Sang-Gil Ryu

Heat transfer across the interface between nanoscale solids and gas.

When solid materials and devices scale down in size, heat transfer from the active region to the gas environment becomes increasingly significant. We show that the heat transfer coefficient across the solid-gas interface behaves very differently when the size of the solid is reduced to the nanoscale, such as that of a single nanowire. Unlike for macroscopic solids, the coefficient is strongly pressure dependent above ∼10 Torr, and at lower pressures it is much higher than predictions of the kinetic gas theory. The heat transfer coefficient was measured between a single, free-standing VO(2) nanowire and surrounding air using laser thermography, where the temperature distribution along the VO(2) nanowire was determined by imaging its domain structure of metal-insulator phase transition. The one-dimensional domain structure along the nanowire results from the balance between heat generation by the focused laser and heat dissipation to the substrate as well as to the surrounding gas, and thus serves as a nanoscale power-meter and thermometer. We quantified the heat loss rate across the nanowire-air interface, and found that it dominates over all other heat dissipation channels for small-diameter nanowires near ambient pressure. As the heat transfer across the solid-gas interface is nearly independent of the chemical identity of the solid, the results reveal a general scaling relationship for gaseous heat dissipation from nanostructures of all solid materials, which is applicable to nanoscale electronic and thermal devices exposed to gaseous environments.

In Situ TEM Near-Field Optical Probing of Nanoscale Silicon Crystallization

Laser-based processing enables a wide variety of device configurations comprising thin films and nanostructures on sensitive, flexible substrates that are not possible with more traditional thermal annealing schemes. In near-field optical probing, only small regions of a sample are illuminated by the laser beam at any given time. Here we report a new technique that couples the optical near-field of the laser illumination into a transmission electron microscope (TEM) for real-time observations of the laser-materials interactions. We apply this technique to observe the transformation of an amorphous confined Si volume to a single crystal of Si using laser melting. By confinement of the material volume to nanometric dimensions, the entire amorphous precursor is within the laser spot size and transformed into a single crystal. This observation provides a path for laser processing of single-crystal seeds from amorphous precursors, a potentially transformative technique for the fabrication of solar cells and other nanoelectronic devices.

On demand shape-selective integration of individual vertical germanium nanowires on a Si(111) substrate via laser-localized heating.

Semiconductor nanowire (NW) synthesis methods by blanket furnace heating produce structures of uniform size and shape. This study overcomes this constraint by applying laser-localized synthesis on catalytic nanodots defined by electron beam lithography in order to accomplish site- and shape-selective direct integration of vertically oriented germanium nanowires (GeNWs) on a single Si(111) substrate. Since the laser-induced local temperature field drives the growth process, each NW could be synthesized with distinctly different geometric features. The NW shape was dialed on demand, ranging from cylindrical to hexagonal/irregular hexagonal pyramid. Finite difference time domain analysis supported the tunability of the light absorption and scattering spectra via controlling the GeNW shape.

On demand-direct synthesis of Si and Ge nanowires on a single platform by focused laser illumination

Laser irradiation can incur spatially confined and rapid heating that enables precisely controlled nucleation and subsequent growth of nanomaterials. This localization of the laser-driven growth can realize on-demand, direct synthesis of nanowires composed of multiple elements on a single platform. In this study, silicon and germanium nanowires are grown by laser-induced vapor-liquid-solid mechanism in a hetero-array configuration by simply switching the reactant gas precursors as the growth of nanowires is limited within the heat-affected zone induced by the laser. Energy dispersive x-ray and Raman spectroscopies were performed to observe the elemental composition and crystallinity of as-grown nanowires, respectively.

Laser crystallization and localized growth of nanomaterials for solar applications

Laser-assisted localized growth of semiconducting nanostructures is reported. As is the case of conventional crystal growth, localized laser enables three kinds of crystal growth: (1) melt growth (recrystallization) of amorphous silicon nanopillars by pulsed laser; (2) vapor growth (chemical vapor deposition) of germanium nanowires; (3) solution growth (hydrothermal growth) of zinc oxide nanowires. The results not only demonstrate programmable and digital fabrication of laser-assisted crystal growth, but also reveal unusual growth chacracteristics (grain morphologies, growth kinetics). Related to solar applications, it is suggested that these structures can act as epitaxial seeds for growth of coarse grains and as multi-spectral centers for enhanced and engineered light absorption.

Incubation behavior of silicon nanowire growth investigated by laser-assisted rapid heating

We investigate the early stage of silicon nanowire growth by the vapor-liquid-solid mechanism using laser-localized heating combined with ex-situ chemical mapping analysis by energy-filtered transmission electron microscopy. By achieving fast heating and cooling times, we can precisely determine the nucleation times for nanowire growth. We find that the silicon nanowire nucleation process occurs on a time scale of ∼10 ms, i.e., orders of magnitude faster than the times reported in investigations using furnace processes. The rate-limiting step for silicon nanowire growth at temperatures in the vicinity of the eutectic temperature is found to be the gas reaction and/or the silicon crystal growth process, whereas at higher temperatures it is the rate of silicon diffusion through the molten catalyst that dictates the nucleation kinetics.

Laser‐Assisted Doping: Site Selective Doping of Ultrathin Metal Dichalcogenides by Laser‐Assisted Reaction (Adv. Mater. 2/2016)

Laser-assisted phosphorus doping is demonstrated by J. Wu, C. P. Grigoropoulos, and co-workers on page 341, on ultrathin transition-metal dichalcogenides (TMDCs), including n-type MoS2 and p-type WSe2 . Temporal and spatial control of the doping is achieved by varying the laser irradiation power and time, demonstrating wide tunability and high site selectivity with high stability. The laser-assisted doping method may enable a new avenue for functionalizing TMDCs for customized nanodevice applications.

Laser processing and in-situ diagnostics for crystallization: from thin films to nanostructures

Recent work on laser-induced crystallization of thin films and nanostructures is presented. Characterization of the morphology of the crystallized area reveals the optimum conditions for sequential lateral growth in a-Si thin films under high-pulsed laser irradiation. Silicon crystal grains of several micrometers in lateral dimensions can be obtained reproducibly. Laser-induced grain morphology change is observed in silicon nanopillars under a transmission electron microscopy (TEM) environment. The TEM is coupled with a near-field scanning optical microscopy (NSOM) pulsed laser processing system. This combination enables immediate scrutiny on the grain morphologies that the pulsed laser irradiation produces. The tip of the amorphous or polycrystalline silicon pillar is transformed into a single crystalline domain via melt-mediated crystallization. The microscopic observation provides a fundamental basis for laser-induced conversion of amorphous nanostructures into coarse-grained crystals. A laser beam shaping strategy is introduced to control the stochastic dewetting of ultrathin silicon film on a foreign substrate under thermal stimulation. Upon a single pulse irradiation of the shaped laser beam, the thermodynamically unstable ultrathin silicon film is dewetted from the glass substrate and transformed to a nanodome. The results suggest that the laser beam shaping strategy for the thermocapillary-induced de-wetting combined with the isotropic etching is a simple alternative for scalable manufacturing of array of nanostructures.

LASER-ASSISTED ON DEMAND GROWTH OF SEMICONDUCTING NANOWIRES

We present laser-assisted direct synthesis of nanowires with site-, composition-, and shape-selectivity on a single substrate by employing a spatially confined laser heat source. Laser-assisted nanowire growth based on vapor-liquid-solid mechanism is conveniently studied with multiple growth parameters such as temperature, time, and illumination direction. On-demand direct integration of silicon and germanium nanowires are demonstrated in a hetero-array configuration by simply switching the reactant gases as the growth of nanowires is limited within the heat-affected zone induced by the laser. Since laser-induced local temperature field is able to drive the individual growth, each germanium nanowire is successfully synthesized with distinctively different geometric features from cylindrical to hexagonal pyramid shape. By regularly patterning gold catalysts prepared by electron beam lithography on Si(111), especially, we accomplished site- and shape-selective direct integration of germanium nanowires on a single substrate in vertical architecture. Considering that blanket furnace heating only produce nanowires with uniform size and shape, therefore, our work shows a route toward the facile fabrication of multifunctional nanowire based devices.

Multi-Parametric Growth of Semiconductor Nanowires in a Single Platform by Laser-Induced Localized Heat Sources

Nanoscale-synthesized materials hold great promise for the realization of future generation devices. In order to fulfill the exceptional promise, new techniques must be developed that will enable the precise layout and assembly of the heterogeneous components into functional ‘superblocks’. As one promising route to this end, rapid and spatially confined heating capability of laser irradiation has enabled precisely controlled nucleation and subsequent direct growth of nanowires at an arbitrary local region based on vapor-liquid-solid (VLS) mechanism. Spatial confinement of the nanowire growth region via focused laser beam illumination provides a convenient way to examine multiple growth parameters (temperature, time, illumination direction, and composition), thereby elucidating fundamental nanowires growth mechanisms. Furthermore, the work demonstrates an advanced method for direct synthesis of nanostructures for the purpose of practical rapid patterning including on demand multi-bandgap materials based nanowires.© 2012 ASME