Nanoscale imaging of phonon dynamics by electron microscopy.

Spatially resolved vibrational mapping of nanostructures is indispensable to the development and understanding of thermal nanodevices1, modulation of thermal transport2 and novel nanostructured thermoelectric materials3-5. Through the engineering of complex structures, such as alloys, nanostructures and superlattice interfaces, one can significantly alter the propagation of phonons and suppress material thermal conductivity while maintaining electrical conductivity2. There have been no correlative experiments that spatially track the modulation of phonon properties in and around nanostructures due to spatial resolution limitations of conventional optical phonon detection techniques. Here we demonstrate two-dimensional spatial mapping of phonons in a single silicon-germanium (SiGe) quantum dot (QD) using monochromated electron energy loss spectroscopy in the transmission electron microscope. Tracking the variation of the Si optical mode in and around the QD, we observe the nanoscale modification of the composition-induced red shift. We observe non-equilibrium phonons that only exist near the interface and, furthermore, develop a novel technique to differentially map phonon momenta, providing direct evidence that the interplay between diffuse and specular reflection largely depends on the detailed atomistic structure: a major advancement in the field. Our work unveils the non-equilibrium phonon dynamics at nanoscale interfaces and can be used to study actual nanodevices and aid in the understanding of heat dissipation near nanoscale hotspots, which is crucial for future high-performance nanoelectronics.

Probing the Roles of Indium Oxides on Copper Catalysts for Enhanced Selectivity during CO2-to-CO Electrochemical Reduction.

The electrochemical CO2 reduction reaction (CO2RR) provides an alternative protocol to producing industrial chemicals with renewable electricity sources, and the highly selective, durable, and economic catalysts should expedite CO2RR applications. Here, we demonstrate a composite Cu-In2O3 catalyst in which a trace amount of In2O3 decorated on Cu surface greatly improves the selectivity and stability for CO2-to-CO reduction as compared to the counterparts (Cu or In2O3), realizing a CO faradaic efficiency (FECO) of 95% at -0.7 V (vs RHE) and no obvious degradation within 7 h. In situ X-ray absorption spectroscopy reveals that In2O3 undergoes the redox reaction and preserves the metallic state of Cu during the CO2RR process. Strong electronic interaction and coupling occur at the Cu/In2O3 interface which serves as the active site for selective CO2RR. Theoretical calculation confirms the roles of In2O3 in preventing oxidation and altering the electronic structure of Cu to assist COOH* formation and demote CO* adsorption at the Cu/In2O3 interface.

Thermoelectric properties of Zn- and Ce-alloyed In2O3and the effect of SiO2nanoparticle additives.

Thermoelectric materials are considered promising candidates for thermal energy conversion. This study presents the fabrication of Zn- and Ce-alloyed In2O3with a porous structure. The electrical conductivity was improved by the alloying effect and an ultra-low thermal conductivity was observed owing to the porous structure, which concomitantly provide a distinct enhancement ofZT. However, SiO2nanoparticle additives react with the matrix to form a third-phase impurity, which weakens the electrical conductivity and increases the thermal conductivity. A thermoelectric module was constructed for the purpose of thermal heat energy conversion. Our experimental results proved that both an enhancement in electrical conductivity and a suppression in thermal conductivity could be achieved through nano-engineering. This approach presents a feasible route to synthesize porous thermoelectric oxides, and provides insight into the effect of additives; moreover, this approach is a cost-effective method for the fabrication of thermoelectric oxides without traditional hot-pressing and spark-plasma-sintering processes.

Enhanced CO2 Electrochemical Reduction Performance over Cu@AuCu Catalysts at High Noble Metal Utilization Efficiency.

The electrochemical CO2 reduction reaction (CO2RR) represents a viable alternative to help close the anthropogenic carbon cycle and convert intermittent electricity from renewable energy sources to chemical energy in the form of value-added chemicals. The development of economic catalysts possessing high faradaic efficiency (FE) and mass activity (MA) toward CO2RR is critical in accelerating CO2 utilization technology. Herein, an elaborate Au-Cu catalyst where an alloyed AuCu shell caps on a Cu core (Cu@AuCu) is developed and evaluated for CO2-to-CO electrochemical conversion. Specific roles of Cu and Au for CO2RR are revealed in the alloyed core-shell structure, respectively, and a compositional-dependent volcano-plot is disclosed for the Cu@AuCu catalysts toward selective CO production. As a result, the Au2-Cu8 alloyed core-shell catalyst (only 17% Au content) achieves an FECO value as high as 94% and an MACO of 439 mA/mgAu at -0.8 V (vs RHE), superior to the values for pure Au, reflecting its high noble metal utilization efficiency.

Design of multifold Ge/Si/Ge composite quantum-dot heterostructures for visible to near-infrared photodetection.

We demonstrate an effective approach to grow high-quality thin film (>1 µm) of multifold Ge/Si/Ge composite quantum dots (CQDs) stacked heterostructures for near infrared photodetection and optical interconnect applications. An otherwise random, self-assembly of variable-fold Ge/Si CQDs has been grown on Si through the insertion of Si spacer layers to produce micron-scale-thick, stacked Ge/Si CQD layers with desired QD morphology and composition distribution. The high crystalline quality of these multifold Ge CQD heterostructures is evidenced by low dark current density of 3.68 pA/µm2, superior photoresponsivity of 267 and 220 mA/W under 850 and 980 nm illumination, respectively, and very fast temporal response time of 0.24 ns measured on the Ge/Si CQD photodetectors.

Superlattice of Fe(x)Ge(1-x) nanodots and nanolayers for spintronics application.

Fe(x)Ge(1-x) superlattices with two types of nanostructures, i.e. nanodots and nanolayers, were successfully fabricated using low-temperature molecular beam epitaxy. Transmission electron microscopy (TEM) characterization clearly shows that both the Fe(x)Ge(1-x) nanodots and nanolayers exhibit a lattice-coherent structure with the surrounding Ge matrix without any metallic precipitations or secondary phases. The magnetic measurement reveals the nature of superparamagnetism in Fe(x)Ge(1-x) nanodots, while showing the absence of superparamagnetism in Fe(x)Ge(1-x) nanolayers. Magnetotransport measurements show distinct magnetoresistance (MR) behavior, i.e. a negative to positive MR transition in Fe(x)Ge(1-x) nanodots and only positive MR in nanolayers, which could be due to a competition between the orbital MR and spin-dependent scatterings. Our results open a new growth strategy for engineering Fe(x)Ge(1-x) nanostructures to facilitate the development of Ge-based spintronics and magnetoelectronics devices.

Enhanced Thermoelectric Properties of P-Type Sn-Substituted Higher Manganese Silicides.

This study introduces Sn-substituted higher manganese silicides (MnSi1.75, HMS) synthesized via an arc-melting process followed by spark plasma sintering (SPS). The influences of Sn concentrations on the thermoelectric performance of Mn(Si1-xSnx)1.75 (x = 0, 0.001, 0.005, 0.01, 0.015) are systematically investigated. Our findings reveal that metallic Sn precipitates within the Mn(Si1-xSnx)1.75 matrix at x ≥ 0.005, with a determined solubility limit of approximately x = 0.001. In addition, substituting Si with Sn effectively reduces the lattice thermal conductivity of HMS by introducing point defect scattering. In contrast to the undoped HMS, the lattice thermal conductivity decreases to a minimum value of 2.0 W/mK at 750 K for the Mn(Si0.999Sn0.001)1.75 sample, marking a substantial 47.4% reduction. Consequently, a figure of merit (ZT) value of ~0.31 is attained at 750 K. This considerable enhancement in ZT is primarily attributed to the suppressed lattice thermal conductivity resulting from Sn substitution.

Suppression of Dehydrofluorination Reactions of a Li0.33La0.557TiO3-Nanofiber-Dispersed Poly(vinylidene fluoride-co-hexafluoropropylene) Electrolyte for Quasi-Solid-State Lithium-Metal Batteries by a Fluorine-Rich Succinonitrile Interlayer.

Solid-state lithium-metal batteries have great potential to simultaneously achieve high safety and high energy density for energy storage. However, the low ionic conductivity of the solid electrolyte and large electrode/electrolyte interfacial impedance are bottlenecks. A composite solid electrolyte (CSE) that integrates electrospun Li0.33La0.557TiO3 (LLTO) nanofibers, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is fabricated in this work. The effects of the LLTO filler fraction and morphology (spherical vs fibrous) on CSE conductivity are examined. Additionally, a fluorine-rich interlayer based on succinonitrile, fluoroethylene carbonate, and LiTFSI, denoted as succinonitrile interlayer (SNI), is developed to reduce the large interfacial impedance. The use of SNI rather than a conventional ester-based interlayer (EBI) effectively decreases the Li//CSE interfacial resistance and suppresses unfavorable interfacial side reactions. The LiF- and CFx-rich solid electrolyte interphase (SEI), derived from SNI, on the Li metal electrode, mitigates the accumulation of dead Li and excessive SEI. Importantly, dehydrofluorination reactions of PVDF-HFP are significantly reduced by the introduction of SNI. A symmetric Li//CSE//Li cell with SNI exhibits a much longer cycle life than that of an EBI counterpart. A Li//CSE@SNI//LiFePO4 cell shows specific capacities of 150 and 112 mAh g-1 at 0.1 and 2 C (based on LiFePO4), respectively. After 100 charge-discharge cycles, 98% of the initial capacity is retained.

Ag Nanoparticle-Decorated Cu2S Nanosheets for Surface Enhanced Raman Spectroscopy Detection and Photocatalytic Applications.

In this article, we demonstrate a facile, rapid, and practical approach to growing high-quality Cu2S nanosheets decorated with Ag nanoparticles (NPs) through the galvanic reduction method. The Ag/Cu2S nanosheets were efficiently applied to the surface-enhanced Raman scattering (SERS) and photocatalytic degradation applications. The photodegradation of RhB dye with the Ag/Cu2S nanosheets composites occurred at a rate of 2.9 times faster than that observed with the undecorated Cu2S nanosheets. Furthermore, the Ag/Cu2S nanosheets displayed highly sensitive SERS detection of organic pollutant (R6G) as low as 10-9 M. The reproducibility experiments indicated that the Ag/Cu2S nanosheets composites could be used for dual functionality in a new generation of outstandingly sensitive SERS probes for detection and stable photocatalysts.

Development of Crystalline Cu2S Nanowires via a Direct Synthesis Process and Its Potential Applications.

Large-scale and uniform copper(I) sulfide (Cu2S) nanowires have been successfully synthesized via a cheap, fast, easily handled, and environmentally friendly approach. In addition to the reductive properties of the biomolecule-assisted method, they also have a strong shape- or size-directing functionality in the reaction process. The field-emission properties of the Cu2S nanowires in a vacuum were studied by the Folwer-Nordheim (F-N) theory. The Cu2S nanowires have a low turn-on field at 1.19 V/µm and a high enhancement factor (ß) of 19,381. The photocatalytic degradation of Cu2S nanowires was investigated by the change in the concentrations of rhodamine B (RhB) under UV illumination. These outstanding results of Cu2S nanowires indicate that they will be developed as good candidates as electron field emitters and chemical photocatalysts in future nanoelectronic devices.

Optimization of Pt-Oxygen-Containing Species Anodes for Ethanol Oxidation Reaction: High Performance of Pt-AuSnOx Electrocatalyst.

Pt-oxygen-containing species (Pt-OCS) catalysts, in which OCS (e.g., metal-oxides) are decorated on a Pt surface, possess enhanced ethanol oxidation reaction (EOR) activity and stability compared with pure Pt and are promising in practical applications of direct ethanol fuel cells. We investigate the promotion roles of Pt-OCS electrocatalysts toward the EOR via a combination of density functional theory (DFT) calculations and experiments, providing a rational design strategy for Pt-OCS catalysts. It is revealed that Pt-AuO and Pt-SnO excel in EOR activity and stability, respectively, among the DFT screening of various Pt-OCS systems, and this is confirmed by the following experiments. Moreover, an optimized Pt-AuSnO catalyst is proposed by DFT calculations, taking advantage of both Pt-AuO and Pt-SnO. The as-prepared Pt-AuSnO catalyst delivers an EOR activity that is 9.7 times higher than that of Pt and shows desired stability. These findings are expected to elucidate the mechanistic insights into Pt-OCS materials and lead to advanced EOR electrocatalysts.

Enhancement of Hippocampal Spatial Decoding Using a Dynamic Q-Learning Method With a Relative Reward Using Theta Phase Precession.

Hippocampal place cells and interneurons in mammals have stable place fields and theta phase precession profiles that encode spatial environmental information. Hippocampal CA1 neurons can represent the animal's location and prospective information about the goal location. Reinforcement learning (RL) algorithms such as Q-learning have been used to build the navigation models. However, the traditional Q-learning ([Formula: see text]Q-learning) limits the reward function once the animals arrive at the goal location, leading to unsatisfactory location accuracy and convergence rates. Therefore, we proposed a revised version of the Q-learning algorithm, dynamical Q-learning ([Formula: see text]Q-learning), which assigns the reward function adaptively to improve the decoding performance. Firing rate was the input of the neural network of [Formula: see text]Q-learning and was used to predict the movement direction. On the other hand, phase precession was the input of the reward function to update the weights of [Formula: see text]Q-learning. Trajectory predictions using [Formula: see text]Q- and [Formula: see text]Q-learning were compared by the root mean squared error (RMSE) between the actual and predicted rat trajectories. Using [Formula: see text]Q-learning, significantly higher prediction accuracy and faster convergence rate were obtained compared with [Formula: see text]Q-learning in all cell types. Moreover, combining place cells and interneurons with theta phase precession improved the convergence rate and prediction accuracy. The proposed [Formula: see text]Q-learning algorithm is a quick and more accurate method to perform trajectory reconstruction and prediction.

Dual-function nanostructured platform for isolation of nasopharyngeal carcinoma circulating tumor cells and EBV DNA detection.

Circulating tumor cells (CTCs) and plasma levels of Epstein-Barr virus (EBV) DNA are sensitive prognostic tools for monitoring disease status in nasopharyngeal carcinoma (NPC) patients. Herein, we introduce a novel and low-cost platform for capturing CTCs, the Si nanowires/microscale pyramids (NWs/MPs) hierarchical substrate, which could capture NPC cells in vitro and also detect EBV DNA at very low concentrations. In this study, Si NWs/MPs hierarchical substrates with varying wire length were fabricated using a metal-assisted chemical etching method. Anti-EpCAM antibodies were further conjugated on the substrate for capturing NPC CTCs in vitro. Capture efficiency was evaluated using immunofluorescence and scanning electronic microscopy (SEM) was utilized to understand cell morphology. The Si NWs/MPs substrate was also transformed into a Surface enhanced Raman scattering (SERS) substrate by coating with Ag nanoparticles (AgNPs) for detection of EBV DNA by Raman spectroscopy. The results demonstrated that Si NWs/MPs with 20 min of etch time had the best capturing performance. Additionally, SEM observations revealed good contact of CTCs with Si NWs/MPs substrates. Moreover, the AgNPs-coated NWs/MPs substrate was shown to be a sensitive EBV DNA detector, by which the DNA detection limit can reach up to 10-13M. In conclusion, the Si NWs/MPs platform not only exhibits superior cell capturing ability, but also can sensitively detect EBV DNA at very low concentrations. This platform has great potential to become a promising diagnostic tool for monitoring disease status and prognostication of NPC patients.

Enhancing the Seebeck effect in Ge/Si through the combination of interfacial design features.

Due to their inherent physical properties, thin-film Si/SiGe heterostructures have specific thermal management applications in advanced integrated circuits and this in turn is essential not only to prevent a high local temperature and overheat inside the circuit, but also generate electricity through the Seebeck effect. Here, we were able to enhance the Seebeck effect in the germanium composite quantum dots (CQDs) embedded in silicon by increasing the number of thin silicon layers inside the dot (multi-fold CQD material). The Seebeck effect in the CQD structures and multi-layer boron atomic layer-doped SiGe epitaxial films was studied experimentally at temperatures in the range from 50 to 300 K and detailed calculations for the Seebeck coefficient employing different scattering mechanisms were made. Our results show that the Seebeck coefficient is enhanced up to ≈40% in a 3-fold CQD material with respect to 2-fold Ge/Si CQDs. This enhancement was precisely modeled by taking into account the scattering of phonons by inner boundaries and the carrier filtering by the CQD inclusions. Our model is also able to reproduce the observed temperature dependence of the Seebeck coefficient in the B atomic layer-doped SiGe fairly well. We expect that the phonon scattering techniques developed here could significantly improve the thermoelectric performance of Ge/Si materials through further optimization of the layer stacks inside the quantum dot and of the dopant concentrations.

Enhanced Biocompatibility in Anodic TaO x Nanotube Arrays.

This study first investigates the biocompatibility of self-organized TaO x nanotube arrays with different nanotube diameters fabricated by electrochemical anodization. All as-anodized TaO x nanotubes were identified to be an amorphous phase. The transition in surface wettability with TaO x nanotube diameters can be explained based on Wenzel's model in terms of geometric roughness. In vitro biocompatibility evaluation further indicates that fibroblast cells exhibit an obvious wettability-dependent behavior on the TaO x nanotubes. The 35-nm-diameter TaO x nanotube arrays reveal the highest biocompatibility among all samples. This enhancement could be attributed to highly dense focal points provided by TaO x nanotubes due to higher surface hydrophilicity. This work demonstrates that the biocompatibility in Ta can be improved by forming TaO x nanotube arrays on the surface with appropriate nanotube diameter and geometric roughness.

Primary human nasal epithelial cell response to titanium surface with a nanonetwork structure in nasal implant applications.

In nasal reconstruction applications, the response of cells to titanium (Ti) implants is largely determined by the surface characteristics of the implant. This study investigated an electrochemical anodization surface treatment intended to improve the response of primary human nasal epithelial cells (HNEpC) to Ti surfaces in nasal implant applications. We used a simple and fast electrochemical anodization treatment, i.e., applying anodic current, to produce a titanium dioxide (TiO2) nanonetwork layer on the Ti surface with average lateral pore size below 100 nm, depending on the current applied. The TiO2 nanonetwork layer exhibited enhanced hydrophilicity and protein adsorption ability compared with untreated Ti surfaces. In addition, the spreading morphology, cytoskeletal arrangement, and proliferation of HNEpC on the nanonetwork layer indicated excellent cell response characteristics. This research advances our understanding regarding the means by which a TiO2 nanonetwork layer can improve the response of HNEpC to Ti surfaces in nasal implant applications.

Designer Ge/Si composite quantum dots with enhanced thermoelectric properties.

An otherwise random, self-assembly of Ge/Si composite quantum dots (CQDs) on Si was controlled by inserting a layer of Si, sub-dot stacks, and post-annealing to produce micron-scale-thick QD layers with desired QD morphology, interface density, and composition distribution. A heterostructure consisting of a deliberate insertion of Si between Ge sub-dots is shown to improve the epitaxial coherence of the Ge QDs by suppression of the Ge surface interdiffusion and coarsening. As compared to regular-QD materials, the thin-film-like multifold-CQD materials are found to exhibit both reduced cross-plane thermal conductivity and enhanced electrical conductivity, and 1.5 times higher ZT value by calculation, providing a promising building block for practical thermoelectric applications in micro- or nanoelectronics.

Both enhanced biocompatibility and antibacterial activity in Ag-decorated TiO2 nanotubes.

In this study, Ag is electron-beam evaporated to modify the topography of anodic TiO2 nanotubes of different diameters to obtain an implant with enhanced antibacterial activity and biocompatibility. We found that highly hydrophilic as-grown TiO2 nanotubes became poorly hydrophilic with Ag incorporation; however they could effectively recover their wettability to some extent under ultraviolet light irradiation. The results obtained from antibacterial tests suggested that the Ag-decorated TiO2 nanotubes could greatly inhibit the growth of Staphylococcus aureus. In vitro biocompatibility evaluation indicated that fibroblast cells exhibited an obvious diameter-dependent behavior on both as-grown and Ag-decorated TiO2 nanotubes. Most importantly, of all samples, the smallest diameter (25-nm-diameter) Ag-decorated nanotubes exhibited the most obvious biological activity in promoting adhesion and proliferation of human fibroblasts, and this activity could be attributed to the highly irregular topography on a nanometric scale of the Ag-decorated nanotube surface. These experimental results demonstrate that by properly controlling the structural parameters of Ag-decorated TiO2 nanotubes, an implant surface can be produced that enhances biocompatibility and simultaneously boosts antibacterial activity.

Diameter-sensitive biocompatibility of anodic TiO2 nanotubes treated with supercritical CO2 fluid.

This work reports on the diameter-sensitive biocompatibility of anodic TiO2 nanotubes with different nanotube diameters grown by a self-ordering process and subsequently treated with supercritical CO2 (ScCO2) fluid. We find that highly hydrophilic as-grown TiO2 nanotubes become hydrophobic after the ScCO2 treatment but can effectively recover their surface wettability under UV light irradiation as a result of photo-oxidation of C-H functional groups formed on the nanotube surface. It is demonstrated that human fibroblast cells show more obvious diameter-specific behavior on the ScCO2-treated TiO2 nanotubes than on the as-grown ones in the range of diameters of 15 to 100 nm. This result can be attributed to the removal of disordered Ti(OH)4 precipitates from the nanotube surface by the ScCO2 fluid, thus resulting in purer nanotube topography and stronger diameter dependence of cell activity. Furthermore, for the smallest diameter of 15 nm, ScCO2-treated TiO2 nanotubes reveal higher biocompatibility than the as-grown sample.

Uniform SiGe/Si quantum well nanorod and nanodot arrays fabricated using nanosphere lithography.

This study fabricates the optically active uniform SiGe/Si multiple quantum well (MQW) nanorod and nanodot arrays from the Si0.4Ge0.6/Si MQWs using nanosphere lithography (NSL) combined with the reactive ion etching (RIE) process. Compared to the as-grown sample, we observe an obvious blueshift in photoluminescence (PL) spectra for the SiGe/Si MQW nanorod and nanodot arrays, which can be attributed to the transition of PL emission from the upper multiple quantum dot-like SiGe layers to the lower MQWs. A possible mechanism associated with carrier localization is also proposed for the PL enhancement. In addition, the SiGe/Si MQW nanorod arrays are shown to exhibit excellent antireflective characteristics over a wide wavelength range. These results indicate that SiGe/Si MQW nanorod arrays fabricated using NSL combined with RIE would be potentially useful as an optoelectronic material operating in the telecommunication range.