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.

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.

beta-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 R-1 and R-2 PL lines at around 1.79eV originate from an internal transition between the first excited state (E-2) and the (4)A(2) ground state of Cr3+. The center is concluded to have monoclinic local symmetry and exhibits a large zero-field splitting (similar to 147 mu eV) 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 g(a) = 1.7, g(b) = 1.5, and g(c*) = 2.1. Our results advance our understanding of the electronic structure of Cr in beta-Ga2O3 and provide a spectroscopic signature of this common residual impurity. (C) 2021 Author(s).

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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.

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.

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.

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.

Gallium oxide (β-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 β-Ga2O3 bulk crystals and powders that were unknown so far. Furthermore, we show that both Co2+ and Cu2+ preferentially reside on the octahedral gallium lattice site.

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.

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.

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 (~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 (Vs-center) were identified.

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.

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 amp;lt; x amp;lt; 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 (amp;gt;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.

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.

Nanowire (NW) lasers operating in the near infrared spectral range are of significant technological importance for applications in telecommunications, sensing, and medical diagnostics. So far, lasing within this spectral range has been achieved using GaAs/AlGaAs, GaAs/GaAsP, and InGaAs/GaAs core/shell NWs. Another promising III-V material, not yet explored in its lasing capacity, is the dilute nitride GaNAs. In this work, we demonstrate, for the first time, optically pumped lasing from the GaNAs shell of a single GaAs/GaNAs core/shell NW. The characteristic "S"-shaped pump power dependence of the lasing intensity, with the concomitant line width narrowing, is observed, which yields a threshold gain, g(th), of 3300 cm(-1) and a spontaneous emission coupling factor beta, of 0.045. The dominant lasing peak is identified to arise from the HE21b, cavity mode, as determined from its pronounced emission polarization along the NW axis combined with theoretical calculations of lasing threshold for guided modes inside the nanowire. Even without intentional pas sivation of the NW surface, the lasing emission can be sustained up to 150 K. This is facilitated by the improved surface quality due to nitrogen incorporation, which partly suppresses the surface-related nonradiative recombination centers via nitridation. Our work therefore represents the first step toward development of room-temperature infrared NW lasers based on dilute nitrides with extended tunability in the lasing wavelength.

In this work, we carry out a comprehensive investigation of structural and optical effects in GaNAsP nanowires (NWs), which are novel materials promising for advanced photovoltaic applications. Despite a significant mismatch in electronegativity between N and As/P atoms, we show that incorporation of nitrogen does not degrade structural quality of the nanowires and the fabricated NW arrays have excellent compositional uniformity among individual wires. From temperature-dependent photoluminescence (PL) measurements, statistical fluctuations of the alloy composition are shown to lead to localization of photoexcited carriers at low temperatures but do not affect material properties at room temperature. According to time-resolved PL measurements, the room-temperature carrier lifetime increases in the GaNAsP NWs as compared with the GaAsP NWs, which indicates reduced nonradiative recombination. Moreover, in spite of the very low N content in the studied NWs (up to 0.16%), their bandgap energy can be tuned by more than 100 meV. This is accompanied by about 30% reduction in the temperature dependence of the bandgap energy. The presented results demonstrate that alloying of GaAsP with nitrogen provides an additional means of design optimization, beneficial for, e.g., NW-based intermediate band solar cells that are highly dependent on the optimum bandgap structure.

A series of solid nanocomposites containing CdS nanoparticles in polymeric matrix with varied conditions on the interface particle/polymer was fabricated and studied by photoluminescence (PL) and optically detected magnetic resonance (ODMR) methods. The results revealed interface-related features in both PL and ODMR spectra. The revealed paramagnetic centers are concluded to be involved in the processes of photo-excited carriers relaxation.

The possibility to engineer nanowire heterostructures with large bandgap variations is particularly interesting for technologically important broadband photodetector applications. Here we report on a combined study of design, fabrication, and optoelectronic properties of infrared photodetectors comprising four million n(+)in(+) InP nanowires periodically ordered in arrays. The nanowires were grown by metalorganic vapor phase epitaxy on InP substrates, with either a single or 20 InAsP quantum discs embedded in the i-segment. By Zn compensation of the residual n-dopants in the i-segment, the room-temperature dark current is strongly suppressed to a level of pA/NW at 1 V bias. The low dark current is manifested in the spectrally resolved photocurrent measurements, which reveal strong photocurrent contributions from the InAsP quantum discs at room temperature with a threshold wavelength of about 2.0 m and a bias-tunable responsivity reaching 7 A/W@1.38 m at 2 V bias. Two different processing schemes were implemented to study the effects of radial self-gating in the nanowires induced by the nanowire/SiOx/ITO wrap-gate geometry. Summarized, our results show that properly designed axial InP/InAsP nanowire heterostructures are promising candidates for broadband photodetectors.

We investigate the transfer of photoexcited charge carriers from GaP and GaNP nanowires to an electrolyte by bias-dependent photocurrent and electron paramagnetic resonance experiments using 5,5-dimethyl-1-pyrroline-N-oxide as a spin trap. The results of the latter show that hydroxyl radicals are created over the entire applied bias range from -1000mV to +1300mV by hole transfer. In contrast, the photocurrent changes from cathodic to anodic at the open circuit potential of the three-electrode setup with the nanowire sample acting as the working electrode. The experiments show that the photoelectrochemical response of GaNP nanowires is significantly stronger compared to that of the GaP nanowires. Published by AIP Publishing.

Photoluminescence and optically detected magnetic resonance (ODMR) spectroscopies are used to investigate the formation and role of defects in GaAs/GaNxAs1-x core/shell nanowires (NWs) grown by molecular beam epitaxy on Si substrates. Gallium vacancies, which act as non-radiative recombination (NRR) centers, are identified by ODMR. It is shown that the defects are formed in bulk regions, i.e., not on the surface, of the GaNAs shell and that their concentration increases with increasing nitrogen content. Temperature dependent photoluminescence experiments reveal, on the other hand, suppressed thermal quenching of the near-band-edge emission with increasing [N]. This leads to the conclusion that the dominant NRR processes in the studied NWs are governed by surface defects, whereas the role of gallium vacancies in the observed thermally activated NRR is minor. Published by AIP Publishing.

GaNP-based nanowires (NWs) represent a novel material system that has a great potential in a variety of optoelectronic and photonic applications. In this paper we review our recent results showing that advantages provided by alloying with nitrogen can be realized and even further enhanced in novel coaxial GaNP NWs grown on Si substrates. Based on combined mu-photoluminescence and optically detected magnetic resonance measurements, we identify the optimum structural design of these nanowires. We also demonstrate that these novel structures have potential as nanoscale light sources of linearly polarized light.

Recent developments in fabrication techniques and extensive investigations of the physical properties of III-V semiconductor nanowires (NWs), such as GaAs NWs, have demonstrated their potential for a multitude of advanced electronic and photonics applications. Alloying of GaAs with nitrogen can further enhance the performance and extend the device functionality via intentional defects and heterostructure engineering in GaNAs and GaAs/GaNAs coaxial NWs. In this work, it is shown that incorporation of nitrogen in GaAs NWs leads to formation of three-dimensional confining potentials caused by short-range fluctuations in the nitrogen composition, which are superimposed on long-range alloy disorder. The resulting localized states exhibit a quantum-dot like electronic structure, forming optically active states in the GaNAs shell. By directly correlating the structural and optical properties of individual NWs, it is also shown that formation of the localized states is efficient in pure zinc-blende wires and is further facilitated by structural polymorphism. The light emission from these localized states is found to be spectrally narrow (similar to 50-130 mu eV) and is highly polarized (up to 100%) with the preferable polarization direction orthogonal to the NW axis, suggesting a preferential orientation of the localization potential. These properties of self-assembled nano-emitters embedded in the GaNAs-based nanowire structures may be attractive for potential optoelectronic applications.

Electron paramagnetic resonance spectroscopy is used to investigate the thermal stability of the Aluminum-Zinc vacancy (Al-Zn-V-Zn) complex created in bulk single crystalline ZnO by room temperature electron irradiation with an energy of 1.2 MeV. Two different stages in the annealing process at 160 and 250 degrees C with apparent activation energies of E-A1 = 1.5 +/- 0.2 eV and E-A2 = 1.9 +/- 0.2 eV, respectively, are observed. The second stage leads to the complete annealing out of the (Al-Zn-V-Zn) complex and is accompanied by restoration of the concentration of the AlZn shallow donor centers to its initial value in as-grown (i.e., not irradiated) material. The obtained results prove that the (Al-Zn-V-Zn) complex is the dominant acceptor responsible for compensation of n-type-dopants in the studied Al-containing ZnO samples. (C) 2016 AIP Publishing LLC.

Unintentional incorporation of nitrogen in ZnO nanowires (NWs) grown by rapid thermal chemical vapor deposition is unambiguously proven by electron paramagnetic resonance spectroscopy. The nitrogen dopants are suggested to be provided from contaminations in the source gases. The majority of incorporated nitrogen atoms are concluded to reside at oxygen sites, i.e. in the atomic configuration of nitrogen substituting for oxygen (N_O). The N_O centers are suggested to be located in proximity to the NW surface, based on their reduced optical ionization energy as compared with that in a bulk material. This implies that the defect formation energy at the NW surface could be lower than its bulk value, consistent with previous theoretical predictions. The obtained results underline that nitrogen can be easily incorporated in ZnO nanostructures which may be of advantage for realizing p-type conducting ZnO via N doping. On the other hand, the awareness of this process can help to prevent such unintentional doping in structures with desired n-type conductivity.

One-dimensional ZnO nanowires (NWs) are a promising materials system for a variety of applications. Utilization of ZnO, however, requires a good understanding and control of material properties that are largely affected by intrinsic defects and contaminants. In this work we provide experimental evidence for unintentional incorporation of nitrogen in ZnO NWs grown by rapid thermal chemical vapor deposition, from electron paramagnetic resonance spectroscopy. The incorporated nitrogen atoms are concluded to mainly reside at oxygen sites (N_O). The N_O centers are suggested to be located in proximity to the NW surface, based on their reduced optical ionization energy as compared with that in bulk. This implies a lower defect formation energy at the NW surface as compared with its bulk value, consistent with theoretical predictions. The revealed facilitated incorporation of nitrogen in ZnO nanostructures may be advantageous for realizing p-type conducting ZnO via N doping. The awareness of this process can also help to prevent such unintentional doping in structures with desired n-type conductivity.

One-dimensional ZnO nanowires (NWs) are a promising materials system for a variety of applications. Utilization of ZnO, however, requires a good understanding and control of material properties that are largely affected by intrinsic defects and contaminants. In this work we provide experimental evidence for unintentional incorporation of nitrogen in ZnO NWs grown by rapid thermal chemical vapor deposition, from electron paramagnetic resonance spectroscopy. The incorporated nitrogen atoms are concluded to mainly reside at oxygen sites (N_O). The N_O centers are suggested to be located in proximity to the NW surface, based on their reduced optical ionization energy as compared with that in bulk. This implies a lower defect formation energy at the NW surface as compared with its bulk value, consistent with theoretical predictions. The revealed facilitated incorporation of nitrogen in ZnO nanostructures may be advantageous for realizing p-type conducting ZnO via N doping. The awareness of this process can also help to prevent such unintentional doping in structures with desired n-type conductivity.

Semiconductor nanowires (NWs) are attracting increasing interest as nanobuilding blocks for optoelectronics and photonics. A novel material system that is highly suitable for these applications are GaNP NWs. In this article, we show that individual GaP/GaNP core/shell nanowires (NWs) grown by molecular beam epitaxy on Si substrates can act as Fabry-Perot (FP) microcavities. This conclusion is based on results of microphotoluminescence (μ-PL) measurements performed on individual NWs, which reveal periodic undulations of the PL intensity that follow an expected pattern of FP cavity modes. The cavity is concluded to be formed along the NW axis with the end facets acting as reflecting mirrors. The formation of the FP modes is shown to be facilitated by an increasing index contrast with the surrounding media. Spectral dependence of the group refractive index is also determined for the studied NWs. The observation of the FP microcavity modes in the GaP/GaNP core/shell NWs can be considered as a first step toward achieving lasing in this quasidirect bandgap semiconductor in the NW geometry.

We report on identification and control of important nonradiative recombination centers in GaNP coaxial nanowires (NWs) grown on Si substrates in an effort to significantly increase light emitting efficiency of these novel nanostructures promising for a wide variety of optoelectronic and photonic applications. A point defect complex, labeled as DD1 and consisting of a P atom with a neighboring partner aligned along a crystallographic ⟨111⟩ axis, is identified by optically detected magnetic resonance as a dominant nonradiative recombination center that resides mainly on the surface of the NWs and partly at the heterointerfaces. The formation of DD1 is found to be promoted by the presence of nitrogen and can be suppressed by reducing the strain between the core and shell layers, as well as by protecting the optically active shell by an outer passivating shell. Growth modes employed during the NW growth are shown to play a role. On the basis of these results, we identify the GaP/GaN_yP_1–y/GaN_xP_1–x (x < y) core/shell/shell NW structure, where the GaN_yP_1–y inner shell with the highest nitrogen content serves as an active light-emitting layer, as the optimized and promising design for efficient light emitters based on GaNP NWs.

In this work we examined optical and defect properties of as-grown and Ni-coated ZnO nanowires (NWs) grown by rapid thermal chemical vapor deposition by means of optically detected magnetic resonance (ODMR). Several grown-in defects are revealed by monitoring visible photoluminescence (PL) emissions and are attributed to Zn vacancies, O vacancies, a shallow (but not effective mass) donor and exchange-coupled pairs of a Zn vacancy and a Zn interstitial. It is also found that the same ODMR signals are detected in the as-grown and Ni-coated NWs, indicating that metal coatings does not significantly affect formation of the aforementioned defects and that the observed defects are located in the bulk of the NWs.

Electron Paramagnetic Resonance was used to study N2-centers in ZnO, which show a 5-line spectrum described by the hyperfine interaction of two nitrogen nuclei (nuclear spin I  = 1, 99.6% abundance). The recharging of this center exhibits two steps, a weak onset at about 1.4 eV and a strongly increasing signal for photon energies above 1.9 eV. The latter energy coincides with the recharging energy of NO centers (substitutional nitrogen atoms on oxygen sites). The results indicate that the N2-centers are deep level defects and therefore not suitable to cause significant hole-conductivity at room temperature.

Photon upconversion materials are attractive for a wide range of applications from medicine, biology, to photonics. Among them, ZnO is of particular interest owing to its outstanding combination of materials and physical properties. Though energy upconversion has been demonstrated in ZnO, the exact physical mechanism is still unknown, preventing control of the processes. Here, defects formed in bulk and nanostructured ZnO synthesized using standard growth techniques play a key role in promoting efficient energy upconversion via two-step two-photon absorption (TS-TPA). From photoluminescence excitation of the anti-Stokes emissions, the threshold energy of the TS-TPA process is determined as being 2.10-2.14 eV in all studied ZnO materials irrespective of the employed growth techniques. This photo-electron paramagnetic resonance studies show that this threshold closely matches the ionization energy of the zinc vacancy (a common grown-in intrinsic defect in ZnO), thereby identifying the zinc vacancy as being the dominant defect responsible for the observed efficient energy upconversion. The upconversion is found to persist even at a low excitation density, making it attractive for photonic and photovoltaic applications.

The aluminum–zinc-vacancy (Al Zn −V Zn ) complex is identified as one of the dominant defects in Al-containing n -type ZnO after electron irradiation at room temperature with energies above 0.8 MeV. The complex is energetically favorable over the isolated V Zn , binding more than 90% of the stable V Zn ’s generated by the irradiation. It acts as a deep acceptor with the (0/− ) energy level located at approximately 1 eV above the valence band. Such a complex is concluded to be a defect of crucial and general importance that limits the n -type doping efficiency by complex formation with donors, thereby literally removing the donors, as well as by charge compensation.