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Cathodoluminescence mapping is used as a contactless method to probe the electron concentration gradient of Te-doped GaAs nanowires. The room temperature and low temperature (10 K) cathodoluminescence analysis method previously developed for GaAs:Si is first validated on five GaAs:Te thin film samples, before extending it to the two GaAs:Te NW samples. We evidence an electron concentration gradient ranging from below 1 × 1018 cm−3 to 3.3 ×1018 cm−3 along the axis of a GaAs:Te nanowire grown at 640 °C, and a homogeneous electron concentration of around 6–8 × 1017 cm−3 along the axis of a GaAs:Te nanowire grown at 620 °C. The differences in the electron concentration levels and gradients between the two nanowires is attributed to different Te incorporation efficiencies by vapor–solid and vapor–liquid–solid processes.

We have investigated the effect of the growth techniques on the structural, the electrically and optically active defects in Indium doped TiO2 thin films grown by pulsed laser deposition (PLD) and sputtering techniques. X-ray diffraction (XRD) and Raman spectroscopy patterns revealed both rutile and anatase phases for the sputtering samples. On the other hand, only the anatase phase was observed for the PLD samples. The photoluminescence (PL) spectra have unveiled several peaks which were explained by defect related optical transitions. Particularly, the PL bands are fully consistent with anatase/rutile TiO2 phases and the formation of In2O3 during the preparation of our samples. It was also observed that at −4 V reverse bias, the PLD samples have lower leakage currents (∼1.4 × 10−7 A) as compared to the sputtering samples (∼5.9 × 10−7 A). In addition, the PLD samples exhibited lower ideality factors and higher barrier heights as compared to those grown by sputtering. Finally, the Deep Level Transient Spectroscopy (DLTS) measurements have shown only one defect in the PLD samples whereas five defects have been detected in the sputtering samples. Therefore, our results provide strong evidence that the PLD technique is better suited for the growth of In-doped TiO2 thin films.

Chiral optical response is an inherent property of molecules and nanostructures, which cannot be superimposed on their mirror images. In specific cases, optical chirality can be observed also for symmetric structures. This so-called extrinsic chirality requires that the mirror symmetry is broken by the geometry of the structure together with the incident or emission angle of light. From the fabrication point of view, the benefit of extrinsic chirality is that there is no need to induce structural chirality at nanoscale. This paper reports demonstration extrinsic chirality of photoluminescence emission from asymmetrically Au-coated GaAs-AlGaAs-GaAs core-shell nanowires fabricated on silicon by a completely lithography-free self-assembled method. In particular, the extrinsic chirality of PL emission is shown to originate from a strong symmetry breaking of fundamental HE

Dopant atoms can be incorporated into nanowires either via the vapor-liquid-solid mechanism through the catalyst droplet or by the vapor-solid growth on the sidewalls. Si is a typical n-type dopant for GaAs, but in nanowires it often suffers from a strongly amphoteric nature in the vapor-liquid-solid process. This issue can be avoided by using Te, which is a promising but less common alternative for n-type doping of GaAs nanowires. Here, we present a detailed investigation of Te-doped self-catalyzed GaAs nanowires. We use several complementary experimental techniques, such as atom probe tomography, off-axis electron holography, micro-Raman spectroscopy, and single-nanowire transport characterization, to assess the Te concentration, the free-electron concentration, and the built-in potential in Te-doped GaAs nanowires. By combing the experimental results with a theoretical model, we show that Te atoms are mainly incorporated by the vapor-liquid-solid process through the Ga droplet, which leads to both axial and radial dopant gradients due to Te diffusion inside the nanowires and competition between axial elongation and radial growth of nanowires. Furthermore, by comparing the free-electron concentration from Raman spectroscopy and the Te-atom concentrations from atom probe tomography, we show that the activation of Te donor atoms is 100% at a doping level of 4×1018cm-3, which is a significant result in terms of future device applications. acceptedVersion

The light interacting on asymmetric nanostructures can give rise to the phenomenon called extrinsic chirality [1–3], even if the nanostructures are not chiral by themselves. In this cases, light can be manipulated in order to obtain interesting behaviour such as anomalous refraction [4] or circular dichroism [5].

Asymmetric nanostructures can mimic a chiral response when circular polarized light interacts with the structures under particular angle of incidence [1]. This phenomenon is called ‘extrinsic chirality’ and usually is present under linear optical investigation with low visibility. Due to the fact that optical second harmonic generation is possible only in samples with some degree of asymmetry, this can be used in order to investigate the extrinsic chirality with a background free technique, thus inducing a high visibility of the artificial circular dichroism [2,3]. Here we present the second harmonic generation (SHG) measurements obtained on samples composed by GaAs nanowires grown on silicon. The wires present resonant leaky modes around 800nm and at 400nm due to the high refractive index contrast ratio between wires and air, even if these wavelengths lie on the absorption band of GaAs [4]. The measurements performed on this sample present good SHG signal due to the second order nonlinear term of GaAs, but did not present any circular dichroism (SHG-CD). By coating the sample with a 20nm thin layer of gold deposited asymmetrically, by evaporating the metal only from one side of the nanowires, the symmetry of the structure is broken, thus induced high SHG-CD. The SHG-CD is measured by shining the sample with circular polarized pump light at the fundamental wavelength of 800nm and by revealing the second harmonic signal at 400nm in s or p polarization, as a function of sample rotation. Four samples were measured with GaAs wires of about 5 micron in length with different diameters ranging from 140nm to 200nm. In this case it is possible to explore different resonance conditions and different SHG-CD is revealed. For each sample, the measured were carried out before and after the asymmetric gold layer deposition, thus allowing direct comparison of the results. References [1] A. Belardini, M. C. Larciprete, M. Centini, E. Fazio, C. Sibilia, D. Chiappe, C. Martella, A. Toma, M. Giordano, and F. Buatier de Mongeot, Phys. Rev. Lett. 107, 257401 (2011). [2] A. Belardini, M. Centini, G. Leahu, D. C. Hooper, R. Li Voti, E. Fazio, J. W. Haus, A. Sarangan, V. K. Valev, C. Sibilia, Sci. Rep. 2016, 6, 31796. [3] G. Leahu, E. Petronijevic, A. Belardini et al., Adv. Optical Mater. 2017, 1601063 (2017). [4] G. Leahu, E. Petronijevic, A. Belardini, M. Centini, R. Li Voti, T. Hakkarainen, E. Koivusalo, M. Guina, C. Sibilia. Sci. Rep. 7, 2833 (2017).

Effective and controllable doping is instrumental for enabling the use of III-V semiconductor nanowires (NWs) in practical electronics and optoelectronics applications. To this end, dopants are incorporated during self-catalyzed growth via vapor-liquid-solid mechanism through the catalyst droplet or by vapor-solid mechanism of the sidewall growth. The interplay of these mechanisms together with the competition between axial elongation and radial growth of NWs can result in dopant concentration gradients along the NW axis. Here, we report an investigation of Be-doped p-type GaAs NWs grown by the self-catalyzed method on lithography-free Si/SiOx templates. The influence of dopant incorporation on the structural properties of the NWs is analyzed by scanning and transmission electron microscopy. By combining spatially resolved Raman spectroscopy and transport characterization, we are able to estimate the carrier concentration, mobility and resistivity on single-NW level. We show that Be dopants are incorporated predominantly by vapor-solid mechanism for low Be flux, while the relative contribution of vapor-liquid-solid incorporation is increased for higher Be flux, resulting in axial dopant gradients that depend on the nominal doping level. acceptedVersion

We have investigated optical and electrical properties of Te and Be doped GaAs nanowires (NW) grown by self-catalyzed molecular beam epitaxy. The NWs were grown on p-Si(111) substrates using a novel technique based on lithography-free Si/SiOx patterns fabricated by droplet epitaxy and spontaneous oxidation, which allows synthesis of highly uniform NWs with controllable size and density. The incorporation of Be- and Te-dopants in GaAs NWs was investigated by using transport, photoluminescence (PL) and Raman spectroscopy techniques.

In this work we report on the resonant absorption properties of GaAs-based nanowires, and on the chiral response when such nanowires are asymmetrically covered by gold. We use photo-acoustic spectroscopy which is a scattering-free, stable and highly sensitive technique that directly measures the absorption of the nanowire ensembles. Highly uniform samples were fabricated by lithography-free process of selfcatalyzed growth on Si substrates. We report on the experimental resonant absorption in the range (300÷1100) nm, which is in great agreement with simulations. We then measure the circular dichroism at 532nm, and discuss on the formation of near chiral fields for enhanced enantioselectivity applications.

We show that photo-acoustic spectroscopy allows determination of the nanowire absorbance properties including resonant peak positions and peak broadening due to collective ensemble properties. Furthermore, we demonstrate chiral optical response in asymmetrically Aucoated nanowires.

Semiconductor nanostructures hybridized with metals have been known to offer new opportunities in nonlinear optics, plasmonics, lasing, biosensors; among them GaAs-based nanowires (NWs) hybridized with gold can offer new functionalities, as chiral sensing and light manipulation, as well as circular polarization sources. This study investigates GaAs–AlGaAs–GaAs NWs fabricated by self-catalyzed growth on Si substrates, and partially covered with gold, thus inducing the symmetry breaking and a potential chiral response. Three different samples are investigated, each of them with a different morphology, as the length and the overall diameter ranging from 4.6 to 5.19 µm and from 138 up to 165 nm, respectively. The samples are first characterized by measuring the absorption spectra by using a scattering-free photoacoustic (PA) technique. Then, the circular dichroism (CD) is investigated by measuring PA absorption for circularly polarized light under different incident angles at 532 and 980 nm. An efficient CD is found for proper configurations, and results are in good agreement with extrinsic chiral theory predictions and numerical simulations. It is therefore proven that these samples exhibit chiral behavior, and can be further optimized. Moreover, PA technique can be used as an extremely sensitive and efficient technique to characterize their “extrinsic” chirality. acceptedVersion

Amostras nanoestruturadas do sistema SrTi1-xMnxO3 (STM) com x = 0%, 0.5%, 1%, 2.5%, 5% e 10% na forma de pó foram sintetizadas através do método dos precursores poliméricos. As propriedades térmicas, estruturais e ópticas das amostras STM calcinadas em diferentes temperaturas foram analisadas a temperatura ambiente através de técnicas de análise térmica, difração de raios-x, espectroscopia de absorção de raios-x e fotoluminescência. Os resultados obtidos através das técnicas de analise térmica mostraram que o íon manganês causa um efeito retardante, aumentando a temperatura onde ocorre o início da cristalização. Os resultados de DRX mostraram que no limite de solubilidade estudado, o íon manganês foi incorporado em solução sólida no sítio B na rede do SrTiO3 (ST), assumindo estados de oxidação entre +3,4 e +3,7, indicando que ocorre a criação de defeitos para compensação de cargas, mantendo a neutralidade elétrica do material. A análise dos espectros de fotoluminescência das amostras STM amorfas mostrou que o aumento da quantidade de manganês até 1% leva a um aumento da intensidade fotoluminescência em relação a amostra SrTiO3. Entretanto, a adição de manganês acima desta quantidade leva a uma diminuição pronunciada da intensidade fotoluminescente. Nas amostras amorfas não foi observada uma variação significativa da ordem local ao redor dos átomos de titânio bem como no estado de oxidação dos átomos de manganês à medida que a quantidade de manganês aumenta. Desta forma, a variação da intensidade fotoluminescente não pôde ser atribuída a estes fatores. O aumento da temperatura de calcinação leva a uma diminuição significativa da intensidade fotoluminescente. Uma análise dos espectros XANES medidos na borda K do titânio destas amostras mostrou que ocorre uma maior ordenação dos átomos de Ti nos octaedros de oxigênio [TiO6] a medida que a temperatura de calcinação aumenta, ou seja, à medida que aumenta o grau de cristalinidade das amostras. Nanostructured SrTi1-xMnxO3 (STM) powder samples with x = 0%, 0.5%, 1%, 2.5%, 5% and 10% were synthesized by the polymeric precursors method. The thermal, structural and optical properties of STM samples heat-treated at different temperatures were analyzed by thermal analysis, X-ray diffraction, X-ray absorption spectroscopy and photoluminescence techniques. The thermal analysis results have shown that manganese ion causes a retarding effect, increasing the onset of the crystallization temperature. The XRD results showed that manganese ion is incorporated in a solid solution in the B site of the SrTiO3 (ST) network for the range of solubility studied, with oxidation states between +3.4 and +3.7, indicating the creation of charge compensation defects, keeping the materials electrical neutrality. The analysis of the photoluminescence (PL) spectra of the STM amorphous samples showed that the PL intensity increases when the amount of manganese is up to 1%. However, higher manganese concentrations leads to a pronounced decrease of the photoluminescence intensity. The amorphous samples showed no significant change of the local order around the titanium atoms, observed as well as in the oxidation state of the manganese atoms as the amount of manganese increases. Thus, the variation of the photoluminescence intensity cannot be explained by these factors. Increasing the calcination temperature leads to a significant decrease of the photoluminescence intensity. An analysis of the XANES spectra measured at the titanium K edge of these samples showed that as the calcination temperature increases, i. e., as it increases the degree of crystallinity, the ordering of the Ti atoms in the oxygen octahedra TiO6 of the samples increases.

Hybridized nanostructures composed by metals and dielectrics, semiconductors or organics offer new opportunities achieving new functionalities in nonlinear optics, plasmonics, sensing [1-4]. In particular GaAs-AlGaAs-GaAs core-shell-supershell nanowires (NWs) fabricated by self-catalyzed growth on Si substrates were partially covered with gold, thus producing a symmetry breaking in the sample geometry that induces an “extrinsic” chiral response.

Electrical contacting and transport measurements of single self-catalyzed GaAs nanowires grown by molecular beam epitaxy is presented. The nanowires are grown directly in silicon using a recently developed technique based on lithography-free Si/SiO x patterns fabricated by a self-assembled method, which allows synthesis of highly uniform nanowires with controllable size and density.