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The growth of Pb on Si(100) 2×1 is found by scanning tunneling microscopy to form one-dimensional ad-dimer chains at a coverage far below a monolayer, analogous to the behavior of group-III elements (Ga, Al, In) on the same surface but with a buckled dimer configuration. The asymmetric dimerized structure is retained for c(8×4) and c(4×4) reconstructions of higher coverage. Tunneling spectra for the Pb dimers exhibit a surface-state band gap of ∼1.2 eV and thus suggest a nonmetallic property for the Pb chains, in agreement with the dimerization and buckling feature of Pb atoms. The parallel ad-dimer adsorption structure also suggests an approach to obtaining long atomic lines via the selection of the single domain Si(100) as substrates. © 2000 American Vacuum Society.