Spectroscopy Measurements Research Articles

Coherent Erbium Spin Defects in Colloidal Nanocrystal Hosts.

We demonstrate nearly a microsecond of spin coherence in Er3+ ions doped in cerium dioxide nanocrystal hosts, despite a large gyromagnetic ratio and nanometric proximity of the spin defect to the nanocrystal surface. The long spin coherence is enabled by reducing the dopant density below the instantaneous diffusion limit in a nuclear spin-free host material, reaching the limit of a single erbium spin defect per nanocrystal. We observe a large Orbach energy in a highly symmetric cubic site, further protecting the coherence in a qubit that would otherwise rapidly decohere. Spatially correlated electron spectroscopy measurements reveal the presence of Ce3+ at the nanocrystal surface, which likely acts as extraneous paramagnetic spin noise. Even with these factors, defect-embedded nanocrystal hosts show tremendous promise for quantum sensing and quantum communication applications, with multiple avenues, including core-shell fabrication, redox tuning of oxygen vacancies, and organic surfactant modification, available to further enhance their spin coherence and functionality in the future.

Effects of transparent conducting electrodes and hole transport layers on the performance of MAPbI3 solar cells fabricated on PET substrates

This study investigates how the performance of perovskite solar cells (PSCs) made on polyethylene terephthalate (PET) substrates depends on transparent conducting electrodes (TCEs) and hole transport layers (HTLs). We fabricated PSCs using commercially available PET/TCEs and compared their performance with PSCs manufactured on Glass/indium tin oxide (ITO) substrates. Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) with varying levels of acidity and NiO nanoparticles were used as HTLs. The current density-voltage characteristics of PSCs made on PET/TCEs were found to be significantly lower when highly acidic PEDOT:PSS was used as the HTL. However, this was not observed for PSCs made on Glass/ITO. To investigate the interaction between HTL and TCE, atomic force microscopy was carried out after dipping the TCEs in PEDOT:PSS solutions of different acidity. X-ray photoelectron spectroscopy measurements further revealed differences in the chemical composition between ITO film on PET vs. on glass. Our results indicate that the performance of PSCs depends both on the TCE substrates and HTLs, which can be explained by their chemical interaction.

Transverse Inscription of Silicon Waveguides by Picosecond Laser Pulses

AbstractIn this work, picosecond laser inscription of segmented waveguides in crystalline silicon based on a deterministic single‐pulse modification process is demonstrated. Pulses of 43 ps duration at 1.55 wavelength are used to transversely inscribe periodic structures with a pulse‐to‐pulse pitch of ≈2 . Infrared shadowgraphy images and Raman spectroscopy measurements indicate that the modifications exhibit a spherical shape. Characterization of waveguide performance at 1.55 for various pulse energies and periods is carried out. Direct comparison with numerical simulations confirms the presence of graded index waveguides, encompassing a micrometer core size and a maximum refractive index change of . This short‐pulse inscription approach can pave the way for 3D integrated photonic devices in the bulk of silicon.

Shining Light on Osteoarthritis: Spatially Offset Raman Spectroscopy as a Window into Cartilage Health.

Articular cartilage is a complex tissue, and early detection of osteoarthritis (OA) is crucial for effective treatment. However, current imaging modalities lack molecular specificity and primarily detect late-stage changes. In this study, we propose the use of spatially offset Raman spectroscopy (SORS) for noninvasive, depth-dependent, and molecular-specific diagnostics of articular cartilage. We demonstrate the potential of SORS to penetrate deep layers of cartilage, providing a comprehensive understanding of disease progression. Our SORS measurements were characterized and validated through mechanical and histological techniques, revealing strong correlations between spectroscopic measurements and both Young's modulus and depth of cartilage damage. By longitudinally monitoring enzymatically degraded condyles, we further developed a depth-dependent damage-tracking method. Our analysis revealed distinct components related to sample depth and glycosaminoglycan (GAG) changes, offering a comprehensive picture of cartilage health. Collectively, these findings highlight the potential of SORS as a valuable tool for enhancing OA management and improving patient outcomes.

Ammonia and Greenhouse Gas Emissions from Organic Manure Composting: The Effect of Membrane Cover

The current scientific literature predominantly focuses on pilot-scale studies concerning the effectiveness of membrane covers in reducing gas emissions during cattle manure composting. Our study centers on the application of a leading market commercial membrane cover (ePTE-TEXcomm) and a locally manufactured one (ProfiCover®) at industrial processing levels, evaluating their efficacy in mitigating gas emission during the fifth day of the thermophilic phase. Taking into account material inhomogeneities, work environment impact, and efficiency, the results are characteristic of industrial-scale processes rarely discussed in the scientific literature. Our results, obtained with a portable gas sampler and FTIR spectroscopy measurements using corresponding standards, indicate that ePTE-TEXcomm manifested a reduction of 90.8% for NH3 and 59.6% for CO2. CH4 emissions increased, suggesting their potential entrapment. N2O and propane equivalent experienced reductions of 23.1% and 44.8%, respectively. On the other hand, ProfiCover® presented emission reductions for NH3 and CO2 of 93.3% and 85.9%, respectively. CH4, contrasting with ePTE-TEXcomm, showed a significant reduction of 55.6%. N2O and propane equivalent followed with reductions of 56.7% and 84.5%, respectively. All of this divergence in performance implies a potential trade-off in emission reduction efficacy between the covers. Knowledge sharing between researchers and industry partners is key to translating these technologies into widespread adoption.

Thermochemical Properties of High Pressure Neodymium Monoxide.

Neodymium monoxide (NdO) is a metastable rare earth oxide material with a unique electronic structure, which has potential applications across various fields such as semiconductors, energy, catalysis, laser technology, and advanced communications. Despite its promising attributes, the thermodynamic properties of NdO remain unexplored. In this study, high pressure, high temperature phases of neodymium monoxide (NdO, with a rocksalt structure) and body-centered cubic (bcc) Nd metal were synthesized at 5 GPa and 1473 K. X-ray photoelectron spectroscopy (XPS) measurements indicate that the Nd 3d peak shifts to higher energy in NdO relative to Nd2O3, suggesting the possibility of complex electronic states in NdO. Formation enthalpies for the reaction 1/3Nd2O3 + 1/3bcc Nd = NdO obtained from high temperature solution calorimetry in molten sodium molybdate and for the reaction dhcp Nd (metal) = bcc Nd (metal) from differential scanning calorimetry are 25.98 ± 8.65 and 5.2 kJ/mol, respectively. Utilizing these enthalpy values, we calculated the pressure-temperature boundary for the reaction 1/3 bcc Nd + 1/3Nd2O3 = NdO, which has a negative P-T slope of -1.68× 10-4 GPa/K. These insights reveal the high pressure behavior of NdO and neodymium metal, underscoring their potential utility in technological applications.

Unlocking the Potential of Liquid Plasma Polymer Films: Characterizing Aging Effects and Their Impact on the Wrinkling Phenomenon.

Here, we present the study of the intricate dynamics between the physicochemical properties of liquid propanethiol plasma polymer films (PPFs) and the formation of wrinkles in PPF/Al bilayers. The study investigates the effect of liquid PPF aging in the air before top Al layer deposition by magnetron sputtering on the wrinkling phenomenon for 4 days. Thanks to atomic force microscopy, the wrinkle dimensions were found to decrease by approximately 55% in amplitude and 66% in wavelength, correlated with an increase in the viscosity of the PPF over the aging duration (i.e., from less than 107 to 1010 Pa·s). This behavior is not linked to alterations in cross-linking degree as evidenced by time-of-flight secondary ion mass spectrometry experiments but rather to network densification driven by the inherent molecular chain mobility due to the viscous state of the PPF. X-ray photoelectron spectroscopy measurements emphasizing the absence of oxidation of the PPF over the aging duration support this, revealing a unique aging mechanism distinct from other plasma polymer families. Overall, this study offers valuable insights into the design and application of mechanically responsive PPFs involved in bilayer systems, paving the way for advancements in nanotechnology and related fields.

Unlocking the Potential of Liquid Plasma Polymer Films: Characterizing Aging Effects and Their Impact on the Wrinkling Phenomenon.

Here, we present the study of the intricate dynamics between the physicochemical properties of liquid propanethiol plasma polymer films (PPFs) and the formation of wrinkles in PPF/Al bilayers. The study investigates the effect of liquid PPF aging in the air before top Al layer deposition by magnetron sputtering on the wrinkling phenomenon for 4 days. Thanks to atomic force microscopy, the wrinkle dimensions were found to decrease by approximately 55% in amplitude and 66% in wavelength, correlated with an increase in the viscosity of the PPF over the aging duration (i.e., from less than 107 to 1010 Pa·s). This behavior is not linked to alterations in cross-linking degree as evidenced by time-of-flight secondary ion mass spectrometry experiments but rather to network densification driven by the inherent molecular chain mobility due to the viscous state of the PPF. X-ray photoelectron spectroscopy measurements emphasizing the absence of oxidation of the PPF over the aging duration support this, revealing a unique aging mechanism distinct from other plasma polymer families. Overall, this study offers valuable insights into the design and application of mechanically responsive PPFs involved in bilayer systems, paving the way for advancements in nanotechnology and related fields.

Towards a scalable production of β-Li3PS4-based all-solid-state batteries: Optimizing pressing parameters of the tape-casted solid electrolyte and composite cathode films

Pressing of all-solid-state batteries (ASSBs) components is one of the most important processes for scalable production. Henceforth, pressing parameters (pressure and temperature) for β-Li3PS4 (β-LPS) solid electrolyte (SE) separator films and LiNi0.6Co0.2Mn0.2 (NCM622)/β-LPS composite cathode films prepared by a slurry-based process were investigated and optimized. Compression of the β-LPS film at a temperature of 100 °C led to higher ionic conductivity than cold-pressed films. Raman and X-ray photoelectron spectroscopic analyses revealed no changes in the chemical nature of β-LPS material after hot pressing. Interestingly, time-of-flight secondary ion mass spectrometric (ToF-SIMS) analyses indicated a binder enrichment in the upper layers of the hot-pressed film. In a similar trend, increasing compression and temperature resulted in higher densification of NCM622/β-LPS composite cathode films. Based on galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) measurements, hot-pressed composite cathode at 200 MPa/100 °C exhibited a higher coverage percent of catholyte on cathode active material and a greater Li+ diffusion coefficient (DLi+) than cold-pressed one at 200 MPa/20 °C. Cycling tests of “Li–In│β-LPS│NCM/β-LPS” ASSBs with hot-pressed films displayed better cycling performance than that with cold-pressed ones, attributed to the higher concentration of electrochemically active NCM in close contact with β-LPS catholyte.

Effect of sintering temperature on the structural, morphological, optical and electrical properties of Ba1 − xLaxFe12O19

La substituted M-type Barium hexaferrite, Ba(1−x)La(x)Fe12O19, (x = 0.25 and 0.30) were synthesized using ball milling followed by heat treatment at 1150˚C and 1300˚C and the influence of sintering temperature as well as La doping were presented. X-ray diffraction, FESEM, dielectric spectroscopy, and ferroelectric measurements were performed to study the structural, morphological, dielectric, and ferroelectric properties of the prepared samples. Rietveld refinement on the X-ray diffraction measurement reveals the formation of a phase magnetoplumbite structure of barium hexaferrite only for the samples sintered at 1300˚C. The secondary phase, along with the major magnetoplumbite structure, was observed for the sample sintered at 1150˚C. Hexagonal plate-like grains of different sizes were observed, and samples sintered at 1300˚C showed large-size grains. Porosity was observed to decrease with La doping. Impedance spectroscopy reveals that Maxwell-Wagner-type polarisation occurs with the relaxation of mobile charges having long-range hopping. However, the ferroelectric property was suppressed for samples sintered at 1300˚C.

Transition Metal Chelation Effect in MOF-253 Materials: Guest Molecule Adsorption Dynamics and Proposed Formic Acid Synthesis Investigated by Atomistic Simulations

The dynamic characterization of guest molecules in the metal–organic frameworks (MOFs) can always provide the insightful and inspiring information to facilitate the synthetic design of MOF materials from the bottom-up design of perspective. Herein, we present a series of atomistic molecular dynamics simulation for investigating the bipyridine dicarboxylate (bpydc) linker rotation effect on guest molecule adsorption with and without considering the transition metal (TM) chelation in MOF-253 materials. The simulated PXRD patterns of the various linker orientations present the challenge of distinguishing these structural varieties by the conventional crystalline spectroscopic measurements. The observed short inter-TM stable structure may subsequently lead to the formation of a binuclear TM catalytic site, and a proposed formic acid generation mechanism from CO2 and H2 is derived based upon the density functional theory calculations for the application of CO2 reduction.

Interrogation of Oxidative Pulsed Methods for the Stabilization of Copper Electrodes for CO2 Electrolysis.

Using copper (Cu) as an electrocatalyst uniquely produces multicarbon products (C2+-products) during the CO2 reduction reaction (CO2RR). However, the CO2RR stability of Cu is presently 3 orders of magnitude shorter than required for commercial operation. One means of substantially increasing Cu catalyst lifetimes is through periodic oxidative processes, such as cathodic-anodic pulsing. Despite 100-fold improvements, these oxidative methods only delay, but do not circumvent, degradation. Here, we provide an interrogation of chemical and electrochemical Cu oxidative processes to identify the mechanistic processes leading to stable CO2RR through electrochemical and in situ Raman spectroscopy measurements. We first examine chemical oxidation using an open-circuit potential (OCP), identifying that copper oxidation is regulated by the transient behavior of the OCP curve and limited by the rate of the oxygen reduction reaction (ORR). Increasing O2 flux to the cathode subsequently increased ORR rates, both extending lifetimes and reducing "off" times by 3-fold. In a separate approach, the formation of Cu2O is achieved through electrochemical oxidation. Here, we establish the minimum electrode potentials required for fast Cu oxidation (-0.28 V vs Ag/AgCl, 1 M KHCO3) by accounting for transient local pH changes and tracking oxidation charge transfer. Lastly, we performed a stability test resulting in a 20-fold increase in stable ethylene production versus the continuous case, finding that spatial copper migration is slowed but not mitigated by oxidative pulsing approaches alone.

Impact of solvation on the photoisomerisation dynamics of a photon-only rotary molecular motor

The optimization of the quantum efficiency of single-molecule light-driven rotary motors typically relies on chemical modifications. While, in isolated conditions, computational methods have been frequently used to design more efficient motors, the role played by the solvent environment has not been satisfactorily investigated. In this study, we used multiscale nonadiabatic molecular dynamics simulations of the working cycle of a 2-stroke photon-only molecular rotary motor. The results, which display dynamics consistent with the available transient spectroscopy measurements, predict a considerable decrease in the isomerisation quantum efficiency in methanol solution with respect to the gas phase. The origin of such a decrease is traced back to the ability of the motor to establish hydrogen bonds with solvent molecules. The analysis suggests that a modified motor with a reduced ability to form hydrogen bonds will display increased quantum efficiency, therefore extending the set of engineering rules available for designing light-driven rotary motors.

Facile synthesis, enhanced annealing-structural investigation and supercapacitive potentials of NiFe2O4 spinel nanopowder

Herein, we examined and optimized the influence of annealing temperature on microstructural and electrochemical charge storage properties of spinel NiFe2O4 nanopowder synthesized from a simple one-pot sol-gel route. Microstructural techniques encompassing Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, x-ray diffractometry, and Fourier transform infra-red spectroscopy indicate the resulting powder are composed of spinel NiFe2O4 nanoparticle with metal oxygen vibration, crystal properties and lattice strain, all dependent on annealing temperature. Electrochemical charge storage performance of the electrode fabricated from the synthesized material were investigated with the aid of cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy measurements. The obtained results showed that the charge storage performance and rate capability of NiFe2O4 electrode is dependent on the annealing temperature. The study also showed that the electrode from the material annealed at 400 °C demonstrated optimum electrochemical charge storage performance having exhibited optimum specific capacitance and capacity values of 1128 Fg−1 and 58 mAh g−1 at 5 mVs−1 scan rate and 0.5 Ag−1 current density, respectively. The electrode EIS fitted equivalent circuit values were also found dependent on annealing temperature indicating the charge transfer process and rate capability of spinel NiFe2O4 nano-powder can be tailored by simply varying the annealing temperature. The study demonstrates cheap route by which spinel NiFe2O4 powder can be prepared. It also unveils the effect annealing temperature on the microstructural build-up and electrochemical charge storage performance of the material.

Structural elucidation, morphological properties, dielectric properties and their physical interpretation of Cerium-substituted Cobalt and Barium-based M-type hexagonal nano ferrites

Abstract 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.

Synthesis, Crystal Structure, Fluorescence and Theoretical Calculations of Three Zn(II)/Cd(II) Complexes with Bis-dentate N,N-Quinoline Schiff Base.

Three d10 metal complexes, ZnL(OAc)2 (1), CdL(OAc)2 (2) and [CdL2(NO3)2]·CH3CN (3) were synthesized using the ligand (E)-N-(3-methoxy-4-methylphenyl)-1-(quinolin-2-yl)methanimine (L) and characterized by FT-IR spectra, NMR spectra, and CHN elemental analysis. Single-crystal X-ray diffraction analysis revealed that complexes 1 and 2 are isostructural, with the central metal adopting a hexacoordinate octahedral geometry, while complex 3 adopts a triangular dodecahedron geometry. Thermal gravimetric analysis showed that these complexes exhibit good thermal stability. Solid-state fluorescence spectroscopy measurements demonstrated that complexes 1-3 exhibit bright yellow-green fluorescence (λem = 564nm for 1; 524nm for 2; 542nm for 3), suggesting their potential as photoluminescent materials. Furthermore, DFT calculations, including frontier molecular orbitals, energy levels, and surface electrostatic potential, provided insights into the structural and electronic spectral properties of complexes 1-3.

A 0.05%–0.08% THD, 762.9 Hz–10 MHz direct digital frequency synthesizer using a reconfigurable DAC for electrochemical impedance spectroscopy measurements

A 0.05%–0.08% THD, 762.9 Hz–10 MHz direct digital frequency synthesizer using a reconfigurable DAC for electrochemical impedance spectroscopy measurements

Detection of Crude Oil in Subsea Environments Using Organic Electrochemical Transistors.

Current methods for detecting pipeline oil leaks depend primarily on optical detection, which can be slow and have deployment limitations. An alternative non-optical approach for earlier and faster detection of oil leaks would enable a rapid response and reduce the environmental impact of oil leaks. Here, we demonstrate that organic electrochemical transistors (OECTs) can be used as non-optical sensors for crude oil detection in subsea environments. OECTs are thin film electronic devices that can be used for sensing in a variety of environments, but they have not yet been tested for crude oil detection in subsea environments. We fabricated OECTs with poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) as the channel and showed that coating the channel with a polystyrene film results in an OECT with a large and measurable response to oil. Oil that comes in contact with the device will adsorb onto the polystyrene film and increases the impedance at the electrolyte interface. We performed electrochemical impedance spectroscopy measurements to quantify the impedance across the device and found an optimal thickness for the polystyrene coating for the detection of oil. Under optimal device characteristics, as little as 10 μg of oil adsorbed on the channel surface produced a statistically significant change in the source-drain current. The OECTs were operable in seawater for the detection of oil, and we demonstrated that the devices can be transferred to flexible substrates which can be easily implemented in vehicles, pipelines, or other surfaces. This work demonstrates a low-cost device for oil detection in subsea environments and provides a new application of OECT sensors for sensing.

Study of temperature-dependent copper iodide thin film by thermal evaporation system

Abstract The development of heterostructure devices has gained significant attention towards scientific communities in the present time. This article reports on the effective use of the horizontal thermal evaporation (TE) method to successfully fabricate copper iodide (CuI) films on silicon (Si) substrates. By using the TE technique, CuI-based heterojunctions have been fabricated here. CuI exhibits semiconductor qualities of the p-type, making it a promising option for optoelectronic devices in the future. The temperature was varied from room temperature (RT) to 230 °C to synthesise the CuI/Si heterojunction. The structural, morphological, optical, and electrical analyses have been carried out with various substrate temperatures. The X-ray diffraction (XRD) data show that CuI films have demonstrated a polycrystalline character and have lattice parameters of 6.03 Å. The Raman spectroscopy study shows the microstructural analysis of CuI films. The field emission scanning electron microscopy (FESEM) study reveals the variation of grain size and shape with synthesis temperature. The atomic force microscope (AFM) was used to estimate the surface roughness. The CuI films were found to be p-type by the Hall effect measurement. The sample synthesised at 130 °C shows the highest mobility of 83.12 cm2 V-1 s-1 with a carrier concentration of 1019 cm-3. The UV-visible (UV-Vis) spectroscopy measurements show good absorption of UV light by the CuI thin films. The CuI/Si heterojunctions are rectifying, as demonstrated by the I-V measurements, and they respond well to UV light irradiation.

Identifying orientation-dependent optical properties of single-crystalline β-Ga2O3 films

We explore the effect of crystallographic anisotropy on the optical properties of high-quality β-Ga2O3 thin films by conducting experimental measurements and theoretical simulations. High resolution x-ray diffraction measurements confirm the high-quality and the single crystalline quality, ruling out the effect of defects for all films. Raman spectra reveal the presence of anisotropy, as evident from a stronger Bg(2) mode related to GaIO4 chain libration in (100) orientation. Conversely, a stronger Ag(10) mode corresponding to tetrahedral bonds is evident in the (010) orientation, while it is suppressed in the (100) orientation. Low-temperature photoluminescence spectra indicate the presence of intrinsic impurity-related emissions in the ultraviolet and blue regions for all films. An anisotropic bandgap is observed, wherein the lowest bandgap value is related to the (010) oriented sample. Spectroscopic ellipsometry measurements confirm different refractive indices and extinction coefficient values depending on crystallographic orientation, which are in good agreement with the theoretical values obtained by density functional theory, confirming the anisotropic characteristics. The theoretical calculations of charge density show that the strength of covalent bonding depends on the β-Ga2O3 orientation, while experimental findings demonstrate that as the covalent bonding character increases, the film bandgap and the refractive index decrease. The anisotropy of β-Ga2O3 with respect to the crystal orientation leads to variations in the extinction coefficient, refractive index, and bandgap energy.