Near infrared high efficiency InAs/GaAsSb QDLEDs: band alignment and carrier recombination mechanisms

The development of high efficiency laser diodes (LD) and light emitting diodes (LED) covering the 1.0 to 1.55 μm region of the spectra using GaAs heteroepitaxy has been long pursued. Due to the lack of materials that can be grown lattice-macthed to GaAs with bandgaps in the 1.0 to 1.55 μm region, quantum wells (QW) or quantum dots (QD) need be used. The most successful approach with QWs has been to use InGaAs, but one needs to add another element, such as N, to be able to reach 1.3/1.5μm. Even though LDs have been successfully demonstrated with the QW approach, using N leads to problems with compositional homogeneity across the wafer, and limited efficiency due to strong non-radiative recombination. The alternative approach of using InAs QDs is an attractive option, but once again, to reach the longest wavelengths one needs very large QDs and control over the size distribution and band alignment. In this work we demonstrate InAs/GaAsSb QDLEDs with high efficiencies, emitting from 1.1 to 1.52 μm, and we analyze the band alignment and carrier loss mechanisms that result from the presence of Sb in the capping layer.

Discriminant Analysis of Geographical Origin of Cork Planks and Stoppers by Near Infrared Spectroscopy

The objective of this study was to assess the potential of visible and near infrared spectroscopy (VIS+NIRS) combined with multivariate analysis for identifying the geographical origin of cork. The study was carried out on cork planks and natural cork stoppers from the most representative cork-producing areas in the world. Two training sets of international and national cork planks were studied. The first set comprised a total of 479 samples from Morocco, Portugal, and Spain, while the second set comprised a total of 179 samples from the Spanish regions of Andalusia, Catalonia, and Extremadura. A training set of 90 cork stoppers from Andalusia and Catalonia was also studied. Original spectroscopic data were obtained for the transverse sections of the cork planks and for the body and top of the cork stoppers by means of a 6500 Foss-NIRSystems SY II spectrophotometer using a fiber optic probe. Remote reflectance was employed in the wavelength range of 400 to 2500 nm. After analyzing the spectroscopic data, discriminant models were obtained by means of partial least square (PLS) with 70% of the samples. The best models were then validated using 30% of the remaining samples. At least 98% of the international cork plank samples and 95% of the national samples were correctly classified in the calibration and validation stage. The best model for the cork stoppers was obtained for the top of the stoppers, with at least 90% of the samples being correctly classified. The results demonstrate the potential of VIS + NIRS technology as a rapid and accurate method for predicting the geographical origin of cork plank and stoppers

Vanadium-Doped In and Sn Sulphides: Photocatalysts able to use the whole visible light spectrum

Using photocatalysis for energy applications depends, more than for environmental purposes or selective chemical synthesis, on converting as much of the solar spectrum as possible; the best photocatalyst, titania, is far from this. Many efforts are pursued to use better that spectrum in photocatalysis, by doping titania or using other materials (mainly oxides, nitrides and sulphides) to obtain a lower bandgap, even if this means decreasing the chemical potential of the electron-hole pairs. Here we introduce an alternative scheme, using an idea recently proposed for photovoltaics: the intermediate band (IB) materials. It consists in introducing in the gap of a semiconductor an intermediate level which, acting like a stepstone, allows an electron jumping from the valence band to the conduction band in two steps, each one absorbing one sub-bandgap photon. For this the IB must be partially filled, to allow both sub-bandgap transitions to proceed at comparable rates; must be made of delocalized states to minimize nonradiative recombination; and should not communicate electronically with the outer world. For photovoltaic use the optimum efficiency so achievable, over 1.5 times that given by a normal semiconductor, is obtained with an overall bandgap around 2.0 eV (which would be near-optimal also for water phtosplitting). Note that this scheme differs from the doping principle usually considered in photocatalysis, which just tries to decrease the bandgap; its aim is to keep the full bandgap chemical potential but using also lower energy photons. In the past we have proposed several IB materials based on extensively doping known semiconductors with light transition metals, checking first of all with quantum calculations that the desired IB structure results. Subsequently we have synthesized in powder form two of them: the thiospinel In2S3 and the layered compound SnS2 (having bandgaps of 2.0 and 2.2 eV respectively) where the octahedral cation is substituted at a â?10% level with vanadium, and we have verified that this substitution introduces in the absorption spectrum the sub-bandgap features predicted by the calculations. With these materials we have verified, using a simple reaction (formic acid oxidation), that the photocatalytic spectral response is indeed extended to longer wavelengths, being able to use even 700 nm photons, without largely degrading the response for above-bandgap photons (i.e. strong recombination is not induced) [3b, 4]. These materials are thus promising for efficient photoevolution of hydrogen from water; work on this is being pursued, the results of which will be presented.

Non-destructive optical characterization of fruits in the red and near infrared.

Increasing attention is being paid to the possible development of non-invasive tests for the assessment of the quality of Fruits. We propose a novel non-destructive method for the measurement of the internal optical properties of fruits and vegetables by means of lime-resolved reflectance spectroscopy in the visible and NIR range. A Fully automated instrumentation for time-resolved reflectance measurements was developed. It is based on mode-locked laser sources and electronics for time-correlated single photon counting, and provides a time-resolution of 120-160 ps. The system was used to probe the optical properties of several species and varieties of Fruits and vegetables in the red and NIR range (650-1000 nm). In most Fruits, the absorption line shape is dominated by the absorption peak of water, centred around 970 nm. Generally, the absorption spectra also show the spectral features typical of chlorophyll, with maximum at 675 nm. In particular, for what concerns apples, variations in peak intensity are observed depending on the variety, the degree of ripeness as well as the position on the apple. For all the species and varieties considered, the transport scattering coefficient decreases progressively upon increasing the wavelength.

Simulation of impulse response for indoor visible light communications using 3D CAD models

n this article, a tool for simulating the channel impulse response for indoor visible light communications using 3D computer-aided design (CAD) models is presented. The simulation tool is based on a previous Monte Carlo ray-tracing algorithm for indoor infrared channel estimation, but including wavelength response evaluation. The 3D scene, or the simulation environment, can be defined using any CAD software in which the user specifies, in addition to the setting geometry, the reflection characteristics of the surface materials as well as the structures of the emitters and receivers involved in the simulation. Also, in an effort to improve the computational efficiency, two optimizations are proposed. The first one consists of dividing the setting into cubic regions of equal size, which offers a calculation improvement of approximately 50% compared to not dividing the 3D scene into sub-regions. The second one involves the parallelization of the simulation algorithm, which provides a computational speed-up proportional to the number of processors used.

Substrate nanopatterning by e-beam lithography to growth ordered arrays of III-nitride nanodetectors, white light emitters, and solar cells

III-nitride nanorods have attracted much scientific interest during the last decade because of their unique optical and electrical properties [1,2]. The high crystal quality and the absence of extended defects make them ideal candidates for the fabrication of high efficiency opto-electronic devices such as nano-photodetectors, light-emitting diodes, and solar cells [1-3]. Nitride nanorods are commonly grown in the self-assembled mode by plasma-assisted molecular beam epitaxy (MBE) [4]. However, self-assembled nanorods are characterized by inhomogeneous heights and diameters, which render the device processing very difficult and negatively affect the electronic transport properties of the final device. For this reason, the selective area growth (SAG) mode has been proposed, where the nanorods preferentially grow with high order on pre-defined sites on a pre-patterned substrate

On-line measurement of soil properties without direct spectral response in near infrared spectral range

So far, the majority of reports on on-line measurement considered soil properties with direct spectral responses in near infrared spectroscopy (NIRS). This work reports on the results of on-line measurement of soil properties with indirect spectral responses, e.g. pH, cation exchange capacity (CEC), exchangeable calcium (Caex) and exchangeable magnesium (Mgex) in one field in Bedfordshire in the UK. The on-line sensor consisted of a subsoiler coupled with an AgroSpec mobile, fibre type, visible and near infrared (vis–NIR) spectrophotometer (tec5 Technology for Spectroscopy, Germany), with a measurement range 305–2200 nm to acquire soil spectra in diffuse reflectance mode. General calibration models for the studied soil properties were developed with a partial least squares regression (PLSR) with one-leave-out cross validation, using spectra measured under non-mobile laboratory conditions of 160 soil samples collected from different fields in four farms in Europe, namely, Czech Republic, Denmark, Netherland and UK. A group of 25 samples independent from the calibration set was used as independent validation set. Higher accuracy was obtained for laboratory scanning as compared to on-line scanning of the 25 independent samples. The prediction accuracy for the laboratory and on-line measurements was classified as excellent/very good for pH (RPD = 2.69 and 2.14 and r2 = 0.86 and 0.78, respectively), and moderately good for CEC (RPD = 1.77 and 1.61 and r2 = 0.68 and 0.62, respectively) and Mgex (RPD = 1.72 and 1.49 and r2 = 0.66 and 0.67, respectively). For Caex, very good accuracy was calculated for laboratory method (RPD = 2.19 and r2 = 0.86), as compared to the poor accuracy reported for the on-line method (RPD = 1.30 and r2 = 0.61). The ability of collecting large number of data points per field area (about 12,800 point per 21 ha) and the simultaneous analysis of several soil properties without direct spectral response in the NIR range at relatively high operational speed and appreciable accuracy, encourage the recommendation of the on-line measurement system for site specific fertilisation.

Photoacoustic effect measurement in aqueous suspensions of gold nanorods caused by low-frequency and low-power near-infrared pulsing laser irradiation

When aqueous suspensions of gold nanorods are irradiated with a pulsing laser (808 nm), pressure waves appear even at low frequencies (pulse repetition rate of 25 kHz). We found that the pressure wave amplitude depends on the dynamics of the phenomenon. For fixed concentration and average laser current intensity, the amplitude of the pressure waves shows a trend of increasing with the pulse slope and the pulse maximum amplitude.We postulate that the detected ultrasonic pressure waves are a sort of shock waves that would be generated at the beginning of each pulse, because the pressure wave amplitude would be the result of the positive interference of all the individual shock waves.

Detection and quantification of peanut traces in wheat flour by near infrared hyperspectral imaging spectroscopy using principal-component analysis

The use of a common environment for processing different powder foods in the industry has increased the risk of finding peanut traces in powder foods. The analytical methods commonly used for detection of peanut such as enzyme-linked immunosorbent assay (ELISA) and real-time polymerase chain reaction (RT-PCR) represent high specificity and sensitivity but are destructive and time-consuming, and require highly skilled experimenters. The feasibility of NIR hyperspectral imaging (HSI) is studied for the detection of peanut traces down to 0.01% by weight. A principal-component analysis (PCA) was carried out on a dataset of peanut and flour spectra. The obtained loadings were applied to the HSI images of adulterated wheat flour samples with peanut traces. As a result, HSI images were reduced to score images with enhanced contrast between peanut and flour particles. Finally, a threshold was fixed in score images to obtain a binary classification image, and the percentage of peanut adulteration was compared with the percentage of pixels identified as peanut particles. This study allowed the detection of traces of peanut down to 0.01% and quantification of peanut adulteration from 10% to 0.1% with a coefficient of determination (r2) of 0.946. These results show the feasibility of using HSI systems for the detection of peanut traces in conjunction with chemical procedures, such as RT-PCR and ELISA to facilitate enhanced quality-control surveillance on food-product processing lines.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

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.

Optoelectronic property analysis of MCrO4 (M=Ba, Sr) with a response to visible light irradiation

Ternary MCrO4 (M = Ba, Sr) semiconductors are materials with a variety of photocatalyst and optoelectronic applications. We present detailed microscopic analyses based on first principles of the structure, the electronic properties and the optical absorption in which the difference between symmetrically non-equivalent atoms has been considered. The high absorption coefficients of these materials are split into chemical species contributions in accordance with the symmetry. The high optical absorption in these materials is mainly because of the Cr–O inter-species transitions.

Photon Management Structures for Absorption Enhancement in Intermediate Band Solar Cells and Crystalline Silicon Solar Cells

El objetivo de la tesis es investigar los beneficios que el atrapamiento de la luz mediante fenómenos difractivos puede suponer para las células solares de silicio cristalino y las de banda intermedia. Ambos tipos de células adolecen de una insuficiente absorción de fotones en alguna región del espectro solar. Las células solares de banda intermedia son teóricamente capaces de alcanzar eficiencias mucho mayores que los dispositivos convencionales (con una sola banda energética prohibida), pero los prototipos actuales se resienten de una absorción muy débil de los fotones con energías menores que la banda prohibida. Del mismo modo, las células solares de silicio cristalino absorben débilmente en el infrarrojo cercano debido al carácter indirecto de su banda prohibida. Se ha prestado mucha atención a este problema durante las últimas décadas, de modo que todas las células solares de silicio cristalino comerciales incorporan alguna forma de atrapamiento de luz. Por razones de economía, en la industria se persigue el uso de obleas cada vez más delgadas, con lo que el atrapamiento de la luz adquiere más importancia. Por tanto aumenta el interés en las estructuras difractivas, ya que podrían suponer una mejora sobre el estado del arte. Se comienza desarrollando un método de cálculo con el que simular células solares equipadas con redes de difracción. En este método, la red de difracción se analiza en el ámbito de la óptica física, mediante análisis riguroso con ondas acopladas (rigorous coupled wave analysis), y el sustrato de la célula solar, ópticamente grueso, se analiza en los términos de la óptica geométrica. El método se ha implementado en ordenador y se ha visto que es eficiente y da resultados en buen acuerdo con métodos diferentes descritos por otros autores. Utilizando el formalismo matricial así derivado, se calcula el límite teórico superior para el aumento de la absorción en células solares mediante el uso de redes de difracción. Este límite se compara con el llamado límite lambertiano del atrapamiento de la luz y con el límite absoluto en sustratos gruesos. Se encuentra que las redes biperiódicas (con geometría hexagonal o rectangular) pueden producir un atrapamiento mucho mejor que las redes uniperiódicas. El límite superior depende mucho del periodo de la red. Para periodos grandes, las redes son en teoría capaces de alcanzar el máximo atrapamiento, pero sólo si las eficiencias de difracción tienen una forma peculiar que parece inalcanzable con las herramientas actuales de diseño. Para periodos similares a la longitud de onda de la luz incidente, las redes de difracción pueden proporcionar atrapamiento por debajo del máximo teórico pero por encima del límite Lambertiano, sin imponer requisitos irrealizables a la forma de las eficiencias de difracción y en un margen de longitudes de onda razonablemente amplio. El método de cálculo desarrollado se usa también para diseñar y optimizar redes de difracción para el atrapamiento de la luz en células solares. La red propuesta consiste en un red hexagonal de pozos cilíndricos excavados en la cara posterior del sustrato absorbente de la célula solar. La red se encapsula en una capa dieléctrica y se cubre con un espejo posterior. Se simula esta estructura para una célula solar de silicio y para una de banda intermedia y puntos cuánticos. Numéricamente, se determinan los valores óptimos del periodo de la red y de la profundidad y las dimensiones laterales de los pozos para ambos tipos de células. Los valores se explican utilizando conceptos físicos sencillos, lo que nos permite extraer conclusiones generales que se pueden aplicar a células de otras tecnologías. Las texturas con redes de difracción se fabrican en sustratos de silicio cristalino mediante litografía por nanoimpresión y ataque con iones reactivos. De los cálculos precedentes, se conoce el periodo óptimo de la red que se toma como una constante de diseño. Los sustratos se procesan para obtener estructuras precursoras de células solares sobre las que se realizan medidas ópticas. Las medidas de reflexión en función de la longitud de onda confirman que las redes cuadradas biperiódicas consiguen mejor atrapamiento que las uniperiódicas. Las estructuras fabricadas se simulan con la herramienta de cálculo descrita en los párrafos precedentes y se obtiene un buen acuerdo entre la medida y los resultados de la simulación. Ésta revela que una fracción significativa de los fotones incidentes son absorbidos en el reflector posterior de aluminio, y por tanto desaprovechados, y que este efecto empeora por la rugosidad del espejo. Se desarrolla un método alternativo para crear la capa dieléctrica que consigue que el reflector se deposite sobre una superficie plana, encontrándose que en las muestras preparadas de esta manera la absorción parásita en el espejo es menor. La siguiente tarea descrita en la tesis es el estudio de la absorción de fotones en puntos cuánticos semiconductores. Con la aproximación de masa efectiva, se calculan los niveles de energía de los estados confinados en puntos cuánticos de InAs/GaAs. Se emplea un método de una y de cuatro bandas para el cálculo de la función de onda de electrones y huecos, respectivamente; en el último caso se utiliza un hamiltoniano empírico. La regla de oro de Fermi permite obtener la intensidad de las transiciones ópticas entre los estados confinados. Se investiga el efecto de las dimensiones del punto cuántico en los niveles de energía y la intensidad de las transiciones y se obtiene que, al disminuir la anchura del punto cuántico respecto a su valor en los prototipos actuales, se puede conseguir una transición más intensa entre el nivel intermedio fundamental y la banda de conducción. Tomando como datos de partida los niveles de energía y las intensidades de las transiciones calculados como se ha explicado, se desarrolla un modelo de equilibrio o balance detallado realista para células solares de puntos cuánticos. Con el modelo se calculan las diferentes corrientes debidas a transiciones ópticas entre los numerosos niveles intermedios y las bandas de conducción y de valencia bajo ciertas condiciones. Se distingue de modelos de equilibrio detallado previos, usados para calcular límites de eficiencia, en que se adoptan suposiciones realistas sobre la absorción de fotones para cada transición. Con este modelo se reproducen datos publicados de eficiencias cuánticas experimentales a diferentes temperaturas con un acuerdo muy bueno. Se muestra que el conocido fenómeno del escape térmico de los puntos cuánticos es de naturaleza fotónica; se debe a los fotones térmicos, que inducen transiciones entre los estados excitados que se encuentran escalonados en energía entre el estado intermedio fundamental y la banda de conducción. En el capítulo final, este modelo realista de equilibrio detallado se combina con el método de simulación de redes de difracción para predecir el efecto que tendría incorporar una red de difracción en una célula solar de banda intermedia y puntos cuánticos. Se ha de optimizar cuidadosamente el periodo de la red para equilibrar el aumento de las diferentes transiciones intermedias, que tienen lugar en serie. Debido a que la absorción en los puntos cuánticos es extremadamente débil, se deduce que el atrapamiento de la luz, por sí solo, no es suficiente para conseguir corrientes apreciables a partir de fotones con energía menor que la banda prohibida en las células con puntos cuánticos. Se requiere una combinación del atrapamiento de la luz con un incremento de la densidad de puntos cuánticos. En el límite radiativo y sin atrapamiento de la luz, se necesitaría que el número de puntos cuánticos de una célula solar se multiplicara por 1000 para superar la eficiencia de una célula de referencia con una sola banda prohibida. En cambio, una célula con red de difracción precisaría un incremento del número de puntos en un factor 10 a 100, dependiendo del nivel de la absorción parásita en el reflector posterior. Abstract The purpose of this thesis is to investigate the benefits that diffractive light trapping can offer to quantum dot intermediate band solar cells and crystalline silicon solar cells. Both solar cell technologies suffer from incomplete photon absorption in some part of the solar spectrum. Quantum dot intermediate band solar cells are theoretically capable of achieving much higher efficiencies than conventional single-gap devices. Present prototypes suffer from extremely weak absorption of subbandgap photons in the quantum dots. This problem has received little attention so far, yet it is a serious barrier to the technology approaching its theoretical efficiency limit. Crystalline silicon solar cells absorb weakly in the near infrared due to their indirect bandgap. This problem has received much attention over recent decades, and all commercial crystalline silicon solar cells employ some form of light trapping. With the industry moving toward thinner and thinner wafers, light trapping is becoming of greater importance and diffractive structures may offer an improvement over the state-of-the-art. We begin by constructing a computational method with which to simulate solar cells equipped with diffraction grating textures. The method employs a wave-optical treatment of the diffraction grating, via rigorous coupled wave analysis, with a geometric-optical treatment of the thick solar cell bulk. These are combined using a steady-state matrix formalism. The method has been implemented computationally, and is found to be efficient and to give results in good agreement with alternative methods from other authors. The theoretical upper limit to absorption enhancement in solar cells using diffractions gratings is calculated using the matrix formalism derived in the previous task. This limit is compared to the so-called Lambertian limit for light trapping with isotropic scatterers, and to the absolute upper limit to light trapping in bulk absorbers. It is found that bi-periodic gratings (square or hexagonal geometry) are capable of offering much better light trapping than uni-periodic line gratings. The upper limit depends strongly on the grating period. For large periods, diffraction gratings are theoretically able to offer light trapping at the absolute upper limit, but only if the scattering efficiencies have a particular form, which is deemed to be beyond present design capabilities. For periods similar to the incident wavelength, diffraction gratings can offer light trapping below the absolute limit but above the Lambertian limit without placing unrealistic demands on the exact form of the scattering efficiencies. This is possible for a reasonably broad wavelength range. The computational method is used to design and optimise diffraction gratings for light trapping in solar cells. The proposed diffraction grating consists of a hexagonal lattice of cylindrical wells etched into the rear of the bulk solar cell absorber. This is encapsulated in a dielectric buffer layer, and capped with a rear reflector. Simulations are made of this grating profile applied to a crystalline silicon solar cell and to a quantum dot intermediate band solar cell. The grating period, well depth, and lateral well dimensions are optimised numerically for both solar cell types. This yields the optimum parameters to be used in fabrication of grating equipped solar cells. The optimum parameters are explained using simple physical concepts, allowing us to make more general statements that can be applied to other solar cell technologies. Diffraction grating textures are fabricated on crystalline silicon substrates using nano-imprint lithography and reactive ion etching. The optimum grating period from the previous task has been used as a design parameter. The substrates have been processed into solar cell precursors for optical measurements. Reflection spectroscopy measurements confirm that bi-periodic square gratings offer better absorption enhancement than uni-periodic line gratings. The fabricated structures have been simulated with the previously developed computation tool, with good agreement between measurement and simulation results. The simulations reveal that a significant amount of the incident photons are absorbed parasitically in the rear reflector, and that this is exacerbated by the non-planarity of the rear reflector. An alternative method of depositing the dielectric buffer layer was developed, which leaves a planar surface onto which the reflector is deposited. It was found that samples prepared in this way suffered less from parasitic reflector absorption. The next task described in the thesis is the study of photon absorption in semiconductor quantum dots. The bound-state energy levels of in InAs/GaAs quantum dots is calculated using the effective mass approximation. A one- and four- band method is applied to the calculation of electron and hole wavefunctions respectively, with an empirical Hamiltonian being employed in the latter case. The strength of optical transitions between the bound states is calculated using the Fermi golden rule. The effect of the quantum dot dimensions on the energy levels and transition strengths is investigated. It is found that a strong direct transition between the ground intermediate state and the conduction band can be promoted by decreasing the quantum dot width from its value in present prototypes. This has the added benefit of reducing the ladder of excited states between the ground state and the conduction band, which may help to reduce thermal escape of electrons from quantum dots: an undesirable phenomenon from the point of view of the open circuit voltage of an intermediate band solar cell. A realistic detailed balance model is developed for quantum dot solar cells, which uses as input the energy levels and transition strengths calculated in the previous task. The model calculates the transition currents between the many intermediate levels and the valence and conduction bands under a given set of conditions. It is distinct from previous idealised detailed balance models, which are used to calculate limiting efficiencies, since it makes realistic assumptions about photon absorption by each transition. The model is used to reproduce published experimental quantum efficiency results at different temperatures, with quite good agreement. The much-studied phenomenon of thermal escape from quantum dots is found to be photonic; it is due to thermal photons, which induce transitions between the ladder of excited states between the ground intermediate state and the conduction band. In the final chapter, the realistic detailed balance model is combined with the diffraction grating simulation method to predict the effect of incorporating a diffraction grating into a quantum dot intermediate band solar cell. Careful optimisation of the grating period is made to balance the enhancement given to the different intermediate transitions, which occur in series. Due to the extremely weak absorption in the quantum dots, it is found that light trapping alone is not sufficient to achieve high subbandgap currents in quantum dot solar cells. Instead, a combination of light trapping and increased quantum dot density is required. Within the radiative limit, a quantum dot solar cell with no light trapping requires a 1000 fold increase in the number of quantum dots to supersede the efficiency of a single-gap reference cell. A quantum dot solar cell equipped with a diffraction grating requires between a 10 and 100 fold increase in the number of quantum dots, depending on the level of parasitic absorption in the rear reflector.

Second international spectroradiometer intercomparison: preliminary results and impact on PV device calibration

This paper describes the preliminary results of an intercomparison of spectroradiometers for global (GNI) and direct normal incidence (DNI) irradiance in the visible (VIS) and near infrared (NIR) spectral regions together with an assessment of the impact these results may have on the calibration of triple-junction photovoltaic devices and on the relevant spectral mismatch calculation. The intercomparison was conducted by six European scientific laboratories and a Japanese industrial partner. Seven institutions and seven spectroradiometer systems, representing different technologies and manufacturers were involved, representing a good cross section of the todays available instrumentation for solar spectrum measurements.