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.

Subband energy in two-band δ-doped semiconductors

We study electron dynamics in a two-band δ-doped semiconductor within the envelope-function approximation. Using a simple parametrization of the confining potential arising from the ionized donors in the δ -doping layer, we are able to find exact solutions of the Dirac-type equation describing the coupling of host bands. As an application we then consider Si δ -doped GaAs. In particular we find that the ground subband energy scales as a power law of the Si concentration per unit area in a wide range of doping levels. In addition, the coupling of host bands leads to a depression of the subband energy due to nonparabolicity effects.

Oxide Semiconductors For Organic Opto-electronic Devices

Development of transparent oxide semiconductors (TOS) from Earth-abundant materials is of great interest for cost-effective thin film device applications, such as solar cells, light emitting diodes (LEDs), touch-sensitive displays, electronic paper, and transparent thin film transistors. The need of inexpensive or high performance electrode might be even greater for organic photovoltaic (OPV), with the goal to harvest renewable energy with inexpensive, lightweight, and cost competitive materials. The natural abundance of zinc and the wide bandgap ($sim$3.3 eV) of its oxide make it an ideal candidate. In this dissertation, I have introduced various concepts on the modulations of various surface, interface and bulk opto-electronic properties of ZnO based semiconductor for charge transport, charge selectivity and optimal device performance. I have categorized transparent semiconductors into two sub groups depending upon their role in a device. Electrodes, usually 200 to 500 nm thick, optimized for good transparency and transporting the charges to the external circuit. Here, the electrical conductivity in parallel direction to thin film, i.e bulk conductivity is important. And contacts, usually 5 to 50 nm thick, are optimized in case of solar cells for providing charge selectivity and asymmetry to manipulate the built in field inside the device for charge separation and collection. Whereas in Organic LEDs (OLEDs), contacts provide optimum energy level alignment at organic oxide interface for improved charge injections. For an optimal solar cell performance, transparent electrodes are designed with maximum transparency in the region of interest to maximize the light to pass through to the absorber layer for photo-generation, plus they are designed for minimum sheet resistance for efficient charge collection and transport. As such there is need for material with high conductivity and transparency. Doping ZnO with some common elements such as B, Al, Ga, In, Ge, Si, and F result in n-type doping with increase in carriers resulting in high conductivity electrode, with better or comparable opto-electronic properties compared to current industry-standard indium tin oxide (ITO). Furthermore, improvement in mobility due to improvement on crystallographic structure also provide alternative path for high conductivity ZnO TCOs. Implementing these two aspects, various studies were done on gallium doped zinc oxide (GZO) transparent electrode, a very promising indium free electrode. The dynamics of the superimposed RF and DC power sputtering was utilized to improve the microstructure during the thin films growth, resulting in GZO electrode with conductivity greater than 4000 S/cm and transparency greater than 90 %. Similarly, various studies on research and development of Indium Zinc Tin Oxide and Indium Zinc Oxide thin films which can be applied to flexible substrates for next generation solar cells application is presented. In these new TCO systems, understanding the role of crystallographic structure ranging from poly-crystalline to amorphous phase and the influence on the charge transport and optical transparency as well as important surface passivation and surface charge transport properties. Implementation of these electrode based on ZnO on opto-electronics devices such as OLED and OPV is complicated due to chemical interaction over time with the organic layer or with ambient. The problem of inefficient charge collection/injection due to poor understanding of interface and/or bulk property of oxide electrode exists at several oxide-organic interfaces. The surface conductivity, the work function, the formation of dipoles and the band-bending at the interfacial sites can positively or negatively impact the device performance. Detailed characterization of the surface composition both before and after various chemicals treatment of various oxide electrode can therefore provide insight into optimization of device performance. Some of the work related to controlling the interfacial chemistry associated with charge transport of transparent electrodes are discussed. Thus, the role of various pre-treatment on poly-crystalline GZO electrode and amorphous indium zinc oxide (IZO) electrode is compared and contrasted. From the study, we have found that removal of defects and self passivating defects caused by accumulation of hydroxides in the surface of both poly-crystalline GZO and amorphous IZO, are critical for improving the surface conductivity and charge transport. Further insight on how these insulating and self-passivating defects cause charge accumulation and recombination in an device is discussed. With recent rapid development of bulk-heterojunction organic photovoltaics active materials, devices employing ZnO and ZnO based electrode provide air stable and cost-competitive alternatives to traditional inorganic photovoltaics. The organic light emitting diodes (OLEDs) have already been commercialized, thus to follow in the footsteps of this technology, OPV devices need further improvement in power conversion efficiency and stable materials resulting in long device lifetimes. Use of low work function metals such as Ca/Al in standard geometry do provide good electrode for electron collection, but serious problems using low work-function metal electrodes originates from the formation of non-conductive metal oxide due to oxidation resulting in rapid device failure. Hence, using low work-function, air stable, conductive metal oxides such as ZnO as electrons collecting electrode and high work-function, air stable metals such as silver for harvesting holes, has been on the rise. Devices with degenerately doped ZnO functioning as transparent conductive electrode, or as charge selective layer in a polymer/fullerene based heterojunction, present useful device structures for investigating the functional mechanisms within OPV devices and a possible pathway towards improved air-stable high efficiency devices. Furthermore, analysis of the physical properties of the ZnO layers with varying thickness, crystallographic structure, surface chemistry and grain size deposited via various techniques such as atomic layer deposition, sputtering and solution-processed ZnO with their respective OPV device performance is discussed. We find similarity and differences in electrode property for good charge injection in OLEDs and good charge collection in OPV devices very insightful in understanding physics behind device failures and successes. In general, self-passivating surface of amorphous TCOs IZO, ZTO and IZTO forms insulating layer that hinders the charge collection. Similarly, we find modulation of the carrier concentration and the mobility in electron transport layer, namely zinc oxide thin films, very important for optimizing device performance.

Filmes de óxido de zinco e nitreto de zinco depositados por magnetron sputtering com diferentes pressões de argônio, oxigênio e nitrogênio.

O óxido de zinco é um material semicondutor que apresenta alta transparência óptica no espectro visível, alta energia de ligação de éxcitons e piezoeletricidade. Por suas propriedades, ele é utilizado na área de sensores, eletrodos transparentes e dispositivos optoeletrônicos. No entanto, sua utilização ainda é limitada pela dificuldade de obtenção de condutividade tipo p, cujo principal dopante é o nitrogênio, devido à assimetria de dopagem ocasionada por defeitos intrínsecos do material, dopagem em valências diferentes das esperadas e formação de níveis de aceitadores profundos na banda proibida. A aplicação em dispositivos piezoelétricos também exige alta resistividade e ótimas propriedades cristalinas. Muitos processos de deposição estabelecidos hoje ainda utilizam altas temperaturas, o que impede sua deposição sobre superfícies ou substratos sensíveis a altas temperaturas. O objetivo deste trabalho é desenvolver técnicas de deposição de filmes de ZnO, principalmente em baixas temperaturas ( 100°C), pelo método de magnetron sputtering de rádio frequência, para avaliar a influência dos gases de processo nas características estruturais, estequiométricas, elétricas e ópticas dos filmes. Para isso, foram obtidos filmes utilizando pressão total de argônio, e pressões parciais de argônio e oxigênio e argônio e nitrogênio, utilizando alvo cerâmico de óxido de zinco ou alvo metálico de zinco. Para alvo de ZnO, filmes com condutividade tipo n foram obtidos em ambiente de argônio, em condições que geraram deficiências de oxigênio. Filmes altamente resistivos foram obtidos com a utilização de pressão parcial de oxigênio no gás de processo, em condições que resultaram em filmes estequiométricos, inclusive com condutividade tipo p. Condutividade tipo p mais alta foi observada, apenas por ponta quente, para uma amostra obtida em argônio logo após a utilização de nitrogênio na câmara de processo, que provavelmente sofreu influência da dopagem não intencional do cobre, que foi identificado como um contaminante do processo devido à estrutura da câmara. Para alvo de Zn, observou-se a formação de nitreto de zinco, que demonstrou alta capacidade de oxidação em ambiente atmosférico, e portanto, transforma-se naturalmente ao longo do tempo ou por processos de oxidação térmica em ZnO dopado com nitrogênio. Filmes de ZnO produzidos a partir de nitreto de zinco foram os únicos dos testados que apresentaram fotoluminescência característica do ZnO, mesmo para processos onde não houve aquecimento intencional.

Anisotropic exchange interaction induced by a single photon in semiconductor microcavities

We investigate coupling of localized spins in a semiconductor quantum dot embedded in a microcavity. The lowest cavity mode and the quantum dot exciton are coupled and close in energy, forming a polariton. The fermions forming the exciton interact with localized spins via exchange. Exact diagonalization of a Hamiltonian in which photons, spins, and excitons are treated quantum mechanically shows that a single polariton induces a sizable indirect anisotropic exchange interaction between spins. At sufficiently low temperatures strong ferromagnetic correlations show up without an appreciable increase in exciton population. In the case of a (Cd,Mn)Te quantum dot, Mn-Mn ferromagnetic coupling is still significant at 1 K: spin-spin correlation around 3 for exciton occupation smaller than 0.3. We find that the interaction mediated by photon-polaritons is 10 times stronger than the one induced by a classical field for equal Rabi splitting.

Optical probing of spin fluctuations of a single paramagnetic Mn atom in a semiconductor quantum dot

We analyzed the photoluminescence intermittency generated by a single paramagnetic spin localized in an individual semiconductor quantum dot. The statistics of the photons emitted by the quantum dot reflect the quantum fluctuations of the localized spin interacting with the injected carriers. Photon correlation measurements, which are reported here, reveal unique signatures of these fluctuations. A phenomenological model is proposed to quantitatively describe these observations, allowing a measurement of the spin dynamics of an individual magnetic atom at zero magnetic field. These results demonstrate the existence of an efficient spin-relaxation channel arising from a spin exchange with individual carriers surrounding the quantum dot. A theoretical description of a spin-flip mechanism involving spin exchange with surrounding carriers gives relaxation times in good agreement with the measured dynamics.

Coherent-light emission from exciton condensates in semiconductor quantum wells

We show that a quasi-two dimensional condensate of optically active excitons emits coherent light even in the absence of population inversion. This allows an unambiguous and clear experimental detection of the condensed phase. We prove that, due to the exciton–photon coupling, quantum and thermal fluctuations do not destroy condensation at finite temperature. Suitable conditions to achieve condensation are temperatures of a few K for typical exciton densities and the use of a pulsed and preferably circularly polarized, laser.

Force-free twisted magnetospheres of neutron stars

Context. The X-ray spectra observed in the persistent emission of magnetars are evidence for the existence of a magnetosphere. The high-energy part of the spectra is explained by resonant cyclotron upscattering of soft thermal photons in a twisted magnetosphere, which has motivated an increasing number of efforts to improve and generalize existing magnetosphere models. Aims. We want to build more general configurations of twisted, force-free magnetospheres as a first step to understanding the role played by the magnetic field geometry in the observed spectra. Methods. First we reviewed and extended previous analytical works to assess the viability and limitations of semi-analytical approaches. Second, we built a numerical code able to relax an initial configuration of a nonrotating magnetosphere to a force-free geometry, provided any arbitrary form of the magnetic field at the star surface. The numerical code is based on a finite-difference time-domain, divergence-free, and conservative scheme, based of the magneto-frictional method used in other scenarios. Results. We obtain new numerical configurations of twisted magnetospheres, with distributions of twist and currents that differ from previous analytical solutions. The range of global twist of the new family of solutions is similar to the existing semi-analytical models (up to some radians), but the achieved geometry may be quite different. Conclusions. The geometry of twisted, force-free magnetospheres shows a wider variety of possibilities than previously considered. This has implications for the observed spectra and opens the possibility of implementing alternative models in simulations of radiative transfer aiming at providing spectra to be compared with observations.

A new code for the Hall-driven magnetic evolution of neutron stars

Over the past decade, the numerical modeling of the magnetic field evolution in astrophysical scenarios has become an increasingly important field. In the crystallized crust of neutron stars the evolution of the magnetic field is governed by the Hall induction equation. In this equation the relative contribution of the two terms (Hall term and Ohmic dissipation) varies depending on the local conditions of temperature and magnetic field strength. This results in the transition from the purely parabolic character of the equations to the hyperbolic regime as the magnetic Reynolds number increases, which presents severe numerical problems. Up to now, most attempts to study this problem were based on spectral methods, but they failed in representing the transition to large magnetic Reynolds numbers. We present a new code based on upwind finite differences techniques that can handle situations with arbitrary low magnetic diffusivity and it is suitable for studying the formation of sharp current sheets during the evolution. The code is thoroughly tested in different limits and used to illustrate the evolution of the crustal magnetic field in a neutron star in some representative cases. Our code, coupled to cooling codes, can be used to perform long-term simulations of the magneto-thermal evolution of neutron stars.

Unifying the observational diversity of isolated neutron stars via magneto-thermal evolution models

Observations of magnetars and some of the high magnetic field pulsars have shown that their thermal luminosity is systematically higher than that of classical radio-pulsars, thus confirming the idea that magnetic fields are involved in their X-ray emission. Here we present the results of 2D simulations of the fully coupled evolution of temperature and magnetic field in neutron stars, including the state-of-the-art kinetic coefficients and, for the first time, the important effect of the Hall term. After gathering and thoroughly re-analysing in a consistent way all the best available data on isolated, thermally emitting neutron stars, we compare our theoretical models to a data sample of 40 sources. We find that our evolutionary models can explain the phenomenological diversity of magnetars, high-B radio-pulsars, and isolated nearby neutron stars by only varying their initial magnetic field, mass and envelope composition. Nearly all sources appear to follow the expectations of the standard theoretical models. Finally, we discuss the expected outburst rates and the evolutionary links between different classes. Our results constitute a major step towards the grand unification of the isolated neutron star zoo.

The imprint of the crustal magnetic field on the thermal spectra and pulse profiles of isolated neutron stars

Isolated neutron stars (NSs) show a bewildering variety of astrophysical manifestations, presumably shaped by the magnetic field strength and topology at birth. Here, using state-of-the-art calculations of the coupled magnetic and thermal evolution of NSs, we compute the thermal spectra and pulse profiles expected for a variety of initial magnetic field configurations. In particular, we contrast models with purely poloidal magnetic fields to models dominated by a strong internal toroidal component. We find that, while the former displays double-peaked profiles and very low pulsed fractions, in the latter, the anisotropy in the surface temperature produced by the toroidal field often results in a single pulse profile, with pulsed fractions that can exceed the 50–60 per cent level even for perfectly isotropic local emission. We further use our theoretical results to generate simulated ‘observed’ spectra, and show that blackbody (BB) fits result in inferred radii that can be significantly smaller than the actual NS radius, even as low as ∼1–2 km for old NSs with strong internal toroidal fields and a high absorption column density along their line of sight. We compute the size of the inferred BB radius for a few representative magnetic field configurations, NS ages and magnitudes of the column density. Our theoretical results are of direct relevance to the interpretation of X-ray observations of isolated NSs, as well as to the constraints on the equation of state of dense matter through radius measurements.

The masses of the neutron and donor star in the high-mass X-ray binary IGR J18027-2016

Aims. We report near-infrared observations of the supergiant donor to the eclipsing high mass X-ray binary pulsar IGR J18027-2016. We aim to determine its spectral type and measure its radial velocity curve and hence determine the stellar masses of the components. Methods. ESO/VLT observations of the donor utilising the NIR spectrograph ISAAC were obtained in the H and K bands. The multi-epoch H band spectra were cross-correlated with RV templates in order to determine a radial solution for the system. Results. The spectral type of the donor was confirmed as B0-1 I. The radial velocity curve constructed has a semi-amplitude of 23.8 ± 3.1 km s-1. Combined with other measured system parameters, a dynamically determined neutron star mass of 1.4  ±  0.2–1.6  ±  0.3 M⊙ is found. The mass range of the B0-B1 I donor was 18.6  ±  0.8–21.8  ±  2.4 M⊙. These lower and upper limits were obtained under the assumption that the system is viewed edge-on (i = 90° with β = 0.89) for the lower limit and the donor fills its Roche lobe (β = 1 with i = 73.1°) for the upper limit respectively.

The evolution and masses of the neutron star and donor star in the high mass X-ray binary OAO 1657−415

We report near-infrared radial velocity (RV) measurements of the recently identified donor star in the high mass X-ray binary (HMXB) system OAO 1657−415 obtained in the H band using ISAAC on the Very Large Telescope. Cross-correlation methods were employed to construct a RV curve with a semi-amplitude of 22.1 ± 3.5 km s−1. Combined with other measured parameters of this system it provides a dynamically determined neutron star (NS) mass of 1.42 ± 0.26 M⊙ and a mass of 14.3 ± 0.8 M⊙ for the Ofpe/WN9 highly evolved donor star. OAO 1657−415 is an eclipsing HMXB pulsar with the largest eccentricity and orbital period of any within its class. Of the 10 known eclipsing X-ray binary pulsars OAO 1657−415 becomes the ninth with a dynamically determined NS mass solution and only the second in an eccentric system. Furthermore, the donor star in OAO 1657−415 is much more highly evolved than the majority of the supergiant donors in other HMXBs, joining a small but growing list of HMXBs donors with extensive hydrogen depleted atmospheres. Considering the evolutionary development of OAO 1657−415, we have estimated the binding energy of the envelope of the mass donor and find that there is insufficient energy for the removal of the donor’s envelope via spiral-in, ruling out a common envelope evolutionary scenario. With its non-zero eccentricity and relatively large orbital period the identification of a definitive evolutionary pathway for OAO 1657−415 remains problematic, we conclude by proposing two scenarios which may account for OAO 1657−415 current orbital configuration.

Spectral features in isolated neutron stars induced by inhomogeneous surface temperatures

The thermal X-ray spectra of several isolated neutron stars display deviations from a pure blackbody. The accurate physical interpretation of these spectral features bears profound implications for our understanding of the atmospheric composition, magnetic field strength and topology, and equation of state of dense matter. With specific details varying from source to source, common explanations for the features have ranged from atomic transitions in the magnetized atmospheres or condensed surface, to cyclotron lines generated in a hot ionized layer near the surface. Here, we quantitatively evaluate the X-ray spectral distortions induced by inhomogeneous temperature distributions of the neutron star surface. To this aim, we explore several surface temperature distributions, we simulate their corresponding general relativistic X-ray spectra (assuming an isotropic, blackbody emission), and fit the latter with a single blackbody model. We find that, in some cases, the presence of a spurious ‘spectral line’ is required at a high significance level in order to obtain statistically acceptable fits, with central energy and equivalent width similar to the values typically observed. We also perform a fit to a specific object, RX J0806.4−4123, finding several surface temperature distributions able to model the observed spectrum. The explored effect is unlikely to work in all sources with detected lines, but in some cases it can indeed be responsible for the appearance of such lines. Our results enforce the idea that surface temperature anisotropy can be an important factor that should be considered and explored also in combination with more sophisticated emission models like atmospheres.