The electrodeposition of tin coatings from deep eutectic solvents and their subsequent whisker growth

Tin electrodeposits produced from aqueous electrolytes are frequently used within the electronics industry due to their high solderability and corrosion protection. One limitation to using these deposits is their spontaneous formation of long conductive filament whiskers. These whiskers grow post-electrodeposition and increase the risk of unwanted electrical shorts within electronic devices. In this thesis, tin electrodeposits produced from a proprietary bright acid Tinmac electrolyte, currently used in industry, were studied. Electrodeposits were produced using a range of current densities with and without agitation and were characterised with respect to crystallographic orientation, topography and surface finish. Moreover, the intermetallic compound (IMC) growth produced at the copper substrate-tin coating interface was assessed over a period of time as its growth is considered to be a significant driving force behind whisker formation. In addition, a technique for the electrochemical anodic oxidation of tin electrodeposits on copper substrates was developed. This technique was used throughout this project for the study of IMC growth from tin electrodeposits as it was able to effectively remove the tin whilst leaving the IMCs and substrate unaffected. Ionic liquids exhibit promising electrochemical characteristics for electrodeposition but are still not widely utilised in industry. Their ability to deposit tin coatings has been studied in the present investigation. Trials concentrated on process optimisation to produce uniform electrodeposits by varying current density, SnCl2.2H2O concentration, and electrolyte composition. These deposits were then characterised and compared to tin coatings of similar thickness produced from Tinmac with respect to topography, surface finish, crystallographic orientation, IMC growth, and whisker propensity. Electrodeposits produced from the ionic liquid electrolyte exhibited a different crystallographic texture, topography, and IMC growth compared to those produced from Tinmac. Moreover, the deposit produced from the ionic liquid featured increased whisker growth compared to those produced from Tinmac, but in a wider context, far less growth than conventional tin electrodeposits in the literature. In addition, by exploiting other electrochemical characteristics of ionic liquids, such as their large potential window, future work may be able to produce novel tin or tin alloy electrodeposits which may further reduce the whisker propensity of deposits produced in this investigation

An investigation of the growth of bismuth whiskers and nanowires during physical vapour deposition

Bismuth thin films of thickness in the region of 500 nm have been prepared by planar magnetron sputtering onto glass, silicon and GaAs substrates. Electron microscopy of these films reveals that bismuth whiskers grow spontaneously when the substrate is heated to temperatures between 110ºC and 140ºC during deposition and the optimum temperature for such growth is largely independent of substrate. Depositing films under similar conditions using thermal evaporation does not, however, produce the whisker growth. X-ray diffraction has been employed to investigate film texture with temperature and it has been shown that the film crystallites are predominantly [110] and [111] oriented. The [110] orientation of the crystallites dominates at deposition temperatures above 110ºC for sputter deposition and the [111] at lower temperatures. The optimum temperature for whisker growth coincides with the temperature for the change between predominant orientations. While sputter deposition appears to favour films with crystallite orientation of [110], thermal evaporation favours [111] and has a higher change-over temperature. The whiskers that grow from the film emerge at off-normal angles between 43.3º and 69.2º with a mean of 54±3º. The projected length of whiskers on a 500 nm film on a GaAs substrate shows a wide distribution to a maximum of more than 100 μm. The mean projected length for this sample was 16±1 μm and the diameter is around 0.5 μm. Measurements of the electrical properties of the whiskers at room temperature reveals ohmic behaviour with an estimated resistivity of 2.2±0.2 μΩm. Detailed examination of scanning electron micrographs, eliminates all growth mechanisms except tip growth by a non-catalysed vapour-solid/vapour-liquid-solid method. By depositing thinner films it is shown that this spontaneous growth of whiskers offers a route to fabricate high quality bismuth nanowires of lengths exceeding 10 μm

Ki67 Is an Independent Predictor of Recurrence in the Largest Randomized Trial of 3 Radiation Fractionation Schedules in Localized Prostate Cancer

Purpose: To assess whether the cellular proliferation marker Ki67 provides prognostic information and predicts response to radiation therapy fractionation in patients with localized prostate tumors participating in a randomized trial of 3 radiation therapy fractionation schedules (74 Gy/37 fractions vs 60 Gy/20 fractions vs 57 Gy/19 fractions). Methods and Materials: A matched case–control study design was used; patients with biochemical/clinical failure >2 years after radiation therapy (BCR) were matched 1:1 to patients without recurrence using established prognostic factors (Gleason score, prostate-specific antigen, tumor stage) and fractionation schedule. Immunohistochemistry was used to stain diagnostic biopsy specimens for Ki67, which were scored using the unweighted global method. Conditional logistic regression models estimated the prognostic value of mean and maximum Ki67 scores on BCR risk. Biomarker–fractionation interaction terms determined whether Ki67 was predictive of BCR by fractionation. Results: Using 173 matched pairs, the median for mean and maximum Ki67 scores were 6.6% (interquartile range, 3.9%-9.8%) and 11.0% (interquartile range, 7.0%-15.0%) respectively. Both scores were significant predictors of BCR in models adjusted for established prognostic factors. Conditioning on matching variables and age, the odds of BCR were estimated to increase by 9% per 1% increase in mean Ki67 score (odds ratio 1.09; 95% confidence interval 1.04-1.15, P =.001). Interaction terms between Ki67 and fractionation schedules were not statistically significant. Conclusions: Diagnostic Ki67 did not predict BCR according to fractionation schedule in CHHiP; however, it was a strong independent prognostic factor for BCR

The development of remote controlled survey equipment to measure abandoned mine workings

The development of remote controlled survey equipment to measure abandoned mine working