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Abstract: A method for small-scale testing and imaging of freestanding, microtomed polymer films using a push-to-pull device is presented. Central to this method was the development of a sample preparation technique which utilized solvents at cryogenic temperatures to transfer and deposit delicate thin films onto the microfabricated push-to-pull devices. The preparation of focused ion beam (FIB)-milled tensile specimens enabled quantitative in situ TEM tensile testing, but artifacts associated with ion and electron beam irradiation motivated the development of a FIB-free specimen preparation method. The FIB-free method was enabled by the design and fabrication of oversized strain-locking push-to-pull devices. An adaptation for push-to-pull devices to be compatible with an instrumented nanoindenter expanded the testing capabilities to include in situ heating. These innovations provided quantitative mechanical testing, postmortem TEM imaging, and the ability to measure the glass transition temperature, via dynamic mechanical analysis, of freestanding polymer films. Results for each of these mentioned characterization methods are presented and discussed in terms of polymer nanomechanics. Graphic Abstract: [Figure not available: see fulltext.]

At temperatures higher than 341 K, vanadium dioxide (VO2) is a strongly correlated metal with resistivity exceeding the Mott-Ioffe-Regel limit. Its electronic thermal conductivity is lower than that predicted by the Wiedemann-Franz (WF) law, and can be explained by nonquasiparticle transport where heat and charge currents follow separate diffusive modes. In contradiction, the Wiedemann-Franz law is a direct consequence of quasiparticle transport where charge carriers are elastically scattered. In this work, we enhance elastic electron scattering in VO2 by introducing atomic disorder with ion irradiation. A gradual and eventually full recovery of the WF law is observed at high defect densities. This observation provides an example that connects hydrodynamic quasiparticle transport to nonquasiparticle transport in metallic systems.

Helium-ion-induced swelling and blistering of single-crystal tungsten is investigated using a Helium Ion Microscope for site-specific dose-controlled irradiation (at 25 keV) with analysis by Helium Ion Microscopy, Atomic Force Microscopy and Transmission Electron Microscopy (cross-sectioning by Focused Ion Beam milling). We show that the blister cavity forms at a depth close to the simulated helium peak and that nanobubbles coalesce to form nanocracks within the envelope of the ion stopping range, swelling the blister shell. These results provide the first direct experimental evidence for the interbubble fracture mechanism proposed in the framework of the gas pressure model for blister formation.

Electric-field switching of polarization is the building block of a wide variety of ferroelectric devices. In turn, understanding the factors affecting ferroelectric switching and developing routes to control it are of great technological significance. This work provides systematic experimental evidence of the role of defects in affecting ferroelectric-polarization switching and utilizes the ability to deterministically create and spatially locate point defects in PbZr0.2Ti0.8O3 thin films via focused-helium-ion bombardment and the subsequent defect-polarization coupling as a knob for on-demand control of ferroelectric switching (e.g., coercivity and imprint). At intermediate ion doses (0.22-2.2×1014ionscm-2), the dominant defects (isolated point defects and small clusters) show a weak interaction with domain walls (pinning potentials from 200-500KMVcm-1), resulting in small and symmetric changes in the coercive field. At high doses (0.22-1×1015ionscm-2), on the other hand, the dominant defects (larger defect complexes and clusters) strongly pin domain-wall motion (pinning potentials from 500 to 1600KMVcm-1), resulting in a large increase in the coercivity and imprint, and a reduction in the polarization. This local control of ferroelectric switching provides a route to produce novel functions; namely, tunable multiple polarization states, rewritable pre-determined 180° domain patterns, and multiple zero-field piezoresponse and permittivity states. Such an approach opens up pathways to achieve multilevel data storage and logic, nonvolatile self-sensing shape-memory devices, and nonvolatile ferroelectric field-effect transistors.

Plasmonic nanoantennas are pushing the limits of optical imaging resolution capabilities in near-field scanning optical microscopy (NSOM). Accordingly, these techniques are driving the basic understanding of photonic and optoelectronic nanoscale devices with applications in sensing, energy conversion, solid-state lighting, and information technology. Imaging the localized surface plasmon resonance (LSPR) at the nanoscale is a key to understanding the optical responses of a given tip geometry in order to engineer better plasmonic nanoantennas for near-field experiments. In recent years the advancement of focused ion beam technology provides the ability to directly modify plasmonic structures with nanometer resolution. Also, scanning transmission electron microscopy (STEM) with electron energy loss spectroscopy (EELS) is an established technique allowing imaging of LSPR. Specifically, the combination of these two techniques provides spectrally sensitive two-dimensional (2D) image information to better visualize and understand LSPR on the nanometer scale. This can be combined with electron tomography to provide the three-dimensional LSPR distribution. Here we demonstrate the fabrication of Au nanopyramids using helium ion microscopy, and analyze the LSPR in 3D reconstructions produced by total variation (TV)-norm minimization of a set of 2D STEM-EELS maps. Additionally, a boundary element simulation method was used to verify the experimentally observed nanopyramid LSPR modes. Finally, we show that the point-spread-functions (PSF) of LSPR mode hot spots in nanopyramids differ to local electric-field enhancement under optical excitation making direct comparison to NSOM experimental resolution difficult. However, the STEM-EELS results show how LSPR modes are influenced by the tip characteristics, which can inform the development of new nanoantenna designs.

Helium implantation can cause the formation of a helium gas-bubble superlattice in crystalline materials. Experimental studies of the mechanical response of a material hosting such a superlattice are lacking, especially at the microstructural level. By employing a novel, high-throughput, high-precision nanoscale helium implantation technique, in combination with in-situ transmission electron microscopy nanomechanical testing, we find that the helium-bubble superlattice structure in copper is disordered or maintained depending on whether the material's plasticity occurs by multiple ordinary full dislocations or by deformation twinning. In addition, helium implantation can harden the material significantly: the higher the dose, the larger the yield stress. The measured hardening behavior agrees well with the trend predicted by the Friedel-Kroupa-Hirsch model. Our findings shed new light on understanding the mechanical and microstructural properties of materials subjected to intense helium generation by neutron and alpha-particle bombardment in nuclear fusion, fission or spallation systems.

The spin-transfer torque magnetic tunneling junction (MTJ) technology may pave a way to a universal memory paradigm. MTJ devices with perpendicular magnetic anisotropy have the potential to have high thermal stability, high tunneling magnetoresistance, and low critical current for energy-efficient current-induced magnetization switching. Using devices fabricated through focused ion beam etching with Ga-and Ne-ion beams, this paper aimed to understand the size dependence of the current/voltage characteristics in the sub-10 nm range. The switching current density drastically dropped around 1 MA/cm2 as the device size was reduced below 10 nm. A stability of over 22 kT measured for a 5 nm device indicated a significantly reduced spin relaxation time.

Improving the performance of organic electronic devices depends on exploiting the complex nanostructures formed in the active layer. Current imaging methods based on transmission electron microscopy provide limited chemical sensitivity, and thus the application to materials with compositionally similar phases or complicated multicomponent systems is challenging. Here, it is demonstrated that monochromated transmission electron microscopes can generate contrast in organic thin films based on differences in the valence electronic structure at energy losses below 10 eV. In this energy range, electronic fingerprints corresponding to interband excitations in organic semiconductors can be utilized to generate significant spectral contrast between phases. Based on differences in chemical bonding of organic materials, high-contrast images are thus obtained revealing the phase separation in polymer/fullerene mixtures. By applying principal component analysis to the spectroscopic image series, further details about phase compositions and local electronic transitions in the active layer of organic semiconductor mixtures can be explored. Monochromated transmission electron microscopes can generate contrast in organic thin films based on differences in the valence electronic structure at energy losses below 10 eV. By applying principal component analysis to the spectroscopic image series, further details about phase compositions and local electronic transitions in the active layer of organic semiconductor mixtures can be explored.

Abstract Objectives Obstructive sleep apnea (OSA) has an impact on an individual's quality of life and general health, and can also affect their oral health. The patient's experiences, together with intraoral signs and symptoms could indicate the presence of OSA. Knowledge that the patient has, or is at high risk for having OSA can help the dental healthcare provider maintain the oral health and general health for these patients. The purpose was to explore dentists and dental hygienists' experiences when encountering adult patients with potential, untreated and treated OSA. Methods A qualitative inductive approach was used. Experienced dentists and dental hygienists working within Swedish Public Dental Service were strategically selected. Semi‐structured face‐to‐face interviews were performed followed by qualitative content analysis. Results Interviews from 13 participants, seven dental hygienist and six dentists, led to three areas describing varied experience: Importance of the patient encounter and identifying intraoral signs both of which describe experiences related to the importance of the initial unstructured conversation and focused clinical assessments, and strategies for nurturing care which point to interest about care, treatment, and collaborations with medical health care providers. Conclusions Dental professionals are not able to consistently recognize patients who have, or are at high risk for OSA. During the patient encounter, is it important to determine if a patient is at risk for, or has oral signs of OSA.

Objective. The purpose of this study was to explore the research on the delivery and evaluation of pediatric health services by non-governmental organizations in low-and middle-income countries to better understand how they contribute to positive and sustainable health outcomes. Methods. A scoping review was completed using a 2-step study selection procedure. Results. Of the 5742 studies, 17 met criteria, including quantitative and mixed method designs, representing 10 different non-governmental organizations with programs in 33 low-and middle-income countries. Health outcomes were reported 89 times across the studies. A total of 56 different outcomes were identified in total, of which 24 were positive, 27 were negative, and 5 were unchanged. Conclusions. Widespread variation between non-governmental organizations exist, however, comprehensive pediatric health outcome evaluation is growing. Further emphasis should be given to adolescent specific research and robust measurement of quality of life.

Nanotube porins form transmembrane nanomaterial-derived scaffolds that mimic the geometry and functionality of biological membrane channels. We report synthesis, transport properties, and osmotic energy harvesting performance of another member of the nanotube porin family: boron nitride nanotube porins (BNNTPs). Cryo-transmission electron microscopy imaging, liposome transport assays, and DNA translocation experiments show that BNNTPs reconstitute into lipid membranes to form functional channels of ~2-nm diameter. Ion transport studies reveal ion conductance characteristics of individual BNNTPs, which show an unusual C 1/4 scaling with ion concentration and pronounced pH sensitivity. Reversal potential measurements indicate that BNNTPs have strong cation selectivity at neutral pH, attributable to the high negative charge on the channel. BNNTPs also deliver very large power density up to 12 kW/m 2 in the osmotic gradient transport experiments at neutral pH, surpassing that of other BNNT-based devices by two orders of magnitude under similar conditions. Our results suggest that BNNTPs are a promising platform for mass transport and osmotic power generation.

The controlled creation and manipulation of defects in 2D materials has become increasingly popular as a means to design and tune new material functionalities. However, defect characterization by direct atomic-scale imaging is often severely limited by surface contamination due to a blanket of hydrocarbons. Thus, analysis techniques that can characterize atomic-scale defects despite the contamination layer are advantageous. In this work, we take inspiration from X-ray absorption spectroscopy and use broad-beam electron energy loss spectroscopy (EELS) to characterize defect structures in 2D hexagonal boron nitride (hBN) based on averaged fine structure in the boron K-edge. Since EELS is performed in a transmission electron microscope (TEM), imaging can be performed in-situ to assess contamination levels and other factors such as tears in the fragile 2D sheets, which can affect the spectroscopic analysis. We demonstrate the TEM-EELS technique for 2D hBN samples irradiated with different ion types and doses, finding spectral signatures indicative of boron-oxygen bonding that can be used as a measure of sample defectiveness depending on the ion beam treatment. We propose that even in cases where surface contamination has been mitigated, the averaging-based TEM-EELS technique can be useful for efficient sample surveys to support atomically resolved EELS experiments., Competing Interests: Conflict of Interest: The authors declare that they have no competing interest., (© The Author(s) 2024. Published by Oxford University Press on behalf of the Microscopy Society of America. All rights reserved. For commercial re-use, please contact reprints@oup.com for reprints and translation rights for reprints. All other permissions can be obtained through our RightsLink service via the Permissions link on the article page on our site—for further information please contact journals.permissions@oup.com.)

We demonstrate the fabrication of sharp nanopillars of high aspect ratio onto specialized atomic force microscopy (AFM) microcantilevers and their use for high-speed AFM of DNA and nucleoproteins in liquid. The fabrication technique uses localized charged-particle-induced deposition with either a focused beam of helium ions or electrons in a helium ion microscope (HIM) or scanning electron microscope (SEM). This approach enables customized growth onto delicate substrates with nanometer-scale placement precision and in situ imaging of the final tip structures using the HIM or SEM. Tip radii of <10 nm are obtained and the underlying microcantilever remains intact. Instead of the more commonly used organic precursors employed for bio-AFM applications, we use an organometallic precursor (tungsten hexacarbonyl) resulting in tungsten-containing tips. Transmission electron microscopy reveals a thin layer of carbon on the tips. The interaction of the new tips with biological specimens is therefore likely very similar to that of standard carbonaceous tips, with the added benefit of robustness. A further advantage of the organometallic tips is that compared to carbonaceous tips they better withstand UV-ozone cleaning treatments to remove residual organic contaminants between experiments, which are inevitable during the scanning of soft biomolecules in liquid. Our tips can also be grown onto the blunted tips of previously used cantilevers, thus providing a means to recycle specialized cantilevers and restore their performance to the original manufacturer specifications. Finally, a focused helium ion beam milling technique to reduce the tip radii and thus further improve lateral spatial resolution in the AFM scans is demonstrated.

We demonstrate a new focused ion beam sample preparation method for atom probe tomography. The key aspect of the new method is that we use a neon ion beam for the final tip-shaping after conventional annulus milling using gallium ions. This dual-ion approach combines the benefits of the faster milling capability of the higher current gallium ion beam with the chemically inert and higher precision milling capability of the noble gas neon ion beam. Using a titanium-aluminum alloy and a layered aluminum/aluminum-oxide tunnel junction sample as test cases, we show that atom probe tips prepared using the combined gallium and neon ion approach are free from the gallium contamination that typically frustrates composition analysis of these materials due to implantation, diffusion, and embrittlement effects. We propose that by using a focused ion beam from a noble gas species, such as the neon ions demonstrated here, atom probe tomography can be more reliably performed on a larger range of materials than is currently possible using conventional techniques., Competing Interests: Conflict of Interest At the time of this research, two of the authors (J.A.N., D.X.) were employed by Carl Zeiss, Inc., which manufactures the ORION NanoFab product used in this research., (© The Author(s) 2023. Published by Oxford University Press on behalf of the Microscopy Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

In a first-order phase transition, critical nucleus size governs nucleation kinetics, but the direct experimental test of the theory and determination of the critical nucleation size have been achieved only recently in the case of ice formation in supercooled water. The widely known metal-insulator phase transition (MIT) in strongly correlated VO&#95;{2} is a first-order electronic phase transition coupled with a solid-solid structural transformation. It is unclear whether classical nucleation theory applies in such a complex case. In this Letter, we directly measure the critical nucleus size of the MIT by introducing size-controlled nanoscale nucleation seeds with focused ion irradiation at the surface of a deeply supercooled metal phase of VO&#95;{2}. The results compare favorably with classical nucleation theory and are further explained by phase-field modeling. This Letter validates the application of classical nucleation theory as a parametrizable model to describe phase transitions of strongly correlated electron materials.

High-throughput grain mapping with sub-nanometer spatial resolution is demonstrated using scanning nanobeam electron diffraction (also known as 4D scanning transmission electron microscopy, or 4D-STEM) combined with high-speed direct-electron detection. An electron probe size down to 0.5 nm in diameter is used and the sample investigated is a gold–palladium nanoparticle catalyst. Computational analysis of the 4D-STEM data sets is performed using a disk registration algorithm to identify the diffraction peaks followed by feature learning to map the individual grains. Two unsupervised feature learning techniques are compared: principal component analysis (PCA) and non-negative matrix factorization (NNMF). The characteristics of the PCA versus NNMF output are compared and the potential of the 4D-STEM approach for statistical analysis of grain orientations at high spatial resolution is discussed.

The helium ion microscope has emerged as a multifaceted instrument enabling a broad range of applications beyond imaging in which the finely focused helium ion beam is used for a variety of defect engineering, ion implantation, and nanofabrication tasks. Operation of the ion source with neon has extended the reach of this technology even further. This paper reviews the materials modification research that has been enabled by the helium ion microscope since its commercialization in 2007, ranging from fundamental studies of beam-sample effects, to the prototyping of new devices with features in the sub-10 nm domain., (Copyright © 2021, Allen.)

Defective graphene holds great potential to enable the permeation of gas molecules at high rates with high selectivity due to its one-atom thickness and resultant atomically small pores at the defect sites. However, precise control and tuning of the size and density of the defects remain challenging. In this work, we introduce atomic-scale defects into bilayer graphene via a decoupled strategy of defect nucleation using helium ion irradiation followed by defect expansion using hydrogen plasma treatment. The cotreated membranes exhibit high permeability and simultaneously high selectivity compared to those singly treated by ion irradiation or hydrogen plasma only. High permeation selectivity values for H 2 /N 2 and H 2 /CH 4 of 495 and 877, respectively, are achieved for optimally cotreated membranes. The method presented can also be scaled up to prepare large-area membranes for gas separation, e.g. , for hydrogen purification and recovery from H 2 /CH 4 and H 2 /N 2 mixtures.

Helium ion beam induced deposition using the gaseous precursor pentamethylcyclopentasiloxane is employed to fabricate high aspect ratio insulator nanostructures (nanopillars and nanocylinders) that exhibit charge induced branching. The branched nanostructures are analyzed by transmission electron microscopy. It is found that the side branches form above a certain threshold height and that by increasing the flow rate of the precursor, the vertical growth rate and branching phenomenon can be significantly enhanced, with fractalesque branching patterns observed. The direct-write ion beam nanofabrication technique described herein offers a fast single-step method for the growth of high aspect ratio branched nanostructures with site-selective placement on the nanometer scale.

In diverse organisms, nanostructures that coherently scatter light create structural color, but how such structures are built remains mysterious. We investigate the evolution and genetic regulation of butterfly scale laminae, which are simple photonic nanostructures. In a lineage of buckeye butterflies artificially selected for blue wing color, we found that thickened laminae caused a color shift from brown to blue. Deletion of the optix patterning gene also altered color via lamina thickening, revealing shared regulation of pigments and lamina thickness. Finally, we show how lamina thickness variation contributes to the color diversity that distinguishes sexes and species throughout the genus Junonia . Thus, quantitatively tuning one dimension of scale architecture facilitates both the microevolution and macroevolution of a broad spectrum of hues. Because the lamina is an intrinsic component of typical butterfly scales, our findings suggest that tuning lamina thickness is an available mechanism to create structural color across the Lepidoptera., Competing Interests: RT, FA, NP No competing interests declared, (© 2020, Thayer et al.)

Considerable advances in manipulating heat flow in solids have been made through the innovation of artificial thermal structures such as thermal diodes, camouflages, and cloaks. Such thermal devices can be readily constructed only at the macroscale by mechanically assembling different materials with distinct values of thermal conductivity. Here, we extend these concepts to the microscale by demonstrating a monolithic material structure on which nearly arbitrary microscale thermal metamaterial patterns can be written and programmed. It is based on a single, suspended silicon membrane whose thermal conductivity is locally, continuously, and reversibly engineered over a wide range (between 2 and 65 W/m·K) and with fine spatial resolution (10-100 nm) by focused ion irradiation. Our thermal cloak demonstration shows how ion-write microthermotics can be used as a lithography-free platform to create thermal metamaterials that control heat flow at the microscale.

Focused ion beam milling of ∼200 nm polymer thin films is investigated using a multibeam ion microscope equipped with a gallium liquid metal ion source and a helium/neon gas field-ionization source. The quality of gallium, neon, and helium ion milled edges in terms of ion implantation artifacts is analyzed using a combination of helium ion microscopy, transmission electron microscopy and light microscopy. Results for a synthetic polymer thin film, in the form of cryo-ultramicrotomed sections from a co-extruded polymer multilayer, and a biological polymer thin film, in the form of the base layer of a butterfly wing scale, are presented. While gallium and neon ion milling result in the implantation of ions up to tens of nanometers from the milled edge and local thinning near the edge, helium ion milling produces much sharper edges with dramatically reduced implantation. These effects can be understood in terms of the minimal lateral scatter and larger stopping distance of helium compared with the heavier ions, whereby due to the thin film geometry, most of the incident helium ions will pass straight through the material. The basic result demonstrated here for polymer thin films is also expected for thin films of hard materials such as metals and ceramics.

Nephrocalcinosis often begins on a calcium phosphate deposit, at the tip of the medullo-papillary complex (MPC) known as Randall's plaque (RP). Contextualizing proximally observed biominerals within the MPC has led us to postulate a mechanobiological switch that can trigger interstitial biomineralization at the MPC tip, remote from the intratubular biominerals. Micro X-ray computed tomography scans of human MPCs correlated with transmission and scanning electron micrographs, and X-ray energy dispersive spectrometry demonstrated novel findings about anatomically-specific biominerals. An abundance of proximal intratubular biominerals were associated with emergence of distal interstitial RP. The fundamental architecture of the MPC and mineral densities at the proximal and distal locations of the MPC differed markedly. A predominance of plate-like minerals or radially oriented plate-like crystallites within spheroidal minerals in the proximal intratubular locations, and core-shell type crystallites within spheroidal minerals in distal interstitial locations were observed. Based on the MPC anatomic location of structure-specific biominerals, a biological switch within the mineral-free zone occurring between the proximal and distal locations is postulated. The "on" and "off" switch is dependent on changes in the pressure differential resulting from changes in tubule diameters; the "Venturi effect" changes the "circumferential strain" and culminates in interstitial crystal deposits in the distal tubule wall in response to proximal tubular obstruction. These distal interstitial mineralizations can emerge into the collecting system of the kidney linking nephrocalcinosis with nephrolithiasis.

We present a modular assembly that enables both in situ Raman spectroscopy and laser-based materials processing to be performed in a transmission electron microscope. The system comprises a lensed Raman probe mounted inside the microscope column in the specimen plane and a custom specimen holder with a vacuum feedthrough for a tapered optical fiber. The Raman probe incorporates both excitation and collection optics, and localized laser processing is performed using pulsed laser light delivered to the specimen via the tapered optical fiber. Precise positioning of the fiber is achieved using a nanomanipulation stage in combination with simultaneous electron-beam imaging of the tip-to-sample distance. Materials modification is monitored in real time by transmission electron microscopy. First results obtained using the assembly are presented for in situ pulsed laser ablation of MoS 2 combined with Raman spectroscopy, complimented by electron-beam diffraction and electron energy-loss spectroscopy., (Copyright © 2016 Elsevier B.V. All rights reserved.)

One of the major challenges to the widespread adoption of plasmonic and nano-optical devices in real-life applications is the difficulty to mass-fabricate nano-optical antennas in parallel and reproducible fashion, and the capability to precisely place nanoantennas into devices with nanometer-scale precision. In this study, we present a solution to this challenge using the state-of-the-art ultraviolet nanoimprint lithography (UV-NIL) to fabricate functional optical transformers onto the core of an optical fiber in a single step, mimicking the 'campanile' near-field probes. Imprinted probes were fabricated using a custom-built imprinter tool with co-axial alignment capability with sub <100 nm position accuracy, followed by a metallization step. Scanning electron micrographs confirm high imprint fidelity and precision with a thin residual layer to facilitate efficient optical coupling between the fiber and the imprinted optical transformer. The imprinted optical transformer probe was used in an actual NSOM measurement performing hyperspectral photoluminescence mapping of standard fluorescent beads. The calibration scans confirmed that imprinted probes enable sub-diffraction limited imaging with a spatial resolution consistent with the gap size. This novel nano-fabrication approach promises a low-cost, high-throughput, and reproducible manufacturing of advanced nano-optical devices.

Gallium-based focused ion beams generated from liquid-metal sources are widely used in micromachining and sample preparation for transmission electron microscopy, with well-known drawbacks such as sample damage and contamination. In this work, an alternative (neon) focused ion beam generated by a gas field-ionization source is evaluated for the preparation of electron-transparent specimens. To do so, electron-transparent sections of Si and an Al alloy are prepared with both Ga and Ne ion beams for direct comparison. Diffraction-contrast imaging and energy dispersive x-ray spectroscopy are used to evaluate the relative damage induced by the two beams, and cross-sections of milled trenches are examined to compare the implantation depth with theoretical predictions from Monte Carlo simulations. Our results show that for the beam voltages and materials systems investigated, Ne ion beam milling does not significantly reduce the focused ion beam induced artefacts. However, the Ne ion beam does enable more precise milling and may be of interest in cases where Ga contamination cannot be tolerated., (Published 2016. This article is a U.S. Government work and is in the public domain in the USA.)

Integration of complex photonic structures onto optical fiber facets enables powerful platforms with unprecedented optical functionalities. Conventional nanofabrication technologies, however, do not permit viable integration of complex photonic devices onto optical fibers owing to their low throughput and high cost. In this paper we report the fabrication of a three-dimensional structure achieved by direct nanoimprint lithography on the facet of an optical fiber. Nanoimprint processes and tools were specifically developed to enable a high lithographic accuracy and coaxial alignment of the optical device with respect to the fiber core. To demonstrate the capability of this new approach, a 3D beam splitter has been designed, imprinted and optically characterized. Scanning electron microscopy and optical measurements confirmed the good lithographic capabilities of the proposed approach as well as the desired optical performance of the imprinted structure. The inexpensive solution presented here should enable advancements in areas such as integrated optics and sensing, achieving enhanced portability and versatility of fiber optic components.

In this Letter, we present a Fresnel lens fabricated on the end of an optical fiber. The lens is fabricated using nanoimprint lithography of a functional high refractive index material, which is suitable for mass production. The main advantage of the presented Fresnel lens compared to a conventional fiber lens is its high refractive index (n=1.68), which enables efficient light focusing even inside other media, such as water or an adhesive. Measurement of the lens performance in an immersion liquid (n=1.51) shows a near diffraction limited focal spot of 810 nm in diameter at the 1/e 2 intensity level for a wavelength of 660 nm. Applications of such fiber lenses include integrated optics, optical trapping, and fiber probes.

Proton transport plays an important role in many biological processes due to the ability of protons to rapidly translocate along chains of hydrogen-bonded water molecules. Molecular dynamics simulations have predicted that confinement in hydrophobic nanochannels should enhance the rate of proton transport. Here, we show that 0.8-nm-diameter carbon nanotube porins, which promote the formation of one-dimensional water wires, can support proton transport rates exceeding those of bulk water by an order of magnitude. The transport rates in these narrow nanotube pores also exceed those of biological channels and Nafion. With larger 1.5-nm-diameter nanotube porins, proton transport rates comparable to bulk water are observed. We also show that the proton conductance of these channels can be modulated by the presence of Ca(2+) ions. Our results illustrate the potential of small-diameter carbon nanotube porins as a proton conductor material and suggest that strong spatial confinement is a key factor in enabling efficient proton transport.

Nafion is an ion-containing random copolymer used as a solid electrolyte in many electrochemical applications thanks to its remarkable ionic conductivity and mechanical stability. Understanding the mechanism of ion transport in Nafion, which depends strongly on hydration, therefore requires a complete picture of its morphology in dry and hydrated form. Here we report on a nanoscale study of dry versus hydrated as-cast 100 nm Nafion membranes using analytical transmission electron microscopy (TEM) and cryogenic TEM tomography, respectively. For the dry membrane, spherical clusters ∼3.5 nm in diameter corresponding to the hydrophilic sulfonic-acid-containing phase are identified. In contrast, cryo TEM tomography of the hydrated membrane reveals an interconnected channel-type network, with a domain spacing of ∼5 nm, and presents the first nanoscale 3D views of the internal structure of hydrated Nafion obtained by a direct-imaging approach.

There is much interest in developing synthetic analogues of biological membrane channels with high efficiency and exquisite selectivity for transporting ions and molecules. Bottom-up and top-down methods can produce nanopores of a size comparable to that of endogenous protein channels, but replicating their affinity and transport properties remains challenging. In principle, carbon nanotubes (CNTs) should be an ideal membrane channel platform: they exhibit excellent transport properties and their narrow hydrophobic inner pores mimic structural motifs typical of biological channels. Moreover, simulations predict that CNTs with a length comparable to the thickness of a lipid bilayer membrane can self-insert into the membrane. Functionalized CNTs have indeed been found to penetrate lipid membranes and cell walls, and short tubes have been forced into membranes to create sensors, yet membrane transport applications of short CNTs remain underexplored. Here we show that short CNTs spontaneously insert into lipid bilayers and live cell membranes to form channels that exhibit a unitary conductance of 70-100 picosiemens under physiological conditions. Despite their structural simplicity, these 'CNT porins' transport water, protons, small ions and DNA, stochastically switch between metastable conductance substates, and display characteristic macromolecule-induced ionic current blockades. We also show that local channel and membrane charges can control the conductance and ion selectivity of the CNT porins, thereby establishing these nanopores as a promising biomimetic platform for developing cell interfaces, studying transport in biological channels, and creating stochastic sensors.

In this study, a hierarchical TiO2 nanostructure with densely-packed and omnidirectional branches grown by a hydrothermal method is introduced. This morphology is achieved via high-concentration TiCl4 treatment of upright backbone nanowires (NWs) followed by hydrothermal growth. Secondary nanobranches grow in all directions from densely distributed, needle-like seeds on the jagged round surface of the backbone NWs. In addition, hierarchical, flower-like branches grow on the top surface of each NW, greatly increasing the surface area. For dye-sensitized solar cell (DSSC) applications, the TiO2 nanostructure demonstrated a photoconversion efficiency of up to 6.2%. A parametric study of the DSSC efficiency showed that branched TiO2 DSSCs can achieve nearly four times the efficiency of non-branched TiO2 nanowire DSSCs, and up to 170% the efficiency of previously-reported sparsely-branched TiO2 NW DSSCs.

Block copolymer thin films with distinct morphologies are prepared by spin casting a nominally lamellar assay of poly(styrene-block-ethylene oxide) from a variety of solvents with and without salt doping. The 3-D morphologies of free-standing thin-film regions, which are obtained by casting directly onto holey substrates, are investigated in detail using various energy-filtering transmission electron microscopy techniques and by electron tomography. Surface characterization is achieved by atomic force microscopy. Our results demonstrate that in order to fully characterize the unique 3-D morphologies of the block copolymer thin films, a multi-method approach is required. When casting from a binary solvent, an unexpected layered honeycomb-type morphology is revealed, which likely results from an expansion of the poly(ethylene oxide) phase. A dramatic effect of selective cation coordination on the morphology of the as-cast block copolymer films is also directly observed., (Published by Elsevier Ltd.)

Energy-filtered transmission electron microscopy spectrum-imaging (EFTEM SI) in the low electron energy-loss range is a valuable technique for probing the chemical structure of a material with nanoscale spatial resolution using a reduced electron dose. By analyzing EFTEM SI datasets using principal component analysis (PCA), the constituent chemical phases of the material can be identified in an efficient manner without prior knowledge of the specimen. We implement low-loss EFTEM SI together with PCA to investigate thin films of the block copolymer electrolyte poly(styrene-block-ethylene oxide) (PS-b-PEO) blended with a sodium salt. PCA identifies three main phases, the first and second phases corresponding to the two blocks of the copolymer and a third phase corresponding to the salt. The low-loss spectra for these phases are extracted from a noise-reduced EFTEM SI dataset and used to generate a chemical map of the material by multiple linear least square fitting. We validate the results of the low-loss EFTEM SI/PCA technique by applying the method to a control PS-b-PEO sample that does not contain the sodium salt, and by conducting spatially resolved X-ray energy-dispersive spectrometry on the salt-containing PS-b-PEO thin film., (Published by Elsevier B.V.)