Overwintering ecology of northern field layer plants : snow and photosynthesis in Vaccinium vitis-idaea L.

Winter is a significant period for the seasonality of northern plants, but is often overlooked when studying the interactions of plants and their environment. This study focuses on the effects of overwintering conditions, including warm winter periods, snow, and snowmelt on boreal and sub-Arctic field layer plants. Wintertime photosynthesis and related physiological factors of evergreen dwarf shrubs, particularly of Vaccinium vitis-idaea, are emphasised. The work combines experiments both in the field and in growth chambers with measurements in natural field conditions. Evergreen dwarf shrubs are predominantly covered by snow in the winter. The protective snow cover provides favourable conditions for photosynthesis, especially during the spring before snowmelt. The results of this study indicate that photosynthesis occurs under the snow in V. vitis-idaea. The light response of photosynthesis determined in field conditions during the period of snow cover shows that positive net CO2 exchange is possible under the snow in the prevailing light and temperature. Photosynthetic capacity increases readily during warm periods in winter and the plants are thus able to replenish carbohydrate reserves lost through respiration. Exposure to low temperatures in combination with high light following early snowmelt can set back photosynthesis as sustained photoprotective measures are activated and photodamage begins to build up. Freezing may further decrease the photosynthetic capacity. The small-scale distribution of many field layer plants, including V. vitis-idaea and other dwarf shrubs, correlates with the snow distribution in a forest. The results of this study indicate that there are species-specific differences in the snow depth affinity of the field and ground layer species. Events and processes taking place in winter can have a profound effect on the overall performance of plants and on the interactions between plants and their environment. Understanding the processes involved in the overwintering of plants is increasingly important as the wintertime climate in the north is predicted to change in the future.

Selective-Area Atomic Layer Deposition

Atomic layer deposition (ALD) is a method to deposit thin films from gaseous precursors to the substrate layer-by-layer so that the film thickness can be tailored with atomic layer accuracy. Film tailoring is even further emphasized with selective-area ALD which enables the film growth to be controlled also on the substrate surface. Selective-area ALD allows the decrease of a process steps in preparing thin film devices. This can be of a great technological importance when the ALD films become into wider use in different applications. Selective-area ALD can be achieved by passivation or activation of a surface. In this work ALD growth was prevented by octadecyltrimethoxysilane, octadecyltrichlorosilane and 1-dodecanethiol SAMs, and by PMMA (polymethyl methacrylate) and PVP (poly(vinyl pyrrolidone) polymer films. SAMs were prepared from vapor phase and by microcontact printing, and polymer films were spin coated. Microcontact printing created patterned SAMs at once. The SAMs prepared from vapor phase and the polymer mask layers were patterned by UV lithography or lift-off process so that after preparation of a continuous mask layer selected areas of them were removed. On these areas the ALD film was deposited selectively. SAMs and polymer films prevented the growth in several ALD processes such as iridium, ruthenium, platinum, TiO2 and polyimide so that the ALD films did grow only on areas without SAM or polymer mask layer. PMMA and PVP films also protected the surface against Al2O3 and ZrO2 growth. Activation of the surface for ALD of ruthenium was achieved by preparing a RuOX layer by microcontact printing. At low temperatures the RuCp2-O2 process nucleated only on this oxidative activation layer but not on bare silicon.

Tuning the interfacial properties of supported metal nanoclusters

Nanoclusters are objects made up of several to thousands of atoms and form a transitional state of matter between single atoms and bulk materials. Due to their large surface-to-volume ratio, nanoclusters exhibit exciting and yet poorly studied size dependent properties. When deposited directly on bare metal surfaces, the interaction of the cluster with the substrate leads to alteration of the cluster properties, making it less or even non-functional. Surfaces modified with self-assembled monolayers (SAMs) were shown to form an interesting alternative platform, because of the possibility to control wettability by decreasing the surface reactivity and to add functionalities to pre-formed nanoclusters. In this thesis, the underlying size effects and the influence of the nanocluster environment are investigated. The emphasis is on the structural and magnetic properties of nanoclusters and their interaction with thiol SAMs. We report, for the first time, a ferromagnetic-like spin-glass behaviour of uncapped nanosized Au islands tens of nanometres in size. The flattening kinetics of the nanocluster deposition on thiol SAMs are shown to be mediated mainly by the thiol terminal group, as well as the deposition energy and the particle size distribution. On the other hand, a new mechanism for the penetration of the deposited nanoclusters through the monolayers is presented, which is fundamentally different from those reported for atom deposition on alkanethiols. The impinging cluster is shown to compress the thiol layer against the Au surface and subsequently intercalate at the thiol-Au interface. The compressed thiols try then to straighten and push the cluster away from the surface. Depending on the cluster size, this restoring force may or may not enable a covalent cluster-surface bond formation, giving rise to various cluster-surface binding patterns. Compression and straightening of the thiol molecules pinpoint the elastic nature of the SAMs, which has been investigated in this thesis using nanoindentation. The nanoindenation method has been applied to SAMs of varied tail groups, giving insight into the mechanical properties of thiol modified metal surfaces.