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We designed and synthesized two resorcin[4]arene scaffolds with four phosphate binding groups. The ligands effectively bind in at least a tridentate fashion at low surface coverage. The superior binding affinity is demonstrated using solution NMR spectroscopy and exceeds that of single phosphonates., Chemical Communications, 57 (38), ISSN:1359-7345, ISSN:1364-548X

Controlling the electronic properties of strongly correlated systems, observing electron-electron correlation-driven metal to insulator transition (MIT) is a key point for the next-generation solid-state Mottronic devices. Thus, the knowledge of the exact nature of the insulating state is an essential need to enhance the functionality of the material. Therefore, we have investigated the electronic nature of the insulating state of a classical Mott insulator V2O3 thin film (epitaxial) using low-temperature (LT) (120 K) resonant photoemission spectroscopy and X-ray absorption near-edge spectroscopy measurements. Temperature-dependent valence band spectra (VBS) reflect the transfer of spectral weight from the metallic coherent band (AM) near the Fermi level (EF) to the insulating Mott-Hubbard screened band (CI) at a binding energy of around 2.4 eV. Such a transfer of spectral weight upon MIT leads to vanishing of the density of states at EF and opens a band gap. The strong presence of the 3dnL final state is observed near the EF of LT VBS, confirming the presence of an O 2p band participating in low-energy charge fluctuation. This study further endorses the charge-transfer (CT)-type (U > Δ) insulating nature of a strained V2O3 thin film at LT, unlike its bulk counterpart, which is placed intermediate (U-Δ) between the CT and the Mott-Hubbard regime. Modifying the electronic ground state of V2O3 to the CT nature via the epitaxial strain in thin films provides a way to tailor the electronic energetics, with its implications to next-generation correlation-derived switching devices.

Picosecond optical and X-ray absorption spectroscopies with time- dependent density functional theory revealed the reaction pathways, electronic and structural conformations of Ir–Co hydrogen evolution photocatalysts. The dyad bearing 2-phenylpyridine ancillary ligands produced more photoreduced Co(II) than its 2-phenylisoquinoline analogue. These findings are important for designs of earth- abundant photosensitizers for photocatalytic applications.

Microgel particles composed of Interpenetrated Polymer Network (IPN) of poly(N-isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAAc) dispersed in water have been investigated through dynamic light scattering. The study of the temperature, concentration and pH dependence of the relaxation time has highlighted the existence of a thermoreversible transition corresponding to the swollen-shrunken volume phase transition. The presence of PAAc introduces an additional pH-sensitivity with respect to the temperature-sensitivity due to PNIPAM and leads to interesting differences in the transition process at acid and neutral pH. © 2014 Elsevier B.V. All rights reserved.

Blue absorbing near infrared (NIR) emitting phosphors are a promising class of materials for phosphor converted NIR LEDs, which can be used in compact NIR spectrometers. Preferably, these phosphors have a broad emission spectrum and show negligible luminescence quenching at LED operating temperatures (100 °C). Here, we investigated ASc(Si1-xGex)2O6 (A = Li/Na, x = 0,0.2,0.4,0.6,0.8,1) solid solutions doped with Cr3+ to tune and optimize the emission maximum and bandwidth to cover the full 700–1100 nm range. With increasing Ge content an emission redshift was observed, along with emission band broadening at intermediate Ge/Si ratio, which is explained by disorder around Cr3+ in the second coordination sphere (mixed Si/Ge). Temperature dependent emission spectra and luminescence decay curves were measured between 90 K and 670 K to determine the quenching temperature TQ. With increasing Ge content TQ drops from 550 K to below 400 K. Interestingly, Cr3+ emission in the highly symmetric site in LiScSi2O6 shows a strongly temperature dependent lifetime before thermal quenching sets in. DFT calculations on LiScSi2O6 indicate that asymmetric vibrations at the Sc site are involved and calculated phonon energies were confirmed by measuring FTIR. Our study indicates that a solid solution is a promising way to increase the emission bandwidth. However, with increasing Ge content TQ decreases. An optimum Ge-content in LiSc(Si1-xGex)2O6:Cr3+ is x = 0.2–0.4 as it redshifts the NIR band maximum close to 900 nm and offers a FWHM bandwidth around 180 nm, while keeping the thermal quenching temperature high enough for application in NIR-LEDs.

We consider a system of fermions with local interactions on a lattice (Hubbard model) and apply a novel extension of the Laplace's method (saddle-point approximation) for evaluating the corresponding partition function. There, we introduce dual free bosonic fields, with a propagator corresponding to an effective (renormalized) interaction with Maki-Thompson and Aslamazov-Larkin type corrections and beyond, and demonstrate that the superconducting pairing originates as an instability of the effective interaction. We derive the corresponding Bethe-Salpeter equation (instability criterion) and show that the interaction enters the equation only in its effective form to all orders, including the exchange part of the self-energy. An important implication of this result is that the effective interaction always remains finite, even at phase-transition points, directly contradicting the often used assumption of linear relationship between the interaction and susceptibility, established within the random-phase approximation. By analyzing the Bethe-Salpeter equation in the context of unconventional superconductivity, we find that the presence of a flat band close the Fermi level, found in materials such as twisted bilayer graphene, has a twofold favorable impact persisting beyond the weak-coupling approximation: a reduced kinetic energy cost of the gap formation and an increased anisotropy of the effective interaction, favoring a momentum dependent order parameter., 28 pages, 6 figures

Oxidized single walled carbon nanohorns (ox-SWCNH) were electrodeposited onto gold microelectrode arrays in conjunction with poly(3,4-ethylenedioxythiophene) (PEDOT) and polystirenesulfonate (PSS), and the properties of the new composite material for neural recording and stimulation were assessed. PEDOT/ox-SWCNH composites were compared with films prepared with one of the most notorious carbonaceous material in this field, the oxidized multi-walled Carbon Nanotubes (ox-MWCNT). The PEDOT/ox-SWCNH exhibited superior charge transfer capability, reflecting greater electroactive surface, as confirmed by SEM and EIS characterizations. As a consequence, a charge injection limit of 11.6mC/cm⁠2 was observed for the new composite, which is higher than the one of PEDOT/ox-MWCNT (8.7mC/cm⁠2). Having confirmed comparable neural recording performance, the PEDOT/ ox-SWCNH composite results very promising for improving therapeutic electrical stimulation in the central and peripheral nervous systems.

P.N. and M.H. contributed equally to this work. H.A.H., P.N., M.H., and E.T. thank the Deutsche Forschungsgemeinschaft (DFG) for generous support (Project HO 4503/5-1). Open access funding enabled and organized by Projekt DEAL. Apart from the energy gap law, control parameters over nonradiative transitions are so far only scarcely regarded. In this work, the impact of both covalence of the lanthanoid–ligand bond and varying bond distance on the magnitude of the intrinsic nonradiative decay rate between the excited 6P5/2 and 6P7/2 spin–orbit levels of Gd3+ is investigated in the chemically related compounds Y2[B2(SO4)6] and LaBO3. Analysis of the temperature-dependent luminescence spectra reveals that the intrinsic nonradiative transition rates between the excited 6PJ ( J = 5/2, 7/2) levels are of the order of only 10 ms−1 (Y2[B2(SO4)6]:Gd3+: 8.9 ms−1; LaBO3:Gd3+: 10.5 ms−1) and differ due to the different degree of covalence of the Gd—O bonds in the two compounds. Comparison to the established luminescent Boltzmann thermometer Er3+ reveals, however, that the nonradiative transition rates between the excited levels of Gd3+ are over three orders of magnitude slower despite a similar energy gap and the presence of a single resonant phonon mode. This hints to a fundamental magnetic dipolar character of the nonradiative coupling in Gd3+. These findings can pave a way to control nonradiative transition rates and how to tune the dynamic range of luminescent Boltzmann thermometers. Publisher PDF

We theoretically investigate laser-induced spin transport in metallic magnetic heterostructures using an effective spin-Transport description that treats itinerant electrons and thermal magnons on an equal footing. Electron-magnon scattering is included and taken as the driving force for ultrafast demagnetization. We assume that in the low-fluence limit, the magnon system remains in a quasiequilibrium, allowing a transient nonzero magnon chemical potential. In combination with the diffusive transport equations for the itinerant electrons, the description is used to chart the full spin dynamics within the heterostructure. In agreement with recent experiments, we find that in the case the spin-current-receiving material includes an efficient spin dissipation channel, the interfacial spin current becomes directly proportional to the temporal derivative of the magnetization. Based on an analytical calculation, we discuss that other relations between the spin current and magnetization may arise in the case the spin-current-receiving material displays inefficient spin-flip scattering. Finally, we discuss the role of (interfacial) magnon transport and show that, a priori, it cannot be neglected. However, its significance strongly depends on the system parameters.

Optically-induced spin currents have proven to be useful in spintronics applications, allowing for sub-ps all-optical control of magnetization. However, the mechanism responsible for their generation is still heavily debated. Here we use the excitation of spin-current induced THz spin-waves in noncollinear bilayer structures to study optically-induced spin currents in the time domain. We measure a significant laser-fluence dependence of the spin-wave phase, which can quantitatively be explained assuming the spin current is proportional to the time derivative of the magnetization. Measurements of the absolute spin-wave phase, supported by theoretical calculations and micromagnetic simulations, suggest that angular momentum transfer via the s-d interaction in combination with ballistic interlayer transport is sufficient to fully explain spin-current generation and transport in our experiments. Finally, we show that the damping-like optical STT dominates THz spin-wave generation. Our findings suggest laser-induced demagnetization and spin-current generation share the same microscopic origin.

A method to obtain full mass over charge (m/z), time-resolved quadruple mass spectrometry (QMS) spectra of an atomic layer deposition (ALD) cycle is proposed. This method allows one to circumvent the limitations of traditional approaches for obtaining QMS information in ALD as all m/z values can be simultaneously screened for the formation of reaction products in an efficient way. As a proof of concept, this method was applied to the trimethylaluminum (TMA)-water process. This process has been studied extensively over the past decades. Besides the expected formation of CH4, formation of gaseous HOAl(CH3)2 during the water pulse is observed, revealing a secondary reaction pathway for the water. The reaction energy and Gibbs free energy for different reactions are investigated computationally using density functional theory calculations and confirm that the secondary reaction pathway is thermodynamically allowed for certain surface conditions.

A novel technique to measure differential group delay and modal birefringence along few mode fibers is presented. The method relies on the analysis of the spectral correlation between two properly-selected sections of the fiber's Rayleigh-backscattered trace, acquired with an optical frequency domain reflectometer. Experiments performed on a two-mode-group fiber confirm the viability of the method.

Hypothesis The shape of colloidal particles affects the structure of colloidal dispersions. The effect of the cube shape on the thermodynamics of colloidal cube dispersions has not yet been studied experimentally. Static light scattering measurements on colloidal cubic silica shells at finite concentrations allows us to measure the structure factor of colloidal cube fluids and to test theoretical predictions for the equation of state of hard convex superballs. Experiments Hollow silica nanocubes of varying concentrations in N,N,-dimethylformamide were studied with static light scattering. The structure factor was extracted from the scattering curves using experimental form factors. From this experimental structure factor, the specific density of the particles, and the osmotic compressibility were obtained. This osmotic compressibility was then compared to a theoretical equation of state of hard superballs. Findings The first experimental structure factors of a stable cube fluid are presented. The osmotic compressibility of the cube fluid can be described by the equation of state of a hard superball fluid, showing that silica cubes in N,N,-dimethylformamide with LiCl effectively interact as hard particles.

Crystal impurities, such as atomic vacancies, are known to modulate the charge transport characteristics of two-dimensional (2D) materials. Here, we apply a first-principles-enriched tight-binding modelling approach to assess the influence of sulfur vacancies on the electronic structure and quantum transport characteristics of MoS2 monolayers. To this end, an sp3d5 orthogonal tight-binding (oTB) model of the pristine and defective MoS2 monolayer is mapped with electronic structure calculations performed at the density functional theory level and subsequently used in the real-space Kubo−Greenwood (KG) scheme for charge transport simulations. The calculated charge carrier mobility is found to be sensitive to both the density and spatial arrangement of vacancies. Our oTB/KG simulations predict a drop of mobility by two orders of magnitude when the vacancy concentration is increased from 0.1 to 3%, in excellent agreement with experimental results. The simulation of realistic samples (including specific types of defects) pave a new route toward the accurate understanding and the possible prediction of 2D materials for nanoelectronic devices.

Bicontinuous particle-stabilized emulsions (bijels) are networks of interpenetrating oil/water channels with applications in catalysis, tissue engineering, and energy storage. Bijels can be generated by arresting solvent transfer induced phase separation (STrIPS) via interfacial jamming of nanoparticles. However, until now, STrIPS bijels have only been formed with silica nanoparticles of low surface charge densities, limiting their potential applications in catalysis and fluid transport. Here, we show how strongly charged silica nanoparticles can stabilize bijels. To this end, we carry out a systematic study employing dynamic light scattering, zeta potential, acid/base titrations, turbidimetry, surface tension, and confocal microscopy. We find that moderating the adsorption of oppositely charged surfactants on the particles is crucial to facilitate particle dispersibility in the bijel casting mixture and bijel stabilization. Our results potentially introduce a general understanding for bijel fabrication with different inorganic nanoparticle materials of variable charge density.

A fully integrated 16-phase 8-branch Dickson charge pump is proposed and implemented to decrease the power dissipation due to parasitic capacitance at the bottom plate of the boost capacitor. By using the charge recycling concept, 87% of the power consumption related to parasitic capacitance is saved. In a 4-stage version of this charge pump, a maximum power efficiency of 41% is achieved at 35 mu A output current and 11V output voltage from a 3.3V supply voltage. The proposed multi-branch charge pump can also reach a very low output voltage ripple of only 0.146% at a load resistance of 1 M Omega, which is attributed to the fact that the 8-branch charge pump can transfer charges to the output node eight times consecutively during one clock period. In addition, a high voltage gain of 4.6 is achieved in the 4-stage charge pump at light load conditions. The total chip area is 0.57 mm(2) in a 0.35 mu m HV CMOS technology.

Hypothesis: The wetting behaviour is a key property of a porous medium that controls hydraulic conductivity in multiphase flow. While many porous materials, such as hydrocarbon reservoir rocks, are initially wetted by the aqueous phase, surface active components within the non-wetting phase can alter the wetting state of the solid. Close to the saturation endpoints wetting phase fluid films of nanometre thickness impact the wetting alteration process. The properties of these films depend on the chemical characteristics of the system. Here we demonstrate that surface texture can be equally important and introduce a novel workflow to characterize the wetting state of a porous medium. Experiments: We investigated the formation of fluid films along a rock surface imaged with atomic force microscopy using zeta-potential measurements and a computational model for drainage. The results were compared to spontaneous imbibition test to link sub-pore-scale and core-scale wetting characteristics of the rock. Findings: The results show a dependency between surface coverage by oil, which controls the wetting alteration, and the macroscopic wetting response. The surface-area coverage is dependent on the capillary pressure applied during primary drainage. Close to the saturation endpoint, where the change in saturation was minor, the oil-solid contact changed more than 80%. (C) 2019 The Authors. Published by Elsevier Inc.

Ni/CoOx sites were supported on an around 2 nm-TiOx modified hematite photoanode for water oxidation. TiOx demonstrates insignificant hole accumulation and a catalytically inactive surface that serves as an ideal platform. We reveal that the NiOx favors the extraction of holes from the TiOx surface, which are efficiently transferred to active CoOx for water oxidation.

High-contrast, high-resolution imaging of biomedical specimens is indispensable for studying organ function and pathologies. Conventional histology, the gold standard for soft-tissue visualization, is limited by its anisotropic spatial resolution, elaborate sample preparation, and lack of quantitative image information. X-ray absorption or phase tomography have been identified as promising alternatives enabling non-destructive, distortion-free three-dimensional (3D) imaging. However, reaching sufficient contrast and resolution with a simple experimental procedure remains a major challenge. Here, we present a solution based on x-ray phase tomography through speckle-based imaging (SBI). We demonstrate on a mouse kidney that SBI delivers comprehensive 3D maps of hydrated, unstained soft tissue, revealing its microstructure and delivering quantitative tissue-density values at a density resolution of better than 2 m g / c m 3 and spatial resolution of better than 8 µm. We expect that SBI virtual histology will find widespread application in biomedicine and will open up new possibilities for research and histopathology.

Although it is generally accepted that structural parameters like width, shape, and edge structure crucially affect the electronic characteristics of graphene nanoribbons (GNRs), the exact relationship between geometry and charge transport remains largely unexplored. In this paper, we present in situ through-transport measurements of various topological GNRs and GNR heterostructures by lifting the ribbon with the tip of a scanning tunneling microscope. At the same time, we develop a comprehensive transport model that enables us to understand various features, such as obscuring of localized states in through transport, the effect of topology on transport, as well as negative differential conductance in heterostructures with localized electronic modes. The combined experimental and theoretical efforts described in this paper serve to elucidate general charge transport phenomena in GNRs and GNR heterostructures.

We numerically determine the robustness of the lasing edge modes in a spin-torque oscillator array that realizes the non-Hermitian Su-Schrieffer-Heeger model. Previous studies found that the linearized dynamics can enter a topological regime in which the edge mode is driven into auto-oscillation, while the bulk dynamics are suppressed. Here we investigate the full non-linear and finite-temperature dynamics, whose understanding is essential for spin-torque oscillators-based applications. Our analysis shows that the lasing edge mode dynamics persist in the non-linear domain for a broad range of parameters and temperatures. We investigate the effects of perturbations relevant to experimental implementations and discuss which ones might be detrimental to the stability of the lasing edge mode. Finally, we map our model onto a photonic model. Our analysis has the potential to shed light onto the dynamics of a plethora of non-Hermitian systems with non-linearities.

Closed-form formulations are difficult to find when the material behavior law is nonlinear. A linear approximation, on the other hand, has a very narrow range of validity. In this communication, the Normal Form (NF) method is employed to solve a 1-D nonlinear magnetodynamic problem. The discrete model is formulated in a state-space form suitable for NF applications. The resulting system is then expanded on a linear mode basis to cubic order. Analytical solutions are obtained using the NF technique and compared to traditional solutions. The results show the cubic polynomial adequately approximates the problem, and the NF solution is valid for some range of magnetic field intensity. This work is a part of the CE2I project, co-financed by the European Union, the European Regional Development Fund (ERDF), the French State, and the Hauts-de-France Region.

The optical absorptance of a single graphene layer over a wide range of wavelengths is known to be remarkably constant at the universal value pi alpha where alpha is the fine structure constant. Using atomistic tight-binding calculations, we show that the absorptance spectra of nanometer-thin layers (quantum wells) of group-IV, III-V, II-VI, or IV-VI semiconductors are characterized by marked plateaus at integer values of pi alpha, in the absence of excitonic effects. In the case of InAs, the results obtained are in excellent agreement with the currently available experimental data. By revisiting experimental data on semiconductor superlattices, we show that pi alpha is also a metric of their absorption when normalized to a single period. We conclude that the pi alpha quantization is universal in semiconductor quantum wells provided that excitonic effects are weak and is therefore not specific to the zero-gap graphene case. The physical origin of this universality and its limits are discussed using analytical models that capture the main underlying physics of the lowest optical transitions in III-V and II-VI semiconductor quantum wells. These models show that the absorptance is ruled by pi alpha independent of the material characteristics because of the presence of a dominant term in the Hamiltonian, linear in the wave vector k (similar to V center dot k), which couples the conduction band to the valence bands. However, the prefactor in front of pi alpha is not unity as in graphene due to the different nature of the electronic states. In particular, the spin-orbit coupling plays an important role in bringing the absorptance plateaus closer to integer values of pi alpha. The case of IV-VI semiconductor (PbSe) quantum wells characterized by a rocksalt lattice and multivalley physics is very similar to that of graphene, with the specification that a "massful gap" is formed around the Dirac points.

Field-effect transistor (FET) sensors are attractive potentiometric (bio)chemical measurement devices because of their fast response, low output impedance, and potential for miniaturization in standard integrated circuit manufacturing technologies. Yet the wide adoption of these sensors for real-world applications is still limited, mainly due to temporal drift and cross-sensitivities that introduce considerable error in the measurements. In this paper, we demonstrate that such non-idealities can be corrected by joint use of an array of FET sensors – selective to target and major interfering ions – with machine learning (ML) methods in order to accurately predict ion concentrations continuously and in the field. We studied the predictive performance of linear regression (LR), support vector regression (SVR), and state-of-art deep neural networks (DNNs) when monitoring pH from combinatorial H+, Na+, and K+ion-sensitive FET (ISFET) sequences of readings collected over a period of 90 consecutive days in real water quality assessment conditions. The proposed ML algorithms were trained against reference online measurements obtained from a commercial pH sensor. Results show a greater capability of DNNs to provide precise pH monitoring for longer than a week, achieving a relative root-mean-square error reduction of 73% over standard two-point sensor calibration methods., The authors acknowledge funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No 747848 and the SNSF-Sinergia WeCare project (No.CRSII5_177255).

Synapses play a critical role in memory, learning, and cognition. Their main functions include converting pre-synaptic voltage spikes to post-synaptic currents, as well as scaling the input signal. Several brain-inspired architectures have been proposed to emulate the behavior of biological synapses. While these are useful to explore the properties of nervous systems, the challenge of making biocompatible and flexible circuits with biologically plausible time constants and tunable gain remains. Here, a physically flexible organic log-domain integrator synaptic circuit is shown to address this challenge. In particular, the circuit is fabricated using organic-based materials that are electrically active, offer flexibility and biocompatibility, as well as time constants (critical in learning neural codes and encoding spatiotemporal patterns) that are biologically plausible. Using a 10 nF synaptic capacitor, the time constant reached 126 ms and 221 ms before and during bending, respectively. The flexible synaptic circuit is characterized before and during bending, followed by studies on the effects of weighting voltage, synaptic capacitance, and disparity in pre-synaptic signals on the time constant., Comment: Accepted by Advanced Electronic Materials (18 pages, 17 figures)

The journal of physical chemistry / C 126(20), 8752 - 8759 (2022). doi:10.1021/acs.jpcc.2c01521, We present the cobalt 2p3d resonant inelastic X-ray scattering (RIXS) spectra of Co$_3$O$_4$. Guided by multiplet simulation, the excited states at 0.5 and 1.3 eV can be identified as the $^4$T$_2$ excited state of the tetrahedral Co$^{2+}$ and the $^3$T$_{2g}$ excited state of the octahedral Co$^{3+}$, respectively. The ground states of Co$^{2+}$ and Co$^{3+}$ sites are determined to be high-spin $^4$A$_2$(T$_d$) and low-spin $^1$A$_{1g}$(O$_h$), respectively. It indicates that the high-spin Co$^{2+}$ is the magnetically active site in Co$_3$O$_4$. Additionally, the ligand-to-metal charge transfer analysis shows strong orbital hybridization between the cobalt and oxygen ions at the Co$^{3+}$ site, while the hybridization is weak at the Co$^{2+}$ site., Published by Soc., Washington, DC

Growing CdSe/CdS nanocrystals from a large CdSe core, and employing a giant CdS shell, a continuous, broadband gain spectrum, covering the spectral range between the CdSe and the CdS band edge, is induced. As revealed by k.p calculations, this feature is enabled by a set of closely spaced S-, P- and, for larger CdSe cores, D-state hole levels, which are thermally occupied at room temperature, combined with a sparse density of electron states. This leads to a range of bleach signals in the transient absorption spectra that persist up to a microsecond. By extending a state-filling model including relevant higher-energy states and a Fermi-Dirac distribution of holes at finite temperature, it is shown that thermal occupancy can lower the gain threshold for excited states. Inclusion of Gaussian broadening of discrete transitions also leads to a smoothening of the gain threshold spectrum. Next to a direct measurement of the gain threshold, a method is also developed to extract this from the gain lifetime, taking advantage that population inversion is limited by Auger recombination and recombination rates scale with the exciton density as < N >.(< N > - 1). The results should be readily extendable to other systems, such as perovskite or III-V colloidal nanocrystals.

Triangulene is the smallest non-Kekulé graphene fragment known as Clar's hydrocarbon. Due to its open-shell electronic structure, triangulene is a promising molecular building block of carbon-based organic materials for spintronics and quantum molecular science. It comprises six benzenoid rings arranged in a triangular shape with two unpaired electrons delocalized over the entire conjugated core, making this molecule highly reactive. A triplet ground state is predicted for this hydrocarbon by Ovchinnikov's rule, or Lieb's theorem, in accord with Hund's rule. The pioneering work on triangulene was performed almost 70 years ago by Erich Clar, who attempted to prepare the pristine compound. Since then, several synthetic approaches to prepare this molecule have been exploited. The extreme reactivity of triangulene can be circumvented using on-surface techniques or by installation of sterically demanding substituents, which kinetically stabilize the diradical core against oligomerization in solution. The first two examples of a persistent derivative of triangulene were simultaneously and independently developed last year. This article presents a historical development in the synthesis of triangulene and its derivatives and outlines possible future applications in ferromagnetic materials, electrically conductive polymers or quantum computing.

A size–strain line-broadening analysis of the XRPD patterns and Raman spectra for two anatase/brookite (TiO2)-based nanocomposites with carbon (C) was carried out and the results compared with those of a similar sample free of carbon. The crystal structures and microstructures of anatase and brookite, as well as their relative abundance ratio, have been refined from XRPD data by the Rietveld method (the low amount of carbon is neglected). The XRPD size–strain analysis resulted in reliable structure and microstructure results for both anatase and brookite. The experimental Raman spectra of all the samples in the region 100–200 cm−1 are dominated by a strong feature primarily composed of the most intense modes of anatase (Eg ) and brookite (A 1g ). The anatase crystallite sizes of 14–17 nm, estimated by XRPD, suggest the application of the phonon confinement model (PCM) for the analysis of the anatase Eg mode, whereas the relatively large brookite crystallite size (27–29 nm) does not imply the use of the PCM for the brookite A 1g mode. Superposition of the anatase Eg mode profile, calculated by the PCM, and the Lorentzian shape of the brookite A 1g mode provide an appropriate simulation of the change in the dominant Raman feature in the spectra of TiO2-based nanocomposites with carbon. Raman spectra measured in the high-frequency range (1000–2000 cm−1) provide information on carbon in the investigated nanocomposite materials. The results from field-emission scanning electron microscope (SEM), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy and nitrogen physisorption measurements support the XRPD and Raman results.

Herein, a new route of sulfur grading in CuInSe2 (CISe) thin-film solar absorbers by introducing an ultrathin (

Ceramic particles-based packed bed systems are attracting the interest from various high-temperature applications such as thermal energy storage, nuclear cooling reactors, and catalytic support structures. Considering that these systems work above 600 ◦C, thermal radiation becomes significant or even the major heat transfer mechanism. The use of coatings with different thermal and optical properties could represent a way to tune and enhance the thermodynamic performances of the packed bed systems. In this study, the thermal stability of several metallic (Inconel, Nitinol, and Stainless Steel) based coatings is investigated at both high temperature and cyclic thermal conditions. Consequently, the optical properties and their temperature dependence are measured. The results show that both Nitinol and Stainless Steel coatings have excellent thermal stability at temperatures as high as 1000 ◦C and after multiple thermal cycles. Contrarily, Inconel (particularly 625) based coatings show abundant coating degradation. The investigated coatings also offer a wide range of thermal emissivity (between0.6 and 0.9 in the temperature range of 400–1000 ◦C), and variable trends against increasing temperature. This work is a stepping-stone towards further detailed experimental and modelling studies on the heat transfer enhancement in different ceramic-based packed bed applications through using metallic coatings. QC 20211103

Spintronics is a quantum technology which aims at adding the spin quantum degree of freedom to conventional CMOS electronics. Since the discovery of the giant magneto-resistance in 1988, considered as the birth of this field, spintronics continues flooding the market with plethora of devices used in everyday life applications such as hard drive read heads or magnetic random-access memories, and so on. From a fundamental research perspective, the field is still blooming bringing post-CMOS perspectives technologically closer to the reality with, for instance, prototypes of all-spin-logic circuits and neuromorphic chips. To sustain this intense research activity, a quest for new platform materials is also taking place not only to enhance existing performances but also to generate novel functionalities. In this vein, carbon nanostructures such as molecules, graphene, and carbon nanotubes are among the most sought-after materials. In this review, spin transport experiments in carbon nanotubes and graphene are first detailed and then, the necessity to consider new hybrid interfaces are highlighted for a better control of the spin injection at the quantum device level.

Triangulene, known as Clar's hydrocarbon, is a prototypical non-Kekul�� diradical comprised of six benzenoid rings fused in a triangular shape. We synthesized and characterized its trimesityl derivative, illustrating that three bulky substituents installed in the centers of the zigzag edges suffice to protect all reactive positions. This work brings prospects to use triangulene and its open-shell analogs in spintronic materials via solution-phase synthesis.

Miniaturization of the sensor active areas to length scales of the order of the analyte has been sought as means to reduce device footprints, and to capitalize on the novel optical and electronic enhancements that arise at this scale. However, little is known on what to expect of the sensor behaviour if the sensor footprints are shrunk to the dimensions of the order of analyte themselves. Our results demonstrate the densities and kinetics of adsorption of analyte to significantly increase with decrease in the sensor footprints to dimensions of the order of few multiples of analyte dimensions. Such increase is found to be generic, irrespective of the nature of interactions that drive adsorption, exhibiting qualitative similarity for electrostatic adsorption of nanoparticles, chemisorption of primary oligonucleotides, or complementary base pairing with target nucleotides. The carryover of these benefits onto a macroscopic sensor however requires high density nanopatterns exhibiting significant fill factors withtout compromising inter-feature isolation. The impact of feature dimensions, pattern fill factors, analyte concentrations, presence of convective flow, or the density of receptors are investigated using quantitative and real-time measurements of the nanostructure-analyte interactions using nanopatterned QCM sensors. The results indicate significant opportunities for rational design of nanopatterned macroscopic sensors, as well as nanoscopic sensors with sensor active areas of the order of analyte dimensions, e.g., electromagnetic hot-spots, or nanowire sensors.

Alkali-ion reservoir organic positive electrode materials with high redox potential emerge as promising candidates for rocking-chair batteries. Despite recent major advances on coordinated Li-enolates and conjugated Li-sulfonamides, alike chemistries remain rare with clearly enormous room to explore and investigate. Herein, we report a new high-voltage redox functionality for alkali-ion storage based on aromatic di-sulfonyl methanide. The versatile paradigm chemistry of di-alkali p-phenylene-bis-diethylsulfonyl methanide (denoted as A2-p-TESO2, where A = Li+, Na+, K+) displays high voltage (3.13 vs Li+/Li), a two-electron reversible redox in both liquid phase and solid phase electrochemistry. A2-p-TESO2 also shows great stability under ambient air conditions in their alkali-ion reservoir states. This work not only suggests a new charge storage mechanism for organic batteries but also highlights the versatility of organic chemistry in designing new redox functionalities for next-generation organic rechargeable batteries.

Li-ion microbatteries are the frontline candidates to fulfill the requirements of powering miniature autonomous devices. However, it still remains challenging to attain the required energy densities of > 0.3mWh cm−2 μm−1 in a planar configuration. To overcome this limitation, 3D architectures of LIMBs have been proposed. However, most deposition techniques are poorly compatible with 3D architectures because they limit the choice of current collectors and selective deposition of the active materials. Electrodeposition was suggested as an alternative for rapidly and reproducibly depositing active materials under mild conditions, and with controlled properties. However, despite the huge potential, electrodeposition remains underexplored for LIMB cathode materials, partly due to challenges associated with the electrodeposition of Li-ion phases. Herein, we review advances in the electrodeposition of Li-ion cathode materials with the main focus set on the direct, one-step deposition of electrochemically active phases. We highlight the merits of electrodeposition over other methods and discuss the various classes of reported materials, including layered transition metal oxides, vanadates, spinel, and olivines. We offer a perspective on the future advances for the adoption of electrodeposition processes for the fabrication of microbatteries to pave the way for future research on the electrodeposition of cathode materials.

Similar to conventional photovoltaics, the path toward higher efficiencies for luminescent solar concentrators (LSCs) shows increased interest in tandem structures. Herein, a numerical calculation that allows for much faster estimates of fundamental LSC performance indicators (power conversion efficiency, average visible transmission, and color-rendering index) compared to ray trace simulations is proposed. Both double and triple structures are assessed, taking into account concentrations, absorption and emission spectra, and quantum yield as luminophore inputs for rectangular LSCs of any size. The waveguide material is modeled using an absorption spectrum and a refractive index. Interactions between the first, second, and/or third LSCs are incorporated into the algorithm. A comparison with ray trace results shows good correspondence. Supplementary Excel files are available with detailed calculations for future research or industry applications.

Dual-fluorescence carbon dots have great potential as nanosensors in life and materials sciences. Such carbon dots can be obtained via a solvothermal synthesis route with glutathione and formamide. In this work, we show that the dual-fluorescence emission of the synthesis products does not originate from a single carbon dot emitter, but rather from a mixture of physically separate compounds. We characterized the synthesis products with UV-vis, Raman, infrared, and fluorescence spectroscopy, and identified blue-emissive carbon dots and red-emissive porphyrin. We demonstrate an easy way to separate the two compounds without the need for time-consuming dialysis. Understanding the nature of the system, we can now steer the synthesis toward the desired product, which paves the way for a cheap and environmentally friendly synthesis route toward carbon dots, water-soluble porphyrin, and mixed systems.

3D characterization of assemblies of nanoparticles is of great importance to determine their structure–property connection. Such investigations become increasingly more challenging when the assemblies become larger and more compact. In this paper, we propose an optimized approach for electron tomography to minimize artifacts related to beam broadening in high angle annular dark-field scanning transmission electron microscopy mode. These artifacts are typically present at one side of the reconstructed 3D data set for thick nanoparticle assemblies. To overcome this problem, we propose a procedure in which two tomographic tilt series of the same sample are acquired. After acquiring the first series, the sample is flipped over 180°, and a second tilt series is acquired. By merging the two reconstructions, blurring in the reconstructed volume is minimized. Next, this approach is combined with an advanced three-dimensional reconstruction algorithm yielding quantitative structural information. Here, the approach is applied to a thick and compact assembly of spherical Au nanoparticles, but the methodology can we used to investigate a broad range of samples.

Topological materials discovery has evolved at a rapid pace over the past 15 years following the identification of the first nonmagnetic topological insulators (TIs), topological crystalline insulators (TCIs), and 3D topological semimetals (TSMs). Most recently, through complete analyses of symmetry-allowed band structures - including the theory of Topological Quantum Chemistry (TQC) - researchers have determined crystal-symmetry-enhanced Wilson-loop and complete symmetry-based indicators for nonmagnetic topological phases, leading to the discovery of higher-order TCIs and TSMs. The recent application of TQC and related methods to high-throughput materials discovery has revealed that over half of all of the known stoichiometric, solid-state, nonmagnetic materials are topological at the Fermi level, over 85% of the known stoichiometric materials host energetically isolated topological bands, and that just under $2/3$ of the energetically isolated bands in known materials carry the stable topology of a TI or TCI. In this Review, we survey topological electronic materials discovery in nonmagnetic crystalline solids from the prediction of the first 2D and 3D TIs to the recently introduced methods that have facilitated large-scale searches for topological materials. We also discuss future venues for the identification and manipulation of solid-state topological phases, including charge-density-wave compounds, magnetic materials, and 2D few-layer devices., Comment: Final version, 27 pages, 7 figures

International audience; The authors present a new configuration for laser-induced plasmas in confined regimes for a 10 ns-range laser pulse in the green wavelength (532 nm) that repulses the breakdown threshold above 20 GW/cm2 compared to 8 GW/cm2 as generally indicated in previous works. Using this new configuration, pressures above 12 GPa have been reached for the first time in confined regimes. This can enlarge the range of appli-cations of laser shock such as the range of treatable materials (very high strength materials) or facilities’ costs since neither vacuum nor heavy laser systems will be needed to reach these levels of pressure. The proposed configuration mainly consists of the usage of a water tank. Hence, a great thickness of water is used instead of the extensively used thin water layer. Therefore, the water breakdown plasma will not ini-tiate at the surface of the water, as the laser beam is still not focused there. Instead, it will occur in the depth of the water. In that case, the breakdown threshold value is increased as either the avalanche breakdown or the multiphoton ionization may start at higher laser intensities than at the air/water interface. The authors experimentally demonstrated this new breakdown threshold with the measurement of transmit-ted intensity, transmitted pulse duration, and the indirect measurement of the plasma pressure. Multiple shots (laser shock treatment) were also performed, and the specimen surface deformation was measured, leading to the same conclusion.

International audience; This paper deals with the temperature-dependent modelling of iron losses in the context of magnetic ageing of electricals steel used in high power electrical machines. First, two electrical steel sheet grades were heat treated at three temperatures in order to study the ageing effect evolution as a function of temperature. Results show a significant increase in iron losses for both steel grades. Then, considering the link between the macroscopic magnetic properties evolution (effect) and the microscopic precipitation (cause), the Johnson – Mehl – Avrami – Kolmogorov (JMAK) law describing the kinetics of precipitation was applied to model the time evolution of magnetic ageing. By coupling this model with the Arrhenius’ law, a model is developed to be able to predict the ageing for several temperature levels.

Satellites in core level spectra of photoelectron spectroscopy (PES) can provide crucial information on the electronic structure and chemical bonding in materials, particularly in transition metal oxides. This paper explores satellites of the Ti 1s and 2p core level spectra of SrTiO3 and TiO2. Conventionally, soft x-ray PES (SXPS) probes the Ti 2p core level; however, it is not ideal to fully capture satellite features due to its inherent spin-orbit splitting (SOS). Here, hard x-ray PES (HAXPES) provides access to the Ti 1s spectrum instead, which allows us to study intrinsic charge responses upon core-hole creation without the complication from SOS and with favorable intrinsic linewidths. The experimental spectra are theoretically analyzed by two impurity models, including an Anderson impurity model (AIM) built on local density approximation (LDA) and dynamical mean-field theory (DMFT), and a conventional TiO6 cluster model. The theoretical results emphasize the importance of explicit inclusion of higher-order Ti-O charge-transfer processes beyond the nearest-neighboring Ti-O bond to simulate the core level spectra of SrTiO3 and TiO2. The AIM approach with continuous bath orbitals provided by LDA+DMFT represents the experimental spectra well. Crucially, with the aid of the LDA+DMFT method, this paper provides a robust prescription of how to use the computationally cheap cluster model in fitting analyses of core level spectra.