Axially Engineered Metal–Insulator Phase Transition by Graded Doping VO₂ Nanowires

The abrupt first-order metal–insulator phase transition in single-crystal vanadium dioxide nanowires (NWs) is engineered to be a gradual transition by axially grading the doping level of tungsten. We also demonstrate the potential of these NWs for thermal sensing and actuation applications. At room temperature, the graded-doped NWs show metal phase on the tips and insulator phase near the center of the NW, and the metal phase grows progressively toward the center when the temperature rises. As such, each individual NW acts as a microthermometer that can be simply read out with an optical microscope. The NW resistance decreases gradually with the temperature rise, eventually reaching 2 orders of magnitude drop, in stark contrast to the abrupt resistance change in undoped VO₂ wires. This novel phase transition yields an extremely high temperature coefficient of resistivity ∼10%/K, simultaneously with a very low resistivity down to 0.001 Ω·cm, making these NWs promising infrared sensing materials for uncooled microbolometers. Lastly, they form bimorph thermal actuators that bend with an unusually high curvature, ∼900 m^–1·K^–1 over a wide temperature range (35–80 °C), significantly broadening the response temperature range of previous VO₂ bimorph actuators. Given that the phase transition responds to a diverse range of stimuliheat, electric current, strain, focused light, and electric fieldthe graded-doped NWs may find wide applications in thermo-opto-electro-mechanical sensing and energy conversion

Minimizing Isolate Catalyst Motion in Metal-Assisted Chemical Etching for Deep Trenching of Silicon Nanohole Array

The instability of isolate catalysts during metal-assisted chemical etching is a major hindrance to achieve high aspect ratio structures in the vertical and directional etching of silicon (Si). In this work, we discussed and showed how isolate catalyst motion can be influenced and controlled by the semiconductor doping type and the oxidant concentration ratio. We propose that the triggering event in deviating isolate catalyst motion is brought about by unequal etch rates across the isolate catalyst. This triggering event is indirectly affected by the oxidant concentration ratio through the etching rates. While the triggering events are stochastic, the doping concentration of silicon offers a good control in minimizing isolate catalyst motion. The doping concentration affects the porosity at the etching front, and this directly affects the van der Waals (vdWs) forces between the metal catalyst and Si during etching. A reduction in the vdWs forces resulted in a lower bending torque that can prevent the straying of the isolate catalyst from its directional etching, in the event of unequal etch rates. The key understandings in isolate catalyst motion derived from this work allowed us to demonstrate the fabrication of large area and uniformly ordered sub-500 nm nanoholes array with an unprecedented high aspect ratio of ∼12

Temperature-Gated Thermal Rectifier for Active Heat Flow Control

Active heat flow control is essential for broad applications of heating, cooling, and energy conversion. Like electronic devices developed for the control of electric power, it is very desirable to develop advanced all-thermal solid-state devices that actively control heat flow without consuming other forms of energy. Here we demonstrate temperature-gated thermal rectification using vanadium dioxide beams in which the environmental temperature actively modulates asymmetric heat flow. In this three terminal device, there are two switchable states, which can be regulated by global heating. In the “Rectifier” state, we observe up to 28% thermal rectification. In the “Resistor” state, the thermal rectification is significantly suppressed (<1%). To the best of our knowledge, this is the first demonstration of solid-state active-thermal devices with a large rectification in the Rectifier state. This temperature-gated rectifier can have substantial implications ranging from autonomous thermal management of heating and cooling systems to efficient thermal energy conversion and storage

Second-Harmonic Generation from Sub‑5 nm Gaps by Directed Self-Assembly of Nanoparticles onto Template-Stripped Gold Substrates

Strong field enhancement and confinement in plasmonic nanostructures provide suitable conditions for nonlinear optics in ultracompact dimensions. Despite these enhancements, second-harmonic generation (SHG) is still inefficient due to the centrosymmetric crystal structure of the bulk metals used, e.g., Au and Ag. Taking advantage of symmetry breaking at the metal surface, one could greatly enhance SHG by engineering these metal surfaces in regions where the strong electric fields are localized. Here, we combine top-down lithography and bottom-up self-assembly to lodge single rows of 8 nm diameter Au nanoparticles into trenches in a Au film. The resultant “double gap” structures increase the <i>surface-to-volume</i> ratio of Au colocated with the strong fields in ∼2 nm gaps to fully exploit the surface SHG of Au. Compared to a densely packed arrangement of AuNPs on a smooth Au film, the double gaps enhance SHG emission by 4200-fold to achieve an effective second-order susceptibility χ⁽²⁾ of 6.1 pm/V, making it comparable with typical nonlinear crystals. This patterning approach also allows for the scalable fabrication of smooth gold surfaces with sub-5 nm gaps and presents opportunities for optical frequency up-conversion in applications that require extreme miniaturization

Solvent-Templated Methylammonium-Based Ruddlesden–Popper Perovskites with Short Interlayer Distances

Two-dimensional (2D) halide perovskites are exquisite semiconductors with great structural tunability. They can incorporate a rich variety of organic species that not only template their layered structures but also add new functionalities to their optoelectronic characteristics. Here, we present a series of new methylammonium (CH3NH3+ or MA)-based 2D Ruddlesden–Popper perovskites templated by dimethyl carbonate (CH3OCOOCH3 or DMC) solvent molecules. We report the synthesis, detailed structural analysis, and characterization of four new compounds: MA2(DMC)PbI4 (n = 1), MA3(DMC)Pb2I7 (n = 2), MA4(DMC)Pb3I10 (n = 3), and MA3(DMC)Pb2Br7 (n = 2). Notably, these compounds represent unique structures with MA as the sole organic cation both within and between the perovskite sheets, while DMC molecules occupy a tight space between the MA cations in the interlayer. They form hydrogen-bonded [MA···DMC···MA]2+ complexes that act as spacers, preventing the perovskite sheets from condensing into each other. We report one of the shortest interlayer distances (∼5.7–5.9 Å) in solvent-incorporated 2D halide perovskites. Furthermore, the synthesized crystals exhibit similar optical characteristics to other 2D perovskite systems, including narrow photoluminescence (PL) signals. The density functional theory (DFT) calculations confirm their direct-band-gap nature. Meanwhile, the phase stability of these systems was found to correlate with the H-bond distances and their strengths, decreasing in the order MA3(DMC)Pb2I7 > MA4(DMC)Pb3I10 > MA2(DMC)PbI4 ∼ MA3(DMC)Pb2Br7. The relatively loosely bound nature of DMC molecules enables us to design a thermochromic cell that can withstand 25 cycles of switching between two colored states. This work exemplifies the unconventional role of the noncharged solvent molecule in templating the 2D perovskite structure

Solvent-Templated Methylammonium-Based Ruddlesden–Popper Perovskites with Short Interlayer Distances

Two-dimensional (2D) halide perovskites are exquisite semiconductors with great structural tunability. They can incorporate a rich variety of organic species that not only template their layered structures but also add new functionalities to their optoelectronic characteristics. Here, we present a series of new methylammonium (CH3NH3+ or MA)-based 2D Ruddlesden–Popper perovskites templated by dimethyl carbonate (CH3OCOOCH3 or DMC) solvent molecules. We report the synthesis, detailed structural analysis, and characterization of four new compounds: MA2(DMC)PbI4 (n = 1), MA3(DMC)Pb2I7 (n = 2), MA4(DMC)Pb3I10 (n = 3), and MA3(DMC)Pb2Br7 (n = 2). Notably, these compounds represent unique structures with MA as the sole organic cation both within and between the perovskite sheets, while DMC molecules occupy a tight space between the MA cations in the interlayer. They form hydrogen-bonded [MA···DMC···MA]2+ complexes that act as spacers, preventing the perovskite sheets from condensing into each other. We report one of the shortest interlayer distances (∼5.7–5.9 Å) in solvent-incorporated 2D halide perovskites. Furthermore, the synthesized crystals exhibit similar optical characteristics to other 2D perovskite systems, including narrow photoluminescence (PL) signals. The density functional theory (DFT) calculations confirm their direct-band-gap nature. Meanwhile, the phase stability of these systems was found to correlate with the H-bond distances and their strengths, decreasing in the order MA3(DMC)Pb2I7 > MA4(DMC)Pb3I10 > MA2(DMC)PbI4 ∼ MA3(DMC)Pb2Br7. The relatively loosely bound nature of DMC molecules enables us to design a thermochromic cell that can withstand 25 cycles of switching between two colored states. This work exemplifies the unconventional role of the noncharged solvent molecule in templating the 2D perovskite structure

Large Thermoelectric Figure-of-Merits from SiGe Nanowires by Simultaneously Measuring Electrical and Thermal Transport Properties

The strongly correlated thermoelectric properties have been a major hurdle for high-performance thermoelectric energy conversion. One possible approach to avoid such correlation is to suppress phonon transport by scattering at the surface of confined nanowire structures. However, phonon characteristic lengths are broad in crystalline solids, which makes nanowires insufficient to fully suppress heat transport. Here, we employed Si–Ge alloy as well as nanowire structures to maximize the depletion of heat-carrying phonons. This results in a thermal conductivity as low as ∼1.2 W/m-K at 450 K, showing a large thermoelectric figure-of-merit (ZT) of ∼0.46 compared with those of SiGe bulks and even ZT over 2 at 800 K theoretically. All thermoelectric properties were “simultaneously” measured from the same nanowires to facilitate accurate ZT measurements. The surface-boundary scattering is prominent when the nanowire diameter is over ∼100 nm, whereas alloying plays a more important role in suppressing phonon transport for smaller ones