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In biology, an immense diversity of protein structural and functional motifs originates from only 20 common proteinogenic native amino acids arranged in various sequences. Is it possible to attain the same diversity in electronic materials based on organic macromolecules composed of non-native residues with different characteristics? This publication describes the design, preparation and characterization of non-native aromatic β-amino acid residues, i.e. derivatives of anthranilic acid, for polyamides that can efficiently mediate hole transfer. Chemical derivatization with three types of substituents at two positions of the aromatic ring allows for adjusting the energy levels of the frontier orbitals of the anthranilamide residues over a range of about one electronvolt. Most importantly, the anthranilamide residues possess permanent electric dipoles, adding to the electronic properties of the bioinspired conjugates they compose, making them molecular electrets.

We conducted a tip-enhanced Raman scattering spectroscopy (TERS) and photoluminescence (PL) study of quasi-1D TaSe 3- δ nanoribbons exfoliated onto gold substrates. At a selenium deficiency of δ ∼ 0.25 (Se/Ta = 2.75), the nanoribbons exhibit a strong, broad PL peak centered around ∼920 nm (1.35 eV), suggesting their semiconducting behavior. Such nanoribbons revealed a strong TERS response under 785 nm (1.58 eV) laser excitation, allowing for their nanoscale spectroscopic imaging. Nanoribbons with a smaller selenium deficiency (Se/Ta = 2.85, δ ∼ 0.15) did not show any PL or TERS response. The confocal Raman spectra of these samples agree with the previously-reported spectra of metallic TaSe 3 . The differences in the optical response of the nanoribbons examined in this study suggest that even small variations in Se content can induce changes in electronic band structure, causing samples to exhibit either metallic or semiconducting character. The temperature-dependent electrical measurements of devices fabricated with both types of materials corroborate these observations. The density-functional-theory calculations revealed that substitution of an oxygen atom in a Se vacancy can result in band gap opening and thus enable the transition from a metal to a semiconductor. However, the predicted band gap is substantially smaller than that derived from the PL data. These results indicate that the properties of van der Waals materials can vary significantly depending on stoichiometry, defect types and concentration, and possibly environmental and substrate effects. In view of this finding, local probing of nanoribbon properties with TERS becomes essential to understanding such low-dimensional systems.

Homogenous single-layer MoS 2 films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS 2 films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS 2 surface. A gas mixture of carbon monoxide (CO) and methanol (CH 3 OH) was partially converted to acetaldehyde (CH 3 CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C 2 species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS 2 facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. The formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors., (© 2021 IOP Publishing Ltd.)

Low turn-on (knee) voltage (∼0.3 V) Schottky-diode behavior of a four-layer (4L) MoS 2 /GaN junction is achieved by optimizing the in situ interface preparation of the GaN substrate prior to MoS 2 overlayer growth in a vacuum system using metallic molybdenum and hydrogen sulfide gas as precursors. The process leads to a clean nitrogen-terminated GaN surface that bonds well to the MoS 2 film revealing a 2 × 2 reconstruction at the interface observed in low-energy electron diffraction (LEED). Atomic force microscopy and X-ray photoelectron spectroscopy provide clear images of the GaN terraces through the MoS 2 overlayer confirming close adhesion and absence of oxygen and other contaminants. Density functional theory calculations predict the formation of the 2 × 2 superstructure at a clean interface. Transport measurements show diode behavior at an on/off ratio of ∼10 5 for ±1 V with a forward direction for the positive voltage applied to the MoS 2 layer. Combining transport and photoelectron spectroscopy measurements with theory, we deduce a Fermi-level position in the MoS 2 gap consistent with interface charge transfer from MoS 2 to the substrate. The high performance of the MoS 2 /Gan diode highlights the technological potential of devices based on GaN/MoS 2 interfaces.

Micron-scale single-crystal nanowires of metallic TaSe 3 , a material that forms -Ta-Se 3 -Ta-Se 3 - stacks separated from one another by a tubular van der Waals (vdW) gap, have been synthesized using chemical vapor deposition (CVD) on a SiO 2 /Si substrate, in a process compatible with semiconductor industry requirements. Their electrical resistivity was found unaffected by downscaling from the bulk to as little as 7 nm in nanowire width and height, in striking contrast to the resistivity of copper for the same dimensions. While the bulk resistivity of TaSe 3 is substantially higher than that of bulk copper, at the nanometer scale the TaSe 3 wires become competitive to similar-sized copper ones. Moreover, we find that the vdW TaSe 3 nanowires sustain current densities in excess of 10 8 A/cm 2 and feature an electromigration energy barrier twice that of copper. The results highlight the promise of quasi-one-dimensional transition metal trichalcogenides for electronic interconnect applications and the potential of van der Waals materials for downscaled electronics.

Wafer-scale MoS 2 growth at arbitrary integer layer number is demonstrated by a technique based on the decomposition of carbon disulfide on a hot molybdenum filament, which yields volatile MoS x precursors that precipitate onto a heated wafer substrate. Colorimetric control of the growth process allows precise targeting of any integer layer number. The method is inherently free of particulate contamination, uses inexpensive reactants without the pyrophoricity common to metal-organic precursors, and does not rely on particular gas-flow profiles. Raman mapping and photoluminescence mapping, as well as imaging by electron microscopy, confirm the layer homogeneity and crystalline quality of the resultant material. Electrical characterization revealed microampere output current, outstanding device-to-device consistency, and exceptionally low noise level unparalleled even by the exfoliated material, while other transport properties are obscured by high-resistance contacts typical to MoS 2 devices.

The ability to control charge transfer at molecular and nanometer scales represents the ultimate level of electronic mastery, and its impacts cannot be overstated. As electrostatic analogues of magnets, electrets possess ordered electric dipoles that present key paradigms for directing transduction of electrons and holes. Herein we describe the design and development of fluorinated aminoanthranilamides, derivatives of non-native aromatic beta-amino acids, as building blocks for hole-transfer molecular electrets. A highly regio-selective nucleophilic aromatic substitution of difluorinated nitrobenzoic acid provides the underpinnings for an array of unprecedented anthranilamide structures. Spin density distribution and electrochemical analyses reveal that fluorine induces about 200 mV positive shifts in reduction potentials without compromising the stability of the oxidized residues, making them invaluable building blocks for hole-transfer systems. These findings open unexplored routes to novel amino-acid structures, setting a foundation for bringing principles of proteomics to designs of charge-transfer systems.

Controlling charge transfer at a molecular scale is critical for efficient light harvesting, energy conversion, and nanoelectronics. Dipole-polarization electrets, the electrostatic analogue of magnets, provide a means for "steering" electron transduction via the local electric fields generated by their permanent electric dipoles. Here, we describe the first demonstration of the utility of anthranilamides, moieties with ordered dipoles, for controlling intramolecular charge transfer. Donor-acceptor dyads, each containing a single anthranilamide moiety, distinctly rectify both the forward photoinduced electron transfer and the subsequent charge recombination. Changes in the observed charge-transfer kinetics as a function of media polarity were consistent with the anticipated effects of the anthranilamide molecular dipoles on the rectification. The regioselectivity of electron transfer and the molecular dynamics of the dyads further modulated the observed kinetics, particularly for charge recombination. These findings reveal the underlying complexity of dipole-induced effects on electron transfer and demonstrate unexplored paradigms for molecular rectifiers.

MoS2(1-x) Se2x single-layer films are prepared using a mixture of organic selenium and sulfur precursors as well as a solid molybdenum source. The direct bandgaps are found to scale nearly linearly with composition in the range of 1.87 eV (pure single-layer MoS2 ) to 1.55 eV (pure single-layer MoSe2 ) permitting straightforward bandgap engineering., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Sputtering of MoS2 films of single-layer thickness by low-energy argon ions selectively reduces the sulfur content of the material without significant depletion of molybdenum. X-ray photoelectron spectroscopy shows little modification of the Mo 3d states during this process, suggesting the absence of significant reorganization or damage to the overall structure of the MoS2 film. Accompanying ab initio molecular dynamics simulations find clusters of sulfur vacancies in the top plane of single-layer MoS2 to be structurally stable. Measurements of the photoluminescence at temperatures between 175 and 300 K show quenching of almost 80% for an ~10% decrease in sulfur content.