Quantifying the Effect of Guest Binding on Host Environment.

The environment around a host-guest complex is defined by intermolecular interactions between the complex, solvent molecules, and counterions. These interactions govern both the solubility of these complexes and the rates of reactions occurring within the host molecules and can be critical to catalytic and separation applications of host-guest systems. However, these interactions are challenging to detect using standard analytical chemistry techniques. Here, we quantify the hydration and ion pairing of a FeII4L4 coordination cage with a set of guest molecules having widely varying physicochemical properties. The impact of guest properties on host ion pairing and hydration was determined through microwave microfluidic measurements paired with principal component analysis (PCA). This analysis showed that introducing guest molecules into solution displaced counterions that were bound to the cage, and that the solvent solubility of the guest has the greatest impact on the solvent and ion-pairing dynamics surrounding the host. Specifically, we found that when we performed PCA of the measured equivalent circuit parameters and the solubility and dipole moment, we observed a high (>90%) explained variance for the first two principal components for each circuit parameter. We also observed that cage-counterion pairing is well-described by a single ion-pairing type, with a one-step reaction model independent of the type of cargo, and that the ion-pairing association constant is reduced for cargo with higher water solubility. Quantifying hydration and cage-counterion interactions is a critical step to building the next generation of design criteria for host-guest chemistries.

Targeted chemical pressure yields tuneable millimetre-wave dielectric.

Epitaxial strain can unlock enhanced properties in oxide materials, but restricts substrate choice and maximum film thickness, above which lattice relaxation and property degradation occur. Here we employ a chemical alternative to epitaxial strain by providing targeted chemical pressure, distinct from random doping, to induce a ferroelectric instability with the strategic introduction of barium into today's best millimetre-wave tuneable dielectric, the epitaxially strained 50-nm-thick n = 6 (SrTiO3)nSrO Ruddlesden-Popper dielectric grown on (110) DyScO3. The defect mitigating nature of (SrTiO3)nSrO results in unprecedented low loss at frequencies up to 125 GHz. No barium-containing Ruddlesden-Popper titanates are known, but the resulting atomically engineered superlattice material, (SrTiO3)n-m(BaTiO3)mSrO, enables low-loss, tuneable dielectric properties to be achieved with lower epitaxial strain and a 200% improvement in the figure of merit at commercially relevant millimetre-wave frequencies. As tuneable dielectrics are key constituents of emerging millimetre-wave high-frequency devices in telecommunications, our findings could lead to higher performance adaptive and reconfigurable electronics at these frequencies.

Measurements of Nonlinear Polarization Dynamics in the Tens of Gigahertz.

Frequency-dependent linear-permittivity measurements are commonplace in the literature, providing key insights into the structure of dielectric materials. These measurements describe a material's dynamic response to a small applied electric field. However, nonlinear dielectric materials are widely used for their responses to large applied fields, including switching in ferroelectric materials, and field tuning of the permittivity in paraelectric materials. These behaviors are described by nonlinear permittivity. Nonlinear-permittivity measurements are fraught with technical challenges because of the complex electrical coupling between a sample and its environment. Here, we describe a technique for measuring the complex nonlinear permittivity that circumvents many of the difficulties associated with other approaches. We validate this technique by measuring the nonlinear permittivity of a tunable Ba0.5Sr0.5TiO3 thin film up to 40 GHz and comparing our results with a phenomenological model. These measurements provide insight into the dynamics of nonlinear dielectric materials down to picosecond timescales.

Label-free detection of conformational changes in switchable DNA nanostructures with microwave microfluidics.

Detection of conformational changes in biomolecular assemblies provides critical information into biological and self-assembly processes. State-of-the-art in situ biomolecular conformation detection techniques rely on fluorescent labels or protein-specific binding agents to signal conformational changes. Here, we present an on-chip, label-free technique to detect conformational changes in a DNA nanomechanical tweezer structure with microwave microfluidics. We measure the electromagnetic properties of suspended DNA tweezer solutions from 50 kHz to 110 GHz and directly detect two distinct conformations of the structures. We develop a physical model to describe the electrical properties of the tweezers, and correlate model parameters to conformational changes. The strongest indicator for conformational changes in DNA tweezers are the ionic conductivity, while shifts in the magnitude of the cooperative water relaxation indicate the addition of fuel strands used to open the tweezer. Microwave microfluidic detection of conformational changes is a generalizable, non-destructive technique, making it attractive for high-throughput measurements.

Modeling electrical double-layer effects for microfluidic impedance spectroscopy from 100 kHz to 110 GHz.

Broadband microfluidic-based impedance spectroscopy can be used to characterize complex fluids, with applications in medical diagnostics and in chemical and pharmacological manufacturing. Many relevant fluids are ionic; during impedance measurements ions migrate to the electrodes, forming an electrical double-layer. Effects from the electrical double-layer dominate over, and reduce sensitivity to, the intrinsic impedance of the fluid below a characteristic frequency. Here we use calibrated measurements of saline solution in microfluidic coplanar waveguide devices at frequencies between 100 kHz and 110 GHz to directly measure the double-layer admittance for solutions of varying ionic conductivity. We successfully model the double-layer admittance using a combination of a Cole-Cole response with a constant phase element contribution. Our analysis yields a double-layer relaxation time that decreases linearly with solution conductivity, and allows for double-layer effects to be separated from the intrinsic fluid response and quantified for a wide range of conducting fluids.

Giant Surface Conductivity Enhancement in a Carbon Nanotube Composite by Ultraviolet Light Exposure.

Carbon nanotube composites are lightweight, multifunctional materials with readily adjustable mechanical and electrical properties-relevant to the aerospace, automotive, and sporting goods industries as high-performance structural materials. Here, we combine well-established and newly developed characterization techniques to demonstrate that ultraviolet (UV) light exposure provides a controllable means to enhance the electrical conductivity of the surface of a commercial carbon nanotube-epoxy composite by over 5 orders of magnitude. Our observations, combined with theory and simulations, reveal that the increase in conductivity is due to the formation of a concentrated layer of nanotubes on the composite surface. Our model implies that contacts between nanotube-rich microdomains dominate the conductivity of this layer at low UV dose, while tube-tube transport dominates at high UV dose. Further, we use this model to predictably pattern conductive traces with a UV laser, providing a facile approach for direct integration of lightweight conductors on nanocomposite surfaces.

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.

Noncontact conductivity and dielectric measurement for high throughput roll-to-roll nanomanufacturing.

Advances in roll-to-roll processing of graphene and carbon nanotubes have at last led to the continuous production of high-quality coatings and filaments, ushering in a wave of applications for flexible and wearable electronics, woven fabrics, and wires. These applications often require specific electrical properties, and hence precise control over material micro- and nanostructure. While such control can be achieved, in principle, by closed-loop processing methods, there are relatively few noncontact and nondestructive options for quantifying the electrical properties of materials on a moving web at the speed required in modern nanomanufacturing. Here, we demonstrate a noncontact microwave method for measuring the dielectric constant and conductivity (or geometry for samples of known dielectric properties) of materials in a millisecond. Such measurement times are compatible with current and future industrial needs, enabling real-time materials characterization and in-line control of processing variables without disrupting production.

Modular apparatus for electrostatic actuation of common atomic force microscope cantilevers.

Piezoelectric actuation of atomic force microscope (AFM) cantilevers often suffers from spurious mechanical resonances in the loop between the signal driving the cantilever and the actual tip motion. These spurious resonances can reduce the accuracy of AFM measurements and in some cases completely obscure the cantilever response. To address these limitations, we developed a specialized AFM cantilever holder for electrostatic actuation of AFM cantilevers. The holder contains electrical contacts for the AFM cantilever chip, as well as an electrode (or electrodes) that may be precisely positioned with respect to the back of the cantilever. By controlling the voltages on the AFM cantilever and the actuation electrode(s), an electrostatic force is applied directly to the cantilever, providing a near-ideal transfer function from drive signal to tip motion. We demonstrate both static and dynamic actuations, achieved through the application of direct current and alternating current voltage schemes, respectively. As an example application, we explore contact resonance atomic force microscopy, which is a technique for measuring the mechanical properties of surfaces on the sub-micron length scale. Using multiple electrodes, we also show that the torsional resonances of the AFM cantilever may be excited electrostatically, opening the door for advanced dynamic lateral force measurements with improved accuracy and precision.

Multi-frequency tapping-mode atomic force microscopy beyond three eigenmodes in ambient air.

We present an exploratory study of multimodal tapping-mode atomic force microscopy driving more than three cantilever eigenmodes. We present tetramodal (4-eigenmode) imaging experiments conducted on a thin polytetrafluoroethylene (PTFE) film and computational simulations of pentamodal (5-eigenmode) cantilever dynamics and spectroscopy, focusing on the case of large amplitude ratios between the fundamental eigenmode and the higher eigenmodes. We discuss the dynamic complexities of the tip response in time and frequency space, as well as the average amplitude and phase response. We also illustrate typical images and spectroscopy curves and provide a very brief description of the observed contrast. Overall, our findings are promising in that they help to open the door to increasing sophistication and greater versatility in multi-frequency AFM through the incorporation of a larger number of driven eigenmodes, and in highlighting specific future research opportunities.