Enhanced Epoxy Composites Reinforced by 3D-Aligned Aluminum Borate Nanowhiskers.

Recently, the durability of high-performance and multifunctional portable electronic devices such as smartphones and tablets, has become an important issue. Electronic device housing, which protects internal components from external stimuli, such as vibration, shock, and electrical hazards, is essential for resolving durability issues. Therefore, the materials used for electronic device housing must possess good mechanical and electrical insulating properties. Herein, we propose a novel high-strength polymer nanocomposite based on 3D-aligned aluminum borate nanowhisker (ABOw) structures. ABOw was synthesized using a facile hydrothermal method, and 3D-aligned ABOw structures were fabricated using a freeze-casting process. The 3D-aligned ABOw/epoxy composites consist of repetitively layered structures, and the microstructures of these composites are controlled by the filler content. The developed 3D-aligned ABOw/epoxy composite had a compressive strength 56.72% higher than that of pure epoxy, indicating that it can provide high durability when applied as a protective material for portable electronic devices.

Metal Nanocomposites Reinforced by Ceramic Nanoarchitecture: Exploiting Extrinsic Size Effects for High Mechanical Strength.

The pursuit of harnessing superior mechanical properties achieved through the size effect on a macroscopic scale has been a prominent focus in engineering, as size-induced strengthening is enabled only in the nanoscale regime. This study presents a metal/ceramic/metal (MCM) nanocomposite reinforced by ceramic nanoarchitectures. Through proximity-field nanopatterning, the inch-scale production of nanoarchitecture films is enabled in a single fabrication step. The developed three-dimensional (3D) Ni/Al2O3/Ni nanocomposite film exhibits significantly high compressive strength, corresponding to an increase of approximately 30% compared with that calculated using the upper limits of the conventional rule of mixtures. The exceptional strength of the 3D MCM nanocomposite can be attributed to the extrinsic size effect of the ceramic nanoarchitectures. By combining size-induced strengthening of ceramics with the strengthening law for composites, a new type of strengthening model is derived and experimentally validated using the 3D MCM nanocomposite.

Enhanced Thermal Pad Composites Using Densely Aligned MgO Nanowires.

Owing to the increasing demand for the miniaturization and integration of electronic devices, thermal interface materials (TIMs) are crucial components for removing heat and improving the lifetime and safety of electronic devices. Among these, thermal pads are reusable alternatives to thermal paste-type TIMs; however, conventional thermal pads comprise a homogeneous polymer with low thermal conductivity. Composite materials of thermally conducting fillers and polymer matrices are considered suitable alternatives to high-performance pad materials owing to their controllable thermal properties. However, they degrade the thermal performance of the filler materials at high loading ratios via aggregation. In this study, we propose novel nanocomposites using densely aligned MgO nanowire fillers and polydimethylsiloxane (PDMS) matrices. The developed nanocomposites ensured the enhanced thermal conducting properties, while maintaining mechanical flexibility. The three-step preparation process involves the (i) fabrication of the MgO structure using a freeze dryer; (ii) compression of the MgO structure; and (iii) the infiltration of PDMS in the structure. The resulting aligned composites exhibited a superior thermal conductivity (approximately 1.18 W m-1K-1) to that of pure PDMS and composites with the same filler ratios of randomly distributed MgO fillers. Additionally, the MgO/PDMS composites exhibited adequate electrical insulating properties, with a room-temperature resistivity of 7.92 × 1015 Ω∙cm.

Optically Activated 3D Thin-Shell TiO2 for Super-Sensitive Chemoresistive Responses: Toward Visible Light Activation.

One of the well-known strategies for achieving high-performance light-activated gas sensors is to design a nanostructure for effective surface responses with its geometric advances. However, no study has gone beyond the benefits of the large surface area and provided fundamental strategies to offer a rational structure for increasing their optical and chemical performances. Here, a new class of UV-activated sensing nanoarchitecture made of highly periodic 3D TiO2, which facilitates 55 times enhanced light absorption by confining the incident light in the nanostructure, is prepared as an active gas channel. The key parameters, such as the total 3D TiO2 film and thin-shell thicknesses, are precisely optimized by finite element analysis. Collectively, this fundamental design leads to ultrahigh chemoresistive response to NO2 with a theoretical detection limit of ≈200 ppt. The demonstration of high responses with visible light illumination proposes a future perspective for light-activated gas sensors based on semiconducting oxides.

Hierarchically porous Au nanostructures with interconnected channels for efficient mass transport in electrocatalytic CO2 reduction.

Electrocatalytic CO2 reduction is a promising way to provide renewable energy from gaseous CO2 The development of nanostructures improves energy efficiency and selectivity for value-added chemicals, but complex nanostructures limit the CO2 conversion rates due to poor mass transport during vigorous electrolysis. Herein, we propose a three-dimensional (3D) hierarchically porous Au comprising interconnected macroporous channels (200-300 nm) and nanopores (∼10 nm) fabricated via proximity-field nanopatterning. The interconnected macropores and nanopores enable efficient mass transport and large active areas, respectively. The roles of each pore network are investigated using reliable 3D nanostructures possessing controlled pore distribution and size. The hierarchical nanostructured electrodes show a high CO selectivity of 85.8% at a low overpotential of 0.264 V and efficient mass activity that is maximum 3.96 times higher than that of dealloyed nanoporous Au. Hence, the systematic model study shows the proposed hierarchical nanostructures have important value in increasing the efficiency of expensive Au.

Highly luminescent polyethylene glycol-passivated graphene quantum dots for light emitting diodes.

The emergence of fluorescent graphene quantum dots (GQDs) is expected to enhance the usefulness of quantum dots (QDs), in terms of their unique luminescence, photostability, low toxicity, chemical resistance, and electron transport properties. Here we prepared blue-photoluminescent polyethylene glycol GQDs (PEG-GQDs) through PEG surface passivation. The photoluminescence (PL) quantum yield (QY) of PEG-GQDs with 320 nm excitation was about 4.9%, which was higher than that of pure GQDs. The as-fabricated PEG-GQDs with high QY were then used as light-emitting diode (PGQD-LED) emitters, in which the GQDs were incorporated into polymeric host layers in a multilayer electroluminescent device; blue emission with a luminance exceeding 800 cd m-2 was achieved, thus demonstrating the potential of PEG-GQDs as emitters in electroluminescence applications. Furthermore, the fluorescence mechanism of PEG-GQDs was investigated and proved that the origin of strong fluorescence of PEG-GQDs is associated with the luminescence from intrinsic states. The highly fluorescent PEG-GQDs will allow new devices, such as multicolor LEDs, to be developed with extraordinary properties, by tailoring the intrinsic and extrinsic states.

Versatile and Tunable Electrical Properties of Doped Nonoxidized Graphene Using Alkali Metal Chlorides.

With the rapid development of wearable and flexible electronics, graphene has been intensively studied for the transparent, hole transport electrode layer (HTL) of field-effect transistors, light-emitting diodes, and organic photovoltaic (OPV) cells. To modulate the sheet resistance and the work function of graphene as a HTL, the surface doping is versatile while retaining high transparency. In this work, we used a chemical doping method to control the charge carrier density, band gap, and work function of graphene with minimizing the damage of the carbon network, for which metal chlorides (NaCl, KCl, and AuCl3) were used as chemical dopants. The high-quality graphene flakes were synthesized with large lateral sizes of more than 5 µm using ternary graphite intercalation compounds. Interestingly, the AuCl3-doped graphene flake film with a film thickness of about 20 nm showed the lowest reported sheet resistance of ∼249 Ω/sq with ∼75% transmittance. Furthermore, it could control the work function from 4.32 to 5.1 eV. The interfacial dipole complexes of metal cations with a low work function and the reactive radicals such as -OH were discussed to explain this result. For the practical application, an OPV device using the AuCl3-doped graphene flake film as the HTL was fabricated and it demonstrated enhanced power conversion efficiency while maintaining high optical transparency in visible light.

Strategies to improve the photocatalytic activity of TiO2: 3D nanostructuring and heterostructuring with graphitic carbon nanomaterials.

TiO2-based photocatalysis has been considered to be one of the most promising avenues for environmental remediation including water purification. However, several technical issues such as the limited surface area of bulk TiO2, the large band gap of TiO2, and rapid charge recombination still limit the practical application of TiO2 photocatalysts. Therefore, here we focus on two structural design strategies: (i) monolithic three-dimensional (3D) nanostructuring, and (ii) heterostructuring with graphitic carbon nanomaterials. A monolithic 3D nanostructure enables maximal surface area in a given volume and efficient reuse of the photocatalyst without recollection. Heterostructuring with carbon nanomaterials helps achieve maximal utilization of the solar spectrum and charge separation and provides efficient TiO2 photocatalysts. In this review, recent progress on TiO2 photocatalysts toward the abovementioned strategies will be summarized. Further discussion and direction will provide insights into the rational design of highly efficient TiO2 photocatalysts, and help develop advanced photocatalyst models.

Emergence of New Density-Strength Scaling Law in 3D Hollow Ceramic Nanoarchitectures.

Density-strength tradeoff appears to be an inherent limitation for most materials and therefore design of cell topology that mitigates strength decrease with density reduction has been a long-lasting engineering pursue for porous materials. Continuum-mechanics-based analyses of mechanical responses of conventional porous materials with bending-dominated structures often give the density-strength scaling law following the power-law relationship with an exponent of 1.5 or higher, which consequentially determines the upper bound of the specific strength for a material to reach. In this work, a new design criterion capable of significantly abating strength degradation in lightweight materials is presented, by successfully combining the size-induced strengthening effect in nanomaterials with the architectural design of cellular porous materials. Hollow-tube-based 3D ceramic nanoarchitectures satisfying such criterion are fabricated in large area using proximity field nano-patterning and atomic layer deposition. Experimental data from micropillar compression confirm that the strengths of these nanoarchitectural materials scale with relative densities with a power-law exponent of 0.93, a hardly observable value in conventional bending-dominated porous materials. This discovery of a new density-strength scaling law in nanoarchitectured materials will contribute to creating new lightweight structural materials attaining unprecedented specific strengths overcoming the conventional limit.

Multifunctional Polymer Nanocomposites Reinforced by 3D Continuous Ceramic Nanofillers.

Polymer nanocomposites with inclusion of ceramic nanofillers have relatively high yield strength, elastic moduli, and toughness that therefore are widely used as functional coating and films for optoelectronic applications. Although the mechanical properties are enhanced with increasing the fraction of nanofiller inclusion, there generally is an upper limit on the amount of nanofiller inclusion because the aggregation of the fillers in the polymer matrix, which typically occurs, degrades the mechanical and/or optical performances above 5 vol % of inclusions. Here, we demonstrate an unconventional polymer nanocomposite composed of a uniformly distributed three-dimensional (3D) continuous ceramic nanofillers, which allows for extremely high loading (∼19 vol %) in the polymer matrix without any concern of aggregation and loss in transparency. The fabrication strategy involves conformal deposition of Al2O3 nanolayer with a precise control in thickness that ranges from 12 to 84 nm on a 3D nanostructured porous polymer matrix followed by filling the pores with the same type of polymer. The 3D continuous Al2O3 nanolayers embedded in the matrix with extremely high filler rate of 19.17 vol % improve compressive strength by 142% compared to the pure epoxy without Al2O3 filler, and this value is in agreement with theoretically predicted strength through the rule of mixture. These 3D nanocomposites show superb transparency in the visible (>85% at 600 nm) and near-IR (>90% at 1 µm) regions and improved heat dissipation beyond that of conventional Al2O3 dispersed nanocomposites with similar filler loading of 15.11 vol % due to the existence of a continuous thermal conduction path through the oxide network.

3D nanostructured N-doped TiO2 photocatalysts with enhanced visible absorption.

Considering the environmental issues, it is essential to develop highly efficient and recyclable photocatalysts in purification systems. Conventional TiO2 nanoparticles have strong intrinsic oxidizing power and high surface area, but are difficult to collect after use and rarely absorb visible light, resulting in low photocatalytic efficiency under sunlight. Here we develop a new type of highly efficient and recyclable photocatalyst made of a three-dimensional (3D) nanostructured N-doped TiO2 monolith with enhanced visible light absorption. To prepare the sample, an ultrathin TiN layer (∼10 nm) was conformally coated using atomic layer deposition (ALD) on 3D nanostructured TiO2. Subsequent thermal annealing at low temperature (550 °C) converted TiN to anatase phase N-doped TiO2. The resulting 3D N-doped TiO2 showed ∼33% enhanced photocatalytic performance compared to pure 3D TiO2 of equivalent thickness under sunlight due to the reduced bandgap, from 3.2 eV to 2.75 eV through N-doping. The 3D N-doped TiO2 monolith could be easily collected and reused at least 5 times without any degradation in photocatalytic performance.

Anomalous thermoelectricity of pure ZnO from 3D continuous ultrathin nanoshell structures.

ZnO is a potential thermoelectric material because of its non-toxicity, high thermal stability, and relatively high Seebeck coefficient (S) of metal oxides. However, the extremely low figure of merit (zT), which comes from a high thermal conductivity (κ) over 40 W m-1 K-1, limits the thermoelectric application of ZnO. In particular, below 500 K, ZnO exhibits a nearly negligible zT (<10-3), unless a dopant is incorporated into the crystal structure. Here, we propose a new strategy for achieving a reduced κ and a correspondingly increased zT of pure ZnO over a wide temperature range from 333 K to 723 K by forming an ∼72 nm thick, 3D continuous ultrathin nanoshell structure. The suppressed κ of the 3D ZnO film is ∼3.6 W m-1 K-1 at 333 K, which is ∼38 times lower than that of the blanket ZnO film (3.2 µm thick), which was set as a reference. The experimental zT of the 3D ZnO film is ∼0.017 at 333 K, which is the highest value among pure ZnO reported to date and is estimated to increase by ∼0.072 at 693 K according to the Debye-Callaway approach. Large-area (∼1 in2) fabrication of the 3D ZnO film with high structural uniformity allows the realization of an integrated thermoelectric device, which generates ∼60 mV at a temperature difference of 40 K along the in-plane direction.

Amplification of hot electron flow by the surface plasmon effect on metal-insulator-metal nanodiodes.

Au-TiO2-Ti nanodiodes with a metal-insulator-metal structure were used to probe hot electron flows generated upon photon absorption. Hot electrons, generated when light is absorbed in the Au electrode of the nanodiode, can travel across the TiO2, leading to a photocurrent. Here, we demonstrate amplification of the hot electron flow by (1) localized surface plasmon resonance on plasmonic nanostructures fabricated by annealing the Au-TiO2-Ti nanodiodes, and (2) reducing the thickness of the TiO2. We show a correlation between changes in the morphology of the Au electrodes caused by annealing and amplification of the photocurrent. Based on the exponential dependence of the photocurrent on TiO2 thickness, the transport mechanism for the hot electrons across the nanodiodes is proposed.

Patternable PEDOT nanofilms with grid electrodes for transparent electrochromic devices targeting thermal camouflage.

This paper reports a new type of transmitting mode electrochromic device that uses the high-contrast electrochromism of poly(3,4-ethylenedioxythiophene) (PEDOT) and operates at long-wavelength infrared (8-12 µm) . To maximize the transmittance contrast and transmittance contrast ratio of the device for thermal camouflage, we control the thickness of the thin PEDOT layer from 25 nm to 400 nm and develop a design of grid-type counter electrodes. The cyclability can be greatly improved by selective deposition of the PEDOT film on grid electrodes as an ion storage layer without any loss of overall transmittance. The device with optimized architectures shows a high transmittance contrast ratio of 83 % at a wavelength of 10 µm with a response rate under 1.4 s when alternating voltage is applied. Captured images of an LED lamp behind the device prove the possibility of active, film-type camouflage against thermal detection.

Monolithic 3D titania with ultrathin nanoshell structures for enhanced photocatalytic activity and recyclability.

Titania has attracted considerable interest for use in water purification applications due to its excellent photocatalytic activity. To further improve the efficiency of photocatalysis, numerous nanostructures (i.e. nanoparticles, nanotubes, and nanowires) have been proposed to increase the surface area of titania. Despite the high photocatalytic performance of the nanostructured titania, subsequent difficulties encountered in recollection and reuse of titania inhibit the practical application for water purification systems. Here we successfully fabricate monolithic, three dimensional (3D) nanoshell titania with high uniformity over large areas (~1 × 1 inch(2)) through proximity field nanopatterning (PnP) and low-temperature atomic layer deposition (ALD) techniques. The higher surface area of 3D nanoshell titania increases the photocatalytic performance more than three-fold relative to that of a thin film of equivalent sample size. Also, the monolithic form of titania enables it to be reused without any degradation of photocatalytic activity. The newly developed nanomaterials in this study can serve as an efficient and reusable photocatalyst for water purification systems.

Soft elastomeric nanopillar stamps for enhancing absorption in organic thin-film solar cells.

An elastomeric poly(dimethylsiloxane) (PDMS) block engraved with periodically arrayed nanopillars serves as a transferable light-trapping stamp for encapsulated organic thin-film solar cells. Diffracted light rays from the stamp interfere with one another and self-focus onto the active layer of the solar cell, generating enhanced absorption, as indicated in the current density-voltage measurements.

Three-dimensional nanonetworks for giant stretchability in dielectrics and conductors.

The realization of levels of stretchability that extend beyond intrinsic limits of bulk materials is of great importance to stretchable electronics. Here we report large-area, three-dimensional nano-architectures that achieve this outcome in materials that offer both insulating and conductive properties. For the elastomer poly(dimethylsiloxane), such geometries enhance the stretchability and fracture strain by ~62% and ~225% over the bulk, unstructured case. The underlying physics involves local rotations of narrow structural elements in the three-dimensional network, as identified by mechanical modelling. To demonstrate the applications of three-dimensional poly(dimethylsiloxane), we create a stretchable conductor obtained by filling the interstitial regions with liquid metal. This stretchable composite shows extremely high electrical conductivity (~24,100 S cm(-1)) even at strains >200%, with good cyclic properties and with current-carrying capacities that are sufficient for interconnects in light-emitting diode systems. Collectively, these concepts provide new design opportunities for stretchable electronics.