Transition metal (TM) ions incorporated into a host from a wide bandgap semiconductor are recognized as a promising system for quantum technologies with enormous potential. In this work, we report on a TM color center in β-Ga2O3 with physical properties attractive for quantum information applications. The center is found to emit at 1.316 μm and exhibits weak coupling to phonons, with optically addressable higher-lying excited states, beneficial for single-photon emission within the telecom range (O-band). Using magneto-photoluminescence (PL) complemented by time-resolved PL measurements, we identify the monitored emission to be internal 1E→3A2 spin-forbidden transitions of a 3d8 TM ion with a spin-triplet ground state—a possible candidate for a spin qubit. We tentatively attribute this color center to a complex involving a sixfold coordinated Cu3+ ion.

GaAs-based nanowires (NWs) are promising materials for nonlinear photonics, owing to their noncentrosymmetric crystal structure and strong nonlinear response, which could be deliberately tailored in nanostructures via e.g. lattice engineering. In this work we show that changes of the NW lattice structure from zinc blende (ZB) to wurtzite (WZ) greatly (by about 7 times) enhances an efficiency of second-harmonic generation (SHG) in subwavelength wurtzite GaAs NWs. This enhancement is attributed to an arial built-in electric field induced by spontaneous polarization in the WZ lattice, via electric field-induced second-order nonlinear susceptibility. Our findings [1], therefore, provide an effective strategy for enhancing and manipulating the nonlinear optical response in subwavelength NWs.

β-Ga2O3 is a wide bandgap semiconductor that is attractive for various applications, including power electronics, transparent conductive electrodes, etc. Electrical and optical properties of Ga2O3 are affected by the presence of dopants/contaminants and/or intrinsic defects. Here, we investigate the electrical and optical properties of transition metals like Co and Cr since they are often unintentionally present during the growth or used as intentional dopants. This is done by using magnetic resonance spectroscopy and magneto-optical characterization techniques. We determine spin- Hamiltonian parameters of the Cr3+ ground-state and first excited-state as well as the spin-Hamiltonian parameters of Co2+.

Nanoparticles (NPs) elicit sterile inflammation, but the underlying signaling pathways are poorly understood. Here, we report that human monocytes are particularly vulnerable to amorphous silica NPs, as evidenced by single-cell-based analysis of peripheral blood mononuclear cells using cytometry by time-of-flight (CyToF), while silane modification of the NPs mitigated their toxicity. Using human THP-1 cells as a model, we observed cellular internalization of silica NPs by nanoscale secondary ion mass spectrometry (nanoSIMS) and this was confirmed by transmission electron microscopy. Lipid droplet accumulation was also noted in the exposed cells. Furthermore, time-of-flight secondary ion mass spectrometry (ToF-SIMS) revealed specific changes in plasma membrane lipids, including phosphatidylcholine (PC) in silica NP-exposed cells, and subsequent studies suggested that lysophosphatidylcholine (LPC) acts as a cell autonomous signal for inflammasome activation in the absence of priming with a microbial ligand. Moreover, we found that silica NPs elicited NLRP3 inflammasome activation in monocytes, whereas cell death transpired through a non-apoptotic, lipid peroxidation-dependent mechanism. Together, these data further our understanding of the mechanism of sterile inflammation.

β-Ga2O3 is a wide bandgap semiconductor that is attractive for various applications, including power electronics and transparent conductive electrodes. Its properties can be strongly affected by transition metal impurities commonly present during the growth such as Cr. In this Letter, we determine the electronic structure of Cr3+ by performing a correlative study of magneto-photoluminescence (magneto-PL) and electron paramagnetic resonance. We unambiguously prove that the so-called R1 and R2 PL lines at around 1.79 eV originate from an internal transition between the first excited state (2E) and the 4A2 ground state of Cr3+. The center is concluded to have monoclinic local symmetry and exhibits a large zero-field splitting (∼147 μeV) of the ground state, which can be directly measured from the fine structure of the R1 transition. Furthermore, g-values of the first excited state are accurately determined as ga = 1.7, gb = 1.5, and gc* = 2.1. Our results advance our understanding of the electronic structure of Cr in β-Ga2O3 and provide a spectroscopic signature of this common residual impurity.

GaAs‐based semiconductors are highly attractive for diverse nonlinear photonic applications, owing to their non‐centrosymmetric crystal structure and huge nonlinear optical coefficients. Nanostructured semiconductors, for example, nanowires (NWs), offer rich possibilities to tailor nonlinear optical properties and further enhance photonic device performance. In this study, it is demonstrated highly efficient second‐harmonic generation in subwavelength wurtzite (WZ) GaAs NWs, reaching 2.5 × 10 −5 W −1 , which is about seven times higher than their zincblende counterpart. This enhancement is shown to be predominantly caused by an axial built‐in electric field induced by spontaneous polarization in the WZ lattice via electric field‐induced second‐order nonlinear susceptibility and can be controlled optically and potentially electrically. The findings, therefore, provide an effective strategy for enhancing and manipulating the nonlinear optical response in subwavelength NWs by utilizing lattice engineering.

Core/shell nanowire (NW) heterostructures based on III-V semiconductors and related alloys are attractive for optoelectronic and photonic applications owing to the ability to modify their electronic structure via bandgap and strain engineering. Post-growth thermal annealing of such NWs is often involved during device fabrication and can also be used to improve their optical and transport properties. However, effects of such annealing on alloy disorder and strain in core/shell NWs are not fully understood. In this work we investigate these effects in novel core/shell/shell GaAs/GaNAs/GaAs NWs grown by molecular beam epitaxy on (111) Si substrates. By employing polarization-resolved photoluminescence measurements, we show that annealing (i) improves overall alloy uniformity due to suppressed long-range fluctuations in the N composition; (ii) reduces local strain within N clusters acting as quantum dot emitters; and (iii) leads to partial relaxation of the global strain caused by the lattice mismatch between GaNAs and GaAs. Our results, therefore, underline applicability of such treatment for improving optical quality of NWs from highly-mismatched alloys. They also call for caution when using ex-situ annealing in strain-engineered NW heterostructures.

Nanowires (NWs) based on ternary GaAsP and quaternary GaNAsP alloys are considered as very promising materials for optoelectronic applications, including in multi-junction and intermediate band solar cells. The efficiency of such devices is expected to be largely controlled by grown-in defects. In this work we use the optically detected magnetic resonance (ODMR) technique combined with photoluminescence measurements to investigate the origin of point defects in Ga(N)AsP NWs grown by molecular beam epitaxy on Si substrates. We identify gallium vacancies, which act as non-radiative recombination centers, as common defects in ternary and quaternary Ga(N)AsP NWs. Furthermore, we show that the presence of N is not strictly necessary for, but promotes, the formation of gallium vacancies in these NWs.

Oxaliplatin typically causes acute neuropathic problems, which may, in a dose-dependent manner, develop into a chronic form of chemotherapy-induced peripheral neuropathy (CIPN), which is associated with retention of Pt2+ in the dorsal root ganglion. A clinical study by Coriat and co-workers suggests that co-treatment with mangafodipir [Manganese(II) DiPyridoxyl DiPhosphate; MnDPDP] cures ongoing CIPN. These authors anticipated that it is the manganese superoxide dismutase mimetic activity of MnDPDP that explains its curative activity. However, this is questionable from a pharmacokinetic perspective. Another, but until recently undisclosed possibility is that Pt2+ outcompetes Mn2+/Ca2+/Zn2+ for binding to DPDP or its dephosphorylated metabolite PLED (diPyridoxyL EthylDiamine) and transforms toxic Pt2+ into a non-toxic complex, which can be readily excreted from the body. We have used electron paramagnetic resonance guided competition experiments between MnDPDP (10logKML ≈ 15) and K2PtCl4, and between MnDPDP and ZnCl2 (10logKML ≈ 19), respectively, in order to obtain an estimate the 10logKML of PtDPDP. Optical absorption spectroscopy revealed a unique absorption line at 255 nm for PtDPDP. The experimental data suggest that PtDPDP has a higher formation constant than that of ZnDPDP, i.e., higher than 19. The present results suggest that DPDP/PLED has a high enough affinity for Pt2+ acting as an efficacious drug in chronic Pt2+-associated CIPN.

Nanostructured ZnO, such as ZnO nanowires (NWs), is a promising material system for a wide range of electronic applications ranging from light emission to water splitting. Utilization of ZnO requires development of effective and controllable p-type doping. Nitrogen is considered among key p-type dopants though the exact origin of N-induced acceptors is not fully understood, especially in the case of nanostructured ZnO. In this work we employ electron paramagnetic resonance (EPR) spectroscopy to characterize N-related acceptors in ZnO NWs. N doping was achieved using ion implantation commonly employed for these purposes. We show that the Fermi level position is lowered in the N implanted NWs, indicating the formation of compensating acceptors. The formed acceptor is unambiguously proven to involve an N atom based on a resolved hyperfine interaction with a 14N nucleus with a nuclear spin I = 1. The revealed center is shown to act as a deep acceptor with an energy level located at about 1.1 eV above the top of the valence band. This work represents the first unambiguous identification of acceptors deliberately introduced in ZnO nanostructures. It also shows that the configuration and electronic structure of the N-related acceptors in nanostructures differ from those in ZnO bulk and thin-films. The present findings are of importance for understanding the electronic properties of nanostructured ZnO required for its future electronic applications.

Two nanocomposites containing CdS nanoparticles in polymeric matrices were studied using the photoluminescence (PL) and optically detected magnetic resonance (ODMR) methods. Due to equal sizes of NPs in the composites (similar to 5 nm) but different matrices - the oxygen-containing polymer PVA (polyvinyl alcohol) and oxygen-free polymer PEI (polyethyleneimine) - differences of nanocomposites properties are predominantly caused by different interfacial conditions. ODMR spectra have revealed five types of centers related to the PL emission - four centers involved in radiative recombination and one center related to non-radiative recombination processes. The oxygen-related interfacial center in CdS/PVA (LK1-center) and sulfur vacancy center in CdS/PEI (V-s-center) were identified.

Gallium oxide (b-Ga2O3) is a wide-bandgap compound semiconductor with a bandgap of ~ 4.9 eV that is currently considered promising for a wide range of applications ranging from transparent conducting electrodes to UV optoelectronic devices and power electronics. However, all of these applications require a reliable and precise control of electrical and optical properties of the material, which can be largely affected by impurities, such as transition metals commonly present during the growth. In this work we employ electron paramagnetic resonance (EPR) spectroscopy to obtain EPR signatures of the 3d-transition metals Co2+ and Cu2+ in b-Ga2O3 bulk crystals and powders that were unknown so far. Furthermore, we show that Co2+ and Cu2+ both preferentially reside on the octahedral gallium lattice site.

We report on the first successful growth of wurtzite (WZ) GaBiAs nanowires (NWs) and reveal the effects of Bi incorporation on the electronic band structure by using polarization-resolved optical spectroscopies performed on individual NWs. Experimental evidence of a decrease in the band-gap energy and an upward shift of the topmost three valence subbands upon the incorporation of Bi atoms is provided, whereas the symmetry and ordering of the valence band states remain unchanged, that is, Γ9, Γ7, and Γ7 within the current range of Bi compositions. The extraordinary valence band structure of WZ GaBiAs NWs is explained by anisotropic hybridization and anticrossing between p-like Bi states and the extended valence band states of host WZ GaAs. Moreover, the incorporation of Bi into GaAs is found to significantly reduce the temperature sensitivity of the band-gap energy in WZ GaBiAs NWs. Our work therefore demonstrates that utilizing dilute bismide alloys provides new avenues for band-gap engineering and thus photonic engineering with NWs.

We report on optimization of growth conditions of GaAs/GaNAs/GaAs core/shell/shell nanowire (NW) structures emitting at ∼1 μm, aiming to increase their light emitting efficiency. A slight change in growth temperature is found to critically affect optical quality of the active GaNAs shell and is shown to result from suppressed formation of non-radiative recombination (NRR) centers under the optimum growth temperature. By employing the optically detected magnetic resonance spectroscopy, we identify gallium vacancies and gallium interstitials as being among the dominant NRR defects. The radiative efficiency of the NWs can be further improved by post-growth annealing at 680 °C, which removes the gallium interstitials.

One-dimensional ZnO nanowires are a promising material system for a wide range of optoelectronic and photonic applications. Utilization of ZnO, however, requires high-quality ZnO with reliable n-type and p-type conductivity, with the latter remaining elusive, so far. In this work we report on effects of N doping via ion implantation on defect formation in ZnO nanowires studied by optically detected paramagnetic resonance (ODMR) spectroscopy complemented by photoluminescence spectroscopy. After N implantation, zinc interstitial shallow donors, which are formed as a result of ion implantation, are observed in addition to effective mass type shallow donors. Additionally, ODMR signals related to oxygen vacancies can be observed. Implantation also causes formation of a new nitrogen related defect center, which acts as an acceptor. The present findings are of importance for understanding impacts of different defects and impurities on electronic properties of nanostructured ZnO and achieving p-type conductivity via nitrogen doping.

Cathodoluminescence (CL) and micro-photoluminescence spectroscopies are employed to investigate effects of structural defects on carrier recombination in GaNAsP nanowires (NWs) grown by molecular beam epitaxy on Si substrates. In the NWs with a low N content of 0.08%, these defects are found to promote non-radiative (NR) recombination, which causes spatial variation of the CL peak position and its intensity. Unexpectedly, these detrimental effects can be suppressed even by a small increase in the nitrogen composition from 0.08% to 0.12%. This is attributed to more efficient trapping of excited carriers/excitons to the localized states promoted by N-induced localization and also the presence of other NR channels. At room temperature, the structural defects no longer dominate in carrier recombination even in the NWs with the lower nitrogen content, likely due to increasing importance of other recombination channels. Our work underlines the need in eliminating important thermally activated NR defects, other than the structural defects, for future optoelectronic applications of these NWs.

Pretreatment of anaerobic digester samples by hydrochloric acid (HCl) resulted in removal of Fe-based mineral and coordination compounds, attenuating their interferences with solution-state nuclear magnetic resonance (NMR) spectroscopic characterization of the solid phase organic matter. Substrate (influent) and digestate (effluent) samples from two full-scale anaerobic digesters, designated CD (co-digester) and SSD (sewage sludge digester), were investigated. Pretreatment of CD samples with 0.2-2.0 mol l(-1) HCl and pretreatment of SSD samples with 1.0-3.0 mol l(-1) HCl removed 96-100% and 76-80% of total Fe, respectively. Pretreatment declined overall paramagnetic characteristics of digestate samples, manifested by 50% (CD) and 70% (SSD) decrease in electron paramagnetic resonance signal intensities. As a result, meaningful solution-state H-1,C-13 heteronuclear single quantum coherence and H-1 NMR spectra of DMSO-d(6) soluble organic matter could be acquired. Sample pretreatment with the lowest concentration of HCl resulted in alteration of C:N ratios in solid phase, likely due to removal of labile organic and inorganic C- and N-containing compounds, while elevating the HCl concentration did not further change the C:N ratios. Furthermore, sample pretreatment increased the solubility of carbohydrates and proteins in DMSO-d(6), enabling the detection of NMR resonances from certain structural units of carbohydrates (e.g. anomeric O2CH) and proteins (e.g. CH alpha in amino acids). Both attenuation of the paramagnetic matrix as well as art enhanced solubility of carbohydrate and protein fractions of the samples in DMSO-d(6) solvent contributed to an improved molecular characterization of anaerobic digester samples by solution-state NMR analysis. (C) 2018 Elsevier Ltd. All rights reserved.

Plasmonic response of free charges confined in nanostructures of plasmonic materials is a powerful means for manipulating the light-material interaction at the nanoscale and hence has influence on various relevant technologies. In particular, plasmonic materials responsive in the mid-infrared range are technologically important as the mid-infrared is home to the vibrational resonance of molecules and also thermal radiation of hot objects. However, the development of the field is practically challenged with the lack of low-loss materials supporting high quality plasmons in this range of the spectrum. Here, we demonstrate that degenerately doped InN nanocrystals (NCs) support tunable and low-loss plasmon resonance spanning the entire midwave infrared range. Modulating free-carrier concentration is achieved by engineering nitrogen-vacancy defects (InN1-x, 0.017 < x < 0.085) in highly degenerate NCs using a nonequilibrium gas-phase growth process. Despite the significant reduction in the carrier mobility relative to intrinsic InN, the mobility in degenerate InN NCs (>60 cm(2)/(V s)) remains considerably higher than the carrier mobility reported for other materials NCs such as doped metal oxides, chalcogenides, and noble metals. These findings demonstrate feasibility of controlled tuning of infrared plasmon resonances in a low-loss material of III-V compounds and open a gateway to further studies of these materials nanostructures for infrared plasmonic applications.

Photoluminescence and magneto-optical measurements are performed on a line peaking at 3.354 eV (labeled as NBX) in electron-irradiated ZnO. Even though the energy position of the NBX line is close to that for bound excitons in ZnO, it has distinctively different magneto-optical properties. Photoelectron paramagnetic resonance measurements reveal a connection and a charge-transfer process involving NBX and Fe and Al centers. The experimental results are explained within a model which assumes that the NBX is a neutral donor bound exciton at a defect center located near a Fe impurity and an Auger-type charge-transfer process occurs between NBX and Fe3+. While the NBX dissociates, its hole is captured by an excited state of Fe3+ and the released energy is transferred to the NBX electron, which is excited to the conduction band and subsequently trapped by a substitutional Al-zn shallow donor.