Abnormal Silicon Etching Behaviors in Nanometer-Sized Channels.

Modern semiconductor fabrication is challenged by difficulties in overcoming physical and chemical constraints. A major challenge is the wet etching of dummy gate silicon, which involves the removal of materials inside confined spaces of a few nanometers. These chemical processes are significantly different in the nanoscale and bulk. Previously, electrical double-layer formation, bubble entrapment, poor wettability, and insoluble intermediate precipitation have been proposed. However, the exact suppression mechanisms remain unclear due to the lack of direct observation methods. Herein, we investigate limiting factors for the etching kinetics of silicon with tetramethylammonium hydroxide at the nanoscale by using liquid-phase transmission electron microscopy, three-dimensional electron tomography, and first-principles calculations. We reveal suppressed chemical reactions, unstripping phenomena, and stochastic etching behaviors that have never been observed on a macroscopic scale. We expect that solutions can be suggested from this comprehensive insight into the scale-dependent limiting factors of fabrication.

Wafer-Scale Fabrication of 2D Nanostructures via Thermomechanical Nanomolding.

With shrinking dimensions in integrated circuits, sensors, and functional devices, there is a pressing need to develop nanofabrication techniques with simultaneous control of morphology, microstructure, and material composition over wafer length scales. Current techniques are largely unable to meet all these conditions, suffering from poor control of morphology and defect structure or requiring extensive optimization or post-processing to achieve desired nanostructures. Recently, thermomechanical nanomolding (TMNM) has been shown to yield single-crystalline, high aspect ratio nanowires of metals, alloys, and intermetallics over wafer-scale distances. Here, TMNM is extended for wafer-scale fabrication of 2D nanostructures. Using In, Al, and Cu, nanomold nanoribbons with widths < 50 nm, depths ≈0.5-1 µm and lengths ≈7 mm into Si trenches at conditions compatible is successfully with back end of line processing . Through SEM cross-section imaging and 4D-STEM grain orientation maps, it is shown that the grain size of the bulk feedstock is transferred to the nanomolded structures up to and including single crystal Cu. Based on the retained microstructures of molded 2D Cu, the deformation mechanism during molding for 2D TMNM is discussed.

Sub-30 nm 2D Perovskites Patterns via Block Copolymer Guided Self-Assembly for Color Conversion Optical Polarizer.

Despite the remarkable advances made in the development of 2D perovskites suitable for various high-performance devices, the development of sub-30 nm nanopatterns of 2D perovskites with anisotropic photoelectronic properties remains challenging. Herein, a simple but robust route for fabricating sub-30 nm 1D nanopatterns of 2D perovskites over a large area is presented. This method is based on nanoimprinting a thin precursor film of a 2D perovskite with a topographically pre-patterned hard poly(dimethylsiloxane) mold replicated from a block copolymer nanopattern consisting of guided self-assembled monolayered in-plane cylinders. 1D nanopatterns of various 2D perovskites (A'2 MAn -1 Pbn X3 n +1 ,A' = BA, PEA, X = Br, I) are developed; their enhanced photoluminescence (PL) quantum yields are approximately four times greater than those of the corresponding control flat films. Anisotropic photocurrent is observed because 2D perovskite nanocrystals are embedded in a topological 1D nanopattern. Furthermore, this 1D metal-coated nanopattern of a 2D perovskite is employed as a color conversion optical polarizer, in which polarized PL is developed. This is due to its capability of polarization of an incident light arising from the sub-30 nm line pattern, as well as the PL of the confined 2D perovskite nanocrystals in the pattern.

Carboxylic Acid-Functionalized, Graphitic Layer-Coated Three-Dimensional SERS Substrate for Label-Free Analysis of Alzheimer's Disease Biomarkers.

Surface-enhanced Raman spectroscopy (SERS)-based protein analysis is a promising alternative to existing early stage diagnoses. However, SERS research conducted thus far accompanies challenges such as nonuniformity of plasmonic nanostructures, irregular coating of analytes, and denaturation of proteins, which seriously limit the practicability of suggested approaches. Here, we introduce a carboxylic acid-functionalized and graphitic nanolayer-coated three-dimensional SERS substrate (CGSS) fabricated by sequential nanotransfer printing. The substrate consists of well-defined, uniform gold nanowire arrays for effective Raman signal enhancement and a strong protein-immobilization layer. With an enhancement factor (EF) of 5.5 × 105, on par with the highest ever reported values, the CGSS allows the detection of protein conformational changes and the determination of protein concentration via Raman measurements. Exploiting the CGSS, we successfully measured the SERS spectra of Alzheimer's biomarkers, tau protein and amyloid ß, based on which secondary structural changes were analyzed quantitatively.

Highly Efficient Deep Blue Cd-Free Quantum Dot Light-Emitting Diodes by a p-Type Doped Emissive Layer.

Environmentally friendly ZnSe/ZnS core/shell quantum dots (QDs) as an alternative blue emission material to Cd-based QDs have shown great potential for use in next-generation displays. However, it remains still challenging to realize a high-efficiency quantum dot light-emitting diode (QLED) based on ZnSe/ZnS QDs due to their insufficient electrical characteristics, such as excessively high electron mobility (compared to the hole mobility) and the deep-lying valence band. In this work, the effects of QDs doped with hole transport materials (hybrid QDs) on the electrical characteristics of a QLED are investigated. These hybrid QDs show a p-type doping effect, which leads to a change in the density of the carriers. Specifically, the hybrid QDs can balance electrons and holes by suppressing the overflow of electrons and improving injection of holes, respectively. These electrical characteristics help to improve device performance. In detail, an external quantum efficiency (EQE) of 6.88% is achieved with the hybrid QDs. This is increased by 180% compared to a device with pure ZnSe/ZnS QDs (EQE of 2.46%). This record is the highest among deep-blue Cd-free QLED devices. These findings provide the importance of p-type doping effect in QD layers and guidance for the study of the electrical properties of QDs.

Surface wrinkle formation by liquid crystalline polymers for significant light extraction enhancement on quantum dot light-emitting diodes.

We propose an optimal outcoupling structure of a quantum-dot light-emitting diode (QLED) and present material properties based on numerical calculations via the ray-tracing method, in which light extraction properties are obtained according to the surface wrinkles on a substrate. After analyzing the designed microstructure elements, the optimal model was derived and applied to the QLEDs; consequently, the outcoupling efficiency enhanced by 31%. The liquid crystalline polymer forming the random surface wrinkles not only achieves an excellent light extraction through plasma crosslinking but also facilitates large-area processes. We propose an optical design rule for high-efficiency QLED design by analyzing the electro-optical efficiency, emission spectrum, and angular radiation pattern of the optical device.

Polarized ultraviolet emitters with Al wire-grid polarizers fabricated by solvent-assisted nanotransfer process.

Polarized ultraviolet (UV) emitters are essential for various applications, such as photoalignment devices for liquid crystals, high-resolution imaging devices, highly sensitive sensors, and steppers. To increase the high polarization ratio (PR) of a UV emitter, the grating period should be decreased than that of the visible emitter. However, the fabrication of the short period grating directly on UV emitters is still limited. In this study, we demonstrate that 200, 100, and 50 nm period aluminum (Al)-based wire-grid polarizers (WGPs) can be fabricated directly on UV emitters by a solvent-assisted nanotransfer process. The UV emitter with a grating period of 100 nm shows a PR of 84%, and an electroluminescence efficiency that is 22.5% and 48% higher than those of UV emitters with 50 nm and 200 nm period WGPs, respectively, due to the increased photon extraction efficiency (PEE). The higher PEE is attributed to the optical cavity property of the Al metal reflector with low light loss and the surface plasmon effect of the Al grating layer.

Order-of-Magnitude, Broadband-Enhanced Light Emission from Quantum Dots Assembled in Multiscale Phase-Separated Block Copolymers.

Achieving high emission efficiency in solid-state quantum dots (QDs) is an essential requirement for high-performance QD optoelectronics. However, most QD films suffer from insufficient excitation and light extraction efficiencies, along with nonradiative energy transfer between closely adjacent QDs. Herein, we suggest a highly effective strategy to enhance the photoluminescence (PL) of QD composite films through an assembly of QDs and poly(styrene-b-4-vinylpyridine)) (PS-b-P4VP) block copolymer (BCP). A BCP matrix casted under controlled humidity provides multiscale phase-separation features based on (1) submicrometer-scale spinodal decomposition between polymer-rich and water-rich phases and (2) sub-10 nm-scale microphase separation between polymer blocks. The BCP-QD composite containing bicontinuous random pores achieves significant enhancement of both light absorption and extraction efficiencies via effective random light scattering. Moreover, the microphase-separated morphology substantially reduces the Förster resonance energy transfer efficiency from 53% (pure QD film) to 22% (BCP-QD composite), collectively achieving an unprecedented 21-fold enhanced PL over a broad spectral range.

Nanopatterned High-Frequency Supporting Structures Stably Eliminate Substrate Effects Imposed on Two-Dimensional Semiconductors.

Despite the outstanding physical and chemical properties of two-dimensional (2D) materials, due to their extremely thin nature, eliminating detrimental substrate effects such as serious degradation of charge-carrier mobility or light-emission yield remains a major challenge. However, previous approaches have suffered from limitations such as structural instability or the need of costly and high-temperature deposition processes. Herein, we propose a new strategy based on the insertion of high-density topographic nanopatterns as a nanogap-containing supporter between 2D materials and substrate to minimize their contact and to block the substrate-induced undesirable effects. We show that well-controlled high-frequency SiO x nanopillar structures derived from the self-assembly of Si-containing block copolymer securely prevent the collapse or deformation of transferred MoS2 and guarantee excellent mechanical stability. The nanogap supporters formed below monolayer MoS2 lead to dramatic enhancement of the photoluminescence emission intensity (8.7-fold), field-effect mobility (2.0-fold, with a maximum of 4.3-fold), and photoresponsivity (12.1-fold) compared to the sample on flat SiO2. Similar favorable effects observed for graphene strongly suggest that this simple but powerful nanogap-supporting method can be extensively applicable to a variety of low-dimensional materials and contribute to improved device performance.

Palladium-Decorated Silicon Nanomesh Fabricated by Nanosphere Lithography for High Performance, Room Temperature Hydrogen Sensing.

A hydrogen (H2 ) gas sensor based on a silicon (Si) nanomesh structure decorated with palladium (Pd) nanoparticles is fabricated via polystyrene nanosphere lithography and top-down fabrication processes. The gas sensor shows dramatically improved H2 gas sensitivity compared with an Si thin film sensor without nanopatterns. Furthermore, a buffered oxide etchant treatment of the Si nanomesh structure results in an additional performance improvement. The final sensor device shows fast H2 response and high selectivity to H2 gas among other gases. The sensing performance is stable and shows repeatable responses in both dry and high humidity ambient environments. The sensor also shows high stability without noticeable performance degradation after one month. This approach allows the facile fabrication of high performance H2 sensors via a cost-effective, complementary metal-oxide-semiconductor (CMOS) compatible, and scalable nanopatterning method.

Extremely Small Pyrrhotite Fe7 S8 Nanocrystals with Simultaneous Carbon-Encapsulation for High-Performance Na-Ion Batteries.

Na/FeSx batteries have remarkable potential applicability due to their high theoretical capacity and cost-effectiveness. However, realization of high power-capability and long-term cyclability remains a major challenge. Herein, ultrafine Fe7 S8 @C nanocrystals (NCs) as a promising anode material for a Na-ion battery that addresses the above two issues simultaneously is reported. An Fe7 S8 core with quantum size (≈10 nm) overcomes the kinetic and thermodynamic constraints of the Na-S conversion reaction. In addition, the high degree of interconnection through carbon shells improves the electronic transport along the structure. As a result, the Fe7 S8 @C NCs electrode achieves excellent power capability of 550 mA h g-1 (≈79% retention of its theoretical capacity) at a current rate of 2700 mA g-1 . Furthermore, a conformal carbon shell acts as a buffer layer to prevent severe volume change, which provides outstanding cyclability of ≈447 mA h g-1 after 1000 cycles (≈71% retention of the initial charge capacity).

Photo-Reconfigurable Azopolymer Etch Mask: Photofluidization-Driven Reconfiguration and Edge Rectangularization.

Directional photofluidization of azobenzene materials has provided unprecedented opportunities for the structural reconfiguration of circular holes, line gaps, ellipsoidal holes, and nanofunnel-shaped micro/nanoarchitectures. However, all the reconfigured structures have a parabolic or round wall due to the tendency of the photofluidized azobenezene materials to minimize the surface area, which limits their use as a reconfigurable etch-mask for the lithography process. In this work, a simple method is presented that can change the round walls of azopolymer architectures into rectangular walls, which is named rectangularization. By irradiating far-field light on reconfigured azopolymer in a conformal contact with a flat polydimethylsiloxane (PDMS) film, the round wall transforms to a rectangular one because the azopolymer adheres along the PDMS surface while being photofluidized. As a result, the rectangularization process creates a variety of structural features and sizes ranging from a few micrometers to 150 nm having a rectangular wall. By exploiting the rectangularization process, the concept of a photo-reconfigurable etch mask is achieved, which transfers the mask patterns to a silicon pattern with a high structural fidelity and imparts a considerable flexibility to the lithography process.

Self-Extinguishing Lithium Ion Batteries Based on Internally Embedded Fire-Extinguishing Microcapsules with Temperature-Responsiveness.

User safety is one of the most critical issues for the successful implementation of lithium ion batteries (LIBs) in electric vehicles and their further expansion in large-scale energy storage systems. Herein, we propose a novel approach to realize self-extinguishing capability of LIBs for effective safety improvement by integrating temperature-responsive microcapsules containing a fire-extinguishing agent. The microcapsules are designed to release an extinguisher agent upon increased internal temperature of an LIB, resulting in rapid heat absorption through an in situ endothermic reaction and suppression of further temperature rise and undesirable thermal runaway. In a standard nail penetration test, the temperature rise is reduced by 74% without compromising electrochemical performances. It is anticipated that on the strengths of excellent scalability, simplicity, and cost-effectiveness, this novel strategy can be extensively applied to various high energy-density devices to ensure human safety.

Topographically-designed triboelectric nanogenerator via block copolymer self-assembly.

Herein, we report a facile and robust route to nanoscale tunable triboelectric energy harvesters realized by the formation of highly functional and controllable nanostructures via block copolymer (BCP) self-assembly. Our strategy is based on the incorporation of various silica nanostructures derived from the self-assembly of BCPs to enhance the characteristics of triboelectric nanogenerators (TENGs) by modulating the contact-surface area and the frictional force. Our simulation data also confirm that the nanoarchitectured morphologies are effective for triboelectric generation.

Illuminating Recent Progress in Nanotransfer Printing: Core Principles, Emerging Applications, and Future Perspectives.

As the demand for diverse nanostructures in physical/chemical devices continues to rise, the development of nanotransfer printing (nTP) technology is receiving significant attention due to its exceptional throughput and ease of use. Over the past decade, researchers have attempted to enhance the diversity of materials and substrates used in transfer processes as well as to improve the resolution, reliability, and scalability of nTP. Recent research on nTP has made continuous progress, particularly using the control of the interfacial adhesion force between the donor mold, target material, and receiver substrate, and numerous practical nTP methods with niche applications have been demonstrated. This review article offers a comprehensive analysis of the chronological advancements in nTP technology and categorizes recent strategies targeted for high-yield and versatile printing based on controlling the relative adhesion force depending on interfacial layers. In detail, the advantages and challenges of various nTP approaches are discussed based on their working mechanisms, and several promising solutions to improve morphological/material diversity are presented. Furthermore, this review provides a summary of potential applications of nanostructured devices, along with perspectives on the outlook and remaining challenges, which are expected to facilitate the continued progress of nTP technology and to inspire future innovations.

Suppressed Lone Pair Electrons Explain Unconventional Rise of Lattice Thermal Conductivity in Defective Crystalline Solids.

Manipulating thermal properties of materials can be interpreted as the control of how vibrations of atoms (known as phonons) scatter in a crystal lattice. Compared to a perfect crystal, crystalline solids with defects are expected to have shorter phonon mean free paths caused by point defect scattering, leading to lower lattice thermal conductivities than those without defects. While this is true in many cases, alloying can increase the phonon mean free path in the Cd-doped AgSnSbSe3 system to increase the lattice thermal conductivity from 0.65 to 1.05 W m-1 K-1 by replacing 18% of the Sb sites with Cd. It is found that the presence of lone pair electrons leads to the off-centering of cations from the centrosymmetric position of a cubic lattice. X-ray pair distribution function analysis reveals that this structural distortion is relieved when the electronic configuration of the dopant element cannot produce lone pair electrons. Furthermore, a decrease in the Grüneisen parameter with doping is experimentally confirmed, establishing a relationship between the stereochemical activity of lone pair electrons and the lattice anharmonicity. The observed "harmonic" behavior with doping suggests that lone pair electrons must be preserved to effectively suppress phonon transport in these systems.

Surface-functionalized SERS platform for deep learning-assisted diagnosis of Alzheimer's disease.

Early diagnosis of Alzheimer's disease is crucial to stall the deterioration of brain function, but conventional diagnostic methods require complicated analytical procedures or inflict acute pain on the patient. Then, label-free Surface-enhanced Raman spectroscopy (SERS) analysis of blood-based biomarkers is a convenient alternative to rapidly obtain spectral information from biofluids. However, despite the rapid acquisition of spectral information from biofluids, it is challenging to distinguish spectral features of biomarkers due to interference from biofluidic components. Here, we introduce a deep learning-assisted, SERS-based platform for separate analysis of blood-based amyloid ß (1-42) and metabolites, enabling the diagnosis of Alzheimer's disease. SERS substrates consisting of Au nanowire arrays are fabricated and functionalized in two characteristic ways to compare the validity of different Alzheimer's disease biomarkers measured on our SERS system. The 6E10 antibody is immobilized for the capture of amyloid ß (1-42) and analysis of its oligomerization process, while various self-assembled monolayers are attached for different dipole interactions with blood-based metabolites. Ultimately, SERS spectra of blood plasma of Alzheimer's disease patients and human controls are measured on the substrates and classified via advanced deep learning techniques that automatically extract informative features to learn generalizable representations. Accuracies up to 99.5% are achieved for metabolite-based analyses, which are verified with an explainable artificial intelligence technique that identifies key spectral features used for classification and for deducing significant biomarkers.

Porous silicon nanowires for lithium rechargeable batteries.

Porous silicon nanowire is fabricated by a simple electrospinning process combined with a magnesium reduction; this material is investigated for use as an anode material for lithium rechargeable batteries. We find that the porous silicon nanowire electrode from the simple and scalable method can deliver a high reversible capacity with an excellent cycle stability. The enhanced performance in terms of cycling stability is attributed to the facile accommodation of the volume change by the pores in the interconnect and the increased electronic conductivity due to a multi-level carbon coating during the fabrication process.

Self-assembly-induced formation of high-density silicon oxide memristor nanostructures on graphene and metal electrodes.

We report the direct formation of ordered memristor nanostructures on metal and graphene electrodes by a block copolymer self-assembly process. Optimized surface functionalization provides stacking structures of Si-containing block copolymer thin films to generate uniform memristor device structures. Both the silicon oxide film and nanodot memristors, which were formed by the plasma oxidation of the self-assembled block copolymer thin films, presented unipolar switching behaviors with appropriate set and reset voltages for resistive memory applications. This approach offers a very convenient pathway to fabricate ultrahigh-density resistive memory devices without relying on high-cost lithography and pattern-transfer processes.