Molecular Architecture Effects on Bulk Nanostructure in Bis(Orthoborate) Ionic Liquids.

A series of 19 ionic liquids (ILs) based on phosphonium and imidazolium cations of varying alkyl-chain lengths with the orthoborate anions bis(oxalato)borate [BOB]- , bis(mandelato)borate, [BMB]- and bis(salicylato)borate, [BScB]- , are synthesized and studied using small-angle neutron scattering (SANS). All measured systems display nanostructuring, with 1-methyl-3-n-alkyl imidazolium-orthoborates forming clearly bicontinuous L3 spongelike phases when the alkyl chains are longer than C6 (hexyl). L3 phases are fitted using the Teubner and Strey model, and diffusely-nanostructured systems are primarily fitted using the Ornstein-Zernicke correlation length model. Strongly-nanostructured systems have a strong dependence on the cation, with molecular architecture variation explored to determine the driving forces for self-assembly. The ability to form well-defined complex phases is effectively extinguished in several ways: methylation of the most acidic imidazolium ring proton, replacing the imidazolium 3-methyl group with a longer hydrocarbon chain, substitution of [BOB]- by [BMB]- , or exchanging the imidazolium for phosphonium systems, irrespective of phosphonium architecture. The results suggest there is only a small window of opportunity, in terms of molecular amphiphilicity and cation:anion volume matching, for the formation of stable extensive bicontinuous domains in pure bulk orthoborate-based ILs. Particularly important for self-assembly processes appear to be the ability to form H-bonding networks, which offer additional versatility in imidazolium systems.

Enhanced simultaneous absorption of NOx and SO2 in oxidation-reduction-absorption process with a compounded system based on Na2SO3.

Oxidation of sulfite and competitive absorption existed in Na2SO3 solution for simultaneous removal of NOx and SO2, inhibited the long-term high-efficiency when used for practical applications. A matching strategy was developed to solve these problems. Antioxidants combination was used to retard the oxidation of antioxidant and enhance inhibition of S(IV) (tetravalent sulfur) oxidation. Hydroquinone (HQ) and sodium thiosulfate (ST) showed a positive synergistic effect on inhibition of S(IV) oxidation. When SO2 concentration was 500 and 2000 ppmV, the addition of 0.1 wt.% HQ and 1 wt.% ST decreased the percentage of S(IV) oxidized by oxygen by over 30% and 40%, respectively. Alkali (Na2CO3) alleviated the competitive absorption between NOx and SO2. Moreover, Na2CO3 exhibited an enhancement effect on the absorption of NOx and SO2 when coupled with anti-oxidants. While the increase of oxygen pressure accelerated the oxidation of S(IV), the anti-oxidants can retard the oxidation. The measurement of pH suggested the removal efficiency of NOx highly depended on SO32⁻ concentration rather than pH. The further investigation of the mechanism suggested the match effect was related to the interaction between ST and the intermediate product of HQ. The match strategy holds a potential for application of SO32⁻ to denitration.

Anomalous Temperature Dependence in Metal-Black Phosphorus Contact.

Metal-semiconductor contact has been the performance limiting problem for electronic devices and also dictates the scaling potential for future generation devices based on novel channel materials. Two-dimensional semiconductors beyond graphene, particularly few layer black phosphorus, have attracted much attention due to their exceptional electronic properties such as anisotropy and high mobility. However, due to its ultrathin body nature, few layer black phosphorus-metal contact behaves differently than conventional Schottky barrier (SB) junctions, and the mechanisms of its carrier transport across such a barrier remain elusive. In this work, we examine the transport characteristic of metal-black phosphorus contact under varying temperature. We elucidated the origin of apparent negative SB heights extracted from classical thermionic emission model and also the phenomenon of metal-insulator transition observed in the current-temperature transistor characteristic. In essence, we found that the SB height can be modulated by the back-gate voltage, which beyond a certain critical point becomes so low that the injected carrier can no longer be described by the conventional thermionic emission theory. The transition from transport dominated by a Maxwell-Boltzmann distribution for the high energy tail states, to that of a Fermi distribution by low energy Fermi sea electrons, is the physical origin of the observed metal-insulator transition. We identified two distinctive tunneling limited transport regimes in the contact: vertical and longitudinal tunneling.

Large, Tunable Magnetoresistance in Nonmagnetic III-V Nanowires.

Magnetoresistance, the modulation of resistance by magnetic fields, has been adopted and continues to evolve in many device applications including hard-disk, memory, and sensors. Magnetoresistance in nonmagnetic semiconductors has recently raised much attention and shows great potential due to its large magnitude that is comparable or even larger than magnetic materials. However, most of the previous work focus on two terminal devices with large dimensions, typically of micrometer scales, which severely limit their performance potential and more importantly, scalability in commercial applications. Here, we investigate magnetoresistance in the impact ionization region in InGaAs nanowires with 20 nm diameter and 40 nm gate length. The deeply scaled dimensions of these nanowires enable high sensibility with less power consumption. Moreover, in these three terminal devices, the magnitude of magnetoresistance can be tuned by the transverse electric field controlled by gate voltage. Large magnetoresistance between 100% at room temperature and 2000% at 4.3 K can be achieved at 2.5 T. These nanoscale devices with large magnetoresistance offer excellent opportunity for future high-density large-scale magneto-electric devices using top-down fabrication approaches, which are compatible with commercial silicon platform.

Long Propagating Polaritonic Heat Transfer: Shaping Radiation to Conduction.

Surface phonon polaritons (SPhPs) originate from the coupling of mid-IR photons and optical phonons, generating evanescent waves along the polar dielectric surface. The emergence of SPhPs gives rise to a phase of quantum matter that facilitates long-range energy transfer (100s µm-scale). Albeit of the recent experimental progress to observe the enhanced thermal conductivity of polar dielectric nanostructures mediated by SPhPs, the potential mechanism to present the high thermal conductivity beyond the Landauer limit has not been addressed. Here, we revisit the comprehensive theoretical framework to unify the distinct pictures of two heat transfer mechanisms by conduction and radiation. We first designed our experimental platform to distinguish contributions of two distinct fundamental modes of SPhPs, resulting in far-field radiation and long propagating conduction, respectively, by tuning the configuration of a nanostructured heat channel integrated into the thermometer. We could effectively control the transmission of long-propagating SPhPs to influence the apparent thermal conductivity of the nanostructure. This study reveals the high thermal conductance of 1.63 nW/K by a fast SPhP mode comparable to that by classical phonons, with measurements showing apparent conductivity values of up to 2 W/m·K at 515 K. The origin of the enhanced thermal conductivity was exploited by observing the interference of dispersive evanescent waves by double heat channels. Furthermore, our experimental observations of length-dependent thermal conductance by SPhPs are in good agreement with the revisited Landauer formula to illustrate a polaritonic mode of heat conduction, considering the dispersive nature of radiation not limited to the physical boundaries of a solid object yet directionally guided along the surface.

Small-Angle Neutron Scattering Insights into 2-Ethylhexyl Laurate: A Remarkable Bioester.

Commercial (protiated) samples of the "green" and biodegradable bioester 2-ethylhexyl laurate (2-EHL) were mixed with D-2-EHL synthesized by hydrothermal deuteration, with the mixtures demonstrating bulk structuring in small-angle neutron scattering measurements. Analysis in a polymer scattering framework yielded a radius of gyration (Rg) of 6.5 Å and a Kuhn length (alternatively described as the persistence length or average segment length) of 11.2 Å. Samples of 2-EHL dispersed in acetonitrile formed self-assembled structures exceeding the molecular dimensions of the 2-EHL, with a mean aggregation number (Nagg) of 3.5 ± 0.2 molecules across the tested concentrations. We therefore present structural evidence that this ester can function as a nonionic (co)surfactant. The available surfactant-like conformations appear to enable performance beyond the low calculated hydrophilic-lipophilic balance value of 2.9. Overall, our data offer an explanation for 2-EHL's interfacial adsorption properties via self-assembly, resulting in strong emolliency and lubricity for this sustainable ester-based bio-oil.

Anion Architecture Controls Structure and Electroresponsivity of Anhalogenous Ionic Liquids in a Sustainable Fluid.

Three nonhalogenated ionic liquids (ILs) dissolved in 2-ethylhexyl laurate (2-EHL), a biodegradable oil, are investigated in terms of their bulk and electro-interfacial nanoscale structures using small-angle neutron scattering (SANS) and neutron reflectivity (NR). The ILs share the same trihexyl(tetradecyl)phosphonium ([P6,6,6,14]+) cation paired with different anions, bis(mandelato)borate ([BMB]-), bis(oxalato)borate ([BOB]-), and bis(salicylato)borate ([BScB]-). SANS shows a high aspect ratio tubular self-assembly structure characterized by an IL core of alternating cations and anions with a 2-EHL-rich shell or corona in the bulk, the geometry of which depends upon the anion structure and concentration. NR also reveals a solvent-rich interfacial corona layer. Their electro-responsive behavior, pertaining to the structuring and composition of the interfacial layers, is also influenced by the anion identity. [P6,6,6,14][BOB] exhibits distinct electroresponsiveness to applied potentials, suggesting an ion exchange behavior from cation-dominated to anion-rich. Conversely, [P6,6,6,14][BMB] and [P6,6,6,14][BScB] demonstrate minimal electroresponses across all studied potentials, related to their different dissociative and diffusive behavior. A mixed system is dominated by the least soluble IL but exhibits an increase in disorder. This work reveals the subtlety of anion architecture in tuning bulk and electro-interfacial properties, offering valuable molecular insights for deploying nonhalogenated ILs as additives in biodegradable lubricants and supercapacitors.

Enhanced far-field coherent thermal emission using mid-infrared bilayer metasurfaces.

A classical thermal source, such as an incandescent filament, radiates according to Planck's law. The feasibility of super-Planckian radiation has been investigated with sub-wavelength-sized sources in the last decade. In such sources, a crystal-dependent coupling of photons and optical phonons is possible at thermal energies corresponding to that at room temperature. This interaction can be used to tailor the far-field thermal emission in a coherent manner; however, understanding heat transfer during this process is still nascent. Here, we used a novel measurement platform to quantify thermal signals in a Ge2Sb2Te5/SiO2 nanoribbon structure. We were able to separate and quantify the radiated and conducted heat transfer mechanisms. The thermal emission from the Ge2Sb2Te5/SiO2 nanoribbons was enhanced by 3.5× compared to that of a bare SiO2 nanoribbon. Our model revealed that this enhancement was directly due to polaritonic heat transfer, which was possible due to the large and lossless dielectric permittivity of Ge2Sb2Te5 at mid-IR frequencies. This study directly probes the far-field emission with a thermal gradient stimulated by Joule heating in temperature ranges from 100 to 400 K, which bridges the gap between mid-IR optics and thermal engineering.

Tuneable interphase transitions in ionic liquid/carrier systems via voltage control.

The structure and interaction of ionic liquids (ILs) influence their interfacial composition, and their arrangement (i.e., electric double-layer (EDL) structure), can be controlled by an electric field. Here, we employed a quartz crystal microbalance (QCM) to study the electrical response of two non-halogenated phosphonium orthoborate ILs, dissolved in a polar solvent at the interface. The response is influenced by the applied voltage, the structure of the ions, and the solvent polarizability. One IL showed anomalous electro-responsivity, suggesting a self-assembly bilayer structure of the IL cation at the gold interface, which transitions to a typical EDL structure at higher positive potential. Neutron reflectivity (NR) confirmed this interfacial structuring and compositional changes at the electrified gold surface. A cation-dominated self-assembly structure is observed for negative and neutral voltages, which abruptly transitions to an anion-rich interfacial layer at positive voltages. An interphase transition explains the electro-responsive behaviour of self-assembling IL/carrier systems, pertinent for ILs in advanced tribological and electrochemical contexts.

Safety-by-design using forward and inverse multi-target machine learning.

The economic and social future of nanotechnology depends on our ability and manufacture nanomaterials that avoid potential toxicity, by identifying them before they are made, used and released into the environment. Safety-by-design is a framework for including these issues at an early stage of the development process, but balancing multiple nanoparticle properties and selection criteria remains challenging. Based on a synthetic data set of over 19,000 possible sunscreen product specifications, we have used multi-target machine learning to predict the corresponding size, shape, concentration and polytype of titania nanoparticle additives. The study considers the optical properties responsible for the sun protection factor and product transparency, including the extinction coefficients for ultra violet and visible light, and the potential for toxicity due to the generation of reactive oxygen species from the photocatalytically active facets of both anatase and rutile nanoparticles, as a function of the size and shape. We predict a number of conventional forward structure/property and property/product relationships, but show that a direct structure/product relationship provides superior performance when predicting multiple properties or product specifications simultaneously. These models are then inverted, re-optimized and re-trained to provide focused, high performing inverse design models that do not require additional optimization, and are capable of identifying nanoparticle configurations outside of the training set. The ability to directly predict suitable nanoparticle structures that conform to prerequisite sun protection, transparently and potential toxicity thresholds represents a new approach to safety-by-design that can be applied to other products and materials where multiple design criteria must be met at the same time.

Buffer effect of MgO on Na2SO3 to stabilize S(IV) for the enhancement in simultaneous absorption of NOx and SO2 from non-ferrous smelting gas.

Oxidation-reduction-absorption based on sulfite is a promising process for simultaneous removal of NOx and SO2. However, excessive oxidation of sulfite and competitive absorption between NOx and SO2 limit its application. A matching strategy between antioxidants and alkaline agents has been proposed to solve these problems and enhance the absorption process. The comparison results of inhibitors showed that hydroquinone exhibited long-term high-efficiency inhibition of S(IV) (SO32-/HSO3-) oxidation. The comparison of alkaline agents showed that the Na2SO3 solution with heterogeneous mixture of MgO and hydroquinone exhibited better absorption performance than that with other combinations. The absorption amounts of NOx in 0.15 mol/L Na2SO3 50 mL solution added 0.1% hydroquinone (HQ) with 0.09 mol/L MgO were 2.24 mmol, which improved 5 times than that without additives. In addition, studies on the influence of pH showed that the pH of MgO mixture could be stabilized at 9-10 for a long time, while the pH of Na2CO3 mixture decreased faster. Further studies suggested that the hydration of MgO resulted in the solution with MgO keeping high pH. This is also the main reason why the combination of MgO and hydroquinone is superior to the combination of Na2CO3 and hydroquinone in desulfurization and denitration performance.

UV-responsive polymeric superamphiphile based on a complex of malachite green derivative and a double hydrophilic block copolymer.

We have prepared a UV-responsive polymeric superamphiphile, formed by a malachite green derivative and the double hydrophilic block copolymer methoxy-poly(ethylene glycol)(114)-block-poly(l-lysine hydrochloride)(200) (PEG-b-PLKC) on the basis of electrostatic interactions. The malachite green derivative undergoes photo-ionization upon UV irradiation, which makes it more hydrophilic, resulting in changes in the self-assembly behavior of the polymeric superamphiphile. For this reason, the polymeric superamphiphile originally self-assembles to form sheetlike aggregates, which disassemble after UV irradiation because of the increased solubility of the malachite green derivative. By use of Nile red as a probe, the polarity of the polymeric superamphiphile solution is confirmed to be increased after UV irradiation by fluorescence spectra, which also explains the disassembly of the polymeric superamphiphile.

Negative transconductance and negative differential resistance in asymmetric narrow bandgap 2D-3D heterostructures.

Two-dimensional layered black phosphorus is an ambipolar narrow bandgap semiconductor with excellent electronic properties. A heterostructure can be formed when black phosphorus is combined with a narrow bandgap n-type semiconductor, which can feasibly be modulated throughout the entire bandgap for both materials in momentum space, creating unique quantum tunneling devices. In this work, a black phosphorus and narrow bandgap n-type indium arsenide heterojunction is created with a broken-gap band alignment, forming two interband tunneling windows that can be modulated electrostatically. We observe simultaneous gate-tunable band-to-band tunneling induced negative differential resistance and negative transconductance in the heterointerface and the access region edge near the gate, respectively. Compared to the stringent conditions for realizing such abrupt heterojunctions with opposite doping polarities in conventional bulk semiconductors, layered two-dimensional materials provide unique opportunities for such quantum tunneling devices. Our results represent advances in the fundamental understanding of heterojunctions and will promote future applications in advanced electronics.

Effect of Dielectric Interface on the Performance of MoS2 Transistors.

Because of their wide bandgap and ultrathin body properties, two-dimensional materials are currently being pursued for next-generation electronic and optoelectronic applications. Although there have been increasing numbers of studies on improving the performance of MoS2 field-effect transistors (FETs) using various methods, the dielectric interface, which plays a decisive role in determining the mobility, interface traps, and thermal transport of MoS2 FETs, has not been well explored and understood. In this article, we present a comprehensive experimental study on the effect of high-k dielectrics on the performance of few-layer MoS2 FETs from 300 to 4.3 K. Results show that Al2O3/HfO2 could boost the mobility and drain current. Meanwhile, MoS2 transistors with Al2O3/HfO2 demonstrate a 2× reduction in oxide trap density compared to that of the devices with the conventional SiO2 substrate. Also, we observe a negative differential resistance effect on the device with 1 µm-channel length when using conventional SiO2 as the gate dielectric due to self-heating, and this is effectively eliminated by using the Al2O3/HfO2 gate dielectric. This dielectric engineering provides a highly viable route to realizing high-performance transition metal dichalcogenide-based FETs.

Double cone of eigendirections in optically active ethylenediammonium selenate crystals.

Circular birefringence (CB) is generally responsible for only a small perturbation to the state of light polarization in crystals that also exhibit linear birefringence (LB). As such, the magnetoelectric tensor of gyration, which gives rise to CB and optical activity, is less well determined than the electric permittivity tensor in optical models of the Mueller matrix. To visualize the effect of the magnetoelectric tensor on polarimetric measurements, reported here are experimental mappings of the Mueller matrix and of the CB in a new chiral crystal with accidental null LB at an accessible optical frequency. Single crystals of ethylenediammonium selenate (EDSeO4) were synthesized and characterized by X-ray diffraction and Mueller matrix measurements in transmission and reflection. The crystals are isomorphous with the corresponding sulfate salt. They are tetragonal, space group P41(3)212. The constitutive relations of EDSeO4 were recovered using a partial wave summation of incoherent reflections. The extraordinary and ordinary refractive indices cross at 364 nm (3.41 eV), a scenario commonly called the 'isotropic point' or 'iso-index point'. At this wavelength, the magnetoelectric tensor fully describes the polarization transformation, giving rise to a double cone of eigendirections.

Mechanisms of current fluctuation in ambipolar black phosphorus field-effect transistors.

Multi-layer black phosphorus has emerged as a strong candidate owing to its high carrier mobility with most of the previous research work focused on its p-type properties. Very few studies have been performed on its n-type electronic characteristics which are important not only for the complementary operation for logic, but also crucial for understanding the carrier transport through the metal-black phosphorus junction. A thorough understanding and proper evaluation of the performance potential of both p- and n-types are highly desirable. In this paper, we investigate the temperature dependent ambipolar operation of both electron and hole transport from 300 K to 20 K. On-currents as high as 85 µA µm(-1) for a 0.2 µm channel length BP nFET at 300 K are observed. Moreover, we provide the first systematic study on the low frequency noise mechanisms for both n-channel and p-channel BP transistors. The dominated noise mechanisms of the multi-layer BP nFET and pFET are mobility fluctuation and carrier number fluctuations with correlated mobility fluctuations, respectively. We have also established a baseline of the low electrical noise of 8.1 × 10(-9)µm(2) Hz(-1) at 10 Hz at room temperature for BP pFETs, which is 3 times improvement over previous reports, and 7.0 × 10(-8)µm(2) Hz(-1) for BP nFETs for the first time.

Performance potential and limit of MoS2 transistors.

High-performance MoS2 transistors scaled down to 100 nm are studied at various temperatures down to 20 K, where a highest drive current of 800 µA µm(-1) can be achieved. Extremely low electrical noise of 2.8 × 10(-10) µm(2) Hz(-1) at 10 Hz is also achieved at room temperature. Furthermore, a negative differential resistance behavior is experimentally observed and its origin of self-heating is identified using pulsed-current-voltage measurements.

Dynamics of a caged imidazolium cation-toward understanding the order-disorder phase transition and the switchable dielectric constant.

A molecular compass-like behaviour is found in a perovskite-type cage compound (HIm)2[KCo(CN)6] (HIm = imidazolium cation). The dynamic changes in the HIm cation from the static to rotating state along with the rearrangement of the host cage result in switchable and anisotropic dielectric constants.

Red light responsive diselenide-containing block copolymer micelles.

We showed here that red light can be used to tune the self-assembly of amphiphilic diselenide-containing block copolymers, via the production of singlet oxygen in the presence of chromophores such as porphyrin derivatives. Furthermore, red light can be used to trigger the release of encapsulated cargo in polymeric micelles.