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Many thermoelectrics like Bi exhibit Rashba spin-orbit surface bands for which topological insulator behavior consisting of ultrahigh mobilities and enhanced thermopower has been predicted. Bi nanowires realize surface-only electronic transport since they become bulk insulators when they undergo the bulk semimetal-semiconductor transition as a result of quantum confinement for diameters close to 50 nm. We studied 20-, 30-, 50- and 200-nm trigonal Bi wires. Shubnikov-de Haas magnetoresistance oscillations caused by surface electrons and bulklike holes enable the determination of their densities and mobilities. Surface electrons have high mobilities exceeding 2(m^2)/(Vsec) and contribute strongly to the thermopower, dominating for temperatures T< 100 K. The surface thermopower is - 1.2 T microvolt/(K^2), a value that is consistent with theory, raising the prospect of developing nanoscale thermoelectrics based on surface bands.
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