Multi-Redox Responsive Behavior in a Mixed-Valence Semiconducting Framework Based on Bis-[1,2,5]-thiadiazolo-tetracyanoquinodimethane.

The two-dimensional (2-D) framework, [Cu(BTDAT)(MeOH)] {BTDAT = bis-[1,2,5]-thiadiazolo-tetracyanoquinodimethane}, possesses remarkable multi-step redox properties, with electrochemical studies revealing six quasi-stable redox states in the solid state. In situ electron paramagnetic resonance and visible-near infrared spectroelectrochemistry elucidated the mechanism for these multi-step redox processes, as well as the optical and electrochromic behavior of the BTDAT ligand and framework. In studying the structural, spectroscopic, and electronic properties of [Cu(BTDAT)(MeOH)], the as-synthesized framework was found to exist in a mixed-valence state with thermally-activated semiconducting behavior. In addition to pressed pellet conductivity measurements, single-crystal conductivity measurements using a pre-patterned polydimethylsiloxane layer on a silicon substrate provide important insights into the anisotropic conduction pathways. As an avenue to further understand the electronic state of [Cu(BTDAT)(MeOH)], computational band structure calculations predicted delocalized electronic transport in the framework. On the balance of probabilities, we propose that [Cu(BTDAT)(MeOH)] is a Mott insulator (i.e., electron correlations cause a metal-insulator transition). This implies that the conductivity is incoherent. However, we are unable to distinguish between activated transport due to Coulombically bound electron-hole pairs and a hopping mechanism. The combined electrochemical, electronic, and optical properties of [Cu(BTDAT)(MeOH)] shine a new light on the experimental and theoretical challenges for electroactive framework materials, which are implicated as the basis of advanced optoelectronic and electrochromic devices.

Systematic in situ hydration neutron reflectometry study on Nafion thin films.

Reported herein is a neutron reflectometry (NR) study on hydrated Nafion thin films (∼30 nm) on a silicon substrate with native oxide. The Nafion morphology is investigated systematically across the whole relative humidity range using both H2O and D2O vapours to enable a comparative study. By utilising this systematic approach two key results have been obtained. The first is that by leveraging the strong positive scattering signal from the D2O vapour, a complete and systematic water adsorption isotherm (Type II) for a Nafion thin film is produced. Utilising the slight negative scattering signal of the H2O enabled the quantification of the hydration dependent evolution of the formation of Nafion/water lamellae near the substrate surface. The number of lamellae layers increases continuously with hydration, and does not form abruptly. We also report the effects of swelling on the thin films across the relative humidity ranges. The work reported should prove useful in quantifying other hydration dependent properties of Nafion thin films such as conductivity and understanding Nafion/semiconductor based devices, as well as showcasing a NR methodology for other hydrophilic polymers.

Postgrowth Shaping and Transport Anisotropy in Two-Dimensional InAs Nanofins.

We report on the postgrowth shaping of free-standing two-dimensional (2D) InAs nanofins that are grown by selective-area epitaxy and mechanically transferred to a separate substrate for device fabrication. We use a citric acid-based wet etch that enables complex shapes, for example, van der Pauw cloverleaf structures, with patterning resolution down to 150 nm as well as partial thinning of the nanofin to improve local gate response. We exploit the high sensitivity of the cloverleaf structures to transport anisotropy to address the fundamental question of whether there is a measurable transport anisotropy arising from wurtzite/zincblende polytypism in 2D InAs nanostructures. We demonstrate a mobility anisotropy of order 2-4 at room temperature arising from polytypic stacking faults in our nanofins. Our work highlights a key materials consideration for devices featuring self-assembled 2D III-V nanostructures using advanced epitaxy methods.

Impact of invasive metal probes on Hall measurements in semiconductor nanostructures.

Recent advances in bottom-up growth are giving rise to a range of new two-dimensional nanostructures. Hall effect measurements play an important role in their electrical characterization. However, size constraints can lead to device geometries that deviate significantly from the ideal of elongated Hall bars with currentless contacts. Many devices using these new materials have a low aspect ratio and feature metal Hall probes that overlap with the semiconductor channel. This can lead to a significant distortion of the current flow. We present experimental data from InAs 2D nanofin devices with different Hall probe geometries to study the influence of Hall probe length and width. We use finite-element simulations to further understand the implications of these aspects and expand their scope to contact resistance and sample aspect ratio. Our key finding is that invasive probes lead to significant underestimation of measured Hall voltage, typically of the order 40-80%. This in turn leads to a subsequent proportional overestimation of carrier concentration and an underestimation of mobility.

Characterization of Ambipolar GaSb/InAs Core-Shell Nanowires by Thermovoltage Measurements.

In semiconductor heterostructures with a type II band alignment, such as GaSb-InAs, conduction can be tuned from electron- to hole-dominated using an electrostatic gate. However, traditional conductance measurements give no direct information on the carrier type, and thus limit the ability to distinguish transport effects originating from the two materials. Here, we employ thermovoltage measurements to GaSb/InAs core-shell nanowires, and reliably identify the dominant carrier type at room temperature as well as in the quantum transport regime at 4.2 K, even in cases where the conductance measurement does not allow for such a distinction. In addition, we show that theoretical modeling using the conductance data as input can reproduce the measured thermovoltage under the assumption that electron and hole states shift differently in energy with the applied gate voltage.

Kinetics of the charge ordering in magnetite below the Verwey temperature.

In this work the kinetics of the charge ordering in magnetite (Fe3O4) below the Verwey transition temperature TV is investigated in time and energy domain. After excitation by a one-second voltage pulse to destruct the charge-ordered state below TV, an alternating current (AC) is used to perturb its recovery process. Upon warming up to above a temperature T(r)(< TV) the charge order recovers despite the ac perturbation, because the temperature-dependent relaxation time becomes shorter than the polarity change of the ac. From the frequency dependence of T(r)(f), an activation energy of ΔE = 126 meV is extracted. Below Tr the real part of the ac conductance Greal follows the relation Greal ∼ f(α) with α = 0.98 ± 0.18, suggesting that the charge reordering is driven by correlated hopping transport. The relaxation time τ = 1/f(T(r)) of the charge-ordered state is determined for temperatures between 70 and 98 K and is extrapolated to τ(TV) = 1.6 ms, continuously slowing down its dynamics as the temperature is decreased.