Engineering topics
Lin, Liwei
Publications and source records attributed to Lin, Liwei.
Zinc stannate microcubes with an integrated microheater for low-temperature NO 2 detection
Low temperature, microcube-shaped zinc stannate (ZnSnO 3 ) nanostructures using a low-power microheater sensor platform to detect NO 2 gas with high sensitivity and selectivity.
Moisture-induced autonomous surface potential oscillations for energy harvesting
A variety of autonomous oscillations in nature such as heartbeats and some biochemical reactions have been widely studied and utilized for applications in the fields of bioscience and engineering. Here, we report a unique phenomenon of moisture-induced electrical potential oscillations on polymers, poly([2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide-co-acrylic acid), during the diffusion of water molecules. Chemical reactions are modeled by kinetic simulations while system dynamic equations and the stability matrix are analyzed to show the chaotic nature of the system which oscillates with hidden attractors to induce the autonomous surface potential oscillation. Using moisture in the ambient environment as the activation source, this self-excited chemoelectrical reaction could have broad influences and usages in surface-reaction based devices and systems. As a proof-of-concept demonstration, an energy harvester is constructed and achieved the continuous energy production for more than 15,000 seconds with an energy density of 16.8 mJ/cm 2 . A 2-Volts output voltage has been produced to power a liquid crystal display toward practical applications with five energy harvesters connected in series.
Laser-sculptured ultrathin transition metal carbide layers for energy storage and energy harvesting applications
Ultrathin transition metal carbides with high capacity, high surface area, and high conductivity are a promising family of materials for applications from energy storage to catalysis. However, large-scale, cost-effective, and precursor-free methods to prepare ultrathin carbides are lacking. Here, we demonstrate a direct pattern method to manufacture ultrathin carbides (MoC x , WC x , and CoC x ) on versatile substrates using a CO 2 laser. The laser-sculptured polycrystalline carbides (macroporous, ~10-20 nm wall thickness, ~10 nm crystallinity) show high energy storage capability, hierarchical porous structure, and higher thermal resilience than MXenes and other laser-ablated carbon materials. A flexible supercapacitor made of MoC x demonstrates a wide temperature range (-50 to 300 °C). Furthermore, the sculptured microstructures endow the carbide network with enhanced visible light absorption, providing high solar energy harvesting efficiency (~72%) for steam generation. The laser-based, scalable, resilient, and low-cost manufacturing process presents an approach for construction of carbides and their subsequent applications.
Metallo‐Hydrogel‐Assisted Synthesis and Direct Writing of Transition Metal Dichalcogenides
Abstract Two dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted interest for their compelling nanoscale new properties and numerous potential applications including fast optoelectronic devices, ultrathin photovoltaics, and high‐performance catalysts. Large‐scale growth of uniform TMDC materials is essential for investigating their physics and for their integration into devices. However, the wafer scale deposition of TMDCs on arbitrary nonselective substrates is still beyond the current state‐of‐the‐art. In this article, a method to synthesize layered TMDCs (MoS 2 and WS 2 ) at the wafer‐scale by sulfurization of transition metal ions (Mo 5+ and W 6+ ) in a gelatin template (metallo‐hydrogel) is reported. This process is adaptable to versatile substrates, including amorphous silicon oxide, high‐temperature quartz, and silicon. Although the products are nominally few layer materials, direct band photoluminescent (≈1.8 eV), similar to single‐ or decoupled multilayer MoS 2 is observed. Finally, the solution‐based deposition enables contact printing of TMDC channels to be useable for device applications including thin film transistors with printed silver contacts using the same process.
Self‐Assembly of Large‐Area 2D Polycrystalline Transition Metal Carbides for Hydrogen Electrocatalysis
Abstract Low‐dimensional (0/1/2 dimension) transition metal carbides (TMCs) possess intriguing electrical, mechanical, and electrochemical properties, and they serve as convenient supports for transition metal catalysts. Large‐area single‐crystalline 2D TMC sheets are generally prepared by exfoliating MXene sheets from MAX phases. Here, a versatile bottom‐up method is reported for preparing ultrathin TMC sheets (≈10 nm in thickness and >100 μm in lateral size) with metal nanoparticle decoration. A gelatin hydrogel is employed as a scaffold to coordinate metal ions (Mo 5+ , W 6+ , Co 2+ ), resulting in ultrathin‐film morphologies of diverse TMC sheets. Carbonization of the scaffold at 600 °C presents a facile route to the corresponding MoC x , WC x , CoC x , and to metal‐rich hybrids (Mo 2− x W x C and W/Mo 2 C–Co). Among these materials, the Mo 2 C–Co hybrid provides excellent hydrogen evolution reaction (HER) efficiency (Tafel slope of 39 mV dec −1 and 48 mVj = 10 mA cm‐2 in overpotential in 0.5 m H 2 SO 4 ). Such performance makes Mo 2 C–Co a viable noble‐metal‐free catalyst for the HER, and is competitive with the standard platinum on carbon support. This template‐assisted, self‐assembling, scalable, and low‐cost manufacturing process presents a new tactic to construct low‐dimensional TMCs with applications in various clean‐energy‐related fields.
Microscopic mechanisms of deformation transfer in high dynamic range branched nanoparticle deformation sensors
Nanoscale stress sensing is of crucial importance to biomechanics and other fields. An ideal stress sensor would have a large dynamic range to function in a variety of materials spanning orders of magnitude of local stresses. In this, we show that tetrapod quantum dots (tQDs) exhibit excellent sensing versatility with stress-correlated signatures in a multitude of polymers. We further show that tQDs exhibit pressure coefficients, which increase with decreasing polymer stiffness, and vary >3 orders of magnitude. This high dynamic range allows tQDs to sense in matrices spanning >4 orders of magnitude in Young's modulus, ranging from compliant biological levels (~100 kPa) to stiffer structural polymers (~5 GPa). We use ligand exchange to tune filler-matrix interfaces, revealing that inverse sensor response scaling is maintained upon significant changes to polymer-tQD interface chemistry. We quantify and explore mechanisms of polymer-tQD strain transfer. An analytical model based on Mori-Tanaka theory presents agreement with observed trends.
Titanium Disulfide Coated Carbon Nanotube Hybrid Electrodes Enable High Energy Density Symmetric Pseudocapacitors
While electrochemical supercapacitors often show high power density and long operation lifetimes, they are plagued by limited energy density. Pseudocapacitive materials, in contrast, operate by fast surface redox reactions and are shown to enhance energy storage of supercapacitors. Furthermore, several reported systems exhibit high capacitance but restricted electrochemical voltage windows, usually no more than 1 V in aqueous electrolytes. Here, it is demonstrated that vertically aligned carbon nanotubes (VACNTs) with uniformly coated, pseudocapacitive titanium disulfide (TiS 2 ) composite electrodes can extend the stable working range to over 3 V to achieve a high capacitance of 195 F g -1 in an Li-rich electrolyte. A symmetric cell demonstrates an energy density of 60.9 Wh kg -1 —the highest among symmetric pseudocapacitors using metal oxides, conducting polymers, 2D transition metal carbides (MXene), and other transition metal dichalcogenides. Nanostructures prepared by an atomic layer deposition/sulfurization process facilitate ion transportation and surface reactions to result in a high power density of 1250 W kg -1 with stable operation over 10 000 cycles. In conclusion, a flexible solid-state supercapacitor prepared by transferring the TiS 2 –VACNT composite film onto Kapton tape is demonstrated to power a 2.2 V light emitting diode (LED) for 1 min.
3D Printed “Earable” Smart Devices for Real-Time Detection of Core Body Temperature
Real-time detection of basic physiological parameters such as blood pressure and heart rate is an important target in wearable smart devices for healthcare. Among these, the core body temperature is one of the most important basic medical indicators of fever, insomnia, fatigue, metabolic functionality, and depression. However, traditional wearable temperature sensors are based upon the measurement of skin temperature, which can vary dramatically from the true core body temperature. Here, we demonstrate a three-dimensional (3D) printed wearable "earable" smart device that is designed to be worn on the ear to track core body temperature from the tympanic membrane (i.e., ear drum) based on an infrared sensor. The device is fully integrated with data processing circuits and a wireless module for standalone functionality. Using this smart earable device, we demonstrate that the core body temperature can be accurately monitored regardless of the environment and activity of the user. In addition, a microphone and actuator are also integrated so that the device can also function as a bone conduction hearing aid. Using 3D printing as the fabrication method enables the device to be customized for the wearer for more personalized healthcare. This smart device provides an important advance in realizing personalized health care by enabling real-time monitoring of one of the most important medical parameters, core body temperature, employed in preliminary medical screening tests.
Characterizing Photon Reabsorption in Quantum Dot-Polymer Composites for Use as Displacement Sensors
The reabsorption of photoluminescence within a medium, an effect known as the inner filter effect (IFE), has been well studied in solutions, but has garnered less attention in regards to solid-state nanocomposites. Photoluminescence from a quantum dot (QD) can selectively excite larger QDs around it resulting in a net red-shift in the reemitted photon. In CdSe/CdS core/shell QD-polymer nanocomposites, we observe a large spectral red-shift of over a third of the line width of the photoluminescence of the nanocomposites over a distance of 100 μm resulting from the IFE. Unlike fluorescent dyes, which do not show a large IFE red-shift, QDs have a component of inhomogeneous broadening that originates from their size distribution and quantum confinement. By controlling the photoluminescence broadening as well as the sample dispersion and concentration, we show that the magnitude of the IFE within the nanocomposite can be tuned. We further demonstrate that this shift can be exploited in order to spectroscopically monitor the vertical displacement of a nanocomposite in a fluorescence microscope. Large energetic shifts in the measured emission with displacement can be maximized, resulting in a displacement sensor with submicrometer resolution. We further show that the composite can be easily attached to biological samples and is able to measure deformations with high temporal and spatial precision.
Encapsulation of Perovskite Nanocrystals into Macroscale Polymer Matrices: Enhanced Stability and Polarization
Lead halide perovskites hold promise for photonic devices, due to their superior optoelectronic properties. However, their use is limited by poor stability and toxicity. We demonstrate enhanced water and light stability of high-surface-area colloidal perovskite nanocrystals by encapsulation of colloidal CsPbBr 3 quantum dots into matched hydrophobic macroscale polymeric matrices. This is achieved by mixing the quantum dots with presynthesized high-molecular-weight polymers. In this work, we monitor the photoluminescence quantum yield of the perovskite-polymer nanocomposite films under water-soaking for the first time, finding no change even after >4 months of continuous immersion in water. Furthermore, photostability is greatly enhanced in the macroscale polymer-encapsulated nanocrystal perovskites, which sustain >10 10 absorption events per quantum dot prior to photodegradation, a significant threshold for potential device use. Control of the quantum dot shape in these thin-film polymer composite enables color tunability via strong quantum-confinement in nanoplates and significant room temperature polarized emission from perovskite nanowires. Not only does the high-molecular-weight polymer protect the perovskites from the environment but also no escaped lead was detected in water that was in contact with the encapsulated perovskites for months. In conclusion, our ligand-passivated perovskite-macroscale polymer composites provide a robust platform for diverse photonic applications.
Mechanisms of Local Stress Sensing in Multifunctional Polymer Films Using Fluorescent Tetrapod Nanocrystals
Nanoscale stress-sensing can be used across fields ranging from detection of incipient cracks in structural mechanics to monitoring forces in biological tissues. We demonstrate how tetrapod quantum dots (tQDs) embedded in block copolymers act as sensors of tensile/compressive stress. Remarkably, tQDs can detect their own composite dispersion and mechanical properties with a switch in optomechanical response when tQDs are in direct contact. Using experimental characterizations, atomistic simulations and finite-element analyses, we show that under tensile stress, densely packed tQDs exhibit a photoluminescence peak shifted to higher energies ("blue-shift") due to volumetric compressive stress in their core; loosely packed tQDs exhibit a peak shifted to lower energies ("red-shift") from tensile stress in the core. The stress shifts result from the tQD's unique branched morphology in which the CdS arms act as antennas that amplify the stress in the CdSe core. Our nanocomposites exhibit excellent cyclability and scalability with no degraded properties of the host polymer. Colloidal tQDs allow sensing in many materials to potentially enable autoresponsive, smart structural nanocomposites that self-predict upcoming fracture.
Cavitation-Induced Stiffness Reductions in Quantum Dot–Polymer Nanocomposites
The elastic stiffness of two polymer nanocomposite systems is investigated. The nanoscale fillers comprise cadmium selenide (CdSe, ~4 nm) and cadmium selenide/cadmium sulfide (CdSe/CdS, ~13 nm) quantum dots (QDs). The QDs are embedded within an electrospun structural block copolymer, poly(styrene-ethylene-butylene-styrene) (SEBS). Tensile testing shows a monotonic decrease in the tensile Young's modulus with increasing partially phase-separated QD concentration; this is to be compared to corresponding nanocomposites reinforced with nanorod (NR) and tetrapod (TP)-SEBS nanocomposites which show a monotonic increase with particle loading. While most studies to date emphasize the increase in Young's modulus in polymer nanocomposites at higher reinforcement loadings, few focus on the tunability of the modulus from reductions in stiffness. The present work reveals up to an ~80% reduction in tensile Young's modulus with the addition of 5 vol % of QDs to electrospun SEBS. In this study, we sought mechanistic insight into this reduction in composite stiffness using a 2D lattice spring model. Simulation results reveal that the stiffness decrease with the addition of QD reinforcements is likely due to cavitation in the polymer in the vicinity of the QD aggregates arising from polymer debonding under tension. We anticipate that this study, performed with a commonly used structural rubber, may find use in designing polymer-matrix nanocomposite fibers with specific Young's moduli for applications requiring a tunable lower stiffness material.
Microcrystalline diamond cylindrical resonators with quality-factor up to 0.5 million
We demonstrate high quality-factor 1.5 mm diameter batch-fabricated microcrystalline diamond cylindrical resonators (CR) with quality-factors limited by thermoelastic damping (TED) and surface loss. Resonators were fabricated 2.6 and 5.3 μm thick in-situ boron-doped microcrystalline diamond films deposited using hot filament chemical vapor deposition. The quality-factor (Q) of as-fabricated CR's was found to increase with the resonator diameter and diamond thickness. Annealing the CRs at 700 °C in a nitrogen atmosphere led to a three-fold increase in Q, a result we attribute to thinning of the diamond layer via reaction with residual O{sub 2} in the annealing furnace. Post-anneal Q exceeding 0.5 million (528 000) was measured at the 19 kHz elliptical wineglass modes, producing a ring-down time of 8.9 s. A model for Q versus diamond thickness and resonance frequency is developed including the effects of TED and surface loss. Measured quality factors are shown to agree with the predictions of this model.
Influence of three-dimensional nanoparticle branching on the Young’s modulus of nanocomposites: Effect of interface orientation
Significance Currently, the effect of branching of nanoparticles tens of nanometers in size on the mechanical properties of structural composites is not well understood due to the limited availability of branched nanoscale fillers. We report that branched nanofillers have the potential for optimization of nanocomposite Young’s modulus over their linear counterparts. Lattice spring model simulations reveal that the mechanism for this improvement involves the ability of branched nanoparticles to optimize the ratio of both filler and stiff interfacial bonds aligned with the tensile axis, as opposed to linear nanoparticles, which optimize only the filler bond orientation when parallel to the stretching axis. We believe this information could inform the design of nanocomposites with optimized mechanical properties for a variety of structural applications.