Nutritional stress has been reported in planted and naturally-regenerated conifers growing in association with an ericaceous species, salal (Gaultheria shallon Pursh), in cutovers previously occupied by old-growth western redcedar (Thuja plicata Donn) and western hemlock (Tsuga heterophylla (Raf.) Sarg.) (CH sites) on northern Vancouver Island. No such stress was apparent in cutovers previously occupied by natural, second growth western hemlock and amabilis fir (Abies amabilis (Dougl.) Forbes) stands (HA sites) that developed following windthrow in 1907. The CH ecosystem type occupies as much as 100,000 ha in coastal British Columbia. In the spring of 1987, a series of field and pot experiments was initiated to investigate some of the ecological processes affecting the early growth of conifers on recently logged and burned 2- to 10-year-old CH and 2- to 4-year-old HA sites. The overall objective of the research was to quantify some of the possible factors limiting early conifer growth on northern Vancouver Island. The research encompassed studies of: (1) below- and above-ground non-crop vegetation recovery, forest floor nutrient availability and soil microenvironmental modification following clear-cutting and burning; (2) competition for nutrients by the non-crop vegetation; (3) interference by salal of the mycorrhizal development on conifer seedling roots; (4) conifer seedling growth under several different experimental conditions, and; (5) relationship between microsite factors and western redcedar seedling growth within clear-cut and burned CH sites. Salal was the main non-crop species found on the CH sites. It reestablished itself rapidly, both above- and below-ground, following clear-cutting and burning on this type of site. The total above-ground vegetation biomass quadrupled from 1372 kg ha ̄¹on the 2-year-old CH sites to 5574 kg ha ̄¹on the 8-year-old CH sites, whereas the total below-ground biomass increased six times from 1908 kg ha ̄¹ on the 2-year-old CH sites to 11415 kg ha ̄¹ on the 8-year-old CH sites. Similar amounts of total above-ground non-crop biomass were found on HA cutovers for the first 4 years, but the non-crop vegetation was composed of half salal half fireweed (Epilobium angustifolium L.). The regrowth of the non-crop vegetation immobilized annually 9 and 0.9 kg ha ̄¹of N and P, respectively, on the CH sites during the first eight years. This was estimated to represent potentially between 30 and 45% of the available N on these sites. A model of the development of live fine-root, leaf, stem and rhizome biomass of salal over a 60 year period is proposed based on the result of this study and of other studies. This model suggests that the net immobilization of nutrients in salal biomass will cease between 10 and 20 years after clear-cutting and burning as salal stops expanding its biomass. This model implies that the nutritional stress caused by salal should decline after 10 to 20 years at which time conifer nutrition and growth should slowly improve, especially as salal is eliminated by light competition as the conifer canopy begins to close. Several biotic and abiotic factors were studied in relation to their possible effects on the early growth of western hemlock, Sitka spruce and western redcedar. The growth of these three conifer species was compared between 2- to 4-year-old CH cutovers (2+B CH), 8- to 10-year-old CH cutovers (8+B CH), and 2- to 4-year-old HA cutovers (2+B HA) with and without the influence of the non-crop vegetation. No moisture deficit was measured in the field throughout the year on all sites. Both the growth of the conifers and the availability of N (+36%) and P (+25%) were increased by the removal of the non-crop vegetation; however, no difference in cellulose decomposition and soil moisture, and only very small difference in soil temperature was measured. The better conifer growth on 2+B HA > 2+B CH > 8+B CH without the influence of the non-crop vegetation was associated with an overall better forest floor nutrient status; however, no difference in soil moisture and pH, and only small difference in soil temperature were measured. Western redcedar and western hemlock were the best growing species on CH and HA sites, respectively. Both western hemlock and Sitka spruce (Picea sitchensis) were very responsive to the different site conditions (CH vs HA sites) and to planting treatments that increased or decreased conventional measures of nutrient availability caused by the different treatments, whereas western redcedar was not. The presence of salal was found to have no effect on the total percent mycorrhizae found on the roots of the three conifer species studied three years after planting. Both field and pot experiments yielded comparable results. Slow-release fertilizer, at the time of planting, increased growth only for the first two years after application. Western redcedar growth was significantly greater in depressions than on flats and mounds, but this difference was not related to any major differences in the forest floor variables measured between the three microtopographic positions. These results indicate that the nutritional stress and poor growth reported in conifers, especially in Sitka spruce, on CH cutovers on northern Vancouver Island can be explained by a combination of (1) inherently low forest floor fertility in cutovers originating from the old-growth CH forests, (2) salal competition for scarce nutrients and their immobilization in salal biomass, and (3) declining site fertility caused by the termination of the flush of nutrients that occurs in the immediate post-logging and burning period on CH sites. / Forestry, Faculty of / Graduate

Concern about potential losses of biological diversity and productivity following clear-cut logging of old-growth forests in British Columbia led me to compare ectomycorrhizas in old-growth and mature stands of Douglas-fir. Two sites were selected, each with an old-growth (288-, 441-yr-old) and a mature stand (87-, 89-yr-old) well-matched in tree species, soil and topography. A total of 120 soil cores ≤15 cm deep by 5 cm diameter were taken at random from four 60 m square plots (one per stand). Samples were taken in spring and fall at each site. All morphological types of ectomycorrhizas in one half of each core were counted and characterized in detail. Ectomycorrhizal abundance and frequency was compared in logs, stumps, the forest floor over bedrock or gravel, the forest floor near the base of trees, the forest floor elsewhere, and mineral soil. Old-growth and mature stands were very similar in richness, diversity and types of ectomycorrhizas. Sixty-nine types of ectomycorrhizas were described. Nineteen types each accounted for more than one percent of the 17,500 ectomycorrhizal root tips examined, and eighteen types were found in five or more of the 120 soil cores. Extrapolation indicates a total richness of roughly 100 types in the four plots. Co-dominant fungi were Cenococcum geophilum Fr. (24% of all ectomycorrhizal root tips), a Rhizopogon Fr. of the section villosuli (10%), Hysterangium vitt. (9%), Lactarius deliciosus (Fr.) S.F.G. (6%), and Piloderma fallax (Libert) Stalpers (4%). Cenococcum geophilum, Rhizopogon Fr. and L. deliciosus were abundant in both mineral soil and organic substrates, Piloderma fallax was associated with decayed wood, and Hysterangium and type 27 were in organic substrates only. A bright greenish-yellow felty type was found in 5 cores in mineral soil only. The similarity of the ectomycorrhizal communities of old-growth and mature stands was probably due to their proximity ($<$200 m apart) and the similarity of their vegetation and soil. Differences may occur at some sites if ectomycorrhizal succession has been delayed or redirected as a result of frequent or severe disturbance, lack of old-growth legacies (logs and stumps), or lack of old-growth stands from which fungi can disperse. / Graduate

Title: Nano-structured multicomponent plasma polymers for controlled immobilization of biomolecules Author: Iurii Melnichuk Department / Institute: Department of Macromolecular Physics/Charles University Supervisor of the doctoral thesis: Doc. Ing. Andrey Shukurov, Ph.D. Abstract: The aim of this thesis is to highlight the feasibility of tailored nano- structures in functionalizing surfaces for biointerfacial interactions. Development of new techniques for the production of nanoscaled biomaterials can be of use in a variety of medical and biological applications, e.g. biosensors, microarrays, drug sensors, implants, blood-contacting devices. This thesis first examines the early stages of nano-structured thin film growth fabricated by vapor phase deposition of poly(ethylene). We discuss island growth within a framework of rate equation theory, dynamic scaling theory and capture zone distribution. In a second stage, we test dielectric barrier discharge to activate PE nano-pattern for covalent immobilization of proteins. Finally, we assess cell behavior on surfaces in dependence on morphology and the presence of cell adhesive protein tropoelastin. We employ plasma polymerization to produce ultrathin hydrocarbon layer capable of protein anchoring. The thesis findings for the first time manifest the critical...

Die vorliegende Arbeit entstand im Rahmen einer Kooperation des Forschungszentrums Dresden-Rossendorf mit Qimonda Dresden GmbH & Co. OHG. Mithilfe der hochauflösenden Rutherford-Streuspektrometrie (HR-RBS) wurden das Diffusionsverhalten und Schichtwachstum von ZrO2 auf SiO2 und TiN im Anfangsstadium untersucht. Auf Grund der exzellenten Tiefenauflösung von 0,3 nm an der Oberfläche stand die Analyse von Konzentrationsprofilen in ultradünnen Schichten, respektive an deren Grenzflächen im Vordergrund. Zur qualitativen Verbesserung der Messergebnisse wurde erstmals ein zweidimensionaler positionsempfindlicher Halbleiterdetektor in den Aufbau der HR-RBS implementiert und charakterisiert. Außerdem wurde ein Messverfahren in Betrieb genommen, das mögliche Schädigungen durch den Ioneneintrag in die Messprobe minimiert. Durch die Optimierung der experimentellen Bedingungen und die Entwicklung eines Programmpaketes zur Unterstützung des Analysten konnte ein effizienter Routine-Messablauf erstellt werden. Im Moment einer binären Kollision zwischen einfallendem Ion und Targetelement kommt es bei kleinem Stoßparameter zu Veränderungen des Ladungszustands der gestreuten Ionen, insbesondere durch die abrupte Geschwindigkeitsänderung des Projektils und der Überlappung der Elektronenwolken. Bei der HR-RBS mit Energie separierendem Dipolmagneten muss zur Interpretation von Streuspektren die Ladungszustandsverteilung der gestreuten Projektile bekannt sein. Erstmalig konnte eine signifikante Abhängigkeit der Ladungszustandsverteilung gestreuter C-Ionen sowohl von der Schichtdicke als auch der Ordnungszahl des detektierten Targetelements, hier der vierten Nebengruppe, nachgewiesen werden. Diese gewonnen Erkenntnisse ermöglichten systematische Untersuchungen zum ZrO2-Schichtwachstum im Anfangsstadium. Zur Herstellung der ZrO2-Schichten wurde die Atomlagenabscheidung (ALD) verwendet. Anhand der nachgewiesenen Agglomeration von ZrO2 auf nativen SiO2 wurde mithilfe der Rasterkraftmikroskopie (AFM) zur Bestimmung von Oberflächenrauigkeiten eine Methode konzipiert, welche die Auswirkung lokaler Schichtdickeninhomogenitäten auf die niederenergetische Flanke eines Streuspektrums berücksichtigt. Auf dieser Grundlage durchgeführte Simulationsrechnungen ergeben, dass keine Diffusion von Zr in die darunter liegende Schicht stattfand, jedoch eine ZrSiO4-Grenzflächenschicht existiert. Für das Wachstum von ZrO2 auf TiN wird aus den hoch aufgelösten Streuspektren ein völlig anderes Verhalten abgeleitet. Messungen zu Oberflächentopografien der TiN-Schicht liefern nicht zu vernachlässigende Werte für die Rauigkeit. Um den Einfluss der Oberflächenrauigkeit auf die Form des hoch aufgelösten Spektrums erfassen zu können, wurde eine Software entwickelt. Auf Basis von AFM-Messungen ermöglicht dieses Programm das Extrahieren einer Energieverteilung aus den Weglängen von ausschließlich an der Oberfläche gestreuten Ionen. Unter Berücksichtigung des Effekts der Oberflächenrauigkeit auf die HR-RBS Spektrenform konnte die Diffusion von Zr in das polykristalline TiN erstmals verifiziert werden. Die Beobachtungen weisen daraufhin, dass bereits nach dem ersten ALD-Zyklus ein geringer Anteil der deponierten Zr-Atome bis in eine Tiefe von etwa 3 nm in das TiN diffundiert. Die vorläufigen Ergebnisse legen Korngrenzendiffusion nahe. / This thesis originated from a cooperation between Research Center Dresden-Rossendorf and Qimonda Dresden GmbH & Co. OHG. By means of High Resolution Rutherford Backscattering Spectrometry (HR-RBS) the diffusion behaviour and layer growth of ZrO2 on SiO2 and TiN in the initial regime were investigated. The analysis of concentration profiles in ultrathin layers and interfaces was the focus of this work, made possible by the excellent depth resolution of less than 0.3 nm near the surface. For the first time a two-dimensional position sensitive semiconductor detector was implemented and characterized in the setup of the HR-RBS for the improvement of the quality of the measurement results. Furthermore, a measurement procedure was put into operation that allowed the reduction of ion induced damage. Through the optimization of the experimental conditions and the development of a program package for the support of the analyst, an efficient measurement procedure could be routinely ensured. At the time of a binary collision between the incident ion and the target element with a small impact factor, the charge state changes frequently, especially due to the abruptly decreasing ion velocity of the projectile and the overlapping of the electron clouds. For HR-RBS with an energy-separating dipole magnet, the charge state distribution of the scattered ions must be known for the interpretation of the measured spectra. For the first time a significant dependence of the charge state distribution of the scattered C ions on the layer thickness as well as atomic number of the detected target elements, here from the fourth subgroup, was emonstrated. This new knowledge allowed systematic investigations of the ZrO2 layer growth in the initial regime. The ZrO2 layers were produced by means of the atomic layer deposition (ALD). Based on the evidence for agglomeration of ZrO2 on SiO2 a method was introduced, which takes local thickness variations into account during the simulation of the HR-RBS spectra. An accurate statement about the ZrO2/SiO2 interface was possible due to the extraction of the thickness variation by the atomic force microscopy (AFM). The boundary surface is sharp except for a small intermediate ZrSiO4 layer and no diffusion of Zr atoms in SiO2 could be detected. A quite different behaviour could be derived from high resolution spectra for the growth of ZrO2 on TiN. Measurements of the surface topography of the TiN layer revealed non negligible values for the surface roughness. A program was developed to capture the influence of the surface roughness on the shape of the high resolution spectrum. This software uses AFM measurements to extract an energy distribution from calculated path length differences for ions scattered at the sample surface. Diffusion of Zr into polycrystalline TiN was demonstrated for the first time taking into account the effect of the surface roughness on the shape of the spectra. This observation indicates that already after the first ALD reaction cycle a small part of the deposited Zr atoms diffuses into the TiN layer up to a depth of 3 nm. Such preliminary results suggest grain boundary diffusion.

Die vorliegende Arbeit entstand im Rahmen einer Kooperation des Forschungszentrums Dresden-Rossendorf mit Qimonda Dresden GmbH & Co. OHG. Mithilfe der hochauflösenden Rutherford-Streuspektrometrie (HR-RBS) wurden das Diffusionsverhalten und Schichtwachstum von ZrO2 auf SiO2 und TiN im Anfangsstadium untersucht. Auf Grund der exzellenten Tiefenauflösung von 0,3 nm an der Oberfläche stand die Analyse von Konzentrationsprofilen in ultradünnen Schichten, respektive an deren Grenzflächen im Vordergrund. Zur qualitativen Verbesserung der Messergebnisse wurde erstmals ein zweidimensionaler positionsempfindlicher Halbleiterdetektor in den Aufbau der HR-RBS implementiert und charakterisiert. Außerdem wurde ein Messverfahren in Betrieb genommen, das mögliche Schädigungen durch den Ioneneintrag in die Messprobe minimiert. Durch die Optimierung der experimentellen Bedingungen und die Entwicklung eines Programmpaketes zur Unterstützung des Analysten konnte ein effizienter Routine-Messablauf erstellt werden. Im Moment einer binären Kollision zwischen einfallendem Ion und Targetelement kommt es bei kleinem Stoßparameter zu Veränderungen des Ladungszustands der gestreuten Ionen, insbesondere durch die abrupte Geschwindigkeitsänderung des Projektils und der Überlappung der Elektronenwolken. Bei der HR-RBS mit Energie separierendem Dipolmagneten muss zur Interpretation von Streuspektren die Ladungszustandsverteilung der gestreuten Projektile bekannt sein. Erstmalig konnte eine signifikante Abhängigkeit der Ladungszustandsverteilung gestreuter C-Ionen sowohl von der Schichtdicke als auch der Ordnungszahl des detektierten Targetelements, hier der vierten Nebengruppe, nachgewiesen werden. Diese gewonnen Erkenntnisse ermöglichten systematische Untersuchungen zum ZrO2-Schichtwachstum im Anfangsstadium. Zur Herstellung der ZrO2-Schichten wurde die Atomlagenabscheidung (ALD) verwendet. Anhand der nachgewiesenen Agglomeration von ZrO2 auf nativen SiO2 wurde mithilfe der Rasterkraftmikroskopie (AFM) zur Bestimmung von Oberflächenrauigkeiten eine Methode konzipiert, welche die Auswirkung lokaler Schichtdickeninhomogenitäten auf die niederenergetische Flanke eines Streuspektrums berücksichtigt. Auf dieser Grundlage durchgeführte Simulationsrechnungen ergeben, dass keine Diffusion von Zr in die darunter liegende Schicht stattfand, jedoch eine ZrSiO4-Grenzflächenschicht existiert. Für das Wachstum von ZrO2 auf TiN wird aus den hoch aufgelösten Streuspektren ein völlig anderes Verhalten abgeleitet. Messungen zu Oberflächentopografien der TiN-Schicht liefern nicht zu vernachlässigende Werte für die Rauigkeit. Um den Einfluss der Oberflächenrauigkeit auf die Form des hoch aufgelösten Spektrums erfassen zu können, wurde eine Software entwickelt. Auf Basis von AFM-Messungen ermöglicht dieses Programm das Extrahieren einer Energieverteilung aus den Weglängen von ausschließlich an der Oberfläche gestreuten Ionen. Unter Berücksichtigung des Effekts der Oberflächenrauigkeit auf die HR-RBS Spektrenform konnte die Diffusion von Zr in das polykristalline TiN erstmals verifiziert werden. Die Beobachtungen weisen daraufhin, dass bereits nach dem ersten ALD-Zyklus ein geringer Anteil der deponierten Zr-Atome bis in eine Tiefe von etwa 3 nm in das TiN diffundiert. Die vorläufigen Ergebnisse legen Korngrenzendiffusion nahe. / This thesis originated from a cooperation between Research Center Dresden-Rossendorf and Qimonda Dresden GmbH & Co. OHG. By means of High Resolution Rutherford Backscattering Spectrometry (HR-RBS) the diffusion behaviour and layer growth of ZrO2 on SiO2 and TiN in the initial regime were investigated. The analysis of concentration profiles in ultrathin layers and interfaces was the focus of this work, made possible by the excellent depth resolution of less than 0.3 nm near the surface. For the first time a two-dimensional position sensitive semiconductor detector was implemented and characterized in the setup of the HR-RBS for the improvement of the quality of the measurement results. Furthermore, a measurement procedure was put into operation that allowed the reduction of ion induced damage. Through the optimization of the experimental conditions and the development of a program package for the support of the analyst, an efficient measurement procedure could be routinely ensured. At the time of a binary collision between the incident ion and the target element with a small impact factor, the charge state changes frequently, especially due to the abruptly decreasing ion velocity of the projectile and the overlapping of the electron clouds. For HR-RBS with an energy-separating dipole magnet, the charge state distribution of the scattered ions must be known for the interpretation of the measured spectra. For the first time a significant dependence of the charge state distribution of the scattered C ions on the layer thickness as well as atomic number of the detected target elements, here from the fourth subgroup, was emonstrated. This new knowledge allowed systematic investigations of the ZrO2 layer growth in the initial regime. The ZrO2 layers were produced by means of the atomic layer deposition (ALD). Based on the evidence for agglomeration of ZrO2 on SiO2 a method was introduced, which takes local thickness variations into account during the simulation of the HR-RBS spectra. An accurate statement about the ZrO2/SiO2 interface was possible due to the extraction of the thickness variation by the atomic force microscopy (AFM). The boundary surface is sharp except for a small intermediate ZrSiO4 layer and no diffusion of Zr atoms in SiO2 could be detected. A quite different behaviour could be derived from high resolution spectra for the growth of ZrO2 on TiN. Measurements of the surface topography of the TiN layer revealed non negligible values for the surface roughness. A program was developed to capture the influence of the surface roughness on the shape of the high resolution spectrum. This software uses AFM measurements to extract an energy distribution from calculated path length differences for ions scattered at the sample surface. Diffusion of Zr into polycrystalline TiN was demonstrated for the first time taking into account the effect of the surface roughness on the shape of the spectra. This observation indicates that already after the first ALD reaction cycle a small part of the deposited Zr atoms diffuses into the TiN layer up to a depth of 3 nm. Such preliminary results suggest grain boundary diffusion.