Rozprawy doktorskie na temat „Indium selenid”

Ce travail allie les propriétés singulières des matériaux 2D à une technique innovante utilisée pour modifier les propriétés électroniques des films ultra-minces pour proposer une nouvelle technologie permettant de réaliser le dispositif électronique le plus simple, la diode. Tout d'abord, nous identifions les matériaux semi-conducteurs pouvant être fabriqué en couches ultra-minces. Deuxièmement, nous utilisons une technique appelée dopage par charge d'espace développée dans notre groupe pour le dopage n ou p des matériaux. Enfin, nous obtenons les caractéristiques de diode des dispositifs. Le manuscrit commence par une revue des matériaux. Dans la famille des matériaux 2D, notre choix s'est porté sur un semi-conducteur en couches III-VI avec une bande interdite directe : InSe. Nous avons aussi choisi un type de matériau très différent, le CdO polycristallin qui n'est pas lamellaire et n'a pas une bande interdite directe, mais qui est facile à fabriquer sous forme de film ultra-mince avec une grande mobilité de porteurs. Après des expériences préliminaires, nous avons choisi InSe et fabriqué des dispositifs de films ultra minces de InSe. Nous avons développé en parallèle deux géométries pour la diode p-n. Nous avons pu obtenir un redressement pour chaque géométrie, ce qui implique que notre approche de dopage par charge d'espace a réussi à produire un dopage différencié spatialement dans chaque dispositif. Nous discutons des caractéristiques I-V obtenues et les limitations inhérentes aux dispositifs (chauffage local, hystérèses) et suggérons des améliorations afin d'obtenir un fonctionnement plus efficace et stable dans le cadre des perspectives de cette thèse
This work combines the singular properties of 2D materials with an innovative technique used for changing the electronic properties of ultra-thin films to propose a new technology for making the simplest bipolar electronic device, the diode. Firstly we identify semiconducting materials which can be fabricated in ultra-thin layers. Secondly, we use a proprietary technique called Space Charge Doping developed in our group for doping the material, either n or p. Finally, we obtain diode characteristics from the device. The manuscript begins with a review of different materials and properties. In the family of 2D materials, our choice was a III-VI layered semiconductor with a direct bandgap: InSe. We also chose a completely different kind of material, polycrystalline CdO, which is neither layered nor has a direct bandgap but is easy to fabricate in the ultra-thin film form and has high carrier mobility. After preliminary experiments, we chose InSe and fabricated devices of ultra-thin, few atomic layer InSe thin films. We chose to develop in parallel two different geometries for the p-n junction diode. We were able to obtain rectifying behavior for each geometry implying that our space charge doping approach was successful in producing microscopically, spatially differentiated doping in each device. We discuss the obtained I-V characteristics and the inherent limitations of the devices (local heating, hysteresis) and suggest improvements for future experiments and ways of obtaining more efficient and stable functioning and geometry as part of the perspectives of this thesis

Thesis (Ph. D.)--University of Oregon, 2002.
Typescript. Includes vita and abstract. Includes bibliographical references (leaves 143-148). Also available for download via the World Wide Web; free to University of Oregon users.

Nous étudions la possibilité de réaliser des cellules à base de diséléniure de cuivre, indium et gallium (CIGSe) à absorbeur ultra-mince, en réduisant l’épaisseur de la couche de CIGSe de 2500 nm jusqu’à 100 nm, tout en conservant un haut rendement de conversion.Grâce à l’utilisation d’outils de simulation numérique, nous étudions l’influence de la réduction d’épaisseur de l’absorbeur sur les paramètres photovoltaïques de la cellule. Une importante dégradation du rendement est observée, principalement attribuée à une réduction de la fraction de lumière absorbée par le CIGSe ainsi qu’à une collecte des porteurs de charge réduite dans les dispositifs ultraminces. Des solutions permettant de surmonter ces problèmes sont proposées et leur influence potentielle est numériquement simulée ; nous démontrons qu’une ingénierie de face avant (couche tampon alternative, couche anti-réfléchissante…) et de face arrière (contact arrière réfléchissant, diffusion de la lumière) sur une cellule CIGSe à absorbeur ultramince permet de potentiellement améliorer le rendement de la cellule solaire au niveau de celui d’une cellule à absorbeur référence (2.5 μm).Grâce à l’utilisation de techniques de gravure chimique sur des échantillons standards de CIGSe épais, nous réalisons des cellules solaires avec différentes épaisseurs d’absorbeurs, et nous étudions l’influence de l’épaisseur du CIGSe sur les paramètres photovoltaïques des cellules. Le comportement similaire aux simulations numériques.Une ingénierie du contact avant sur des cellules CIGSe à différentes épaisseurs est réalisée pour spécifiquement améliorer l’absorption dans la couche de CIGSe. Nous étudions l’influence d’une couche tampon alternative de ZnS, de la texturation de la fenêtre avant de ZnO:Al, et d’une couche anti-reflet sur la cellule solaire. D’importantes améliorations sont observées quelque soit l’épaisseur de la couche de CIGSe, ce qui permet d’obtenir des rendements de conversions supérieurs à ceux obtenus dans la configuration standard des dispositifs.Une ingénierie du contact arrière à basse température est également réalisée avec l’utilisation d’un procédé novateur combinant la gravure chimique du CIGSe avec un « lift-off » mécanique de la couche de CIGSe afin de la séparer du substrat de Molybdène. De nouveaux matériaux fortement réflecteur de lumière et précédemment incompatible avec le procédé de croissance du CIGSe sont utilisés comme contact arrière pour des cellules CIGSe ultra-minces. Une étude comparative en fonction de l’épaisseur de CIGSe entre des cellules avec contact arrière réfléchissant en Or (Au) et cellules solaires avec contact arrière standard Mo est effectuée. Le contact Au permet d’augmenter significativement le rendement de conversion des cellules solaires à absorbeur sub-microniques comparé au contact standard Mo avec un rendement de conversion supérieur à 10% obtenu sur une cellule CIGSe de 400 nm (comparé à 7.9% avec Mo).Afin de réduire encore plus l’épaisseur de la couche de CIGSe, jusque 100-200 nm, les modèles numériques montrent qu’il est nécessaire d’utiliser un réflecteur lambertien sur la face arrière de la cellule afin de maximiser l’absorption de la lumière. Un dispositif preuve de concept expérimental est réalisé avec une épaisseur de CIGSe de 200 nm et un réflecteur arrière lambertien, et ce dispositif est caractérisé par spectroscopie de transmission/réflexion. La réponse spectrale est déterminée en combinant des valeurs issues de simulation numérique et la mesure expérimental de l’absorption du dispositif. Nous calculons un courant de court circuit de 26 mA.cm-2 pour ce dispositif avec réflecteur lambertien, bien supérieur à ce qui est calculé pour la même structure sans réflecteur (15 mA.cm-2), et comparable au courant mesuré sur une cellule de référence de 2500 nm (28 mA.cm-2). L’utilisation de réflecteur lambertien pour des cellules CIGSe ultraminces est donc particulièrement adaptée pour maintenir de hauts rendements
In this thesis, we investigate on the possibility to realize ultrathin absorber Copper Indium Gallium Di-Selenide (CIGSe) solar cells, by reducing the CIGSe thickness from 2500 nm down to 100 nm, while conserving a high conversion efficiency.Using numerical modeling, we first study the evolution of the photovoltaic parameters when reducing the absorber thickness. A strong decrease of the efficiency of the solar cell is observed, mainly related to a reduced light absorption and carrier collection for thin and ultrathin CIGSe solar cells. Solutions to overcome these problems are proposed and the potential improvements are modeled; we show that front side (buffer layer, antireflection coating) and back side (reflective back contact, light scattering) engineering of an ultrathin device can potentially increase the conversion efficiency up to the level of a standard thick CIGSe solar cell.By using chemical bromine etching on a standard thick CIGSe layer, we realize solar cells with different absorber thicknesses and experimentally study the influence of the absorber thickness on the photovoltaic parameters of the devices. Experiments show a similar trends to that observed in numerical modeling.Front contact engineering on thin CIGSe solar cell is realized to increase the specific absorption in CIGSe, including alternative ZnS buffer, front ZnO:Al window texturation and anti-reflection coating. Substantial improvements are observed whatever the CIGSe thickness, with efficiencies higher that the default configuration.A back contact engineering at low temperature is realized by using an innovative approach combining chemical etching of the CIGSe and mechanical lift-off of the CIGSe from the original Molybdenum (Mo) substrate. New highly reflective materials previously incompatible with the standard solar cell process are used as back contact for thin and ultrathin CIGSe solar cells, and a comparative study between standard Mo back contact and alternative reflective Au back contact solar cells is performed. The Au back reflector significantly enhance the efficiency of solar cell with sub-micrometer absorbers compared to the standard Mo back reflector; an efficiency higher than 10 % on a 400 nm CIGSe is obtained with Au back contact (7.9% with standard Mo back contact). For further reduction of the absorber thickness down to 100-200 nm, numerical modeling show that a lambertian back reflector is needed to fully absorb the incident light in the CIGSe. An experimental proof of concept device with a CIGSe thickness of 200 nm and a lambertian back reflector is realized and characterized by reflection/transmission spectroscopy, and the experimental spectral response is determined by combining simulation and experimentally measured absorption. A short circuit current of 26 mA.cm-2 is determined with the lambertian back reflector, which is much higher than what is obtained for the same device with no reflector (15 mA.cm-2), and comparable to the short circuit current measured on a reference 2500 nm thick CIGSe solar cell (28 mA.cm-2). Lambertian back reflectors are therefore found to be the most effective way to enhance the efficiency of an ultrathin CIGSe solar cell up to the level of a reference thick CIGSe solar cell

Thesis (Ph. D.)--University of Oregon, 2007.
Typescript. Includes vita and abstract. Includes bibliographical references (leaves 81-84). Also available online in Scholars' Bank; and in ProQuest, free to University of Oregon users.

Layered Van der Waals solids, due to their highly anisotropic structure as well as their availability in mono, few and multi-layer form constitute a perfect playground, where a variety of possibility in structural variation as well as functionalities are expected. This potentially gives rise to a library of unique and fascinating 2D materials systems. These systems appear to demonstrate some spectacular variety of fundamental physics as well as indicate that some of these systems can be beneficial for several niche applications directly or indirectly resulting from their electrical and optical properties.

Ingots containing single crystals were grown from melts of Cu, In and Se in either stoichiometric proportions (CuInSe2) or with an excess of Se (CuInSe2.2). In addition, either sodium selenide (Na 2Se) or elemental sodium (Na0) was introduced to both sets of compositions in concentrations ranging from 0 to 3 at. %. The starting constituents were placed in quartz ampoules, which were evacuated and sealed before undergoing a vertical-Bridgman growth procedure. Analysis of deposits seen on the ampoule walls and on the ingot surface after growth revealed the presence of Na, as well as various forms of the other starting elements; however, no Na was found within the crystals. Electrical measurements revealed trends in the thermoelectric power of the ingots to correspond with additions of Na, as well as the presence of excess Se. A sign conversion from p- to n-type was confirmed with addition of sodium to stoichiometric CuInSe2. A suggested mechanism used to explain the effects of Na on the material, based on these experimental observations, is presented.

In today's "silicon age" in which we live, field-effect transistors (FET) are the workhorse of virtually all modern-day electronic gadgets. Although silicon currently dominates most of these electronics, layered 2D transition metal dichalcogenides (TMDCs) have great potential in low power optoelectronic applications due to their indirect-to-direct band gap transition from bulk to few-layer and high on/off switching ratios. TMDC WSe2 is studied here, mechanically exfoliated from CVT-grown bulk WSe2 crystals, to create a few-layered ambipolar FET, which transitions from dominant p-type behavior to n-type behavior dominating as temperature decreases. A high electron mobility μ>150 cm2V-1s-1 was found in the low temperature region near 50 K. Temperature-dependent photoconduction measurements were also taken, revealing that both the application of negative gate bias and decreasing the temperature resulted in an increase of the responsivity of the WSe2 sample. Besides TMDCs, Group III-VI van der Waals structures also show promising anisotropic optical, electronic, and mechanical properties. In particular, mechanically exfoliated few-layered InSe is studied here for its indirect band gap of 1.4 eV, which should offer a broad spectral response. It was found that the steady state photoconduction slightly decreased with the application of positive gate bias, likely due to the desorption of adsorbates on the surface of the sample. A room temperature responsivity near 5 AW-1 and external quantum efficiency of 207% was found for the InSe FET. Both TMDC’s and group III-VI chalcogenides continue to be studied for their remarkably diverse properties that depend on their thickness and composition for their applications as transistors, sensors, and composite materials in photovoltaics and optoelectronics.

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The design and optimization of higher efficiency Copper Indium Gallium Selenide (CIGS) solar cells are investigated in this thesis. Optimizing the thickness layers of a cell for various band gaps was conducted in order to design a cell that exceeds the current industry efficiency record of 20.8%. Silvaco provides a modeling program called ATLAS that is specifically designed to model semiconductor devices. ATLAS was used to model a CIGS cell that is currently being produced to verify the validity of the model. Various thicknesses were then swept to determine the optimum thickness for a given band gap. Solar spectrum intensity varies by location around the Earth. Optimizing CIGS cells for various band gaps yields higher overall power output when dealing with drastic climate and location variations. Cells for five band gaps ranging from 1.14 eV to 1.69 eV were optimized in this thesis. The highest achieved efficiency was for a band gap of 1.69 eV with an overall theoretical efficiency of 22.4%.

Thesis (Ph.D.)--University of Delaware, 2007.
Principal faculty advisor: Babatunde Ogunnaike, Dept. of Chemical Engineering, and Robert W. Birkmire, Dept. of Materials Science & Engineering. Includes bibliographical references.

[ES] El objetivo principal de esta tesis es contribuir al avance de nuevas técnicas de elaboración con bajo coste, utilizando materiales tipo de cobre, indio, galio y selenio CIGS y Perovskita para aplicaciones en energía solar fotovoltaica. CIGS parecen ser adecuadas ya que son de bajo costo de producción y se han reportado eficiencias de conversión del 23,35%. Por otro lado, las perovskitas híbridas de haluros de plomo orgánicos-inorgánicos han aparecido como nuevos materiales excepcionales para celdas solares, especialmente porque la eficiencia de las celdas solares basadas en perovskita ha aumentado del 3.8% al 22.7% en menos de un lustro. Este trabajo se ha dedicado a experimentar sobre la elaboración y caracterización de CIGS y los perovskitas de metilamonio de yoduro de plomo de (MAPbI3) y formamidinio de yoduro de plomo (FAPbI3), que se utilizo tanto en la aplicación a las células solares de perovskitas y en las células Tándem CIGS-perovskita. Las películas se caracterizaron por difracción de rayos X, espectroscopía Raman, microscopía electrónica de barrido, análisis de espectroscopía de energía dispersiva, microscopía de fuerza atómica, transmisión electrónica microscopía, fotoluminiscencia y espectroscopia UV-Vis. En las capas de CIGS depositadas por electrodeposición se investigó el efecto de diferentes parámetros, También investigamos en detalle el efecto del contacto posterior en las propiedades estructurales y ópticas de CIGS. Constatamos que el tipo de contacto posterior tiene un efecto significativo en el rendimiento posterior de las películas delgadas CIGS. Además, estudiamos la técnica de espray pirólisis para producir películas CIGS. Se estudió el proceso de recocido, que es el factor clave para mejorar el rendimiento de las células solares. Se elaboraron diferentes películas delgadas constituidas de nuestro dispositivo CdZnS/CdS/CIGS/Mo eso utilizó una capa conductora transparente de CdZnS para minimizar la alineación de la interfaz. Por otro lado, se analizó el proceso de cristalización y la estabilidad de las capas MAPbI3. Las capas de MAPbI3 se trataron añadiendo antisolvente a diferentes velocidades. Durante el tratamiento se producen intercambios complejos que influencian muchas propiedades fisicoquímicas. Se investigaron las propiedades ópticas y eléctricas de las películas de MAPbI3. Para mejorar la estabilidad de MAPbI3, se incorporó tetrabutilamonio (TBA), observando una mejora en la formación de la estructura perovskita que crece en la dirección preferente (110). La fase cristalina de MAPbI3 dopada con TBA presenta mejor cristalinidad, gran tamaño de grano, morfología superficial sin poros lo que es adecuado para la fabricación de dispositivos optoelectrónicas con mayor rendimiento. Además, hemos identificado el impacto de TBA en las propiedades foto físicas de MAPbI3. En las muestras de TBA:MAPbI3 aumenta la intensidad de la fotoluminiscencia al reducir la densidad de los estados de trampa y la absorción óptica muestra un cambio significativo hacia longitudes de onda más largas y la banda prohibida óptica varió de 1.8 a 1.52 eV. Finalmente, las muestras dopadas con 5% TBA mejoraron su estabilidad y se encontró que después de 15 días la estabilidad permanecía excelente en una humedad de ~ 60%. Por otra parte, investigamos el efecto de guanidinio (GA) sobre las propiedades estructurales y ópticas de FAPbI3. La relación entre la fase a de perovskita deseable y la fase indeseable y se ha estudiado en función del contenido de GA. Se comprobó que el dopaje con GA es eficaz en el control de la relación de fases a/y y luego en la estabilización de la fase a. Los resultados muestran que añadiendo una cantidad adecuada del 10% GA conduce a una mejora de película de perovskita que se evidencia en la homogeneidad de la fase a estable, granos de mayor tamaño y capas libres de poros. Además, 10% GA:FaPbI3 demostraron una excelente estabilidad después de ser envejecidas durante 15 días en un ambiente con humedad relativa del 60%.
[EN] The thesis work presented is part of the work in the Laboratory of New Materials for Photovoltaic Energy in the main target to use low cost techniques for elaboration of Perovskite and Copper, indium, gallium, and selenium CIGS materials for photovoltaic application. Organic-inorganic lead halides perovskites have currently and exceptionally appeared as new materials for low cost thin film solar cells specially that the efficiency of perovskite based solar cell have jumped from 3.8% to 22.7% in short time.in other hand, CIGS solar cells record 23.35% efficiency and still can be boosted. Here, we report the elaboration and characterization of CIGS as well as methylammonium lead iodide perovskites MAPbI3 and formamidinuim iodide lead iodide perovskites FAPbI3 absorbers for perovskite-based solar cells and Tandem Perovskites/ CIGS. The thin films prepared were characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) analysis, atomic force microscopy (AFM), transmission electron microscopy (TEM), Photoluminescence analysis (PL) and UV-Vis spectroscopy. The first stage was devoted for the effect of different parameters on the growth of CIGS by electrodeposition and we investigate the impact of different back contact in structural and optical proprieties. In a second stage, we report the growth of CIGS films by spray pyrolysis, we studied the effect of experimental parameter also the annealing process which is the key factor for improving the performance of solar cells,subsequently we elaborated different films constituted CdZnS/CdS/CIGS/Mo solar cells, the approach is to change the toxic ZnO by using a transparent, conductive CdZnS layer. In other hand, MAPbI3 film was investigated in order to optimize the chemical composition and to study the crystallization process also to get sight about the stability of perovskite materials to meet the requirement of their application as an active layer in perovskite solar cell. For this purpose. the MAPbI3 film surface was treated by adding diethyl ether antisolvent with different rates. during the treatment complex exchanges are appearing at the same time under the influence of quite a lot of physicochemical properties. A whole understanding of this topic is critically important for improving solar cell performance. MAPbI3 doped by the tetrabutylammonium TBA is boosting the formation of perovskite structure, leading to a higher orientation along the (110) and shows better crystallinity, large grain size, pinhole-free, which is suitable for the manufacturing of the optoelectronic devices with higher performance. Also, we have identified the impact of TBA in the photo-physical properties, we have noticed that the TBA improve the photoluminescence emission by reducing the density of trap states and the optical absorption indicates a significant shift to the lower wavelength and optical bandgap varied from 1.8 to 1.52 eV. Finally, the stability was explored for 5% TBA, it found that after 15 days the stability remained excellent in relative humidity of ~60%. These results would be helpful for realizing stable and high performance MAPbI3-based devices. Furthermore, we inspect the effect of monovalent cation substitution of Guanidinium (GA) on the structural and optical properties of FAPbI3 thin films perovskites. The ratio between the desirable a-phase and the undesirable y yellow phase is studied as a function of GA content. GA doping is shown to be efficient in the control of a/y phases ratio and then in the stabilization of the a-FaPbI3 phase. We qualitatively evaluate the impact of 10% of guanidinium on the phase composition and microstructure of films. The results show that an adequate amount of 10% GA:FaPbI3 leads to a homogeneous perovskite film with stable a phase, large grains, and free pinholes. 10% GA: FaPbI3 films demonstrate excellent stability after aging for 15 days in relative humidity of~60%.
[CA] L'objectiu principal d'aquesta tesi és contribuir a l'avanç de noves tècniques d'elaboració de baix cost, fent servir materials d'aliatges del tipus de coure, indi, gal·li i seleni (CIGS) i perovskites, per a aplicacions en energia solar fotovoltaica. El CIGS sembla ser adequat ja que són de baix cost de producció i s'han reportat eficiències de conversió del 23,35%. D'altra banda, les perovskites híbrides d'halurs de plom orgànics-inorgànics han aparegut com a nous materials excepcionals per cel·les solars, especialment perquè l'eficiència de les cel·les solars basades en perovskites ha augmentat del 3.8% al 22.7% en menys d'un lustre. En el present treball, reportem l'elaboració i caracterització de CIGS y de perovskitas de iodur de plom de metilamoni (MAPbI3) i de iodur de plom de formamidini (FaPbI3) per a les cèl·lules solars de CIGS i tàndem Perovskites/CIGS. En les capes de CIGS dipositades per electrodeposició es va investigar l'efecte dels diferents paràmetres sobre el procés d'electrodeposició, així com l'efecte del contacte posterior sobre les propietats estructurals i òptiques del CIGS. Ens trobem que el tipus de contacte posterior té un efecte significatiu en la posterior interpretació de pel·lícules primes CIGS. A més, vam estudiar la tècnica de polvorització de la piròlisi per produir pel·lícules de CIGS. Es va estudiar el procés de recuit, que és el factor clau per millorar el rendiment de les cèl·lules solars. Es van produir diferents pel·lícules fines formades pel nostre dispositiu CdZnS/CdS/CIGS/Mo que utilitzaven una capa conductiva CdZnS transparent per minimitzar l'alineació de la interfície. D'altra banda, es van investigar perovskites MAPbI3, amb la finalitat d'optimitzar la composició química i estudiar el procés de cristal·lització també per a conèixer l'estabilitat dels materials de perovskita. la cristal·lització s'aconsegueix alentint la solubilitat en una solució saturada mitjançant l'addició d'una quantitat diferent de l'antisolvent d'èter dietílic. Durant el tractament apareixen al mateix temps intercanvis complexos sota la influència de moltes propietats fisicoquímiques. Una comprensió completa d'aquest tema és de vital importància per a millorar el rendiment. Amb l'objectiu principal d'augmentar l'estabilitat de MAPbI3, el tetrabutilamoni (TBA) es pot incorporar a MAPbI3, impulsant la formació de l'estructura de perovskita, la qual cosa porta a una major orientació al llarg de (110). MAPbI3 dopades amb TBA presenten una millora de la cristalinitat, major grandària, la qual cosa és adequada per a la fabricació de dispositius optoelectròniques de major rendiment. A més, hem identificat l'impacte de TBA en les propietats foto físiques de MAPbI3. Hem notat que el dopatge amb TBA millora tant l'emissió de la fotoluminiscència en reduir la densitat dels estats de trampes com l'absorció òptica on apareix un canvi significatiu de la banda òptica prohibida cap a longituds d'ona més llargues que significa disminuir l'energia del gap, que va variar de 1.8 a 1.52 eV. Finalment, es va explorar l'estabilitat per les perovsquites dopades amb 5%TBA. Es va trobar que després de 15 dies l'estabilitat romania excel·lent en un humitat de 60%. A més, hem estudiat FAPbI3 com un dels materials de perovskita més atractius. Hem investigat l'efecte de la substitució de guanidini (GA) sobre les propietats estructurals i òptiques de FAPbI3. La relació entre la fase a de perovskita desitjable i la fase indesitjable y es va estudiar en funció del contingut de GA. Es mostra que el dopatge amb GA és eficaç en el control de la relació de fases a /y i després en l'estabilització de la fase a-FaPbI3. Els resultats mostren que una quantitat adequada de 10% GA condueix a una pel·lícula homogènia amb fase a estable, grans grans lliures de porus i forats. Les pel·lícules de 10% GA:FaPbI3 demostraren una excel·lent estabilitat després de l'envelliment durant 15 dies en un ambient humit (humitat relativa de 60%).
Bouich, A. (2020). Study and Characterization of Hybrid Perovskites and Copper-Indium-Gallium Selenide thin films for Tandem Solar Cells [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/160621
TESIS

In2Se3 thin films with different thicknesses have been deposited by thermal evaporation method on glass substrate under vacuum pressure of 10-6 Torr. Structural Properties of these films were studied by different analytical techniques. X- ray diffraction revealed as deposited films have amorphous nature and annealing effect enhanced crystalline structure. Structural studies by XRD results showed the polycrystalline nature of the films. The Full Width at Half Maximum (FWHM) values were observed from the XRD pattern and used to evaluate the microstructural parameters like crystallite size, strain, dislocation density. The optical absorption spectra of In2Se3 films were studied in the wavelength region of 250–2500 nm. The optical properties show that the band gap (Eg) values vary from 2.5 to 3.34 eV as an-nealing temperature varies from 150 to 350C. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35133

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Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Investigations performed in order to understand the electronic and optoelectronic properties of field effect transistors based on few layers of 2D Copper Indium Selenide (CuIn7Se11) are reported. In general, field effect transistors (FETs), electric double layer field effect transistors (EDL-FETs), and photodetectors are crucial part of several electronics based applications such as tele-communication, bio-sensing, and opto-electronic industry. After the discovery of graphene, several 2D semiconductor materials like TMDs (MoS2, WS2, and MoSe2 etc.), group III-VI materials (InSe, GaSe, and SnS2 etc.) are being studied rigorously in order to develop them as components in next generation FETs. Traditionally, thin films of ternary system of Copper Indium Selenide have been extensively studied and used in optoelectronics industry as photoactive component in solar cells. Thus, it is expected that atomically thin 2D layered structure of Copper Indium Selenide can have optical properties that could potentially be more advantageous than its thin film counterpart and could find use for developing next generation nano devices with utility in opto/nano electronics. Field effect transistors were fabricated using few-layers of CuIn7Se11 flakes, which were mechanically exfoliated from bulk crystals grown using chemical vapor transport technique. Our FET transport characterization measurements indicate n-type behavior with electron field effect mobility µFE ≈ 36 cm^2 V^-1 s^-1 at room temperature when Silicon dioxide (SiO2) is used as a back gate. We found that in such back gated field effect transistor an on/off ratio of ~ 10^4 and a subthreshold swing ≈ 1 V/dec can be obtained. Our investigations further indicate that Electronic performance of these materials can be increased significantly when gated from top using an ionic liquid electrolyte [1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6)]. We found that electron field effect mobility µFE can be increased from ~ 3 cm^2 V^-1 s^-1 in SiO2 back gated device to ~ 18 cm^2 V^-1 s^-1 in top gated electrolyte devices. Similarly, subthreshold swing can be improved from ~ 30 V/dec to 0.2 V/dec and on/off ratio can be increased from 10^2 to 10^3 by using an electrolyte as a top gate. These FETs were also tested as phototransistors. Our photo-response characterization indicate photo-responsivity ~ 32 A/W with external quantum efficiency exceeding 10^3 % when excited with a 658 nm wavelength laser at room temperature. Our phototransistor also exhibit response times ~ tens of µs with specific detectivity (D*) values reaching ~ 10^12 Jones. The CuIn7Se11 phototransistor properties can be further tuned & enhanced by applying a back gate voltage along with increased source drain bias. For example, photo-responsivity can gain substantial improvement up to ~ 320 A/W upon application of a gate voltage (Vg = 30 V) and/or increased source-drain bias. The photo-responsivity exhibited by these photo detectors are at least an order of magnitude better than commercially available conventional Si based photo detectors coupled with response times that are orders of magnitude better than several other family of layered materials investigated so far. Further photocurrent generation mechanisms, effect of traps is discussed in detail.

xiii, 84 p. ; ill.
This dissertation describes the deposition and characterization of an amorphous thin film with a composition near that of CuInSe 2 (CIS). The creation of an amorphous intermediate leads to a crystalline film at low annealing temperatures. Thin films were deposited from elemental sources in a custom built high vacuum chamber. Copper-selenium and indium-selenium binary layered samples were investigated to identify interfacial reactions that would form undesired binary intermediate compounds resulting in the need for high temperature annealing. Although the indium-selenium system did not form interfacial compounds on deposit, indium crystallized when the indium layer thickness exceeded 15 angstroms, disrupting the continuity of the elemental layers. Copper-selenium elemental layers with a repeat thickness of over 30 angstroms or compositions with less than 63% selenium formed CuSe on deposit. Several deposition schemes were investigated to identify the proper deposition pattern and thicknesses to form the CIS amorphous film. Simple co-deposition resulted in the nucleation of CIS. A simple stacking of the three elements in the older Se-In-Cu at a repeat thickness of 60 angstroms resulted in the nucleation of CuSe and sometimes CIS. The CIS most likely formed due to the disruption of the elemental layers by the growth of the CuSe. Reduction of the repeat thickness to 20 angstroms eliminated the nucleation of CuSe, as predicted by the study of the binary Cu-Se layered samples, but resulted in the nucleation of CIS, similar to the co-deposited samples. To eliminate both the thick Cu-Se region, and prevent the intermixing of all three elements, a more complex deposition pattern was initiated. The copper and selenium repeat thicknesses were reduced into a Se-Cu-Se-Cu-Se pattern followed by deposition of the indium layer at a total repeat thickness of 60 angstroms. At a Se:Cu ratio of 2:1 and the small repeat thickness, no Cu-Se phases nucleated. Additionally, the Cu-In interface was eliminated. For this deposition scheme, films with a selenium rich composition relative to CuInSez were generally amorphous. Those that were Cu-In rich always nucleated CIS on deposit. Annealing of all samples produced crystalline CIS.
Adviser: David C. Johnson

Geólogo
La globalización junto al constante crecimiento demográfico, ha generado un aumento en la demanda energética a través de nuevas tecnologías capaces de producir, transmitir o conservar energía, como avanzados paneles fotovoltaicos. Para esto, se requiere de una variedad de elementos que incluyen al indio, telurio y selenio (Jaffe et al., 2011). La producción comercial de estos elementos se restringe a la refinación de commodities provenientes de pórfidos o epitermales enriquecidos en In-Te-Se. Esta investigación tiene como objetivo caracterizar los fluidos que formaron la veta Leona perteneciente al distrito de Chancón, ubicado en la Cordillera de la Costa de Chile central. En este estudio se identifican diferencias en la geoquímica de roca total y contenido metálico del fluido con el uso de inclusiones fluidas, la que junto a la petrografía permiten una mejor comprensión del transporte y deposición metálica en vetas de la Cordillera de la Costa. Esta veta muestra una zonación mineral de superficie a profundidad. En superficie se encuentra abundante cuarzo con mineralización de pirita, oro y plata. Mientras que en profundidad se encuentra escaso cuarzo con mineralización de calcopirita, esfalerita, galena y menor pirita. Por otra parte, el análisis geoquímico de roca total en 12 especímenes, reportaron presencia de indio, telurio y selenio en la veta. La interpretación de los datos permite definir tres etapas de mineralización: (1) Etapa pre-mineralización, caracterizada por pirita y calcopirita en cuarzo, (2) Etapa de Au-Ag-metales base, caracterizado por pirita, calcopirita, esfalerita, galena y Au-Ag en pirita y calcopirita, (3) Etapa post mineralizada, caracterizada por calcita, clorita y epidota. La petrografía de inclusiones fluidas mostró Arreglos de Inclusiones Fluidas (FIA s) primarias y secundarias, clasificables como: (a) primarias con inclusiones ricas en líquido coexistiendo con ricas en vapor, en cuarzo euhedral, con temperaturas de homogeneización (Th) entre 250 y 245º C y salinidades entre 6.0 y 7.6% en peso NaCl eq; (b) secundarias con inclusiones ricas en vapor en cuarzo euhedral; (c) secundarias con inclusiones ricas en líquido en cuarzo zonal, con Th entre 250 y 249º C y salinidades entre 0.5 y 0.9% en peso NaCl eq; (d) primarias con inclusiones ricas en líquido con mineralización de calcopirita, con Th entre 240 y 125º C, con salinidades entre 1.6 y 12.6% en peso NaCl eq. Por último, la ablación laser en inclusiones fluidas, mostró enriquecimiento de In, Te, Se, Au, Ag en esfalerita, de lo que se infiere que el transporte metálico habría ocurrido por participación de complejos sulfurados y clorurados.

A novel analytical technique was developed where gaseous hydrogen selenide formed by sodium tetrahydroborate reduction is transported to and trapped on a resistively heated gold-coated W-coil atom trap for in situ preconcentration. The atom trap is held at 165 º
C during the collection stage and is heated up to 675 º
C for revolatilization
analyte species formed are transported to an externally heated quartz T-tube where the atomization takes place and the transient signal is obtained. For gold, a high volume gas liquid separator (HVGLS) was designed to improve the detection limit of Au down to the ng mL-1 levels. In this apparatus, analyte and reductant solutions are collected in a limited volume and volatile analyte species are formed. After separation of the volatile analyte species from liquid phase, the entire analyte vapor is sent to an atomizer. A W-coil trap was used to further decrease the detection limit. The enhancement factor for the characteristic concentration was found to be 10.7 when compared to HG-AAS performance without W-coil trap by using peak height values. Furthermore, the generation of analytically useful volatile form of Au has been studied. The flow injection generation was performed in a dedicated generator consisting of a special mixing apparatus and gas-liquid separator design. The on-line atomization in the quartz tube multiatomizer for atomic absorption (AAS) detection has been employed as the convenient atomization/detection mean. 198Au, 199Au radioactive indicator of high specific activity together with AAS measurements was used to track quantitatively the transfer of analyte in the course of generation and transport to the atomizer. In-situ trapping in GF for AAS was explored as an alternative to the on-line atomization. Transmission electron microscopy measurements proved the presence of Au nanoparticles of diameter of approximately 10 nm and smaller transported from the generator by the flow of carrier Ar. For silver, three types of GLS which are U-shaped, cylindrical and high volume gas liquid separators (HVGLS) were used to compare the sensitivities of these GLSs during Ag determination. The DL (3s) values were found as 29 ng mL-1, 0.4 ng mL-1 and 0.05 ng mL-1 for U-shaped GLS, cylindrical GLS with W-coil trap and HVGLS with W-coil trap, respectively. For indium, two types of GLS which are cylindrical and HVGLS with W-coil trap were used. The LOD and characteristic concentration were found as 148 and 317 ng mL-1 with cylindrical shape GLS. HVGLS with W-coil trap was used to improve sensitivity. In this case, LOD and characteristic concentration were found to be 0.46 and 0.98 ng mL-1, respectively. Moreover, to increase the reactivity between indium and reductant solutions, Ru(acac)3 catalyst was used. In this case, LOD and characteristic concentration were found to be 0.13 and 0.23 ng mL-1, respectively. In the case of using this catalyst, sensitivity was enhanced around 1378 fold with respect to cylindrical GLS.

Ternary chalcopyrite compounds are the semiconductors with suitable properties to be used as absorber materials in thin film solar cells. AgInSe2 is a promising candidate with its several advantages over the widely used CuInSe2. The purpose of this study was to optimize the physical properties of the Ag-In-Se (AIS) thin films that were deposited by e-beam evaporation of Ag3In5Se9 single crystal powder for solar cell applications by means of post-annealing process under nitrogen atmosphere. The as-grown AIS thin films were annealed at 200, 300 and 400oC and their structural, optical, electrical and photoelectrical properties were examined to observe the effects of post-annealing process. Structural characterization of the films was performed by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) analyses. Optical properties of the films were investigated by optical transmittance measurements. Electrical and photoelectrical properties of the films were examined by temperature dependent conductivity, photoconductivity under different illumination intensities and spectral photoresponse measurements. It was discovered that the annealing of AIS thin films at 200oC resulted in the best physical properties for solar cell applications. The obtained films were polycrystalline with mixed binary and ternary crystalline phases, such as Ag3In5Se9, AgInSe2 and InSe, and showed n-type conductivity with room temperature conductivity value of 2.3x10-6 (Ohm­
cm)-1. The band gap energy of the 200oC-annealed films was determined as 1.68 eV from spectral photoresponse measurements. The results of the study revealed that the inadequate Ag incorporation and segregation and/or reevaporation of Se atoms at high annealing temperatures were the major problems encountered in producing single phase polycrystalline AgInSe2 thin films. The required stoichiometry of thin films should be maintained during the growth of the films by means of an alternative deposition procedure and the films should be selenized during post-annealing process.

 Molecular Beam Epitaxy is an advanced method for the synthesis of single-crystal thin-film structures. However, the growth behavior varies case by case due to the complicated kinetic process. In this thesis, the epitaxial growth processes of AlxIn1-xN alloy and Bi2Se3 thin-films are studied. Heteroepitaxial growth of AlxIn1-xN alloy on GaN(0001) substrate is carried out in the Nitrogen-rich flux conditions. A series of transient growth stages are identified from the initiation of the deposition. A significant effect of source beam-flux on the incorporation rate of Indium atoms is observed and measured. A correlation between the incorporation rate and the growth conditions (flux ratio and growth temperature) is revealed by the dependence of the growth-rate of the film on beam fluxes. A mathematic model is then suggested to explain the effect, through which the measured results indicating a surface diffusing and trapping process is indicated. Unexpected behavior of the lattice-parameter evolution of the growth front during deposition is also observed, indicating a complex strain-relaxation process of the epilayers. For three-dimensional (3D) topological insulator of Bi2Se3, growths are attempted on various substrate surfaces, including clean Si(111)-(7x7), Hydrogen terminated Si(111), Bismuth induced Si(111) reconstructed surfaces, GaN(0001), and some selenide “psudo-substrates”. The specific formation process of this quintuple-layered material in MBE is investigated, from which the Van der Waals epitaxy growth characteristics inherent to deposition of Bi2Se3 is determined, and the mechanism of the “two-step growth” technique for this material is further clarified. Among the various substrates, those that are inert to chemical reaction with Bi/Se are important for the growth. The epilayers’ lattice-misfit with the substrate is also a crucial factor to the structural quality of the Bi2Se3 epifilms, such as the defects density and the single-crystalline domain size. The effect of a vicinal substrate on suppressing the twin-defects in film is also addressed. Using a suitable substrate and adapting an optimal condition, ultra-thin films of Bi2Se3 with a superior structural quality have been achieved. Multilayered Bi2Se3 structures with ZnSe and In2Se3 spacers are attempted. Finally the high-quality superlattices of Bi2Se3/In2Se3 are successfully synthesized. The hetero-interfaces in the superlattice structure of Bi2Se3/In2Se3 are sharp, and the individual layers are uniform with thicknesses being strictly controlled. The behaviors of strain evolution during the hetero-growth process are finally investigated. An exponential relaxation of misfit strain is observed. And the correlation between the residual strain and the starting surface in the initial growth stage is also identified.
published_or_final_version
Physics
Doctoral
Doctor of Philosophy

With the advent of the 21st century, one of the serious problems facing mankind is harmful effects of global warming. Add to that the ever increasing cost of fuel and the importance of development of clean energy resources as alternative to fossil fuel has becomes one of the prime and pressing challenges for modern science and technology in the 21st century. Recent studies have shown that energy related sources account for 50% of the total emission of carbon dioxide in the atmosphere. All research activities are focused on developing various technologies that are capable of converting sunlight into electricity with high efficiency and can be produced using a cost-effective process. One of such technologies is the CuIn[sub1-x]Ga[subx]Se[sub2] (CIGS) and its alloys that can be produced using cost-effective techniques and also exhibit high photo-conversion efficiency. The work presented here discusses some of the fundamental issues related to high volume production of CIGS thin film solar cells. Three principal issues that have been addressed in this work are effect of reduction in absorber thickness on device performance, micrononuniformity involved with amount of sodium and its effect on device performance and lastly the effect of working distance on the properties of molybdenum back contact. An effort has been made to understand the effect of absorber thickness on PV parameters and optimize the process parameters accordingly. Very thin (<1 [micro]m) absorber film were prepared by selenization using metallorganic selenium source in a conventional furnace and by RTP using Se vapor. Sulfurization was carried out using H2S gas. Devices with efficiencies reaching 9% were prepared for very thin (<1 [micro]m) CIGS and CIGSeS thin films. It was shown through this work that the absorber thickness reduction of 64% results in the efficiency drop of only 32%. With further optimization of the reaction process of the absorber layer as well as the other layers higher efficiencies can be achieved. The effect of sodium on the device performance is experimentally verified in this work. To the best of our knowledge the detrimental effect of excess sodium has been verified by experimental data and effort has been made to correlate the variation in PV parameter to theoretical models of effect of sodium. It has been a regular practice to deposit thin barrier layer prior to molybdenum deposition to reduce the micrononuniformities caused due to nonuniform out diffusion of sodium from the soda lime glass. However, it was proven in this work that an optimally thick barrier layer is necessary to reduce the out diffusion of sodium to negligible quantities and thus reduce the micrononuniformities. Molybdenum back contact deposition is a bottleneck in high volume manufacturing due to the current state of art where multi layer molybdenum film needs to be deposited to achieve the required properties. In order to understand and solve this problem experiments were carried out. The effect of working distance (distance between the target and the substrate) on film properties was studied and is presented in this work. During the course of this work efforts were taken to carry out a systematic and detailed study of some of the fundamental issues related to CIGS technology and particular for high volume manufacturing of CIGS PV modules and lay a good foundation for further improvement of PV performance of CIGS thin film solar cells prepared by the two step process of selenization and sulfurization of sputtered metallic precursors.
ID: 030423396; System requirements: World Wide Web browser and PDF reader.; Mode of access: World Wide Web.; Thesis (Ph.D.)--University of Central Florida, 2010.; Includes bibliographical references (p. 108-116).
Ph.D.
Doctorate
Department of Electrical Engineering and Computer Science
Engineering and Computer Science

We developed a three-step colloidal synthesis of near-infrared active Cu-In-Se (CISe)/ZnS core/shell nanocrystals (NCs) via a sequential partial cation exchange. In the first step binary highly copper deficient Cu2‒xSe NCs were synthesized, followed by a partial cation exchange of copper to indium ions yielding CISe NCs. In order to enhance the stability and the photoluminescence (PL) properties of the NCs, a subsequent ZnS shell was grown, resulting in CISe/ZnS core/shell NCs. These core/shell hetero-NCs exhibited a dramatic increase in size and a restructuring to trigonal pyramidal particles. The reaction parameters, e.g. the Cu:Se-ratio, the temperature and the time were carefully tuned enabling a distinct control over the size and the composition of the NCs. By varying only the size of the CISe/ZnS NCs (from 9 to 18 nm) the PL spectra could be tuned covering a wide range with maxima from 990 nm to 1210 nm. Thus, in these experiments we demonstrate a clear dependence of the optical properties of these materials on their size and extend the PL range of CISe-based nanoparticles further to the infrared part of the spectrum. Furthermore, the relatively large size of these NCs allows their detailed structural analysis via electron microscopy techniques, which is particularly challenging in the case of small particles and especially important to relate the size, composition and crystal structure to their optoelectronic properties.

Objetivou-se determinar os efeitos de dietas contendo três fontes de lipídeos (semente de girassol, caroço de algodão e soja em grão \"in natura\") e duas de selênio (orgânico ou inorgânico) sobre o desempenho animal, características de carcaça e qualidade da carne de bovinos da raça Nelore (Bos taurus indicus). Foram utilizados 54 machos, castrados, com idade média de 30 meses e com peso vivo médio de 458 ± 39 kg no início do experimento. Os animais foram distribuídos em blocos, de acordo com o peso inicial, com delineamento em arranjo fatorial de tratamentos do tipo 3x2, cujos fatores de variação foram três fontes de lipídeos e duas fontes de selênio. Cada grupo de três animais foi alojado em uma baia por um período de 120 dias. As características de rendimento de carcaça, área de olho de lombo, espessura de gordura subcutânea, índice de marmorização, perdas totais ao cozimento e maciez objetiva não foram influenciadas pelo tipo de fontes de lipídeos ou de selênio na dieta. A inclusão de fonte orgânica de selênio resultou em maior concentração deste elemento no tecido muscular, quando comparada à fonte de selênio inorgânica. As fontes de lipídeos utilizadas na dieta influenciaram o atributo de suculência e sabor estranho da carne dos animais estudados enquanto a fonte de selênio influenciou apenas no atributo de sabor estranho.
This study was carried out to determine the effects of the inclusion of three sources of fat (sunflower seed, whole cottonseed and raw soybean ) and two sources of selenium (organic or inorganic) in the diets fed to Nellore cattle (Bos taurus indicus) on the animal performance and carcass and meat quality characteristics. Fifty-four bovine males, castrated, with an average age of 30 months and 458 ± 39 kg at the beginning of the experiment were distributed, according to initial weight, in blocks with a 3x2 factorial arrangement: three sources of lipids and two sources of selenium. The animals were housed in stalls, three per pen, during 120 days. Carcass characteristics (carcass yield, the rib eye area, fat thickness, marbling index and shear force) were not influenced by the fat or selenium sources in the diet. The inclusion of organic source of selenium resulted in higher concentration in the muscle, compared to the inorganic source. The fat source used in diet influenced the attribute of juiciness and strange flavor of the animals meat studied, however the selenium source influenced only the attribute of taste.

The objective of this study is analysing the characteristics of five different solar cell technologies regarding their efficiency, fill factor, cost and environmental impacts and comparing their improvement records over years considering their efficiency. The five solar cell technologies of interest are amorphous silicon, monocrystalline silicon, polycrystalline silicon, cupper indium gallium selenide thin film and cadmium telluride thin film. The structure and manufacturing process of each of cell technologies were discussed. The study was conducted by the aid of available scientific reports regarding the electrical characteristics of different solar cell technologies. The extracted information regarding efficiency rate and fill factor was analysed using graphs and significant findings are discussed. The five technologies are also compared regarding their cost and ease of fabrication and their impacts on environment and recycling challenges. The result of this study is suggesting the most promising technology that may be the optimal option for further investment and research.

Mesures de conductivite et d'effet hall entre 4 et 300k. Les comportements des echantillons recuits ou trempes s'interpretent par des processus de diffusion des electrons impliquant phonons acoustiques et impuretes neutres. L'etude d'un cycle chauffage-refroidissement traversant la temperature de transition revele un effet d'hysteresis pouvant etre attribue a l'existence de multidomasines. L'effet de plusieurs cycles successifs se traduit par une decoissance graduelle de la conductivite en fonction du nombre de cycles repetes

Conselho Nacional de Desenvolvimento Científico e Tecnológico
Indium(III) benzenechalcogenolates (chalcogen = sulfur, selenium) prepared from elemental indium and diphenyl dichalcogenide provide an alternative synthetic route to produce carbon-chalcogen bonds. These compounds promote the regioselective hydrochalcogenation of terminal aminoalkynes to produce the Markovnikov adducts; provide a pratical method to prepare organyl phenyl chalcogenides from organyl halides; and their reaction with vinylarenes in aqueous media produces the respectives β-hydroxy selenides. Ditellurides present a different performance compared to others studied dichalcogenides. Indium(I) salts react with tellurium compounds and through extrusion of one tellurium atom produce diaryl tellurides. This work presents new synthetic methodologies and discusses the general aspects and limitations of indium chalcogenolates in the different systems investigated.
Fenilcalcogenolatos de índio(III) (calcogênio = enxofre e selênio), preparados a partir de índio metálico e difenil dicalcogenetos, são uma alternativa em síntese para geração de ligações carbono-calcogênio. Estes compostos promovem a hidrocalcogenação Markovnikov de alquinilaminas terminais com rigorosa regiosseletividade; conduzem, de modo prático, ao preparo de organil fenilcalcogenetos frente a haletos orgânicos; e na reação com estirenos possibilitam a síntese de β-hidroxisselenetos em meio aquoso. Já os diteluretos empregados apresentam comportamento diferenciado em relação aos demais dicalcogenetos estudados. A reação de sais de índio(I) com os compostos de telúrio conduzem a extrusão de telúrio e a obtenção de diaril teluretos. O trabalho desenvolvido, além de apresentar novas metodologias sintéticas, discute as generalidades e limitações dos calcogenolatos de índio nos diferentes sistemas investigados.

L'etude des echantillons massifs de cuin::(1-x)ga::(x)se::(2) de type p permet de mettre au point la solution electrolytique acide en presence du couple redix v**(2+/3+). Etude des positions energetiques des bandes par mesures capacitives. Etude de la variation de la bande interdite en fonction de x et mesure des longueurs de diffusion par l'evolution du photocourant en fonction du potentiel. Etude des proprietes optiques et electroniques des couches minces cugase::(2) de type p en fonction des ecarts a la stoechiometrie

De nombreux métaux tels que, par exemple le Zn, le Fe, le Cu ou le Ni jouent un rôle essentiel dans la croissance et le développement normal des plantes car ils sont impliqués dans différents processus physiologiques pouvant être cependant perturbés par une carence ou un excès en métaux. Par conséquent, afin de réguler l'absorption des métaux, leur translocation et leur accumulation, les plantes ont développé des mécanismes divers, comme la production de métabolites de faible poids moléculaire pouvant se lier aux métaux. La connaissance de ces complexes métalliques et des processus qu'ils subissent dans les plantes peut être utilisée dans des études environnementales, nutritionnelles et toxicologiques. Cependant, cette connaissance était très limitée à cause de l'absence de méthodologie appliquée avec succès pour étudier la spéciation des traces de métaux dans les végétaux. Par conséquent, le but de cette étude fut le développement d'une méthodologie d'analyse des espèces métalliques dans des échantillons de plantes. La nouvelle approche est basée sur l'utilisation conjointe du (i) couplage HPLC – ICP MS permettant la détection de nombreuses espèces, souvent peu concentrées, contenant des métaux avec (ii) une identification en parallèle par couplage HPLC – electrospray Orbitrap MS/MS. Elle a permis l'identification (i) d’environ 60 espèces métalliques, la plupart jamais observées précédemment dans différents fluides (xylème, endosperme liquide) de Pisum sativum (petit pois) et (ii) de plusieurs complexes mixtes fer - aluminium - citrate chez Plantago almogravensis. La méthodologie développée a également été appliquée à (iii) la spéciation du sélénium dans Brassica nigra permettant l'identification de plus de 30 composés de faible poids moléculaire contenant du sélénium
Numerous metals, such as, e.g. Zn, Fe, Cu or Ni play an essential role in normal plant growth and development as they are involved in different physiological processes that may be, however, disrupted by metal deficiency or excess. Therefore, to regulate metal uptake, translocation and accumulation plants have developed diverse mechanisms including the production of low molecular mass metal binding metabolites. The knowledge of these forms of metals and the processes they undergo in plants can be used in environmental, nutrition and toxicological studies. However, this knowledge was very limited as there was a lack of methodology that could be successfully applied to investigate trace metal speciation in plants. Therefore, the aim of this study was the development of the methodology for the analysis of metal species in complex plant samples. The novel approach is based on the use of combination of (i) HPLC – ICP MS coupling allowing the detection of numerous, often low concentrated, metal-containing species with (ii) a parallel identification using HPLC – electrospray Orbitrap MS/MS coupling. The developed approach allowed the identification of (i) ca. 60 different, mainly previously unreported metal species in saps of Pisum Sativum (green pea) and (ii) several mixed iron – aluminum – citrate complexes in Plantago almogravensis. This developed methodology was also applied to (iii) investigate selenium speciation in Brassica nigra allowing the identification of more than 30 selenium-containing low molecular mass compounds

Differentes methodes de calcul des proprietes optiques des couches minces optiques a profil d'indice continu sont presentees. Dans le cas des filtres rugates, l'utilisation de methodes analytiques a notamment permis un calcul des enveloppes des spectres ainsi que l'optimisation du profil d'indice. Un nouveau systeme de coevaporation sous vide a ete developpe pour realiser des filtres a profil d'indice continu. Des couches minces homogenes de zns, znse, mgf#2, ainsi que de zns-mgf#2 et de znfe-mgf#2 de differentes compositions ont ete realisees. Il apparait que le zns presente un probleme de condensation lorsqu'il est codepose avec du mgf#2, meme sur substrat froid. Le znse ne presente pas ce probleme lorsque celui-ci est majoritaire dans un melange realise a froid. Des filtres rugates a profil d'indice sinusoidal, comportant jusqu'a 20 periodes, ont ete realises en znse-mgf#2 depose sur substrat froid. Leurs spectres de reflexion et de transmission sont conformes aux simulations numeriques. Un atout important des filtres rugates par rapport aux multicouches a par ailleurs ete mis en evidence: les faibles contraintes dans les couches de melanges znse-mgf#2 et dans les filtres realises devraient autoriser la realisation de films epais, ce qui est une necessite pour la realisation de miroirs de faible largeur de bande

碩士
國立中山大學
電機工程學系研究所
102
Low cost and high efficiency are continuous interests for the fabrication of solar cells. I-III-VI compound semiconductor Cu(In,Ga)Se2 (CIGS) is the most important absorber material in developing thin film solar cells. The band gap of CIGS varies from about 1.0 to 1.7 eV, which is within the maximum solar absorption region. This is very important for the optimum conversion efficiency. The extraordinarily high absorption coefficient from direct band gap leads to thinner thickness and lower fabrication cost for its use in thin film solar cells. In this experiment, we deposited CuInGa and Cu(In,Ga)Se2 alloy layers on soda-lime glasses by RF sputtering separately and then used selenization process to form Cu(In,Ga)Se2 thin films. We study the effects of selenized temperatures and processes on the qualities and characteristics of CIGS thin film.

碩士
大同大學
電機工程學系(所)
107
Van der Waals epitaxial thin films are payed attention duo to the potential application in the atomic-layer transistors. The unique two-dimensional (2-D) layer by layer structure make a chance to demonstrate the mono-atomic electrical device. The Van der Waal’s Indium Selenide (InSe) thin films were grown by home-made molecular beam epitaxial system. According to the phase diagram of In-Se, the deformation temperature difference between InSe and In2Se3 is as high as 200 degrees. In order to grow the high crystal quality, the high temperature process is better than the lower one. When the growth temperature is high as 560 ℃, α type di-indium tri-selenide (α-In2Se3) is demonstrated on c-plane sapphire. Next topics is to grow InSe, it means that the atomic concentration ratio of In/Se needs to transfer from 2/3 to 1. However, either increase indium or decrease selenium temperature, the pure InSe cannot be found. There are several methods were employed, such as interface pretreatment, migration-enhanced epitaxy, annealing process, and the post-indium treatment. The post-Indium treatment, which process the deposited layer under the indium flow at higher substrate temperature, exhibits outstanding performance. The as grown α-In2Se3 is successfully transformed to pure InSe thin films. The crystal structure and phase transformation were defined by X-ray diffraction and Raman spectra. Transmission electron microscopy images exhibit the clear InSe layer structure. An ultra-thin InSe, which is around 9 mono-layers, is demonstrated by reduce the growth time and post indium treatment. Finally, the ultra-thin InSe MOSFET is successfully demonstrated.

碩士
國立交通大學
電子物理系所
106
1/f noise is a common phenomenon in electric devices. The noise magnitude depends inversely with frequency and sample volume. Due to the requirement of high speed, low power consumption, low cost, smaller devices are demanded. However, the 1/f noise will limit the performance of small devices. For instance, sensor with high sensitivity demands high resolution. Thus, exploring the mechanism of 1/f noise in small devices is important. In this study, we have performed Id(Vg) and 1/f measurement simultaneously in 2D InSe transistors. According to our measurement, the parameters such as low field mobility μ0, field effect mobility μFE, interface trap density Dit, oxide trap density Not, and Coulomb scattering parameter S, can be extracted. These parameters govern the Id(Vg) and 1/f noise microscopically.

Thesis (M.S.)--Florida State University, 2006.
Advisor: Peter Kalu, Florida State University, College of Engineering, Dept. of Mechanical Engineering. Title and description from dissertation home page (viewed Sept. 22, 2006). Document formatted into pages; contains x, 77 pages. Includes bibliographical references.

碩士
國立成功大學
化學系碩博士班
95
Two new quaternary compounds of Ba4AgInSe6 and Ba4Cu3In3Se10 have been synthesized by the flux-growth methods at 800℃. The compound of Ba4AgInSe6 crystallizes in triclinic, P-1, a = 4.509 Å, b = 9.19480(10) Å, c = 17.8841(2) Å, α = 89.9980(10)°, β= 90.0010(10)°, γ= 90.0020(10)°, z = 4 and V = 741.447(12) Å3. The structure is composed of [MSe4] (M = Ag and In) tetrahedra to form one-dimensional chains by corner-sharing. The bond distances of M-Se are between 2.6140(9) Å and 2.6655(9) Å, which values correspond to the average distances as the metal sites occupied by both indium and silver ions. The barium ions are located between these chains and surrounded by seven selenium anions with the Ba-Se distances distributed between 3.2118(8) Å and 3.4812(8) Å. The measure band-gap of the compound is 1.81eV .The compound of Ba4Cu3In3Se10 crystallizes in monoclinic, P21/c, a = 4.0839(8) Å, b = 27.148(5) Å, c = 21.599(4) Å, α = 90°, β= 90.05(3)°, γ= 90°, z = 8 and V = 2394.7(8) Å3. The structure is composed of [CuSe5] square pyramids and [CuSe6] octahedra to form two-dimensional slabs by edge-sharing where [InSe4] tetrahedra surround the periphery of slabs by corner-sharing. Interestingly, the copper polyhedra are arranged as the antifluorite-like connectivity in the slabs. The barium ions are located between these slabs and surrounded by eight selenium anions.