Direct atomically resolved observation of dynamics deep in the glassy regime has proved elusive for atomic and molecular glasses. Studies below the glass transition temperature T g are especially rare due to long waiting times required to observe dynamics. Here we directly visualize surface glass dynamics deep in the glassy regime. We analyze scanning tunneling microscopy movies of the surface of metallic glasses with time resolution as fast as 1 minute and extending up to 1,000 minutes. Rearrangements of surface cluster occur almost exclusively by two-state hopping (P 3-state ≈ 0.06). All clusters are compact structures with a width of 2-8 atomic spacings along the surface plane. The two-state dynamics is both spatially and temporally heterogeneous. We estimate an average activation free energy of 14 k B T for surface clusters.TOC Figure:

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Theory predicts, and experiments have shown, that dynamics is faster at glass surfaces than in the bulk, allowing the glass to settle into deeper energy landscape minima, or "age more." Is it possible that a glass surface could survive at temperatures where the bulk crystallizes, or that it could remain glassy after the bulk is heated all the way to its melting temperature and re-cooled? We image in real-time and with sub-nanometer resolution the two-state surface dynamics on a cerium-based glass surface, from deep within the glassy regime to above the crystallization temperature. Unlike other surfaces that we have studied, this glass surface remains amorphous even after the bulk re-crystallizes. The surface retains non-crystalline structure and two state dynamics of cooperatively rearranging regions even after heat annealing to just below the bulk melting temperature. The heat-annealed cooperatively rearranging regions are larger than originally, a sign that the surface is well aged. The surface dynamics depends weakly on temperature, showing no sign of the superexponential increase in bulk dynamics expected near T(g).

Direct visualization of the dynamics of structural glasses and amorphous solids on the sub-nanometer scale provides rich information unavailable from bulk or conventional single molecule techniques. We study the surface of hafnium diboride, a conductive ultrahigh temperature ceramic material that can be grown in amorphous films. Our scanning tunneling movies have a second-to-hour dynamic range and single-point current measurements extend that to the millisecond-to-minute time scale. On the a-HfB2 glass surface, two-state hopping of 1-2 nm diameter cooperatively rearranging regions or "clusters" occurs from sub-milliseconds to hours. We characterize individual clusters in detail through high-resolution (<0.5 nm) imaging, scanning tunneling spectroscopy and voltage modulation, ruling out individual atoms, diffusing adsorbates, or pinned charges as the origin of the observed two-state hopping. Smaller clusters are more likely to hop, larger ones are more likely to be immobile. HfB2 has a very high bulk glass transition temperature Tg, and we observe no three-state hopping or sequential two-state hopping previously seen on lower Tg glass surfaces. The electronic density of states of clusters does not change when they hop up or down, allowing us to calibrate an accurate relative z-axis scale. By directly measuring and histogramming single cluster vertical displacements, we can reconstruct the local free energy landscape of individual clusters, complete with activation barrier height, a reaction coordinate in nanometers, and the shape of the free energy landscape basins between which hopping occurs. The experimental images are consistent with the compact shape of α-relaxors predicted by random first order transition theory, whereas the rapid hopping rate, even taking less confined motion at the surface into account, is consistent with β-relaxations. We make a proposal of how "mixed" features can show up in surface dynamics of glasses.

Scanning tunneling microscopy (STM) measurements have been made on single-crystal epitaxial layers of CuInSe2 grown on GaAs substrates. Results were obtained for as-grown, air-exposed, and cleaned surfaces; in situ cleaved surfaces; surfaces sputtered and annealed in the STM system; and samples prepared by a light chemical etch. Conventional constant-current topographs, current-voltage curves, and current imaging tunneling spectroscopy (CITS) scans were obtained. Topographic images show that the surfaces appear rough on the atomic scale and often exhibit regular features consistent with a previously proposed surface ad-dimer reconstruction. CITS scans show a spatially varying energy gap consistent with band-edge fluctuations on a scale of a few atomic spacings. Energy variations were observed in both band edges. Although quantitative description of the magnitude of these fluctuations is difficult, the fluctuations on the atomic scale appear much larger than observed by methods such as photoluminescence, which average over larger volumes.