京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21062号 / 工博第4426号 / 新制||工||1688(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 河野 広隆, 准教授 服部 篤史, 准教授 山本 貴士 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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With the reliability requirements of automobile microelectronics pushing towards near 0 ppb levels of failure control, halide induced corrosion issues in wire bonded devices have to be tightly controlled to achieve such a high reliability goal. With real-time corrosion monitoring, for the first time we demonstrated that the explosive H2 evolution coupled with the oxygen reduction reaction, occurring at the critical Al/Cu interfaces, is the key driving force for the observed aggressive corrosion. Several types of passivation coating on Cu wire surfaces to effectively block the cathodic H2 evolution were explored with an aim to disrupt this explosive corrosion cycle. The properties of the protective coating were evaluated using various analytical techniques. The surface coating exhibited high thermal stability up to 260 °C (evaluated using TGA analysis). A uniform, highly hydrophobic coating (surface contact angle of >130° with water), was achieved by carefully controlling CVD parameters such as time of deposition, surface control of Cu metal, amount of inhibitor compound loading, temperature of coating process etc. FTIR spectroscopy combined with corrosion screening was used to optimize the CVD passivated coating with strong chemisorption. SEM and EDX, XPS were carried out on various coated surfaces to understand the composition and selectivity of the film formed through this surface treatment. The surface selective nature of this coating (towards Cu) proved helpful in preventing potential delamination issues during epoxy molding process. The corrosion testing was carried out via HAST testing at 130°C, 2 atm pressure and 100% RH for 48 hours. Delamination analysis and continuity test showed that the inhibitor compound was able to effectively prevent the corrosion even after exposure to harsh HAST conditions.

An electrochromic (EC) material is able to change colour under the influence of an electric potential. The development of energy efficient smart windows for architectural applications is at present the subject of intense research for both economic and environmental reasons. Thus there is now a considerable research effort to develop smart windows with natural colour switching properties, i.e. shades of grey. In this regard, a promising metal oxide with a brown-black anodic colouring state is NiO or hydrated nickel oxide (also called nickel hydroxide , Ni(OH)2). The present work outlines the preparation and optimisation of EC nickel oxide-based ceramic precursor films onto various conducting substrates towards smart window applications. The literature review chapter outlines the different methods used for generating ceramic materials, a review of electrochromism and history of nickel oxide-based EC materials are also provided. Thins films have been deposited by an electrochemical cathodic deposition and by aerosol assisted chemical vapour deposition (AACVD) technique. For hydrated NiO films prepared by electrochemical cathodic deposition, various deposition factors at small-scale area (30 x 7 mm) have been investigated in order to optimise the films properties towards EC applications. With deposition on fluorine-doped tin oxide (SnO2:F, FTO) on glass, use of nickel nitrate (0.01 mol dm-3) solution at an applied current of -0.2 mA (-0.1 mA cm-2) for 800 s was optimal for preparing uniform deposits with a porous interconnecting flake-like structure, which is generally regarded as favourable for the intercalation/deintercalation of hydroxide ions during redox cycling. The as-deposited hydrated NiO films showed excellent transmittance modulation (Δ%T = 83.2 at 432 nm), with average colouration efficiency (CE) of 29.6 cm2 C-1 and low response times. However, after 50 voltammetric cycles, the cycle life was found to fade by 17.2% from charge measurements, and 28.8 % from in-situ transmittance spectra measurements. In an attempt to prepare films with improved durability, AACVD has been used for the first time in the preparation of thin-film EC nickel(II) oxide (NiO). The as-deposited films were confirmed to be cubic NiO from analysis of powder X-ray diffraction data, with an optical band gap that decreased from 3.61 to 3.48 eV with an increase in film thickness (in the range 330 820 nm). The EC properties of the films were investigated as a function of film thickness, following 50, 100 and 500 conditioning oxidative voltammetric cycles in aqueous KOH (0.1 mol dm-3). Light modulation of the films increased with the number of conditioning cycles. EC response times were < 10 s and generally longer for the colouration than the bleaching process. The films showed excellent stability when tested for up to 10000 colour/bleach cycles. Using a calculation method based on the integration of experimental spectral power distributions derived from in-situ visible region spectra over the CIE 1931 colour-matching functions, the colour stimuli of the NiO-based films, and the changes that take place on reversibly switching between the bleached and coloured forms have been calculated. Films prepared by both deposition techniques gave positive a* and b* values to produce orange. However, in combination with low L* values, the films were perceived as brown-grey. Hydrated NiO prepared via electrochemical cathodic deposition suffers from two well-known limitations; firstly, it shows catalytic properties towards the oxygen evolution reaction (OER), which is a process very close to the Ni(II)/Ni(III) redox process. Secondly, hydrated NiO shows poor cycling durability in alkaline solution. The co-deposition of single or bimetallic additives is an effective way to overcome these problems. Electrochemical studies revealed that the combination of cobalt (10%) with lanthanum (5%) was found to be the optimal composition for preparing hydrated NiO films with improved film durability. Finally, the emphasis of this work was on scale-up of deposition. Therefore, optimised deposition conditions from small scale (3.0 x 0.7 cm) have been used to successfully deposit films on two different sized large-area (10 x 7.5 and 30 x 30 cm) conducting substrates.