Mario Capizzi

The GaAs-like longitudinal-optical (LO) phonon frequency in hydrogenated GaAs_1−xN_x (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 GaAs_1−xN_x 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.

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 illumination—coupled to the ultra-sharp diffusion profile of H in dilute nitrides—allow 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.

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 m_e^∥ = (0.078 ± 0.002) m₀ (m₀ is the electron mass in vacuum) and perpendicular to ĉ is m_e^⊥ = (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 m_h^∥ = (0.81 ± 0.18) m₀ and m_h^⊥ = (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.

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 (E_g) decreases continuously with increasing annealing temperature, T_a, and reaches its minimum at T_a ∼ 273 °C. E_g 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 E_g value is developed. Ordering results in narrower Raman peaks without affecting the shape of the photoluminescence spectrum—except for the change in E_g—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 post-growth hydrogen irradiation at temperatures of 400 °C. Hydrogen incorporation increases by one order of magnitude the saturation magnetization (up to ~1.50 μB/Co) and increases by about a factor of two the carrier density and mobility. 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 of the n carrier density 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.

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, ΔT, increases exponentially with lattice temperature and depends inversely on the NW diameter. ΔT 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 ∼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 (∼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 electronic properties of In(AsN) before and after post-growth sample irradiation with increasing doses of atomic hydrogen have been investigated by photoluminescence. The electron density increases in In(AsN) but not in N-free InAs, until a Fermi stabilization energy is established. A hydrogen ^+/− transition level just below the conduction band minimum accounts for the dependence of donor formation on N, in agreement with a recent theoretical report highlighting the peculiarity of InAs among III–V compounds. Raman scattering measurements indicate the formation of N–H complexes that are stable under thermal annealing up to ~500 K. Finally, hydrogen does not passivate the electronic activity of N, thus leaving the band gap energy of In(AsN) unchanged, once more in stark contrast to what has been reported in other dilute nitride alloys.