Carbon nanotube survivability in marine environments and method for biofouling removal.

The deep sea survivability and biofouling characteristics of corrosion-resistant bulk carbon nanotubes (CNTs) have been studied after deployment in the Atlantic Ocean over the course of 12 months. Quantification of barnacle count, biofouling density, and non-combustible residue shows cyanoacrylate coatings increase durability and reduce the colonization of biofouling compared to as-received CNTs. Scanning electron microscopy was performed on the biofouled CNTs, and the majority of species were identified as diatoms, consisting of an ordered silica cell wall. Both the as-received and cyanoacrylate-treated CNTs were successfully acid purified to remove biogrowth, leading to complete recovery of tensile strength and electrical transport properties. Thermogravimetric analysis, scanning electron microscopy, contact angle, dynamic mechanical analysis, and current carrying capacity measurements validated the refunctionalization results. Thus, the multifunctional property recovery and enhanced durability confirms that CNTs are electrochemically stable in saltwater environments and are resilient to biofouling conditions in real-world environments after extended exposure.

Unveiling Electron Optics in Two-Dimensional Materials by Nonlocal Resistance Mapping.

We propose a technique based on nonlocal resistance measurements for mapping transport in electron optics experiments. Utilizing tight-binding transport methods, we show how to use a four-terminal measurement to isolate the ballistic transport from a single lead of interest and reconstruct its contribution to the local density of states. This enables us to propose an experimentally tractable four-terminal device with via contacts for measuring Veselago lensing in a graphene p-n junction. Furthermore, we demonstrate how to extend this method as a scanning probe technique, implementing mapping of complex electron optics experiments including angled junctions, collimation optics, and beam steering. Our results highlight the fundamental importance of electron dephasing in ballistic transport and provide guidelines for isolating electron optics signals of interest. These findings unveil a fresh approach to performing electron optics experiments, with a plethora of two-dimensional material platforms to explore.

Hexagonal Boron Nitride Slab Waveguides for Enhanced Spectroscopy of Encapsulated 2D Materials.

The layered insulator hexagonal boron nitride (hBN) is a critical substrate that brings out the exceptional intrinsic properties of two-dimensional (2D) materials such as graphene and transition metal dichalcogenides (TMDs). In this work, the authors demonstrate how hBN slabs tuned to the correct thickness act as optical waveguides, enabling direct optical coupling of light emission from encapsulated layers into waveguide modes. Molybdenum selenide (MoSe2 ) and tungsten selenide (WSe2 ) are integrated within hBN-based waveguides and demonstrate direct coupling of photoluminescence emitted by in-plane and out-of-plane transition dipoles (bright and dark excitons) to slab waveguide modes. Fourier plane imaging of waveguided photoluminescence from MoSe2 demonstrates that dry etched hBN edges are an effective out-coupler of waveguided light without the need for oil-immersion optics. Gated photoluminescence of WSe2 demonstrates the ability of hBN waveguides to collect light emitted by out-of-plane dark excitons.Numerical simulations explore the parameters of dipole placement and slab thickness, elucidating the critical design parameters and serving as a guide for novel devices implementing hBN slab waveguides. The results provide a direct route for waveguide-based interrogation of layered materials, as well as a way to integrate layered materials into future photonic devices at arbitrary positions whilst maintaining their intrinsic properties.

High-speed metamagnetic switching of FeRh through Joule heating.

Due to its proximity to room temperature and demonstrated high degree of temperature tunability, FeRh's metamagnetic ordering transition is attractive for novel high-performance computing devices seeking to use magnetism as the state variable. We demonstrate electrical control of the antiferromagnetic-to-ferromagnetic transition via Joule heating in FeRh wires. The magnetic transition of FeRh is accompanied by a change in resistivity, which can be probed electrically and allows for integration into switching devices. Finite element simulations based on abrupt state transition within each domain result in a globally smooth transition that agrees with the experimental findings and provides insight into the thermodynamics involved. We measure a 150 K decrease in transition temperature with currents up to 60 mA, limited only by the dimensions of the device. The sizeable shift in transition temperature scales with current density and wire length, suggesting the absolute resistance and heat dissipation of the substrate are also important. The FeRh phase change is evaluated by pulsed I-V using a variety of bias conditions. We demonstrate high speed (~ ns) memristor-like behavior and report device performance parameters such as switching speed and power consumption that compare favorably with state-of-the-art phase change memristive technologies.

Acoustic cavities in 2D heterostructures.

Two-dimensional (2D) materials offer unique opportunities in engineering the ultrafast spatiotemporal response of composite nanomechanical structures. In this work, we report on high frequency, high quality factor (Q) 2D acoustic cavities operating in the 50-600 GHz frequency (f) range with f × Q up to 1 × 1014. Monolayer steps and material interfaces expand cavity functionality, as demonstrated by building adjacent cavities that are isolated or strongly-coupled, as well as a frequency comb generator in MoS2/h-BN systems. Energy dissipation measurements in 2D cavities are compared with attenuation derived from phonon-phonon scattering rates calculated using a fully microscopic ab initio approach. Phonon lifetime calculations extended to low frequencies (<1 THz) and combined with sound propagation analysis in ultrathin plates provide a framework for designing acoustic cavities that approach their fundamental performance limit. These results provide a pathway for developing platforms employing phonon-based signal processing and for exploring the quantum nature of phonons.

Direct-Write of Nanoscale Domains with Tunable Metamagnetic Order in FeRh Thin Films.

We have directly written nanoscale patterns of magnetic ordering in FeRh films using focused helium-ion beam irradiation. By varying the dose, we pattern arrays with metamagnetic transition temperatures that range from the as-grown film temperature to below room temperature. We employ transmission electron microscopy, X-ray diffraction, and temperature-dependent transport measurements to characterize the as-grown film, and magneto-optic Kerr effect imaging to quantify the He+ irradiation-induced changes to the magnetic order. Moreover, we demonstrate temperature-dependent optical microscopy and conductive atomic force microscopy as indirect probes of the metamagnetic transition that are sensitive to the differences in dielectric properties and electrical conductivity, respectively, of FeRh in the antiferromagnetic (AF) and ferromagnetic (FM) states. Using density functional theory, we quantify strain- and defect-induced changes in spin-flip energy to understand their influence on the metamagnetic transition temperature. This work holds promise for in-plane AF-FM spintronic devices, by reducing the need for multiple patterning steps or different materials, and potentially eliminating interfacial polarization losses due to cross material interfacial spin scattering.

Processing-Structure-Property Relations for Radiation Tolerance of Relaxor-Ferroelectric Thin Films.

This work investigates the role of microstructure on the radiation tolerance of relaxor-ferroelectric, lead magnesium niobate-lead titanate, thin films for piezoelectric microelectromechanical system (MEMS) applications. Thin films comprised of 0.7Pb[Mg1/3Nb2/3]O3-0.3PbTiO3 were fabricated via chemical solution deposition on platinized silicon wafers. Processing parameters, i.e., pyrolysis and annealing temperatures and durations, were varied to change the microstructure of the films. The functional response of the films was characterized before and after exposure to gamma radiation [up to 10 Mrad(Si)]. Within the total ionization dose studied, all films showed a <5% change in dielectric response and polarization and <15% change in piezoelectric response, after irradiation. While all films showed substantial radiation tolerance, those with large columnar grains showed the highest dielectric and piezoelectric response and, therefore, might offer the best approach for enabling piezoelectric MEMS devices for applications in radiative environments.

Effects of Gamma Irradiation on Functional Response of Relaxor-Ferroelectric Thin Films.

This work investigates the radiation response of relaxor-ferroelectric, lead magnesium niobate-lead titanate (PMN-PT) thin films, as an alternative material for microelectromechanical system (MEMS) devices in harsh environments. PMN-PT (0.7Pb[Mg1/3Nb2/3]O3-0.3PbTiO3) thin films were fabricated via chemical solution deposition onto platinized Si wafers and exposed to gamma radiation doses up to 10 Mrad(Si). The functional response of the thin films was measured before and after irradiation, and the resulting changes were reported. Within the radiation dose range studied, dielectric permittivity, tunability, and saturated polarization showed <5% change, and saturated piezoelectric coefficient <10% change. Additionally, PMN-PT thin films showed equivalent or superior radiation tolerance compared with lead zirconate titanate thin films previously studied. Higher chemical heterogeneity and greater domain wall mobility are expected to contribute to overall greater radiation tolerance in PMN-PT thin films. Nonlinear trends were found in dielectric and piezoelectric response with increasing dose, showing enhanced response at low doses of radiation before degradation at high doses. However, such variations were also within the experimentally observed dispersion of the data. The results are expected to impact systems to be deployed in areas of high radiation exposure, including systems used in aerospace, medical physics, X-ray/high-energy source measurement tools, and continuous monitoring of nuclear power applications.

Enabling remote quantum emission in 2D semiconductors via porous metallic networks.

Here we report how two-dimensional crystal (2DC) overlayers influence the recrystallization of relatively thick metal films and the subsequent synergetic benefits this provides for coupling surface plasmon-polaritons (SPPs) to photon emission in 2D semiconductors. We show that annealing 2DC/Au films on SiO2 results in a reverse epitaxial process where initially nanocrystalline Au films gain texture, crystallographically orient with the 2D crystal overlayer, and form an oriented porous metallic network (OPEN) structure in which the 2DC can suspend above or coat the inside of the metal pores. Both laser excitation and exciton recombination in the 2DC semiconductor launch propagating SPPs in the OPEN film. Energy in-/out- coupling occurs at metal pore sites, alleviating the need for dielectric spacers between the metal and 2DC layer. At low temperatures, single-photon emitters (SPEs) are present across an OPEN-WSe2 film, and we demonstrate remote SPP-mediated excitation of SPEs at a distance of 17 µm.

Multi-walled carbon nanotube paper anodes for lithium ion batteries.

The lithium ion capacity has been measured for multi-walled carbon nanotubes (MWCNTs) synthesized by injection chemical vapor deposition (CVD) using a cyclopentadienyl iron dicarbonyl dimer catalyst. The high quality of the as-synthesized MWCNTs has enabled free-standing electrodes to be fabricated independent of polymeric binder or copper support. Galvanostatic cycling of these electrodes demonstrates excellent reversibility and coulombic efficiency (> 97% after cycle 3) using propylene carbonate based electrolytes, with no evidence for material degradation. A reversible capacity exceeding 225 mAh/g was measured after 20 cycles when using the electrolyte combination of (1:1:1 v/v) ethylene carbonate (EC):propylene carbonate (PC):diethyl carbonate (DEC) at a constant current of 74 mA/g (equivalent of C/5 for LiC6). Modification of the catalyst solvent during synthesis from xylenes to pyridine improved the lithium ion capacity in the resulting MWCNT paper to 340 mAh/g. In addition, this MWCNT paper showed a stable reversible capacity after 10 cycles, exceeding 225 mAh/g when cycled at an equivalent 1C rate. Therefore, the use of a nitrogen source during synthesis can lead to improved lithium ion capacity in novel MWCNT anodes.

Phenomenological Model for Defect Interactions in Irradiated Functional Materials.

The ability to tailor the performance of functional materials, such as semiconductors, via careful manipulation of defects has led to extraordinary advances in microelectronics. Functional metal oxides are no exception - protonic-defect-conducting oxides find use in solid oxide fuel cells (SOFCs) and oxygen-deficient high-temperature superconductors are poised for power transmission and magnetic imaging applications. Similarly, the advantageous functional responses in ferroelectric materials that make them attractive for use in microelectromechanical systems (MEMS), logic elements, and environmental energy harvesting, are derived from interactions of defects with other defects (such as domain walls) and with the lattice. Chemical doping has traditionally been employed to study the effects of defects in functional materials, but complications arising from compositional heterogeneity often make interpretation of results difficult. Alternatively, irradiation is a versatile means of evaluating defect interactions while avoiding the complexities of doping. Here, a generalized phenomenological model is developed to quantify defect interactions and compare material performance in functional oxides as a function of radiation dose. The model is demonstrated with historical data from literature on ferroelectrics, and expanded to functional materials for SOFCs, mixed ionic-electronic conductors (MIECs), He-ion implantation, and superconductors. Experimental data is used to study microstructural effects on defect interactions in ferroelectrics.

Modification of Silver/Single-Wall Carbon Nanotube Electrical Contact Interfaces via Ion Irradiation.

Introduction of defects via ion irradiation ex situ to modify silver/single-wall carbon nanotube (Ag-SWCNT) electrical contacts and the resulting changes in the electrical properties were studied. Two test samples were fabricated by depositing 0.1 µm Ag onto SWCNT thin films with average thicknesses of 10 and 60 nm, followed by ion irradiation (150 keV 11B+ at 5 × 1014 ions/cm2). The contact resistance (Rc) between the Ag and SWCNT thin films was determined using transfer length method (TLM) measurements before and after ion irradiation. Rc increases for both test samples after irradiation, while there is no change in Rc for control structures with thick Ag contacts (1.5 µm), indicating that changes in Rc originate from changes in the SWCNT films and at the Ag-SWCNT interface caused by ion penetration through the Ag contact electrodes. Rc increases by ∼4× for the 60 nm SWCNT structure and increases by ∼2.4× for the 10 nm SWCNT structure. Raman spectroscopy measurements of the SWCNTs under the contacts compared to the starting SWCNT film show that the degradation of the 10 nm SWCNT structure was less significant than that of the 60 nm SWCNT structure, suggesting that the smaller change in Rc for the 10 nm SWCNT structure is a result of the thickness-dependent damage profile in the SWCNTs. Despite the increase in overall contact resistance, further TLM analysis reveals that the specific contact resistance actually decreases by ∼3.5-4× for both test samples, suggesting an enhancement of the electrical properties at the Ag-SWCNT interface. Irradiation simulations provide a physical description of the underlying mechanism, revealing that Ag atoms are forward-scattered into the SWCNTs, creating an Ag/C interfacial layer several nanometers in depth. The collective results indicate competing effects of improvement of the Ag-SWCNT interface versus degradation of the bulk SWCNT films, which has implications for scaled high-performance devices employing thinner SWCNT films.

Radiation-Hard Complementary Integrated Circuits Based on Semiconducting Single-Walled Carbon Nanotubes.

Increasingly complex demonstrations of integrated circuit elements based on semiconducting single-walled carbon nanotubes (SWCNTs) mark the maturation of this technology for use in next-generation electronics. In particular, organic materials have recently been leveraged as dopant and encapsulation layers to enable stable SWCNT-based rail-to-rail, low-power complementary metal-oxide-semiconductor (CMOS) logic circuits. To explore the limits of this technology in extreme environments, here we study total ionizing dose (TID) effects in enhancement-mode SWCNT-CMOS inverters that employ organic doping and encapsulation layers. Details of the evolution of the device transport properties are revealed by in situ and in operando measurements, identifying n-type transistors as the more TID-sensitive component of the CMOS system with over an order of magnitude larger degradation of the static power dissipation. To further improve device stability, radiation-hardening approaches are explored, resulting in the observation that SWNCT-CMOS circuits are TID-hard under dynamic bias operation. Overall, this work reveals conditions under which SWCNTs can be employed for radiation-hard integrated circuits, thus presenting significant potential for next-generation satellite and space applications.

Graphene Strained by Defects.

Using graphene nanomechanical resonators we demonstrate the extent to which the mechanical properties of multilayer graphene films are controllable, in real time, through introduction and rearrangement of defects. We show both static and re-entrant (cyclical) changes in the tensile stress using a combination of ion implantation, chemical functionalization, and thermal treatment. While the dramatic increase in static tensile stress achievable through laser annealing can be of importance for various MEMS applications, we view the direct observation of a time-variable stress as even more significant. We find that defect-rich films exhibit a slow relaxation component of the tensile stress that remains in the resonator long after the laser exposure is finished (trelax ≈ 100 s ≫ tcooling), analogous to a wind-up toy. We attribute this persistent component of the time-variable stress to a set of metastable, multivacancy structures formed during the laser anneal. Our results indicate that significant stress fields generated by multivacancies, in combination with their finite lifetime, could make them a powerful and flexible tool in nanomechanics.

Removal of sodium dodecyl sulfate surfactant from aqueous dispersions of single-wall carbon nanotubes.

A reagent-based treatment method was developed for the removal of sodium dodecyl sulfate (SDS) from aqueous dispersions of single-wall carbon nanotubes (SWCNTs). Based on a survey of various reagents, organic solvents emerged as the most effective at interrupting the SDS:SWCNT interaction without producing deleterious side reactions or causing precipitation of the surfactant. Specifically, treatment with acetone or acetonitrile allows for the facile isolation of SWCNTs with near complete removal of SDS through vacuum filtration, resulting in a 100x reduction in processing time. These findings were validated via quantitative analysis using thermogravimetric analysis, Raman spectroscopy, 4-point probe electrical measurement, and X-ray photoelectron spectroscopy. Subsequent thermal oxidation further enhances the purity of the reagent treated samples and yields bulk SWCNT samples with >95% carbonaceous purity. The proposed reagent treatment method thus demonstrates potential for large volume SWCNT processing.

Carbon Nanotube Thin-Film Antennas.

Multiwalled carbon nanotube (MWCNT) and single-walled carbon nanotube (SWCNT) dipole antennas have been successfully designed, fabricated, and tested. Antennas of varying lengths were fabricated using flexible bulk MWCNT sheet material and evaluated to confirm the validity of a full-wave antenna design equation. The ∼20× improvement in electrical conductivity provided by chemically doped SWCNT thin films over MWCNT sheets presents an opportunity for the fabrication of thin-film antennas, leading to potentially simplified system integration and optical transparency. The resonance characteristics of a fabricated chlorosulfonic acid-doped SWCNT thin-film antenna demonstrate the feasibility of the technology and indicate that when the sheet resistance of the thin film is >40 ohm/sq no power is absorbed by the antenna and that a sheet resistance of <10 ohm/sq is needed to achieve a 10 dB return loss in the unbalanced antenna. The dependence of the return loss performance on the SWCNT sheet resistance is consistent with unbalanced metal, metal oxide, and other CNT-based thin-film antennas, and it provides a framework for which other thin-film antennas can be designed.

Nitrogen-Doped Graphene and Twisted Bilayer Graphene via Hyperthermal Ion Implantation with Depth Control.

We investigate hyperthermal ion implantation (HyTII) as a means for substitutionally doping layered materials such as graphene. In particular, this systematic study characterizes the efficacy of substitutional N-doping of graphene using HyTII over an N(+) energy range of 25-100 eV. Scanning tunneling microscopy results establish the incorporation of N substituents into the graphene lattice during HyTII processing. We illustrate the differences in evolution of the characteristic Raman peaks following incremental doses of N(+). We use the ratios of the integrated D and D' peaks, I(D)/I(D') to assess the N(+) energy-dependent doping efficacy, which shows a strong correlation with previously reported molecular dynamics (MD) simulation results and a peak doping efficiency regime ranging between approximately 30 and 50 eV. We also demonstrate the inherent monolayer depth control of the HyTII process, thereby establishing a unique advantage over other less-specific methods for doping. We achieve this by implementing twisted bilayer graphene (TBG), with one layer of isotopically enriched (13)C and one layer of natural (12)C graphene, and modify only the top layer of the TBG sample. By assessing the effects of N-HyTII processing, we uncover dose-dependent shifts in the transfer characteristics consistent with electron doping and we find dose-dependent electronic localization that manifests in low-temperature magnetotransport measurements.

Tunable Radiation Response in Hybrid Organic-Inorganic Gate Dielectrics for Low-Voltage Graphene Electronics.

Solution-processed semiconductor and dielectric materials are attractive for future lightweight, low-voltage, flexible electronics, but their response to ionizing radiation environments is not well understood. Here, we investigate the radiation response of graphene field-effect transistors employing multilayer, solution-processed zirconia self-assembled nanodielectrics (Zr-SANDs) with ZrOx as a control. Total ionizing dose (TID) testing is carried out in situ using a vacuum ultraviolet source to a total radiant exposure (RE) of 23.1 µJ/cm(2). The data reveal competing charge density accumulation within and between the individual dielectric layers. Additional measurements of a modified Zr-SAND show that varying individual layer thicknesses within the gate dielectric tuned the TID response. This study thus establishes that the radiation response of graphene electronics can be tailored to achieve a desired radiation sensitivity by incorporating hybrid organic-inorganic gate dielectrics.

Purity assessment of single-wall carbon nanotubes, using optical absorption spectroscopy.

A demand currently exists for a method of assessing the purity of single-wall carbon nanotubes (SWNTs), which will allow for meaningful material comparisons. An established metric and protocol will enable accurate and reproducible purity claims to be substantiated. In the present work, the ability to accurately quantify the mass fraction of SWNTs in the carbonaceous portion of a given sample is demonstrated, using optical absorption spectroscopy on both laser and arc discharge-generated SWNT-N,N-dimethylacetamide (DMA) dispersions. Verification of purity assessment protocols is based upon constructed sample sets comprising designed mass fractions of purified SWNTs and representative carbonaceous synthesis byproducts. Application of a previously reported method based on a ratio of the areal absorbance from linear subtractions of the second interband electronic transitions of semiconducting SWNTs ((S)E(22)) has shown a severe overestimation of SWNT purity (average error >24%). Instead, the development of a nonlinear pi-plasmon model, which considers overlap of electronic transitions and peak broadening, has dramatically improved the purity assessment accuracy (average error <7%), derived from a strong correlation to the constructed sample sets. This approach has enabled corroboration of rapid assessment procedures, such as absorbance peak maxima ratio and Beer's law analysis, directed at purification monitoring and synthesis sample screening. Specifically, a simple protocol for purity assessment of laser and arc-discharge SWNTs has been established that can be extended to other synthetic types (i.e. CVD, HiPco, etc.) and diameter distributions.

Enhanced Electrical Conductivity in Extruded Single-Wall Carbon Nanotube Wires from Modified Coagulation Parameters and Mechanical Processing.

Single-wall carbon nanotubes (SWCNTs) synthesized via laser vaporization have been dispersed using chlorosulfonic acid (CSA) and extruded under varying coagulation conditions to fabricate multifunctional wires. The use of high purity SWCNT material based upon established purification methods yields wires with highly aligned nanoscale morphology and an over 4× improvement in electrical conductivity over as-produced SWCNT material. A series of eight liquids have been evaluated for use as a coagulant bath, and each coagulant yielded unique wire morphology based on its interaction with the SWCNT-CSA dispersion. In particular, dimethylacetamide as a coagulant bath is shown to fabricate highly uniform SWCNT wires, and acetone coagulant baths result in the highest specific conductivity and tensile strength. A 2× improvement in specific conductivity has been measured for SWCNT wires following tensioning induced both during extrusion via increased coagulant bath depth and during solvent evaporation via mechanical strain, over that of as-extruded wires from shallower coagulant baths. Overall, combination of the optimized coagulation parameters has yielded acid-doped wires with the highest reported room temperature electrical conductivities to date of 4.1-5.0 MS/m and tensile strengths of 210-250 MPa. Such improvements in bulk electrical conductivity can impact the adoption of metal-free, multifunctional SWCNT materials for advanced cabling architectures.