Photoconductivity and Electro-Optical Properties of Wide Band Gap Metal Oxides

The PhD activity described in this Thesis was focused on the study of metal-oxide wide-bandgap materials, aiming at fabricating new optoelectronic devices such as solar-blind UV photodetectors, high power electronics, and gas sensors. Photocurrent spectroscopy and DC photocurrent time evolution were used to investigate the performance of prototypes under different atmospheres, temperatures and excitation wavelengths (or dark conditions). Cathodoluminescence, absorption spectroscopy, XRD and SEM were used to assess structural, morphologic, electrical and optical properties of materials. This thesis is divided into two main sections, each describing the work done on a different metal-oxide semiconductor. 1) MOVPE-grown Ga2O3 thin films for UV solar-blind photodetectors and high power devices The semiconducting oxides, among them Ga2O3, have been employed for several decades as transparent conducting oxide (TCO) electrodes for fabrication of solar cells, displays, electronic, and opto-electronic devices. The interest was mainly confined to such applications, as these materials tend to grow intrinsically n-type, and attempts to get an effective p-type doping has consistently failed. The key requirements of TCO electrodes are indeed high electrical conductivity and good transparency, while crystallographic perfection is a minor issue. Furthermore, for a long period no high-quality substrates and epi-layers were available, which in turn impeded the development of a truly full-oxide electronics. Recently, Ga2O3 has attracted renewed interest, as large single crystals and high-quality homo- and hetero-epitaxial layers became available, which paved the way to novel application areas. Our research group spent the last two years in developing a low temperature (500-700°C) MOVPE growth procedure to obtain thin films of Ga2O3 on different substrates (Dept. of Physics and IMEM-CNR at UNIPR). We obtained a significant result growing on oriented sapphire epitaxial films of high crystalline, undoped, pure phase -Ga2O3 (hexagonal). The crystallographic properties of this phase were investigated by XRD, in order to clarify the lattice parameters of the hexagonal cell. First design and development of solar blind UV photodetectors based on -phase was carried out and the optoelectronic performance is evaluated by means of photocurrent spectroscopy. The UV-response is adequately fast and reliable to render this unusual phase a subject of great interest for future applications. The availability of a hexagonal phase of Ga2O3 stable up to 700°C, belonging to the same space group of gallium nitride, with high crystallinity and tunable electrical properties, is intriguing in view of the development of nitride-based devices, by taking advantage of the more favorable symmetry and epitaxial relationships with respect to the monoclinic β-phase. In addition, annealing at temperatures higher than 700°C demonstrate that the hexagonal phase converts totally in the monoclinic one. 2) ZnO nano-tetrapods: charge transport mechanisms and time-response in optoelectronic devices and sensors Size and morphology of ZnO at the nanometer scale play a key role in tailoring its physical and chemical properties. Thanks to the possibility of growing zinc oxide in a variety of different nanostructures, there is a great variety of applications, among which gas sensors, light emitting diodes, transparent conducting oxides, solar cells. Even if the operation of ZnO nanostructure-based devices has been recently demonstrated, the mechanisms of charge transport in these assembly is still under debate. The candidate performed an accurate investigation by photocurrent spectroscopy and DC-photocurrent time evolution of electrical response of both single-tetrapod and tetrapod-assembly devices. During the research done for this thesis, a thermal activation energy enables the performance of samples at high temperatures (above about 300°C). The energy barrier is related to the leg-to-leg interconnection in the assembly of nanotetrapods. Percolation mechanisms are responsible for both the very slow photo-response (minutes to hours or days) and the significant persistent photocurrent. Below the bandgap energy, electronic states were investigated but their contribution to the photocurrent are two-three order of magnitude lower than the band edge. Such devices are suitable for employ in photodetectors as well as in gas sensors, provided that the mechanism by which the photo-current is generated and gas adsorption on the surface modify the conductivity of the material are known.

Azimuthal asymmetry in the risetime of the surface detector signals of the Pierre Auger Observatory.

The azimuthal asymmetry in the risetime of signals in Auger surface detector stations is a source of information on shower development. The azimuthal asymmetry is due to a combination of the longitudinal evolution of the shower and geometrical effects related to the angles of incidence of the particles into the detectors. The magnitude of the effect depends upon the zenith angle and state of development of the shower and thus provides a novel observable, (sec theta)(max), sensitive to the mass composition of cosmic rays above 3 x 10(18) eV. By comparing measurements with predictions from shower simulations, we find for both of our adopted models of hadronic physics (QGSJETII-04 and EPOS-LHC) an indication that the mean cosmic-ray mass increases slowly with energy, as has been inferred from other studies. However, the mass estimates are dependent on the shower model and on the range of distance from the shower core selected. Thus the method has uncovered further deficiencies in our understanding of shower modeling that must be resolved before the mass composition can be inferred from (sec theta)(max).

Signal Processing Techniques for Chipless UWB RFID Thermal Threshold Detector Detection.

This letter presents signal processing techniques to detect a passive thermal threshold detector based on a chipless time-domain ultrawideband (UWB) radio frequency identification (RFID) tag. The tag is composed by a UWB antenna connected to a transmission line, in turn loaded with a biomorphic thermal switch. The working principle consists of detecting the impedance change of the thermal switch. This change occurs when the temperature exceeds a threshold. A UWB radar is used as the reader. The difference between the actual time sample and a reference signal obtained from the averaging of previous samples is used to determine the switch transition and to mitigate the interferences derived from clutter reflections. A gain compensation function is applied to equalize the attenuation due to propagation loss. An improved method based on the continuous wavelet transform with Morlet wavelet is used to overcome detection problems associated to a low signal-to-noise ratio at the receiver. The average delay profile is used to detect the tag delay. Experimental measurements up to 5 m are obtained.

Instabilidades MHD no Tokamak TCABR

Este trabalho descreve o estudo das instabilidades magneto-hidro-dinâmicas (MHD) comumente observadas nas descargas elétricas de plasma no tokamak TCABR, do Instituto de Física da USP. Dois diagnósticos principais foram empregados para observar essas instabilidades: um conjunto poloidal de 24 bobinas magnéticas (bobinas de Mirnov) colocadas próximas à borda do plasma e um medidor de emissões na faixa do Ultra Violeta e de raios X moles com 20 canais (sistema SXR), cujo circuito de condicionamento de sinais foi aprimorado como parte deste trabalho. Esses diagnósticos foram escolhidos porque fornecem informações complementares, uma vez que o sistema SXR observa a parte central da coluna de plasma, enquanto as bobinas de Mirnov detectam as instabilidades MHD na região mais externa da coluna. As informações coletadas por esses diagnósticos foram submetidas à análise espectral com resolução temporal e espacial, possibilitando determinar a evolução das características espectrais e espaciais das instabilidades MHD observadas. Essas análises revelaram que durante a etapa inicial da formação do plasma (quando a corrente de plasma ainda está aumentando) ilhas magnéticas com números de onda decrescente, identificadas como sendo modos kink de borda, são detectadas nas bobinas de Mirnov. Após a formação do plasma, quando os parâmetros de equilíbrio estão relativamente estáveis (platô), oscilações são detectadas tanto nas bobinas de Mirnov quanto no sistema de SXR, indicando a presença de instabilidades MHD em toda a coluna de plasma. Em geral as oscilações medidas nas bobinas de Mirnov tem baixa amplitude e correspondem a pequenas ilhas magnéticas que foram identificadas como sendo modos de ruptura (modos tearing). Por outro lado, as instabilidades na região central foram identificadas como dentes de serra, que correspondem a relaxações periódicas da região interna à superfície magnética com fator de segurança q=1 e que são acompanhadas de oscilações precursoras, cuja amplitude depende da fase do ciclo de relaxação. Devido à essa modulação de amplitude, aparecem picos de frequência satélite nos espectrogramas dos sinais do SXR. Além disso, devido ao fato dos ciclos de relaxação não serem sinusoidais, os harmônicos da frequência de relaxação também aparecem nesses espectrogramas. No entanto, em muitas descargas do TCABR, a intensidade das oscilações medidas nas bobinas de Mirnov aumentam significativamente durante o platô, com efeitos sobre a frequência de todas as instabilidades MHD, até mesmo sobre os dentes de serra localizados na região central da coluna. Em todos os casos, observou-se que durante o platô a frequência das ilhas magnéticas coincide com a frequência das oscilações precursoras do dente de serra, apesar de serem duas instabilidades distintas, localizadas em posições radiais muito diferentes. Essa coincidência de frequências possibilitou descrever a evolução em frequência de todas as oscilações detectadas em diversos diagnósticos com base em apenas duas frequências básicas: a dos ciclos de relaxação dente de serra e a das ilhas magnéticas.

Fabricação e caracterização de detector de Barreira de superfície a partir de substrato de silício comercial

Neste trabalho foram desenvolvidos detectores de radiação Barreira de superfície de silício que fossem capazes de detectar a presença da radiação gama de baixa energia proveniente de sementes de iodo-125 utilizada em tratamentos de braquiterapia. A partir de substratos comerciais de silício foram desenvolvidos os detectores, de uma sequência que partiu de tratamentos químicos nas superfícies destes substratos com a intenção de minimizar os possíveis ruídos gerados, validação das amostras obtidas como diodos, assegurando características detectoras, e a efetiva utilização como detector para fontes radioativas de iodo-125 com energia em torno de 25 kev e amerício-251 com energia na ordem de 59 kev. Finalizou realizando a análise dos espectros de energia obtidos e assim foi possível observar a capacidade destes detectores para mensuração da energia proveniente destas sementes.

On the Edge of the World: Trauma and Twinship Selfobject Needs in Mrs. Dalloway

Alienation and aloneness appear as common themes in the experience of those impacted by trauma. Self psychology theorists, including contemporary proponents of intersubjectivity theory, have also discussed the ways in which alienation and disconnection from others permeate the experience of post-traumatic stress disorder. This discussion has highlighted the importance and centrality of twinship selfobject needs in providing a relational home for the emotional pain associated with trauma. These phenomena are especially apparent when one encounters the experiences of those combat veterans who have attempted to readjust to society upon returning home from military service. Using self psychology and intersubjectivity theory, this paper explores the ways that fiction, specifically Virginia Woolf's Mrs. Dalloway, can illuminate the ways that trauma negatively impacts twinship selfobject needs in combat veterans. In examining the character of Septimus Smith, this paper illustrates the estrangement, singularity, and alienation associated with post-traumatic stress, and how this state of being can collude with societal misunderstanding and repression to shatter the self's sense of belongingness with and connection to others.

Fermi-edge singularities in linear and nonlinear ultrafast spectroscopy

We discuss Fermi-edge singularity effects on the linear and nonlinear transient response of an electron gas in a doped semiconductor. We use a bosonization scheme to describe the low-energy excitations, which allows us to compute the time and temperature dependence of the response functions. Coherent control of the energy absorption at resonance is analyzed in the linear regime. It is shown that a phase shift appears in the coherent control oscillations, which is not present in the excitonic case. The nonlinear response is calculated analytically and used to predict that four wave-mixing experiments would present a Fermi-edge singularity when the exciting energy is varied. A new dephasing mechanism is predicted in doped samples that depends linearly on temperature and is produced by the low-energy bosonic excitations in the conduction band.

Spin-filtered edge states in graphene

Spin–orbit coupling changes graphene, in principle, into a two-dimensional topological insulator, also known as quantum spin Hall insulator. One of the expected consequences is the existence of spin-filtered edge states that carry dissipationless spin currents and undergo no backscattering in the presence of non-magnetic disorder, leading to quantization of conductance. Whereas, due to the small size of spin–orbit coupling in graphene, the experimental observation of these remarkable predictions is unlikely, the theoretical understanding of these spin-filtered states is shedding light on the electronic properties of edge states in other two-dimensional quantum spin Hall insulators. Here we review the effect of a variety of perturbations, like curvature, disorder, edge reconstruction, edge crystallographic orientation, and Coulomb interactions on the electronic properties of these spin filtered states.

Ultrafast coherent spectroscopy of the Fermi edge singularity

Paper submitted to the XVI Sitges Conference on Statistical Mechanics, Sitges, Barcelona, Spain, 7-11 June 1999.

Local probe of fractional edge states of S=1 Heisenberg spin chains

Spin chains are among the simplest physical systems in which electron-electron interactions induce novel states of matter. Here we propose to combine atomic scale engineering and spectroscopic capabilities of state of the art scanning tunnel microscopy to probe the fractionalized edge states of individual atomic scale S=1 spin chains. These edge states arise from the topological order of the ground state in the Haldane phase. We also show that the Haldane gap and the spin-spin correlation length can be measured with the same technique.

Massive open star clusters using the VVV survey III. A young massive cluster at the far edge of the Galactic bar

Context. Young massive clusters are key to map the Milky Way’s structure, and near-infrared large area sky surveys have contributed strongly to the discovery of new obscured massive stellar clusters. Aims. We present the third article in a series of papers focused on young and massive clusters discovered in the VVV survey. This article is dedicated to the physical characterization of VVV CL086, using part of its OB-stellar population. Methods. We physically characterized the cluster using JHKS near-infrared photometry from ESO public survey VVV images, using the VVV-SkZ pipeline, and near-infrared K-band spectroscopy, following the methodology presented in the first article of the series. Results. Individual distances for two observed stars indicate that the cluster is located at the far edge of the Galactic bar. These stars, which are probable cluster members from the statistically field-star decontaminated CMD, have spectral types between O9 and B0 V. According to our analysis, this young cluster (1.0 Myr < age < 5.0 Myr) is located at a distance of 11+5-6 kpc, and we estimate a lower limit for the cluster total mass of (2.8+1.6-1.4) · 103 M⊙. It is likely that the cluster contains even earlier and more massive stars.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction for determination of mercury in water samples

A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid–liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L−1 was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L−1, which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L−1 and 1 µg L−1, respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L−1) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained.