No description available.

No description available.

This thesis is concerned with the study of morphology and properties of sub-micron thin Nafion® films. The motivation of the work arises from the need to characterize the 4 -10 nm thin ionomer films in the catalyst layer of polymer electrolyte fuel cell (PEFC). A protocol for the fabrication of self-assembled ultra-thin Nafion® films on planar substrates was successfully developed. Films of thickness ranging 4 nm-300 nm, determined by three different techniques - variable angle spectroscopy ellipsometry (VASE), atomic force microscope (AFM) and x-ray photo-electron spectroscopy (XPS), could be reproducibly generated on SiO2/Si wafer. The 4 nm thin film is one of the thinnest, continuous film of Nafion® ever reported. This is the first time that the structure/properties of such thin Nafion® film have been investigated. An interesting finding is the thickness-dependent structure and property of these films. Films with thickness <55 nm exhibited hydrophilic-free surface but thicker films (>55 nm) had hydrophobic surface. Similarly, sub-55 nm films had a lower and thickness-independent protonic conductivity compared to thicker films that exhibited thickness-dependent conductivity. Anomalously high water uptake (by quartz crystal microbalance) and swelling (by ellipsometry) of sub-55nm films indicate that low conductivity is not due to low water content However, differences in surface morphology were observed by the AFM phase contrast analysis. The lack of ionic domain was also observed in the thinner films (4-30 nm) from the grazing incidence small x-ray scattering (GISAXS) experiments. Thermal annealing over a range of temperature (110-160 oC) revealed a dramatic switching of the film surface from hydrophilic to hydrophobic was observed for sub-55 nm films with lower thickness film requiring higher annealing temperature. Bulk proton conductivity was significantly reduced after annealing for all films. An interesting finding was the regeneration of conductivity after to prolonged liquid water exposure and a corresponding switching back of the surface to hydrophilic. The thickness-dependent structure/property of ultra-thin Nafion® films is attributed to substrate induced confinement effect. Self-assembly of Nafion® on various substrates (SiO2, carbon, Pt and Au) was studied. The ionomer/substrate interaction and resulting film morphology followed a trend with respect to substrate surface energies and Nafion® dispersion compositions. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2013-09-29 12:36:19.05

Thin film material properties and measurement characterisation techniques are crucial for the development of micro-electromechanical systems (MEMS) devices. Furthermore, as the technology scales down from microtechnology towards nanotechnology, nanoscale materials such as carbon nanotubes (CNTs) are required in electronic devices to overcome the limitations encountered by conventional materials at the nanoscale. The integration of CNTs into micro-electronics and material applications is expected to provide a wide range of new applications. The work presented in this thesis has contributed to the development of thin film material characterisation through research on the thermal conductivity measurement and the control of the residual stress of thin film materials used commonly in MEMS devices. In addition, the use of CNTs in micro-electronics and as filler reinforcement in composite materials applications have been investigated, leading to low resistivity CNTs interconnects and CNTs-Polyimide (PI) composites based resistive humidity sensors. In the first part of this thesis, the thermal conductivity of conductive thin films as well as the control of the residual stress arising from fabrication process in PI micro-cantilevers have been studied. A MEMS device has been developed for the thermal conductivity characterisation of conductive thin films showing good agreement with thermal conductivity of bulk material. Low energy Ar+ ion bombardment in a plasma has been used to control the residual stress present in PI cantilevers. Appropriate ion energy and exposure time have led to stress relaxation of the beams resulting in a straight PI cantilever beam. In the second part of this thesis, low resistivity CNTs interconnects have been developed using both dielectrophoresis (DEP) and Focused Ion Beam (FIB) techniques. An investigation of the effects of CNT concentration, applied voltage and frequency on the CNTs alignment between Al and Ti electrodes has resulted in the lowering of the CNTs’ resistance. The deposition of Pt contact using FIB at the CNTs-metal electrodes interface has been found to decrease the high contact resistances of the devices by four and two orders of magnitude for Al and Ti electrodes respectively. The last part of this thesis focuses on the preparation of CNTs-PI composite materials, its characterisation and its application as resistive humidity sensor. The integration of CNTs inside the PI matrix has resulted in enhancing significantly the electrical and mechanical properties of the composites. In particular, a DEP technique employed to induce CNTs alignment inside the PI matrix during curing has been attributed to play an important role in improving the composite properties and lowering the percolation threshold. In addition, the fabrication and testing of CNTs-PI resistive humidity sensors have been carried out. The sensing performance of the devices have shown to be dependent highly on the CNT concentration. Finally, the alignment of CNTs by DEP has improved the sensing properties of CNTs-PI humidity sensors and confirmed that the change of resistance in response to humidity is governed by the change of the CNTs’ resistances due to charge transfer from the water molecules to the CNTs.

The increase in unconventional shale gas extraction in Pennsylvania has resulted in an increased number of groundwater contamination claims. Well water quality was investigated in southern Butler County, PA where 387 unconventional gas wells have been drilled since 2006. A total of 121 households participated in a survey and 238 well water samples were tested. Specific conductivity, pH, and dissolved oxygen in these samples were measured in the field and seven anion concentrations and thirty metal concentrations were measured in the lab. A subset of 91 water wells was also tested for light hydrocarbons (methane, ethane, ethylene, propylene, propane, butane). Pennsylvania DEP file reviews were used to create GIS maps indicating legacy oil and gas, unconventional wells, and plot water testing results. Results indicate few wells had high quality groundwater, with 86% containing one or more contaminants above (secondary) Maximum Contaminant Levels, with manganese (56%), iron (47%), fluoride (18%), TDS (18%), pH (17%), aluminum (17%) the most common. / Bayer School of Natural and Environmental Sciences; / Environmental Science and Management (ESM) / MS; / Thesis;

No description available.

Electroporation affects the dielectric properties of cells. Dielectric measurement techniques can provide a label-free and non-invasive modality to study this phenomenon. In this thesis we introduce a dielectrophoresis (DEP) based technique to study changes in the cytoplasm conductivity of single Chinese hamster ovary (CHO) cells immediately after electroporation. Using a microfluidic chip, we study changes in the DEP response of single CHO cells a few seconds after electroporation. First, in order to quantify our DEP measurement results and relate them to the cells internal conductivity, we introduce a dielectric model for CHO cells. This is achieved by measuring the DEP response of many individual cells in the β-dispersion frequency region and curve fitting to the measured data. Second, we present quantitative results for changes in the cytoplasm conductivity of single cells subjected to pulsed electric fields with various intensities. We observe that when electroporation is performed in media with lower ionic concentration than cells cytoplasm, their internal conductivity decreases after electroporation depending on the intensity of applied pulses. We also observe that with reversible electroporation there is a limit on the decrease in the cells’ internal conductivity. We hypothesize the reason is the presence of large and relatively immobile negative ions inside the cell which attract mobile positive ions (mainly sodium and potassium) to maintain cell electrical neutrality. We monitor the temporal response of cells after electroporation to measure the time constant of changes due to ion transport and observe this ranges from seconds to tens of seconds depending on the applied pulse intensity. This result can be used to infer information about the density and resealing time of very small pores (not measurable with conventional marker molecules). Lastly, we measure the electroporation of cells in media with different conductivities. Our results show that electroporation in very low conductivity media requires stronger pulses to achieve a similar poration extent as in high conductivity media. The outcome of this thesis can be used to improve our understanding of the dynamics of electroporation as well as its modelling in order to make more accurate predictions or optimize the process for specific applications. / February 2017

The thermodynamic equation of seawater - 2010 (TEOS-10) is hampered by the inability to measure absolute salinity or density in situ. No new advances for in situ salinity or density measurement have taken place since the adoption of the practical salinity scale in 1978. In this thesis three possible technologies for in situ measurements are developed and assessed: phased conductivity, an in situ density sensor and sound speed sensors. Of these, only sound speed sensors showed the potential for an in situ TEOS-10 measurement solution. To be implemented, sensor response times need to be matched and the sound speed sensor accuracy must be improved. Sound speed sensor accuracy is primarily limited by the calibration reference, pure water. Test results indicate the TEOS-10 sound speed coefficients may also need to be improved. A calibration system to improve sound speed sensor accuracy and verify the TEOS-10 coefficients is discussed. / Graduate / 0415 / 0986 / TDakin@UVic.ca

In this thesis, the structural, optical, and electrical properties of wurtzite MgxZn1-xO:Al and MgxZn1-xO:Ga thin films have been investigated in dependence on Mg and dopant concentration. Among the transparent conductive oxides (TCOs), ZnO based compounds have gained renewed interest as a transparent electrode for large scale applications such as defroster windows, at panel displays, touch screens, and thin film solar cells due to low material and processing cost, non-toxicity, and suitable physical properties. In general, these applications require transparent electrodes with lowest possible resistivity of rho < 10^-3 Ohmcm and lower [1]. Recently, it has been reported that Ga and Al doped ZnO thin films can be deposited with respective resistivity of 5x10^-5 Ohmcm [2] and 3 x10^-5 Ohmcm [3] which are similar to the data obtained for other practical TCOs, i.e. the resistivity of about 4x 10^-5 Ohmcm for Sn doped In2O3 (ITO) thin films [4]. Moreover, the bandgap of ZnO can be increased by alloying with Mg offering band alignment between transparent electrode and active (or buffer) layer of the device, e.g. Cu(In,Ga)Se2 solar cells [5]. The tunable bandgap of these transparent electrodes can further increase the efficiency of the devices by avoiding energy losses in the interface region of the layers. From this point of view, this work has been aimed to investigate the doping efficiency and limits in transparent conductive (Mg,Zn)O alloys. For this purpose, the samples investigated in this work have been grown by pulsed-laser deposition (PLD) using a novel, continuous composition spread method (CCS). In general, this method allows to grow thin films with lateral composition gradient(s) [6, 7]. All MgxZn1-xO:Al and MgxZn1-xO:Ga thin films have been deposited on 2-inch in diameter glass, c- or r-plane sapphire substrates using threefold segmented PLD targets in order to grow thin films with two perpendicular, lateral composition gradients, i.e. the Mg composition is varied in one direction whereas the Al/Ga concentration is varied in a perpendicular direction [7, 8]. In order to investigate the influence of the temperature, samples grown at different substrate temperatures in the range of 25 to 600 C were investigated. The optical and electrical measurements have been carried out on (5x 5)mm^2 samples that were cut from the CCS wafers along the respective composition gradients, i.e. Mg and Al/Ga contents. Subsequently, physical properties of thin films have been analyzed for a large range of Al/Ga content between 0.5 and 7 at.%, which corresponds to doping concentrations between 2x 10^20 and 3x 10^21 cm^-3, for different Mg contents x(Mg) ranging from 0.01 to 0.1. It has been found that practically the limiting the dopant concentrations is about 2 x10^21 cm^-3. Further, the electrical data suggests, that the compensating intrinsic defect is doubly chargeable hinting to the zinc vacancy (V_Zn) as microscopic origin. Increasing the dopant concentration above 2 x10^21 cm^-3 leads to a degradation of electrical and structural properties [8]. Further, the influence of growth and annealing temperatures on structural, electrical and optical properties of the films has been studied. For that purpose, Al and Ga doped (2.5 at.% = 1x10^21 cm^-3) Mg0.05Zn0.95O thin films have been chosen from CCS samples grown at T_g = (25 - 600) C . For both doping series, the samples grown at higher temperatures exhibit better crystalline quality compared to the samples grown at lower growth temperatures. As a result, samples grown at higher temperatures reveal higher Hall mobility. For the Al-doping series, the highest free charge carrier density of n = 8.2x 10^20 cm^-3 was obtained for an Mg0.05Zn0.95O:Al thin film grown at 200 C, with corresponding Hall mobility of mu = 13.3 cm^2/Vs, a resistivity of rho = 5.7x10^-4 Ohmcm, and optical bandgap of E_g = 3.8 eV. Interestingly, the free charge carrier density of n = (5 - 8) x 10^20 cm^-3 for samples grown with T_g > 300 C is clearly higher than the value of n = 1.25 x 10^20 cm^-3 that was obtained for the high temperature grown sample, i.e. at T_g = 600 C. Furthermore, for all T_g, Al-doped films have a higher doping efficiency than the Ga-doped counterparts. In order to look deeper into the microscopic origin of this behavior, the samples were post-annealed in vacuum at 400 C. Experimental results showed that the free charge carrier density of Al-doped samples first decreased and saturated afterward with increasing annealing time. On the other hand, the free charge carrier density of the Ga-doped samples first slightly increased and saturated with increasing annealing time. For both doping series, the saturation value of n ~ 1 x 10^20 cm^-3 was very close to the data that has been observed for (i) high temperature grown samples and (ii) the solubility limit of Al in ZnO of 0.3 at.% = 1.2x 10^20 cm^-3, that has been determined by Shirouzu et al. for high temperature grown (T_g > 600 C) Al-doped ZnO [9]. Correspondingly, the optical bandgap also changed, i.e. increased (decreased) for Al- (Ga-) doping series, and approached a constant value of 3.5 0 +- 0.1 eV which is explained by generation of acceptor-like compensating defects, and the solubility limit of the dopants. From XRD data, no secondary phases were found for as-grown and post-annealed films. However, the slight improvement of crystalline quality has been observed on post-annealed samples. Further, it has been shown that the growth and annealing temperatures are important as they strongly affect the metastable state of the solid solution that samples grown at low temperature represent. The low solubility limit of the dopants, i.e. 0.3 at.% for Al in ZnO under equilibrium condition, can be increased by preparing samples by non-equilibrium growth techniques [10]. This is also consistent with experimental results of this work that Al- as well as Ga-doped metastable ZnO and (Mg,Zn)O thin films can be prepared with highest possible doping efficiency for the dopant concentration up to 2.5 at.% when growth or annealing temperatures below 400 C are used.

This study presents a method developed to achieve the roll-to-roll sintering of printed Ag patterns based on exposure to hot air, near-infrared, and mid-infrared sources. The sintering energy was quantified and evaluated based on theoretical and experimental calculations. Moreover, the effect of the sintering energy on the web tension was simultaneously considered. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.