Optical and electrical properties of electrochemically lithium ion intercalated thin films of x-ray amorphous tungsten oxide made by magnetron sputtering on glass substrates coated with a thin layer of conductive tin doped indium oxide, have been studied. The composition and the density of the films were characterized by the ion beam analysis methods Rutherford Backscattering Spectroscopy and Elastic Recoil Detection Analysis. The optical properties, transmittance and reflectance were investigated by spectophotometry in the wavelength range 300-2500 nm. The absorption coefficients were calculated at different lithium intercalation levels. It was found that the absorption coefficient in an as-deposited blue film has a similar asymmetric shape as for films intercalated to a Li/W ratio of ~0.03. It was possible to electrochemically bleach this film to transparency. Stoichiometric films show optical irreversibility between the bleached and the colored state in the first cycle. A polaron absorption model has been compared to the absorption coefficient for films of different intercalation levels. An increase in the Fermi level and in the polaron band width, and a nearly constant activation energy was found as the Li/W value increased. The radius of the polaron wavefunction for different lithium intercalation levels and film compositions has been estimated from electrical measurements. The total absorption coefficient has been compared to the site-saturation model. The model is good for films intercalated in the optically reversible region. A modified site-saturation model that could be applied also in the optically irreversible region and involves electron transitions between W6+, W5+ and W4+ sites, has also been compared to experimental values. It was found that the total absorption, optical density and the coloration efficiency is higher for the WO2.63 film than in the less oxygen deficient films and that this film is optically more durable in an electrochemically cyclic lifetime device test.

Supported metal oxides (SMOs) are important catalytic materials that find numerous applications in important industrial processes. Improving the structural properties of SMOs is a challenging objective due to material synthesis and characterization limitations. Recent developments in the characterization of SMOs, specifically tungstated zirconia (WO x /ZrO 2 ), have revealed structural information that renewed scientific interest in developing more sophisticated synthetic protocols for SMOs. The current work aims to provide a robust characterization of WO x /ZrO 2 by using different characterization techniques and probe reactions. Conventional and non-conventional synthetic methods are investigated to cover the whole spectrum of published methods in order to understand the properties and limitations of these techniques. In the second part of this work, a new synthetic approach is presented that successfully produces ultrasmall (smaller than 2 nm) tungsten oxide nanoparticles (WO x NPs). By using conventional tungsten precursors and oleylamine, WO x NPs are synthesized, characterized, and finally supported to test their propene metathesis activity. Conventional WO x /ZrO 2 catalysts were prepared and extensively studied by probing their n -pentane isomerization activity and methanol dehydration activity. WO x /ZrO 2 prepared via incipient wetness impregnation shows maximum n -pentane isomerization turnover rates ( TOR ) at intermediate surface densities ( � surf ). This method delivers the most active n -pentane isomerization WO x /ZrO 2 catalysts since it maximizes the number density of the active sub-nm slightly distorted Zr-WO x sites at � surf between 5.2-6.2 W/nm 2 . By comparing the n -pentane isomerization activity with the methanol dehydration activity of WO x /ZrO 2 , n -pentane isomerization is shown to be an excellent probe reaction for qualitatively identifying the relative (to the other species) population density of Zr-WO x clusters. Bimolecular n -pentane isomerization is the prevailing mechanism and requires a higher population density of Zr-WO x clusters than methanol dehydration. In the second part of this work, a new solvothermal synthesis route for the preparation of ultrasmall tungsten oxide nanoparticles (WO x NPs) is introduced. By using ammonium polyanionic salts and oleylamine, high yields (92±5%) of oleylaminecoated WO x NPs were consistently synthesized. The co-addition of an organic oxidant during the synthesis led to smaller WO x NPs thereby providing insight into the NP synthesis mechanism. Deposition and activation of the NPs on SiO 2 support by removal of oleylamine allows better control over the WO x domain size than conventional methods. Oleylamine suppresses WO x NP sintering during calcination and prevents the formation of larger polytungstates present in conventional catalysts. The supported WO x NPs were found to be up to 3 times more selective for metathesis products than conventionally prepared tungstated silica likely due to their controlled structure.

This thesis presents thermodynamic studies performed by electrochemical methods (cyclic voltammetry, electrochemical impedance and chronopotenciometry) in three of the most important electrochromic materials: a-WO3, conducting polymers and viologens. Electrochromic materials are very promising as a low-consuming technology. By incorporating these materials in windows of buildings or vehicles, approximately a 30% of the consumed energy in these systems can be saved.Regarding the a-WO3, apart from other contributions, a new model based on lattice distortions, able to explain the intercalation thermodynamic in this material, is proposed. In the conducting polymers field, a Gaussian energy distribution is proved to account for the initial part of the so broad oxidation peaks observed in cyclic voltammetry. Finally, the coloration kinetics of the viologen modified n-TiO2 electrode is explained.

In recent years, the conventional Flash memory with floating structure is expected to reach physical limits as devices scaling down in near future. In order to overcome this problem, alternative memory technologies have been widely investigated. And the resistance random access memory (RRAM) has attracted extensive attention for the application in next generation nonvolatile memory, due to the excellent memory property including lower consumption of energy, lower operating voltage, higher density, fast operating speed, simple structure, higher endurance, retention and process compatibility with CMOS. In this study, the tungsten-based oxide is chosen as RRAM switching layer because the tungsten is compatible with the present complementary metal oxide semiconductor (CMOS) process. The Pt/WOX/TiN structure device cells had the resistance switching property successfully. However, the experiment result revealed the inferior resistance switching property. The resistance switching characteristic of the WOX thin film is extremely unstable, it is impossible to become the products. Compared with WOX, the resistance switching property of WSiOX RRAM device is improved substantially such as stability of resistance states and reliability of device. In second parts, we purposed two methods to enhance the device switching characteristic, including controlling the filament formation/ interruption in the W doped SiOX layer and restricting oxygen movement in the WSiON layer. Finally, the transport mechanisms of carrier is analyzed and researched from the current-voltage (I-V) switching characteristic of the device. A designed circuit was used in this study to accurately observe the resistance switching process with a pulse generator and oscilloscope, which reveals that the switching process is related to both time and voltage. The oxygen movement will drift in the low temperature due to the electrical field and restricted the crystal lattice vibration. But, it will diffuse through thermal dynamics in the high temperature.

No description available.

This thesis investigates the electrochromic NixW1-x oxide thin film system, where 0 < x < 1. The thin films were deposited by reactive DC magnetron co-sputtering from one Ni and one W metal target. In addition, Ni oxide was deposited with water vapor added to the sputtering gas. The different compositions were structurally characterized by X-ray diffraction, X-ray photoelectron-, Rutherford backscattering- and Raman spectroscopy. Possible nanostructures were studied by ellipsometry together with effective medium theory. Optical and electrochemical properties were investigated by spectrophotometry and cyclic voltammetry in 1 M lithium perchlorate in propylene carbonate (Li-PC). Li-PC electrolyte was used as it is being compatible with both W and Ni oxides. Few studies have previously been made on Ni oxides in Li-PC. Films with high Ni content, 0.85 < x < 1, were polycrystalline and all other films were amorphous. W-rich films, x < 0.5, consisted of a mixture of W oxide and NiWO4 -phases, and the Ni-rich samples, x > 0.5, probably consisted of hydrated Ni oxide and NiWO4 -phases. Films with 0 < x < 0.3 showed electrochromic properties similar to W oxide, and films with 0.7 < x < 1 behaved as Ni oxide. For 0.4 < x < 0.7 no optical change was seen. At the border of cathodic electrochromic and non-electrochromic behavior, i.e. x ~ 0.4, the sample behaved as an optically passive intercalation material. The transmittance change was 0.45 and 0.15 for the W-rich and Ni-rich films, respectively. Ni addition to W oxide improved the coloration efficiency. For the Ni-rich films the charge insertion/extraction and optical modulation was low and an aging effect resulted in strong bleaching of the samples. The advantage of W addition to Ni oxide was that the transparency at the bleached state was enhanced. Moreover, it was found that the hydrous character of the Ni oxide had a large impact on the electrochromic performance, both when electrochemically cycled in KOH and in the non-aqueous Li-PC.

Neste trabalho foram obtidos filmes de óxido de tungstênio pelo método sol-gel modificado, tendo como precursor o tungstato de sódio dihidratado (Na2WO4.2H2O) e como agente estruturante o surfactante cloreto de dodeciltrimetilamônio (DTAC). O comportamento dos sistemas em meio aquoso foi avaliado por medidas de pH, condutividade e viscosidade. Foram avaliadas duas metodologias de obtenção dos filmes de óxido de tungstênio: a primeira consistiu na obtenção de filmes de tungstato de sódio, através de sistemas contendo 10 mmol.L-1 de Na2WO4.2H2O em diferentes concentrações de DTAC, por casting, e conversão do tungstato de sódio a óxido de tungstênio pela acidificação dos filmes; a segunda metodologia consistiu na conversão dos sistemas aquosos contendo 20 mmol.L-1 de Na2WO4.2H2O, em diferentes concentrações de DTAC, em ácido tungstico, obtenção dos filmes por spin coating e, calcinação em presença de ar. Os filmes foram obtidos em substratos de silício (100) recobertos com dióxido de silício e avaliados por Difração de Raios-X, Espectrometria de retroespalhamento Rutherford, Espectroscopia Raman, Microscopia Eletrônica de Varredura e ensaios fotocatalíticos. As alterações na concentração precursor e agente estruturante não afetaram significativamente o pH e a viscosidade dos sistemas precursores. A determinação da concentração micelar crítica (cmc) do DTAC, obtida através da condutividade, foi de 13 mmol.L-1 e 9,88 mmol.L-1 para os sistemas contendo 10 e 20 mmol.L-1 de Na2WO4.2H2O, respectivamente. Em ambas metodologias o produto final foi o óxido de tungstênio em forma de disco e placas. As espessuras dos filmes obtidos na primeira metodologia variaram de 4 a 5 μm e as estruturas tiveram diâmetros médios de 4,37 μm e 114 nm. Na segunda metodologia as espessuras foram de 0,5-1,0 μm e as estruturas obtidas tiveram diâmetros médios em torno de 95-103 nm. Os filmes obtidos apresentaram atividade fotocatalítica, uma vez que duplicaram a velocidade da reação de degradação do corante alaranjado de metila em relação ao sistema sem o filme. / In this work tungsten oxide films have been obtained bymodified sol-gel method, with sodium tungstate dehydrate (Na2WO4.2H2O) as the precursor and the cationic surfactant dodecyltrimethylammonium chloride (DTAC) as structuring agent.The behavior in aqueous media of precursor/structuring agent systems was characterized by pH, conductivity and viscosity measurements. Two methods for obtaining tungsten oxide films were evaluated: the first consisted in obtaining sodium tungstate films from the systems containing 10 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations, by casting, converting the sodium tungstate to tungsten oxide; the second method consisted in the conversion of the aqueous systems containing 20 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations to tungstic acid, obtaining the films by spin coating and, posteriorly, calcination in the presence of air. The films were obtained on silicon substrate (100) with a 50 nm layer of silicon dioxide and were characterized by X-ray diffraction, Rutherford backscattering spectrometry, Raman spectroscopy, Scanning Electron Microscopy and photocatalytic tests. The precursor concentration and structuring agent do not affect significantly the pH and the viscosity of the precursor systems in aqueous media.The values of critical micelle concentration (CMC) of DTAC, obtained by the conductivity, were of13 mmol.L-1 and 9,88 mmol.L-1, for the systems containing 10 and 20 mmol.L-1 de Na2WO4.2H2O, respectively.In both adopted methods the final product is the tungsten oxide, with nano and micrometric structures in the form of discs and plates. The thickness of the films obtained in the first method varied from 4 to 5 μm and the structures presented an average diameter around 4,37 μm and 114 nm. The thickness of the films obtained with the second methodvariedfrom0,5to 1 μm and the structures presented an average diameter from 95 to103 nm.The obtained tungsten oxide films presented photocatalytic activity, since doubled the reaction rate of methyl orange dye degradation with respect to the system without the film.

Mesoporous WO3 powders were prepared via sol-gel processing synthesis using nonionic surfactant Pluronic (P-123) as the template. The influences of heating temperature on the pore structure and properties of WO3 powders were investigated. Three kinds of modifications were compared and evaluated after finding out the best heating condition. Different amount of lanthanum was doped into mesoporous WO3 to improve its Oxygen Reduction Reaction (ORR) activity. Several factors contributing to the increase of catalytic performance were discussed. Vulcan carbon powder was also used as a support to increase the catalysts’ electrical conductivity as well as dispersity. The component, microstructure and specific surface area of samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and N2 adsorption-desorption analysis. A three-electrode system with a rotating disk electrode (RDE) was used to detect samples’ electrochemical performance towards ORR in alkaline solutions. The as-prepared mesoporous La/WO3 powder with a ratio of La: W = 1: 10, calcined at 550℃ and supported by 25 wt% Vulcan carbon powder, exhibited highest ORR catalytic activity.

Neste trabalho foram obtidos filmes de óxido de tungstênio pelo método sol-gel modificado, tendo como precursor o tungstato de sódio dihidratado (Na2WO4.2H2O) e como agente estruturante o surfactante cloreto de dodeciltrimetilamônio (DTAC). O comportamento dos sistemas em meio aquoso foi avaliado por medidas de pH, condutividade e viscosidade. Foram avaliadas duas metodologias de obtenção dos filmes de óxido de tungstênio: a primeira consistiu na obtenção de filmes de tungstato de sódio, através de sistemas contendo 10 mmol.L-1 de Na2WO4.2H2O em diferentes concentrações de DTAC, por casting, e conversão do tungstato de sódio a óxido de tungstênio pela acidificação dos filmes; a segunda metodologia consistiu na conversão dos sistemas aquosos contendo 20 mmol.L-1 de Na2WO4.2H2O, em diferentes concentrações de DTAC, em ácido tungstico, obtenção dos filmes por spin coating e, calcinação em presença de ar. Os filmes foram obtidos em substratos de silício (100) recobertos com dióxido de silício e avaliados por Difração de Raios-X, Espectrometria de retroespalhamento Rutherford, Espectroscopia Raman, Microscopia Eletrônica de Varredura e ensaios fotocatalíticos. As alterações na concentração precursor e agente estruturante não afetaram significativamente o pH e a viscosidade dos sistemas precursores. A determinação da concentração micelar crítica (cmc) do DTAC, obtida através da condutividade, foi de 13 mmol.L-1 e 9,88 mmol.L-1 para os sistemas contendo 10 e 20 mmol.L-1 de Na2WO4.2H2O, respectivamente. Em ambas metodologias o produto final foi o óxido de tungstênio em forma de disco e placas. As espessuras dos filmes obtidos na primeira metodologia variaram de 4 a 5 μm e as estruturas tiveram diâmetros médios de 4,37 μm e 114 nm. Na segunda metodologia as espessuras foram de 0,5-1,0 μm e as estruturas obtidas tiveram diâmetros médios em torno de 95-103 nm. Os filmes obtidos apresentaram atividade fotocatalítica, uma vez que duplicaram a velocidade da reação de degradação do corante alaranjado de metila em relação ao sistema sem o filme. / In this work tungsten oxide films have been obtained bymodified sol-gel method, with sodium tungstate dehydrate (Na2WO4.2H2O) as the precursor and the cationic surfactant dodecyltrimethylammonium chloride (DTAC) as structuring agent.The behavior in aqueous media of precursor/structuring agent systems was characterized by pH, conductivity and viscosity measurements. Two methods for obtaining tungsten oxide films were evaluated: the first consisted in obtaining sodium tungstate films from the systems containing 10 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations, by casting, converting the sodium tungstate to tungsten oxide; the second method consisted in the conversion of the aqueous systems containing 20 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations to tungstic acid, obtaining the films by spin coating and, posteriorly, calcination in the presence of air. The films were obtained on silicon substrate (100) with a 50 nm layer of silicon dioxide and were characterized by X-ray diffraction, Rutherford backscattering spectrometry, Raman spectroscopy, Scanning Electron Microscopy and photocatalytic tests. The precursor concentration and structuring agent do not affect significantly the pH and the viscosity of the precursor systems in aqueous media.The values of critical micelle concentration (CMC) of DTAC, obtained by the conductivity, were of13 mmol.L-1 and 9,88 mmol.L-1, for the systems containing 10 and 20 mmol.L-1 de Na2WO4.2H2O, respectively.In both adopted methods the final product is the tungsten oxide, with nano and micrometric structures in the form of discs and plates. The thickness of the films obtained in the first method varied from 4 to 5 μm and the structures presented an average diameter around 4,37 μm and 114 nm. The thickness of the films obtained with the second methodvariedfrom0,5to 1 μm and the structures presented an average diameter from 95 to103 nm.The obtained tungsten oxide films presented photocatalytic activity, since doubled the reaction rate of methyl orange dye degradation with respect to the system without the film.

One-dimensional (1D) nanomaterials are of great importance for a number of potential applications. However, in order to realize this potential a thorough understanding of the charge-carrier dynamics in these materials is required, since these largely determine the optoelectronic properties of the materials in question. This thesis investigates the charge-carrier dynamics of two 1D nanomaterials, single-walled carbon nanotubes (CNTs) and tungsten-oxide nanowires (WOxNWs), with the goal of better understanding the nature of their optoelectronic responses, and how nanomaterial geometry and morphology influence these responses. We do this using terahertz time-domain spectroscopy (THz-TDS) and optical pump - terahertz probe time-domain spectroscopy (OPTP). Firstly, we discuss how to properly analyse and interpret the data obtained from these experiments when measuring 1D nanomaterials. While the data obtained from THz-TDS is fairly straight-forward to analyse, OPTP experimental data can be far from trivial. Depending on the relative size of the sample geometry compared to the probe wavelength, various approximations can be used to simplify the extraction of their ultrafast response. We present a general method, based on the transfer matrix method, for evaluating the applicability of these approximations for a given multilayer structure, and show the limitations of the most commonly used approximations. We find that these approximations are only valid in extreme cases where the thickness of the sample is several orders of magnitude smaller or larger than the wavelength, which highlight the danger originating from improper use of these approximations. We then move on to investigate how the charge-carrier dynamics of our CNTs is influenced by nanotube length and density. This is done through studying the nature of the broad THz resonance observed in finite-length CNTs, and how the nanotube length and density affects this resonance. We do this by measuring the conductivity spectra of thin films comprising bundled CNTs of different average lengths in the frequency range 0.3-1000 THz and temperature interval 10-530 K. From this we show that the observed temperature-induced changes in the terahertz conductivity spectra depend strongly on the average CNT length, with a conductivity around 1 THz that increases/decreases as the temperature increases for short/long tubes. This behaviour originates from the temperature dependence of the electron scattering rate, which results in a subsequent broadening of the observed THz conductivity peak at higher temperatures and a shift to lower frequencies for increasing CNT length. Finally, we show that the change in conductivity with temperature depends not only on tube length, but also varies with tube density. We record the effective conductivities of composite films comprising mixtures of WS2 nanotubes and CNTs vs CNT density for frequencies in the range 0.3-1 THz, finding that the conductivity increases/decreases for low/high density films as the temperature increases. This effect arises due to the density dependence of the effective length of conducting pathways in the composite films, which again leads to a shift and temperature dependent broadening of the THz conductivity peak. Next, we investigate the conflicting reports regarding the ultrafast photoconductive response of films of CNTs, which apparently exhibit photoconductivities that can vastly differ, even in sign. Here we observe explicitly that the THz photoconductivity of CNT films is a highly variable quantity which correlates with the length of the CNTs, while the specific type of CNT has little influence. Moreover, by comparing the photo-induced change in THz conductivity with heat-induced changes, we show that both occur primarily due to heat-generated modification of the Drude electron relaxation rate, resulting in a broadening of the plasmonic resonance present in finite-length metallic and doped semiconducting CNTs. This clarifies the nature of the photo-response of CNT films and demonstrates the need to carefully consider the geometry of the CNTs, specifically the length, when considering them for application in optoelectronic devices. We then move on to consider our WOxNWs. We measure the terahertz conductivity and photoconductivity spectra of thin films compromising tungsten-oxide (WOx) nanowires of average diameters 4 nm and 100 nm, and oxygen deficiencies WO2.72 and WO3 using THz-TDS and OPTP. From this we present the first experimental evidence of a metal-to-insulator transition in WOx nanowires, which occurs when the oxygen content is increased from x=2.72 -> 3 and manifests itself as a massive drop in the THz conductivity due to a shift in the Fermi level from the conduction band down into the bandgap. Furthermore we present the first experimental measurements of the photoexcited charge-carrier dynamics of WOx nanowires on a picosecond timescale and map the influence of oxygen-content and nanowire diameter. From this we show that the decay-dynamics of the nanowires is characterized by a fast decay of < 1 ps, followed by slow decay of 3-10 ps, which we attribute to saturable carrier trapping at the surface of the nanowires.