H(3)PW(12)O(40)-functionalized tip for scanning tunneling microscopy

Recent reports of C(60)-functionalized metal tips [Kelly, K. F., Sarkar, D., Hale, G. D., Oldenburg, S. J. & Halas, N. J. (1996) Science 273, 1371–1373] and carbon nanotube tips [Dai, H., Hafner, J. H., Rinzler, A. G., Colbert, D. T. & Smalley, R. E. (1996) Nature (London) 384, 147–151] demonstrate the potential of controlling the chemical identity and geometric structure of tip atoms in scanning tunneling microscopy (STM). This work reports the performance of a heteropolyacid (HPA)-functionalized Pt/Ir tip, which was formulated by contacting a mechanically formed tip with a solution of H(3)PW(12)O(40) molecules. Attachment of an H(3)PW(12)O(40) molecule on the metal tip was confirmed by observing the characteristic negative differential resistance (NDR) behavior of H(3)PW(12)O(40) in tunneling spectroscopy. Atomic resolution images of bare graphite as well as of H(6)P(2)W(18)O(62) HPA monolayers on graphite were successfully obtained with a Pt/Ir-HPA tip. In the H(3)PW(12)O(40) molecule on a metal tip, it is likely that a terminal oxygen of W⩵O (an oxygen species projecting outward from the pseudospherical H(3)PW(12)O(40) molecule) serves as an atomically sharp and stable tip. Additionally, superimposed superperiodic structures commensurate with the underlying graphite lattice were regularly observed with the modified tips. This result suggests that tip functionalization with these metal oxide molecules may enhance resolution in a fashion analogous to functionalization with C(60).