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On-demand switchable “additive/subtractive” patterning of two-dimensional (2D) nanomaterials is an essential capability for developing new concepts of functional nanomaterials and their device realizations. Traditionally, this is performed viaa multistep process using photoresist coating and patterning by conventional photo or electron beam lithography, which is followed by bulk dry/wet etching or deposition. This limits the range of functionalities and structural topologies that can be achieved as well as increases the complexity, cost, and possibility of contamination, which are significant barriers to device fabrication from highly sensitive 2D materials. Focused electron beam-induced processing (FEBIP) enables a material chemistry/site-specific, high-resolution multimode atomic scale processing and provides unprecedented opportunities for “direct-write”, single-step surface patterning of 2D nanomaterials with an in situimaging capability. It allows for realizing a rapid multiscale/multimode approach, ranging from an atomic scale manipulation (e.g., viatargeted defect introduction as an active site) to a large-area surface modification on nano- and microscales, including patterned doping and material removal/deposition with 2D (in-plane)/three-dimensional (3D) (out-of-plane) control. In this work, we report on a new capability of FEBIP for nanoscale patterning of graphene oxide viaremoval of oxygenated carbon moieties with no use of reactive gas required for etching complemented by carbon atom deposition using a focused electron beam. The mechanism of experimentally observed phenomena is explored using the density functional theory (DFT) calculations, revealing that interactions of e-beam that liberated reactive oxygen radicals with carbon atoms on the graphene basal plane lead to the creation of atomic vacancies in the material. The reaction byproducts are volatile carbon dioxides, which are dissociated and volatilized from the graphene oxide surface functional groups by interactions with an energetic focused electron beam. Along with selective subtractive patterning of graphene oxide, the same electron beam with increased irradiation doses can deposit out-of-plane 3D carbon nanostructures on top of or around the 2D etched pattern, thus forming a hybrid 2D/3D nanocomposite with a feature control down to a few nanometers. This in operandodual nanofabrication capability of FEBIP is unmatched by any other nanopatterning techniques and opens a new design window for forming 2D/3D complex nanostructures and functional nanodevices.

A substantially enhanced purity of tungsten nanostructures, with up to 95% of metal content relative to carbon contaminants with no postprocessing, is achieved by using a supersonic inert carrier gas jet in the continuum flow regime to deliver the organometallic precursor for focused electron beam induced deposition (FEBID). Through impact-enhanced desorption of residual organic ligands at the deposition site, high kinetic energy of the gas jet assists in completing the secondary electron induced dissociation of precursor molecules, resulting in both increased metal purity and enhanced deposit growth rate. The inert gas jet at low Knudsen numbers also serves as a carrier gas to increase precursor flux to the substrate. Operating in the continuum flow regime reduces jet spreading and allows the use of smaller diameter nozzles to increase localization of precursor delivery to the deposition site. This drastic increase in localized precursor flux to the substrate is shown to compensate for the diminished sticking coefficient resulting from an increased impingement velocity of the continuum-flow gas jet relative to a molecular-flow gas jet. Increasing the jet temperature increases the delivered kinetic energy and allows tuning the balance between enhanced ligand contaminant desorption to increase deposit purity and the reduced sticking coefficient, resulting in the net increase of pure metal growth rate. Relevant physical mechanisms are discussed with support of experimental observations and multiscale numerical simulations of the gas jet, comparing the conventional molecular gas flow versus continuum gas flow. Collectively, our results suggest a promising path forward for delivery of organometallic precursors in gas phase that results in high purity metal deposition without sacrificing the high growth rate.

Interfacial contact of two-dimensional graphene with three-dimensional metal electrodes is crucial to engineering high-performance graphene-based nanodevices with superior performance. Here, we report on the development of a rapid “nanowelding” method for enhancing properties of interface to graphene buried under metal electrodes using a focused electron beam induced deposition (FEBID). High energy electron irradiation activates two-dimensional graphene structure by generation of structural defects at the interface to metal contacts with subsequent strong bonding via FEBID of an atomically thin graphitic interlayer formed by low energy secondary electron-assisted dissociation of entrapped hydrocarbon contaminants. Comprehensive investigation is conducted to demonstrate formation of the FEBID graphitic interlayer and its impact on contact properties of graphene devices achieved via strong electromechanical coupling at graphene–metal interfaces. Reduction of the device electrical resistance by ∼50% at a Dirac point and by ∼30% at the gate voltage far from the Dirac point is obtained with concurrent improvement in thermomechanical reliability of the contact interface. Importantly, the process is rapid and has an excellent insertion potential into a conventional fabrication workflow of graphene-based nanodevices through single-step postprocessing modification of interfacial properties at the buried heterogeneous contact.

Focused electron-beam-induced deposition (FEBID) is a promising nanolithography technique using “direct-write” patterning by carbon line and dot deposits on graphene. Understanding interactions between deposited carbon molecules and graphene enables highly localized modification of graphene properties, which is foundational to the FEBID utility as a nanopatterning tool. In this study, we demonstrate a unique possibility to induce dramatically different adsorption states of FEBID-produced carbon deposits on graphene, through density functional theory calculations and complementary Raman experiments. Specifically, an amorphous carbon deposit formed by direct irradiation of high energy primary electrons exhibits unusually strong interactions with graphene viacovalent bonding, whereas the FEBID carbon formed due to low-energy secondary electrons is only weakly interacting with graphene viaphysisorption. These observations not only are of fundamental importance to basic physical chemistry of FEBID carbon–graphene interactions but also enable the use of selective laser-assisted postdeposition ablation to effectively remove the parasitically deposited, physisorbed carbon films for improving FEBID patterning resolution.

Effective intracellular delivery is a significant impediment to research and therapeutic applications at all processing scales. Physical delivery methods have long demonstrated the ability to deliver cargo molecules directly to the cytoplasm or nucleus, and the mechanisms underlying the most common approaches (microinjection, electroporation, and sonoporation) have been extensively investigated. In this review, we discuss established approaches, as well as emerging techniques (magnetofection, optoinjection, and combined modalities). In addition to operating principles and implementation strategies, we address applicability and limitations of various in vitro, ex vivo, and in vivo platforms. Importantly, we perform critical assessments regarding (1) treatment efficacy with diverse cell types and delivered cargo molecules, (2) suitability to different processing scales (from single cell to large populations), (3) suitability for automation/integration with existing workflows, and (4) multiplexing potential and flexibility/adaptability to enable rapid changeover between treatments of varied cell types. Existing techniques typically fall short in one or more of these criteria; however, introduction of micro-/nanotechnology concepts, as well as synergistic coupling of complementary method(s), can improve performance and applicability of a particular approach, overcoming barriers to practical implementation. For this reason, we emphasize these strategies in examining recent advances in development of delivery systems.

The ability to fabricate 3D spiraling structures using metal-assisted chemical etching (MaCE) is one of the unique advantages of MaCE over traditional etching methods. However, control over the chirality of the spiraling structures has not been established. In this work, a systematic parametric study was undertaken for MaCE of star-shaped catalysts, examining the influence of arm shape, arm length, number of arms, center core diameter, and catalyst thickness on the rotation direction. This data was used to identify a set of geometric parameters that reliably induce rotation in a predefined direction such that large arrays of 3D spiraling structures can be fabricated with the same chirality. Electroless deposition into the MaCE template was used to examine the full etch path of the catalyst and an experimental fit was established to control rotation angle by adjusting the catalyst’s center core diameter. The ability to fabricate large arrays of 3D spiraling structures with predefined chirality could have important applications in photonics and optoelectronics.

The radiative properties of dense nanofluids are investigated. For nanofluids, scattering and absorbing of electromagnetic waves by nanoparticles, as well as light absorption by the matrix/fluid in which the nanoparticles are suspended, should be considered. We compare five models for predicting apparent radiative properties of nanoparticulate media and evaluate their applicability. Using spectral absorption and scattering coefficients predicted by different models, we compute the apparent transmittance of a nanofluid layer, including multiple reflecting interfaces bounding the layer, and compare the model predictions with experimental results from the literature. Finally, we propose a new method to calculate the spectral radiative properties of dense nanofluids that shows quantitatively good agreement with the experimental results.

Highly localized light‐induced phase transformation of electron beam induced deposited carbon nanostructures (dots and squares) on noble metal surfaces is reported. The phase transformation from the amorphous phase to the disordered graphitic phase is analyzed using the characteristic Raman signatures for amorphous and graphitized carbon and conductive force microscopy. The extent of the transformation is found to be largely dependent on the plasmon absorption properties of the underlying metal film. It is observed that the amorphous carbon deposits on the silver films consisting of 12 nm particles with the plasmon absorption near the laser excitation wavelength (514 nm), undergo fast graphitization to a nanocrystalline or a disordered graphitic phase. This transformation results in the formation of a highly conductive carbon/metal interface with at least seven orders of magnitude lower electrical resistivity than the initial insulating interface. It is suggested that the fast graphitization of nanoscale carbon deposits might serve as an efficient path for the formation of complex patterned nanoscale metal‐carbon interconnects with high electrical conductivity.

Controlling coalescence events in a heterogeneous ensemble of condensing droplets on a surface is an outstanding fundamental challenge in surface and interfacial sciences, with a broad practical importance in applications ranging from thermal management of high-performance electronic devices to moisture management in high-humidity environments. Nature-inspired superhydrophobic surfaces have been actively explored to enhance heat and mass transfer rates by achieving favorable dynamics during dropwise condensation; however, the effectiveness of such chemically homogeneous surfaces has been limited because condensing droplets tend to form as pinned Wenzel drops rather than mobile Cassie ones. Here, we introduce an amphiphilic nanostructured surface, consisting of a hydrophilic base with hydrophobic tips, which promotes the periodic regeneration of nucleation sites for small droplets, thus rendering the surface self-rejuvenating. This unique amphiphilic nanointerface generates an arrangement of condensed Wenzel droplets that are fluidically linked by a wetted sublayer, promoting previously unobserved coalescence events where numerous droplets simultaneously merge, without direct contact. Such ensemble coalescences rapidly create fresh nucleation sites, thereby shifting the overall population toward smaller droplets and enhancing the rates of mass and heat transfer during condensation.

We studied the thermally induced phase transformations of electron-beam-induced deposited (EBID) amorphous carbon nanostructures by correlating the changes in its morphology with internal microstructure by using combined atomic force microscopy (AFM) and high resolution confocal Raman microscopy. These carbon deposits can be used to create heterogeneous junctions in electronic devices commonly known as carbon−metal interconnects. We compared two basic shapes of EBID deposits: dots/pillars with widths from 50 to 600 nm and heights from 50 to 500 nm and lines with variable heights from 10 to 150 nm but having a constant length of 6 μm. We observed that during thermal annealing, the nanoscale amorphous deposits go through multistage transformation including dehydration and stress-relaxation around 150 °C, dehydrogenation within 150−300 °C, followed by graphitization (>350 °C) and formation of nanocrystalline, highly densified graphitic deposits around 450 °C. The later stage of transformation occurs well below commonly observed graphitization for bulk carbon (600−800 °C). It was observed that the shape of the deposits contribute significantly to the phase transformations. We suggested that this difference is controlled by different contributions from interfacial footprints area. Moreover, the rate of graphitization was different for deposits of different shapes with the lines showing a much stronger dependence of its structure on the density than the dots.

In this work, we introduce a maskless, resist-free rapid prototyping method to fabricate three-dimensional structures using electron beam induced deposition (EBID) of amorphous carbon (aC) from a residual hydrocarbon precursor in combination with metal-assisted chemical etching (MaCE) of silicon. We demonstrate that EBID-made patterned aC coating, with thickness of even a few nanometers, acts as a negative “mask” for the etching process and is sufficient for localized termination of the MaCE of silicon. Optimal aC deposition settings and gold film thickness for fabrication of high-aspect-ratio nanoscale 3D silicon structures are determined. The speed necessary for optimal aC feature deposition is found to be comparable to the writing speed of standard Electron Beam Lithography and the MaCE etching rate is found to be comparable to standard deep reactive ion etching (DRIE) rate.

Thermo-mechanical failure of components in planar-type solid oxide fuel cells (SOFCs) depends strongly on the local temperature gradients at the interfaces of different materials. Therefore, it is of paramount importance to accurately predict the temperature fields within the stack, especially near the interfaces. Because of elevated operating temperatures (of the order of 1000K or even higher), radiation heat transfer could become a dominant mode of heat transfer in the SOFCs. In this study, we extend our recent work on radiative effects in solid oxide fuel cells [J. Power Sources, 124, No. 2, pp. 453–458] by accounting for the spectral dependence of the radiative properties of the electrolyte material. The measurements of spectral radiative properties of the polycrystalline yttria-stabilized zirconia electrolyte we performed indicate that an optically thin approximation can be used for treatment of radiative heat transfer. To this end, the Schuster–Schwartzchild two-flux approximation is used to solve the radiative transfer equation for the spectral radiative heat flux, which is then integrated over the entire spectrum using an N-band approximation to obtain the total heat flux due to thermal radiation. The divergence of the total radiative heat flux is then incorporated as a heat sink into a three-dimensional thermo-fluid model of a SOFC through the user-defined function utility in the commercial FLUENT computational fluid dynamics software. The results of sample calculations are reported and compared against the base line cases when no radiation effects are included and when the spectrally gray approximation is used for treatment of radiative heat transfer.

Thermo-mechanical failure of components in planar-type solid oxide fuel cells (SOFCs) depends strongly on the local temperature gradients at the interfaces of different materials. Therefore, it is of paramount importance to accurately predict the temperature fields within the stack, especially near the interfaces. Because of elevated operating temperatures (of the order of 1000K or even higher), radiation heat transfer could become a dominant mode of heat transfer in the SOFCs. In this study, we extend our recent work on radiative effects in solid oxide fuel cells [J. Power Sources, 124, No. 2, pp. 453–458] by accounting for the spectral dependence of the radiative properties of the electrolyte material. The measurements of spectral radiative properties of the polycrystalline yttria-stabilized zirconia electrolyte we performed indicate that an optically thin approximation can be used for treatment of radiative heat transfer. To this end, the Schuster–Schwartzchild two-flux approximation is used to solve the radiative transfer equation for the spectral radiative heat flux, which is then integrated over the entire spectrum using an N-band approximation to obtain the total heat flux due to thermal radiation. The divergence of the total radiative heat flux is then incorporated as a heat sink into a three-dimensional thermo-fluid model of a SOFC through the user-defined function utility in the commercial FLUENT computational fluid dynamics software. The results of sample calculations are reported and compared against the base line cases when no radiation effects are included and when the spectrally gray approximation is used for treatment of radiative heat transfer.

This paper presents an approach for predicting the thickness of isothermal foams produced by blowing gas in a liquid solution under steady-state conditions. The governing equation for the transient foam thickness has been nondimensionalized, and two-dimensionless numbers have been identified to describe the formation and stability of this type of foam: Π1=Re/Frand Π2=CaH∞/r0. Physical interpretation of the dimensionless numbers has been proposed; a power-law type relation has been assumed between Π1and Π2(i.e., Π2=KΠn1). Experimental data available in the literature have been used to determine the empirical parameters of the correlation Kand n. The experimental conditions cover a wide range of viscosity, density, surface tension, gas superficial velocity, and average bubble radius. The model is valid for foams formed from high-viscosity liquids bubbled with nitrogen, air, helium, hydrogen, and argon injected through single, multiorifice nozzles or porous medium. A comparison between the correlation developed and the experimental data yields reasonable agreement (within 35% error), given the broadness of the bubble radius distribution around the mean value and the uncertainty of the experimental data and of the thermophysical properties. Predictions have been found to be very sensitive to the average bubble radius. A more refined model is still needed which should be supported by careful experimental studies. Finally, suggestions are given to extend the present work to foams generated from low-viscosity solutions.

The objective of this paper is to present an engineering model, based on fundamentally sound but simplified treatment of mass diffusion phenomena, for practical predictions of the effective diffusion coefficient of gases through closed-cell foams. All assumptions and simplifications that define the range of applicability of the proposed model are clearly stated. The model developed is based on the electrical circuit analogy and on the first principles. The analysis suggests that the effective diffusion coefficient through the foam can be expressed as a product of the geometric factor and the gas diffusion coefficient through the foam membrane. Comparison of model predictions with experimental data available in the literature shows satisfactory agreement. Discrepancies between predictions and data have been noted for gases with high solubility in the condensed phase for which Henry's law does not apply. Additional experimental data for both the foam morphologyand the diffusion coefficient in the membrane are needed to fully validate the model.