Adsorbate-driven morphological changes on Cu(111) nano-pits

Mudiyanselage, K.; Xu, F.; Hoffmann, F. M.; Hrbek, J.; Waluyo, I.; Boscoboinik, J. A.; Stacchiola, D. J.

doi:10.1039/c4cp05088f

Adsorbate-driven morphological changes on Cu(111) nano-pits

Journal Article · Mon Dec 08 23:00:00 EST 2014 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c4cp05088f· OSTI ID:1183264

Mudiyanselage, K. ^[1]; Xu, F. ^[2]; Hoffmann, F. M. ^[3]; Hrbek, J. ^[4]; Waluyo, I. ^[4]; Boscoboinik, J. A. ^[5]; Stacchiola, D. J. ^[4]

Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.; BMCC-CUNY, New York, NY (United States). Dept. of Science
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.; State Univ. of New York (SUNY), Stony Brook, NY (United States). Chemistry Dept.
BMCC-CUNY, New York, NY (United States). Dept. of Science
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials

Adsorbate-driven morphological changes of pitted-Cu(111) surfaces have been investigated following the adsorption and desorption of CO and H. The morphology of the pitted-Cu(111) surfaces, prepared by Ar⁺ sputtering, exposed a few atomic layers deep nested hexagonal pits of diameters from 8 to 38 nm with steep step bundles. The roughness of pitted-Cu(111) surfaces can be healed by heating to 450-500 K in vacuum. Adsorption of CO on the pitted-Cu(111) surface leads to two infrared peaks at 2089-2090 and 2101-2105 cm^-1 for CO adsorbed on under-coordinated sites in addition to the peak at 2071 cm^-1 for CO adsorbed on atop sites of the close-packed Cu(111) surface. CO adsorbed on under-coordinated sites is thermally more stable than that of atop Cu(111) sites. Annealing of the CO-covered surface from 100 to 300 K leads to minor changes of the surface morphology. In contrast, annealing of a H covered surface to 300 K creates a smooth Cu(111) surface as deduced from infrared data of adsorbed CO and scanning tunnelling microscopy (STM) imaging. The observation of significant adsorbate-driven morphological changes with H is attributed to its stronger modification of the Cu(111) surface by the formation of a sub-surface hydride with a hexagonal structure, which relaxes into the healed Cu(111) surface upon hydrogen desorption. These morphological changes occur ~150 K below the temperature required for healing of the pitted-Cu(111) surface by annealing in vacuum. In contrast, the adsorption of CO, which only interacts with the top-most Cu layer and desorbs by 160 K, does not significantly change the morphology of the pitted-Cu(111) surface.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-98CH10886

OSTI ID:: 1183264

Report Number(s):: BNL-107689-2015-JA; BNL-107689-2015-JAAM; KC0302010

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 5 Vol. 17; ISSN 1463-9076; ISSN PPCPFQ

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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