Precursor adsorption on copper surfaces as the first step during the deposition of copper: a density functional study with van der Waals correction

Copper dimethylamino-2-propoxide [Cu(dmap)2] is used as a precursor for low-temperature atomic layer deposition (ALD) of copper thin films. Chemisorption of the precursor is the necessary first step of ALD, but it is not known in this case whether there is selectivity for adsorption sites, defects, or islands on the substrate. Therefore, we study the adsorption of the Cu(dmap)2 molecule on the different sites on flat and rough Cu surfaces using PBE, PBE-D3, optB88-vdW, and vdW-DF2 methods. We found the relative order of adsorption energies for Cu(dmap)2 on Cu surfaces is Eads (PBE-D3) > Eads (optB88-vdW) > Eads (vdW-DF2) > Eads (PBE). The PBE and vdW-DF2 methods predict one chemisorption structure, while optB88-vdW predicts three chemisorption structures for Cu(dmap)2 adsorption among four possible adsorption configurations, whereas PBE-D3 predicts a chemisorbed structure for all the adsorption sites on Cu(111). All the methods with and without van der Waals corrections yield a chemisorbed molecule on the Cu(332) step and Cu(643) kink because of less steric hindrance on the vicinal surfaces. Strong distortion of the molecule and significant elongation of Cu–N bonds are predicted in the chemisorbed structures, indicating that the ligand–Cu bonds break during the ALD of Cu from Cu(dmap)2. The molecule loses its initial square-planar structure and gains linear O–Cu–O bonding as these atoms attach to the surface. As a result, the ligands become unstable and the precursor becomes more reactive to the coreagent. Charge redistribution mainly occurs between the adsorbate O–Cu–O bond and the surface. Bader charge analysis shows that electrons are donated from the surface to the molecule in the chemisorbed structures, so that the Cu center in the molecule is partially reduced.

Step-count accuracy of three motion sensors for older and frail medical inpatients

Objectives: To measure the step-count accuracy of an ankle-worn accelerometer, a thigh-worn accelerometer and one pedometer in older and frail inpatients. Design: Cross-sectional design study. Setting: Research room within a hospital. Participants: Convenience sample of inpatients aged ≥65 years, able to walk 20 metres unassisted, with or without a walking-aid. Intervention: Patients completed a 40-minute programme of predetermined tasks while wearing the three motion sensors simultaneously. Video-recording of the procedure provided the criterion measurement of step-count. Main Outcome Measures: Mean percentage (%) errors were calculated for all tasks, slow versus fast walkers, independent versus walking-aid-users, and over shorter versus longer distances. The Intra-class Correlation was calculated and accuracy was visually displayed by Bland-Altman plots. Results: Thirty-two patients (78.1 ±7.8 years) completed the study. Fifteen were female and 17 used walking-aids. Their median speed was 0.46 m/sec (interquartile range, IQR 0.36-0.66). The ankle-worn accelerometer overestimated steps (median 1% error, IQR -3 to 13). The other motion sensors underestimated steps (40% error (IQR -51 to -35) and 38% (IQR -93 to -27), respectively). The ankle-worn accelerometer proved more accurate over longer distances (3% error, IQR 0 to 9), than shorter distances (10%, IQR -23 to 9). Conclusions: The ankle-worn accelerometer gave the most accurate step-count measurement and was most accurate over longer distances. Neither of the other motion sensors had acceptable margins of error.

“Step by step”: high frequency short-distance epizoochorous dispersal of aquatic macrophytes

Aquatic macrophytes can successfully colonise and re-colonise areas separated by space and time. The mechanisms underlying such “mobility” are not well understood, but it has often been hypothesised that epizoochory (external dispersal) plays an important role. Yet, there is only limited, and mostly anecdotal, evidence concerning successful epizoochorous dispersal of aquatic macrophytes, particularly in the case of short-distance dispersal. Here we examine in situ and ex situ dispersal of aquatic macrophytes, including three invasive alien species. A high frequency of Lemna minor Linnaeus dispersal was observed in situ, and this was linked to bird-mediated epizoochory. We concluded that wind had no effect on dispersal. Similarly, in an ex situ examination Lemna minuta Kunth and Azolla filiculoides Lamarck, were found to be dispersed with a high frequency by mallard ducks (Anas platyrhynchos). No dispersal was measured for Elodea nuttalli (Planchon) H. St. John. It is concluded that short-distance or “stepping-stone” dispersal via bird-mediated epizoochory can occur with high frequencies, and therefore can play an important role in facilitating colonisation, range expansion and biological invasion of macrophytes.