Photodetectors are used in many applications such as digital and thermal cameras or in solar panels. They can also be designed to detect the omnipresent high-energy radiation/particles, and for radiation imaging in biomedical applications. Novel nanostructures offer significant advantages compared to traditional designs for the realization of fast, sensitive, compact and cheap sensors and efficient solar cells. Examples of such nanostructures include quantum dots (QDs), quantum wells (QWs) and NW arrays. This thesis is devoted to experimental investigations of effects of high-energy (1 MeV) protons on the optical and electrical performance of InP/InAsP NW-based QDiscs-in wire photodetectors. The proton-induced degradation of the optical performance has been studied by means of Fourier Transform Infrared (FTIR) photocurrent spectroscopy. The spectrally resolved photocurrent (PC) and current-voltage (I-V) characteristics were measured at low temperature (5 K and 77K) and at room temperature (300K) before and after 1 MeV proton irradiation under vacuum conditions with fluences ranging from 1.0×1012–3.0×1013 cm-2. The particle radiation exposure has been done in the Ion Beam Accelerator at the Department of Nuclear Physics Department at Lund University. Considering both PC and I-V characteristics, it was found that the devices were sensitive to all proton irradiation at all fluences. In general, the PC intensity significantly increased after radiation for all fluences, however, a week after exposure the PC and dark current gradually recovered. At 3×1012 p/cm2 fluence level, it was figured out that photocurrent which attributed to QDiscs disappeared for a couple of days after exposure, however, over time and gradually, those started to manifest again even at low and room temperatures, causing radiation-induced changes in device parameters to be time-dependent; however, it was not recorded any signals related to QDiscs at fluence of 3×1013 p/cm2. Substantial changes in the dark I-V characteristics, as well as increases in the dark current, are observed after irradiation. The influence of proton irradiation on light and dark current characteristics also indicated that NW structures are a good potential candidate for radiation harsh-environment applications. It was also observed a significant increase in dark current after the radiation for all devices, however, by applying the voltage to the photodetectors, the PC and I-V characteristics gradually being to diminish, which may be attributed to an annealing process.

Neste trabalho desenvolvemos rotinas computacionais em Python para o cálculo de propriedades dinâmicas (espectros de fotocorrente e absorção) de heteroestruturas semicondutoras baseadas em Dinâmica Quântica. Em uma primeira etapa do desenvolvimento do projeto, a formulação baseada na evolução temporal das soluções da equação de Schrödinger dependente do tempo foi aplicada a sistemas com soluções analíticas conhecidas ou com resultados já reportados na literatura. Devido à excelente concordância entre nossos dados e aqueles já conhecidos, em uma etapa seguinte, foram calculadas as energias de transição observadas em espectros de fotoluminescência para poços quânticos de InGaAs/GaAs, crescidos por MBE, levando-se em conta os efeitos de tensão e segregação de átomos de índio. Na continuidade do projeto, especial atenção foi dada ao desenvolvimento de estratégias para calcular os espectros de absorção e fotocorrente para dispositivos do Estado Sólido. O conjunto de resultados apresentados neste trabalho demonstra que a metodologia desenvolvida é precisa e pode ser utilizada com baixo custo computacional para o modelamento de heteroestruturas semicondutoras mais complexas, que servem de base para o desenvolvimento de dispositivos optoeletrônicos. / In this work we developed computational routines in Python for the calculation of the dynamic properties (spectrum of photocurrent and absorption) of semiconductor heterostructures based on Quantum Dynamics Theory. In a first stage of the development of the project the formulation based on the time evolution of the solutions of the time dependent Schrödinger equation was applied to systems with known analytical solutions or results already reported in the literature. Due to the excellent agreement between our data and those already known, in the next stage the transition energies observed in photoluminescence spectra for InGaAs/GaAs quantum wells, grown by MBE, were calculated taking into account the effects of stress and segregation of indium atoms. In the continuity of the project, special attention was given to the development of strategies to calculate absorption and photocurrent spectra for solid state devices. The set of results presented in this work demonstrates that the methodology developed is accurate and can be used with low computational cost for the modeling of more complex semiconductor heterostructures, which are used for the development of optoelectronic devices.

As células solares orgânicas, também conhecidas como (OPVs), fazem parte da terceira geração dos dispositivos fotovoltaicos. Entre outras tecnologias emergentes, a dos OPVs tem a vantagem de ser de fácil processamento e de baixo custo. Ou seja, uma tecnologia comercialmente promissora na área de conversão de energia solar em energia elétrica. No entanto, grandes desafios precisam ser superados para colocar estas células no mercado dos fotovoltaicos. Dentre esses desafios, pode estar incluído, inevitavelmente, a compreensão dos processos físicos envolvidos na fotogeração em OPVs, dentre os quais pode-se destacar o da recombinação de cargas fotogeradas. A recombinação é o principal responsável pela perda de eficiência em OPVs, uma vez que ela elimina uma fração relativamente grande de portadores de carga, diminuindo consideravelmente a potência de saída da célula. Para estudar este efeito indesejado em células orgânicas, desenvolvemos um modelo analítico para fotocorrente em OPVs do tipo bulk heterojunction (BHJ), assumindo uma recombinação bimolecular de cinética de segunda ordem. O modelo é representado por uma expressão analítica obtida a partir das equações fundamentais da eletrodinâmica clássica, onde despreza-se a contribuição da corrente de difusão e as mobilidades dos elétrons e dos buracos são consideradas iguais. Essa expressão foi de grande valia na análise dos resultados experimentais, sobretudo os de corrente-tensão (J-V) sob iluminação, e além disso, ela permitiu extrair parâmetros intrínsecos do transporte de carga, como mobilidade e coeficiente de recombinação. Neste sentido, foram fabricados dispositivos cuja estrutura foi ITO/PEDOT:PSS/P3HT:PCBM/Ca/Al, e com eles foram realizados inúmeros experimentos. As técnicas usadas na parte experimental foram: medidas J-V, no escuro e sob iluminação, medidas de transiente de fotovoltagem (TPV), de transiente de fotocorrente (TPC), e de Foto-CELIV (Charge Extraction Linear Increasing Voltage). Usamos como parâmetros experimentais a temperatura e intensidade de iluminação. Das medidas J-V sob iluminação, foram extraídos os parâmetros essenciais da célula: corrente de curto (Jsc), potencial de circuito aberto (Voc), fator de preenchimento (FF) e a eficiência (PCE). A partir das abordagens experimental e teórica, exploramos a influência da recombinação bimolecular no comportamento fotovoltaico dos dispositivos. O desenvolvimento do modelo teve contribuição de trabalhos que se basearam em modelagem numérica a partir de condições físicas semelhantes às usadas em nosso tratamento e que foram levadas em consideração no processo de análise dos resultados experimentais. / Organic solar cells, also known as (OPVs), are part of the third generation of photovoltaic devices. Among other emerging technologies, OPVs have the advantage of being easy to process and exhibits low cost of production. That is, it is a promising commercial technology in the area of converting solar energy into electricity. However, major challenges need to be overcome to put these cells in the photovoltaic market. Among them, it can be included, inevitably, the comprehension of the physical processes involved in photogeneration in OPVs, of which, the recombination of photogenerated carriers is included. Recombination is primarily factor responsible for the loss of efficiency in OPVs, since recombination eliminates a large fraction of the carriers, considerably reducing the output power of the cell. To study this undesirable effect in organic cells, we developed an analytical model for the photocurrent in bulk heterojunction cells (BHJ), which assumes the bimolecular recombination of second order kinetics. The model is represented by an analytical expression obtained by the equations of the classical electrodynamics, where we neglected the contribution of the diffusion current and assumed that electrons and holes have equal mobilities. The expression was of great value for the analysis of the experimental results, especially the current-voltage (J-V) measurements under illumination, and it allowed to extract intrinsic parameters of charge transport effects, such as mobility and recombination coefficient. For this, it were fabricated devices whose structure was ITO/PEDOT:PSS/P3HT:PCBM/Ca-Al, and with them were performed numerous experiments. The techniques used in the experimental part were: J-V measurements, in the dark and under illumination, transient photovoltage (TPV), transient photocurrent (TPC), and of Charge Extraction Linear Increasing Voltage (Photo-CELIV). We used as experimental parameters the temperature and the intensity of. From J-V measurements under illumination we extracted the essential cell parameters: short current (Jsc), open circuit potential (Voc), fill factor (FF) and efficiency (PCE). From the experimental and theoretical approaches, we explored the influence of bimolecular recombination on the photovoltaic behavior of the devices. The development of the model had contributions of works based on numerical modelings from physical conditions similar to those used in our treatment and that were taken into account in the process of analysis of the experimental results.

A thorough study on the distribution of defect-related active energy levels has been performed on nanocrystalline TiO2. Films have been deposited on thick-alumina printed circuit boards equipped with electrical contacts, heater and temperature sensors, to carry out a detailed thermally stimulated currents analysis on a wide temperature range (5-630 K), in view to evidence contributions from shallow to deep energy levels within the gap. Data have been processed by numerically modelling electrical transport. The model considers both free and hopping contribution to conduction, a density of states characterized by an exponential tail of localized states below the conduction band and the convolution of standard Thermally Stimulated Currents (TSC) emissions with gaussian distributions to take into account the variability in energy due to local perturbations in the highly disordered network. Results show that in the low temperature range, up to 200 K, hopping within the exponential band tail represents the main contribution to electrical conduction. Above room temperature, electrical conduction is dominated by free carriers contribution and by emissions from deep energy levels, with a defect density ranging within 10(14)-10(18) cm(-3), associated with physio- and chemi-sorbed water vapour, OH groups and to oxygen vacancies.

Des films du type polyoxométallates-porphyrines ont été synthetisés et sont basés sur des interactions du types covalentes ou électrostatiques. Les films polyoxométallates–porphyrines sont obtenus par électro-oxydation de l’octaéthylporphyrine de zinc (ZnOEP) ou la 5,15-ditolylporphyrine (H2T2P) en présence de différents types of polyoxométallates (POMs) portant deux groupes pyridyles pendants (py-POM-py) Trois type de systèmes py-POM-py ont été utilises : i) un Lindqvist polyoxovanadate fonctionalisé via deux groupes tris-alkoxo , ii) un derive organosilyl fonctionalisé du type Keggin ou Dawson, et iii) des briques du type Dawson [P2W15V3O62]9− fonctionalisée avec des groupements organiques bis-pyridine de géométrie variée via un greffage diolamide). Tous ces films ont été testé pour la génération de photocourant et la photocatalyse de la réduction de métaux (Ag et Pt). Des films électrostatiques POM-porphyrin ont été également préparés par incorporation de polyanion du type Preyssler [NaP5W30O110]14- sur les films de porphyrine polycationic (poly-ZnOEP) électropolymérisés avec des espaceurs viologènes ou bis-viologènes. [NaP5W30O110]14- agit comme relais d’électron entre une porphyrine excitée ZnOEP* et le viologène (ou le bis-viologène) retardant la recombinaison de charge ce qui permet une augmentation du photocourant. Enfin, des nanoparticules POM@NPs (Pt, Au, Ag) ont été introduites en surface de copolymère polycationique à base de bis-porphyrine par métathèse afin d’augmenter l’efficacité de la génération de photocourant. La résonance de plasmon de surface localisée qui se produit à la surface des nanoparticules d'argent a sensiblement améliorée l'excitation électronique de porphyrine. / Polyoxometalates-porphyrin hybrid films were synthesized based on covalent or electrostatic interactions. Copolymeric polyoxometalate–porphyrin films were obtained by the electro-oxidation of zinc octaethylporphyrin (ZnOEP) or 5,15-ditolyl porphyrin (H2T2P) in the presence of a different type of polyoxometalates (POMs) bearing two pyridyl groups (py-POM-py). Three type of py-POM-py have been used: i) a tris-alkoxo functionalized Lindqvist polyoxovanadate, ii) an organosilyl functionalized Keggin-type [PW11Si2O40C26H16N2]3- and Dawson-type [P2W17Si2O62C26H16N2]6-, and iii) a bis-pyridine-substituted organo-polyoxometallic bricks using [P2W15V3O62]9− diolamide-grafting method with various geometries of the pendant group. All are applied for photocurrent generation and photocatalytical recovery of metals (Ag and Pt). Electrostatic POM-porphyrin films were also prepared by incorporated Preyssler type polyanion [NaP5W30O110]14- onto the electropolymerized polycationic porphyrin (poly-ZnOEP) with viologen or bis-viologen as spacers. [NaP5W30O110]14- as an efficient electron shuttle between the excited ZnOEP and viologen (or bis-viologen) which effectively retarded the fast charge pair recombination and enhanced the photocurrent magnitude. Later, we introduced nanoparticles POM@MNPs to a bis-porphyrin copolymer through metathesis reaction to further improve the efficiency of the photocurrent generation in which the localized surface plasmon resonance that occurs at the surface of silver nanoparticles has substantially enhanced the electronic excitation of surface-anchored porphyrin.

Measurements of DC photocurrent-voltage characteristic, photocurrents spectral response and laser induced transient current technique enable investigation of surface recombination centers, bulk trap levels and distribution of the inner electric field. In the presented work, the n- type planar CdZnTe detectors with quasi Ohmic contacts were studied by above mentioned methods. It has been shown that in the case of strongly absorbed light under the DC regime of illumination not only surface recombination influences the detector's transport properties. The effect of the space charge, created as a consequence of carriers trapped by the impurity levels, must be taken into account. Therefore some new theoretical models were created in order to describe measured photocurrent-voltage dependencies. Obtained data were fitted with the new theory and the mobility and surface recombination velocity for electrons were determined.

Esta tese de doutorado é resultado do estudo da fotocondutividade em materiais poliméricos, com particular enfoque em diodos poliméricos com camada ativa de derivados do poli (p-fenileno vinileno) (PPV): OC10-PPV, SY e MEH-PPV, em estrutura tipo sanduíche (ITO/polimérico/Metal) de camada única, utilizando eletrodos metálicos com diferentes funções trabalho depositados sobre o mesmo filme. Para isso, foi necessária a realização de todas as etapas de fabricação de dispositivos orgânicos, como descritas neste trabalho, para obter resultados com o máximo de reprodutibilidade, bem como o domínio das técnicas de caracterização. As propriedades ópticas dos filmes poliméricos foram analisadas através dos espetros de absorção e de fluorescência estacionária na região do visível. O comportamento fotocondutivo dos dispositivos foi realizado através de medidas de corrente-tensão (I-V) e da espectroscopia de fotocorrente no estado estacionário em regime dc sob incidência de luz com diferentes comprimentos de onda, ora através do ITO, ora através dos eletrodos metálicos semitransparente, para o dispositivo sob diferentes valores de tensões aplicadas. A variação desses parâmetros permitiu verificar como estes influenciam na fotogeração e no transporte de portadores de cargas e assim adaptar e aplicar um modelo teórico que levasse em consideração o campo elétrico aplicado para ajustar a fotocorrente obtida experimentalmente, obtendo informações sobre as propriedades de fotocondutividade dos materiais estudos. / This thesis is a study about photoconductivity in polymeric materials, in particular diodes with single-layer sandwich structure derivates of poly(para-phenylene vinylene) (PPV): OC10-PPV, SY and MEH-PPV. Different metallic electrodes were deposited on the same polymeric layer. Therefore, it was necessary to realize the devices fabrication process step by step as well to dominate the characterization techniques. The optical properties of polymeric film were analyzed through the absorption and emission spectrum in the visible region. The photoconductivity behavior was studied by dc current-voltage (I-V) and photocurrent action spectra through the absorption and emission spectrum in the visible region. The photoconductivity behavior was studied by dc current-voltage (I-V) and photocurrent action spectra through the both side of device under applied voltages. The variation of these parameters allowed verifying how are influencing in the charge carrier photo-generation and the charge transport and then to adapt and apply a theoretical model wich considers the electric field applied to fit the photocurrent action spectra of devices. The values of the parameters allow to survey important about photoconductivity properties of the materials

Les recherches sur les matériaux en couches minces dédiées à l'industrie solaire restent un sujet d'intérêt avec le nombre croissant de types de matériaux incorporés en tant qu'absorbeur dans un dispositif solaire. Le besoin de techniques de caractérisation est donc aigu pour l'optimisation des matériaux et leur incorporation dans des cellules photovoltaïques. Dans cette thèse, une méthode de photo-courant basée sur la spectroscopie de photo-courant à transformée de Fourier (FTPS) est utilisée pour effectuer des mesures sur des matériaux en couches minces et des cellules solaires. Notre FTPS a été développée pour réaliser 3 types de mesures: 1.) mesure de réflexion et de transmission (R/T), 2.) spectroscopie du coefficient d'absorption, et 3.) mesure de réponse spectrale, efficacité quantique externe et densité de photo-courant court-circuit. Cette dernière est spécifiquement utilisée pour les cellules solaires. Nous avons utilisé les résultats de R/T pour effectuer une simulation numérique donnant l'épaisseur, l'indice de réfraction, la rugosité du film et le coefficient d'absorption optique. Une modélisation de la densité d'états (DOS) en utilisant le logiciel DeOSt automatisé avec l'algorithme TLBO (Teacher Learner Based Optimization) a été développée pour trouver les valeurs des paramètres de DOS les mieux adaptées afin de reproduire le ∝ expérimental. Une analyse de sensibilité a été faite pour trouver les paramètres DOS les plus importants parmi 15-17 paramètres. Nous avons mesuré plusieurs échantillons de a-Si: H déposés sous différentes conditions de dépôt, et utilisé nos résultats pour étudier leur DOS. Une comparaison des mesures de α sur a-Si: H déposé sur un substrat de verre et incorporé dans une cellule solaire a également été réalisée. Cette étude a conclu qu'une correction du spectre de coefficient d'absorption doit être effectuée pour les mesures sur les cellules solaires. / Investigations on thin film materials dedicated to the solar industry are still a matter of interest with the growing numbers of material types incorporated as absorbers in a solar cell device. The need of characterization techniques is therefore acute for the optimization of materials and their incorporation in solar devices. In this thesis, a photocurrent method based on Fourier Transform Photocurrent Spectroscopy (FTPS) is used to perform the measurements of thin film materials and solar cells. Our FTPS was further developed to perform 3 types of measurements: 1.) reflection and transmission (R/T) measurement, 2.) absorption coefficient spectroscopy and 3.) spectral response, external quantum efficiency, and short circuit photocurrent density measurements. This latter is specifically used for solar cells. We used the R/T results to perform numerical simulations giving the thickness, refractive index, film roughness, and optical absorption coefficient. A modeling of the density of states (DOS) using the software DeOSt automated with the Teacher Learner Based Optimization (TLBO) algorithm was achieved to find the best suited DOS parameter values to reproduce the experimental spectrum of alpha. A sensitivity analysis was performed to find the most important DOS parameters among 15-17 parameters. For the experimental studies, we have measured several a-Si:H thin film samples prepared under different deposition conditions, and used their absorption coefficient; spectra to study their DOS. A comparison of absorption coefficient; measurements on a-Si:H thin films deposited on a glass substrate and incorporated in a solar cell device stack was also conducted. This study concluded that a correction of the absorption coefficient spectrum measured on solar cells had to be done.

This thesis is focused on a study of CdTe and CdZnTe semiconductor detectors working under high flux of radiation. We studied experimentally an influence of high flux of X-rays and optical radiation on polarization of the detector. The polarization phenomenon decreases the efficiency of the detector due to a screening of an applied electric field by a space charge accumulated at deep levels due to a trapping of photogenerated carriers. In order to measure the electric field profiles in the detectors we employed a method based on cross polarizers technique and Pockels effect. The main objective of this work was to study the possibilities of an optical de-polarization of CdTe and CdZnTe detectors for different photon energies of additional light, its dynamics and physical origin. We have found that detectors can be de-polarized by above bandgap light. Moreover, CdZnTe detector can be depolarized by near infrared light and in a pulse mode. The de- polarization is associated with a compensation of the space charge at deep traps.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19193号 / 農博第2132号 / 新制||農||1034(附属図書館) / 学位論文||H27||N4939(農学部図書室) / 32185 / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 髙野 俊幸, 教授 西尾 嘉之, 教授 木村 恒久 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM