Segregation and chemical ordering on Pt25Co75(111) are studied by quantitat
ive low-energy electron diffraction (LEED) analysis and scanning tunnelling
microscopy (STM). Although LEED patterns do not show any sign of superstru
cture, LEED calculations undoubtedly point to a surface that contains about
the same amount of both species and reveal a significant short-range chemi
cal ordering (down to the third layer). Pt and Co surface sites are locally
arranged with a (1 x 2) unit cell, in the manner of the ordered tetragonal
L1(0) phase. More direct evidence is given by STM images that exhibit para
llel Pt and Co monoatomic chains a few lattice constants long and an appare
nt height difference of about 0.2 Angstrom for Pt and Co sites. LEED shows
that the Pt sublattice in the top layer actually resides 0.1 Angstrom above
the Co one. Otherwise the surface is bulk-like, with weak relaxations of i
nterlayer distances. The use of a chemically ordered model for the LEED ana
lysis, in which sublattice occupancies are optimized, results in a remarkab
le improvement of the fit with experiment as compared to a totally random d
istribution; however, most interestingly, it does not modify the average la
yer concentration profile versus depth (55, 5 and 35 at.% Pt, respectively,
for the three outermost layers). The distortions needed for the tetragonal
L1(0) phase with respect to the fee L1(2) phase explain why chemical order
does not extend over larger domains. Finally, both techniques yield comple
mentary pictures and quite consistent results as to the top layer content a
nd chemical order. (C) 2000 Elsevier Science B.V. All rights reserved.