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Table of contents

Volume 28

Number 14, 7 April 2017

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Topical Reviews

142001

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Lipids are a class of biological small molecules with hydrophilic and hydrophobic constituents forming the structural membranes in cells. Over the past century an extensive understanding of lipid biology and biophysics has been developed illuminating lipids as an intricate, highly tunable, and hierarchical soft-matter system. In addition to serving as cell membrane models, lipids have been investigated as microphase separated structures in aqueous solutions. In terms of applications lipids have been realized as powerful structural motifs for the encapsulation and cellular delivery of genetic material. More recently, lipids have also revealed promise as thin film materials, exhibiting long-range periodic nano-scale order and tunable orientation. In this review we summarize the pertinent understanding of lipid nanostructure development in bulk aqueous systems followed by the current and potential perturbations to these results induced by introduction of a substrate. These effects are punctuated by a summary of our published results in the field of lipid thin films with added nucleic acids and key results introducing hard materials into lipid nanostructured substrates.

142002

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During the last three decades, the remarkable dynamic features of microelectromechanical systems (MEMS) and nanoelectromechanical systems (NEMS), and advances in solid-state electronics hold much potential for the fabrication of extremely sensitive charge sensors. These sensors have a broad range of applications, such as those involving the measurement of ionization radiation, detection of bio-analyte and aerosol particles, mass spectrometry, scanning tunneling microscopy, and quantum computation. Designing charge sensors (also known as charge electrometers) for electrometry is deemed significant because of the sensitivity and resolution issues in the range of micro- and nano-scales. This article reviews the development of state-of-the-art micro- and nano-charge sensors, and discusses their technological challenges for practical implementation.

142003

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Focus on Scanning Probe Microscopy

Force microscopy enables a variety of approaches to manipulate and/or modify surfaces. Few of those methods have evolved into advanced probe-based lithographies. Oxidation scanning probe lithography (o-SPL) is the only lithography that enables the direct and resist-less nanoscale patterning of a large variety of materials, from metals to semiconductors; from self-assembled monolayers to biomolecules. Oxidation SPL has also been applied to develop sophisticated electronic and nanomechanical devices such as quantum dots, quantum point contacts, nanowire transistors or mechanical resonators. Here, we review the principles, instrumentation aspects and some device applications of o-SPL. Our focus is to provide a balanced view of the method that introduces the key steps in its evolution, provides some detailed explanations on its fundamentals and presents current trends and applications. To illustrate the capabilities and potential of o-SPL as an alternative lithography we have favored the most recent and updated contributions in nanopatterning and device fabrication.

Focus Issue Paper

144001

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Focus on Inorganic Semiconductor Nanowires for Device Applications

Single crystal rutile titania nanowires grown by solvothermal synthesis are actively being researched for use as electron transporting scaffolds in perovskite solar cells, in low detection limit ultraviolet photodetectors, in photoelectrochemical water-splitting, and in chemiresistive and electrochemical sensing. The electron drift mobility (μn) in solution-grown TiO2 nanowires is very low due to a high density of deep traps, and reduces performance in optoelectronic devices. In this study, the effects of molecular passivation of the nanowire surface by octadecylphosphonic acid (ODPA), on carrier transport in TiO2 nanowire ensembles, were investigated using transient space charge limited current measurements. Infrared spectroscopy indicated the formation of a highly ordered phosphonate monolayer with a high likelihood of bidentate binding of ODPA to the rutile surface. We report the hole drift mobility (μp) for the first time in unpassivated solvothermal rutile nanowires to be 8.2 × 10−5 cm2 V−1 s−1 and the use of ODPA passivation resulted in μp improving by nearly two orders of magnitude to 7.1 × 10−3 cm2 V−1 s−1. Likewise, ODPA passivation produced between a 2 and 3 order of magnitude improvement in μn from ∼10−5–10−6 cm2 V−1 s−1 to ∼10−3 cm2 V−1 s−1. The bias dependence of the post-transit photocurrent decays in ODPA-passivated nanowires indicated that minority carriers were lost to trapping and/or monomolecular recombination for small values of bias (<5 V). Bimolecular recombination was indicated to be the dominant recombination mechanism at higher bias values.

Papers

Biology and medicine

145101

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Long wavelength light-responsive drug delivery systems based on mesoporous silica nanoparticles (MSNs) have attracted much attention in the last few years. In this paper, a red light (660 nm)-responsive drug delivery system based on low-cost cyclodextrin (CD)-gated MSNs containing a photodynamic therapy (PDT) photosensitizer (Chlorin e6, Ce6) was developed for the first time. The drug release experiment in water demonstrated that with the irradiation of red light, Ce6 can be excited to generate singlet oxygen, which can further cleave the singlet oxygen sensitive linker to trigger the departure of CD and the release of cargo. Further in vitro release experiments confirmed that cargo can be released from MSNs with the irradiation of red light and spread into the entire cell. The relative low power density (0.5 W cm−2) of excitation light together with the short irradiation time (one–three min) result in a low light dose (30–90 J cm−2) for the drug delivery, contributing to their potential clinical applications.

Electronics and photonics

145201

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A field-effect phototransistor based on a graphene and lead sulfide quantum dot (PbS QD) hybrid in which PbS QDs are embedded in a graphene matrix has been fabricated with a vertical architecture through a solution process. The n-type Si/SiO2 substrate (gate), Au/Ag nanowire transparent source electrode, active layer and Au drain electrode are vertically stacked in the device, which has a downscaled channel length of 250 nm. Photoinduced electrons in the PbS QDs leap into the conduction band and fill in the trap states, while the photoinduced holes left in the valence band transfer to the graphene and form the photocurrent under biases from which the photoconductive gain is evaluated. The graphene/QD-based vertical phototransistor shows a photoresponsivity of 2 × 103 A W−1, and specific detectivity up to 7 × 1012 Jones under 808 nm laser illumination with a light irradiance of 12 mW cm−2. The solution-processed vertical phototransistor provides a new facile method for optoelectronic device applications.

145202

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Silk protein has been used as a biopolymer substrate for flexible photonic devices. Here, we demonstrate ZnO nanorod array hybrid photodetectors on Au nanoparticle-embedded silk protein for flexible optoelectronics. Hybrid samples exhibit optical absorption at the band edge of ZnO as well as plasmonic energy due to Au nanoparticles, making them attractive for selective UV and visible wavelength detection. The device prepared on Au-silk protein shows a much lower dark current and a higher photo to dark-current ratio of ∼105 as compared to the control sample without Au nanoparticles. The hybrid device also exhibits a higher specific detectivity due to higher responsivity arising from the photo-generated hole trapping by Au nanoparticles. Sharp pulses in the transient photocurrent have been observed in devices prepared on glass and Au-silk protein substrates due to the light induced pyroelectric effect of ZnO, enabling the demonstration of self-powered photodetectors at zero bias. Flexible hybrid detectors have been demonstrated on Au-silk/polyethylene terephthalate substrates, exhibiting characteristics similar to those fabricated on rigid glass substrates. A study of the performance of photodetectors with different bending angles indicates very good mechanical stability of silk protein based flexible devices. This novel concept of ZnO nanorod array photodetectors on a natural silk protein platform provides an opportunity to realize integrated flexible and self-powered bio-photonic devices for medical applications in near future.

145203

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While significant advances have been made for gold nanoparticle (AuNP)-coupled zinc oxide (ZnO) as visibly blind, ultraviolet photodetection devices, very few ZnO nanomaterial systems have been developed specifically for use in the visible wavelength regime. Further efforts to develop ZnO-based visible photodetectors (PDs) are still highly warranted in order to better understand the precise effect of AuNP load, operation wavelength, and beam position on the device output. In this study, we demonstrate significantly enhanced, photoresponse behaviors of AuNP-coupled ZnO nanorod (NR) network devices in the visible wavelength range with their photoresponse capacity comparable to, if not far exceeding, most commercial PDs as well as recently reported, visible, AuNP-coupled ZnO detectors. In addition, the nature and degree of the photoresponsivity enhancement are systematically elucidated by investigating their light-triggered electrical signals under varying incident wavelengths, AuNP amounts, and illumination positions. We discuss a possible photoconduction mechanism of our AuNP-coupled ZnO NR PDs and the origins of the high photoresponsivity. Specifically related to the AuNP amount-dependent photoresponse behaviors, the nanoparticle density yielding photoresponse maxima is explained as the interplay between localized surface plasmon resonance, plasmonic heating, and scattering in our photothermoelectric effect-driven device. We show that the AuNP-coupled ZnO NR PDs can be constructed via a straightforward method without the need for ultrahigh vacuum, sputtering procedures, or photo/electron-beam lithographic tools. Hence, the approach demonstrated in this study may serve as a convenient and viable means to advance the current state of ZnO-based PDs for operation in the visible spectral range with greatly increased photoresponsivity.

Patterning and nanofabrication

145301

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The self-assembly of block copolymers with large feature sizes is inherently challenging as the large kinetic barrier arising from chain entanglement of high molecular weight (MW) polymers limits the extent over which long-range ordered microdomains can be achieved. Here, we illustrate the evolution of thin film morphology from a diblock copolymer of polystyrene-block-poly(dimethylsiloxane) exhibiting total number average MW of 123 kg mol−1, and demonstrate the formation of layers of well-ordered cylindrical microdomains under appropriate conditions of binary solvent mix ratio, commensurate film thickness, and solvent vapor annealing time. Directed self-assembly of the block copolymer within lithographically patterned trenches occurs with alignment of cylinders parallel to the sidewalls. Fabrication of ordered cobalt nanowire arrays by pattern transfer was also implemented, and their magnetic properties and domain wall behavior were characterized.

145302

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Tremendous progress has been made in synthesizing various types of one-dimensional (1D) nanostructures (NSs), such as nanotubes and nanowires, but some technical challenges still remain in the deterministic assembly of the solution-processed 1D NSs for device integration. In this work we investigate a scalable yet inexpensive nanomaterial assembly method, namely filtration-guided assembly (FGA), to place nanomaterials into desired locations as either an individual entity or ensembles, and form functional devices. FGA not only addresses the assembly challenges but also encompasses the notion of green nanomanufacturing, maximally utilizing nanomaterials and eliminating a waste stream of nanomaterials into the environment. FGA utilizes selective filtration of 1D NSs through the open windows on the nanoporous filter membrane whose surface is patterned by a polymer mask for guiding the 1D NS deposition. The modified soft-lithographic technique called blanket transfer (BT) is employed to create the various photoresist patterns of sub-10-micron resolution on the nanoporous filter membrane like mixed cellulose acetate. We use single-walled carbon nanotubes (SWCNTs) as a model 1D NS and demonstrate the fabrication of an array pattern of homogeneous 1D NS network films over an area of 20 cm2 within 10 min. The FGA-patterned SWCNT network films are transferred onto the substrate using the adhesive-based transfer technique, and show the highly uniform film thickness and resistance measurements across the entire substrate. Finally, the electrical performance of the back-gated transistors made from the FGA and transfer method of 95% pure SWCNTs is demonstrated.

Energy at the nanoscale

145401

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Mesoporous amorphous binary Ru–Ti oxides were prepared as bifunctional catalysts for non-aqueous Li–O2 batteries, and their electrochemical performance was investigated for the first time. A Li–O2 battery with mesoporous amorphous binary Ru–Ti oxides exhibited a remarkably high capacity of 27100 mAh g−1 as well as a reduced overpotential. A GITT analysis suggested that the introduction of amorphous TiO2 to amorphous RuO2 was responsible for the enhanced kinetics toward both the oxygen reduction reaction and oxygen evolution reaction. Excellent cyclic stability up to 230 cycles was achieved, confirming the applicability of the new bifunctional catalyst in non-aqueous Li–O2 batteries.

145402

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The main obstacles to building better supercapacitors are still trade-offs between energy and power parameters. To promote commercial supercapacitor behaviors, proper optimization toward electrode configurations/architectures may be a feasible and effective way. We herein propose a smart and reliable electrode engineering protocol, by in situ implantation of carbon nanotubes (CNTs) on total activated carbon (AC) surfaces via a mild chemical vapor deposition process at ∼550 °C, using nickel nitrate hydroxide (NNH) thin films and waste ethanol solvents as the catalyst and carbon sources, respectively. The direct and conformal growth of NNH layers onto carbonaceous scaffold guarantees the later uniform implantation of long and high-quality CNTs on total AC outer surfaces. Such fluffy and entangled CNTs preserve ionic diffusion channels, well connect neighboring ACs and function as superhighways for electrons transfer, endowing electrodes with outstanding capacitive behaviors including large output capacitances of ∼230 F g−1 in 1 M Na2SO4 neutral solution and ∼502.5 F g−1 in 6 M KOH using Ni valence state variation, and very negligible capacity decay in long-term cycles. Furthermore, a full symmetric supercapacitor device of CNTs@ACs//CNTs@ACs has been constructed, capable of delivering both high specific energy and power densities (maximum values reaching up to ∼97.2 Wh kg−1 and ∼10.84 kW kg−1), which holds great potential in competing with current mainstream supercapacitors.

145403

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Uniform carbon wrapped copper telluride nanowires were successfully prepared by using an in situ conversion reaction. The length of these nanowires is up to several micrometers and the width is around 30–40 nm. The unique one dimensional structure and the presence of conformal carbon coating of copper telluride greatly accommodate the large volumetric changes during cycling, significantly increase the electrical conductivity and reduce charge transfer resistance. The copper telluride nanowires show promising performance in a lithium ion battery with a discharge capacity of 130.2 mA h g−1 at a high current density of 6.0 A g−1 (26.74 C) and a stable cycling performance of 673.3 mA h g−1 during the 60th cycle at 100 mA g−1. When evaluated as anode material for a sodium ion battery, the copper telluride nanowires deliver a reversible capacity of 68.1 mA h g−1 at 1.0 A g−1 (∼4.46 C) and have a high capacity retention of 177.5 mA h g−1 during the 500th cycle at 100 mA g−1.

145404

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The electrical transport and thermoelectric property of boron carbide nanowires synthesized by a carbothermal method are reported. It is demonstrated that the nanowires achieve a higher Seebeck coefficient and power factor than those of the bulk samples. The conduction mechanism of the nanowires at low temperatures below 300 K is different from that of the sintered-polycrystalline and single-crystal bulk samples. In a temperature range of 200–450 K, there is a crossover between electrical conduction by variable-range hopping and phonon-assisted hopping. The inhomogeneous carbon concentration and planar defects, such as twins and stacking faults, in the nanowires are thought to modify the bonding nature and electronic structure of the boron carbide crystal substantially, causing differences in the electrical conductivity and Seebeck coefficient. The effect of boundary scattering of phonon at nanostructured surface on the thermal conductivity reduction is discussed.

Sensing and actuating

145501

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Surface plasmon resonance (SPR) biosensing is based on the detection of small changes in the refractive index on a gold surface modified with molecular recognition materials, thus being mostly limited to detecting large molecules. In this paper, we report on a SPR biosensing platform suitable to detect small molecules by making use of the mediator-type enzyme microperoxidase-11 (MP11) in layer-by-layer films. By depositing a top layer of glucose oxidase or uricase, we were able to detect glucose or uric acid with limits of detection of 3.4 and 0.27 μmol l−1, respectively. Measurable SPR signals could be achieved because of the changes in polarizability of MP11, as it is oxidized upon interaction with the analyte. Confirmation of this hypothesis was obtained with finite difference time domain simulations, which also allowed us to discard the possible effects from film roughness changes observed in atomic force microscopy images. The main advantage of this mediator-type enzyme approach is in the simplicity of the experimental method that does not require an external potential, unlike similar approaches for SPR biosensing of small molecules. The detection limits reported here were achieved without optimizing the film architecture, and therefore the performance can in principle be further enhanced, while the proposed SPR platform may be extended to any system where hydrogen peroxide is generated in enzymatic reactions.

Materials: synthesis or self-assembly

145601

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We report on an ultrafast plasma-based graphene oxide reduction method superior to conventional vacuum thermal annealing and/or chemical reduction. The method is based on the effect of non-equilibrium atmospheric-pressure plasma generated by the diffuse coplanar surface barrier discharge in proximity of the graphene oxide layer. As the reduction time is in the order of seconds, the presented method is applicable to the large-scale production of reduced graphene oxide layers. The short reduction times are achieved by the high-volume power density of plasma, which is of the order of 100 W cm−3. Monolayers of graphene oxide on silicon substrate were prepared by a modified Langmuir–Schaefer method and the efficient and rapid reduction by methane and/or hydrogen plasma was demonstrated. The best results were obtained for the graphene oxide reduction in hydrogen plasma, as verified by x-ray photoelectron spectroscopy and Raman spectroscopy.  

145602

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A network structure consisting of nanomaterials with a stable structural support and charge path on a large area is desirable for various electronic and optoelectronic devices. Generally, network structures have been fabricated via two main strategies: (1) assembly of pre-grown nanostructures onto a desired substrate and (2) direct growth of nanomaterials onto a desired substrate. In this study, we utilized the surface defects of graphene to form a nano-network of ZnO via atomic layer deposition (ALD). The surface of pure and structurally perfect graphene is chemically inert. However, various types of point and line defects, including vacancies/adatoms, grain boundaries, and ripples in graphene are generated by growth, chemical or physical treatments. The defective sites enhance the chemical reactivity with foreign atoms. ZnO nanoparticles formed by ALD were predominantly deposited at the line defects and agglomerated with increasing ALD cycles. Due to the formation of the ZnO nano-network, the photocurrent between two electrodes was clearly changed under UV irradiation as a result of the charge transport between ZnO and graphene. The line patterned ZnO/graphene (ZnO/G) nano-network devices exhibit sensitivities greater than ten times those of non-patterned structures. We also confirmed the superior operation of a fabricated flexible photodetector based on the line patterned ZnO/G nano-network.

145603

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Individual carbon nanotubes (CNTs) exhibit exceptional mechanical properties. However, difficulties remain in fully realizing these properties in CNT macro-assemblies, because the weak inter-tube forces result in the CNTs sliding past one another. Herein, a simple solid-state reaction is presented that enhances the mechanical properties of carbon nanotube fibers (CNTFs) through simultaneous covalent functionalization and crosslinking. This is the first chemical crosslinking proposed without the involvement of a catalyst or byproducts. The specific tensile strength of CNTFs obtained from the treatment employing a benzocyclobutene-based polymer is improved by 40%. Such improvement can be attributed to a reduced number of voids, impregnation of the polymer, and the formation of covalent crosslinks. This methodology is confirmed using both multiwalled nanotube (MWNT) powders and CNTFs. Thermogravimetric analysis, differential scanning calorimetry, x-ray photoelectron spectroscopy, and transmission electron microscopy of the treated MWNT powders confirm the covalent functionalization and formation of inter-tube crosslinks. This simple one-step reaction can be applied to industrial-scale production of high-strength CNTFs.

Materials: properties, characterization or tools

145701

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We design an efficient optically controlled microdevice based on CdSe nanoplates. Two-dimensional CdSe nanoplates exhibit lighting patterns around the edges and can be realized as a new type of optically controlled programmable encoder. The light source is used to excite the nanoplates and control the logical position under vertical pumping mode by the objective lens. At each excitation point in the nanoplates, the preferred light-propagation routes are along the normal direction and perpendicular to the edges, which then emit out from the edges to form a localized lighting section. The intensity distribution around the edges of different nanoplates demonstrates that the lighting part with a small scale is much stronger, defined as '1', than the dark section, defined as '0', along the edge. These '0' and '1' are the basic logic elements needed to compose logically functional devices. The observed propagation rules are consistent with theoretical simulations, meaning that the guided-light route in two-dimensional semiconductor nanoplates is regular and predictable. The same situation was also observed in regular CdS nanoplates. Basic theoretical analysis and experiments prove that the guided light and exit position follow rules mainly originating from the shape rather than material itself.

145702

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We investigated the current–voltage and noise characteristics of two-dimensional (2D) monolayer molybdenum disulfide (MoS2) synthesized by chemical vapor deposition (CVD). A large number of trap states were produced during the CVD process of synthesizing MoS2, resulting in a disordered monolayer MoS2 system. The interface trap density between CVD-grown MoS2 and silicon dioxide was extracted from the McWhorter surface noise model. Notably, generation–recombination noise which is attributed to charge trap states was observed at the low carrier density regime. The relation between the temperature and resistance following the power law of a 2D inverted-random void model supports the idea that disordered CVD-grown monolayer MoS2 can be analyzed using a percolation theory. This study can offer a viewpoint to interpret synthesized low-dimensional materials as highly disordered systems.

145703

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The performance of heterogeneous 3D transistor structures critically depends on the composition and strain state of the buffer, channel and source/drain regions. In this paper we used an in-line high resolution x-ray diffraction (HRXRD) tool to study in detail the composition and strain in selectively grown SiGe/Ge fin structures with widths down to 20 nm. For this purpose we arranged fins of identical dimensions into larger arrays which were then analyzed using an x-ray beam several tens of micrometers in size. Asymmetric reciprocal space maps measured both parallel and perpendicular to the fins allowed us to extract the lattice parameters in all three spatial directions. Our results demonstrate an anisotropic in-plane strain state of the selectively grown SiGe buffer in case of narrower fins with significantly reduced relaxation in the direction along the fin. This observation was verified using nano-beam electron diffraction, and is explained based on the reduced probability for dislocation half-loops to evolve in trenches narrower than a few times the critical radius. Moreover, we introduce and discuss in detail a methodology for the determination of the composition in case of an anisotropic in-plane strain state which differs from the procedure commonly used for blanket layers. Our findings verify the importance of in-line HRXRD measurements for process development and monitoring as well as the fundamental study of relaxation and defect formation in confined volumes.

145704

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This article reports the characterization of WTe2 thin flake magnetoresistance and Hall resistivity. We found it does not exhibit magnetoresistance saturation when subject to high fields, in a manner similar to their bulk characteristics. The linearity of Hall resistivity in our devices confirms the compensation of electrons and holes. By relating experimental results to a classic two-band model, the lower magnetoresistance values in our samples is demonstrated to be caused by decreased carrier mobility. The dependence of mobility on temperature indicates the main role of optical phonon scattering at high temperatures. Our results provide more detailed information on carrier behavior and scattering mechanisms in WTe2 thin films.

145705

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We report the successful formation of an immutable array of α-PbO2 phase TiO2 nanotubes by compression of a TiO2 nanotube array in an anatase phase. During compression to 31.3 GPa, the TiO2 nanotubes started to directly transform from an anatase phase to a baddeleyite phase at 14.5 GPa and completed the transition at 30.1 GPa. Under decompression, the baddeleyite phase transformed to an α-PbO2 phase at 4.6 GPa, which was quenchable to ambient pressure. Notably the tubular array microstructure was retained after the application of ultra high pressure and undergoing a series of phase transformations. Measurements indicated that the nanotubes in the array possessed higher compressibility than in the bulk form. The highly aligned array structure is believed to reinforce the nanotubes themselves, giving exceptional stability. This, as well as the wall thickness, may also account for their different phase transition pathway.

145706

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We explored the transfer of a single-layered graphene membrane assisted by substrate adhesion. A relatively larger adhesion force was measured on the SiO2 substrate compared with its van der Waals contribution, which is expected to result from the additional contribution of the chemical bonding force. Density functional theory calculations verified that the strong adhesion force was indeed accompanied by chemical bonding. The transfer of single-layered graphene and subsequent deposition of the dielectric layer were best performed on the SiO2 substrate exhibiting a larger adhesion force. This study suggests the selection and/or modification of the underlying substrate for proper transfer of graphene as well as other 2D materials similar to graphene.