Self-organized patterning of supported nanoclusters by virtue of low cost and readiness for mass production is considered as one of the most promising methods; however, this approach is challenging, since the capability of controlling the patterns relies on a suitable combination of clusters and templates. In this paper we demonstrate that Co nanoclusters grown from vapour deposition over Al2O3 thin films on NiAl(100) substrate make a perfect combination for self-organized patterning. Uniform and sizeable Co nanoclusters are formed only on crystalline Al2O3 films and they are highly aligned by protrusion structures of the crystalline Al2O3. Through simple thermal treatments we can pattern the crystalline Al2O3 films and consequently the grown Co nanoclusters. The patterns are robust as they are sustained even when the Co nanoclusters are flashed to 750 K, exposed to atmosphere or the coverage is increased to coalescence. Moreover, the patterns can be further refined by using STM tips. The results imply potential applications in both fundamental and applied researches for electronic and magnetic nanodevices as well as catalysis.

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With a variety of surface probe techniques, we investigated low-temperature decomposition of methanol on Au nanoclusters formed by vapor deposition onto an ordered Al(2)O(3)/NiAl(100) thin film. Upon adsorption of methanol on the Au clusters (with mean diameter 1.5-3.8 nm and height 0.45-0.85 nm) at 110 K, some of the adsorbed methanol dehydrogenates directly into carbon monoxide (CO); the produced hydrogen atoms (H) begin to desorb near 125 K whereas most of the CO desorbs above 240 K. The reaction exhibits a significant dependence on the Au coverage: the produced CO increases in quantity with the Au coverage, reaches a maximum at about 1.0-1.5 ML Au, whereas decreases with further increase of the Au coverage. The coverage-dependence is rationalized partly by an altered number of reactive sites associated with low-coordinated Au in the clusters. At least two kinds of reactive sites for the low-temperature decomposition are distinguished through distinct C-O stretching frequencies (2050 cm(-1) and 2092 cm(-1)) while the produced CO co-adsorbs with H and methanol.

We present a scanning tunnel microscopy study of Co clusters grown through vapor deposition on Al(2)O(3) thin films over NiAl(100) at different coverages and temperatures. Formation of Co clusters was observed at 90, 300, 450, and 570 K. At the three lower temperatures, we find narrow cluster size distributions and the mean sizes (with a diameter of 2.6 nm and a height of 0.7 nm) do not change significantly with the coverage and temperature, until the clusters start to coalesce. Even on 3-4-nm-wide crystalline Al(2)O(3) strips where the deposited Co atoms are confined, the same features sustain. Only at 570 K the normal growth mode where the cluster size increases with the deposition coverage is observed, although the data are less conclusive. A simple modeling of kinetic surface processes on a strip confirms the normal growth mode, but fails to show a favored size unless additional energetic constraints are applied on the cluster sizes. Increasing Co coverages to cluster coalescence, a larger preferable size (mean diameter of 3.5 nm and height of 1.4 nm) appears for growth at 450 K. These two sizes are corroborated by morphology evolution of high Co coverages deposited at 300 K and annealed to 750 K, in which the coalescence is eliminated and the two preferable geometries appear and coexist.

Adsorption and decomposition of methanol on Au nanoclusters supported on an ordered ultrathin film of Al 2 O 3 /NiAl(100) have been investigated by means of their photoelectron spectra excited with synchrotron radiation and scanning tunneling microscopy. The results show adsorption sites on the clusters of at least two types: one catalyzes the decomposition of methanol via scission of the O-H bond into CO at a temperature as low as 120 K, whereas the other activates dehydrogenation only into methoxy. The CO from the decomposition remains on the surface up to 250 K, begins to desorb above 250 K, and decomposes further into elemental carbon around 350 K. All carbon species are removable from the surface at 450 K, a temperature much lower than on other metals studied. Regarding effects of morphology of the clusters on the reactivity, smaller Au clusters, of height 1-2 atomic layers, exhibit inactivity toward the decomposition of methanol.