The Electronic Structure of Co-Sputtered Zinc Indium Tin Oxide Thin Films

Zinc indium tin oxide (ZITO) transparent conductive oxide layers were deposited via radio frequency (RF) magnetron co-sputtering at room temperature. A series of samples with gradually varying zinc content was investigated. The samples were characterized with x-ray and ultraviolet photoemission spectroscopy (XPS, UPS) to determine the electronic structure of the surface. Valence and conduction bands maxima (VBM, CBM), and work function were determined. The experiments indicate that increasing Zn content results in films with a higher defect rate at the surface leading to the formation of a degenerately doped surface layer if the Zn content surpasses 50%. Furthermore, the experiments demonstrate that ZITO is susceptible to ultraviolet light induced work function reduction, similar to what was earlier observed on ITO and TiO2 films.

Estudi de la reductibilitat de catalitzadors basats en cobalt i el seu comportament en la reacció de desplaçament de gas d'aigua de CO

Projecte de recerca elaborat a partir d’una estada a la universitat d'Udine, Itàlia, entre setembre i desembre del 2006.S'han caracteritzat mitjançant la reducció a temperatura programada i tests catalítics catalitzadors en pols basats en cobalt i supostats en òxid de zinc i monòlits ceràmics funcionaliltzats també amb cobalt i òxid de zinc. L'addició de promotors (manganès, crom i ferro ) als catalitzadors en pols, preparats per impregnació i precipitació, no afecta significativament ni la temperatura a la qual té lloc la reducció ni al percentatge global de reducció. En els cicles de reducció-oxidació sí que s'observen diferències entre el primer perfil de reducció i els següents, especialment en el cas de la mostra que té ferro com a promotor, on les diferències s'accentuen en cicles successius (fins al quart). S'ha evaluat l'activitat d'aquests catalitzadors en la reacció de desplaçament de gas d'aigua, obtenint uns resultats satisfactoris. Finalment s'han realitzat reduccions a temperatura programada i tests catalítics en la reacció de desplaçament de gas d'aigua amb monòlits funcionalitzats amb cobalt i òxid de zinc (en cap d'ells s'ha introduït promotors). El nivell de conversió assolit és menor que en el cas de catalitzadors en pols, fet que s'associa a la geometria d'aquests sistemes catalítics, però la relació CH4/CO2 és més favorable que en els catalitzadors en pols, el que els converteix en sistemes molt selectius.

Size-dependent recombination dynamics in ZnO nanowires.

A deep understanding of the recombination dynamics of ZnO nanowires NWs is a natural step for a precise design of on-demand nanostructures based on this material system. In this work we investigate the influence of finite-size on the recombination dynamics of the neutral bound exciton around 3.365 eV for ZnO NWs with different diameters. We demonstrate that the lifetime of this excitonic transition decreases with increasing the surface-to-volume ratio due to a surface induced recombination process. Furthermore, we have observed two broad transitions around 3.341 and 3.314 eV, which were identified as surface states by studying the dependence of their life time and intensitiy with the NWs dimensions.

Enhancement of the photoelectrochemical properties of Cl-doped ZnO nanowires by tuning their coaxial doping profile

Arrays of vertically aligned ZnO:Cl/ZnO core-shell nanowires were used to demonstrate that the control of the coaxial doping profile in homojunction nanostructures can improve their surface charge carrier transfer while conserving potentially excellent transport properties. It is experimentally shown that the presence of a ZnO shell enhances the photoelectrochemical properties of ZnO:Cl nanowires up to a factor 5. Likewise, the ZnO shell promotes the visible photoluminescence band in highly conducting ZnO:Cl nanowires. These lines of evidence are associated with the increase of the nanowires" surface depletion layer

Influence of RF power on the properties of sputtered ZnO:Al thin films

Transparent conducting, aluminium doped zinc oxide thin films (ZnO:Al) were deposited by radio frequency (RF) magnetron sputtering. The RF power was varied from 60 to 350Wwhereas the substrate temperature was kept at 160 °C. The structural, electrical and optical properties of the as-deposited films were found to be influenced by the deposition power. The X-ray diffraction analysis showed that all the films have a strong preferred orientation along the [001] direction. The crystallite size was varied from 14 to 36 nm, however no significant change was observed in the case of lattice constant. The optical band gap varied in the range 3.44-3.58 eV. The lowest resistivity of 1.2×10 -3Vcm was shown by the films deposited at 250 W. The mobility of the films was found to increase with the deposition power.

Electrical and optical properties of Zn-In-Sn-O transparent conducting thin films

Indium tin oxide (ITO) is one of the widely used transparent conductive oxides (TCO) for application as transparent electrode in thin film silicon solar cells or thin film transistors owing to its low resistivity and high transparency. Nevertheless, indium is a scarce and expensive element and ITO films require high deposition temperature to achieve good electrical and optical properties. On the other hand, although not competing as ITO, doped Zinc Oxide (ZnO) is a promising and cheaper alternative. Therefore, our strategy has been to deposit ITO and ZnO multicomponent thin films at room temperature by radiofrequency (RF) magnetron co-sputtering in order to achieve TCOs with reduced indium content. Thin films of the quaternary system Zn-In-Sn-O (ZITO) with improved electrical and optical properties have been achieved. The samples were deposited by applying different RF powers to ZnO target while keeping a constant RF power to ITO target. This led to ZITO films with zinc content ratio varying between 0 and 67%. The optical, electrical and morphological properties have been thoroughly studied. The film composition was analysed by X-ray Photoelectron Spectroscopy. The films with 17% zinc content ratio showed the lowest resistivity (6.6 × 10 - 4 Ω cm) and the highest transmittance (above 80% in the visible range). Though X-ray Diffraction studies showed amorphous nature for the films, using High Resolution Transmission Electron Microscopy we found that the microstructure of the films consisted of nanometric crystals embedded in a compact amorphous matrix. The effect of post deposition annealing on the films in both reducing and oxidizing atmospheres were studied. The changes were found to strongly depend on the zinc content ratio in the films.

Histopathological evaluation of root canal filling materials for primary teeth

This study aimed to assess the response of apical and periapical tissues of dogs¿ teeth after root canal filling with different materials. Forty roots from dogs¿ premolars were prepared biomechanically and assigned to 4 groups filled with: Group I: commercial calcium hydroxide and polyethylene glycol-based paste (Calen®) thickened with zinc oxide; Group II: paste composed of iodoform, Rifocort® and camphorated amonochlorophenol; Group III: zinc oxide-eugenol cement; Group IV: sterile saline. After 30 days, the samples were subjected to histological processing. The histopathological findings revealed that in Groups I and IV the apical and periapical regions exhibited normal appearance, with large number of fibers and cells and no resorption of mineralized tissues. In Group II, mild inflammatory infiltrate and mild edema were observed, with discrete fibrogenesis and bone resorption. Group III showed altered periapical region and thickened periodontal ligament with presence of inflammatory cells and edema. It may be concluded that the Calen paste thickened with zinc oxide yielded the best tissue response, being the most indicated material for root canal filling of primary teeth with pulp vitality.

Spatial mapping of exciton lifetimes in single ZnO nanowires

We investigate the spatial dependence of the exciton lifetimes in single ZnO nanowires. We have found that the free exciton and bound exciton lifetimes exhibit a maximum at the center of nanowires, while they decrease by 30% towards the tips. This dependence is explained by considering the cavity-like properties of the nanowires in combination with the Purcell effect. We show that the lifetime of the bound-excitons scales with the localization energy to the power of 3/2, which validates the model of Rashba and Gurgenishvili at the nanoscale.

Up-conversion effect of Er- and Yb-doped ZnO thin films

Visible up-conversion in ZnO:Er and ZnO:Er:Yb thin films deposited by RF magnetron sputtering under different O2-rich atmospheres has been studied. Conventional photoluminescence (325 nm laser source) and up-conversion (980 nm laser source) have been performed in the films before and after an annealing process at 800 °C. The resulting spectra demonstrate that the thermal treatment, either during or post-deposition, activates optically the Er3+ ions, being the latter process much more efficient. Moreover, the atmosphere during deposition was also found to be an important parameter, as the deposition under O2 flow increases the optical activity of Er+3 ions. In addition, the inclusion of Yb3+ ions into the films has shown an enhancement of the visible up-conversion emission at 660 nm by a factor of 4, which could be associated to either a better energy transfer from the 2F5/2 Yb level to the 4I11/2 Er one, or to the prevention of having Er2O3 clustering in the films.

ZnO nanorods for efficient third harmonic UV generation.

ZnO nanorods grown by both high temperature vapour phase transport and low temperature chemical bath deposition are very promising sources for UV third harmonic generation. Material grown by both methods show comparable efficiencies, in both cases an order of magnitude higher than surface third harmonic generation at the quartz-air interface of a bare quartz substrate. This result is in stark contrast to the linear optical properties of ZnO nanorods grown by these two methods, which show vastly different PL efficiencies. The third harmonic generated signal is analysed using intensity dependent measurements and interferometric frequency resolved optical gating, allowing extraction of the laser pulse parameters. The comparable levels of efficiency of ZnO grown by these very different methods as sources for third harmonic UV generation provides a broad suite of possible growth methods to suit various substrates, coverage and scalability requirements. Potential application areas range from interferometric frequency resolved optical gating characterization of few cycle fs pulses to single cell UV irradiation for biophysical studies.

Spatial mapping of exciton lifetimes in single ZnO nanowires

We investigate the spatial dependence of the exciton lifetimes in single ZnO nanowires. We have found that the free exciton and bound exciton lifetimes exhibit a maximum at the center of nanowires, while they decrease by 30% towards the tips. This dependence is explained by considering the cavity-like properties of the nanowires in combination with the Purcell effect. We show that the lifetime of the bound-excitons scales with the localization energy to the power of 3/2, which validates the model of Rashba and Gurgenishvili at the nanoscale.

Recombination dynamics in ZnO nanowires: Surfaces states versus mode quality factor

In this work, we investigate the influence of finite size on the recombinations dynamics of ZnO nanowires. We demonstrate that diameter as well as lenght of nanowires determine the lifetime of the neutral donor bound excitons. Our findings suggest that while the length is mainly responsible for different mode quality factors of the cavity-like nanowires, the diameter determines the influence of surface states as alternative recombinations channels for the optical modes trapped in the nanocavity. In addition, comparing nanowires grown using different catalyst we show that the surfaces states strongly depend on each precursor characteristics.

Characterization of nano-oxide layers fabricated by ion beam oxidation

In this paper, a remote O2 ion source is used for the formation of nano-oxide layers. The oxidation efficiency was measured in CoFe-oxide films, and a decrease of the oxide layer with the pan angle and the oxidation pressure is observed. For the same oxidation pressure, the oxidation efficiency depends on the O2 content in the Ar-O2 plasma. These results were applied in optimizing the fabrication of Al2O3 barrier for tunnel junctions. This method was also used to fabricate junctions with Fe-oxide layers inserted at the Al2O3-CoFe interface. TEM and magnetization data indicate that after anneal at 385°C, a homogeneous ferromagnetic Fe-oxide layer (Fe3O4?) is formed.

Compositional influence on the electrical performance of zinc indium tin oxide transparent thin-film transistors

In this work, zinc indium tin oxide layers with different compositions are used as the active layer of thin film transistors. This multicomponent transparent conductive oxide is gaining great interest due to its reduced content of the scarce indium element. Experimental data indicate that the incorporation of zinc promotes the creation of oxygen vacancies. In thin-film transistors this effect leads to a higher threshold voltage values. The field-effect mobility is also strongly degraded, probably due to coulomb scattering by ionized defects. A post deposition annealing in air reduces the density of oxygen vacancies and improves the fieldeffect mobility by orders of magnitude. Finally, the electrical characteristics of the fabricated thin-film transistors have been analyzed to estimate the density of states in the gap of the active layers. These measurements reveal a clear peak located at 0.3 eV from the conduction band edge that could be attributed to oxygen vacancies.