Spectroscopy Measurements Research Articles

Hole-Carrier-Dominant Transport in 2D Single-Crystal Copper.

In 2D noble metals like copper, the carrier scattering at grain boundaries has obscured the intrinsic nature of electronic transport. However, it is demonstrated that the intrinsic nature of transport by hole carriers in 2D copper can be revealed by growing thin films without grain boundaries. As even a slight deviation from the twin boundary is perceived as grain boundaries by electrons, it is only through the thorough elimination of grain boundaries that the hidden hole-like attribute of 2D single-crystal copper can be unmasked. Two types of Fermi surfaces, a large hexagonal Fermi surface centered at the zone center and the triangular Fermi surface around the zone corner, tightly matching to the calculated Fermi surface topology, confirmed by angle-resolved photoemission spectroscopy (ARPES) measurements and vivid nonlinear Hall effects of the 2D single-crystal copper account for the presence of hole carriers experimentally. This breakthrough suggests the potential to manipulate the majority carrier polarity in metals by means of grain boundary engineering in a 2D geometry.

Edge-Passivated Monolayer WSe2 Nanoribbon Transistors.

The ongoing reduction in transistor sizes drives advancements in information technology. However, as transistors shrink to the nanometer scale, surface and edge states begin to constrain their performance. 2Dsemiconductorsliketransition metal dichalcogenides (TMDs)have dangling-bond-free surfaces, hence achieving minimal surface states. Nonetheless, edge state disorder still limits the performance of width-scaled 2D transistors. This work demonstrates a facile edge passivation method to enhance the electrical properties of monolayer WSe2 nanoribbons, by combining scanning transmission electron microscopy, optical spectroscopy, and field-effect transistor (FET) transport measurements. Monolayer WSe2 nanoribbons are passivated with amorphous WOxSey at the edges, which is achievedusing nanolithography and a controlled remote O2 plasma process. The same nanoribbons, with and without edge passivation are sequentially fabricated and measured. The passivated-edge nanoribbon FETs exhibit 10 ± 6 times higher field-effect mobility than the open-edge nanoribbon FETs, which are characterized with dangling bonds at the edges. WOxSey edge passivation minimizes edge disorder and enhances the material quality of WSe2 nanoribbons. Owing to its simplicity and effectiveness, oxidation-based edge passivation could become a turnkey manufacturing solution for TMD nanoribbons in beyond-silicon electronics and optoelectronics.

Fabrication of covalently bonded MoS2–graphene heterostructures with different organic linkers

Achieving stable and reliable 2D-2D van der Waals heterostructures remains challenging. The broadest strategy for synthesizing these heterostructures is growth or manually stacking one material on top of the other, yet it is inefficient. Here, we present a strategy for synthesizing covalently bonded MoS2-graphene heterostructures using organic linkers with two anchor sites at a low cost. Our covalent heterostructures exhibit a more homogeneously alternating structure than the corresponding randomly alternating structure of vdW heterostructures, as confirmed by surface-enhanced Raman spectroscopy (SERS) measurements. Moreover, different linkers can be used to adjust the interlayer distance between graphene and MoS2, leading to significant impacts on their optical and electrochemical properties, including Photoluminescence (PL), cyclic voltammetry (CV), Ultraviolet-visible spectroscopy (UV-Vis), and SERS. Our strategy offers opportunities to advance fundamental research and enable the practical application of 2D/2D van der Waals heterostructures in various fields, including optoelectronics, energy storage, and catalysis.

Extended X-ray absorption spectroscopy using an ultrashort pulse laboratory-scale laser-plasma accelerator

Laser-driven compact particle accelerators can provide ultrashort pulses of broadband X-rays, well suited for undertaking X-ray absorption spectroscopy measurements on a femtosecond timescale. Here the Extended X-ray Absorption Fine Structure (EXAFS) features of the K-edge of a copper sample have been observed over a 250 eV window in a single shot using a laser wakefield accelerator, providing information on both the electronic and ionic structure simultaneously. This capability will allow the investigation of ultrafast processes, and in particular, probing high-energy-density matter and physics far-from-equilibrium where the sample refresh rate is slow and shot number is limited. For example, states that replicate the tremendous pressures and temperatures of planetary bodies or the conditions inside nuclear fusion reactions. Using high-power lasers to pump these samples also has the advantage of being inherently synchronised to the laser-driven X-ray probe. A perspective on the additional strengths of a laboratory-based ultrafast X-ray absorption source is presented.

Salinity effect on corrosion inhibition of 2-mercaptopyrimidine as an inhibitor in CO2-containing solution

In this work, the effects of Cl-, Ca2+, and Mg2+ on the corrosion inhibition performance of 2-mercaptopyrimidine (2-MP) were investigated. The analysis reveals a marked reduction in the inhibition efficiency of 2-MP, from 91.24 % to 76.29 %, as the NaCl content in the solution rises from 1 wt% to 20 wt%. UV–visible absorption spectroscopy and quartz crystal microbalance measurements indicate that the desorption of 2-MP worsens with an increasing content of corrosive ions. Molecular dynamics simulations reveal the inhibitor desorption mechanism. This work enhances understanding of ion effects on corrosion inhibition and film degradation in high salinity environments.

Strong Interaction between Molybdenum Compounds and Mesoporous CMK‐5 Supports Boosts Hydrogen Evolution Reaction

AbstractStrong metal‐support interaction (SMSI) between transition metal nanoparticles and carbon matrix offers significant structure advantages due to the ability to modulate the electronic structure of metal nanoparticles, increase the density of active sites, and improve the conductivity of catalysts. Here, ultrafine nanoparticles of metallic molybdenum compounds (MoP, Mo2C, and MoS2) strongly coupled with mesoporous carbon CMK‐5 are synthesized. The confinement growth of nanoparticles in the pores of CMK‐5 produces encapsulated nanoparticles, affording facilitated electron transfer, and enhancing the HER activity induced by the SMSI effect. The hierarchical nanostructure and strong electronic interactions between the carbon substrate and molybdenum‐based nanoparticles allow efficient mass/electron transport between the carbon substrate and molybdenum‐based nanoparticles, improving the catalytic hydrogen evolution reaction (HER) activity. The effective electron exchange between the Mo species and the CMK‐5 support is studied by X‐ray photoelectron spectroscopy (XPS) measurement, confirming the presence of the SMSI effect. The resulting MoP/CMK‐5 catalyst exhibits outstanding HER performance in alkaline (65 mV@10 mA cm−2), acidic (123 mV@10 mA cm−2), and simulated seawater electrolytes (103 mV@10 mA cm−2), making it one of the most promising catalysts reported for HER. This work provides guidance on designing high‐performance electrocatalysts with SMSI for the enhancement of the electrochemical reaction.

Oxide‐Encapsulated Silver Electrocatalysts for Selective and Stable Syngas Production from Reactive Carbon Capture Solutions

AbstractElectrolysis of bicarbonate‐containing CO2 capture solutions is a promising approach towards achieving low‐cost carbon‐neutral chemicals production. However, the parasitic bicarbonate‐mediated hydrogen evolution reaction (HER) and electrode instability in the presence of trace impurities remain major obstacles to overcome. This work demonstrates that the combined use of titanium dioxide (TiO2) overlayers with the chelating agent ethylene diamine tetra‐acetic acid (EDTA) significantly enhances the selectivity and stability of Ag‐based electrocatalysts for bicarbonate electrolysis. The amorphous TiO2 overlayers suppress the HER by over 50 % at potentials more negative than −0.7 V vs. RHE, increasing the CO faradaic efficiency (FE) by 33 % (relative). In situ surface‐enhanced Raman spectroscopy (SERS) measurements reveal the absence of near‐surface bicarbonate species and an abundance of CO2 reduction intermediates at the Ag|TiO2 buried interface, suggesting that the overlayers suppress HER by blocking bicarbonate ions from reaching the buried active sites. In accelerated degradation tests with 5 ppm of Fe(III) impurity, the addition of EDTA allows stable CO production with >47 % FE, while the electrodes rapidly deactivate in the absence of EDTA. This work highlights the use of TiO2 overlayers for enhancing the CO : H2 ratio while simultaneously protecting electrocatalysts from impurities likely to be present in “open” carbon capture systems.

Structural elucidation, morphological properties, dielectric properties and their physical interpretation of cerium-substituted cobalt and barium-based M-type hexagonal nano ferrites

This research uses the sol–gel method to look into how adding Co2+ and Ce3+ dopant cations changes the structure, shape, and electrical properties of M-type Ba hexagonal ferrites that have been synthesized. x-ray diffraction (XRD) analysis confirms the successful formation of the targeted hexagonal M-type crystal structure. We observed a reduction in unit cell volume and lattice parameters as the dopant concentration increased, indicating the effective incorporation of dopant ions into the crystal lattice. When the doping process happened, needle-like grain shapes appeared, which could be seen with a field emission scanning electron microscope (FESEM). As the concentration of the dopant increased, the dielectric spectroscopic measurements revealed an increase in the loss tangent (tan δ) from 0.05 to 3.68, and a decrease in the dielectric constant (ε′) from 283 to 3.41. This suggests a reduction in polarization and dielectric permittivity, as well as increased energy dissipation within the material. The electric modulus spectra showed relaxation behaviour that was non-Debye-type, which is another sign that there are complex and multifaceted ways for charges to move. The measurements of relaxation time and AC conductivity showed that the relaxation intervals were not regular and that the conductivity dropped from 2.22*10–4 Ω−1m−1 to 1.4*10–7 Ω−1m−1 as the doping concentration increased. Based on these findings, it seems that the processes of conductivity and dielectric relaxation play a big role in how charges move around in the doped ferrites. We validated complex impedance data obtained through electrochemical impedance spectroscopy (EIS) software against calculated impedance values. The derived grain and grain boundary characteristics also agreed with the observed grain distribution and boundaries from the micrographs, further corroborating the analysis.

Harnessing Cold Sintering to Fabricate Composite Polymer Electrolytes - A Paradigm Shift in Organic-Inorganic Material Assembly

Abstract The development of composite electrolytes for all-solid-state batteries is an emerging field, but the creation of predominantly inorganic electrolytes remains challenging. In this study, Li6.25Al0.25La3Zr2O12 (Al-LLZO), a ceramic material selected for its high ionic conductivity (1x104 S.cm-1 at ambient temperature) was shaped by the cold-sintering process (CSP). The organic phase was synthesized by free-radical polymerization of two poly(ethylene oxide) methacrylate derivatives in the presence of lithium bis(trifluoromethanesulfonyl)imide salts (LiTFSI). The polymethacrylate network with dangling poly(ethylene oxide) (PEO) chains was thus obtained. This in-situ polymerization allows the one-pot synthesis of the composite electrolyte during CSP. Remarkably, the ionic conductivity of the CSP pellet varied with the nature of the organic phase, ranging from 1x10−4 to 1x10−5 S.cm-1 for non-grafted and grafted TFSI anion on the PEO-based network, respectively. Additionally, the transport of Li+ remained unaffected by the inorganic material's nature as long as it contained Li species. Furthermore, a significant enhancement of the ionic conductivity was observed in the composite pellet compared to the TFSI grafted network (10−5 to 10−7 S.cm-1, respectively). Electrochemical impedance spectroscopy measurements revealed changes in the Al-LLZOPEO-based polymer interface during CSP with the formation of an interphase, confirmed by a low activation energy value (0.1 eV).

Maleic Anhydride and (Ethoxy)pentafluorocyclotriphosphazene as Electrolyte Additives for High-Voltage LiCoO2/Si-Graphite Lithium-Ion Batteries.

Anhydride additives including maleic anhydride and succinic anhydride are initially selected as additives in the commercial electrolytes for high-voltage lithium-ion batteries with a Si-based anode. The introduction of (ethoxy)pentafluorocyclotriphosphazene as a flame retardant realizes the nonflammability of electrolytes, and the conductivity of electrolytes exceeds 10 mS cm-1 at 25 °C. Maleic anhydride and (ethoxy)pentafluorocyclotriphosphazene jointly contribute to the exceptional performances of 4.45 V LiCoO2/Si-graphite pouch cells at 25 °C. The capacity retention at 1C of 300 cycles reaches 78%, and the discharge capacity ratio of 6C/1C is approximately 83%. These results suggest that this nonflammable electrolyte has good application prospect. Scanning electron microscopy and X-ray photoelectron spectroscopy measurements are implemented to analyze the interface properties of electrodes.

Laser-patterned epoxy-based 3D microelectrode arrays for extracellular recording.

Microelectrode arrays are commonly used to study the electrophysiological behavior of cells. Recently, there has been a growing interest in fabricating three-dimensional microelectrode arrays. Here, we present a novel process for the fast fabrication of epoxy-based 3D microelectrode array platforms with the assistance of laser-patterning technology. To this end, we photopatterned 3D pillars as scaffolds using epoxy-based dry films. Electrodes and conductor traces were fabricated by laser patterning of sputtered platinum films on top of the 3D structures, followed by deposition of parylene-C for insulation. Microelectrodes at the tip of the 3D structures were exposed using a vertical laser ablation process. The final electrodes demonstrated a low impedance of ∼10 kΩ at 1 kHz in electrochemical impedance spectroscopy measurements under physiological conditions. We investigated the maximum compression force of the 3D structures, which could withstand approximately 0.6 N per pillar. The 3D microelectrode arrays were used to record extracellular signals from HL-1 cells in culture as a proof of principle. Our results show regular firing of action potentials recorded at the tip of the 3D structures, demonstrating the possibility of recording cell signals in non-planar environments.

Examination of acute spin exercise on GABA levels in aging and stroke: The EASE study protocol.

Changes in regional levels of the inhibitory neurotransmitter gamma-aminobutyric acid (GABA) may indicate the potential for favorable responses to the treatment of stroke affecting the upper extremity. By selectively altering GABA levels during training, we may induce long-term potentiation and adjust excitatory/inhibitory balance (E/I balance). However, the impact of this alteration may be limited by neural damage or aging. Aerobic exercise has been shown to increase GABA levels in the sensorimotor cortex and improve motor learning by widening the dynamic range of E/I balance. The cross-sectional project, Effects of Acute Exercise on Functional Magnetic Resonance Spectroscopy Measures of GABA in Aging and Chronic Stroke (EASE), is designed to assess the functional relevance of changes in GABA concentration within the sensorimotor cortex before and after an acute aerobic exercise session. EASE will enroll 30 participants comprised of healthy younger adults (18-35 years; n = 10), older adults (60+ years; n = 10), and persons with chronic stroke (n = 10) affecting distal upper extremity function. We will use resting magnetic resonance spectroscopy to measure all participants' GABA levels at rest before and after aerobic exercise. In addition, we will employ functional magnetic resonance spectroscopy using motor skill acquisition and recall tasks in healthy adults. We hypothesize that acute aerobic exercise will increase resting sensorimotor GABA concentration and that higher GABA resting levels will predict better motor learning performance on measures taken both inside and outside the magnet. We also hypothesize that a higher dynamic range of GABA during task-based spectroscopy in healthy adults will predict better motor skill acquisition and recall. The EASE project will evaluate the effect of acute exercise on GABA levels as a biomarker of upper extremity motor skill learning with two populations (aging adults and those with chronic stroke). We predict that acute exercise, higher sensorimotor GABA levels, and broader dynamic range will be related to better motor skill acquisition.

Rapid-scan broadband frequency-domain terahertz spectroscopy via dynamic optical phase lock

Frequency-domain terahertz (THz) spectroscopy using photomixing devices has unique advantages such as high dynamic range and high spectral resolution. Thus, many applications for solid-state and gas-phase spectroscopy have been proposed. In this study, we developed a feedback controlled technique to dynamically compensate for the optical phase accompanied by frequency sweep, enabling both fast and high-resolution data acquisition across a wide frequency region. From gas-phase THz spectroscopy measurements of dilute acetonitrile gas in a wide frequency range up to 1.1 THz, fine structures with linewidths less than 10 MHz were clearly resolved, while the data acquisition rate was improved by two orders compared to the previously reported value.

Robustness of linear bands in epitaxial planar silicene heterostructure against surface doping

In this study, we investigate the electronic structure of epitaxial planar silicene heterostructure grown on ultrathin gold films on the Si(111) substrates, covered by 0.1 monolayer of silver, antimony and lead. Angle-Resolved Photoemission Spectroscopy measurements reveal that the electronic structure of planar silicene, that shows bands with linear dispersion, remains largely unaffected by the presence of these dopants, with only a slight energy shift observed in the case of antimony. Density functional theory calculations corroborate these experimental observations, confirming the robustness of the epitaxial planar silicene heterostructure against surface doping. The results suggest that the intrinsic electronic properties of planar silicene are well-protected against surface contamination.

Rotational and translational diffusion of biomolecules in complex liquids and HeLa cells.

Diffusive motion accompanies many physical and biological processes. The Stokes-Sutherland-Einstein relation for the translational diffusion coefficient, DT, agrees with experiments done in simple fluids but fails for complex fluids. Moreover, the interdependence between DT and rotational diffusion coefficient, DR, also deviates in complex fluids from the classical relation of DT/DR = 4r2/3 known in simple fluids. Makuch et al. Soft Matter, 2020, 16, 114-124 presented a generalization of the classical translational and rotational diffusion theory for complex fluids. In this work, we empirically verify this model based on simultaneous translational and rotational diffusion measurements. We use fluorescently stained cowpea chlorotic mottle virus (CCMV) particles as monodisperse probes and aqueous polyethylene glycol (PEG) solutions as a model complex fluid. The theory and experimental data obtained from fluorescence correlation spectroscopy (FCS) measurements agreed. Finally, we used the same model and analyzed the diffusion of Yo-Pro-1 stained large ribosomal subunits (LSU) in the cytoplasm and nucleus of living HeLa cells.

On-Demand Catalysed n-Doping of Organic Semiconductors.

A new approach to control the n-doping reaction of organic semiconductors is reported using surface-functionalized gold nanoparticles (f-AuNPs) with alkylthiols acting as the catalyst only upon mild thermal activation. To demonstrate the versatility of this methodology, the reaction of the n-type dopant precursor N-DMBI-H with several molecular and polymeric semiconductors at different temperatures with/without f-AuNPs, vis-à-vis the unfunctionalized catalyst AuNPs, was investigated by spectroscopic, morphological, charge transport, and kinetic measurements as well as, computationally, the thermodynamic of catalyst activation. The combined experimental and theoretical data demonstrate that while f-AuNPs is inactive at room temperature both in solution and in the solid state, catalyst activation occurs rapidly at mild temperatures (~70 °C) and the doping reaction completes in few seconds affording large electrical conductivities (~10-140 S cm-1). The implementation of this methodology enables the use of semiconductor+dopant+catalyst solutions and will broaden the use of the corresponding n-doped films in opto-electronic devices such as thin-film transistors, electrochemical transistors, solar cells, and thermoelectrics well as guide the design of new catalysts.

On‐Demand Catalysed n‐Doping of Organic Semiconductors

AbstractA new approach to control the n‐doping reaction of organic semiconductors is reported using surface‐functionalized gold nanoparticles (f‐AuNPs) with alkylthiols acting as the catalyst only upon mild thermal activation. To demonstrate the versatility of this methodology, the reaction of the n‐type dopant precursor N‐DMBI‐H with several molecular and polymeric semiconductors at different temperatures with/without f‐AuNPs, vis‐à‐vis the unfunctionalized catalyst AuNPs, was investigated by spectroscopic, morphological, charge transport, and kinetic measurements as well as, computationally, the thermodynamic of catalyst activation. The combined experimental and theoretical data demonstrate that while f‐AuNPs is inactive at room temperature both in solution and in the solid state, catalyst activation occurs rapidly at mild temperatures (~70 °C) and the doping reaction completes in few seconds affording large electrical conductivities (~10–140 S cm−1). The implementation of this methodology enables the use of semiconductor+dopant+catalyst solutions and will broaden the use of the corresponding n‐doped films in opto‐electronic devices such as thin‐film transistors, electrochemical transistors, solar cells, and thermoelectrics well as guide the design of new catalysts.

Swift Au+9 ion irradiation-induced defects and alloy complexity effect on the mechanical hardness of NiCoCrFePd HEA and NiCoCrFe MEA

The outstanding radiation damage stability of an NiCoCrFePd high entropy alloy (HEA) as compared to conventional alloys poses the question for the mechanism of an ion–matter interaction. The positron annihilation lifetime spectroscopic and TEM (transmission electron microscopic) measurements are implemented to trace different kinds of defects produced by 120 MeV Au+9 ion irradiation and their evolution as a function of ion fluence. The variation of lifetimes and corresponding intensities with the ion fluence indicates the formation of dislocation-type defects at a lower ion fluence and vacancy clusters at a higher ion fluence caused by coalescence or agglomeration of dislocation defects. Formation of different types of defects in turn modulates the strain development inside the crystal. Additionally, the HR-TEM investigation of NiCoCrFePd HEA also exhibits the formation of dislocation and vacancy clusters with the average size of vacancy clusters increases from ∼2.9 ± 0.1 to ∼3.8 ± 0.1 nm with the increases in the ion fluence. Surprisingly, the average defect cluster size in NiCoCrFePd HEA is suppressed compared to NiCoCrFe MEA, thereby showing the enhanced radiation stability on Pd incorporation due to the high defect recombination caused by reduced thermal conductivity and high lattice distortion. Nano-indentation measurement shows that the radiation hardening behavior of the NiCoCrFePd HEA responded slowly owing to its damage suppression property as compared to the NiCoCrFe MEA. Additionally, softening behavior also appeared at an early fluence in NiCoCrFe MEA compared to the NiCoCrFePd HEA signifying its excellent resistance to defect accumulation.

Exploring the Structural, Optical and Photoluminescence Performances of CuCo2O4 and ZnMn2O4 Alloying

Abstract The performance of the structural, linear/ nonlinear optical and photoluminescent properties of CuCo2O4 and ZnMn2O4 alloying was investigated. (1-x)CuCo2O4/(x)ZnMn2O4 (x=0, 0.10, 0.15, 0.2) samples were prepared by the sol-gel and hydrothermal procedures. Synchrotron X-ray diffraction measurements were employed to investigate the structural and microstructural properties applying the Rietveld refinement method. Fourier transform infraed and Raman techniques were applied to explore the structures’ variation and chemical bonding of the obtained phases. Ultraviolet–visible diffuse reflectance spectroscopy measurements were collected to explore the optical properties. The optical band gap values were determined using the Kubelka-Munk method. All samples exhibited two band gaps in the visible-NIR regions. Upon composing with ZnMn2O4, the band gaps of CuCo2O4 declined for x=0.1 and 0.15, followed by an increase at x=0.2. The possible electronic band structure of the samples and the photoluminescent performance of the prepared samples was investigated. The observed PL patterns manifest wide and asymmetrical emissions. The CIE chromaticity diagram for all samples was plotted. The obtained findings of (1-x)CuCo2O4/(x)ZnMn2O4 nominate their efficient role in optical device fabrication and photocatalyst applications.

In Situ Ni(II) Complexation Induced Deprotonation of Bis-Thiourea-Based Tweezers in DMSO-Water Medium: An Approach toward Recognition of Fluoride Ions in Water with Organic Probe Molecules.

Recognition of fluoride in water through the fluoride-induced Brönsted acid-base deprotonation reaction of an organic probe molecule is still a challenging task owing to the lower basicity of fluoride ions and the instability of the conjugate base of the probe molecules in aqueous medium. Herein, we report a complementary strategy in which the conjugate base of the studied bis-thiourea molecule in dimethyl sulfoxide (DMSO) medium is simultaneously stabilized through chelation of the Ni(II) ion, which eventually facilitates the recognition of the fluoride ion in water samples. The recognition methodology is validated colorimetrically and electrochemically, and finally, the applicability of the approach is explored with water samples collected from fluoride-affected areas. The limit of detection value for the fluoride ion in water medium was found to be 0.2 and 0.3 ppm with UV-visible spectroscopy and differential pulse voltammetry measurements, respectively. The methodology is also demonstrated on a paper strip for the detection of the fluoride ion with the naked eye and a smartphone-based RGB sensor. The scheme has been shown to be effective in enhancing the aqueous fluoride recognition ability of the organic probe molecules with acidic hydrogen prone to deprotonation by the fluoride ion.