Spelling suggestions: "subject:"metalloxide"" "subject:"metalloxiden""
1 |
Preparation et performance d'une cellule photocatalytique à base d'hématite pour la génération d'hydrogèneBouhjar, Feriel 27 July 2018 (has links)
El hidrógeno es un portador de energía que ya ha demostrado su capacidad para reemplazar el
petróleo como combustible. Sin embargo, los medios de producción actualmente en uso
siguen siendo altamente emisores de gases de efecto invernadero. La foto-electrólisis del agua
es un proceso que, a partir de la energía solar, separa los compuestos elementales del agua
como el hidrógeno y el oxígeno utilizando un semiconductor con propiedades físicas
adecuadas. La hematita (¿-Fe2O3) es un material prometedor para esta aplicación debido a su
estabilidad química y su capacidad para absorber una porción significativa de la luz (con una
banda prohibida entre 2.0 - 2.2 eV). A pesar de estas propiedades ventajosas, existen
limitaciones intrínsecas al uso de óxido de hierro para la descomposición fotoelectroquímica
del agua. La primera restricción es la posición de su banda de conducción que es menor que el
potencial de reducción de agua. Esta limitación se puede superar mediante la adición en serie
de un segundo material, en tándem, que absorberá una parte complementaria del espectro
solar y llevar a los electrones a un nivel de energía más alto que el potencial para la liberación
de hidrógeno. El segundo obstáculo proviene del desacuerdo entre la corta longitud de
difusión de los portadores de carga y la profundidad de penetración larga de la luz. Por lo
tanto, es necesario controlar la morfología de los electrodos de hematita en una escala de
tamaño similar a la longitud de transporte del orificio.
En esta tesis, se introduce un nuevo concepto para mejorar el rendimiento fotoelectroquímico
de la hematita. Usando el método hidrotermal depositamos capas delgadas de hematita dopada
con Cr en sustratos de vidrio conductivo. También se ha preparado por medios
electroquímicos una heterounión del tipo p-CuSCN/n-Fe2O3 depositando secuencialmente una
capa de ¿-Fe2O3 y una película de CuSCNsobre sustratos de FTO (SnO2: F).Finalmente, se ha
preparado células solares de perovskitas y óxido de hierro. Para ello se depositó una capa
delgada, densa y uniformede óxido de hierro (¿-Fe2O3) como capa de transporte de electrones
(ETL) en lugar de dióxido de titanio (TiO2) que se utiliza convencionalmente en las células
fotovoltaicas perovskitastipoCH3NH3PbI3 (SGP). Este último dispositivo mostró un aumento
en la fotocorriente del 20% y un IPCE30 veces mayor que la hematita simple, lo que sugiere
una mejor conversión de las longitudes de onda por encima de 500 nm.
Palabras clave:
Fotoelectroquímica, división de agua, producción de hidrógeno, evolución de oxígeno,
semiconductores de óxido de metal, hematita, óxido de hierro, nanoestructuras / Hydrogen is an energy carrier that has already demonstrated its ability to replace oil as a fuel.
However, the means of production currently used remain highly emitting greenhouse gases.
Photo-electrolysis of water is a process that uses solar energy to separate the elemental
compounds of water such as hydrogen and oxygen using a semiconductor with adequate
physical properties. Hematite (¿-Fe2O3) is a promising material for this application because of
its chemical stability and ability to absorb a significant portion of light (with a band-gap
between 2.0 - 2.2 eV). Despite these advantageous properties, there are intrinsic limitations to
the use of iron oxide for the photoelectrochemical cracking of water. The first constraint is the
position of its conduction band, which is lower than the water reduction potential. This
constraint can be overcome by the addition in series of a second material, in tandem, which
will absorb a complementary part of the solar spectrum and bring the electrons to a higher
energy level than the potential of hydrogen release. The second obstacle comes from the
disagreement between the short diffusion length of the charge carriers and the long light
penetration depth. It is therefore necessary to control the morphology of the hematite
electrodes on a scale of similar size to the transport length of the hole.
In this thesis a new concept is introduced to improve the photoelectrochemical performances.
Using the hydrothermal method we deposited thin layers of Cr-doped hematite on conductive
glass substrates. We also electrochemically prepared a p-CuSCN / n-Fe2O3 heterojunction by
sequentially depositing ¿-Fe2O3 and CuSCN films on FTO (SnO2: F) substrates. Finally, we
have used uniform and dense thin layers of iron oxide (¿-Fe2O3) as an electron transport layer
(ETL) in place of titanium dioxide (TiO2) conventionally used in photovoltaic cells based on
perovskites CH3NH3PbI3 (PSC). This latter concept showed a 20% increase of the
photocurrent and an IPCE 30 times greater than the simple hematite, suggesting better
conversion of high wavelengths (> 500 nm).
Keywords:
Photoelectrochemistry, Water Splitting, Hydrogen Production, Oxygen Evolution, MetalOxide
Semiconductors, Hematite, Iron Oxide, Nanostructures, Surface. / L'hidrogen és un proveïdor d'energia que ja ha demostrat la seva capacitat per reemplaçar el
petroli com a combustible, però els mitjans de producció actuals continuen essent fortament
emissors dels gasos responsables d'efecte hivernacle. La fotoelectròlisi de l'aigua és un procés
que, a partir de l'energia solar, separa els compostos elementals d'aigua com l'hidrogen i
l'oxigen utilitzant un semiconductor amb propietats físiques adequades. La hematita (¿-Fe2O3)
és un material prometedor per a aquesta aplicació a causa de la seva estabilitat química i
capacitat d'absorbir una porció significativa de la llum (amb un gap entre 2,0 i 2,2 eV).
Malgrat aquestes propietats avantatjoses, hi ha limitacions intrínseques per a l'ús d'òxid de
ferro per a la descomposició fotoelectroquímica de l'aigua. La primera restricció és la posició
de la seva banda de conducció que és inferior al potencial de reducció d'aigua. Aquesta
limitació es pot superar mitjançant l'addició en sèrie d'un segon material, en tàndem, que
absorbirà una part complementària de l'espectre solar i portar els electrons a un nivell
d'energia més alt que el potencial per a l'alliberament d'hidrogen. El segon obstacle prové del
desacord entre la curta durada de la difusió dels portadors de càrrega i la llarga profunditat de
penetració de la llum. Per tant, és necessari controlar la morfologia dels elèctrodes d'hematita
en una escala de mida similar a la longitud del forat del transport.
En aquesta tesi, es presenta un nou concepte per millorar el rendiment fotoelectroquímic.
Mitjançant el mètode hidrotermal es van dipositar capes primes de hematita Cr-doped sobre
substrats de vidre conductor. També s'han preparat electroquímicamentheterounions de tipus
p-CuSCN/n-Fe2O3 dipositant seqüencialment una capa de ¿-Fe2O3 i altra de CuSCN sobre
substrats FTO (SnO2: F).Finalment, s'han produït cél·lules solars de perovskitesi óxid de
ferro. Per això es va depositaruna capa prima,densai uniforme d'òxid de ferro (¿-Fe2O3) com
a capa de transport d'electrons (ETL) en lloc de diòxid de titani (TiO2) que s'utilitza
convencionalment en les cèl·lules fotovoltaiques de perovskita híbrida del tipus CH3NH3PbI3
(SGP). Aquest últim dispositiu va mostrar un augment del fotocorrent del 20% i una IPCE30
vegades superior a la hematita simple, la qual cosa suggereix una millor conversió a longitud
d'ones per sobre de 500 nm.
Paraules clau:Fotoelectroquímica, divisió d'aigua, producció d'hidrogen, evolució d'oxigen,
semiconductors d'òxids metàl·lics, hematita, òxid de ferro, nanoestructures. / Bouhjar, F. (2018). Preparation et performance d'une cellule photocatalytique à base d'hématite pour la génération d'hydrogène [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/106345 / TESIS
|
2 |
Atomistic Study of Carrier Transmission in Hetero-phase MoS2 StructuresSaha, Dipankar January 2017 (has links) (PDF)
In recent years, the use of first-principles based atomistic modeling technique has become extremely popular to gain better insights on the various locally modulated electronic properties of nano materials and structures. Atomistic modeling offers the benefit of predicting crystal structures, visualizing orbital distribution and electron density, as well as understanding material properties which are hard to access experimentally.
The single layer MoS2 has emerged as a suitable choice for the next generation nano devices, owing to its distinctive electrical, optical and mechanical properties like, better electrostatics, increased photo luminescence, higher mechanical flexibility, etc. The realization of decananometer scale digital switches with the single layer MoS2 as the channel may provide many significant advantages such as, high On/Off current ratio, excellent electrostatic control of the gate, low leakage, etc.
However, there are quite a few critical issues such as, forming low resistance source/drain contacts, achieving higher effective mobility, ensuring large scale controlled growth, etc. which need to be addressed for successful implementation of the atomically thin transistors in integrated circuits. Recent experimental demonstration showing the coexistence of metallic and semiconducting phases in the same monolayer MoS2, has attracted much attention for its use in ultra-low contact resistance-MoS2 transistors. Howbeit, the electronic structures of the metallic-to-semiconducting phase boundaries, which appear to dictate the carrier injection in such transistors, are not yet well understood.
In this work, we first develop the geometrically optimized atomistic models of the 2H-1T′ hetero-phase structures with two distinct phase boundaries, β and γ. We then apply density functional theory to calculate the electronic structures for those optimized geometries. Furthermore, we employ non equilibrium Green’s function formalism to evaluate the transmission spectra and the local density of states in order to assess the Schottky barrier nature of the phase boundaries.
Nonetheless, the symmetry of the source-channel and drain-channel junction, is a unique property of a metal-oxide semiconductor field effect transistor (MOSFET), which needs to be preserved while realizing sub-10 nm channel length devices using advanced technology. Employing experimental-findings-driven atomistic modeling technique, we demonstrate that such symmetry might not be preserved in an atomically thin phase-engineered MoS2- based MOSFET. It originates from the two distinct atomic patterns at phase boundaries (β and β*) when the semiconducting phase (channel) is sandwiched between the two metallic phases (source and drain).
Next, using first principles based quantum transport calculations we demonstrate that due to the clusterization of “Mo” atoms in 1T′ MoS2, the transmission along the zigzag direction is significantly higher than that in the armchair direction. Moreover, to achieve excellent impedance matching with various metal contacts (such as, “Au”, “Pd”, etc.), we further develop the atomistic models of metal-1T′ MoS2 edge contact geometries and compute their resistance values.
Other than the charge carrier transport, analysing the heat transport across the channel is also crucial in designing the ultra-thin next generation transistors. Hence, in this thesis work, we have investigated the electro-thermal transport properties of single layer MoS2, in quasi ballistic regime. Besides the perfect monolayer in its pristine form, we have also considered various line defects which have been experimentally observed in mechanically exfoliated MoS2 samples. Furthermore, a comprehensive study on the phonon thermal conductivity of a suspended monolayer MoS2, has been incorporated in this thesis.
The studies presented in this thesis could be useful for understanding the carrier transport in atomically thin devices and designing the ultra-thin next generation transistors.
|
3 |
Studies On CVD And ALD Of Thin Films Of Substituted And Composite Metal Oxides, Including Potential High-k DielectricsGairola, Anshita 09 1900 (has links) (PDF)
The work carried out as a part of this thesis has been focussed on understanding different aspects of the chemical vapor deposition process namely, ALD / MOCVD. A large part of the thesis is aimed at solving the problem of a single-source precursor for the MOCVD process to obtain substituted metal oxide thin films. For a chemical vapor deposition technique, it is important to understand the requisite salient features of precursor for deposition of thin films. For this purpose, not only is the structural characterization of the chemical precursor is required but also an in-depth thermal analysis of the precursor to know its vapor pressure. Vapor pressure of a metalorganic complex is one of the important properties to evaluate the applicability of a metalorganic complex as a MOCV/ALD precursor. The thesis discusses a novel approach to use thermal analysis as a tool to gauge the viability of substituted metal “single source” precursor for MOCVD/ALD. The other half deals with material characterization of thin films grown by an ALD process using hydrogen and Ti(OiPr)2(tbob)2 as precursors. The films were further studied for their potential application as high-k dielectric in DRAM applications.
The first chapter is an overview of topics that are relevant to the work carried out in this thesis. The chapter focuses on the description of techniques used for thin film deposition. A detailed review of CVD-type techniques (ALD/ MOCVD) is then given. Chapter1 reviews the various process parameters involved in ALD,i.e. film growth(specifically as a function of the reactant pulse length, the nature of the chemical reactant/precursor and that of the metal precursor, and purge length) and growth temperature. Following the discussion of ALD, CVD and its growth kinetics are also discussed. Chapter 1 then outlines a holistic understanding of precursors, followed the differences in requirement for using them in ALD and MOCVD. Further, an introduction to the titanium oxide (Stoichiometric titanium dioxide and various Magneli phases) system, its phase diagram, oxide properties and their applications is given. Chapter 1 concludes by delineating the scope of the work carried out which is presented in the thesis.
The second chapter deals with the synthesis of a series of substituted metal “single source” precursors to be used for MOCVD of substituted metal oxides thin films. The precursor complexes were of the type AlxCr1-x (acac)3 where 0<x<1. The complexes were synthesized using the novel approach of co-synthesis and were characterized by various spectroscopic techniques. Single crystal X-ray diffraction at low temperature was carried out to understand the substitution of metal in the complex crystallographically.
The substituted metal complexes synthesized and characterized in chapter 2 were further evaluated for their viability as single source precursors for MOCVD application, using thermo-gravimetry as discussed in chapter 3. Vapor pressure of these complexes was determined by using the Langmuir equation, while the enthalpies of submission and evaporation were calculated using the Clausius-Clapeyron equation. One of the composition of the series of substituted metal complexes, viz., Al0.9Cr0.1(acac)3, was employed on MOCVD reactor as precursor to obtain thin films on three substrates, Si(100), fused silica, and polycrystalline x- alumina, simultaneously. The resultant thin films were characterized using XRD, electron microscopy, FTIR, EDS, X-ray mapping, and UV-vis spectroscopy.
Chapter 4 deals with the growth of titanium oxide thin films using ALD. The metal precursor used was Ti(OiPr)2(tbob)2 and the reactant gas was hydrogen. Hydrogen, a reducing gas, was deliberately used to obtain the reduced defect oxide phases of titanium, commonly called Magneli phases. The growth rate of films grown on p-Si(100) was studied with respect to the substrate temperature, vaporizer temperature, pulse duration of metal precursor and pulse duration of the reactive gas. Also, the concept of complementarity of a reaction and self-limiting behavior in a true ALD process was illustrated. The deposition conditions such as substrate temperature and reactive gas flows have been varied to optimize the phase content and the morphology of the films. The films grown were characterized to determine the various phases of titanium oxide present using XRD, TEM, FTIR spectroscopy, Raman spectroscopy, and UV-vis spectroscopy. The presence of carbon was revealed by Raman spectroscopy. By using these characterization techniques, it was concluded that the film grown is a composite made of stiochiometric TiOx matrix embedded with crystallites of (reduced) Magneli phases.
Chapter 5 deals with the electrical properties of the composite thin films grown in chapter 4. the films behave as percolative capacitor which could be used for application as novel high-k dielectric material for DRAM. The effect of change in flow rates of reactive gas (H2) on the dielectric constant (k) and leakage current of the film were studied. It was found that phase composition of the film plays an important role in tuning the dielectric properties of the film was also studied. The effect of thickness of the film also studied on the dielectric properties of the film. The trend observed was correlated to the morphology of the film as a function of its thickness and the grain growth mechanism as observed from high resolution scanning electron microscopy. Further, the effect of change in substrate temperature, metal precursor pulse length, and of the metal used as top electrode, on C-V and I-V characteristics were studied. It was interesting to see that the presence of the more conductingTi5O9 (than Ti3O5) enhances the dielectric constant, which is a requisite for a high-k material for DRAM application. On the other hand, the presence of Ti5O9 also increased the leakage current in the film, which was not desirable.
It therefore suggested itself that an optimum embedment of Ti5O9 in the composite helps in enhancing the dielectric constant, while maintaining a low leakage current. Under optimum conditions, a dielectric constant of 210 at 1MHz was measured with a leakage current of 17 nA. The effect of the presence of carbon in the film was studied using Raman Spectroscopy, and it was found that a high leakage was associated with films having greater carbon content. In this chapter, electrical properties of composite thin films were also compared with those of stoichiometric titanium dioxide (a known dielectric). Further, a multilayer sandwich structure was proposed, such that it had a 53 mm thick stoichiometric TiO2 layer followed by 336nm thick composite film and again a 53nm thick stoichiometric titanium dioxide layer. The dielectric characteristics of this structure were found to be better than those of either of the other two.viz., stoichiometric titanium dioxide film or the composite thin film of titanium oxide.
|
Page generated in 0.0527 seconds