Reconfigurable Multilevel Optical PUF by Spatiotemporally Programmed Crystallization of Supersaturated Solution.

Physical unclonable functions (PUFs) are emerging as an alternative to information security by providing an advanced level of cryptographic keys with non-replicable characteristics, yet the cryptographic keys of conventional PUFs are not reconfigurable from the ones assigned at the manufacturing stage and the overall authentication process slows down as the number of entities in the dataset or the length of cryptographic key increases. Herein, a supersaturated solution-based PUF (S-PUF) is presented that utilizes stochastic crystallization of a supersaturated sodium acetate solution to allow a time-efficient, hierarchical authentication process together with on-demand rewritability of cryptographic keys. By controlling the orientation and the average grain size of the sodium acetate crystals via a spatiotemporally programmed temperature profile, the S-PUF now includes two global parameters, that is, angle of rotation and divergence of the diffracted beam, in addition to the speckle pattern to produce multilevel cryptographic keys, and these parameters function as prefixes for the classification of each entity for a fast authentication process. At the same time, the reversible phase change of sodium acetate enables repeated reconfiguration of the cryptographic key, which is expected to offer new possibilities for a next-generation, recyclable anti-counterfeiting platform.

Spin Coating Promotes the Epitaxial Growth of AgCN Microwires on 2D Materials.

Epitaxial growth of inorganic crystals on 2D materials is expected to greatly advance nanodevices and nanocomposites. However, because pristine surfaces of 2D materials are chemically inert, it is difficult to grow inorganic crystals epitaxially on 2D materials. Previously, successful results were achieved only by vapor-phase deposition at high temperature, and solution-based deposition including spin coating made the epitaxial growth unaligned, sparse, or nonuniform on 2D materials. Here, we show that solvent-controlled spin coating can uniformly deposit a dense layer of epitaxial AgCN microwires onto various 2D materials. Adding ethanol to an aqueous AgCN solution facilitates uniform formation of the thin supersaturated solution layer during spin coating, which promotes heterogeneous crystal nucleation on 2D material surfaces over homogeneous nucleation in the bulk solution. Microscopic analysis confirms highly aligned, uniform, and dense growth of epitaxial AgCN microwires on graphene, MoS2, hBN, WS2, and WSe2. The epitaxial microwires, which are optically observable and chemically removable, enable crystallographic mapping of grains in millimeter-sized polycrystalline graphene as well as precise control of twist angles (<∼1°) in van der Waals heterostructures. In addition to these practical applications, our study demonstrates the potential of 2D materials as epitaxial templates even in spin coating of inorganic crystals.

Fabrication of Perforated PDMS Microchannel by Successive Laser Pyrolysis.

Poly(dimethylsiloxane) has attracted much attention in soft lithography and has also been preferred as a platform for a photochemical reaction, thanks to its outstanding characteristics including ease of use, nontoxicity, and high optical transmittance. However, the low stiffness of PDMS, an obvious advantage for soft lithography, is often treated as an obstacle in conducting precise handling or maintaining its structural integrity. For these reasons, a Glass-PDMS-Glass structure has emerged as a straightforward alternative. Nevertheless, several challenges are remaining in fabricating Glass-PDMS-Glass structure through the conventional PDMS patterning techniques such as photolithography and etching processes for master mold. The complicated techniques are not suitable for frequent design modifications in research-oriented fields, and fabrication of perforated PDMS is hard to achieve using mold replication. Herein, we utilize the successive laser pyrolysis technique to pattern thin-film PDMS for microfluidic applications. The direct use of thin film at the glass surface prevents the difficulties of thin-film handling. Through the precise control of photothermal pyrolysis phenomena, we provide a facile fabrication process for perforated PDMS microchannels. In the final demonstration, the laminar flow has been successfully created owing to the smooth surface profile. We envision further applications using rapid prototyping of the perforated PDMS microchannel.

A Transformative Gold Patterning through Selective Laser Refining of Cyanide.

Gold is an essential noble metal for electronics, and its application area is increasing continuously through the introduction of gold nanoparticle ink that enables rapid prototyping and direct writing of gold electrodes on versatile substrates at a low temperature. However, the synthesis of gold nanoparticles has certain limitations involving high cost, long synthesis time, large waste of material, and frequent use of chemicals. In this study, we suggest simultaneous laser refining of gold cyanide and selective fabrication of gold electrodes directly on the substrate without a separate synthesis step. Gold cyanide is commonly the first product of gold from the primitive ore, and the gold can be extracted directly from the rapid photothermal decomposition of gold cyanide by the laser. It was confirmed that laser-induced thermocapillary force plays an important role in creating the continuous gold patterns by aligning the refined gold. The resultant gold electrodes exhibited a low resistivity analogous to the conventional direct writing method using nanoparticles, and the facile repair process of a damaged electrode was demonstrated as the proof-of-concept. The proposed transformative approach for gold patterning, distinguished from the previous top-down and bottom-up approaches, has the potential to replace the well-known techniques and provide a new branch of electrode manufacturing scheme.

Continuous-Wave Laser-Induced Transfer of Metal Nanoparticles to Arbitrary Polymer Substrates.

Laser-induced forward transfer (LIFT) and selective laser sintering (SLS) are two distinct laser processes that can be applied to metal nanoparticle (NP) ink for the fabrication of a conductive layer on various substrates. A pulsed laser and a continuous-wave (CW) laser are utilized respectively in the conventional LIFT and SLS processes; however, in this study, CW laser-induced transfer of the metal NP is proposed to achieve simultaneous sintering and transfer of the metal NP to a wide range of polymer substrates. At the optimum laser parameters, it was shown that a high-quality uniform metal conductor was created on the acceptor substrate while the metal NP was sharply detached from the donor substrate, and we anticipate that such an asymmetric transfer phenomenon is related to the difference in the adhesion strengths. The resultant metal electrode exhibits a low resistivity that is comparable to its bulk counterpart, together with strong adhesion to the target polymer substrate. The versatility of the proposed process in terms of the target substrate and applicable metal NPs brightens its prospects as a facile manufacturing scheme for flexible electronics.

Shear-Assisted Laser Transfer of Metal Nanoparticle Ink to an Elastomer Substrate.

Selective laser sintering of metal nanoparticle ink is an attractive technology for the creation of metal layers at the microscale without any vacuum deposition process, yet its application to elastomer substrates has remained a highly challenging task. To address this issue, we introduced the shear-assisted laser transfer of metal nanoparticle ink by utilizing the difference in thermal expansion coefficients between the elastomer and the target metal electrode. The laser was focused and scanned across the absorbing metal nanoparticle ink layer that was in conformal contact with the elastomer with a high thermal expansion coefficient. The resultant shear stress at the interface assists the selective transfer of the sintered metal nanoparticle layer. We expect that the proposed method can be a competent fabrication route for a transparent conductor on elastomer substrates.

Micropatterning of Metal Nanoparticle Ink by Laser-Induced Thermocapillary Flow.

Selective laser sintering of metal nanoparticle ink is a low-temperature and non-vacuum technique developed for the fabrication of patterned metal layer on arbitrary substrates, but its application to a metal layer composed of large metal area with small voids is very much limited due to the increase in scanning time proportional to the metal pattern density. For the facile manufacturing of such metal layer, we introduce micropatterning of metal nanoparticle ink based on laser-induced thermocapillary flow as a complementary process to the previous selective laser sintering process for metal nanoparticle ink. By harnessing the shear flow of the solvent at large temperature gradient, the metal nanoparticles are selectively pushed away from the scanning path to create metal nanoparticle free trenches. These trenches are confirmed to be stable even after the complete process owing to the presence of the accompanying ridges as well as the bump created along the scanning path. As a representative example of a metal layer with large metal area and small voids, dark-field photomask with Alphabetic letters are firstly created by the proposed method and it is then demonstrated that the corresponding letters can be successfully reproduced on the screen by an achromatic lens.