Valence band offset of MgO/InN heterojunction measured by x-ray photoelectron spectroscopy

MgO may be a promising gate dielectric and surface passivation film for InN based devices and the valence band offset of MgO/InN heterojunction has been measured by x-ray photoelectron spectroscopy. The valence band offset is determined to be 1.59 +/- 0.23 eV. Given the experimental band gap of 7.83 for the MgO, a type-I heterojunction with a conduction band offset of 5.54 +/- 0.23 eV is found. The accurate determination of the valence and conduction band offsets is important for use of MgO/InN electronic devices. (c) 2008 American Institute of Physics.

Determination of MgO/AlN heterojunction band offsets by x-ray photoelectron spectroscopy

MgO is a promising gate dielectric and surface passivation film for GaN/AlGaN transistors, but little is known of the band offsets in the MgO/AlN system. X-ray photoelectron spectroscopy was used to measure the energy discontinuity in the valence band (Delta E-v) of MgO/AlN heterostructures. A value of Delta E-v=0.22 +/- 0.08 eV was obtained. Given the experimental band gap of 7.83 eV for MgO, a type-I heterojunction with a conduction band offset of similar to 1.45 eV is found. The accurate determination of the valence and conduction band offsets is important for use of III-N alloys based electronic devices.

Effects of different modified underlayer surfaces on growth and optical properties of InGaN quantum dots

InGaN/GaN quantum dots were grown on the sapphire (0 0 0 1) substrate in a metalorganic chemical vapor deposition system. The morphologies of QDs deposited on different modified underlayer (GaN) surfaces, including naturally as grown, Ga-mediated, In-mediated, and air-passivated ones, were investigated by atomic force microscopy (AFM). Photo luminescence (PL) method is used to evaluate optical properties. It is shown that InGaN QDs can form directly on the natural GaN layer. However, both the size and distribution show obvious inhomogeneities. Such a heavy fluctuation in size leads to double peaks for QDs with short growth time, and broad peaks for QDs with long growth time in their low-temperature PL spectra. QDs grown on the Ga-mediated GaN underlayer tends to coalesce. Distinct transform takes place from 3D to 2D growth on the In-mediated ones, and thus the formation of QDs is prohibited. Those results clarify Ga and In's surfactant behavior. When the GaN underlayer is passivated in the air, and together with an additional low-temperature-grown seeding layer, however, the island growth mode is enhanced. Subsequently, grown InGaN QDs are characterized by a relatively high density and an improved Gaussian-like distribution in size. Short surface diffusion length at low growth temperature accounts for that result. It is concluded that reduced temperature favors QD's 3D growth and surface passivation can provide another promising way to obtain high-density QDs that especially suits MOCVD system. (c) 2004 Elsevier Ltd. All rights reserved.

Luminescence properties of multi-layer InGaN quantum dots grown on C- and R-plane sapphire substrates

In this study, we report comparative luminescence properties of multi-layer InGaN quantum dots grown on C- and R-plane sapphire substrates by metal organic chemical vapor deposition (MOCVD). High-density InGaN quantum dots (QDs) are formed on GaN templates by decreasing the growth temperature and increasing the adatom hopping-barrier through surface passivation. Atomic force microscopy (AFM) has been employed to estimate the size and height of these dots. Photoluminescence (PL) spectra recorded from (1120) InGaN QDs/(1102) sapphire show much stronger emission intensity compared to spectra recorded from (0001) InGaN QDs/(0001) sapphire. Due to the absence of strong spontaneous polarization and piezoelectric field, such (1150) InGaN QDs in the active layers would lead to high efficiency light emitting devices. (c) 2005 Elsevier B.V. All rights reserved.

Growth and characterization of 0.8-mu m gate length AlGaN/GaN HEMTs on sapphire substrates

AlGaN/GaN high electron mobility transistor (HEMT) structures were grown on 2 inch sapphire substrates by MOCVD, and 0.8-mu m gate length devices were fabricated and measured. It is shown by resistance mapping that the HEMT structures have an average sheet resistance of approximately 380 Omega/sq with a uniformity of more than 96%. The 1-mm gate width devices using the materials yielded a pulsed drain current of 784 mA/mm at V-gs=0.5 V and V-ds=7 V with an extrinsic transconductance of 200 mS/mm. A 20-GHz unity current gain cutoff frequency (f(T)) and a 28-GHz maximum oscillation frequency (f(max)) were obtained. The device with a 0.6-mm gate width yielded a total output power of 2.0 W/mm (power density of 3.33 W/mm) with 41% power added efficiency (PAE) at 4 GHz.

The structure and current-voltage characteristics of multi-sheet InGaN quantum dots grown by a new multi-step method

Multi-sheet InGaN/GaN quantum dots (QDs) were grown successfully by surface passivation processing and low-temperature growth in metalorganic chemical vapor deposition. This method based on the principle of increasing the energy barrier of adatom hopping by surface passivation and low-temperature growth, is quite different from present methods. The InGaN quantum dots in the first layer of about 40-nm-wide and 15-nm-high grown by this method were revealed by atomic force microscopy. The InGaN QDs in upper layer grew bigger. To our knowledge, the current-voltage characteristics of multi-sheet InGaN/GaN QDs were measured for the fist time. Two kinds of resonance-tunneling-current features were observed which were attributed to the low-dimensional localization effect. Some current peaks only appeared in positive voltage for sample due to the non-uniformity of the QDs in the structure. (C) 2002 Elsevier Science B.V. All rights reserved.

A new method to fabricate InGaN quantum dots by metalorganic chemical vapor deposition

A new method to form nanoscale InGaN quantum dots using MOCVD is reported, This method is much different from a method. which uses surfactant or the Stranski-Krastannow growth mode. The dots were formed by increasing the energy barrier for adatoms, which are hopping by surface passivation, and by decreasing the growth temperature. Thus, the new method can be called as a passivation-low-temperature method. Regular high-temperature GaN films were grown first and were passivated. A low-temperature thin layer of GaN dot was then deposited on the surface that acted as the adjusting layer. At last the high-density InGaN dots could be fabricated on the adjusting layer. Atomic force microscopy measurement revealed that InGaN dots were small enough to expect zero-dimensional quantum effects: The islands were typically 80 nm wide and 5 nm high. Their density was about 6 x 10(10) cm(-2). Strong photoluminescence emission from the dots is observed at room temperature, which is much stronger than that of the homogeneous InGaN film with the same growth time. Furthermore, the PL emission of the GaN adjusting layer shows 21 meV blueshift compared with the band edge emission of the GaN due to quantum confine effect. (C) 2002 Elsevier Science B.V. All rights reserved.

Plasma induced damage in GaN-based light emitting diodes - art. no. 68410X

The effects of plasma induced damage in different conditions of ICP and PECVD processes on LEDs were presented. For ICP mesa etch, in an effort to confirm the effects of dry etch damage on the optical properties of p-type GaN, a photoluminescence (PL) measurement was investigated with different rf chuck power. It was founded the PL intensity of the peak decreased with increasing DC bias and the intensity of sample etched at a higher DC bias of -400V is less by two orders of magnitude than that of the as-grown sample. Meanwhile, In the IN curve for the etched samples with different DC biases, the reverse leakage current of higher DC bias sample was obviously degraded than the lower one. In addition, plasma induced damage was also inevitable during the deposition of etch masks and surface passivation films by PECVD. The PL intensity of samples deposited with different powers sharply decreased when the power was excessive. The PL spectra of samples deposited under the fixed condition with the different processing time were measured, indicating the intensity of sample deposited with a lower power did not obviously vary after a long time deposition. A two-layer film was made in order to improve the compactness of sparse dielectric film deposited with a lower power.

Photostimulated luminescence of BaFBr:Eu2+ phosphors

After x-irradiation for 10 s, luminescence from BaFBr:Eu2+ phosphors by photostimulation of longer wavelength than F absorption bands was observed and assigned to the surface states or intrinsic defects of the powders. It is found that the luminescence by photostimulation into F bands can be reduced via electron migration from F centers into the surface states or intrinsic defects, thus reducing the x-ray storage or image stability. Surface passivation can lower these defects and improve the phosphors or imaging plate quality. (C) 1996 American Institute of Physics.

LUMINESCENCE-CENTERS IN POROUS SILICON

Photoluminescence studies on porous silicon show that there are luminescence centers present in the surface states. By taking photoluminescence spectra of porous silicon with respect to temperature, a distinct peak can be observed in the temperature range 100-150 K. Both linear and nonlinear relationships were observed between excitation laser power and the photoluminescence intensity within this temperature range. In addition, there was a tendency for the photoluminescence peak to red shift at low temperature as well as at low excitation power. This is interpreted as indicating that the lower energy transition becomes dominant at low temperature and excitation power. The presence of these luminescence centers can be explained in terms of porous silicon as a mixture of silicon clusters and wires in which quantum confinement along with surface passivation would cause a mixing of Gamma and X band structure between the surface states and the bulk. This mixing would allow the formation of luminescence centers.

Real-time PCR microfluidic devices with concurrent electrochemical detection

Electrochemistry-based detection methods hold great potential towards development of hand-held nucleic-acid analyses instruments. In this work, we demonstrate the implementation of in situ electrochemical (EC) detection method in a microfluidic flow-through EC-qPCR (FTEC-qPCR) device, where both the amplification of the target nucleic-acid sequence and subsequent EC detection of the PCR amplicon are realized simultaneously at selected PCR cycles in the same device. The FTEC-qPCR device utilizes methylene blue (MB), an electroactive DNA intercalator, for electrochemical signal measurements in the presence of PCR reagent components. Our EC detection method is advantageous, when compared to other existing EC methods for PCR amplicon analysis, since FTEC-qPCR does not require probe-modified electrodes, or asymmetric PCR, or solid-phase PCR. Key technical issues related to surface passivation, electrochemical measurement, PCR inhibition by metal electrode, bubble-free PCR, were investigated. By controlling the concentration of MB and the exposure of PCR mixture to the bare metal electrode, we successfully demonstrated electrochemical measurement of MB in solution-phase, symmetric PCR by amplifying a fragment of lambda phage DNA.

Photoelectrocatalysis: Principles, nanoemitter applications and routes to bio-inspired systems

An overview on processes that are relevant in light-induced fuel generation, such as water photoelectrolysis or carbon dioxide reduction, is given. Considered processes encompass the photophysics of light absorption, excitation energy transfer to catalytically active sites and interfacial reactions at the catalyst/solution phase boundary. The two major routes envisaged for realization of photoelectrocatalytic systems, e.g. bio-inspired single photon catalysis and multiple photon inorganic or hybrid tandem cells, are outlined. For development of efficient tandem cell structures that are based on non-oxidic semiconductors, stabilization strategies are presented. Physical surface passivation is described using the recently introduced nanoemitter concept which is also applicable in photovoltaic (solid state or electrochemical) solar cells and first results with p-Si and p-InP thin films are presented. Solar-to-hydrogen efficiencies reach 12.1% for homoepitaxial InP thin films covered with Rh nanoislands. In the pursuit to develop biologically inspired systems, enzyme adsorption onto electrochemically nanostructured silicon surfaces is presented and tapping mode atomic force microscopy images of heterodimeric enzymes are shown. An outlook towards future envisaged systems is given. © 2010 The Royal Society of Chemistry.

Probing the functionalization of gold surfaces and protein adsorption by PM-IRRAS

The control of morphology and coating of metal surfaces is essential for a number of organic electronic devices including photovoltaic cells and sensors. In this study, we monitor the functionalization of gold surfaces with 11-mercaptoundecanoic acid (MUA, HS(CH(2))(10)CO(2)H) and cysteamine, aiming at passivating the surfaces for application in surface plasmon resonance (SPR) biosensors. Using polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS), cyclic voltammetry, atomic force microscopy and quartz crystal microbalance, we observed a time-dependent organization process of the adsorbed MUA monolayer with alkyl chains perpendicular to the gold surface. Such optimized condition for surface passivation was obtained with a systematic search for experimental parameters leading to the lowest electrochemical signal of the functionalized gold electrode. The ability to build supramolecular architectures was also confirmed by detecting with PM-IRRAS the adsorption of streptavidin on the MUA-functionalized gold. As the approaches used for surface functionalization and its verification with PM-IRRAS are generic, one may now envisage monitoring the fabrication of tailored electrodes for a variety of applications.

Field dependent transition to the non-linear regime in magnetic hyperthermia experiments: Comparison between maghemite, copper, zinc, nickel and cobalt ferrite nanoparticles of similar sizes

Further advances in magnetic hyperthermia might be limited by biological constraints, such as using sufficiently low frequencies and low field amplitudes to inhibit harmful eddy currents inside the patient's body. These incite the need to optimize the heating efficiency of the nanoparticles, referred to as the specific absorption rate (SAR). Among the several properties currently under research, one of particular importance is the transition from the linear to the non-linear regime that takes place as the field amplitude is increased, an aspect where the magnetic anisotropy is expected to play a fundamental role. In this paper we investigate the heating properties of cobalt ferrite and maghemite nanoparticles under the influence of a 500 kHz sinusoidal magnetic field with varying amplitude, up to 134 Oe. The particles were characterized by TEM, XRD, FMR and VSM, from which most relevant morphological, structural and magnetic properties were inferred. Both materials have similar size distributions and saturation magnetization, but strikingly different magnetic anisotropies. From magnetic hyperthermia experiments we found that, while at low fields maghemite is the best nanomaterial for hyperthermia applications, above a critical field, close to the transition from the linear to the non-linear regime, cobalt ferrite becomes more efficient. The results were also analyzed with respect to the energy conversion efficiency and compared with dynamic hysteresis simulations. Additional analysis with nickel, zinc and copper-ferrite nanoparticles of similar sizes confirmed the importance of the magnetic anisotropy and the damping factor. Further, the analysis of the characterization parameters suggested core-shell nanostructures, probably due to a surface passivation process during the nanoparticle synthesis. Finally, we discussed the effect of particle-particle interactions and its consequences, in particular regarding discrepancies between estimated parameters and expected theoretical predictions. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. [http://dx.doi. org/10.1063/1.4739533]

MOVPE growth of III-V semiconductors on silicon for third generation solar cells

Esta Tesis trata sobre el desarrollo y crecimiento -mediante tecnología MOVPE (del inglés: MetalOrganic Vapor Phase Epitaxy)- de células solares híbridas de semiconductores III-V sobre substratos de silicio. Esta integración pretende ofrecer una alternativa a las células actuales de III-V, que, si bien ostentan el récord de eficiencia en dispositivos fotovoltaicos, su coste es, a día de hoy, demasiado elevado para ser económicamente competitivo frente a las células convencionales de silicio. De este modo, este proyecto trata de conjugar el potencial de alta eficiencia ya demostrado por los semiconductores III-V en arquitecturas de células fotovoltaicas multiunión con el bajo coste, la disponibilidad y la abundancia del silicio. La integración de semiconductores III-V sobre substratos de silicio puede afrontarse a través de diferentes aproximaciones. En esta Tesis se ha optado por el desarrollo de células solares metamórficas de doble unión de GaAsP/Si. Mediante esta técnica, la transición entre los parámetros de red de ambos materiales se consigue por medio de la formación de defectos cristalográficos (mayoritariamente dislocaciones). La idea es confinar estos defectos durante el crecimiento de sucesivas capas graduales en composición para que la superficie final tenga, por un lado, una buena calidad estructural, y por otro, un parámetro de red adecuado. Numerosos grupos de investigación han dirigido sus esfuerzos en los últimos años en desarrollar una estructura similar a la que aquí proponemos. La mayoría de éstos se han centrado en entender los retos asociados al crecimiento de materiales III-V, con el fin de conseguir un material de alta calidad cristalográfica. Sin embargo, prácticamente ninguno de estos grupos ha prestado especial atención al desarrollo y optimización de la célula inferior de silicio, cuyo papel va a ser de gran relevancia en el funcionamiento de la célula completa. De esta forma, y con el fin de completar el trabajo hecho hasta el momento en el desarrollo de células de III-V sobre silicio, la presente Tesis se centra, fundamentalmente, en el diseño y optimización de la célula inferior de silicio, para extraer su máximo potencial. Este trabajo se ha estructurado en seis capítulos, ordenados de acuerdo al desarrollo natural de la célula inferior. Tras un capítulo de introducción al crecimiento de semiconductores III-V sobre Si, en el que se describen las diferentes alternativas para su integración; nos ocupamos de la parte experimental, comenzando con una extensa descripción y caracterización de los substratos de silicio. De este modo, en el Capítulo 2 se analizan con exhaustividad los diferentes tratamientos (tanto químicos como térmicos) que deben seguir éstos para garantizar una superficie óptima sobre la que crecer epitaxialmente el resto de la estructura. Ya centrados en el diseño de la célula inferior, el Capítulo 3 aborda la formación de la unión p-n. En primer lugar se analiza qué configuración de emisor (en términos de dopaje y espesor) es la más adecuada para sacar el máximo rendimiento de la célula inferior. En este primer estudio se compara entre las diferentes alternativas existentes para la creación del emisor, evaluando las ventajas e inconvenientes que cada aproximación ofrece frente al resto. Tras ello, se presenta un modelo teórico capaz de simular el proceso de difusión de fosforo en silicio en un entorno MOVPE por medio del software Silvaco. Mediante este modelo teórico podemos determinar qué condiciones experimentales son necesarias para conseguir un emisor con el diseño seleccionado. Finalmente, estos modelos serán validados y constatados experimentalmente mediante la caracterización por técnicas analíticas (i.e. ECV o SIMS) de uniones p-n con emisores difundidos. Uno de los principales problemas asociados a la formación del emisor por difusión de fósforo, es la degradación superficial del substrato como consecuencia de su exposición a grandes concentraciones de fosfina (fuente de fósforo). En efecto, la rugosidad del silicio debe ser minuciosamente controlada, puesto que éste servirá de base para el posterior crecimiento epitaxial y por tanto debe presentar una superficie prístina para evitar una degradación morfológica y cristalográfica de las capas superiores. En este sentido, el Capítulo 4 incluye un análisis exhaustivo sobre la degradación morfológica de los substratos de silicio durante la formación del emisor. Además, se proponen diferentes alternativas para la recuperación de la superficie con el fin de conseguir rugosidades sub-nanométricas, que no comprometan la calidad del crecimiento epitaxial. Finalmente, a través de desarrollos teóricos, se establecerá una correlación entre la degradación morfológica (observada experimentalmente) con el perfil de difusión del fósforo en el silicio y por tanto, con las características del emisor. Una vez concluida la formación de la unión p-n propiamente dicha, se abordan los problemas relacionados con el crecimiento de la capa de nucleación de GaP. Por un lado, esta capa será la encargada de pasivar la subcélula de silicio, por lo que su crecimiento debe ser regular y homogéneo para que la superficie de silicio quede totalmente pasivada, de tal forma que la velocidad de recombinación superficial en la interfaz GaP/Si sea mínima. Por otro lado, su crecimiento debe ser tal que minimice la aparición de los defectos típicos de una heteroepitaxia de una capa polar sobre un substrato no polar -denominados dominios de antifase-. En el Capítulo 5 se exploran diferentes rutinas de nucleación, dentro del gran abanico de posibilidades existentes, para conseguir una capa de GaP con una buena calidad morfológica y estructural, que será analizada mediante diversas técnicas de caracterización microscópicas. La última parte de esta Tesis está dedicada al estudio de las propiedades fotovoltaicas de la célula inferior. En ella se analiza la evolución de los tiempos de vida de portadores minoritarios de la base durante dos etapas claves en el desarrollo de la estructura Ill-V/Si: la formación de la célula inferior y el crecimiento de las capas III-V. Este estudio se ha llevado a cabo en colaboración con la Universidad de Ohio, que cuentan con una gran experiencia en el crecimiento de materiales III-V sobre silicio. Esta tesis concluye destacando las conclusiones globales del trabajo realizado y proponiendo diversas líneas de trabajo a emprender en el futuro. ABSTRACT This thesis pursues the development and growth of hybrid solar cells -through Metal Organic Vapor Phase Epitaxy (MOVPE)- formed by III-V semiconductors on silicon substrates. This integration aims to provide an alternative to current III-V cells, which, despite hold the efficiency record for photovoltaic devices, their cost is, today, too high to be economically competitive to conventional silicon cells. Accordingly, the target of this project is to link the already demonstrated efficiency potential of III-V semiconductor multijunction solar cell architectures with the low cost and unconstrained availability of silicon substrates. Within the existing alternatives for the integration of III-V semiconductors on silicon substrates, this thesis is based on the metamorphic approach for the development of GaAsP/Si dual-junction solar cells. In this approach, the accommodation of the lattice mismatch is handle through the appearance of crystallographic defects (namely dislocations), which will be confined through the incorporation of a graded buffer layer. The resulting surface will have, on the one hand a good structural quality; and on the other hand the desired lattice parameter. Different research groups have been working in the last years in a structure similar to the one here described, being most of their efforts directed towards the optimization of the heteroepitaxial growth of III-V compounds on Si, with the primary goal of minimizing the appearance of crystal defects. However, none of these groups has paid much attention to the development and optimization of the bottom silicon cell, which, indeed, will play an important role on the overall solar cell performance. In this respect, the idea of this thesis is to complete the work done so far in this field by focusing on the design and optimization of the bottom silicon cell, to harness its efficiency. This work is divided into six chapters, organized according to the natural progress of the bottom cell development. After a brief introduction to the growth of III-V semiconductors on Si substrates, pointing out the different alternatives for their integration; we move to the experimental part, which is initiated by an extensive description and characterization of silicon substrates -the base of the III-V structure-. In this chapter, a comprehensive analysis of the different treatments (chemical and thermal) required for preparing silicon surfaces for subsequent epitaxial growth is presented. Next step on the development of the bottom cell is the formation of the p-n junction itself, which is faced in Chapter 3. Firstly, the optimization of the emitter configuration (in terms of doping and thickness) is handling by analytic models. This study includes a comparison between the different alternatives for the emitter formation, evaluating the advantages and disadvantages of each approach. After the theoretical design of the emitter, it is defined (through the modeling of the P-in-Si diffusion process) a practical parameter space for the experimental implementation of this emitter configuration. The characterization of these emitters through different analytical tools (i.e. ECV or SIMS) will validate and provide experimental support for the theoretical models. A side effect of the formation of the emitter by P diffusion is the roughening of the Si surface. Accordingly, once the p-n junction is formed, it is necessary to ensure that the Si surface is smooth enough and clean for subsequent phases. Indeed, the roughness of the Si must be carefully controlled since it will be the basis for the epitaxial growth. Accordingly, after quantifying (experimentally and by theoretical models) the impact of the phosphorus on the silicon surface morphology, different alternatives for the recovery of the surface are proposed in order to achieve a sub-nanometer roughness which does not endanger the quality of the incoming III-V layers. Moving a step further in the development of the Ill-V/Si structure implies to address the challenges associated to the GaP on Si nucleation. On the one hand, this layer will provide surface passivation to the emitter. In this sense, the growth of the III-V layer must be homogeneous and continuous so the Si emitter gets fully passivated, providing a minimal surface recombination velocity at the interface. On the other hand, the growth should be such that the appearance of typical defects related to the growth of a polar layer on a non-polar substrate is minimized. Chapter 5 includes an exhaustive study of the GaP on Si nucleation process, exploring different nucleation routines for achieving a high morphological and structural quality, which will be characterized by means of different microscopy techniques. Finally, an extensive study of the photovoltaic properties of the bottom cell and its evolution during key phases in the fabrication of a MOCVD-grown III-V-on-Si epitaxial structure (i.e. the formation of the bottom cell; and the growth of III-V layers) will be presented in the last part of this thesis. This study was conducted in collaboration with The Ohio State University, who has extensive experience in the growth of III-V materials on silicon. This thesis concludes by highlighting the overall conclusions of the presented work and proposing different lines of work to be undertaken in the future.