Current lithography techniques, which employ photon, electron, or ion beams to induce chemical or physical reactions for micro/nano-fabrication, have remained challenging in patterning chemically synthesized colloidal particles, which are emerging as building blocks for functional devices. Herein, we develop a new technique - bubble-pen lithography (BPL) - to pattern colloidal particles on substrates using optically controlled microbubbles. Briefly, a single laser beam generates a microbubble at the interface of colloidal suspension and a plasmonic substrate via plasmon-enhanced photothermal effects. The microbubble captures and immobilizes the colloidal particles on the substrate through coordinated actions of Marangoni convection, surface tension, gas pressure, and substrate adhesion. Through directing the laser beam to move the microbubble, we create arbitrary single-particle patterns and particle assemblies with different resolutions and architectures. Furthermore, we have applied BPL to pattern CdSe/ZnS quantum dots on plasmonic substrates and polystyrene (PS) microparticles on two-dimensional (2D) atomic-layer materials. With the low-power operation, arbitrary patterning and applicability to general colloidal particles, BPL will find a wide range of applications in microelectronics, nanophotonics, and nanomedicine.
Semiconductor quantum dots (QDs) feature excellent properties, such as high quantum efficiency, tunable emission frequency, and good fluorescence stability. Incorporation of QDs into new devices relies upon high-resolution and high-throughput patterning techniques. Herein, we report a new printing technique known as bubble printing (BP), which exploits a light-generated microbubble at the interface of colloidal QD solution and a substrate to directly write QDs into arbitrary patterns. With the uniform plasmonic hot spot distribution for high bubble stability and the optimum light-scanning parameters, we have achieved full-color QD printing with submicron resolution (650 nm), high throughput (scanning rate of ∼10−2 m/s), and high adhesion of the QDs to the substrates. The printing parameters can be optimized to further control the fluorescence properties of the patterned QDs, such as emission wavelength and lifetime. The patterning of QDs on flexible substrates further demonstrates the wide applicability of this new technique. Thus, BP technique addresses the barrier of achieving a widely applicable, high-throughput and user-friendly patterning technique in the submicrometer regime, along with simultaneous fluorescence modification capability.
We have developed moiré nanosphere lithography (M-NSL), which incorporates in-plane rotation between neighboring monolayers, to extend the patterning capability of conventional nanosphere lithography (NSL). NSL, which uses self-assembled layers of monodisperse micro/nanospheres as masks, is a low-cost, scalable nanofabrication technique and has been widely employed to fabricate various nanoparticle arrays. Combination with dry etching and/or angled deposition has greatly enriched the family of nanoparticles NSL can yield. In this work, we introduce a variant of this technique, which uses sequential stacking of polystyrene nanosphere monolayers to form a bilayer crystal instead of conventional spontaneous self-assembly. Sequential stacking leads to the formation of moiré patterns other than the usually observed thermodynamically stable configurations. Subsequent O2 plasma etching results in a variety of complex nanostructures. Using the etched moiré patterns as masks, we have fabricated complementary gold nanostructures and studied their optical properties. We believe this facile technique provides a strategy to fabricate complex nanostructures or metasurfaces.
The synthesis of a carbazole-derived, well-defined ladder polymer was achieved under thermodynamic control by employing reversible ring-closing olefin metathesis.
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