Impact of metal-organic vapor phase epitaxy environment on silicon bulk lifetime for III–V-on-Si multijunction solar cells

With the final goal of integrating III-V materials on silicon substrates for tandem solar cells, the influence of the Metal-Organic Vapor Phase Epitaxy (MOVPE) environment on the minority carrier properties of silicon wafers has been evaluated. These properties will essentially determine the photovoltaic performance of the bottom cell in a III-V-on-Si tandem solar cell. A comparison of the base minority carrier lifetimes obtained for different thermal processes carried out in a MOVPE reactor on Czochralski silicon wafers has been carried out. An important degradation of minority carrier lifetime during the surface preparation (i.e. H2 anneal) has been observed. Three different mechanisms have been proposed for explaining this behavior: 1) the introduction of extrinsic impurities coming from the reactor; 2) the activation of intrinsic lifetime killing impurities coming from the wafer itself; and finally, 3) the formation of crystal defects, which eventually become recombination centers. The effect of the emitter formation by phosphorus diffusion has also been evaluated. In this sense, it has been reported that lifetime can be recovered during the emitter formation either by the effect of the P on extracting impurities, or by the role of the atomic hydrogen on passivating the defects.

Improved modeling of photoluminescent and electroluminescent coupling in multijunction solar cells

The performance of tandem stacks of Group III?V multijunction solar cells continues to improve rapidly, both through improved performance of the individual cells in the stack and throughi ncrease in the number of stacked cells. As the radiative efficiency of these individual cells increases, radiative coupling between the stacked cells becomes an increasingly important factor not only in cell design, but also in accurate efficiency measurement and in determining performance of cells and systems under varying spectral conditions in the field. Past modeling has concentrated on electroluminescent coupling between the cells, although photoluminescent coupling is shown to be important for cells operating near their maximum power point voltage or below or when junction defect recombination is significant. Extension of earlier models i sproposed to allow this non-negligible component of luminescent coupling to be included. Therefined model is validated by measurement of the closely related external emission from both single and double junction cells.

Correlation among Growth Conditions, Morphology, and Optical Properties of Nanocolumnar InGaN/GaN Heterostructures Selectively Grown by Molecular Beam Epitaxy

This work reports on the selective area growth mechanism of green-emitting InGaN/GaN nanocolumns. The evolution of the morphology of the InGaN segment is found to depend critically on the nominal III/V ratio as well as the diameter of the GaN section. In addition, the In distribution inside the InGaN segment is found to depend on the local III/V and In/Ga ratios.

Crecimiento, fabricación y caracterización de heteroestructuras y nanocolumnas ordenadas basadas en nitruros del grupo III para aplicaciones sensoras

Esta memoria está basada en el crecimiento y caracterización de heteroestructuras Al(Ga)N/GaN y nanocolumnas ordenadas de GaN, y su aplicación en sensores químicos. El método de crecimiento ha sido la epitaxia de haces moleculares asistida por plasma (PAMBE). En el caso de las heteroestructuras Al(Ga)N/GaN, se han crecido barreras de distinto espesor y composición, desde AlN de 5 nm, hasta AlGaN de 35 nm. Además de una caracterización morfológica, estructural y eléctrica básica de las capas, también se han fabricado a partir de ellas dispositivos tipo HEMTs. La caracterización eléctrica de dichos dispositivos (carga y movilidad de en el canal bidimensional) indica que las mejores heteroestructuras son aquellas con un espesor de barrera intermedio (alrededor de 20 nm). Sin embargo, un objetivo importante de esta Tesis ha sido verificar las ventajas que podían tener los sensores basados en heteroestructuras AlN/GaN (frente a los típicos basados en AlGaN/GaN), con espesores de barrera muy finos (alrededor de 5 nm), ya que el canal de conducción que se modula por efecto de cambios químicos está más cerca de la superficie en donde ocurren dichos cambios químicos. De esta manera, se han utilizado los dispositivos tipo HEMTs como sensores químicos de pH (ISFETs), y se ha comprobado la mayor sensibilidad (variación de corriente frente a cambios de pH, Ids/pH) en los sensores basados en AlN/GaN frente a los basados en AlGaN/GaN. La mayor sensibilidad es incluso más patente en aplicaciones en las que no se utiliza un electrodo de referencia. Se han fabricado y caracterizado dispositivos ISFET similares utilizando capas compactas de InN. Estos sensores presentan peor estabilidad que los basados en Al(Ga)N/GaN, aunque la sensibilidad superficial al pH era la misma (Vgs/pH), y su sensibilidad en terminos de corriente de canal (Ids/pH) arroja valores intermedios entre los ISFET basados en AlN/GaN y los valores de los basados en AlGaN/GaN. Para continuar con la comparación entre dispositivos basados en Al(Ga)N/GaN, se fabricaron ISFETs con el área sensible más pequeña (35 x 35 m2), de tamaño similar a los dispositivos destinados a las medidas de actividad celular. Sometiendo los dispositivos a pulsos de voltaje en su área sensible, la respuesta de los dispositivos de AlN presentaron menor ruido que los basados en AlGaN. El ruido en la corriente para dispositivos de AlN, donde el encapsulado no ha sido optimizado, fue tan bajo como 8.9 nA (valor rms), y el ruido equivalente en el potencial superficial 38.7 V. Estos valores son más bajos que los encontrados en los dispositivos típicos para la detección de actividad celular (basados en Si), y del orden de los mejores resultados encontrados en la literatura sobre AlGaN/GaN. Desde el punto de vista de la caracterización electro-química de las superficies de GaN e InN, se ha determinado su punto isoeléctrico. Dicho valor no había sido reportado en la literatura hasta el momento. El valor, determinado por medidas de “streaming potential”, es de 4.4 y 4 respectivamente. Este valor es una importante característica a tener en cuenta en sensores, en inmovilización electrostática o en la litografía coloidal. Esta última técnica se discute en esta memoria, y se aplica en el último bloque de investigación de esta Tesis (i.e. crecimiento ordenado). El último apartado de resultados experimentales de esta Tesis analiza el crecimiento selectivo de nanocolumnas ordenadas de GaN por MBE, utilizando mascaras de Ti con nanoagujeros. Se ha estudiado como los distintos parámetros de crecimiento (i.e. flujos de los elementos Ga y N, temperatura de crecimiento y diseño de la máscara) afectan a la selectividad y a la morfología de las nanocolumnas. Se ha conseguido con éxito el crecimiento selectivo sobre pseudosustratos de GaN con distinta orientación cristalina o polaridad; templates de GaN(0001)/zafiro, GaN(0001)/AlN/Si, GaN(000-1)/Si y GaN(11-20)/zafiro. Se ha verificado experimentalmente la alta calidad cristalina de las nanocolumnas ordenadas, y su mayor estabilidad térmica comparada con las capas compactas del mismo material. Las nanocolumnas ordenadas de nitruros del grupo III tienen una clara aplicación en el campo de la optoelectrónica, principalmente para nanoemisores de luz blanca. Sin embargo, en esta Tesis se proponen como alternativa a la utilización de capas compactas o nanocolumnas auto-ensambladas en sensores. Las nanocolumnas auto-ensambladas de GaN, debido a su alta razón superficie/volumen, son muy prometedoras en el campo de los sensores, pero su amplia dispersión en dimensiones (altura y diámetro) supone un problema para el procesado y funcionamiento de dispositivos reales. En ese aspecto, las nanocolumnas ordenadas son más robustas y homogéneas, manteniendo una alta relación superficie/volumen. Como primer experimento en el ámbito de los sensores, se ha estudiado como se ve afectada la emisión de fotoluminiscencia de las NCs ordenadas al estar expuestas al aire o al vacio. Se observa una fuerte caída en la intensidad de la fotoluminiscencia cuando las nanocolumnas están expuestas al aire (probablemente por la foto-adsorción de oxigeno en la superficie), como ya había sido documentado anteriormente en nanocolumnas auto-ensambladas. Este experimento abre el camino para futuros sensores basados en nanocolumnas ordenadas. Abstract This manuscript deals with the growth and characterization of Al(Ga)N/GaN heterostructures and GaN ordered nanocolumns, and their application in chemical sensors. The growth technique has been the plasma-assisted molecular beam epitaxy (PAMBE). In the case of Al(Ga)N/GaN heterostructures, barriers of different thickness and composition, from AlN (5 nm) to AlGaN (35 nm) have been grown. Besides the basic morphological, structural and electrical characterization of the layers, HEMT devices have been fabricated based on these layers. The best electrical characteristics (larger carriers concentration and mobility in the two dimensional electron gas) are those in AlGaN/GaN heterostructures with a medium thickness (around 20 nm). However, one of the goals of this Thesis has been to verify the advantages that sensors based on AlN/GaN (thickness around 7 nm) have compared to standard AlGaN/GaN, because the conduction channel to be modulated by chemical changes is closer to the sensitive area. In this way, HEMT devices have been used as chemical pH sensors (ISFETs), and the higher sensitivity (conductance change related to pH changes, Ids/pH) of AlN/GaN based sensors has been proved. The higher sensibility is even more obvious in application without reference electrode. Similar ISFETs devices have been fabricated based on InN compact layers. These devices show a poor stability, but its surface sensitivity to pH (Vgs/pH) and its sensibility (Ids/pH) yield values between the corresponding ones of AlN/GaN and AlGaN/GaN heterostructures. In order to a further comparison between Al(Ga)N/GaN based devices, ISFETs with smaller sensitive area (35 x 35 m2), similar to the ones used in cellular activity record, were fabricated and characterized. When the devices are subjected to a voltage pulse through the sensitive area, the response of AlN based devices shows lower noise than the ones based on AlGaN. The noise in the current of such a AlN based device, where the encapsulation has not been optimized, is as low as 8.9 nA (rms value), and the equivalent noise to the surface potential is 38.7 V. These values are lower than the found in typical devices used for cellular activity recording (based on Si), and in the range of the best published results on AlGaN/GaN. From the point of view of the electrochemical characterization of GaN and InN surfaces, their isoelectric point has been experimentally determined. Such a value is the first time reported for GaN and InN surfaces. These values are determined by “streaming potential”, being pH 4.4 and 4, respectively. Isoelectric point value is an important characteristic in sensors, electrostatic immobilization or in colloidal lithography. In particular, colloidal lithography has been optimized in this Thesis for GaN surfaces, and applied in the last part of experimental results (i.e. ordered growth). The last block of this Thesis is focused on the selective area growth of GaN nanocolumns by MBE, using Ti masks decorated with nanoholes. The effect of the different growth parameters (Ga and N fluxes, growth temperature and mask design) is studied, in particular their impact in the selectivity and in the morphology of the nanocolumns. Selective area growth has been successful performed on GaN templates with different orientation or polarity; GaN(0001)/sapphire, GaN(0001)/AlN/Si, GaN(000- 1)/Si and GaN(11-20)/sapphire. Ordered nanocolumns exhibit a high crystal quality, and a higher thermal stability (lower thermal decomposition) than the compact layers of the same material. Ordered nanocolumns based on III nitrides have a clear application in optoelectronics, mainly for white light nanoemitters. However, this Thesis proposes them as an alternative to compact layers and self-assembled nanocolumns in sensor applications. Self-assembled GaN nanocolumns are very appealing for sensor applications, due to their large surface/volume ratio. However, their large dispersion in heights and diameters are a problem in terms of processing and operation of real devices. In this aspect, ordered nanocolumns are more robust and homogeneous, keeping the large surface/volume ratio. As first experimental evidence of their sensor capabilities, ordered nanocolumns have been studied regarding their photoluminiscence on air and vacuum ambient. A big drop in the intensity is observed when the nanocolumns are exposed to air (probably because of the oxygen photo-adsortion), as was already reported in the case of self-assembled nanocolumns. This opens the way to future sensors based on ordered III nitrides nanocolumns.

Nanostructured tungsten as a first wall material for the future nuclear fusion reactors

The lack of materials able to withstand the severe radiation conditions (high thermal loads and atomistic damage) expected in fusion reactors is the actual bottle neck for fusion to become a reality. The main requisite for plasma facing materials (PFM) is to have excellent structural stability since severe cracking or mass loss would hamper their protection role which turns out to be unacceptable. Additional practical requirements for plasma facing materials are among others: (i) high thermal shock resistance, (ii) high thermal conductivity (iii) high melting point (iv) low physical and chemical sputtering, and (v) low tritium retention.

Photovoltaic application of the V, Cr and Mn-doped cadmium thioindate

The CdIn2S4 spinel semiconductor is a potential photovoltaic material due to its energy band gap and absorption properties. These optoelectronic properties can be potentiality improved by the insertion of intermediate states into the energy bandgap. We explore this possibility using M = Cr, V and Mn as an impurity. We analyze with first-principles almost all substitutions of the host atoms by M at the octahedral and tetrahedral sites in the normal and inverse spinel structures. In almost all cases, the impurities introduce deeper bands into the host energy bandgap. Depending on the site substitution, these bands are full, empty or partially-full. It increases the number of possible inter-band transitions and the possible applications in optoelectronic devices. The contribution of the impurity states to these bands and the substitutional energies indicate that these impurities are energetically favorable for some sites in the host spinel. The absorption coefficients in the independent-particle approximation show that these deeper bands open additional photon absorption channels. It could therefore increase the solar-light absorption with respect to the host.

V-substituted In2S3: an intermediate band material with photocatalytic activity in the whole visible light range

We proposed in our previous work V-substituted In2S3 as an intermediate band (IB) material able to enhance the efficiency of photovoltaic cells by combining two photons to achieve a higher energy electron excitation, much like natural photosynthesis. Here this hyper-doped material is tested in a photocatalytic reaction using wavelength-controlled light. The results evidence its ability to use photons with wavelengths of up to 750 nm, i.e. with energy significantly lower than the bandgap (=2.0 eV) of non-substituted In2S3, driving with them the photocatalytic reaction at rates comparable to those of non-substituted In2S3 in its photoactivity range (λ ≤ 650 nm). Photoluminescence spectra evidence that the same bandgap excitation as in V-free In2S3 occurs in V-substituted In2S3 upon illumination with photons in the same sub-bandgap energy range which is effective in photocatalysis, and its linear dependence on light intensity proves that this is not due to a nonlinear optical property. This evidences for the first time that a two-photon process can be active in photocatalysis in a single-phase material. Quantum calculations using GW-type many-body perturbation theory suggest that the new band introduced in the In2S3 gap by V insertion is located closer to the conduction band than to the valence band, so that hot carriers produced by the two-photon process would be of electron type; they also show that the absorption coefficients of both transitions involving the IB are of significant and similar magnitude. The results imply that V-substituted In2S3, besides being photocatalytically active in the whole visible light range (a property which could be used for the production of solar fuels), could make possible photovoltaic cells of improved efficiency.

Analysis of SnS2 hyperdoped with V proposed as efficient absorber material

Intermediate-band materials can improve the photovoltaic efficiency of solar cells through the absorption of two subband-gap photons that allow extra electron-hole pair formations. Previous theoretical and experimental findings support the proposal that the layered SnS2 compound, with a band-gap of around 2 eV, is a candidate for an intermediate-band material when it is doped with a specific transition-metal. In this work we characterize vanadium doped SnS2 using density functional theory at the dilution level experimentally found and including a dispersion correction combined with the site-occupancy-disorder method. In order to analyze the electronic characteristics that depend on geometry, two SnS2 polytypes partially substituted with vanadium in symmetry-adapted non-equivalent configurations were studied. In addition the magnetic configurations of vanadium in a SnS2 2H-polytype and its comparison with a 4H-polytype were also characterized. We demonstrate that a narrow intermediate-band is formed, when these dopant atoms are located in different layers. Our theoretical predictions confirm the recent experimental findings in which a paramagnetic intermediate-band material in a SnS2 2H-polytype with 10% vanadium concentration is obtained.