The manipulation of light through its interactions with artificially structured media is a cornerstone of photonics. The rescaling of this concept to the X-ray realm-which will enable us to control X-ray light with the same precision routinely available in the visible/IR range-has so far been hindered by the inherent difficulty of realizing photonic structures with the sub-nanometric resolution dictated by X-ray wavelengths. A promising approach to this challenge is based on the so-called Berry-phase effect, the large beam translations undergone by X-ray photons propagating in a deformed crystal, due to the simultaneous presence of Berry curvatures in real and reciprocal space. In this work, the controlled crystal distortions required to rein in this effect are obtained by pairing the lattice expansion observed upon H irradiation of GaAsN with a spatially selective hydrogenation technique. The macroscopic beam translations measured here are striking manifestations of the Berry curvatures associated with the sub-nanometric lattice distortions induced by H incorporation. Through the comparison with a dedicated theoretical model, the individual translation branches observed in X-ray transmission can be traced back to specific deformation features present within the samples, establishing a predictive framework for the control of X-ray propagation in the fabricated structures.

The fabrication of integrated quantum dot (QD)-optical microcavity systems is a requisite step for the realization of a wide range of nanophotonic experiments (and applications) that exploit the ability of QDs to emit nonclassical light, e.g., single photons. Thanks to their ∼ 20-nm positioning accuracy and to their proven potential for single-photon operation, the QDs obtained by spatially selective hydrogen irradiation of dilute-nitride semiconductors — such as Ga(AsN) and Ga(PN)—are uniquely suited for integration with photonic nanodevices. In the present work, we demonstrate the ability to deterministically integrate single, site-controlled Ga(AsN) / Ga(AsN):H QDs within a photonic crystal (PhC) cavity. The properties of the fabricated QD-PhC cavity systems are then probed by photon correlation—providing clear evidence of single-photon emission—and time-resolved microphotoluminescence spectroscopy. Detailed information on the dynamics of our integrated nanodevices can be inferred by comparing these experiments to the solutions of a rate-equations system, developed by taking into account all the main processes leading to the capture, relaxation, and recombination of carriers in and out of the QD. This allows us to follow the evolution of the relevant recombination rates in our system for varying energy detuning, (cid:2) E , between the QD and the PhC cavity. When the QD exciton transition is nearly resonant with the cavity mode, a large ( > tenfold) enhancement of the spontaneous emission rate is observed, in substantial agreement with Jaynes-Cummings (JC) theory. For intermediate detunings ( (cid:2) E ∼ 1.5–3.5 meV), on the other hand, the observed enhancement is significantly larger than that predicted by JC theory, due to the important role played by acoustic phonons in mediating the QD-PhC cavity coupling in a solid-state environment. Apart from its fundamental interest, the observation of such phonon-mediated, broadband enhancement of light-matter interaction significantly relaxes the requirements for the realization of a large variety of cavity QED-based experiments and applications. These include many photonic devices for which the use of site-controlled Ga(AsN) / Ga(AsN):H QDs would be inherently advantageous, such as those based on the coupling between more than one QD and a single cavity mode (e.g., few-QD nanolasers and QD solids).

The GaAs-like longitudinal-optical (LO) phonon frequency in hydrogenated GaAs1−xNx (x = 0.01) layers—with different H doses and similar low-energy irradiation conditions—was investigated by micro-Raman measurements in different scattering geometries and compared with those of epitaxial GaAs and as-grown GaAs1−xNx reference samples. A relaxation of the GaAs selection rules was observed, to be explained mainly on the basis of the biaxial strain affecting the layers. The evolution of the LO phonon frequency with increasing hydrogen dose was found to heavily depend on light polarization, thus suggesting that a linear relation between strain and the frequency of the GaAs-like LO phonon mode should be applied with some caution. Moreover, photoreflectance measurements in fully passivated samples of identical N concentration show that the blueshift of the GaAs-like LO frequency, characteristic of the hydrogenated structures, is dose-dependent and strictly related to the strain induced by the specific type of the dominant N-H complexes. A comparison of photoreflectance results with the finite element method calculations confirms that this dependence on the H dose is due to the gradual replacement of the N-2H complexes responsible for the electronic passivation of N with N-3H complexes, which are well known to induce an additional and sizeable lattice expansion.

Highly doped semiconductors (HDSCs) are promising candidates for plasmonic applications in the mid‐infrared (MIR) spectral range. This work examines a recent addition to the HDSC family, the dilute nitride alloy In(AsN). Postgrowth hydrogenation of In(AsN) creates a highly conducting channel near the surface and a surface plasmon polariton detected by attenuated total reflection techniques. The suppression of plasmonic effects following a photoannealing of the semiconductor is attributed to the dissociation of the NH bond. This offers new routes for direct patterning of MIR plasmonic structures by laser writing.

In article number 1705450, Francesco Biccari and co-workers describe a novel and versatile approach for the post-growth fabrication of site-controlled, single-photon-emitting quantum dots. This approach, which deploys the hot spot of a near-field microscope to locally remove hydrogen from nanometer-sized regions of a standard GaAs/GaAsN:H/ GaAs quantum well, features state-of-the-art control over both the nanostructure position (<100 nm) and emission energy (≈20 meV).

Many of the most advanced applications of semiconductor quantum dots (QDs) in quantum information technology require a fine control of the QDs' position and confinement potential, which cannot be achieved with conventional growth techniques. Here, a novel and versatile approach for the fabrication of site‐controlled QDs is presented. Hydrogen incorporation in GaAsN results in the formation of N–2H and N–2H–H complexes, which neutralize all the effects of N on GaAs, including the N‐induced large reduction of the bandgap energy. Starting from a fully hydrogenated GaAs/GaAsN:H/GaAs quantum well, the NH bonds located within the light spot generated by a scanning near‐field optical microscope tip are broken, thus obtaining site‐controlled GaAsN QDs surrounded by a barrier of GaAsN:H (laterally) and GaAs (above and below). By adjusting the laser power density and exposure time, the optical properties of the QDs can be finely controlled and optimized, tuning the quantum confinement energy over more than 100 meV and resulting in the observation of single‐photon emission from both the exciton and biexciton recombinations. This novel fabrication technique reaches a position accuracy <100 nm and it can easily be applied to the realization of more complex nanostructures.

We review an innovative approach for the fabrication of site-controlled quantum emitters (i.e., single-photon emitting quantum dots) based on the spatially selective incorporation and/or removal of hydrogen in dilute nitride semiconductors (e.g., GaAsN). In such systems, the formation of stable N-H complexes removes the effects that nitrogen has on the alloy properties, thus enabling the in-plane engineering of the band bap energy of the system. Both a lithographic approach and/or a near-field optical illuminationcoupled to the ultra-sharp diffusion profile of H in dilute nitridesallow us to control the hydrogen implantation and/or removal on a nanometer scale. This, eventually, makes it possible to fabricate site-controlled quantum dots that are able to emit single photons on demand. The strategy for a deterministic spatial and spectral coupling of such quantum emitters with photonic crystal cavities is also presented.

One hour annealing at 300 °C changes the optical emission characteristics of InAs nanowires (NWs) from the wurtzite (WZ) phase into that of zincblende (ZB). These results are accounted for by the conversion of a small fraction of the NW WZ metastable structure into the stable ZB structure. Several paths toward the polytype transformation in the configuration space are also demonstrated using first-principles calculations. For lower annealing temperatures, emission which is likely related to WZ polytypes is observed at energies that agree with theoretical predictions. These results demonstrate severe constraints on thermal processes to which devices made from InAs WZ NWs can be exposed.

We report on a novel lithographic approach for the fabrication of integrated quantum dot (QD)-photonic crystal (PhC) nanocavity systems. We exploit unique hydrogen's ability to tailor the band gap energy of dilute nitride semiconductors to fabricate isolated site-controlled QDs via a spatially selective hydrogenation at the nanometer-scale. A deterministic integration of the realized site-controlled QDs with PhC nanocavities is provided by the inherent realignment precision (~20nm) of the electron beam lithography system used for the fabrication of both QDs and PhC cavities. A detailed description of the fabrication steps leading to the realization of integrated QD-PhC cavity systems is provided, together with the experimental evidence of a weak coupling effect between the single-photon emitter and the PhC cavity.

Heat management mechanisms play a pivotal role in driving the design of nanowire (NW)-based devices. In particular, the rate at which charge carriers cool down after an external excitation is crucial for the efficiency of solar cells, lasers, and high-speed transistors. Here, we investigate the thermalization properties of photogenerated carriers by continuous-wave (cw) photoluminescence (PL) in InP and GaAs NWs. A quantitative analysis of the PL spectra recorded up to 310 K shows that carriers can thermalize at a temperature much higher than that of the lattice. We find that the mismatch between carrier and lattice temperature, Delta T, increases exponentially with lattice temperature and depends inversely on the NW diameter. Delta T is instead independent of other NW characteristics, such as crystal structure (wurtzite vs zincblende), chemical composition (InP vs GaAs), shape (tapered vs columnar NWs), and growth method (vapor liquid solid vs selective-area growth). Remarkably, carrier temperatures as high as 500 K are reached at the lattice temperature of 310 K in NWs with similar to 70 nm diameter. While a population of nonequilibrium carriers, usually referred to as "hot carriers", is routinely generated by high-power laser pulses and detected by ultrafast spectroscopy, it is quite remarkable that it can be observed in cw PL measurements, when a steady-state population of carriers is established. Time-resolved PL measurements show that even in the thinnest NWs carriers have enough time (similar to 1 ns) after photoexcitation to interact with phonons and thus to release their excess energy. Nevertheless, the inability of carriers to reach a full thermal equilibrium with the lattice points to inhibited phonon emission primarily caused by the large surface-to-volume ratio of small diameter NWs.

The effect of the order-disorder transition on the band gap of kesterite Cu2ZnSnS4, an interesting material for solar cells, has been investigated by optical spectroscopy. The band gap energy (Eg) decreases continuously with increasing annealing temperature, Ta, and reaches its minimum at Ta ∼ 273 °C. Eg is about 200 meV higher in the most ordered state, than in the fully disordered state. Its value and the transition kinetic depend on the sample stoichiometry. A simplified model able to explain the order degree and stoichiometry effects on the Eg value is developed. Ordering results in narrower Raman peaks without affecting the shape of the photoluminescence spectrum—except for the change in Eg—or the characteristic energy of the exponential tail below the fundamental absorption edge. Although a prolonged annealing increases the order degree, the material properties are still influenced by residual disorder as well as by defects related to the off-stoichiometry composition.

Impressive changes in the transport and ferromagnetic properties of Co-doped ZnO thin films have been obtained by postgrowth hydrogen irradiation at temperatures of 400 °C. Hydrogen incorporation increases the saturation magnetization by one order of magnitude (up to ∼1.50 μB/Co) and increases the carrier density and mobility by about a factor of two. In addition to the magnetic characterization, the transport and structural properties of hydrogenated ZnO:Co have been investigated by Hall effect, local probe conductivity measurements, micro-Raman, and X-ray absorption spectroscopy. Particular care has been given to the detection of Co oxides and metal Co nanophases, whose influence on the increase in the transport and ferromagnetic properties can be excluded on the ground of the achieved results. The enhancement in ferromagnetism is directly related to the dose of H introduced in the samples. On the contrary, despite the shallow donor character of H atoms, the increase in carrier density n is not related to the H dose. These apparently contradictory effects of H are fully accounted for by a mechanism based on a theoretical model involving Co-VO (Co-O vacancy) pairs.

The effective mass of electrons and holes in semiconductors is pivotal in determining the dynamics of carriers and their confinement energy in nanostructured materials. Surprisingly, this quantity is still unknown in wurtzite (WZ) nanowires (NWs) made of III-V compounds (e.g., GaAs, InAs, GaP, InP), where the WZ phase has no bulk counterpart. Here, we investigate the magneto-optical properties of InP WZ NWs grown by selective-area epitaxy that provides perfectly ordered NWs featuring high-crystalline quality. The combined analysis of the energy of free exciton states and impurity levels under magnetic field (B up to 29 T) allows us to disentangle the dynamics of oppositely charged carriers from the Coulomb interaction and thus to determine the values of the electron and hole effective mass. By application of B⃗ along different crystallographic directions, we also assess the dependence of the transport properties with respect to the NW growth axis (namely, the WZ ĉ axis). The effective mass of electrons along ĉ is me∥ = (0.078 ± 0.002) m0 (m0 is the electron mass in vacuum) and perpendicular to ĉ is me⊥ = (0.093 ± 0.001) m0, resulting in a 20% mass anisotropy. Holes exhibit a much larger (∼320%) and opposite mass anisotropy with their effective mass along and perpendicular to ĉ equal to mh∥ = (0.81 ± 0.18) m0 and mh⊥ = (0.250 ± 0.016) m0, respectively. While no full consensus is found with current theoretical results on WZ InP, our findings show trends remarkably similar to the experimental data available in WZ bulk materials, such as InN, GaN, and ZnO.

InAs nanowires (NWs) have been grown on semi-insulating InAs (111)B substrates by metal-organic chemical vapor deposition catalyzed by 50, 100, and 150 nm-sized Au particles. The pure wurtzite (WZ) phase of these NWs has been attested by high-resolution transmission electron microscopy and selected area diffraction pattern measurements. Low temperature photoluminescence measurements have provided unambiguous and robust evidence of a well resolved, isolated peak at 0.477 eV, namely 59 meV higher than the band gap of ZB InAs. The WZ nature of this energy band has been demonstrated by high values of the polarization degree, measured in ensembles of NWs both as-grown and mechanically transferred onto Si and GaAs substrates, in agreement with the polarization selection rules for WZ crystals. The value of 0.477 eV found here for the bandgap energy of WZ InAs agrees well with theoretical calculations.

We show that the n-type conductivity of the narrow band gap In(AsN) alloy can be increased within a thin (∼100 nm) channel below the surface by the controlled incorporation of H-atoms. This channel has a large electron sheet density of ∼1018 m−2 and a high electron mobility (μ > 0.1 m2V−1s−1 at low and room temperature). For a fixed dose of impinging H-atoms, its width decreases with the increase in concentration of N-atoms that act as H-traps thus forming N-H donor complexes near the surface.

We report a substantial increase in the quality and photoluminescence (PL) emission efficiency of In(AsN) dilute nitride alloys grown on both p-type InAs and semi-insulting GaAs substrates, in response to rapid thermal annealing. At 4 K the PL emission efficiency increases by 25 times due to a reduction in non-radiative Shockley-Read-Hall recombination originating from elimination of point defects. For annealing temperatures up to 500 degrees C the activation energy for thermal quenching increases by a factor of three, with no change in the residual electron concentration and mobility. Temperature dependent PL, together with X-ray diffraction measurements, reveals an improvement in compositional uniformity. Our results are significant for photonic device applications and particularly for the development of cryogenic mid-infrared photodiodes, monolithic detectors and focal plane arrays. (C) 2014 Elsevier B.V. All rights reserved.

Substitution of constituent atoms and/or changes of crystal structure are routinely used to tailor the fundamental properties of a semiconductor. Here, it is shown that such a tailoring can also be realized thanks to a novel hydrogen effect. Four hydrogen atoms can screen the effect the crystal potential has on a constituent cation, thus generating a solitary cation: an effectively isolated impurity, so chemically different from the unscreened constituent cations that it strongly perturbs the electronic properties of the material by increasing its fundamental band‐gap energy. Such a hydrogen‐induced screening effect is removed by thermal treatments, thus permitting reversible modifications of both the “crystal chemistry” and material's properties. This phenomenon, observed in InN and other topical nitrides, should permit the development of a new class of materials as well as the fabrication of photonic devices and optical integrated circuits with distinct, tailor‐made regions emitting or absorbing light, all integrated onto a monolithic semiconductor structure.

Semiconductor nanowires (NWs) formed by non-nitride III-V compounds grow preferentially with wurtzite (WZ) lattice. This is contrary to bulk and two-dimensional layers of the same compounds, where only zincblende (ZB) is observed. The absorption spectrum of WZ materials differs largely from their ZB counterparts and shows three transitions, referred to as A, B, and C in order of increasing energy, involving the minimum of the conduction band and different critical points of the valence band. In this work, we determine the temperature dependence (T = 10-310 K) of the energy of transitions A, B, and C in ensembles of WZ InP NWs by photoluminescence (PL) and PL excitation (PLE) spectroscopy. For the whole temperature and energy ranges investigated, the PL and PLE spectra are quantitatively reproduced by a theoretical model taking into account contribution from both exciton and continuum states. WZ InP is found to behave very similarly to wide band gap III-nitrides and II-VI compounds, where the energy of A, B, and C displays the same temperature dependence. This finding unveils a general feature of the thermal properties of WZ materials that holds regardless of the bond polarity and energy gap of the crystal. Furthermore, no differences are observed in the temperature dependence of the fundamental band gap energy in WZ InP NWs and ZB InP (both NWs and bulk). This result points to a negligible role played by the WZ/ZB differences in determining the deformation potentials and the extent of the electron-phonon interaction that is a direct consequence of the similar nearest neighbor arrangement in the two lattices.