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In order to gain further insight into the details of charge transport in organic semiconductor devices it is necessary to characterize the density of trap states at the semiconductor/gate dielectric interface. Here we use the technique of gate bias stress to quantitatively determine the interface trap density in rubrene single-crystal field-effect transistors with two different types of interfaces. A reversible and reproducible shift of the I-V characteristics is observed upon both negative and positive gate bias stress, whose physical origin is identified as charge trapping and detrapping at the crystal/SiO2 insulator interface. We can thus quantify the density of interface traps that are alternately filled and emptied on a time scale of ≅1 h in the energy range defined by the applied bias stress. For a typical rubrene/SiO2 interface we extract a density of ∼2×1012 cm-2 at a stress bias of ±50 V, corresponding to a volume density of ≅1019/(cm3 eV). An octadecyltrichlorosilane treatment of the SiO2 dielectric surface reduced this charge density by more than a factor of 2. The bulk trap density derived from space-charge-limited current measurements is typically three orders of magnitude lower, highlighting the dominant role in charge trapping played by the crystal/dielectric interface. [ABSTRACT FROM AUTHOR]

We demonstrate controllable shift of the threshold voltage and the turn-on voltage in pentacene thin film transistors and rubrene single crystal field effect transistors (FET) by the use of nine organosilanes with different functional groups. Prior to depositing the organic semiconductors, the organosilanes were applied to the SiO2 gate insulator from solution and form a self-assembled monolayer (SAM). The observed shifts of the transfer characteristics range from -2 to 50 V and can be related to the surface potential of the layer next to the transistor channel. Concomitantly the mobile charge carrier concentration at zero gate bias reaches up to 4×1012/cm2. In the single crystal FETs the measured transfer characteristics are also shifted, while essentially maintaining the high quality of the subthreshold swing. The shift of the transfer characteristics is governed by the built-in electric field of the SAM and can be explained using a simple energy level diagram. In the thin film devices, the subthreshold region is broadened, indicating that the SAM creates additional trap states, whose density is estimated to be of order 1×1012/cm2. [ABSTRACT FROM AUTHOR]

A method has been developed to inject mobile charges at the surface of organic molecular crystals, and the dc transport of field-induced holes has been measured at the surface of pentacene single crystals. To minimize damage to the soft and fragile surface, the crystals are attached to a prefabricated substrate which incorporates a gate dielectric (SiO[sub 2]) and four probe pads. The surface mobility of the pentacene crystals ranges from 0.1 to 0.5 cm[sup 2]/V s and is nearly temperature independent above ∼150 K, while it becomes thermally activated at lower temperatures when the induced charges become localized. Ruling out the influence of electric contacts and crystal grain boundaries, the results contribute to the microscopic understanding of trapping and detrapping mechanisms in organic molecular crystals. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Imogolite nanotubes (INTs) are predicted as a unique 1D material with spatial separation of conduction and valence band edges but their large band gaps have inhibited their use as photocatalysts. The first step toward using these NTs in photocatalysis and exploiting the polarization-promoted charge separation across their walls is to reduce their band gap. Here, the modification of double-walled aluminogermanate INTs by incorporation of titanium into the NT walls is explored. The precursor ratio x = [Ti]/([Ge]+[Ti]) is modulated between 0 and 1. Structural and optical properties are determined at different scales and the photocatalytic performance is evaluated for H 2 production. Although the incorporation of Ti atoms into the structure remains limited, the optimal condition is found around x = 0.4 for which the resulting NTs reveal a remarkable hydrogen production of ≈1500 µmol g -1 after 5 h for a noble metal-free photocatalyst, a 65-fold increase relative to a commercial TiO 2 -P25. This is correlated to a lowering of the recombination rate of photogenerated charge carriers for the most active structures. These results confirm the theoretical predictions regarding the potential of modified INTs as photoactive nanoreactors and pave the way for investigating and exploiting their polarization properties for energy applications., (© 2023 The Authors. Small Methods published by Wiley‐VCH GmbH.)

The limitations of conventional template-based methods for the deposition of nanoparticle assemblies into defined patterns on solid substrates call for the development of techniques that do not require templates or lithographic masks. The use of optically-induced thermal gradients to drive the migration of colloids toward or away from a laser spot, known as opto-thermophoresis, has shown promise for the low-power trapping and optical manipulation of a variety of colloidal species. However, the printing of colloids using this technique has so far not been established. Herein, a method for the optically directed printing of noble metal nanoparticles, specifically gold nanospheres is reported. The thermophoresis of the polymer polyvinylpyrrolidone and gold nanospheres toward a laser spot led to the deposition of nanoparticle aggregates, capable of serving as surface-enhanced Raman scattering substrates. The influence of heating laser power and the concentrations of polymer, salt, and surfactant on the nanoparticle deposition rate and structure of the printed pattern are studied, showing that a variety of conditions can permit printing, suggesting facile generalization to different nanoparticle compositions, sizes, and shapes. These findings will greatly benefit future efforts for directed nanoparticle assembly, and drive applications in sensing, photothermal heating, and relevant applications in biomedicine and devices., (© 2024 The Author(s). Small Methods published by Wiley‐VCH GmbH.)

Hypothesis: Imogolite nanotubes (INTs) are unique anisometric particles with monodisperse nanometric diameters. Aluminogermanate double-walled INTs (Ge-DWINTs) are obtained with variable aspect ratios by controlling the synthesis conditions. It thus appears as an interesting model system to investigate how aspect ratio and ionic valence influence the colloidal behavior of highly anisometric rods., Experiments: The nanotubes were synthesized by hydrothermal treatment for 5 or 20 days to modify the aspect ratio while the electrostatic interactions were investigated by comparing the colloidal stability in symmetric and asymmetric electrolytes. The phase behavior and their related microstructure were determined by optical observations and small-angle X-ray scattering measurements, coupled with interparticle distance modelling., Findings: We revealed that colloidal suspensions of Ge-DWINTs prepared in NaCl are guided by repulsive double layer forces, undergoing different liquid crystal phase transitions before stiffen into a glass-like state. We found that the microstructure can be rationalized by taking into account the anisometric nature of the particles. By contrast, dispersions prepared with asymmetric electrolytes are governed by strong attractive forces and thus form space-filling gels containing large nanotubes aggregates., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

Manganese (Mn) is of particular concern in groundwater, as low-level chronic exposure to aqueous Mn concentrations in drinking water can result in a variety of health and neurodevelopmental effects. Much of the global population relies on drinking water sourced from karst aquifers. Thus, we seek to assess the relative risk of Mn contamination in karst by investigating the Shenandoah Valley, VA region, as it is underlain by both karst and non-karst aquifers and much of the population relies on water wells and spring water. Water and soil samples were collected throughout the Shenandoah Valley, to supplement pre-existing well water and spring data from the National Water Information System and the Virginia Household Water Quality Program, totaling 1815 wells and 119 springs. Soils were analyzed using X-ray fluorescence and Mn K-Edge X-ray absorption near-edge structure spectroscopy. Factors such as soil type, soil geochemistry, and aquifer lithology were linked with each location to determine if correlations exist with aqueous Mn concentrations. Analyzing the distribution of Mn in drinking water sources suggests that water wells and springs within karst aquifers are preferable with respect to chronic Mn exposure, with < 4.9% of wells and springs in dolostone and limestone aquifers exceeding 100 ppb Mn, while sandstone and shale aquifers have a heightened risk, with > 20% of wells exceeding 100 ppb Mn. The geochemistry of associated soils and spatial relationships to various hydrologic and geologic features indicates that water interactions with aquifer lithology and soils contribute to aqueous Mn concentrations. Relationships between aqueous Mn in spring waters and Mn in soils indicate that increasing aqueous Mn is correlated with decreasing soil Mn(IV). These results point to redox conditions exerting a dominant control on Mn in this region., (© 2024. The Author(s).)

Throughout history scientists have looked to Nature for inspiration and attempted to replicate intricate complex structures formed by self-assembly. In the context of synthetic supercrystals, achieving such complexity remains a challenge due to the highly symmetric nature of most nanoparticles (NPs). Previous works have shown intricate coupling between the self-assembly of NPs and confinement in templates, such as emulsion droplets (spherical confinement) or tubes (cylindrical confinement). This study focuses on the interplay between anisotropic NP shape and tunable "prismatic confinement" leading to the self-assembly of supercrystals in cavities featuring polygonal cross sections. A multiscale characterization strategy is employed to investigate the orientation and structure of the supercrystals locally and at the ensemble level. Our findings highlight the role of the mold interface in guiding the growth of distinct crystal domains: each side of the mold directs the formation of a monodomain that extends until it encounters another, leading to the creation of grain boundaries. Computer simulations in smaller prismatic cavities were conducted to predict the effect of an increased confinement. Comparison between prismatic and cylindrical confinements shows that flat interfaces are key to orienting the growth of supercrystals. This work shows a method of inducing orientation in plasmonic supercrystals and controlling their textural defects, thus offering insight into the design of functional metasurfaces and hierarchically structured devices.

We report here the highly ordered restacking of the layered phosphatoantimonic dielectric materials H 3(1- x ) M 3 x Sb 3 P 2 O 14 , (where M = Li, Na, K, Rb, Cs and 0 ≤ x ≤ 1), from their nanosheets dispersed in colloidal suspension, induced by a simple pH change using alkaline bases. H 3 Sb 3 P 2 O 14 aqueous suspensions are some of the rare examples of colloidal suspensions based on 2D materials exhibiting a lamellar liquid crystalline phase. Because the lamellar period can reach several hundred nanometers, the suspensions show vivid structural colors and because these colors are sensitive to various chemicals, the suspensions can be used as sensors. The structures of the lamellar liquid crystalline phase and the restacked phase have been studied by X-ray scattering (small and wide angle), which has followed the dependence of the lamellar/restacked phase equilibrium on the cation exchange rate, x . The X-ray diffraction pattern of the restacked phase is almost identical to that of the M 3 Sb 3 P 2 O 14 crystalline phase, showing that the restacking is highly accurate and avoids the turbostratic disorder of the nanosheets classically observed in nanosheet stacking of other 2D materials. Strikingly, the restacking process exhibits features highly reminiscent of a first-order phase transition, with the existence of a phase coexistence region where both ∼1 nm (interlayer spacing of the restacked phase) and ∼120 nm lamellar periods can be observed simultaneously. Furthermore, this first-order phase transition is well described theoretically by incorporating a Lennard-Jones-type lamellar interaction potential into an entropy-based statistical physics model of the lamellar phase of nanosheets. Our work shows that the precise cation exchange produced at room temperature by a classical neutralization reaction using alkaline bases leads to a crystal-like restacking of the exfoliated free Sb 3 P 2 O 14 3- nanosheets from suspension, avoiding the turbostratic disorder typical of van der Waals 2D materials, which is detrimental to the controlled deposition of nanosheets into complex integrated electronic, spintronic, photonic or quantum structures.

Depletion-induced self-assembly is routinely used to separate plasmonic nanoparticles (NPs) of different shapes, but less often for its ability to create supercrystals (SCs) in suspension. Therefore, these plasmonic assemblies have not yet reached a high level of maturity and their in-depth characterization by a combination of in situ techniques is still very much needed. In this work, gold triangles (AuNTs) and silver nanorods (AgNRs) are assembled by depletion-induced self-assembly. Small Angle X-ray Scattering (SAXS) and scanning electron microscopy (SEM) analysis shows that the AuNTs and AgNRs form 3D and 2D hexagonal lattices in bulk, respectively. The colloidal crystals are also imaged by in situ Liquid-Cell Transmission Electron Microscopy. Under confinement, the affinity of the NPs for the liquid cell windows reduces their ability to stack perpendicularly to the membrane and lead to SCs with a lower dimensionality than their bulk counterparts. Moreover, extended beam irradiation leads to disassembly of the lattices, which is well described by a model accounting for the desorption kinetics highlighting the key role of the NP-membrane interaction in the structural properties of SCs in the liquid-cell. The results shed light on the reconfigurability of NP superlattices obtained by depletion-induced self-assembly, which can rearrange under confinement., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)