430 resultados para HETEROSTRUCTURES


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In the work, the results of an investigation of GaInP/GaInAs/Ge MJ SCs intended for converting concentrated solar radiation, when operating at low temperatures (down to -190 degrees C) are presented. A kink of the cell I-V characteristic has been observed in the region close to V-oc starting from -20 degrees C at operation under concentrated sunlight. The causes for its occurrence have been analyzed and the reasons for formation of a built-in potential barrier for majority charge carriers at the n-GaInP/n-Ge isotype hetero-interface are discussed. The effect of charge carrier transport in n-GaInP/n-p Ge heterostructures on MJ SC output characteristics at low temperatures has been studied including EL technique.

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GaN based high electron mobility transistors have draw great attention due to its potential in high temperature, high power and high frequency applications [1, 2]. However, significant gate leakage current is still one of the issues which need to be solved to improve the performance and reliability of the devices [3]. Several research groups have contributed to solve this problem by using metal–oxide–semiconductor HEMTs (MOSHEMTs), with a thin dielectric layer, such as SiO2 [4], Al2O3 [5], HfO2 [6] and Gd2O3 [7] between the gate and the barrier layer on AlGaN/GaN heterostructures. Gd2O3 has shown low interfacial density of states(Dit) with GaN and a high dielectric constant and low electrical leakage currents [8], thus is considered as a promising candidate for the gate dielectrics on GaN. MOS-HEMTs using Gd2O3 grown by electron-beam heating [7] or molecular beam epitaxy (MBE) [8] on GaN or AlGan/GaN structure have been investigated, but further research is still needed in Gd2O3 based AlGaN/GaN MOSHEMTs.

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En la presente tesis doctoral se ha realizado un estudio utilizando diferentes técnicas de crecimiento (RPE-MOCVD y spray pyrolysis) y estructuras (nanohilos, pozos y puntos cuánticos y capas) con el objetivo de desarrollar dispositivos que cubran desde el rango visible hasta el ultravioleta. Es por esta razón por la que se han elegido materiales basados en ZnO, debido a la posibilidades que estos ofrecen para variar su bandgap en un amplio rango de energías. Prueba de ello es que en este estudio se ha conseguido cubrir un rango espectral desde 1.86 hasta 4.11 eV, estudiandose además fenómenos físicos como son la difusión e incorporaci ón de la aleación o la adsorción de gases en la super_cie, lo que ha permitido la fabricación de diferentes fotodetectores de gran sensibilidad. Por todo ello, los resultados obtenidos en esta tesis suponen una gran contribución al conocimiento de las propiedades físicas de las aleaciones de Zn(Cd)O y Zn(Mg)O para potenciales aplicaciónes en dispositivos que operen en el rango visible y ultravioleta del espectro, respectivamente. En esta memoria se da en primer lugar una visión de las propiedades de materiales basados en ZnO, entrando en detalle en una de las ventajas que este presenta, la facilidad que tiene este material para formar nanoestructuras. En el capítulo 3 se dan los conceptos teóricos necesarios para comprender las propiedades ópticas de este tipo de materiales, mostrando también los resultados más reseñables obtenidos en ZnO. En los capítulos referentes a los resultados se pueden diferenciar dos grandes bloques. En el primer bloque de resultados se han analizado nanohilos y pozos cuánticos de Zn(Cd)O crecidos por la técnica de RPE-MOCVD (Capítulos 4 y 5). En el segundo se expondrá el estudio realizado sobre capas y puntos cuánticos de Zn(Mg)O crecidos por la técnica spray pyrolysis como se describe en mayor detalle a continuación. Nanohilos y pozos cuánticos de Zn(Cd)O crecidos por RPE-MOCVD Teóricamente aleando el ZnO con CdO es posible disminuir el valor del band- gap desde 3.37 eV hasta 0.95 eV, cubriendo por completo el espectro visible. El desarrollo del ternario Zn(Cd)O permitiría la fabricación de heteroestructuras y pozos cuánticos, muy importantes en el desarrollo de dispositivos optoelectrónicos que cubran la parte visible del espectro. Sin embargo, la diferencia de estructura cristalina entre estos dos materiales junto a la baja solubilidad del Cd y su alta presión de vapor, di_culta la obtención de material de alta calidad cristalina con alto contenido en Cd. En esta tesis doctoral se ha realizado una completa caracterización óptica y estructural de nanohilos de Zn(Cd)O credidos por la técnica de RPE-MOCVD. Estos nanohilos tinene unas longitudes comprendidas entre 1 y 3 _m y diámetros entre 100 y 200 nm. La concentración máxima introducida de Cd en estas estructuras ha sido de hasta un 54% manteniendo la estructura wurtzita del ZnO, siendo este el mayor contenido de Cd introducido hasta la fecha en nanostructuras basada en ZnO. Este hecho se traduce en una variación de la energía de emisión entre 3.31 y 1.86 eV con el aumento en Cd. El uso de diferentes técnicas de alta resoluci ón de caracterización estructural ha permitido demostrar la presencia de una sola fase estructural wurtzita sin observarse ningún indicio de separación de fases ni acumulación de Cd a lo largo del nanohilo para todos los contenidos de Cd. Con el propósito de fabricar dispositivos en nanohilos individuales, parte de esta tesis doctoral ha estado dedicada a estudiar el impacto que el recocido térmico tiene en las propiedades ópticas y eléctricas de nanohilos de Zn(Cd)O. El recocido térmico es un proceso clave en la optimización de dispositivos, ya sea para la obtenci ón de contactos óhmicos, reducción de defectos o difusión de dopantes por ejemplo. En este estudio se ha observado una mejora muy signi_cativa de las propiedades de emisión de los nanohilos cuando estos eran recocidos a temperaturas mayores que la de crecimiento (300 oC). En las muestras con Cd se ha observado además que el recocido también produce un desplazamiento de la emisión hacia mayores energías debido a una reducción homogénea del contenido de Cd. Medidas de fotoluminiscencia con resolución temporal muestran el impacto que tiene la localización del excitón en las _uctuaciones de potencial, debidas a una distribución estadística del Cd, en la dinámica de los portadores. Comparando el tiempo de vida de los portadores entre los nanohilos recocidos y sin recocer se ha observado un aumento de este parámetro en las estructuras recocidas. Este aumento es fundamentalmente debido a una reducción de centros de recombinación no radiativa asociados a defectos presentes a lo largo del nanohilo. Además, se ha estudiado la evolución de los tiempos de vida de los portadores en función de la temperatura, registrándose una menor estabilidad con la temperatura de los tiempos de vida en las muestras recocidas. Este resultado sugiere que el recocido térmico consigue reducir parte del desorden de la aleación en la estructura. Tras haber caracterizados los nanohilos se desarrollaron una serie de procesa dos para la fabricación de dispositivos basados en nanohilos individuales. Se fabricaron en concreto fotodetectores sensibles al UV, en los que se observó también la alta sensibilidad que muestran a la adsorción de gases en la super_cie, incrementada por la gran relación super_cie/volúmen característica de las nanoestructuras. Estos procesos de adsorción observados tienen un impacto directo sobre las propiedades ópticas y electricas de los dispositivos como se ha demostrado. Por ello que en esta tesis se hayan estudiado en detalle este tipo de procesos, ideando maneras para tener un mayor control sobre ellos. Finalmente se crecieron estructuras de pozos cuántico de ZnCdO/ZnO en nanohilos con contenidos de Cd nominales de 54 %. Las medidas ópticas realizadas mostraron como al aumentar la anchura del pozo de 0.7 a 10 nm, la emisión relacionada con el pozo se desplazaba entre 3.30 y 1.97 eV. Este gran desplazamiento representa el mayor obtenido hasta la fecha en pozos cuánticos de ZnCdO/ZnO. Sin embargo, al caracterizar estructuralmente estas muestras se observó la presencia de procesos de difusión de Cd entre el pozo y la barrera. Como se ha podido medir, este tipo de procesos reducen sustancialmente la concentración de Cd en el pozo al difundirse parte a la barrera. cambiando completamente la estructura de bandas nominal de estas estructuras. Este estudio demuestra la importancia del impacto de los procesos de difusión en la interpretación de los efectos de con_namiento cuántico para este tipo de estructuras. Capas y puntos cuánticos de Zn(Mg)O crecidos por spray pyrolysis La técnica de spray pyrolysis, debido a su simplicidad, bajo coste y capacidad de crecer sobre grandes áreas conservando una alta calidad cristalina presenta un gran interés en la comunidad cientí_ca para el potencial desarrollo de dispositivos comerciales. En esta tesis se ha estudiado las propiedades ópticas y eléctricas de capas y puntos cuánticos de Zn(Mg)O crecidos por esta técnica. Al contrario que pasa con el Cd, al introducir Mg en la estructura wurtzita de ZnO se consigue aumentar el bandgap del semiconductor. Sin embargo, al igual que pasa con el CdO, la diferencia de estructura cristalina entre el ZnO y el MgO limita la cantidad de Mg que se puede incorporar, haciendo que para una cierta concentración de Mg aparezcan el fenómeno de separación de fases. En esta tesis se ha conseguido incorporar hasta un contenido de Mg del 35% en la estructura wurtzita del ZnO utilizando la técnica de spray pyrolysis, resultado que representa la mayor concentración de Mg publicada hasta la fecha. Este hecho ha posibilitado variar la energía del borde de absorción desde 3.30 a 4.11 eV. En estas capas se ha realizado una completa caracterización óptica observándose una diferencia entre las energías del borde de absorción y del máximo de emisión creciente con el contenido en Mg. Esta diferencia, conocida como desplazamiento de Stokes, es debida en parte a la presencia de _uctuaciones de potencial producidas por un desorden estadístico de la aleación. Se han fabricado fotodetectores MSM de alta calidad utilizando las capas de Zn(Mg)O previamente caracterizadas, observándose un desplazamiento del borde de absorción con el aumento en Mg desde 3.32 a 4.02 eV. Estos dispositivos muestran altos valores de responsividad (10-103 A/W) y altos contrastes entre la responsividad bajo iluminación y oscuridad (10-107). Estos resultados son en parte debidos a la presencia de mecanismos de ganancia y una reducción de la corriente de oscuridad en las muestras con alto contenido de Mg. Utilizando esta misma técnica de crecimiento se han crecido puntos de Zn(Mg)O con concentraciones nominales de Mg entre 0 y 100 %, con dimensiones medias entre 4 y 6 nm. Las medidas estructurales realizadas muestran que hasta un valor de Mg de 45 %, los puntos están compuestos por una única fase estructural, wurtzita. A partir de esa concentración de Mg aparece una fase cúbica en los puntos, coexistiendo con la fase hexagonal hasta una concentración nominales del 85 %. Para concentraciones mayores de Mg, los puntos muestran una única fase estructural cúbica. Medidas de absorción realizadas en estos puntos de Zn(Mg)O muestran un desplazamiento del borde de absorción entre 3.33 y 3.55 eV cuando la concentraci ón de Mg en los puntos aumenta hasta el 40 %. Este desplazamiento observado es debido solamente a la fase wurtzita del Zn(Mg)O donde se incorpora el Mg. ABSTRACT This PhD theis presents a study using di_erent growth techniques (RPEMOCVD and spray pyrolysis) and structures (nanowires, quantum dots and wells and layers) in order to develop devices that extend from the visible to the ultraviolet range. For this reason ZnO based materials have been choosen, because they o_er the possibility to tunne the bandgap in this energy range. Proof of this is that this study has managed to cover a spectral range from 1.86 to 4.11 eV, also being studied physical phenomena such as di_usion and incorporation of alloy or adsorption of gases on the surface, allowing the develop di_erent highly sensitive photodetectors. Therefore, the results obtained in this thesis are a great contribution two large blockso the knowledge of the physical properties of alloys Zn(Cd)O and Zn(Mg)O for potential applications in devices that operate in the visible and ultraviolet range, respectively. In the _rst chapter, the general properties of ZnO-based materials are presented, showing the facilities that these kind of materials o_er to obtain di_erent nanoestructures. In Chapter 3, optical theoretical concepts are given to understand the optical properties of these materials, also showing the most signi_cant results of ZnO. In the chapters related with the results, two blocks could be distinguish. In the _rst one, Zn(Cd)O nanowires and quantum wells grown by RPE-MOCVD have been analyzed (Chapters 4 and 5). The second block of results shows the study performed in Zn(Mg)O _lms and quantum dots grown by spray pyrolysis. Zn(Cd)O nanowires and quantum wells grown by RPE-MOCVD In summary, the results of the PhD thesis are a great contribution to the knowledge of the physical properties of Zn(Cd)O and Zn(Mg)O alloys and their application for high performance devices operating in the visible and UV ranges, respectively. The performance of the device is still limited due to alloy solubility and p-doping stability, which opens a door for future research in this _eld. Theoretically, annealing ZnO with CdO allows to reduce the bandgap from 3.37 to 0.95 eV, covering the whole visible spectrum. The development of ZnCdO alloys allows the fabrication of heterostructures and quantum wells, necessary for the development of high performance optoelectronic devices. However, the di_erent crystal structures between CdO and ZnO and the low solubility of Cd and its high vapor pressure, hinders the growth of ZnCdO alloys with high Cd contents. In this PhD thesis Zn(Cd)O nanowires have been optically and structurally characterized, obtaining a maximum Cd content of 54% while maintaining their wurtzite structure. This Cd content, which allows lowering the bandgap down to 1.86 eV, is the highest concentration ever reported in nanostructures based on ZnO. The combination of optical and structural characterization techniques used during this thesis has allowed the demonstration of the presence of a single wurtzite structure, without observing any indication of phase separation or Cd accumulation along the nanowire. Annealing processes are essential in the fabrication of optoelectronic devices. For this reason, a complete study of the annealing e_ects in the optical and electrical properties of Zn(Cd)O nanowires has been performed. In the _rst place, annealing nanowires at higher temperatures than their growth temperature (300 oC) allows a signi_cant improvement of their emission properties. However, in the samples that contain Cd a shift in the emission towards higher energies has been observed due to a homogeneous reduction of the Cd content in the nanowires. Time resolved photoluminescence measurements show the impact of the exciton localization in the potential _uctuations due to a statistical alloy disorder. An increase in the carrier lifetime has been obtained for the annealed nanowires. This increase is mainly due to the reduction of non-radiative recombination centers associated with the defects present in the material. Furthermore, temperature dependent time resolved photoluminescence measurements suggest a reduction of the alloy disorder in the annealed samples. In this thesis, single nanowire photodetectors with a high responsivity in the UV range have been demonstrated. Due to the high surface/volume ratio, these structures are very sensitive to gas adsorption at the surface, which largely de_nes the optical and electrical properties of the material and, therefore, of the device. With the aim of obtaining time stable devices, the dynamic adsorption-desorption processes have been studied, developing di_erent approaches that allow a higher control over them. Finally, ZnCdO/ZnO quantum wells have been grown with a nominal Cd concentration of 54% inside the well. The performed optical measurements show that increasing the well width from 0.7 to 10 nm, shifts the emission related with the well from 3.30 to 1.97 eV. This result represents the highest shift reported in the literature. However, a detailed structural characterization shows the presence of di_usion phenomena which substantially reduce the concentration of Cd in the well, while increasing it in the barrier. This type of phenomena should be considered when ac curately interpretating the quantum con_nement e_ects in Zn(Cd)O/ZnO quantum wells. Theoretically, annealing ZnO with CdO allows to decrease the bandgap from 3.37 to 0.95 eV, covering the whole visible spectrum. Zn(Mg)O _lms and quantum dots grown by spray pyrolysis Due to its simplicity, low-cost and capacity to grow over large areas conserving a high crystal quality, spray pyrolysis technique presents a great interest in the scienti_c community for developing comercial devices. In this thesis, a complete study of the optical and structural properties of Zn(Mg)O _lms and quantum dots grown by spray pyrolysis has been performed. Contrary to Zn(Cd)O alloys, when introducing Mg in the ZnO wurtzite structure an increase in the bandgap in obtained. Once again, the di_erence in the crystal structure of ZnO and MgO limits the amount of Mg that can be introduced before phase separation appears. In this PhD thesis, a maximum Mg content of 35% has been incorporated in the wurtzite structure using spray pyrolysis. This variation in the Mg content translates into an increase of the absorption edge from 3.30 to 4.11 eV. Up to this date, this result represents the highest Mg content introduced by spray pyrolysis in a ZnO wurzite structure reported in the literature. The comparison of the emission and absorption spectra shows the presence of an increasing Stokes shift with Mg content. This phenomenon is partialy related with the presence of potential _uctuations due to an statistic alloy disorder. MSM photodetectors have been processed on previously characterized Zn(Mg)O _lms. These devices have shown a shift in the absorption edge from 3.32 to 4.02 eV with the increase in Mg content, high responsivity values (10-103 A/W) and high contrast ratios between illuminated and dark responsivities (10-107). These values are explained by the presence of a gain mechanism and a reduction of dark current in the ZnMgO samples. Zn(Mg)O quantum dots have also been grown using spray pyrolysis with Mg concentrations between 0 and 100% and with average widths ranging 4 to 6 nm. Structural measurements show that at a Mg concentration of 45% the cubic phase appears, coexisting with the hexagonal phase up to an 85% concentration of Mg content. From 85% onwards the quantum dots show only the cubic phase. Absorption measurements performed in these structures reveal a shift in the absorption edge from 3.33 to 3.55 eV when the Mg content increases up to 40 %.

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We study the electronic structure of a heterojunction made of two monolayers of MoS2 and WS2. Our first-principles density functional calculations show that, unlike in the homogeneous bilayers, the heterojunction has an optically active band gap, smaller than the ones of MoS2 and WS2 single layers. We find that the optically active states of the maximum valence and minimum conduction bands are localized on opposite monolayers, and thus the lowest energy electron-holes pairs are spatially separated. Our findings portray the MoS2-WS2 bilayer as a prototypical example for band-gap engineering of atomically thin two-dimensional semiconducting heterostructures.

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We model the quantum Hall effect in heterostructures made of two gapped graphene stripes with different gaps, Δ1 and Δ2. We consider two main situations, Δ1=0,Δ2≠0, and Δ1=−Δ2. They are different in a fundamental aspect: only the latter features kink states that, when intervalley coupling is absent, are protected against backscattering. We compute the two-terminal conductance of heterostructures with channel length up to 430 nm, in two transport configurations, parallel and perpendicular to the interface. By studying the effect of disorder on the transport along the boundary, we quantify the robustness of kink states with respect to backscattering. Transport perpendicular to the boundary shows how interface states open a backscattering channel for the conducting edge states, spoiling the perfect conductance quantization featured by the homogeneously gapped graphene Hall bars. Our results can be relevant for the study of graphene deposited on hexagonal boron-nitride, as well as to model graphene with an interaction-driven gapped phase with two equivalent phases separated by a domain wall.

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This work reports on the synthesis of nanosheets of layered titanosilicate JDF-L1 supported on commercial E-type glass fibers with the aim of developing novel nanoarchitectures useful as robust and easy to handle hydrogen adsorbents. The preparation of those materials is carried out by hydrothermal reaction from the corresponding gel precursor in the presence of the glass support. Because of the basic character of the synthesis media, silica from the silicate-based glass fibers can be involved in the reaction, cementing its associated titanosilicate and giving rise to strong linkages on the support with the result of very stable heterostructures. The nanoarchitectures built up by this approach promote the growth and disposition of the titanosilicate nanosheets as a house-of-cards radially distributed around the fiber axis. Such an open arrangement represents suitable geometry for potential uses in adsorption and catalytic applications where the active surface has to be available. The content of the titanosilicate crystalline phase in the system represents about 12 wt %, and this percentage of the adsorbent fraction can achieve, at 298 K and 20 MPa, 0.14 wt % hydrogen adsorption with respect to the total mass of the system. Following postsynthesis treatments, small amounts of Pd (<0.1 wt %) have been incorporated into the resulting nanoarchitectures in order to improve their hydrogen adsorption capacity. In this way, Pd-layered titanosilicate supported on glass fibers has been tested as a hydrogen adsorbent at diverse pressures and temperatures, giving rise to values around 0.46 wt % at 298 K and 20 MPa. A mechanism of hydrogen spillover involving the titanosilicate framework and the Pd nanoparticules has been proposed to explain the high increase in the hydrogen uptake capacity after the incorporation of Pd into the nanoarchitecture.

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The so-called quantum spin Hall phase is a topologically nontrivial insulating phase that is predicted to appear in graphene and graphenelike systems. In this paper we address the question of whether this topological property persists in multilayered systems. We consider two situations: purely multilayer graphene and heterostructures where graphene is encapsulated by trivial insulators with a strong spin-orbit coupling. We use a four-orbital tight-binding model that includes full atomic spin-orbit coupling and we calculate the Z2 topological invariant of the bulk states as well as the edge states of semi-infinite crystals with armchair termination. For homogeneous multilayers we find that even when the spin-orbit interaction opens a gap for all possible stackings, only those with an odd number of layers host gapless edge states while those with an even number of layers are trivial insulators. For heterostructures where graphene is encapsulated by trivial insulators, it turns out that interlayer coupling is able to induce a topological gap whose size is controlled by the spin-orbit coupling of the encapsulating materials, indicating that the quantum spin Hall phase can be induced by proximity to trivial insulators.

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The power of advanced transmission electron microscopy in determining the nanostructures and chemistry of nanosized materials on the applications in semiconductor quantum structures was demonstrated.

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Molecular dynamics simulations were carried out for Si/Ge axial nanowire heterostructures using modified effective atom method (MEAM) potentials. A Si–Ge MEAM interatomic cross potential was developed based on available experimental data and was used for these studies. The atomic distortions and strain distributions near the Si/Ge interfaces are predicted for nanowires with their axes oriented along the [111] direction. The cases of 10 and 25 nm diameter Si/Ge biwires and of 25 nm diameter Si/Ge/Si axial heterostructures with the Ge disk 1 nm thick were studied. Substantial distortions in the height of the atoms adjacent to the interface were found for the biwires but not for the Ge disks. Strains as high as 3.5% were found for the Ge disk and values of 2%–2.5% were found at the Si and Ge interfacial layers in the biwires. Deformation potential theory was used to estimate the influence of the strains on the band gap, and reductions in band gap to as small as 40% of bulk values are predicted for the Ge disks. The localized regions of increased strain and resulting energy minima were also found within the Si/Ge biwire interfaces with the larger effects on the Ge side of the interface. The regions of strain maxima near and within the interfaces are anticipated to be useful for tailoring band gaps and producing quantum confinement of carriers. These results suggest that nanowire heterostructures provide greater design flexibility in band structure modification than is possible with planar layer growth.

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Light modulation is an essential operation in photonics and optoelectronics. With existing and emerging technologies increasingly demanding compact, efficient, fast and broadband optical modulators, high-performance light modulation solutions are becoming indispensable. The recent realization that 2D layered materials could modulate light with superior performance has prompted intense research and significant advances, paving the way for realistic applications. In this Review, we cover the state of the art of optical modulators based on 2D materials, including graphene, transition metal dichalcogenides and black phosphorus. We discuss recent advances employing hybrid structures, such as 2D heterostructures, plasmonic structures, and silicon and fibre integrated structures. We also take a look at the future perspectives and discuss the potential of yet relatively unexplored mechanisms, such as magneto-optic and acousto-optic modulation.

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Experimental and theoretical studies regarding noise processes in various kinds of AlGaAs/GaAs heterostructures with a quantum well are reported. The measurement processes, involving a Fast Fourier Transform and analog wave analyzer in the frequency range from 10 Hz to 1 MHz, a computerized data storage and processing system, and cryostat in the temperature range from 78 K to 300 K are described in detail. The current noise spectra are obtained with the “three-point method”, using a Quan-Tech and avalanche noise source for calibration. ^ The properties of both GaAs and AlGaAs materials and field effect transistors, based on the two-dimensional electron gas in the interface quantum well, are discussed. Extensive measurements are performed in three types of heterostructures, viz., Hall structures with a large spacer layer, modulation-doped non-gated FETs, and more standard gated FETs; all structures are grown by MBE techniques. ^ The Hall structures show Lorentzian generation-recombination noise spectra with near temperature independent relaxation times. This noise is attributed to g-r processes in the 2D electron gas. For the TEGFET structures, we observe several Lorentzian g-r noise components which have strongly temperature dependent relaxation times. This noise is attributed to trapping processes in the doped AlGaAs layer. The trap level energies are determined from an Arrhenius plot of log (τT2) versus 1/T as well as from the plateau values. The theory to interpret these measurements and to extract the defect level data is reviewed and further developed. Good agreement with the data is found for all reported devices. ^

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Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.

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Epitaxial heterostructures combining ferroelectric (FE) and ferromagnetic (FiM) oxides are a possible route to explore coupling mechanisms between the two independent order parameters, polarization and magnetization of the component phases. We report on the fabrication and properties of arrays of hybrid epitaxial nanostructures of FiM NiFe(2)O(4) (NFO) and FE PbZr(0.52)Ti(0.48)O(3) or PbZr(0.2)Ti(0.8)O(3), with large range order and lateral dimensions from 200 nm to 1 micron. METHODS: The structures were fabricated by pulsed-laser deposition. High resolution transmission electron microscopy and high angle annular dark-field scanning transmission electron microscopy were employed to investigate the microstructure and the epitaxial growth of the structures. Room temperature ferroelectric and ferrimagnetic domains of the heterostructures were imaged by piezoresponse force microscopy (PFM) and magnetic force microscopy (MFM), respectively. RESULTS: PFM and MFM investigations proved that the hybrid epitaxial nanostructures show ferroelectric and magnetic order at room temperature. Dielectric effects occurring after repeated switching of the polarization in large planar capacitors, comprising ferrimagnetic NiFe2O4 dots embedded in ferroelectric PbZr0.52Ti0.48O3 matrix, were studied. CONCLUSION: These hybrid multiferroic structures with clean and well defined epitaxial interfaces hold promise for reliable investigations of magnetoelectric coupling between the ferrimagnetic / magnetostrictive and ferroelectric / piezoelectric phases.

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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.

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Two-dimensional (2D) materials have generated great interest in the last few years as a new toolbox for electronics. This family of materials includes, among others, metallic graphene, semiconducting transition metal dichalcogenides (such as MoS2) and insulating Boron Nitride. These materials and their heterostructures offer excellent mechanical flexibility, optical transparency and favorable transport properties for realizing electronic, sensing and optical systems on arbitrary surfaces. In this work, we develop several etch stop layer technologies that allow the fabrication of complex 2D devices and present for the first time the large scale integration of graphene with molybdenum disulfide (MoS2) , both grown using the fully scalable CVD technique. Transistor devices and logic circuits with MoS2 channel and graphene as contacts and interconnects are constructed and show high performances. In addition, the graphene/MoS2 heterojunction contact has been systematically compared with MoS2-metal junctions experimentally and studied using density functional theory. The tunability of the graphene work function significantly improves the ohmic contact to MoS2. These high-performance large-scale devices and circuits based on 2D heterostructure pave the way for practical flexible transparent electronics in the future. The authors acknowledge financial support from the Office of Naval Research (ONR) Young Investigator Program, the ONR GATE MURI program, and the Army Research Laboratory. This research has made use of the MI.