Electrical transport mechanisms and structure of hydrogenated and non-hydrogenated nanocrystalline Ga1-xMnxAs films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Fluoropolymer piezoelectrets with tubular channels: resonance behavior controlled by channel geometry

Ferro- or piezoelectrets are dielectric materials with two elastically very different macroscopic phases and electrically charged interfaces between them. One of the newer piezoelectret variants is a system of two fluoroethylenepropylene (FEP) films that are first laminated around a polytetrafluoroethylene (PTFE) template. Then, by removing the PTFE template, a two-layer FEP structure with open tubular channels is obtained. After electrical charging, the channels form easily deformable macroscopic electric dipoles whose changes under mechanical or electrical stress lead to significant direct or inverse piezoelectricity, respectively. Here, different PTFE templates are employed to generate channel geometries that vary in height or width. It is shown that the control of the channel geometry allows a direct adjustment of the resonance frequencies in the tubular-channel piezoelectrets. By combining several different channel widths in a single ferroelectret, it is possible to obtain multiple resonance peaks that may lead to a rather flat frequency-response region of the transducer material. A phenomenological relation between the resonance frequency and the geometrical parameters of a tubular channel is also presented. This relation may help to design piezoelectrets with a specific frequency response.

Order induced charge carrier mobility enhancement in columnar liquid crystal diodes

Discotic molecules comprising a rigid aromatic core and flexible side chains have been promisingly applied in OLEDs as self-organizing organic semiconductors. Due to their potentially high charge carrier mobility along the columns, device performance can be readily improved by proper alignment of columns throughout the bulk. In the present work, the charge mobility was increased by 5 orders of magnitude due to homeotropic columnar ordering induced by the boundary interfaces during thermal annealing in the mesophase. State-of-the-art diodes were fabricated using spin-coated films whose homeotropic alignment with formation of hexagonal germs was observed by polarizing optical microscopy. The photophysical properties showed drastic changes at the mesophase-isotropic transition, which is supported by the gain of order observed by X-ray diffraction. The electrical properties were investigated by modeling the current−voltage characteristics by a space-charge-limited current transport with a field dependent mobility.

Bare-tether sheath and current: comparison of asymptotic theory and kinetic simulations in stationary plasma

Analytical expressions for current to a cylindrical Langmuir probe at rest in unmagnetized plasma are compared with results from both steady-state Vlasov and particle-in-cell simulations. Probe bias potentials that are much greater than plasma temperature (assumed equal for ions and electrons), as of interest for bare conductive tethers, are considered. At a very high bias, both the electric potential and the attracted-species density exhibit complex radial profiles; in particular, the density exhibits a minimum well within the plasma sheath and a maximum closer to the probe. Excellent agreement is found between analytical and numerical results for values of the probe radiusR close to the maximum radius Rmax for orbital-motion-limited (OML) collection at a particular bias in the following number of profile features: the values and positions of density minimum and maximum, position of sheath boundary, and value of a radius characterizing the no-space-charge behavior of a potential near the high-bias probe. Good agreement between the theory and simulations is also found for parametric laws jointly covering the following three characteristic R ranges: sheath radius versus probe radius and bias for Rmax; density minimum versus probe bias for Rmax; and (weakly bias-dependent) current drop below the OML value versus the probe radius for R > Rmax.

A theory of electron collection by a grid sphere

Use of a spherical grid as electron collector at the anodic end of a tether, as recently proposed, is considered. The standard analysis of space-charge limited current to a solid sphere (with neither magnetic nor plasma-motion effects), which has been shown to best fit TSS1R in-orbit results at very high bias, is used to determine effects from grid transparency on current collected; the analysis is first reformulated in the formalism recently introduced in the two-dimensional analysis of bare-tethers. A discussion of the electric potential created by a spherical grid in vacuum is then carried out; it is shown that each grid-wire collects current well below its maximum OML current, the effective grid transparency being close to its optical value. Formulae for the current to a spherical grid, showing the effects of grid transparency, is determined. A fully consistent analysis of electric potential and electron density, outside and inside the grid, is completed.

Photovoltaic LiNbO3particles: Applications to Biomedicine/Biophotonics

Recently, a novel method to trap and pattern ensembles of nanoparticles has been proposed and tested. It relies on the photovoltaic (PV) properties of certain ferroelectric crystals such as LiNbO3 [1,2]. These crystals, when suitably doped, develop very high electric fields in response to illumination with light of suitable wavelength. The PV effect lies in the asymmetrical excitation of electrons giving rise to PV currents and associated space-charge fields (photorefractive effect). The field generated in the bulk of the sample propagates to the surrounding medium as evanescent fields. When dielectric or metal nanoparticles are deposited on the surface of the sample the evanescent fields give rise to either electrophoretic or dielectrophoretic forces, depending on the charge state of the particles, that induce the trapping and patterning effects [3,4]. The purpose of this work has been to explore the effects of such PV fields in the biology and biomedical areas. A first work was able to show the necrotic effects induced by such fields on He-La tumour cells grown on the surface of an illuminated iron-doped LiNbO3 crystal [5]. In principle, it is conceived that LiNbO3 nanoparticles may be advantageously used for such biomedical purposes considering the possibility of such nanoparticles being incorporated into the cells. Previous experiments using microparticles have been performed [5] with similar results to those achieved with the substrate. Therefore, the purpose of this work has been to fabricate and characterize the LiNbO3 nanoparticles and assess their necrotic effects when they are incorporated on a culture of tumour cells. Two different preparation methods have been used: 1) mechanical grinding from crystals, and 2) bottom-up sol-gel chemical synthesis from metal-ethoxide precursors. This later method leads to a more uniform size distribution of smaller particles (down to around 50 nm). Fig. 1(a) and 1(b) shows SEM images of the nanoparticles obtained with both method. An ad hoc software taking into account the physical properties of the crystal, particullarly donor and aceptor concentrations has been developped in order to estimate the electric field generated in noparticles. In a first stage simulations of the electric current of nanoparticles, in a conductive media, due to the PV effect have been carried out by MonteCarlo simulations using the Kutharev 1-centre transport model equations [6] . Special attention has been paid to the dependence on particle size and [Fe2+]/[Fe3+]. First results on cubic particles shows large dispersion for small sizes due to the random number of donors and its effective concentration (Fig 2). The necrotic (toxicity) effect of nanoparticles incorporated into a tumour cell culture subjected to 30 min. illumination with a blue LED is shown in Fig.3. For each type of nanoparticle the percent of cell survival in dark and illumination conditions has been plot as a function of the particle dilution factor. Fig. 1a corresponds to mechanical grinding particles whereas 1b and 1c refer to chemically synthesized particles with two oxidation states. The light effect is larger with mechanical grinding nanoparticles, but dark toxicity is also higher. For chemically synthesized nanoparticles dark toxicity is low but only in oxidized samples, where the PV effect is known to be larger, the light effect is appreciable. These preliminary results demonstrate that Fe:LiNbO· nanoparticles have a biological damaging effect on cells, although there are many points that should be clarified and much space for PV nanoparticles optimization. In particular, it appears necessary to determine the fraction of nanoparticles that become incorporated into the cells and the possible existence of threshold size effects. This work has been supported by MINECO under grant MAT2011-28379-C03.

Low Work-Function Thermionic Emission and Orbital-Motion-Limited Ion Collection at Bare-Tether Cathodic Contact

Una amarra electrodinámica (electrodynamic tether) opera sobre principios electromagnéticos intercambiando momento con la magnetosfera planetaria e interactuando con su ionosfera. Es un subsistema pasivo fiable para desorbitar etapas de cohetes agotadas y satélites al final de su misión, mitigando el crecimiento de la basura espacial. Una amarra sin aislamiento captura electrones del plasma ambiente a lo largo de su segmento polarizado positivamente, el cual puede alcanzar varios kilómetros de longitud, mientras que emite electrones de vuelta al plasma mediante un contactor de plasma activo de baja impedancia en su extremo catódico, tal como un cátodo hueco (hollow cathode). En ausencia de un contactor catódico activo, la corriente que circula por una amarra desnuda en órbita es nula en ambos extremos de la amarra y se dice que ésta está flotando eléctricamente. Para emisión termoiónica despreciable y captura de corriente en condiciones limitadas por movimiento orbital (orbital-motion-limited, OML), el cociente entre las longitudes de los segmentos anódico y catódico es muy pequeño debido a la disparidad de masas entre iones y electrones. Tal modo de operación resulta en una corriente media y fuerza de Lorentz bajas en la amarra, la cual es poco eficiente como dispositivo para desorbitar. El electride C12A7 : e−, que podría presentar una función de trabajo (work function) tan baja como W = 0.6 eV y un comportamiento estable a temperaturas relativamente altas, ha sido propuesto como recubrimiento para amarras desnudas. La emisión termoiónica a lo largo de un segmento así recubierto y bajo el calentamiento de la operación espacial, puede ser más eficiente que la captura iónica. En el modo más simple de fuerza de frenado, podría eliminar la necesidad de un contactor catódico activo y su correspondientes requisitos de alimentación de gas y subsistema de potencia, lo que resultaría en un sistema real de amarra “sin combustible”. Con este recubrimiento de bajo W, cada segmento elemental del segmento catódico de una amarra desnuda de kilómetros de longitud emitiría corriente como si fuese parte de una sonda cilíndrica, caliente y uniformemente polarizada al potencial local de la amarra. La operación es similar a la de una sonda de Langmuir 2D tanto en los segmentos catódico como anódico. Sin embargo, en presencia de emisión, los electrones emitidos resultan en carga espacial (space charge) negativa, la cual reduce el campo eléctrico que los acelera hacia fuera, o incluso puede desacelerarlos y hacerlos volver a la sonda. Se forma una doble vainas (double sheath) estable con electrones emitidos desde la sonda e iones provenientes del plasma ambiente. La densidad de corriente termoiónica, variando a lo largo del segmento catódico, podría seguir dos leyes distintas bajo diferentes condiciones: (i) la ley de corriente limitada por la carga espacial (space-charge-limited, SCL) o (ii) la ley de Richardson-Dushman (RDS). Se presenta un estudio preliminar sobre la corriente SCL frente a una sonda emisora usando la teoría de vainas (sheath) formada por la captura iónica en condiciones OML, y la corriente electrónica SCL entre los electrodos cilíndricos según Langmuir. El modelo, que incluye efectos óhmicos y el efecto de transición de emisión SCL a emisión RDS, proporciona los perfiles de corriente y potencial a lo largo de la longitud completa de la amarra. El análisis muestra que en el modo más simple de fuerza de frenado, bajo condiciones orbitales y de amarras típicas, la emisión termoiónica proporciona un contacto catódico eficiente y resulta en una sección catódica pequeña. En el análisis anterior, tanto la transición de emisión SCL a RD como la propia ley de emisión SCL consiste en un modelo muy simplificado. Por ello, a continuación se ha estudiado con detalle la solución de vaina estacionaria de una sonda con emisión termoiónica polarizada negativamente respecto a un plasma isotrópico, no colisional y sin campo magnético. La existencia de posibles partículas atrapadas ha sido ignorada y el estudio incluye tanto un estudio semi-analítico mediante técnica asintóticas como soluciones numéricas completas del problema. Bajo las tres condiciones (i) alto potencial, (ii) R = Rmax para la validez de la captura iónica OML, y (iii) potencial monotónico, se desarrolla un análisis asintótico auto-consistente para la estructura de plasma compleja que contiene las tres especies de cargas (electrones e iones del plasma, electrones emitidos), y cuatro regiones espaciales distintas, utilizando teorías de movimiento orbital y modelos cinéticos de las especies. Aunque los electrones emitidos presentan carga espacial despreciable muy lejos de la sonda, su efecto no se puede despreciar en el análisis global de la estructura de la vaina y de dos capas finas entre la vaina y la región cuasi-neutra. El análisis proporciona las condiciones paramétricas para que la corriente sea SCL. También muestra que la emisión termoiónica aumenta el radio máximo de la sonda para operar dentro del régimen OML y que la emisión de electrones es mucho más eficiente que la captura iónica para el segmento catódico de la amarra. En el código numérico, los movimientos orbitales de las tres especies son modelados para potenciales tanto monotónico como no-monotónico, y sonda de radio R arbitrario (dentro o más allá del régimen de OML para la captura iónica). Aprovechando la existencia de dos invariante, el sistema de ecuaciones Poisson-Vlasov se escribe como una ecuación integro-diferencial, la cual se discretiza mediante un método de diferencias finitas. El sistema de ecuaciones algebraicas no lineal resultante se ha resuelto de con un método Newton-Raphson paralelizado. Los resultados, comparados satisfactoriamente con el análisis analítico, proporcionan la emisión de corriente y la estructura del plasma y del potencial electrostático. ABSTRACT An electrodynamic tether operates on electromagnetic principles and exchanges momentum through the planetary magnetosphere, by continuously interacting with the ionosphere. It is a reliable passive subsystem to deorbit spent rocket stages and satellites at its end of mission, mitigating the growth of orbital debris. A tether left bare of insulation collects electrons by its own uninsulated and positively biased segment with kilometer range, while electrons are emitted by a low-impedance active device at the cathodic end, such as a hollow cathode, to emit the full electron current. In the absence of an active cathodic device, the current flowing along an orbiting bare tether vanishes at both ends and the tether is said to be electrically floating. For negligible thermionic emission and orbital-motion-limited (OML) collection throughout the entire tether (electron/ion collection at anodic/cathodic segment, respectively), the anodic-to-cathodic length ratio is very small due to ions being much heavier, which results in low average current and Lorentz drag. The electride C12A7 : e−, which might present a possible work function as low as W = 0.6 eV and moderately high temperature stability, has been proposed as coating for floating bare tethers. Thermionic emission along a thus coated cathodic segment, under heating in space operation, can be more efficient than ion collection and, in the simplest drag mode, may eliminate the need for an active cathodic device and its corresponding gas-feed requirements and power subsystem, which would result in a truly “propellant-less” tether system. With this low-W coating, each elemental segment on the cathodic segment of a kilometers-long floating bare-tether would emit current as if it were part of a hot cylindrical probe uniformly polarized at the local tether bias, under 2D probe conditions that are also applied to the anodic-segment analysis. In the presence of emission, emitted electrons result in negative space charge, which decreases the electric field that accelerates them outwards, or even reverses it, decelerating electrons near the emitting probe. A double sheath would be established with electrons being emitted from the probe and ions coming from the ambient plasma. The thermionic current density, varying along the cathodic segment, might follow two distinct laws under different con ditions: i) space-charge-limited (SCL) emission or ii) full Richardson-Dushman (RDS) emission. A preliminary study on the SCL current in front of an emissive probe is presented using the orbital-motion-limited (OML) ion-collection sheath and Langmuir’s SCL electron current between cylindrical electrodes. A detailed calculation of current and bias profiles along the entire tether length is carried out with ohmic effects considered and the transition from SCL to full RDS emission is included. Analysis shows that in the simplest drag mode, under typical orbital and tether conditions, thermionic emission provides efficient cathodic contact and leads to a short cathodic section. In the previous analysis, both the transition between SCL and RDS emission and the current law for SCL condition have used a very simple model. To continue, considering an isotropic, unmagnetized, colissionless plasma and a stationary sheath, the probe-plasma contact is studied in detail for a negatively biased probe with thermionic emission. The possible trapped particles are ignored and this study includes both semianalytical solutions using asymptotic analysis and complete numerical solutions. Under conditions of i) high bias, ii) R = Rmax for ion OML collection validity, and iii) monotonic potential, a self-consistent asymptotic analysis is carried out for the complex plasma structure involving all three charge species (plasma electrons and ions, and emitted electrons) and four distinct spatial regions using orbital motion theories and kinetic modeling of the species. Although emitted electrons present negligible space charge far away from the probe, their effect cannot be neglected in the global analysis for the sheath structure and two thin layers in between the sheath and the quasineutral region. The parametric conditions for the current to be space-chargelimited are obtained. It is found that thermionic emission increases the range of probe radius for OML validity and is greatly more effective than ion collection for cathodic contact of tethers. In the numerical code, the orbital motions of all three species are modeled for both monotonic and non-monotonic potential, and for any probe radius R (within or beyond OML regime for ion collection). Taking advantage of two constants of motion (energy and angular momentum), the Poisson-Vlasov equation is described by an integro differential equation, which is discretized using finite difference method. The non-linear algebraic equations are solved using a parallel implementation of the Newton-Raphson method. The results, which show good agreement with the analytical results, provide the results for thermionic current, the sheath structure, and the electrostatic potential.

Comparative theoretical analysis between parallel and perpendicular geometries for 2D particle patterning in photovoltaic ferroelectric substrates

This paper describes the dielectrophoretic potential created by the evanescent electric field acting on a particle near a photovoltaic crystal surface depending on the crystal cut. This electric field is obtained from the steady state solution of the Kukhtarev equations for the photovoltaic effect, where the diffusion term has been disregarded. First, the space charge field generated by a small, square, light spot where d _ l (being d a side of the square and l the crystal thickness) is studied. The surface charge density generated in both geometries is calculated and compared as their relation determines the different properties of the dielectrophoretic potential for both cuts. The shape of the dielectrophoretic potential is obtained and compared for several distances to the sample. Afterwards other light patterns are studied by the superposition of square spots, and the resulting trapping profiles are analysed. Finally the surface charge densities and trapping profiles for different d/l relations are studied.

Low work-function thermionic emission and orbital-motion-limited ion collection at bare-tether cathodic contact

With a thin coating of low-work-function material, thermionic emission in the cathodic segment of bare tethers might be much greater than orbital-motion-limited (OML) ion collection current. The space charge of the emitted electrons decreases the electric field that accelerates them outwards, and could even reverse it for high enough emission, producing a potential hollow. In this work, at the conditions of high bias and relatively low emission that make the potential monotonic, an asymptotic analysis is carried out, extending the OML ion-collection analysis to investigate the probe response due to electrons emitted by the negatively biased cylindrical probe. At given emission, the space charge effect from emitted electrons increases with decreasing magnitude of negative probe bias. Although emitted electrons present negligible space charge far away from the probe, their effect cannot be neglected in the global analysis for the sheath structure and two thin layers in between sheath and the quasineutral region. The space-charge-limited condition is located. It is found that thermionic emission increases the range of probe radius for OML validity and is greatly more effective than ion collection for cathodic contact of tethers.

Polímeros de coordenação à base de cobalto(II) e N,N'-bis(4-piridil)-1,4,5,8-naftaleno diimida como ligante e suas propriedade estruturais, espectroscópicas e fotoelétricas

Polímeros de coordenação têm atraído a atenção de pesquisadores na última década por conta de sua incrível versatilidade e virtualmente infinito número de possibilidades de combinação de ligantes orgânicos e centros metálicos. Estes compostos normalmente herdam as características magnéticas, eletrônicas e espectroscópicas de seus componentes base. Entretanto, apesar do crescente número de trabalhos na área, ainda são raros os polímeros de coordenação que apresentem condutividade elétrica. Para este fim, utilizou-se a N,N\'-bis(4-piridil)-1,4,5,8-naftaleno diimida, ou NDI-py, que pertence a uma classe de compostos rígidos, planares, quimicamente e termicamente estáveis e que já foram extensamente estudados por suas propriedades fotoeletroquímicas e semicondução do tipo n. O primeiro polímero de coordenação sintetizado, MOF-CoNDI-py-1, indicou ser um polímero linear, de estrutura 1D. O segundo, MOF-CoNDI-py-2, que conta com ácido tereftálico como ligante suporte, é um sólido cristalino com cela unitária monoclínica pertencente ao grupo espacial C2/c, determinado por difração de raios-X de monocristal. A rede apresenta um arranjo trinuclear de íons Co(II) alto spin com coordenados em uma geometria de octaedro distorcido, enquanto os ligantes NDI-py se encontram em um arranjo paralelo na estrutura, em distâncias apropriadas para transferência eletrônica. Com o auxílio de cálculo teóricos a nível de DFT, foi realizado um estudo aprofundado dos espectros eletrônicos e vibracionais, com atribuição das transições observadas, tanto para o MOF-CoNDI-py-2 quanto para o ligante NDI-py livre. A rede de coordenação absorve em toda a região do espectro eletrônico analisada, de 200 nm a 2500 nm, além de apresentar luminescência com característica do ligante. Dispositivos eletrônicos fabricados com um cristal do MOF-CoNDI-py-2 revelaram condutividades da ordem de 7,9 10-3 S cm -1, a maior já observada para um MOF. Além de elevada, a condutividade elétrica dos cristais demonstrou-se altamente anisotrópica, sendo significativamente menos condutor em algumas direções. Os perfis de corrente versus voltagem foram analisados em termos de mecanismos de condutividade, sendo melhores descritos por um mecanismo limitado pelo eletrodo to tipo Space-Charge Limited Current, concordando com a proposta de condutividade através dos planos de NDI-py na rede. A condutividade dos cristais também é fortemente dependente de luz, apresentando fotocondução quando irradiado por um laser vermelho, de 632 nm, enquanto apresenta um comportamento fotorresistivo frente a uma fonte de luz branca. Estes resultados, combinados, trazem um MOF em uma estrutura incomum e com elevada condutividade elétrica, modulada por luz, em medidas diretas de corrente. Não existem exemplos conhecidos de MOFs na literatura com estas características.

Investigation of photorefractive subharmonics in the absence of wavemixing

Using a new optical configuration free from the influence of photorefractive optical nonlinearity, we investigate the main characteristics of the spatial subharmonic K/2 excited in a Bi12SiO20 crystal by a light-intensity pattern with wave vector K and frequency O. It is shown that in a large region of intensity and applied electric field the optimum value O of the frequency corresponds to the conditions of parametric excitation of the weakly damped eigenmodes of the medium: the space-charge waves. The threshold and above-threshold characteristics of the subharmonic regime are in good agreement with the theory.

Resonant two-wave mixing in photorefractive materials with the aid of dc and ac fields

A recently predicted resonant effect for the enhancement of two-wave mixing in photorefractive materials is investigated. The resonance occurs when the frequency of the applied ac field agrees with the eigenfrequency of the excited space-charge wave. Experimentally a clear resonance is found, as predicted by the theory, for high dc electric fields, but the resonance is smeared out for lower fields. A modified theory, taking into account the second temporal harmonic of the space-charge wave, shows good agreement with the experimental results.

Investigation of photorefractive subharmonics in the absence of wavemixing

Using a new optical configuration free from the influence of photorefractive optical nonlinearity, we investigate the main characteristics of the spatial subharmonic K/2 excited in a Bi12SiO20 crystal by a light-intensity pattern with wave vector K and frequency O. It is shown that in a large region of intensity and applied electric field the optimum value O of the frequency corresponds to the conditions of parametric excitation of the weakly damped eigenmodes of the medium: the space-charge waves. The threshold and above-threshold characteristics of the subharmonic regime are in good agreement with the theory.

Resonant two-wave mixing in photorefractive materials with the aid of dc and ac fields

A recently predicted resonant effect for the enhancement of two-wave mixing in photorefractive materials is investigated. The resonance occurs when the frequency of the applied ac field agrees with the eigenfrequency of the excited space-charge wave. Experimentally a clear resonance is found, as predicted by the theory, for high dc electric fields, but the resonance is smeared out for lower fields. A modified theory, taking into account the second temporal harmonic of the space-charge wave, shows good agreement with the experimental results.

Multiscale Analysis for Field-Effect Penetration through Two-Dimensional Materials

Gate-tunable two-dimensional (2D) materials-based quantum capacitors (QCs) and van der Waals heterostructures involve tuning transport or optoelectronic characteristics by the field effect. Recent studies have attributed the observed gate-tunable characteristics to the change of the Fermi level in the first 2D layer adjacent to the dielectrics, whereas the penetration of the field effect through the one-molecule-thick material is often ignored or oversimplified. Here, we present a multiscale theoretical approach that combines first-principles electronic structure calculations and the Poisson–Boltzmann equation methods to model penetration of the field effect through graphene in a metal–oxide–graphene–semiconductor (MOGS) QC, including quantifying the degree of “transparency” for graphene two-dimensional electron gas (2DEG) to an electric displacement field. We find that the space charge density in the semiconductor layer can be modulated by gating in a nonlinear manner, forming an accumulation or inversion layer at the semiconductor/graphene interface. The degree of transparency is determined by the combined effect of graphene quantum capacitance and the semiconductor capacitance, which allows us to predict the ranking for a variety of monolayer 2D materials according to their transparency to an electric displacement field as follows: graphene > silicene > germanene > WS2 > WTe2 > WSe2 > MoS2 > phosphorene > MoSe2 > MoTe2, when the majority carrier is electron. Our findings reveal a general picture of operation modes and design rules for the 2D-materials-based QCs.