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Ice is one of the most abundant materials on the earth's surface, and its growth governs various natural phenomena. Hence, the molecular-level understanding of ice crystal surfaces is crucially important. However, it is generally acknowledged that the molecular-level observation of ice crystal surfaces by ordinary microscopy techniques, such as atomic force microscopy and scanning electron microscopy, is very difficult at temperatures near the melting point (0 °C). To overcome such difficulties, we have developed laser confocal microscopy combined with differential interference contrast microscopy (LCM-DIM). We proved that LCM-DIM can visualize individual elementary steps (0.37 nm in thickness) on a basal face by observing two-dimensional nucleation growth. Then we found by LCM-DIM that spiral steps on a basal face exhibit a double-spiral pattern, which can be expected from ice's crystallographic structure. In addition, we revealed that temperature dependence of growth kinetics of elementary spiral steps on a basal face exhibits complicated behaviors, which show the presence of unknown phenomena in the growth kinetics. Furthermore, we proved that surface diffusion of water admolecules on a basal face plays a crucially important role in the lateral growth of elementary steps when the distance between adjacent spiral steps is smaller than 15 µm. These findings will provide a clue for unlocking growth kinetics of ice crystals. In addition, through the use of LCM-DIM much progress has been made in studies on the surface melting of ice and the interaction between ice and atmospheric gasses.

Surface melting of ice crystals forms quasi-liquid layers (QLLs) on ice surfaces, and affects a wide variety of natural phenomena. Since QLLs enhance various chemical reactions in ice clouds, the formation of QLLs by atmospheric gases has been studied intensively. However, such studies were performed using spectroscopy techniques, which have low spatial resolution. Here we show the first direct visualization of QLLs on ice basal faces in the presence of hydrogen chloride (HCl) gas (model atmospheric gas) by advanced optical microscopy, which can visualize individual 0.37 nm-thick elementary steps on ice crystal surfaces. We found that the HCl gas induced the appearances of QLLs with a droplet shape in the temperature range from −15.0 to −1.5 °C, where no QLL appears in the absence of HCl gas. This result indicates that HCl gas adsorbed on ice crystal surfaces probably changed the surface structure of ice crystals and then induced the subsequent melting of ice surfaces. We also observed the movement, shape...

Surface melting of ice significantly governs a wide variety of phenomena in nature. We recently succeeded in directly observing the surface melting on ice basal faces (Proc. Natl. Acad. Sci. U.S.A. 2012, 109, 1052–1055) by our advanced optical microscopy, which can detect 0.37-nm-thick elementary steps on basal faces. However, the direct observation of surface melting on the other prism and high-index faces remains an experimental challenge. To fully obtain a comprehensive understanding, we need to examine the surface melting on these faces. Here we show the appearance of two types of quasi-liquid layers (QLLs) on prism and high-index faces just below the melting point. We quickly raised the temperature of ice crystals and then observed prism and high-index faces during a roughening process. We found that with increasing temperature, round liquid-like droplets (α-QLLs) first appeared at temperatures higher than −1.4 to −0.5 °C, and then thin liquid-like layers (β-QLLs) also appeared at temperatures higher...

The free growth of ice crystals in supercooled bulk water containing an impurity of glycoprotein, a bio-macromolecule that functions as ‘antifreeze’ in living organisms in a subzero environment, was observed under microgravity conditions on the International Space Station. We observed the acceleration and oscillation of the normal growth rates as a result of the interfacial adsorption of these protein molecules, which is a newly discovered impurity effect for crystal growth. As the convection caused by gravity may mitigate or modify this effect, secure observations of this effect were first made possible by continuous measurements of normal growth rates under long-term microgravity condition realized only in the spacecraft. Our findings will lead to a better understanding of a novel kinetic process for growth oscillation in relation to growth promotion due to the adsorption of protein molecules and will shed light on the role that crystal growth kinetics has in the onset of the mysterious antifreeze effect in living organisms, namely, how this protein may prevent fish freezing.

During the growth of ice crystals, spiral growth is one of the important growth mechanisms that dominate their growth. However, the structure of spiral steps on ice crystal surfaces at temperatures near the melting point has not been identified. Here we show a possible model structure of spiral steps on basal and prism faces of Ih ice crystals grown from water vapor just below 0 °C. We observed in situ the coalescences of spiral steps and steps of two-dimensional (2D) islands by our advanced optical microscopy, which can visualize individual elementary steps (single-bilayer height) of 2D islands on ice basal faces. We found that both spiral steps and 2D island steps on basal and prism faces show single-bilayer heights, though Burgers’ vectors of screw dislocations on both faces need to have double-bilayer heights because of a crystallographic requirement. These results suggest that at the center of a spiral growth hillock, steps of two adjacent single bilayers coincide and then form a double-bilayer step ...

Ice crystal surfaces melt at temperatures below 0 °C, and then quasi-liquid layers (QLLs) are formed. However, revealing the dynamic behavior of QLLs, which dominates the surface properties of ice crystals at temperatures near the melting point, remains an experimental challenge. Here, we demonstrate the similarities and differences in the generation mechanisms of two types of QLL phases, which show different morphologies and dynamics. We directly visualized the appearance of round liquidlike droplets (α-QLLs) and thin liquidlike layers (β-QLLs) on ice basal faces by advanced optical microscopy, which can allow visualization of the individual elementary steps on basal faces. We found that α-QLLs always appear at outcrops of dislocations, and that β-QLLs emerge from crystal surfaces where many microdefects are embedded. These results clearly demonstrate the similar function that strain induces the appearance of both types of QLLs. We also found that β-QLLs are spontaneously formed at interfaces between bas...

Since the pioneering prediction of surface melting by Michael Faraday, it has been widely accepted that thin water layers, called quasi-liquid layers (QLLs), homogeneously and completely wet ice surfaces. Contrary to this conventional wisdom, here we both theoretically and experimentally demonstrate that QLLs have more than two wetting states and that there is a first-order wetting transition between them. Furthermore, we find that QLLs are born not only under supersaturated conditions, as recently reported, but also at undersaturation, but QLLs are absent at equilibrium. This means that QLLs are a metastable transient state formed through vapor growth and sublimation of ice, casting a serious doubt on the conventional understanding presupposing the spontaneous formation of QLLs in ice–vapor equilibrium. We propose a simple but general physical model that consistently explains these aspects of surface melting and QLLs. Our model shows that a unique interfacial potential solely controls both the wetting and thermodynamic behavior of QLLs.

We have experimentally determined the surface tension-to-shear viscosity ratio (the so-called characteristic velocity) of quasiliquid layers (QLLs) on ice crystal surfaces from their wetting dynamics. Using an advanced optical microscope, whose resolution reaches the molecular level in the height direction, we directly observed the coalescent process of QLLs and followed the relaxation modes of their contact lines. The relaxation dynamics is known to be governed by the characteristic velocity, which allows us to access the physical properties of QLLs in a noninvasive way. Here we quantitatively demonstrate that QLLs, when completely wetting ices, have a thickness of 9 +/- 3 nm and an approximately 200 times lower characteristic velocity than bulk water, whereas QLLs, when partially wetting ices, have a velocity that is 20 times lower than the bulk. This indicates that ice crystal surfaces significantly affect the physical properties of QLLs localized near the surfaces at a nanometer scale.