The Impact of Carbon Nanotube Length and Diameter on their Global Alignment by Dead-End Filtration.

Dead-end filtration has proven to effectively prepare macroscopically (3.8 cm2 ) aligned thin films from solutionbased single-wall carbon nanotubes (SWCNTs). However, to make this technique broadly applicable, the role of SWCNT length and diameter must be understood. To date, most groups report the alignment of unsorted, large diameter (≈1.4 nm) SWCNTs, but systematic studies on their small diameter are rare (≈0.78 nm). In this work, films with an area of A = 3.81 cm2 and a thickness of ≈40 nm are prepared from length-sorted fractions comprising of small and large diameter SWCNTs, respectively. The alignment is characterized by cross-polarized microscopy, scanning electron microscopy, absorption and Raman spectroscopy. For the longest fractions (Lavg = 952 nm ± 431 nm, Δ = 1.58 and Lavg = 667 nm ± 246 nm, Δ = 1.55), the 2D order parameter, S2D, values of ≈0.6 and ≈0.76 are reported for the small and large diameter SWCNTs over an area of A = 625 µm2 , respectively. A comparison of Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory calculations with the aligned domain size is then used to propose a law identifying the required length of a carbon nanotube with a given diameter and zeta potential.

Dependence of Single-Wall Carbon Nanotube Alignment on the Filter Membrane Interface in Slow Vacuum Filtration.

The recent introduction of slow vacuum filtration (SVF) technology has shown great promise for reproducibly creating high-quality, large-area aligned films of single-wall carbon nanotubes (SWCNTs) from solution-based dispersions. Despite clear advantages over other SWCNT alignment techniques, SVF remains in the developmental stages due to a lack of an agreed-upon alignment mechanism, a hurdle which hinders SVF optimization. In this work, the filter membrane surface is modified to show how the resulting SWCNT nematic order can be significantly enhanced. It is observed that directional mechanical grooving on filter membranes does not play a significant role in SWCNT alignment, despite the tendency for nanotubes to follow the groove direction. Chemical treatments to the filter membrane are shown to increase SWCNT alignment by nearly 1/3. These findings suggest that membrane surface structure acts to create a directional flow along the filter membrane surface that can produce global SWCNT alignment during SVF, rather serving as an alignment template.

Advanced characterization of magnetization dynamics in iron oxide magnetic nanoparticle tracers.

Characterization of the magnetization dynamics of single-domain magnetic nanoparticles (MNPs) is important for magnetic particle imaging (MPI), magnetic resonance imaging (MRI), and emerging medical diagnostic/therapeutic technologies. Depending on particle size and temperature, nanoparticle magnetization relaxation time constants span from nanoseconds to seconds. In solution, relaxation occurs via coupled Brownian and Néel relaxation mechanisms. Even though their coexistence complicates analysis, the presence of two timescales presents opportunities for more direct control of magnetization behavior if the two processes can be understood, isolated, and tuned. Using high frequency coils and sample temperature tunability, we demonstrate unambiguous determination of the specific relaxation processes for iron oxide nanoparticles using both time and frequency domain techniques. Furthermore, we study the evolution of the fast dynamics at ≈ 10 nanosecond timescales, for magnetic field amplitudes relevant to MPI.

Magnon-phonon hybridization in 2D antiferromagnet MnPSe3.

Magnetic excitations in van der Waals (vdW) materials, especially in the two-dimensional (2D) limit, are an exciting research topic from both the fundamental and applied perspectives. Using temperature-dependent, magneto-Raman spectroscopy, we identify the hybridization of two-magnon excitations with two phonons in manganese phosphorus triselenide (MnPSe3), a magnetic vdW material that hosts in-plane antiferromagnetism. Results from first-principles calculations of the phonon and magnon spectra further support our identification. The Raman spectra's rich temperature dependence through the magnetic transition displays an avoided crossing behavior in the phonons' frequency and a concurrent decrease in their lifetimes. We construct a model based on the interaction between a discrete level and a continuum that reproduces these observations. Our results imply a strong hybridization between each phonon and a two-magnon continuum. This work demonstrates that the magnon-phonon interactions can be observed directly in Raman scattering and provides deep insight into these interactions in 2D magnetic materials.

Examining Experimental Raman Mode Behavior in Mono- and Bilayer 2H-TaSe2 via Density Functional Theory: Implications for Quantum Information Science.

Tantalum diselenide (TaSe2) is a metallic transition metal dichalcogenide whose structure and vibrational behavior strongly depend on temperature and thickness, and this behavior includes the emergence of charge density wave (CDW) states at very low temperatures. In this work, observed Raman modes for mono- and bilayer are described across several spectral regions and compared to those seen in the bulk case. These modes, which include an experimentally observed forbidden Raman mode and low-frequency CDWs, are then matched to corresponding vibrations predicted by density functional theory (DFT). The reported match between experimental and computational results supports the presented vibrational visualizations of these modes. Support is also provided by experimental phonons observed in additional Raman spectra as a function of temperature and thickness. These results highlight the importance of understanding CDWs since they are likely to play a fundamental role in the future realization of solid-state quantum information platforms based on nonequilibrium phenomena.

Quasi-Two-Dimensional Magnon Identification in Antiferromagnetic FePS3via Magneto-Raman Spectroscopy.

Recently it was discovered that van der Waals-bonded magnetic materials retain long range magnetic ordering down to a single layer, opening many avenues in fundamental physics and potential applications of these fascinating materials. One such material is FePS3, a large spin (S=2) Mott insulator where the Fe atoms form a honeycomb lattice. In the bulk, FePS3 has been shown to be a quasi-two-dimensional-Ising antiferromagnet, with additional features in the Raman spectra emerging below the Néel temperature (TN) of approximately 120 K. Using magneto-Raman spectroscopy as an optical probe of magnetic structure, we show that one of these Raman-active modes in the magnetically ordered state is actually a magnon with a frequency of ≈3.7 THz (122 cm-1). Contrary to previous work, which interpreted this feature as a phonon, our Raman data shows the expected frequency shifting and splitting of the magnon as a function of temperature and magnetic field, respectively, where we determine the g-factor to be ≈2. In addition, the symmetry behavior of the magnon is studied by polarization-dependent Raman spectroscopy and explained using the magnetic point group of FePS3.

Phonon origin and lattice evolution in charge density wave states.

Metallic transition metal dichalcogenides, such as tantalum diselenide (TaSe2), display quantum correlated phenomena of superconductivity and charge density waves (CDW) at low temperatures. Here, the photophysics of 2H-TaSe2 during CDW transitions is revealed by combining temperature-dependent, low-frequency Raman spectroscopy and density functional theory (DFT). The spectra contain amplitude, phase, and zone-folded modes that are assigned to specific phonons and lattice restructuring predicted by DFT calculations with superb agreement. The non-invasive and efficient optical methodology detailed here demonstrates an essential link between atomic-scale and microscopic quantum phenomena.

Atypical Quantized Resistances in Millimeter-Scale Epitaxial Graphene p-n Junctions.

We have demonstrated the millimeter-scale fabrication of monolayer epitaxial graphene p-n junction devices using simple ultraviolet photolithography, thereby significantly reducing device processing time compared to that of electron beam lithography typically used for obtaining sharp junctions. This work presents measurements yielding nonconventional, fractional multiples of the typical quantized Hall resistance at ν = 2 (R H ≈ 12906 Ω) that take the form: a b R H . Here, a and b have been observed to take on values such 1, 2, 3, and 5 to form various coefficients of R H. Additionally, we provide a framework for exploring future device configurations using the LTspice circuit simulator as a guide to understand the abundance of available fractions one may be able to measure. These results support the potential for drastically simplifying device processing time and may be used for many other two-dimensional materials.

Phase Modulators Based on High Mobility Ambipolar ReSe2 Field-Effect Transistors.

We fabricated ambipolar field-effect transistors (FETs) from multi-layered triclinic ReSe2, mechanically exfoliated onto a SiO2 layer grown on p-doped Si. In contrast to previous reports on thin layers (~2 to 3 layers), we extract field-effect carrier mobilities in excess of 102 cm2/Vs at room temperature in crystals with nearly ~10 atomic layers. These thicker FETs also show nearly zero threshold gate voltage for conduction and high ON to OFF current ratios when compared to the FETs built from thinner layers. We also demonstrate that it is possible to utilize this ambipolarity to fabricate logical elements or digital synthesizers. For instance, we demonstrate that one can produce simple, gate-voltage tunable phase modulators with the ability to shift the phase of the input signal by either 90° or nearly 180°. Given that it is possible to engineer these same elements with improved architectures, for example on h-BN in order to decrease the threshold gate voltage and increase the carrier mobilities, it is possible to improve their characteristics in order to engineer ultra-thin layered logic elements based on ReSe2.

High-throughput assessment of vacancy formation and surface energies of materials using classical force-fields.

In this work, we present an open access database for surface and vacancy-formation energies using classical force-fields (FFs). These quantities are essential in understanding diffusion behavior, nanoparticle formation and catalytic activities. FFs are often designed for a specific application, hence, this database allows the user to understand whether a FF is suitable for investigating particular defect and surface-related material properties. The FF results are compared to density functional theory and experimental data whenever applicable for validation. At present, we have 17 506 surface energies and 1000 vacancy formation energies calculation in our database and the database is still growing. All the data generated, and the computational tools used, are shared publicly at the following websites: www.ctcms.nist.gov/~knc6/periodic.html, https://jarvis.nist.gov and https://github.com/usnistgov/jarvis. Approximations used during the high-throughput calculations are clearly mentioned. Using some of the example cases, we show how our data can be used to directly compare different FFs for a material and to interpret experimental findings such as using Wulff construction for predicting equilibrium shape of nanoparticles. Similarly, the vacancy formation energies data can be useful in understanding diffusion related properties.

Resonance Raman signature of intertube excitons in compositionally-defined carbon nanotube bundles.

Electronic interactions in low-dimensional nanomaterial heterostructures can lead to novel optical responses arising from exciton delocalization over the constituent materials. Similar phenomena have been suggested to arise between closely interacting semiconducting carbon nanotubes of identical structure. Such behavior in carbon nanotubes has potential to generate new exciton physics, impact exciton transport mechanisms in nanotube networks, and place nanotubes as one-dimensional models for such behaviors in systems of higher dimensionality. Here we use resonance Raman spectroscopy to probe intertube interactions in (6,5) chirality-enriched bundles. Raman excitation profiles for the radial breathing mode and G-mode display a previously unobserved sharp resonance feature. We show the feature is evidence for creation of intertube excitons and is identified as a Fano resonance arising from the interaction between intratube and intertube excitons. The universality of the model suggests that similar Raman excitation profile features may be observed for interlayer exciton resonances in 2D multilayered systems.

Comprehensive optical characterization of atomically thin NbSe2.

Transition-metal dichalcogenides (TMDCs) have offered experimental access to quantum confinement in one dimension. In recent years, metallic TMDCs like NbSe2 have taken center stage with many of them exhibiting interesting temperature-dependent properties such as charge density waves and superconductivity. In this paper, we perform a comprehensive optical analysis of NbSe2 by utilizing Raman spectroscopy, differential reflectance contrast, and spectroscopic ellipsometry. These analyses, when coupled with Kramers-Kronig analysis, allow us to extract the dielectric functions of bulk and atomically thin NbSe2 and relate them to the resonant behavior of the Raman spectra.

Toward Clean Suspended CVD Graphene.

The application of suspended graphene as electron transparent supporting media in electron microscopy, vacuum electronics, and micromechanical devices requires the least destructive and maximally clean transfer from their original growth substrate to the target of interest. Here, we use thermally evaporated anthracene films as the sacrificial layer for graphene transfer onto an arbitrary substrate. We show that clean suspended graphene can be achieved via desorbing the anthracene layer at temperatures in the 100 °C to 150 °C range, followed by two sequential annealing steps for the final cleaning, using Pt catalyst and activated carbon. The cleanliness of the suspended graphene membranes was analyzed employing the high surface sensitivity of low energy scanning electron microscopy and x-ray photoelectron spectroscopy. A quantitative comparison with two other commonly used transfer methods revealed the superiority of the anthracene approach to obtain larger area of clean, suspended CVD graphene. Our graphene transfer method based on anthracene paves the way for integrating cleaner graphene in various types of complex devices, including the ones that are heat and humidity sensitive.

Detecting Carbon in Carbon: Exploiting Differential Charging to Obtain Information on the Chemical Identity and Spatial Location of Carbon Nanotube Aggregates in Composites by Imaging X-ray Photoelectron Spectroscopy.

To better assess risks associated with nano-enabled products including multiwalled carbon nanotubes (MWCNT) within polymer matrices, it is important to understand how MWCNT are dispersed throughout the composite. The current study presents a method which employs imaging X-ray photoelectron spectroscopy (XPS) to chemically detect spatially segregated MWCNT rich regions at an epoxy composites surface by exploiting differential charging. MWCNT do not charge due to high conductivity and have previously been shown to energetically separate from their insulating surroundings when characterized by XPS. XPS in imaging mode revealed that these conductive regions were spatially separated due to micrometer-scale MWCNT aggregation and poor dispersion during the formation of the composite. Three MWCNT concentrations were studied; (1, 4 and 5) % by mass MWCNT within an epoxy matrix. Images acquired in periodic energy intervals were processed using custom algorithms designed to efficiently extract spectra from regions of interest. As a result, chemical and electrical information on aggregate and non-aggregate portions of the composite was extracted. Raman imaging and scanning electron microscopy were employed as orthogonal techniques for validating this XPS-based methodology. Results demonstrate that XPS imaging of differentially charging MWCNT composite samples is an effective means for assessing dispersion quality.

Charge Carrier Dynamics and Mobility Determined by Time-Resolved Terahertz Spectroscopy on Films of Nano-to-Micrometer-Sized Colloidal Tin(II) Monosulfide.

Tin(II) monosulfide (SnS) is a semiconductor material with an intermediate band gap, high absorption coefficient in the visible range, and earth abundant, non-toxic constituent elements. For these reasons, SnS has generated much interest for incorporation into optoelectronic devices, but little is known concerning the charge carrier dynamics, especially as measured by optical techniques. Here, as opposed to prior studies of vapor deposited films, phase-pure colloidal SnS was synthesized by solution chemistry in three size regimes, ranging from nanometer- to micron-scale (SnS small nanoparticles, SnS medium 2D nanosheets, and SnS large 2D µm-sheets), and evaluated by time-resolved terahertz spectroscopy (TRTS); an optical, non-contact probe of the photoconductivity. Dropcast films of the SnS colloids were studied by TRTS and compared to both thermally annealed films and dispersed suspensions of the same colloids. TRTS results revealed that the micron-scale SnS crystals and all of the annealed films undergo decay mechanisms during the first 200 ps following photoexcitation at 800 nm assigned to hot carrier cooling and carrier trapping. The charge carrier mobility of both the dropcast and annealed samples depends strongly on the size of the constituent colloids. The mobility of the SnS colloidal films, following the completion of the initial decays, ranged from 0.14 cm2/V·s for the smallest SnS crystals to 20.3 cm2/V·s for the largest. Annealing the colloidal films resulted in a ~ 20 % improvement in mobility for the large SnS 2D µm-sheets and a ~ 5-fold increase for the small nanoparticles and medium nanosheets.

Raman analysis of bond conformations in the rotator state and premelting of normal alkanes.

We perform Raman spectroscopic measurements on normal alkanes (CnH2n+2) to quantify the n dependence of the conformational disorder that occurs below the melt temperature. We employ a three-state spectral analysis method originally developed for semi-crystalline polyethylene that posits crystalline, amorphous, and non-crystalline consecutive trans (NCCT) conformations to extract their respective mass fractions. For the alkanes studied that melt via a rotator phase (21 ≤n≤ 37), we find that conformational disorder can be quantified by the loss of NCCT mass fraction, which systematically decreases with increasing chain length. For those that melt directly via the crystal phase (n≥ 40), we observe NCCT conformational mass fractions that are independent of chain length but whose disordered mass fraction increases with length. These complement prior IR measurements which measure disorder via gauche conformations, but have not been able to measure the mass fraction of this disorder as a function of n. An interesting feature of the three-state analysis when applied to alkanes is that the measured fraction of disordered chain conformations in the rotator phase of (10 to 30)% greatly exceeds the mass fraction of gauche bonds (1 to 7)% as measured from IR; we reconcile this difference through DFT calculations.

Lightweight, Flexible, High-Performance Carbon Nanotube Cables Made by Scalable Flow Coating.

Coaxial cables for data transmission are ubiquitous in telecommunications, aerospace, automotive, and robotics industries. Yet, the metals used to make commercial cables are unsuitably heavy and stiff. These undesirable traits are particularly problematic in aerospace applications, where weight is at a premium and flexibility is necessary to conform with the distributed layout of electronic components in satellites and aircraft. The cable outer conductor (OC) is usually the heaviest component of modern data cables; therefore, exchanging the conventional metallic OC for lower weight materials with comparable transmission characteristics is highly desirable. Carbon nanotubes (CNTs) have recently been proposed to replace the metal components in coaxial cables; however, signal attenuation was too high in prototypes produced so far. Here, we fabricate the OC of coaxial data cables by directly coating a solution of CNTs in chlorosulfonic acid (CSA) onto the cable inner dielectric. This coating has an electrical conductivity that is approximately 2 orders of magnitude greater than the best CNT OC reported in the literature to date. This high conductivity makes CNT coaxial cables an attractive alternative to commercial cables with a metal (tin-coated copper) OC, providing comparable cable attenuation and mechanical durability with a 97% lower component mass.

Metal to Insulator Quantum-Phase Transition in Few-Layered ReS2.

In ReS2, a layer-independent direct band gap of 1.5 eV implies a potential for its use in optoelectronic applications. ReS2 crystallizes in the 1T'-structure, which leads to anisotropic physical properties and whose concomitant electronic structure might host a nontrivial topology. Here, we report an overall evaluation of the anisotropic Raman response and the transport properties of few-layered ReS2 field-effect transistors. We find that ReS2 exfoliated on SiO2 behaves as an n-type semiconductor with an intrinsic carrier mobility surpassing µ(i) ∼ 30 cm(2)/(V s) at T = 300 K, which increases up to ∼350 cm(2)/(V s) at 2 K. Semiconducting behavior is observed at low electron densities n, but at high values of n the resistivity decreases by a factor of >7 upon cooling to 2 K and displays a metallic T(2)-dependence. This suggests that the band structure of 1T'-ReS2 is quite susceptible to an electric field applied perpendicularly to the layers. The electric-field induced metallic state observed in transition metal dichalcogenides was recently claimed to result from a percolation type of transition. Instead, through a scaling analysis of the conductivity as a function of T and n, we find that the metallic state of ReS2 results from a second-order metal-to-insulator transition driven by electronic correlations. This gate-induced metallic state offers an alternative to phase engineering for producing ohmic contacts and metallic interconnects in devices based on transition metal dichalcogenides.

Toward clean and crackless transfer of graphene.

We present the results of a thorough study of wet chemical methods for transferring chemical vapor deposition grown graphene from the metal growth substrate to a device-compatible substrate. On the basis of these results, we have developed a "modified RCA clean" transfer method that has much better control of both contamination and crack formation and does not degrade the quality of the transferred graphene. Using this transfer method, high device yields, up to 97%, with a narrow device performance metrics distribution were achieved. This demonstration addresses an important step toward large-scale graphene-based electronic device applications.

Preferential outward diffusion of Cu during unconventional galvanic replacement reactions between HAuCl4 and surface-limited Cu nanocrystals.

Metal diffusion in nanoscale materials is of great interest, yet the detailed kinetic behavior of such diffusion remains elusive. We observe direction-controlled Cu diffusion during unconventional galvanic replacement reactions between surface-limited Cu nanocrystals (NCs) and HAuCl(4). Using presynthesized Cu-Cu(1.81)S hetero-oligomer and Cu-Cu(2)S heterodimer NCs as templates and reactants, the controlled addition of HAuCl(4) leads to the preferential outward diffusion of Cu, visualized by the formation of single-crystalline and straight, or polycrystalline and kinked, CuAu nanowires, respectively. The time-dependent growth of these nanowires enables determination of nanoscale diffusion coefficients of Cu during these processes, for the first time.