Preparation and characterization of stable aqueous suspensions of up-converting Er3+/Yb3+-doped LiNbO3 nanocrystals

The preparation of LiNbO3:Er3+/Yb3+ nanocrystals and their up-conversion properties have been studied. It is demonstrated that polyethyleneimine- (PEI) assisted dispersion procedures allow obtaining stable aqueous LiNbO3:Er3+/Yb3+ powder suspensions, with average size particles well below the micron range (100–200 nm) and the isoelectric point of the suspension reaching values well above pH 7. After excitation of Yb3+ ions at a wavelength of 980 nm, the suspensions exhibit efficient, and stable, IR-to-visible (green and red) up-conversion properties, easily observed by the naked eye, very similar to those of the starting crystalline bulk material.

Analysis and optimization of propagation losses in LiNbO3 optical waveguides produced by swift heavy-ion irradiation

The propagation losses (PL) of lithium niobate optical planar waveguides fabricated by swift heavy-ion irradiation (SHI), an alternative to conventional ion implantation, have been investigated and optimized. For waveguide fabrication, congruently melting LiNbO3 substrates were irradiated with F ions at 20 MeV or 30 MeV and fluences in the range 1013–1014 cm−2. The influence of the temperature and time of post-irradiation annealing treatments has been systematically studied. Optimum propagation losses lower than 0.5 dB/cm have been obtained for both TE and TM modes, after a two-stage annealing treatment at 350 and 375∘C. Possible loss mechanisms are discussed.

Calculation of the spatial distribution of photovoltaic field by arbitrary 2D ilumination patterns en LiNbO3; application to photovoltaic particle trapping.

Patterns of evanescent photovoltaic field induced by illumination on a surface of lithium niobate (LN) have been calculated and compared with the experimental patterns of nano- and microparticles trapped by dielectrophoretic forces. A tool for this calculation has been developed. Calculo de distribución espacial de campo por efecto fotovoltaico con patrones arbitrarios de iluminación, en LiNbO3

Calculation of dielectrophoretic potential generated under illumination patterns on x- and z-cut LiNbO3 : application to photovoltaic particle trapping

The dielectrophoretic potential generated near the surface of a z-cut LiNbO3 by photovoltaic charge transport has been calculated for first time. The procedure and results are compared with the ones corresponding to x-cut. Diferences in the position, sharpness and time evolution are reported, and their implication on particle trapping are discussed.

1D and 2D neutral particle patterning by dielectrophoretic forces on z-cut Fe:LiNbO3 crystals

1D and 2D patterning of uncharged micro- and nanoparticles via dielectrophoretic forces on photovoltaic z-cut Fe:LiNbO3 have been investigated for the first time. The technique has been successfully applied with dielectric micro-particles of CaCO3 (diameter d = 1-3 μm) and metal nanoparticles of Al (d = 70 nm). At difference with previous experiments in x- and y-cut, the obtained patterns locally reproduce the light distribution with high fidelity. A simple model is provided to analyse the trapping process. The results show the remarkably good capabilities of this geometry for high quality 2D light-induced dielectrophoretic patterning overcoming the important limitations presented by previous configurations.

Efficient photo-induced dielectrophoretic particle trapping on Fe:LiNbO3 for arbitrary two dimensional patterning

1D and 2D patterning of uncharged micro- and nanoparticles via dielectrophoretic forces on photovoltaic z-cut Fe:LiNbO3 have been investigated for the first time. The technique has been successfully applied with dielectric micro-particles of CaCO3 (diameter d = 1-3 ?m) and metal nanoparticles of Al (d = 70 nm). At difference with previous experiments in x- and y-cut, the obtained patterns locally reproduce the light distribution with high fidelity. A simple model is provided to analyse the trapping process. The results show the remarkably good capabilities of this geometry for high quality 2D light-induced dielectrophoretic patterning overcoming the important limitations presented by previous configurations.

Elastic (stress-strain) halo associated to ion-induced nano-tracks in lithium niobate: role of crystal anisotropy

The elastic strain/stress fields (halo) around a compressed amorphous nano-track (core) caused by a single high-energy ion impact on LiNbO3 are calculated. A method is developed to approximately account for the effects of crystal anisotropy of LiNbO3 (symmetry 3m) on the stress fields for tracks oriented along the crystal axes (X, Y or Z). It only considers the zero-order (axial) harmonic contribution to the displacement field in the perpendicular plane and uses effective Poisson moduli for each particular orientation. The anisotropy is relatively small; however, it accounts for some differential features obtained for irradiations along the crystallographic axes X, Y and Z. In particular, the irradiation-induced disorder (including halo) and the associated surface swelling appear to be higher for irradiations along the X- or Y-axis in comparison with those along the Z-axis. Other irradiation effects can be explained by the model, e.g. fracture patterns or the morphology of pores after chemical etching of tracks. Moreover, it offers interesting predictions on the effect of irradiation on lattice parameters

Recrystallization of amorphous nano-tracks and uniform layers generated by swift-ion-beam irradiation in lithium niobate.

The thermal annealing of amorphous tracks of nanometer-size diameter generated in lithium niobate (LiNbO3) by Bromine ions at 45 MeV, i.e., in the electronic stopping regime, has been investigated by RBS/C spectrometry in the temperature range from 250°C to 350°C. Relatively low fluences have been used (<1012 cm−2) to produce isolated tracks. However, the possible effect of track overlapping has been investigated by varying the fluence between 3×1011 cm−2 and 1012 cm−2. The annealing process follows a two-step kinetics. In a first stage (I) the track radius decreases linearly with the annealing time. It obeys an Arrhenius-type dependence on annealing temperature with activation energy around 1.5 eV. The second stage (II) operates after the track radius has decreased down to around 2.5 nm and shows a much lower radial velocity. The data for stage I appear consistent with a solid-phase epitaxial process that yields a constant recrystallization rate at the amorphous-crystalline boundary. HRTEM has been used to monitor the existence and the size of the annealed isolated tracks in the second stage. On the other hand, the thermal annealing of homogeneous (buried) amorphous layers has been investigated within the same temperature range, on samples irradiated with Fluorine at 20 MeV and fluences of ∼1014 cm−2. Optical techniques are very suitable for this case and have been used to monitor the recrystallization of the layers. The annealing process induces a displacement of the crystalline-amorphous boundary that is also linear with annealing time, and the recrystallization rates are consistent with those measured for tracks. The comparison of these data with those previously obtained for the heavily damaged (amorphous) layers produced by elastic nuclear collisions is summarily discussed.

Amorphization kinectics under swift heavy ion irradiation: a cumulative overlapping-track approach

A simple illustrative physical model is presented to describe the kinetics of damage and amorphization by swiftheavyions (SHI) in LiNbO3. The model considers that every ion impact generates initially a defective region (halo) and a full amorphous core whose relative size depends on the electronic stopping power. Below a given stopping power threshold only a halo is generated. For increasing fluences the amorphized area grows monotonically via overlapping of a fixed number N of halos. In spite of its simplicity the model, which provides analytical solutions, describes many relevant features of the kinetic behaviour. In particular, it predicts approximate Avrami curves with parameters depending on stopping power in qualitative accordance with experiment that turn into Poisson laws well above the threshold value

Ultra high frequency thin film saw devices

Durante los últimos años el flujo de datos en la transmisión que tiene lugar en los sistemas de comunicación ha aumentado considerablemente de forma que día a día se requieren más aplicaciones trabajando en un rango de frecuencias muy alto (3-30 GHz). Muchos de estos sistemas de comunicación incluyen dispositivos de onda acústica superficial (SAW) y por tanto se hace necesario el aumento de frecuencia a la que éstos trabajan. Pero este incremento de frecuencia de los dispositivos SAW no sólo es utilizado en los sistemas de comunicación, varios tipos de sensores, por ejemplo, aumentan su sensibilidad cuando la frecuencia a la que trabajan también lo hace. Tradicionalmente los dispositivos SAW se han fabricado sobre cuarzo, LiNbO3 y LiTaO3 principalmente. Sin embargo la principal limitación de estos materiales es su velocidad SAW. Además, debido a la alta temperatura a la que se depositan no pueden ser integrados en la tecnología de fabricación CMOS. El uso de la tecnología de capa delgada, en la que un material piezoeléctrico es depositado sobre un substrato, se está utilizando en las últimas décadas para incrementar la velocidad SAW de la estructura y poder obtener dispositivos trabajando en el rango de frecuencias requerido en la actualidad. Por otra parte, esta tecnología podría ser integrada en el proceso de fabricación CMOS. Durante esta tesis nos hemos centrado en la fabricación de dispositivos SAW trabajando a muy alta frecuencia. Para ello, utilizando la tecnología de capa delgada, hemos utilizado la estructura nitruro de aluminio (AlN) sobre diamante que permite conseguir velocidades SAW del sustrato que no se pueden alcanzar con otros materiales. El depósito de AlN se realizó mediante sputtering reactivo. Durante esta tesis se han realizado diferentes experimentos para optimizar dicho depósito de forma que se han obtenido los parámetros óptimos para los cuales se pueden obtener capas de AlN de alta calidad sobre cualquier tipo de sustrato. Además todo el proceso se realizó a baja temperatura para que el procesado de estos dispositivos pueda ser compatible con la tecnología CMOS. Una vez optimizada la estructura AlN/diamante, mediante litografía por haz de electrones se fabricaron resonadores SAW de tamaño nanométrico que sumado a la alta velocidad resultante de la combinación AlN/diamante nos ha permitido obtener dispositivos trabajando en el rango de 10-28 GHz con un alto factor de calidad y rechazo fuera de la banda. Estás frecuencias y prestaciones no han sido alcanzadas por el momento en resonadores de este tipo. Por otra parte, se han utilizado estos dispositivos para fabricar sensores de presión de alta sensibilidad. Estos dispositivos son afectados altamente por los cambios de temperatura. Se realizó también un exhaustivo estudio de cómo se comportan en temperatura estos resonadores, entre -250ºC y 250ºC (rango de temperaturas no estudiado hasta el momento) diferenciándose dos regiones una a muy baja temperatura en la que el dispositivo muestra un coeficiente de retraso en frecuencia (TCF) relativamente bajo y otra a partir de los -100ºC en la que el TCF es similar al observado en la bibliografía. Por tanto, durante esta tesis se ha optimizado el depósito de AlN sobre diamante para que sea compatible con la tecnología CMOS y permita el procesado de dispositivos trabajando a muy alta frecuencia con altas prestaciones para comunicaciones y sensores. ABSTRACT The increasing volume of information in data transmission systems results in a growing demand of applications working in the super-high-frequency band (3–30 GHz). Most of these systems work with surface acoustic wave (SAW) devices and thus there is a necessity of increasing their resonance frequency. Moreover, sensor application includes this kind of devices. The sensitivity of them is proportional with its frequency. Traditionally, quartz, LiNbO3 and LiTaO3 have been used in the fabrication of SAW devices. These materials suffer from a variety of limitations and in particular they have low SAW velocity as well as being incompatible with the CMOS technology. In order to overcome these problems, thin film technology, where a piezoelectric material is deposited on top of a substrate, has been used during the last decades. The piezoelectric/substrate structure allows to reach the frequencies required nowadays and could be compatible with the mass electronic production CMOS technology. This thesis work focuses on the fabrication of SAW devices working in the super-high-frequency range. Thin film technology has been used in order to get it, especially aluminum nitride (AlN) deposited by reactive sputtering on diamond has been used to increase the SAW velocity. Different experiments were carried out to optimize the parameters for the deposit of high quality AlN on any kind of substrates. In addition, the system was optimized under low temperature and thus this process is CMOS compatible. Once the AlN/diamond was optimized, thanks to the used e-beam lithography, nanometric SAW resonators were fabricated. The combination of the structure and the size of the devices allow the fabrication of devices working in the range of 10-28 GHz with a high quality factor and out of band rejection. These high performances and frequencies have not been reached so far for this kind of devices. Moreover, these devices have been used as high sensitivity pressure sensors. They are affected by temperature changes and thus a wide temperature range (-250ºC to 250ºC) study was done. From this study two regions were observed. At very low temperature, the temperature coefficient of frequency (TCF) is low. From -100ºC upwards the TCF is similar to the one appearing in the literature. Therefore, during this thesis work, the sputtering of AlN on diamond substrates was optimized for the CMOS compatible fabrication of high frequency and high performance SAW devices for communication and sensor application.

Fallo mecánico debido a grietas en Niobato de Litio bajo irradiación, simulación mediante elementos finitos

Ion-induced nano-track in LiNbO3. Motivation. From macro to nanoscale. Finite element method for nano-structured materials. Simulations of X-cut and Z-cut in LiNbO3. Experiments versus Simulations. Conclusions

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.

Optoelectronic tweezers under arbitrary illumination patterns: theoretical simulations and comparison to experiment

Photovoltaic tweezers are a promising tool to place and move particles on the surface of a photovoltaic material in a controlled way. To exploit this new technique it is necessary to accurately know the electric field created by a specific illumination on the surface of the crystal and above it. This paper describes a numerical algorithm to obtain this electric field generated by several relevant light patterns, and uses them to calculate the electrophoretic potential acting over neutral, polarizable particles in the proximity of the crystal. The results are compared to experiments carried out in LiNbO3 with good overall agreement.

Electro y dielectroforesis de nanopartículas por efecto fotovoltaico

El objetivo de esta tesis doctoral es la investigación del nuevo concepto de pinzas fotovoltaicas, es decir, del atrapamiento, ordenación y manipulación de partículas en las estructuras generadas en la superficie de materiales ferroeléctricos mediante campos fotovoltaicos o sus gradientes. Las pinzas fotovoltaicas son una herramienta prometedora para atrapar y mover las partículas en la superficie de un material fotovoltaico de una manera controlada. Para aprovechar esta nueva técnica es necesario conocer con precisión el campo eléctrico creado por una iluminación específica en la superficie del cristal y por encima de ella. Este objetivo se ha dividido en una serie de etapas que se describen a continuación. La primera etapa consistió en la modelización del campo fotovoltaico generado por iluminación no homogénea en substratos y guías de onda de acuerdo al modelo de un centro. En la segunda etapa se estudiaron los campos y fuerzas electroforéticas y dielectroforéticas que aparecen sobre la superficie de substratos iluminados inhomogéneamente. En la tercera etapa se estudiaron sus efectos sobre micropartículas y nanopartículas, en particular se estudió el atrapamiento superficial determinando las condiciones que permiten el aprovechamiento como pinzas fotovoltaicas. En la cuarta y última etapa se estudiaron las configuraciones más eficientes en cuanto a resolución espacial. Se trabajó con distintos patrones de iluminación inhomogénea, proponiéndose patrones de iluminación al equipo experimental. Para alcanzar estos objetivos se han desarrollado herramientas de cálculo con las cuales obtenemos temporalmente todas las magnitudes que intervienen en el problema. Con estas herramientas podemos abstraernos de los complicados mecanismos de atrapamiento y a partir de un patrón de luz obtener el atrapamiento. Todo el trabajo realizado se ha llevado a cabo en dos configuraciones del cristal, en corte X ( superficie de atrapamiento paralela al eje óptico) y corte Z ( superficie de atrapamiento perpendicular al eje óptico). Se ha profundizado en la interpretación de las diferencias en los resultados según la configuración del cristal. Todas las simulaciones y experimentos se han realizado utilizando como soporte un mismo material, el niobato de litio, LiNbO3, con el f n de facilitar la comparación de los resultados. Este hecho no ha supuesto una limitación en los resultados pues los modelos no se limitan a este material. Con respecto a la estructura del trabajo, este se divide en tres partes diferenciadas que son: la introducción (I), la modelización del atrapamiento electroforético y dielectroforético (II) y las simulaciones numéricas y comparación con experimentos (III). En la primera parte se fijan las bases sobre las que se sustentarán el resto de las partes. Se describen los efectos electromagnéticos y ópticos a los que se hará referencia en el resto de los capítulos, ya sea por ser necesarios para describir los experimentos o, en otros casos, para dejar constancia de la no aparición de estos efectos para el caso en que nos ocupa y justificar la simplificación que en muchos casos se hace del problema. En esta parte, se describe principalmente el atrapamiento electroforético y dielectroforético, el efecto fotovoltaico y las propiedades del niobato de litio por ser el material que utilizaremos en experimentos y simulaciones. Así mismo, como no debe faltar en ninguna investigación, se ha analizado el state of the art, revisando lo que otros científicos del campo en el que estamos trabajando han realizado y escrito con el fin de que nos sirva de cimiento a la investigación. Con el capítulo 3 finalizamos esta primera parte describiendo las técnicas experimentales que hoy en día se están utilizando en los laboratorios para realizar el atrapamiento de partículas mediante el efecto fotovoltaico, ya que obtendremos ligeras diferencias en los resultados según la técnica de atrapamiento que se utilice. En la parte I I , dedicada a la modelización del atrapamiento, empezaremos con el capítulo 4 donde modelizaremos el campo eléctrico interno de la muestra, para a continuación modelizar el campo eléctrico, los potenciales y las fuerzas externas a la muestra. En capítulo 5 presentaremos un modelo sencillo para comprender el problema que nos aborda, al que llamamos Modelo Estacionario de Separación de Carga. Este modelo da muy buenos resultados a pesar de su sencillez. Pasamos al capítulo 6 donde discretizaremos las ecuaciones que intervienen en la física interna de la muestra mediante el método de las diferencias finitas, desarrollando el Modelo de Distribución de Carga Espacial. Para terminar esta parte, en el capítulo 8 abordamos la programación de las modelizaciones presentadas en los anteriores capítulos con el fn de dotarnos de herramientas para realizar las simulaciones de una manera rápida. En la última parte, III, presentaremos los resultados de las simulaciones numéricas realizadas con las herramientas desarrolladas y comparemos sus resultados con los experimentales. Fácilmente podremos comparar los resultados en las dos configuraciones del cristal, en corte X y corte Z. Finalizaremos con un último capítulo dedicado a las conclusiones, donde resumiremos los resultados que se han ido obteniendo en cada apartado desarrollado y daremos una visión conjunta de la investigación realizada. ABSTRACT The aim of this thesis is the research of the new concept of photovoltaic or optoelectronic tweezers, i.e., trapping, management and manipulation of particles in structures generated by photovoltaic felds or gradients on the surface of ferroelectric materials. Photovoltaic tweezers are a promising tool to trap and move the particles on the surface of a photovoltaic material in a monitored way. To take advantage of this new technique is necessary to know accurately the electric field created by a specifc illumination in the crystal surface and above it. For this purpose, the work was divided into the stages described below. The first stage consisted of modeling the photovoltaic field generated by inhomogeneous illumination in substrates and waveguides according to the one-center model. In the second stage, electrophoretic and dielectrophoretic fields and forces appearing on the surface of substrates and waveguides illuminated inhomogeneously were studied. In the third stage, the study of its effects on microparticles and nanoparticles took place. In particular, the trapping surface was studied identifying the conditions that allow its use as photovoltaic tweezers. In the fourth and fnal stage the most efficient configurations in terms of spatial resolution were studied. Different patterns of inhomogeneous illumination were tested, proposing lightning patterns to the laboratory team. To achieve these objectives calculation tools were developed to get all magnitudes temporarily involved in the problem . With these tools, the complex mechanisms of trapping can be simplified, obtaining the trapping pattern from a light pattern. All research was carried out in two configurations of crystal; in X section (trapping surface parallel to the optical axis) and Z section (trapping surface perpendicular to the optical axis). The differences in the results depending on the configuration of the crystal were deeply studied. All simulations and experiments were made using the same material as support, lithium niobate, LiNbO3, to facilitate the comparison of results. This fact does not mean a limitation in the results since the models are not limited to this material. Regarding the structure of this work, it is divided into three clearly differentiated sections, namely: Introduction (I), Electrophoretic and Dielectrophoretic Capture Modeling (II) and Numerical Simulations and Comparison Experiments (III). The frst section sets the foundations on which the rest of the sections will be based on. Electromagnetic and optical effects that will be referred in the remaining chapters are described, either as being necessary to explain experiments or, in other cases, to note the non-appearance of these effects for the present case and justify the simplification of the problem that is made in many cases. This section mainly describes the electrophoretic and dielectrophoretic trapping, the photovoltaic effect and the properties of lithium niobate as the material to use in experiments and simulations. Likewise, as required in this kind of researches, the state of the art have been analyzed, reviewing what other scientists working in this field have made and written so that serve as a foundation for research. With chapter 3 the first section finalizes describing the experimental techniques that are currently being used in laboratories for trapping particles by the photovoltaic effect, because according to the trapping technique in use we will get slightly different results. The section I I , which is dedicated to the trapping modeling, begins with Chapter 4 where the internal electric field of the sample is modeled, to continue modeling the electric field, potential and forces that are external to the sample. Chapter 5 presents a simple model to understand the problem addressed by us, which is called Steady-State Charge Separation Model. This model gives very good results despite its simplicity. In chapter 6 the equations involved in the internal physics of the sample are discretized by the finite difference method, which is developed in the Spatial Charge Distribution Model. To end this section, chapter 8 is dedicated to program the models presented in the previous chapters in order to provide us with tools to perform simulations in a fast way. In the last section, III, the results of numerical simulations with the developed tools are presented and compared with the experimental results. We can easily compare outcomes in the two configurations of the crystal, in section X and section Z. The final chapter collects the conclusions, summarizing the results that were obtained in previous sections and giving an overview of the research.