Planar Spin Glass with Topologically Protected Mazes in the Liquid Crystal Targeting for Reconfigurable Micro Security Media.

The planar spin glass pattern is widely known for its inherent randomness, resulting from the geometrical frustration. As such, developing physical unclonable functions (PUFs)-which operate with device randomness-with planar spin glass patterns is a promising candidate for an advanced security systems in the upcoming digitalized society. Despite their inherent randomness, traditional magnetic spin glass patterns pose considerable obstacles in detection, making it challenging to achieve authentication in security systems. This necessitates the development of facilely observable mimetic patterns with similar randomness to overcome these challenges. Here, a straightforward approach is introduced using a topologically protected maze pattern in the chiral liquid crystals (LCs). This maze exhibits a comparable level of randomness to magnetic spin glass and can be reliably identified through the combination of optical microscopy with machine learning-based object detection techniques. The "information" embedded in the maze can be reconstructed through thermal phase transitions of the LCs in tens of seconds. Furthermore, incorporating various elements can enhance the optical PUF, resulting in a multi-factor security medium. It is expected that this security medium, based on microscopically controlled and macroscopically uncontrolled topologically protected structures, may be utilized as a next-generation security system.

Synthesis of MAPbBr3 -Polymer Composite Films by Photolysis of DMF: Toward Transparent and Flexible Optical Physical Unclonable Functions (PUFs) with Hierarchical Multilevel Complexity.

Physical entities with inherent randomness have been investigated as anti-counterfeiting labels based on physical unclonable functions (PUFs). Herein, a transparent and flexible optical PUF label associated with multilevel complexity is demonstrated by taking advantage of the optical properties of hierarchical morphologies of the composite film composed of metal halide perovskite nanoparticles (MAPbBr3 NPs) and the intrinsic spinodal-decomposition-like phase separation of polymer blend (PMMA/PS blend). Due to the combinatorial effects of the photolysis synthesis of MAPbBr3 and the thermodynamic instability of the PMMA/PS blend, randomized patterns emerge at two-level scales. These patterns are intrinsically non-deterministic, and therefore, the PUF labels from the multilevel random patterns are challenging to replicate. This is mainly attributed to random spot patterns (higher-level patterns) confined within intricate bicontinuous patterns (lower-level patterns).

3D-Printed Sugar Scaffold for High-Precision and Highly Sensitive Active and Passive Wearable Sensors.

In this study, a pairing of a previously unidentified 3D printing technique and soft materials is introduced in order to achieve not only high-resolution printed features and flexibility of the 3D-printed materials, but also its light-weight and electrical conductivity. Using the developed technique and materials, high-precision and highly sensitive patient-specific wearable active or passive devices are fabricated for personalized health monitoring. The fabricated biosensors show low density and substantial flexibility because of 3D microcellular network-type interconnected conductive materials that are readily printed using an inkjet head. Using high-resolution 3D scanned body-shape data, on-demand personalized wearable sensors made of the 3D-printed soft and conductive materials are fabricated. These sensors successfully detect both actively changing body strain signals and passively changing signals such as electromyography (EMG), electrodermal activity (EDA), and electroencephalogram EEG. The accurately tailored subject-specific shape of the developed sensors exhibits higher sensitivity and faster real-time sensing performances in the monitoring of rapidly changing human body signals. The newly developed 3D printing technique and materials can be widely applied to various types of wearable, flexible, and light-weight biosensors for use in a variety of inexpensive on-demand and personalized point-of-care diagnostics.

Long-distance transmission of broadband near-infrared light guided by a semi-disordered 2D array of metal nanoparticles.

Near-infrared (NIR) waveguides are a key component of planar photonic devices such as optical communication couplers, image sensors, and spectroscopes for chemical or biological molecules. Conventional NIR waveguides used for signal transmission include silicon-on-insulator (SOI) waveguides and channel/ridge-type metal micro-strips. However, these waveguides usually have limitations of either signal delay or signal loss in optically integrated devices. In this study, a novel NIR waveguide composed of a semi-disordered array of metal nanoparticles (sDAMNPs) on Si substrate was proposed, fabricated, and tested. The disordered metallic nanoparticles array is geometrically localized in the form of 1D metal strips, thus replacing sDAMNPs with less lossy micro strip channel waveguides. From the measurements supported by various computational models, the fabricated waveguides operate effectively in the broadband NIR region (1100 to 1700 nm). The waveguide does not support signal transmission in the ultra violet-visible spectrum due to strong signal absorption, scattering, and localization effects inside the metal nanoparticles. Instead, it is capable of transmitting NIR over a distance longer than 100 µm (signal loss ∼3.85 dB per 100 µm for NIR from 1200 to 1600 nm), which is also sufficiently longer than the conventional surface plasmon polariton propagation distance at the metal-Si interface. Compared to a waveguide-free reference, the waveguide exhibited greatly improved signal transmission efficiency up to a factor of 7.42 × 104 at 1367 nm. It also exhibits a high deflection angle sensitivity of 1.89 dB per 0.01 rad, thus efficiently and straightly guiding the broadband NIR signal over a long distance.

On-Demand Drug Release from Gold Nanoturf for a Thermo- and Chemotherapeutic Esophageal Stent.

Stimuli-responsive delivery systems for cancer therapy have been increasingly used to promote the on-demand therapeutic efficacy of anticancer drugs and, in some cases, simultaneously generate heat in response to a stimulus, resulting in hyperthermia. However, their application is still limited due to the systemic drawbacks of intravenous delivery, such as rapid clearance from the bloodstream and the repeat injections required for sustained safe dosage, which can cause overdosing. Here, we propose a gold (Au)-coated nanoturf structure as an implantable therapeutic interface for near-infrared (NIR)-mediated on-demand hyperthermia chemotherapy. The Au nanoturf possessed long-lasting doxorubicin (DOX) duration, which helps facilitate drug release in a sustained and prolonged manner. Moreover, the Au-coated nanoturf provides reproducible hyperthermia induced by localized surface plasmon resonances under NIR irradiation. Simultaneously, the NIR-mediated temperature increase can promote on-demand drug release at desired time points. For in vivo analysis, the Au nanoturf structure was applied on an esophageal stent, which needs sustained anticancer treatment to prevent tumor recurrence on the implanted surface. This thermo- and chemo-esophageal stent induced significant cancer cell death with released drug and hyperthermia. These phenomena were also confirmed by theoretical analysis. The proposed strategy provides a solution to achieve enhanced thermo-/chemotherapy and has broad applications in sustained cancer treatments.

Long-term efficient organic photovoltaics based on quaternary bulk heterojunctions.

A major impediment to the commercialization of organic photovoltaics (OPVs) is attaining long-term morphological stability of the bulk heterojunction (BHJ) layer. To secure the stability while pursuing optimized performance, multi-component BHJ-based OPVs have been strategically explored. Here we demonstrate the use of quaternary BHJs (q-BHJs) composed of two conjugated polymer donors and two fullerene acceptors as a novel platform to produce high-efficiency and long-term durable OPVs. A q-BHJ OPV (q-OPV) with an experimentally optimized composition exhibits an enhanced efficiency and extended operational lifetime than does the binary reference OPV. The q-OPV would retain more than 72% of its initial efficiency (for example, 8.42-6.06%) after a 1-year operation at an elevated temperature of 65 °C. This is superior to those of the state-of-the-art BHJ-based OPVs. We attribute the enhanced stability to the significant suppression of domain growth and phase separation between the components via kinetic trapping effect.

Two-Dimensional Nanoparticle Supracrystals: A Model System for Two-Dimensional Melting.

In a Langmuir trough, successive compression cycles can drive a two-dimensional (2D) nanoparticle supracrystal (NPSC) closer to its equilibrium structure. Here, we show a series of equilibrated 2D NPSCs consisting of gold NPs of uniform size, varying solely in the length of their alkanethiol ligands. The ordering of the NPSC is governed by the ligand length, thus providing a model system to investigate the nature of 2D melting in a system of NPs. As the ligand length increases the supracrystal transitions from a crystalline to a liquid-like phase with evidence of a hexatic phase at an intermediate ligand length. The phase change is interpreted as an entropy-driven phenomenon associated with steric constraints between ligand shells. The density of topological defects scales with ligand length, suggesting an equivalence between ligand length and temperature in terms of melting behavior. On the basis of this equivalence, the experimental evidence indicates a two-stage 2D melting of NPSCs.

Upconversion luminescence enhancement in plasmonic architecture with random assembly of metal nanodomes.

We report an experimental study on the highly enhanced upconversion luminescence (UCL) of ß-NaYF4:Yb(3+)/Er(3+) nanocrystals (NCs) in a plasmonic architecture. For the architecture, we designed a thin film device composed of a thin layer of NCs capped with an upper layer of a plasmonic nanodome array (pNDA) and lower substrate of a back reflector (BR). Compared to the UCL intensity observed in a glass reference substrate, the designed plasmonic architecture exhibits distinctively strong luminescence enhanced by up to 800-fold. The intensity considerably exceeds the previously reported luminescence intensity regardless of the excitation power. We elucidated a mechanism explaining the large UCL enhancement, which quantitatively analyzes the combination of plasmonic effects as well as multiple large scattering. More importantly, we provided a detailed analysis of the Ag NDA-derived and BR-assisted plasmonic effects that contribute to an increase in the radiative decay rate and an enhancement of the absorption of incident light. The present study is expected to be beneficial for designing a thin film-based plasmonic structure with a randomized metal nanostructure for high-efficiency photovoltaic devices and infrared detectors.

Single-step fabrication of quantum funnels via centrifugal colloidal casting of nanoparticle films.

Centrifugal casting of composites and ceramics has been widely employed to improve the mechanical and thermal properties of functional materials. This powerful method has yet to be deployed in the context of nanoparticles--yet size-effect tuning of quantum dots is among their most distinctive and application-relevant features. Here we report the first gradient nanoparticle films to be constructed in a single step. By creating a stable colloid of nanoparticles that are capped with electronic-conduction-compatible ligands we were able to leverage centrifugal casting for thin-films devices. This new method, termed centrifugal colloidal casting, is demonstrated to form films in a bandgap-ordered manner with efficient carrier funnelling towards the lowest energy layer. We constructed the first quantum-gradient photodiode to be formed in a single deposition step and, as a result of the gradient-enhanced electric field, experimentally measured the highest normalized detectivity of any colloidal quantum dot photodetector.

Structural Origin of the Band Gap Anomaly of Quaternary Alloy Cd(x)Zn(1-x)S(y)Se(1-y) Nanowires, Nanobelts, and Nanosheets in the Visible Spectrum.

Single-crystalline alloy II-VI semiconductor nanostructures have been used as functional materials to propel photonic and optoelectronic device performance in a broad range of the visible spectrum. Their functionality depends on the stable modulation of the direct band gap (Eg), which can be finely tuned by controlling the properties of alloy composition, crystallinity, and morphology. We report on the structural correlation of the optical band gap anomaly of quaternary alloy CdxZn1-xSySe1-y single-crystalline nanostructures that exhibit different morphologies, such as nanowires (NWs), nanobelts (NBs), and nanosheets (NSs), and cover a wide range of the visible spectrum (Eg = 1.96-2.88 eV). Using pulsed laser deposition, the nanostructures evolve from NWs via NBs to NSs with decreasing growth temperature. The effects of the growth temperature are also reflected in the systematic variation of the composition. The alloy nanostructures firmly maintain single crystallinity of the hexagonal wurtzite and the nanoscale morphology, with no distortion of lattice parameters, satisfying the virtual crystal model. For the optical properties, however, we observed distinct structure-dependent band gap anomalies: the disappearance of bowing for NWs and maximum and slightly reduced bowing for NBs and NSs, respectively. We tried to uncover the underlying mechanism that bridges the structural properties and the optical anomaly using an empirical pseudopotential model calculation of electronic band structures. From the calculations, we found that the optical bowings in NBs and NSs were due to residual strain, by which they are also distinguishable from each other: large for NBs and small for NSs. To explain the origin of the residual strain, we suggest a semiempirical model that considers intrinsic atomic disorder, resulting from the bond length mismatch, combined with the strain relaxation factor as a function of the width-to-thickness ratio of the NBs or NSs. The model agreed well with the observed optical bowing of the alloy nanostructures in which a mechanism for the maximum bowing for NBs is explained. The present systematic study on the structural-optical properties correlation opens a new perspective to understand the morphology- and composition-dependent unique optical properties of II-VI alloy nanostructures as well as a comprehensive strategy to design a facile band gap modulation method of preparing photoconverting and photodetecting materials.

Simultaneous enhancement of upconversion and downshifting luminescence via plasmonic structure.

We describe a metal nanodisk-insulator-metal (MIM) structure that enhances lanthanide-based upconversion (UC) and downshifting (DS) simultaneously. The structure was fabricated using a nanotransfer printing method that facilitates large-area applications of nanostructures for optoelectronic devices. The proposed MIM structure is a promising way to harness the entire solar spectrum by converting both ultraviolet and near-infrared to visible light concurrently through resonant-mode excitation. The overall photoluminescence enhancements of the UC and DS were 174- and 29-fold, respectively.

Germanium microflower-on-nanostem as a high-performance lithium ion battery electrode.

We demonstrate a new design of Ge-based electrodes comprising three-dimensional (3-D) spherical microflowers containing crystalline nanorod networks on sturdy 1-D nanostems directly grown on a metallic current collector by facile thermal evaporation. The Ge nanorod networks were observed to self-replicate their tetrahedron structures and form a diamond cubic lattice-like inner network. After etching and subsequent carbon coating, the treated Ge nanostructures provide good electrical conductivity and are resistant to gradual deterioration, resulting in superior electrochemical performance as anode materials for LIBs, with a charge capacity retention of 96% after 100 cycles and a high specific capacity of 1360 mA h g(-1) at 1 C and a high-rate capability with reversible capacities of 1080 and 850 mA h g(-1) at the rates of 5 and 10 C, respectively. The improved electrochemical performance can be attributed to the fast electron transport and good strain accommodation of the carbon-filled Ge microflower-on-nanostem hybrid electrode.

Dynamic instability of a sol-gel-derived thin film.

We present a study on the dynamic instability of a sol-gel-derived (SG) thin film on a nonwettable substrate. Because of the structural instability accompanied by syneresis stress in a film deposited on the substrate, there exists a regular distribution of dewetting patterns required to relieve the in-plane stress, such as holes in the earlier stages, and droplets accompanying a regular polygonal distribution in the later stages of the dynamic instability. The characteristic length scales in each stage scaled linearly with the film thickness during the duration of dewetting. For the formation of holes during the earlier stages of rupture of the film, the dewetting velocity was analyzed with a viscous sintering theory of a SG thin film. In the earlier stages of the dynamic instability, the dewetting velocity decreases with increasing dewetting time and increases with increasing the initial film thickness, which indicates that the SG thin film behaves partially like a slipping polymer thin film. In the final times of the film rupture, the radius of the hole has a linear relationship with the film thickness, and the growth rate of the hole (dewetting velocity) is nearly constant, regardless of the film thickness. These dewetting behaviors indicate that the SG thin film in the final times of the rupture is somewhat similar to nonslipping film. From these observations, we found that the dewetting behavior of a SG thin film has ambivalent dewetting characteristics of slipping and nonslipping films and that a SG thin film is not a purely viscous film.

Highly conductive coaxial SnO(2)-In(2)O(3) heterostructured nanowires for Li ion battery electrodes.

Novel SnO(2)-In(2)O(3) heterostructured nanowires were produced via a thermal evaporation method, and their possible nucleation/growth mechanism is proposed. We found that the electronic conductivity of the individual SnO(2)-In(2)O(3) nanowires was 2 orders of magnitude better than that of the pure SnO(2) nanowires, due to the formation of Sn-doped In(2)O(3) caused by the incorporation of Sn into the In(2)O(3) lattice during the nucleation and growth of the In(2)O(3) shell nanostructures. This provides the SnO(2)-In(2)O(3) nanowires with an outstanding lithium storage capacity, making them suitable for promising Li ion battery electrodes.

Dewetting of a sol-gel-derived thin film.

We report on the dewetting of a thin film produced by the sol-gel method. In the early stages of dynamic morphological instability, the drying stress in the capillary wave model determines the linearly scaling behaviors of the characteristic wavelength with the initial film thickness and the square law dependence of the number density of the dewetted holes on the film thickness. These power law dependences are weaker than those observed in the case of the spinodal dewetting of a polymer thin film. The wavelength determined in the early stages also dominates the scaling behaviors of the average length of the sides and number density of the polygons and the diameter of the droplets of the dewetting pattern with the film thickness in the final stages of the dynamic instability. We also observed that further drying eventually induces wrinkles in the droplets, rim, and film, which have a characteristic wavelength that can be theoretically predicted.

Theoretical analysis of non-catalytic growth of nanorods on a substrate.

A theoretical analysis explaining the whole process of the growth of nanorods on a substrate without a catalyst is presented. Prior to the growth of the nanorods, the reaction precursors form nuclei on the substrate. The nuclei undergo cluster migration caused by the surface diffusion of adatoms on the substrate, and this migration continues until the mean free time of the adatoms is larger than surface diffusion time. The most probable mechanism by which cluster migration takes place is the one that leads to the minimization of the cluster free-energy, namely the migration of six adatoms into one fixed adatom. This cluster migration continues during several (typically smaller than 6) consecutive nuclei growth steps. After the process of cluster migration comes to an end, the nuclei grow in an isotropic manner by collection of the adatoms, until the nucleus reaches the thermodynamic size limit. The one-dimensional growth of nanorods on the nuclei, which is associated with the critical radius, begins when the reactant dose is smaller than a certain value, which is determined by the thermodynamic size limit and the mass transport parameter. The mass transport of the reaction precursors leads to the expansion of the radius and elongation of the height of the nanorods, and the growth rate of the height is greater than that of the radius. This difference in the growth rate causes the aspect ratio to increase with increasing growth time. By comparing the experimental data in the literature (ZnO nanorods), the presented analysis explains well the noncatalytic growth of nanorods on a substrate.

Theoretical analysis of growth of ZnO nanorods on the amorphous surfaces.

Semiconductor nanorod arrays on a substrate have a preferential alignment orientation that minimizes the excessive free energy of the system. In the case of wet chemically synthesized zinc oxide (ZnO) nanorod on the amorphous surfaces, the thermodynamic driving force determines the orientation to be normal to the surface. Among the various kinds of amorphous surfaces, the spherical seed layer composed of ZnO precursors gives isotropic radially aligned arrays. For other surfaces, such as wrinkled and planar ZnO precursor thin film, nanorod arrays are aligned to be perpendicular to the tangential line of the surface. The maximum value of the aspect ratio of the nanorod is determined by the thermodynamic relationship. The number density of nanorods per unit precursor particles decreases with increasing contact angle of the seed particles.

Morphological dynamics of swelling-induced surface patterns in metal-capped polymer bilayer.

We report on the morphological dynamics of surface patterns induced by swelling of metal-capped polymer bilayer on a substrate. When the bilayer is subject to solvent vapor, the strain is generated in the polymer layer that is confined by the substrate and the metal capping layer. An increase in the strain induces the development of the stress in the bilayer to deform the lower polymer layer perpendicularly to the surface of the bilayer. Isotropic surface wave patterns results from the stress relaxation, the wave number of the patterns shows a characteristic temporal dependency on the swelling time, such that km(t) approximately t(-1/8). This temporal evolution accompanied by the morphological dynamics gives smaller value of the growth rate of the characteristic wavelength than that of the case of swelling of gel.