Measuring the roughness of buried interfaces by sputter depth profiling.

We report results of high-resolution sputter depth profiling of an alternating MgO/ZnO nanolayer stack grown by atomic layer deposition (ALD) of ≈5.5 nm per layer. We used an improved dual beam time-of-flight secondary ion mass spectrometer to measure (24)Mg(+) and (64)Zn(+) intensities as a function of sample depth. Analysis of depth profiles by the mixing-roughness-information model yields a 1.5 nm nanolayer interfacial roughness within the MgO/ZnO multilayer. This finding was cross-validated using specular x-ray reflectivity. Such an analysis further suggested that the 1.5 nm roughness corresponds to native/jig-sawed interfacial roughness rather than interfacial interdiffusion during the ALD growth.

Increased silver activity for direct propylene epoxidation via subnanometer size effects.

Production of the industrial chemical propylene oxide is energy-intensive and environmentally unfriendly. Catalysts based on bulk silver surfaces with direct propylene epoxidation by molecular oxygen have not resolved these problems because of substantial formation of carbon dioxide. We found that unpromoted, size-selected Ag3 clusters and approximately 3.5-nanometer Ag nanoparticles on alumina supports can catalyze this reaction with only a negligible amount of carbon dioxide formation and with high activity at low temperatures. Density functional calculations show that, relative to extended silver surfaces, oxidized silver trimers are more active and selective for epoxidation because of the open-shell nature of their electronic structure. The results suggest that new architectures based on ultrasmall silver particles may provide highly efficient catalysts for propylene epoxidation.

GaPO4 sensors for gravimetric monitoring during atomic layer deposition at high temperatures.

The quartz crystal microbalance is extremely useful for in situ monitoring of thin-film growth by atomic layer deposition (ALD) in a viscous flow environment. Unfortunately, conventional AT-quartz sensors are limited to growth temperatures below approximately 300 degrees C. Gallium orthophosphate (GaPO4) is an alternative piezoelectric material offering much greater high-temperature frequency stability than AT-quartz (SiO2). Our measurements reveal that the temperature coefficient for Y-11 degrees GaPO4 decreases linearly with temperature reaching 3 Hz/ degrees C at 450 degrees C. In contrast, the temperature coefficient for the SiO2 sensor increases as the cube of the sensor temperature to 650 Hz/ degrees C at 390 degrees C. To examine the effect of temperature fluctuations on the sensor frequency, we exposed the SiO2 and GaPO4 sensors to helium pulses at 400 degrees C. The resulting frequency change measured for the SiO2 sensor was approximately 40 times greater than that of the GaPO4 sensor. Next, we performed Al2O3 ALD using alternating tri-methylaluminum/water exposures at 400 degrees C and monitored the growth using the SiO2 and GaPO4 sensors. The GaPO4 sensor yielded well-defined pulse shapes in agreement with predictions, while the SiO2 pulses were severely distorted. Measurements during TiO2 ALD using alternating titanium tetrachloride/water exposures at 450 degrees C with the GaPO4 sensor also showed well-defined ALD mass steps.