Alloying at surfaces by the migration of reactive two-dimensional islands.

We have studied the formation kinetics of the copper-tin alloy bronze when tin is deposited on the (111) surface of copper at room temperature. Low-energy electron microscopy and atomic-resolution scanning tunneling microscopy reveal that bronze forms on the surface by a complicated, unanticipated cooperative mechanism: Ordered two-dimensional tin islands containing several hundred thousand atoms spontaneously sweep across the surface, leaving bronze alloys in their tracks. We propose that this process, driven by surface free energy, is a version of the "camphor dance" observed on liquid surfaces, and should be a general mechanism of surface alloying when surface diffusion is faster than exchange into the substrate.

Chemically amplified soft-x-ray resists: sensitivity, resolution, and molecular photodesorption.

The sensitivity, ion photodesorption, and lithographic performance of selected novolac-based chemically amplified resists have been studied at an exposure wavelength of 140 Å. Flood exposures of the resits AZ PF514, AZ PN114, and SAL 601 yield D(0.9) values of 2.5-3.5 mJ/cm(2) for 0.25-µm-thick films. Contrast values range from 3 for AZ PN114 to 5 for SAL 601. Photodesorption of fragment ions induced by 140-Å radiation has been examined in AZ PN114 by using time-of-flight mass spectrometry and compared with poly(methylmethacrylate) (PMMA). Mass-integrated ion desorption yields from AZ PN114 are found to be ∼ 90 times less per exposure than from PMMA. Soft-x-ray projection imaging in AZ PF514 and SAL 601 has been characterized by use of a multilayer-coated 20 × Schwarzschild objective and a transmissive Ge/Si mask illuminated by a laser plasma source.

Self-assembly via adsorbate-driven dislocation reactions.

Deposition of S onto a monolayer of Ag/Ru(0001) transforms the herringbone pattern of the clean Ag film into a strikingly regular array of 2D-vacancy islands [Nature (London) 397, 238 (1999)]]. Time-resolved scanning tunneling microscopy reveals that this nanometer-scale restructuring occurs by a cooperative mechanism involving the sequential formation of triangular regions with fcc and hcp stacking. Using a 2D Frenkel-Kontorova model, we can simulate the creation of these triangular building blocks via basic dislocation motions and reactions.

Enhanced self-diffusion on Cu(111) by trace amounts of s: chemical-reaction-limited kinetics.

We find that less than 0.01 monolayer of S can enhance surface self-diffusion on Cu(111) by several orders of magnitude. The measured dependence of two-dimensional island decay rates on S coverage (theta(S)) is consistent with the proposal that Cu3S3 clusters are responsible for the enhancement. Unexpectedly, the decay and ripening are diffusion limited with very low and very high theta(S) but not for intermediate theta(S). To explain this result we propose that surface mass transport in the intermediate region is limited by the rate of reaction to form Cu3S3 clusters on the terraces.

Linking surface stress to surface structure: measurement of atomic strain in a surface alloy using scanning tunneling microscopy.

Annealed submonolayer CoAg/Ru(0001) films form an alloy with a structure that contains droplets of Ag surrounded by Co [G. E. Thayer, V. Ozolins, A. K. Schmid, N. C. Bartelt, M. Asta, J. J. Hoyt, S. Chiang, and R. Q. Hwang, Phys. Rev. Lett. 86, 660 (2001)]. To understand how surface stress contributes to the formation of this structure, we use scanning tunneling microscopy to extract atomic displacements at the boundaries between regions of Co and Ag. Comparing our measurements to Frenkel-Kontorova model calculations, we show how stress due to lattice mismatch contributes to the formation of the alloy droplet structure. In particular, we quantitatively evaluate how competing strain and chemical energy contributions determine surface structure.

Role of stress in thin film alloy thermodynamics: competition between alloying and dislocation formation.

Using scanning tunneling microscopy (STM) and first-principles local-spin-density-approximation calculations to study submonolayer films of Co (1-c)Ag (c)/Ru(0001) alloys, we have discovered a novel phase-separation mechanism. When the Ag concentration c exceeds 0.4, the surface phase separates between a dislocated, pure Ag phase and a pseudomorphically strained Co(0.6)Ag (0.4) surface alloy. We attribute the phase separation to the competition between two stress relief mechanisms: surface alloying and dislocation formation. The agreement between STM measurements and our calculated phase diagram supports this interpretation.

Strain relief through heterophase interface reconstruction: Ag(111)/Ru(0001).

We report an experimental (scanning tunneling microscopy) and theoretical (embedded atom method) study of a heterophase interface reconstruction between Ag(111) and Ru(0001). Despite the large 7% mismatch, the second layer of Ag from the Ru exhibits a hexagonal structure with Ag bulk spacing, providing a close match to bulk Ag. The first layer of Ag (next to Ru) is reconstructed in a highly symmetrical and regular structure containing monolayer long threading dislocations. We argue that this structure may generally occur to relieve strain in a certain class of heterophase interfaces.

Direct observation of misfit dislocation glide on surfaces.

Using scanning tunneling microscopy we have observed thermally induced dislocation glide in monolayer Cu films on Ru(0001) at room temperature. The motion is governed by a Peierls barrier that depends on the detailed structure of the dislocations, in particular upon whether the threading dislocations that terminate them are dissociated or not. Calculations based on the Frenkel-Kontorova model reproduce the threading dislocation structure and provide estimates of the Peierls barrier and dislocation stiffness which are consistent with experiment.