Algorithm-Based Linearly Graded Compositions of GeSn on GaAs (001) via Molecular Beam Epitaxy.

The growth of high-composition GeSn films in the future will likely be guided by algorithms. In this study, we show how a logarithmic-based algorithm can be used to obtain high-quality GeSn compositions up to 16% on GaAs (001) substrates via molecular beam epitaxy. Herein, we use composition targeting and logarithmic Sn cell temperature control to achieve linearly graded pseudomorph Ge1-xSnx compositions up to 10% before partial relaxation of the structure and a continued gradient up to 16% GeSn. In this report, we use X-ray diffraction, simulation, secondary ion mass spectrometry, and atomic force microscopy to analyze and demonstrate some of the possible growths that can be produced with the enclosed algorithm. This methodology of growth is a major step forward in the field of GeSn development and the first ever demonstration of algorithmically driven, linearly graded GeSn films.

The growth of Ge and direct bandgap Ge1-xSnx on GaAs (001) by molecular beam epitaxy.

Germanium tin (GeSn) is a tuneable narrow bandgap material, which has shown remarkable promise for the industry of near- and mid-infrared technologies for high efficiency photodetectors and laser devices. Its synthesis is challenged by the lattice mismatch between the GeSn alloy and the substrate on which it is grown, sensitively affecting its crystalline and optical qualities. In this article, we investigate the growth of Ge and GeSn on GaAs (001) substrates using two different buffer layers consisting of Ge/GaAs and Ge/AlAs via molecular beam epitaxy. The quality of the Ge layers was compared using X-ray diffraction, atomic force microscopy, reflection high-energy electron diffraction, and photoluminescence. The characterization techniques demonstrate high-quality Ge layers, including atomic steps, when grown on either GaAs or AlAs at a growth temperature between 500-600 °C. The photoluminescence from the Ge layers was similar in relative intensity and linewidth to that of bulk Ge. The Ge growth was followed by the growth of GeSn using a Sn composition gradient and substrate gradient approach to achieve GeSn films with 9 to 10% Sn composition. Characterization of the GeSn films also indicates high-quality gradients based on X-ray diffraction, photoluminescence, and energy-dispersive X-ray spectroscopy measurements. Finally, we were able to demonstrate temperature-dependent PL results showing that for the growth on Ge/GaAs buffer, the direct transition has shifted past the indirect transition to a longer wavelength/lower energy suggesting a direct bandgap GeSn material.

Band Offsets of the MOCVD-Grown ß-(Al0.21Ga0.79)2O3/ß-Ga2O3 (010) Heterojunction.

The band offsets for the ß-(Al0.21Ga0.79)2O3/ß-Ga2O3 (010) heterojunction have been experimentally measured by X-ray photoelectron spectroscopy. High-quality ß-(Al0.21Ga0.79)2O3 films were grown by metal-organic chemical vapor deposition for characterization. The indirect band gap of ß-(Al0.21Ga0.79)2O3 was determined by optical transmission to be 4.69 ± 0.03 eV with a direct transition of 5.37 ± 0.03 eV, while ß-Ga2O3 was confirmed to have an indirect band gap of 4.52 ± 0.03 eV with a direct transition of 4.94 ± 0.03 eV. The resulting band alignment at the heterojunction was determined to be of type II with the valence and conduction band edges of ß-(Al0.21Ga0.79)2O3 being -0.26 ± 0.08 and 0.43 ± 0.08 eV, respectively, above those of ß-Ga2O3 (010). These values can now be used to help better design and predict the performance of ß-(AlxGa1-x)2O3 heterojunction-based devices.

The Growth of Polarization Domains in Ultrathin Ferroelectric Films Seeded by the Tip of an Atomic Force Microscope.

Piezoresponse force microscopy is used to study the velocity of the polarization domain wall in ultrathin ferroelectric barium titanate (BTO) films grown on strontium titanate (STO) substrates by molecular beam epitaxy. The electric field due to the cone of the atomic force microscope tip is demonstrated as the dominant electric field for domain expansion in thin films at lateral distances greater than about one tip diameter away from the tip. The velocity of the domain wall under the applied electric field by the tip in BTO for thin films (less than 40 nm) followed an expanding process given by Merz's law. The material constants in a fit of the data to Merz's law for very thin films are reported as about 4.2 KV/cm for the activation field, [Formula: see text], and 0.05 nm/s for the limiting velocity, [Formula: see text]. These material constants showed a dependence on the level of strain in the films, but no fundamental dependence on thickness.

Coherent-interface-induced strain in large lattice-mismatched materials: A new approach for modeling Raman shift.

Strain engineering as one of the most powerful techniques for tuning optical and electronic properties of Ill-nitrides requires reliable methods for strain investigation. In this work, we reveal, that the linear model based on the experimental data limited to within a small range of biaxial strains (< 0.2%), which is widely used for the non-destructive Raman study of strain with nanometer-scale spatial resolution is not valid for the binary wurtzite-structure group-III nitrides GaN and AlN. Importantly, we found that the discrepancy between the experimental values of strain and those calculated via Raman spectroscopy increases as the strain in both GaN and AlN increases. Herein, a new model has been developed to describe the strain-induced Raman frequency shift in GaN and AlN for a wide range of biaxial strains (up to 2.5%). Finally, we proposed a new approach to correlate the Raman frequency shift and strain, which is based on the lattice coherency in the epitaxial layers of superlattice structures and can be used for a wide range of materials. Electronic Supplementary Material: Supplementary material (Table S1: Values of bulk phonon deformation potentials and elastic constants for GaN and AlN from each reference used in Table 1, Fig. S1: Lattice parameters of SL layers using Eq. (8), and Fig. S2: Raman mapping using Eq. (7)) is available in the online version of this article at 10.1007/s12274-021-3855-4.

Photoluminescence characterization of wetting layer and carrier dynamics for coupled InGaAs/GaAs surface quantum dot pair structures.

The optical properties are investigated by spectroscopic characterizations for bilayer InGaAs/GaAs quantum dot (QD) structures consisting of a layer of surface quantum dots (SQDs) separated from a layer of buried quantum dots (BQDs) by different GaAs spacers with thicknesses of 7 nm, 10.5 nm and 70 nm. The coupling from the BQDs to SQDs leads to carrier transfer for the two samples with thin spacers, 7 nm and 10.5 nm, in which QD pairs are obtained while not for the 70 nm spacer sample. The carrier tunneling time is measured to be 0.145 ns and 0.275 ns from BQDs to SQD through the 7 nm and 10.5 nm spacers, respectively. A weak emission band can be observed at the wavelength of ∼ 960 nm, while the excitation intensity dependent PL and PLE spectra show that this is from the wetting layer (WL) of the SQDs. This WL is very important for carrier dynamics in bilayer structures of BQDs and SQDs, including for carrier generation, capture, relaxation, tunneling, and recombination. These results provide useful information for understanding the optical properties of InGaAs SQDs and for using such hybrid structures as building blocks for surface sensing devices.

Photoluminescence of InAs/GaAs quantum dots under direct two-photon excitation.

Self-assembled quantum dots grown by molecular beam epitaxy have been a hotbed for various fundamental research and device applications over the past decades. Among them, InAs/GaAs quantum dots have shown great potential for applications in quantum information, quantum computing, infrared photodetection, etc. Though intensively studied, some of the optical nonlinear properties of InAs/GaAs quantum dots, specifically the associated two-photon absorption of the wetting and barrier layers, have not been investigated yet. Here we report a study of the photoluminescence of these dots by using direct two-photon excitation. The quadratic power law dependence of the photoluminescence intensity, together with the ground-state resonant peak of quantum dots appearing in the photoluminescence excitation spectrum, unambiguously confirms the occurrence of the direct two-photon absorption in the dots. A three-level rate equation model is proposed to describe the photogenerated carrier dynamics in the quantum dot-wetting layer-GaAs system. Moreover, higher-order power law dependence of photoluminescence intensity is observed on both the GaAs substrate and the wetting layer by two-photon excitation, which is accounted for by a model involving the third-harmonic generation at the sample interface. Our results open a door for understanding the optical nonlinear effects associated with this fundamentally and technologically important platform.

Type-II GaSb quantum dots grown on InAlAs/InP (001) by droplet epitaxy.

GaSb quantum dots (QDs) have been grown by droplet epitaxy within InAlAs barrier layers on an InP (001) substrate. The droplet growth mode facilitates a larger size (average height ∼4.5 nm) and a lower density (∼6.3 × 109 cm-2) for the QDs than would be expected for the 4% lattice mismatch between GaSb and InAlAs. A type-II band alignment between the GaSb QDs and the InAlAs barriers is revealed by photoluminescence (PL) through a prominent blue-shift of ∼0.11 eV resulting from a six orders of magnitude increase in excitation power. Further confirmation of the type-II nature of these QDs is found through time-resolved PL studies showing a biexponential decay with a long carrier lifetime of ∼10.9 ns. These observations reveal new information for understanding the formation and properties of GaSb/InAlAs/InP QDs, which may be an optimum system for the development of both efficient memory cells and photovoltaic devices.

An Effective Electric Dipole Model for Voltage-induced Gating Mechanism of Lysenin.

Lysenin is a pore-forming toxin, which self-inserts open channels into sphingomyelin containing membranes and is known to be voltage regulated. The mechanistic details of its voltage gating mechanism, however, remains elusive despite much recent efforts. Here, we have employed a novel combination of experimental and computational techniques to examine a model for voltage gating, that is based on the existence of an "effective electric dipole" inspired by recent reported structures of lysenin. We support this mechanism by the observations that (i) the charge-reversal and neutralization substitutions in lysenin result in changing its electrical gating properties by modifying the strength of the dipole, and (ii) an increase in the viscosity of the solvent increases the drag force and slows down the gating. In addition, our molecular dynamics (MD) simulations of membrane-embedded lysenin provide a mechanistic picture for lysenin conformational changes, which reveals, for the first time, the existence of a lipid-dependent bulge region in the pore-forming module of lysenin, which may explain the gating mechanism of lysenin at a molecular level.

Quantification of cellular associated graphene and induced surface receptor responses.

The use of graphene for biomedical and other applications involving humans is growing and shows practical promise. However, quantifying the graphitic nanomaterials that interact with cells and assessing any corresponding cellular response is extremely challenging. Here, we report an effective approach to quantify graphene interacting with single cells that utilizes combined multimodal-Raman and photoacoustic spectroscopy. This approach correlates the spectroscopic signature of graphene with the measurement of its mass using a quartz crystal microbalance resonator. Using this technique, we demonstrate single cell noninvasive quantification and multidimensional mapping of graphene with a detection limit of as low as 200 femtograms. Our investigation also revealed previously unseen graphene-induced changes in surface receptor expression in dendritic cells of the immune system. This tool integrates high-sensitivity real-time detection and monitoring of nanoscale materials inside single cells with the measurement of induced simultaneous biological cell responses, providing a powerful method to study the impact of nanomaterials on living systems and as a result, the toxicology of nanoscale materials.

Plasmonically-powered hot carrier induced modulation of light emission in a two-dimensional GaAs semiconductor quantum well.

A hot-electron-enabled route to controlling light with dissipative loss compensation in semiconductor quantum light emitters has been realized for tunable quantum optoelectronic devices via a two-species plasmon system. The dual species nano-plasmonic system is achieved by combining UV-plasmonic gallium metal nanoparticles (GaNPs) with visible-plasmonic gold metal nanoparticles (AuNPs) on a near-infrared two-dimensional GaAs/AlGaAs quantum well emitter. It has been demonstrated that while hot carrier-powered charge-transfer processes can result in semiconductor doping and increased optical absorption, photo-generated carrier density in the quantum well can also be modulated by off-resonant plasmonic interaction without thermal dissipation. Merging these essential emitter-friendly optical characteristics in the two-species plasmon system, we effectively modulate the frequency of the emitted light. The wavelength of the emitted light is tuned by the plasmonically powered hot electron process induced by the AuNPs with a 10-fold emission enhancement induced by the GaNPs. The additional plasmonic element provides functionality to achieving an active plasmonic light emitter that is otherwise far from reach with conventional single plasmonic material-based semiconductors.

Interplay Effect of Temperature and Excitation Intensity on the Photoluminescence Characteristics of InGaAs/GaAs Surface Quantum Dots.

We investigate the optical properties of InGaAs surface quantum dots (SQDs) in a composite nanostructure with a layer of similarly grown buried quantum dots (BQDs) separated by a thick GaAs spacer, but with varied areal densities of SQDs controlled by using different growth temperatures. Such SQDs behave differently from the BQDs, depending on the surface morphology. Dedicated photoluminescence (PL) measurements for the SQDs grown at 505 °C reveal that the SQD emission follows different relaxation channels while exhibiting abnormal thermal quenching. The PL intensity ratio between the SQDs and BQDs demonstrates interplay between excitation intensity and temperature. These observations suggest a strong dependence on the surface for carrier dynamics of the SQDs, depending on the temperature and excitation intensity.

Correlation between photoluminescence and morphology for single layer self-assembled InGaAs/GaAs quantum dots.

Single layer self-assembled InGaAs quantum dots (QDs) are manipulated by using different arsenic species on GaAs (100) surface. The As4 molecules are experimentally observed to be more promising than As2 to promote the formation of one-dimensionally-aligned QD-chain arrays. The lateral alignment of QDs and the corresponding formation of dot chains are explained by the anisotropic surface kinetics in combination with the different reactivities of the two molecules with bonding sites on the GaAs (100) surface. Photoluminescence (PL) measurements demonstrate that the spectra of the QD-chains broaden to higher energy and increases in intensity with increasing excitation laser power. The PL band of the QD-chains also exhibits a 9 meV reduction in linewidth as temperature increases starting from 8 K. These observations confirm an efficient lateral coupling between neighboring QDs and thereafter polarized QD emission, whereas the randomly distributed QDs grown with As2 show no preferential polarization. Such QD-chains exhibiting anisotropic properties have the potential for nanophotonics applications like electro-optic modulators with very low drive voltage and ultra-wide bandwidth operation.

Polarization Effects in Graded AlGaN Nanolayers Revealed by Current-Sensing and Kelvin Probe Microscopy.

We experimentally demonstrate that the conductivity of graded AlxGa1-xN increases as a function of the magnitude of the Al concentration gradient (%Al/nm) due to polarization doping effects, without the use of impurity dopants. Using three up/down-graded AlxGa1-xN nanolayers with Al gradients ranging from ∼0.16 to ∼0.28%Al/nm combined in one structure, the effects of polarization engineering for localized electric fields and current transport were investigated. Cross-sectional Kelvin probe force microscopy and conductive atomic force microscopy were used to directly probe the electrical properties of the films with spatial resolution along the thickness of the growth. The experimental profiles of the built-in electric fields and the spreading current found in the graded layers are shown to be consistent with simulations of the field distribution as well as of the electron and hole densities. Finally, it was directly observed that for gradients less than 0.28%Al/nm the native n-type donors still limit polarization-induced hole doping, making p-type conductivity still a challenge due to background impurities and defects.

Non-avalanche single photon detection without carrier transit-time delay through quantum capacitive coupling.

Searching for innovative approaches to detect single photons remains at the center of science and technology for decades. This paper proposes a zero transit-time, non-avalanche quantum capacitive photodetector to register single photons. In this detector, the absorption of a single photon changes the wave function of a single electron trapped in a quantum dot (QD), leading to a charge density redistribution nearby. This redistribution translates into a voltage signal through capacitive coupling between the QD and the measurement probe. Using InAs QD/AlAs barrier as a model system, the simulation shows that the output signal reaches ~4 mV per absorbed photon, promising for high-sensitivity, ps single-photon detection.

Toward Single Atom Chains with Exfoliated Tellurium.

We demonstrate that the atom chain structure of Te allows it to be exfoliated as ultra-thin flakes and nanowires. Atomic force microscopy of exfoliated Te shows that thicknesses of 1-2 nm and widths below 100 nm can be exfoliated with this method. The Raman modes of exfoliated Te match those of bulk Te, with a slight shift (4 cm-1) due to a hardening of the A1 and E modes. Polarized Raman spectroscopy is used to determine the crystal orientation of exfoliated Te flakes. These experiments establish exfoliation as a route to achieve nanoscale trigonal Te while also demonstrating the potential for fabrication of single atom chains of Te.

Physicochemical characteristics of pristine and functionalized graphene.

Graphene-based nanomaterials have received significant attention in the last decade due to their interesting properties. Its electrical and thermal conductivity and strength make graphene well suited for a variety of applications, particularly for use as a composite material in plastics. Furthermore, much work is taking place to utilize graphene as a biomaterial for uses such as drug delivery and tissue regeneration scaffolds. Owing to the rapid progress of graphene and its potential in many marketplaces, the potential toxicity of these materials has garnered attention. Graphene, while simple in its purest form, can have many different chemical and physical properties. In this paper, we describe our toxicity evaluation of pristine graphene and a functionalized graphene sample that has been oxidized for enhanced hydrophilicity, which was synthesized from the pristine sample. The samples were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, infrared spectroscopy, thermogravimetric analysis, zeta-potential, atomic force microscopy and electron microscopy. We discuss the disagreement between the size of imaged samples analyzed by atomic force microscopy and by transmission electron microscopy. Furthermore, the samples each exhibit quite different surface chemistry and structure, which directly affects their interaction with aqueous environments and is important to consider when evaluating the toxicity of materials both in vitro and in vivo. Copyright © 2017 John Wiley & Sons, Ltd.

Infrared Reflectance Analysis of Epitaxial n-Type Doped GaN Layers Grown on Sapphire.

Infrared (IR) reflectance spectroscopy is applied to study Si-doped multilayer n+/n0/n+-GaN structure grown on GaN buffer with GaN-template/sapphire substrate. Analysis of the investigated structure by photo-etching, SEM, and SIMS methods showed the existence of the additional layer with the drastic difference in Si and O doping levels and located between the epitaxial GaN buffer and template. Simulation of the experimental reflectivity spectra was performed in a wide frequency range. It is shown that the modeling of IR reflectance spectrum using 2 × 2 transfer matrix method and including into analysis the additional layer make it possible to obtain the best fitting of the experimental spectrum, which follows in the evaluation of GaN layer thicknesses which are in good agreement with the SEM and SIMS data. Spectral dependence of plasmon-LO-phonon coupled modes for each GaN layer is obtained from the spectral dependence of dielectric of Si doping impurity, which is attributed to compensation effects by the acceptor states.

Adhesive force between graphene nanoscale flakes and living biological cells.

We report on a measurement technique that quantifies the adhesive force between multi-layers of graphene flakes and the cell wall of live Escherichia coli cells using atomic force microscopy (AFM) in-fluid Peak Force- Quantitative Nanomechanical Mapping mode. To measure the adhesive force, we made use of the negative charge of E. coli cells to allow them to stick to positively charged surfaces, such as glass or silicon, that were covered by poly-L-Lysine. With this approach, cells were held in place for AFM characterization. Both pristine graphene (PG) flakes and functionalized graphene (FG) flakes were put on the E. coli cells and measurements of lateral size, flake thickness, and adhesion were made. Using this approach, the measured values of the adhesive force between multi-layers of graphene flakes (total thickness of 50 nm) and E. coli was determined to be equal or greater than 431 ± 65pN for (PG) and 694 ± 98pN for the (FG). More interestingly, the adhesive force of a graphene flake (thickness 1.3 nm) with the cell is determined to be equal or greater than 38.2 ± 16.4pN for the (PG) and 34.8 ± 15.3pN for the (FG). These interaction values can play an important role in determining and understanding the possible toxicity of graphene flakes. Copyright © 2017 John Wiley & Sons, Ltd.