientation. Finally, these radial nonpolar quantum wells were used in room-temperature single-wire electroluminescent devices emitting at 392 nm by exploiting sidewall emission.

LaueNN: neural-network-based hkl recognition of Laue spots and its application to polycrystalline materials.

A feed-forward neural-network-based model is presented to index, in real time, the diffraction spots recorded during synchrotron X-ray Laue microdiffraction experiments. Data dimensionality reduction is applied to extract physical 1D features from the 2D X-ray diffraction Laue images, thereby making it possible to train a neural network on the fly for any crystal system. The capabilities of the LaueNN model are illustrated through three examples: a two-phase nano-structure, a textured high-symmetry specimen deformed in situ and a polycrystalline low-symmetry material. This work provides a novel way to efficiently index Laue spots in simple and complex recorded images in <1 s, thereby opening up avenues for the realization of real-time analysis of synchrotron Laue diffraction data.

Stretchable Transparent Light-Emitting Diodes Based on InGaN/GaN Quantum Well Microwires and Carbon Nanotube Films.

We propose and demonstrate both flexible and stretchable blue light-emitting diodes based on core/shell InGaN/GaN quantum well microwires embedded in polydimethylsiloxane membranes with strain-insensitive transparent electrodes involving single-walled carbon nanotubes. InGaN/GaN core-shell microwires were grown by metal-organic vapor phase epitaxy, encapsulated into a polydimethylsiloxane film, and then released from the growth substrate. The fabricated free-standing membrane of light-emitting diodes with contacts of single-walled carbon nanotube films can stand up to 20% stretching while maintaining efficient operation. Membrane-based LEDs show less than 15% degradation of electroluminescence intensity after 20 cycles of stretching thus opening an avenue for highly deformable inorganic devices.

Role of Underlayer for Efficient Core-Shell InGaN QWs Grown on m-plane GaN Wire Sidewalls.

Different types of buffer layers such as InGaN underlayer (UL) and InGaN/GaN superlattices are now well-known to significantly improve the efficiency of c-plane InGaN/GaN-based light-emitting diodes (LEDs). The present work investigates the role of two different kinds of pregrowth layers (low In-content InGaN UL and GaN UL namely "GaN spacer") on the emission of the core-shell m-plane InGaN/GaN single quantum well (QW) grown around Si-doped c̅-GaN microwires obtained by silane-assisted metal organic vapor phase epitaxy. According to photo- and cathodoluminescence measurements performed at room temperature, an improved efficiency of light emission at 435 nm with internal quantum efficiency >15% has been achieved by adding a GaN spacer prior to the growth of QW. As revealed by scanning transmission electron microscopy, an ultrathin residual layer containing Si located at the wire sidewall surfaces favors the formation of high density of extended defects nucleated at the first InGaN QW. This contaminated residual incorporation is buried by the growth of the GaN spacer and avoids the structural defect formation, therefore explaining the improved optical efficiency. No further improvement is observed by adding the InGaN UL to the structure, which is confirmed by comparable values of the effective carrier lifetime estimated from time-resolved experiments. Contrary to the case of planar c-plane QW where the improved efficiency is attributed to a strong decrease of point defects, the addition of an InGaN UL seems to have no influence in the case of radial m-plane QW.

UV Emission from GaN Wires with m-Plane Core-Shell GaN/AlGaN Multiple Quantum Wells.

The present work reports high-quality nonpolar GaN/Al0.6Ga0.4N multiple quantum wells (MQWs) grown in core-shell geometry by metal-organic vapor-phase epitaxy on the m-plane sidewalls of c̅-oriented hexagonal GaN wires. Optical and structural studies reveal ultraviolet (UV) emission originating from the core-shell GaN/AlGaN MQWs. Tuning the m-plane GaN QW thickness from 4.3 to 0.7 nm leads to a shift of the emission from 347 to 292 nm, consistent with Schrödinger-Poisson calculations. The evolution of the luminescence with temperature displays signs of strong localization, especially for samples with thinner GaN QWs and no evidence of quantum-confined Stark effect, as expected for nonpolar m-plane surfaces. The internal quantum efficiency derived from the photoluminescence (PL) intensity ratio at low and room temperatures is maximum (∼7.3% measured at low power excitation) for 2.6 nm thick quantum wells, emitting at 325 nm, and shows a large drop for thicker QWs. An extensive study of the PL quenching with temperature is presented. Two nonradiative recombination paths are activated at different temperatures. The low-temperature path is found to be intrinsic to the heterostructure, whereas the process that dominates at high temperature depends on the QW thickness and is strongly enhanced for QWs larger than 2.6 nm, causing a rapid decrease in the internal quantum efficiency.

Mapping Inversion Domain Boundaries along Single GaN Wires with Bragg Coherent X-ray Imaging.

Gallium nitride (GaN) is of technological importance for a wide variety of optoelectronic applications. Defects in GaN, like inversion domain boundaries (IDBs), significantly affect the electrical and optical properties of the material. We report, here, on the structural configurations of planar inversion domain boundaries inside n-doped GaN wires measured by Bragg coherent X-ray diffraction imaging. Different complex domain configurations are revealed along the wires with a 9 nm in-plane spatial resolution. We demonstrate that the IDBs change their direction of propagation along the wires, promoting Ga-terminated domains and stabilizing into {11̅00}, that is, m-planes. The atomic phase shift between the Ga- and N-terminated domains was extracted using phase-retrieval algorithms, revealing an evolution of the out-of-plane displacement (∼5 pm, at maximum) between inversion domains along the wires. This work provides an accurate inner view of planar defects inside small crystals.

Heat Dissipation in Flexible Nitride Nanowire Light-Emitting Diodes.

We analyze the thermal behavior of a flexible nanowire (NW) light-emitting diode (LED) operated under different injection conditions. The LED is based on metal-organic vapor-phase deposition (MOCVD)-grown self-assembled InGaN/GaN NWs in a polydimethylsiloxane (PDMS) matrix. Despite the poor thermal conductivity of the polymer, active nitride NWs effectively dissipate heat to the substrate. Therefore, the flexible LED mounted on a copper heat sink can operate under high injection without significant overheating, while the device mounted on a plastic holder showed a 25% higher temperature for the same injected current. The efficiency of the heat dissipation by nitride NWs was further confirmed with finite-element modeling of the temperature distribution in a NW/polymer composite membrane.

Flexible Capacitive Piezoelectric Sensor with Vertically Aligned Ultralong GaN Wires.

We report a simple and scalable fabrication process of flexible capacitive piezoelectric sensors using vertically aligned gallium nitride (GaN) wires as well as their physical principles of operation. The as-grown N-polar GaN wires obtained by self-catalyst metal-organic vapor phase epitaxy are embedded into a polydimethylsiloxane (PDMS) matrix and directly peeled off from the sapphire substrate before metallic electrode contacting. This geometry provides an efficient control of the wire orientation and an additive contribution of the individual piezoelectric signals. The device output voltage and efficiency are studied by finite element calculations for compression mechanical loading as a function of the wire geometrical growth parameters (length and density). We demonstrate that the voltage output level and sensitivity increases as a function of the wire length and that a conical shape is not mandatory for potential generation as it was the case for horizontally assembled devices. The optimal design to improve the overall device response is also optimized in terms of wire positioning inside PDMS, wire density, and total device thickness. Following the results of these calculations, we have fabricated experimental devices exhibiting outputs of several volts with a very good reliability under cyclic mechanical excitation.

Piezo-Potential Generation in Capacitive Flexible Sensors Based on GaN Horizontal Wires.

We report an example of the realization of a flexible capacitive piezoelectric sensor based on the assembly of horizontal c¯-polar long Gallium nitride (GaN) wires grown by metal organic vapour phase epitaxy (MOVPE) with the Boostream® technique spreading wires on a moving liquid before their transfer on large areas. The measured signal (<0.6 V) obtained by a punctual compression/release of the device shows a large variability attributed to the dimensions of the wires and their in-plane orientations. The cause of this variability and the general operating mechanisms of this flexible capacitive device are explained by finite element modelling simulations. This method allows considering the full device composed of a metal/dielectric/wires/dielectric/metal stacking. We first clarify the mechanisms involved in the piezo-potential generation by mapping the charge and piezo-potential in a single wire and studying the time-dependent evolution of this phenomenon. GaN wires have equivalent dipoles that generate a tension between metallic electrodes only when they have a non-zero in-plane projection. This is obtained in practice by the conical shape occurring spontaneously during the MOVPE growth. The optimal aspect ratio in terms of length and conicity (for the usual MOVPE wire diameter) is determined for a bending mechanical loading. It is suggested to use 60⁻120 µm long wires (i.e., growth time less than 1 h). To study further the role of these dipoles, we consider model systems with in-plane 1D and 2D regular arrays of horizontal wires. It is shown that a strong electrostatic coupling and screening occur between neighbouring horizontal wires depending on polarity and shape. This effect, highlighted here only from calculations, should be taken into account to improve device performance.

Crystallographic orientation of facets and planar defects in functional nanostructures elucidated by nano-focused coherent diffractive X-ray imaging.

The physical and chemical properties of nanostructures depend on their surface facets. Here, we exploit a pole figure approach to determine the three-dimensional orientation matrix of a nanostructure from a single Bragg reflection measured with a coherent nano-focused X-ray beam. The signature of any truncated (faceted) crystal produces a crystal truncation rod, which corresponds to a streak of intensity in reciprocal space normal to the surface. When two or more non-parallel facets are present, both the crystal orientation and the crystal facets can be identified. This enables facets to be rapidly indexed and uncommon facets, and planar defects, that have been difficult to study before to be identified. We demonstrate the technique with (i) epitaxial core-shell InGaN/GaN multiple quantum-wells grown on GaN nanowires, where surface facets and planar defects are determined, and (ii) single randomly oriented highly faceted tetrahedrahexal Pt nanoparticles. The methodology is applicable to a broad range of nanocrystals and provides a unique insight into the connection between structure and properties of nanomaterials.

Flexible White Light Emitting Diodes Based on Nitride Nanowires and Nanophosphors.

We report the first demonstration of flexible white phosphor-converted light emitting diodes (LEDs) based on p-n junction core/shell nitride nanowires. GaN nanowires containing seven radial In0.2Ga0.8N/GaN quantum wells were grown by metal-organic chemical vapor deposition on a sapphire substrate by a catalyst-free approach. To fabricate the flexible LED, the nanowires are embedded into a phosphor-doped polymer matrix, peeled off from the growth substrate, and contacted using a flexible and transparent silver nanowire mesh. The electroluminescence of a flexible device presents a cool-white color with a spectral distribution covering a broad spectral range from 400 to 700 nm. Mechanical bending stress down to a curvature radius of 5 mm does not yield any degradation of the LED performance. The maximal measured external quantum efficiency of the white LED is 9.3%, and the wall plug efficiency is 2.4%.

Flexible Photodiodes Based on Nitride Core/Shell p-n Junction Nanowires.

A flexible nitride p-n photodiode is demonstrated. The device consists of a composite nanowire/polymer membrane transferred onto a flexible substrate. The active element for light sensing is a vertical array of core/shell p-n junction nanowires containing InGaN/GaN quantum wells grown by MOVPE. Electron/hole generation and transport in core/shell nanowires are modeled within nonequilibrium Green function formalism showing a good agreement with experimental results. Fully flexible transparent contacts based on a silver nanowire network are used for device fabrication, which allows bending the detector to a few millimeter curvature radius without damage. The detector shows a photoresponse at wavelengths shorter than 430 nm with a peak responsivity of 0.096 A/W at 370 nm under zero bias. The operation speed for a 0.3 × 0.3 cm2 detector patch was tested between 4 Hz and 2 kHz. The -3 dB cutoff was found to be ∼35 Hz, which is faster than the operation speed for typical photoconductive detectors and which is compatible with UV monitoring applications.