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.

Trade-off between the Mechanical Strength and Microwave Electrical Properties of Functionalized and Irradiated Carbon Nanotube Sheets.

Carbon nanotube (CNT) sheets represent a novel implementation of CNTs that enable the tailoring of electrical and mechanical properties for applications in the automotive and aerospace industries. Small molecule functionalization and postprocessing techniques, such as irradiation with high-energy particles, are methods that can enhance the mechanical properties of CNTs. However, the effect that these modifications have on the electrical conduction mechanisms has not been extensively explored. By characterizing the mechanical and electrical properties of multiwalled carbon nanotube (MWCNT) sheets with different functional groups and irradiation doses, we can expand our insights into the extent of the trade-off that exists between mechanical strength and electrical conductivity for commercially available CNT sheets. Such insights allow for the optimization of design pathways for engineering applications that require a balance of material property enhancements.

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.

Electro-thermo-mechanical model for bulk acoustic wave resonators.

We present the electro-thermo-mechanical constitutive relations, expanded up to the third order, for a BAW resonator. The relations obtained are implemented into a circuit model, which is validated with extensive linear and nonlinear measurements. The mathematical analysis, along with the modeling, allows us to identify the dominant terms, which are the material temperature derivatives and two intrinsic nonlinear terms, and explain, for the first time, all observable effects in a BAW resonator by use of a unified physical description. Moreover, the terms that are responsible for the second-harmonic generation and the frequency shift with dc voltage are shown to be the same.

Exploiting dimensionality and defect mitigation to create tunable microwave dielectrics.

The miniaturization and integration of frequency-agile microwave circuits--relevant to electronically tunable filters, antennas, resonators and phase shifters--with microelectronics offers tantalizing device possibilities, yet requires thin films whose dielectric constant at gigahertz frequencies can be tuned by applying a quasi-static electric field. Appropriate systems such as BaxSr1-xTiO3 have a paraelectric-ferroelectric transition just below ambient temperature, providing high tunability. Unfortunately, such films suffer significant losses arising from defects. Recognizing that progress is stymied by dielectric loss, we start with a system with exceptionally low loss--Srn+1TinO3n+1 phases--in which (SrO)2 crystallographic shear planes provide an alternative to the formation of point defects for accommodating non-stoichiometry. Here we report the experimental realization of a highly tunable ground state arising from the emergence of a local ferroelectric instability in biaxially strained Srn+1TinO3n+1 phases with n ≥ 3 at frequencies up to 125 GHz. In contrast to traditional methods of modifying ferroelectrics-doping or strain-in this unique system an increase in the separation between the (SrO)2 planes, which can be achieved by changing n, bolsters the local ferroelectric instability. This new control parameter, n, can be exploited to achieve a figure of merit at room temperature that rivals all known tunable microwave dielectrics.

Manipulating particle trajectories with phase-control in surface acoustic wave microfluidics.

We present a 91 MHz surface acoustic wave resonator with integrated microfluidics that includes a flow focus, an expansion region, and a binning region in order to manipulate particle trajectories. We demonstrate the ability to change the position of the acoustic nodes by varying the electronic phase of one of the transducers relative to the other in a pseudo-static manner. The measurements were performed at room temperature with 3 µm diameter latex beads dispersed in a water-based solution. We demonstrate the dependence of nodal position on pseudo-static phase and show simultaneous control of 9 bead streams with spatial control of -0.058 µm/deg ± 0.001 µm/deg. As a consequence of changing the position of bead streams perpendicular to their flow direction, we also show that the integrated acoustic-microfluidic device can be used to change the trajectory of a bead stream towards a selected bin with an angular control of 0.008 deg/deg ± 0.000(2) deg/deg.