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Community interaction webs describe both direct and indirect interactions among species. Changes in direct interactions often become noticeable soon after a perturbation, but time lags in the responses of many species may delay the appearance of indirect effects and lead to temporal or spatial variation in interaction webs. Accurately identifying these shifts in the field requires time‐specific, spatially differentiated interaction webs. We explore how variation in browsing affects interaction webs in a long‐unburned chaparral shrubland near the central California coast. Most prior work in chaparral focused on rapid changes for <5 years after a wildfire that were assumed to determine community patterns until the next fire. Here, we report the results of the first 15 years of an ongoing experiment monitoring how interaction webs in long‐unburned chaparral (at least 100 years postfire) respond to experimental variation in browsing by deer and rabbits on dominant shrubs (Arctostaphylos pumila, Ceanothus cuneatus var. rigidus, and Ericameria ericoides). We hypothesized that variation in browsing would directly affect foodplants, indirectly modify growth and survival of other shrubs, and impact habitat needed by herbaceous plants. We found a dynamic web of plant–herbivore and plant–plant interactions that responded rapidly to changes in deer browsing on Ceanothus followed by indirect interactions that continued developing over several years, affecting shrubs, open space, herbaceous plants, and small mammals. Experimental variation in the intensity of deer browsing led to temporal and spatial changes in interactions that produced three different community interaction webs. With deer, community webs were complex, having numerous direct and indirect interactions. Removing deer simplified the community web, changed outcomes of interactions, and reduced open space and herbaceous plant densities. Finally, changes in Ceanothus morphology without deer allowed woodrats to browse these shrubs, with negative impacts on Ceanothus growth and survival. General field observations also showed that all three alternative interaction webs occurred naturally at our fieldsite, varying across space and over time. Long‐unburned chaparral communities browsed by deer maintain high biological diversity, but maintenance of this diversity involves many key direct and indirect biotic interactions. [ABSTRACT FROM AUTHOR]

Abstract: The effect of H2–Ar plasma pre-treatment prior to thermal atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) of Al2O3 films on steel for corrosion protection was investigated. Time-of-flight secondary ion mass spectrometry and transmission electron microscopy were used to observe the changes in the interface. The electrochemical properties of the samples were studied with polarization measurements, and the coating porosities were calculated from the polarization results for easier comparison of the coatings. Prior to thermal ALD the plasma pre-treatment was observed to reduce the amount of impurities at the interface and coating porosity by 1–3 orders of magnitude. The anti-corrosion properties of the PEALD coatings could also be improved by the pre-treatment. However, exposure of the pre-treatment plasma activated steel surface to oxygen plasma species in PEALD led to facile oxide layer formation in the interface. The oxide layer formed this way was thicker than the native oxide layer and appeared to be detrimental to the protective properties of the coating. The best performance for PEALD Al2O3 coatings was achieved when, after the plasma pre-treatment, the surface was given time to regrow a thin protective interfacial oxide prior to exposure to the oxygen plasma. The different effects that thermal and plasma-enhanced ALD have on the substrate-coating interface were compared. The reactivity of the oxygen precursor was shown to have a significant influence on substrate surface in the early stages of film growth and thereafter also on the overall quality of the protective film. [Copyright &y& Elsevier]

The authors have been investigating the use of [Al(CH3)2(μ-OiPr)]2 (DMAI) as an alternative Al precursor to [Al(CH3)3] (TMA) for remote plasma-enhanced and thermal ALD over wide temperature ranges of 25-400 and 100-400 °C, respectively. The growth per cycle (GPC) obtained using in situ spectroscopic ellipsometry for plasma-enhanced ALD was 0.7-0.9 Å/cycle, generally lower than the >0.9 Å/cycle afforded by TMA. In contrast, the thermal process gave a higher GPC than TMA above 250 °C, but below this temperature, the GPC decreased rapidly with decreasing temperature. Quadrupole mass spectrometry data confirmed that both CH4 and HOiPr were formed during the DMAI dose for both the plasma-enhanced and thermal processes. CH4 and HOiPr were also formed during the H2O dose but combustion-like products (CO2 and H2O) were observed during the O2 plasma dose. Rutherford backscattering spectrometry showed that, for temperatures >100 °C and >200 °C for plasma-enhanced and thermal ALD, respectively, films from DMAI had an O/Al ratio of 1.5-1.6, a H content of ∼5 at. % and mass densities of 2.7-3.0 g cm-3. The film compositions afforded from DMAI were comparable to those from TMA at deposition temperatures ≥150 °C. At lower temperatures, there were differences in O, H, and C incorporation. 30 nm thick Al2O3 films from the plasma-enhanced ALD of DMAI were found to passivate n- and p-type Si floatzone wafers (∼3.5 and ∼2 Ω cm, respectively) with effective carrier lifetimes comparable to those obtained using TMA. Surface recombination velocities of < 3 and < 6 cm s-1 were obtained for the n- and p-type Si, respectively. Using these results, the film properties obtained using DMAI and TMA are compared and the mechanisms for the plasma-enhanced and thermal ALD using DMAI are discussed. [ABSTRACT FROM AUTHOR]

Abstract: The Lewis acid/base adducts [MCl4{NH(R)(SiR′3)}] (M=Zr, Hf; R= tBu, R′=Me; R=SiR′3 =SiMe3, SiMe2H) were synthesized by the 1:1 reaction of MCl4 with NH(R)(SiR′3) in dichloromethane solution at room temperature. The decomposition of [MCl4{NH(R)(SiR′3)}] proceeds with the elimination of R′3SiCl, as shown by thermogravimetric analysis. Pyrolysis of the compounds at 620°C under inert conditions (N2, vacuum) afforded powders of composition [ClMN] or [Cl2MNH]. Preliminary low pressure chemical vapour deposition experiments show that [MCl4{NH(R)(SiR′3)}] deposits thin films of metal nitride contaminated with metal oxide. [Copyright &y& Elsevier]