Absorption Spectroscopy Research Articles

Broadband cavity-enhanced optical flux monitoring

This work describes a new type of sensor for growth process monitoring named broadband cavity-enhanced optical flux monitoring sensor (BBCE-OFM). Like existing optical flux monitoring (OFM) solutions, it relies on absorption spectroscopy. However, the implementation of an optical cavity reduces the measurement uncertainty, enabling efficient operation even at very low growth rates. Using the BBCE-OFM sensor mounted in our solid-source oxide molecular beam epitaxy reactor, we achieved an uncertainty of ±2% on the measurement of Sr and Ti growth rates in SrTiO3 at around 1 Ml/min, to be compared to the ±16% obtained in the same conditions using a conventional OFM setup. Furthermore, our sensor architecture, based on an echelle monochromator and LEDs replacing the hollow cathode lamps used in standard OFM sensors, is more robust against drift.

Interband cascade laser absorption sensor for sensitive measurement of hydrogen chloride in smoke-laden gases using wavelength modulation spectroscopy

A tunable interband cascade laser sensor, based on wavelength modulation absorption spectroscopy near 3.73 µm, was developed to measure hydrogen chloride gas concentration in smoke-laden environments associated with the overhaul stages of firefighting. Wavelength selection near 2678cm−1 targets the P(0,9) transition within the fundamental vibrational band of HCl, chosen for its absorption strength and isolation from CO2, H2O, and CH4, as well as proximity to absorption features of other toxicant gases of interest in firefighting applications. Both scanned-wavelength direct absorption with a Voigt lineshape-fitting routine and a wavelength modulation spectroscopy absorption method are employed to recover species concentration. The laser sensor is paired with a compact commercial off-the-shelf 1 m multipass optical gas cell modified to use polished Alloy 20 steel mirrors for increased corrosion resistance against humid and acidic gases, and it is tested by sampling effluent gases from pyrolyzing and burning solid samples of polyvinyl chloride under a radiant heating apparatus in a laboratory fume hood. The wavelength modulation spectroscopy method is demonstrated to enable measurement at the near-ppm-level within a compact form-factor and to provide insights into the thermochemical pyrolysis processes that lead to the formation of hydrogen chloride when polyvinyl chloride is exposed to radiant heating.

Tailoring Intrinsic Oxygen Vacancies in P3‐Type Na0.66Mn0.66Mg0.33O1.93 to Enhance Oxygen Redox Activity

Integrating oxygen redox reactions with transition metal redox reactions offers a promising strategy to double or triple the energy density for large‐capacity battery cathodes. In this study, we have introduced intrinsic oxygen vacancies (VO) into a P3 layered cathode to modulate the electronic structure of O atoms and enhance oxygen redox activity. Rietveld‐refined X‐ray diffraction (XRD), X‐ray absorption spectroscopy (XAS), and X‐ray photoelectron spectroscopy confirm the successful creation of VO in Na0.66Mn0.66Mg0.33O1.93 (OV‐NMM). Density functional theory (DFT) calculations reveal that VO in OV‐NMM positively enhances the antibonding interaction between Mn and O, directing excess electrons from O holes toward adjacent Mn t2g and O 2p orbitals. This modification significantly improves the reversibility and accelerates Na+ transport kinetics for O2−/O− redox reactions. Ex situ synthon‐based XRD demonstrates that VO effectively eliminates the O3 phase, reduces Mg2+ migration, and suppresses irreversible structural changes. XAS of Mn K‐edge and O K‐edge further illustrate the advantageous role of oxygen vacancies in facilitating oxygen redox reactions. These findings highlight the potential of defect engineering, particularly VO, to boost anionic redox activity for high‐capacity energy storage applications.

Enhance the Proportion of Fe3+ in NiFe-Layered Double Hydroxides by utilizing Citric Acid to Improve the Efficiency and Durability of the Oxygen Evolution Reaction.

NiFe-layered double hydroxides (NiFe-LDH) are a type of catalyst known for their exceptional catalytic performance during the oxygen evolution reaction (OER). In this study, citric acid was incorporated into the synthesis process of NiFe-LDH, resulting in the NiFe-LDH-CA catalyst with superior OER performance. The catalytic efficacy was evaluated using linear sweep voltammetry (LSV), which demonstrated a significant reduction in the overpotential for OER from 320 mV to 240 mV at a current density of 100 mA cm-2. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) indicate that the distribution of nickel valence states showed no significant difference between two samples. However, the NiFe-LDH-CA exhibits a markedly higher proportion of Fe3+ ions in its iron content. In-situ Raman spectroscopes reveal that Fe3+ broadens the redox potential of nickel and Pourbaix diagrams indicate that higher Fe3+ levels could facilitate the interaction with oxygen active sites. Based on the analysis of test data, we propose a hypothesis that the high proportion of Fe3+ in catalysts may accelerate the oxygen evolution process by modulating the redox potential of nickel and engaging with reactive oxygen species. This provides valuable insights into how to improve the reaction rate of nickel-based catalysts.

Unconventional Hexagonal Close‐Packed High‐Entropy Alloy Surfaces Synergistically Accelerate Alkaline Hydrogen Evolution

AbstractAccelerating the alkaline hydrogen evolution reaction (HER), which involves the slow cleavage of HO‐H bonds and the adsorption/desorption of hydrogen (H*) and hydroxyl (OH*) intermediates, requires developing catalysts with optimal binding strengths for these intermediates. Here, the unconventional hexagonal close‐packed (HCP) high‐entropy alloy (HEA) atomic layers are prepared composed of five platinum‐group metals to enhance the alkaline HER synergistically. The breakthrough is made by layer‐by‐layer heteroepitaxial deposition of subnanometer RuRhPdPtIr HEA layers on the HCP Ru seeds, despite the thermodynamic stability of Rh, Pd, Pt, and Ir in a face‐centered cubic (FCC) structure except for Ru. The synchrotron X‐ray absorption spectroscopy (XAS) confirms the atomic mixing and coordination environment of HCP RuRhPdPtIr HEA. Most importantly, they exhibit notable improvements in both electrocatalytic activity and durability for the HER in an alkaline environment, as compared to their FCC RuRhPdPtIr counterparts. Electrochemical measurements, operando XAS analysis, and density functional theory unveil that the binding strengths of H* and OH* intermediates on the active Pt and Ir sites can be weakened and strengthened to a moderate level, respectively, by mixing non‐active Ru, Rh, and Pd atoms with Pt and Ir atoms within the HCP HEA with strong synergistic electronic effects.

Impact of the surface on He(23S1) and He2(a3Σu +) metastables densities in atmospheric pressure RF plasma

Abstract The dynamic of helium metastable formation along an atmospheric pressure helium plasma channel with different bounding surfaces is analysed. The densities of He(23S1) and He2(a3Σu +) are measured using optical absorption spectroscopy. A simple model for helium metastable creation, quenching by water impurities and destruction upon surface impact, is developed. The model shows a very good agreement if one assumes that surfaces mainly control secondary electron emission, affecting the local heating at the plasma boundary sheath. This, in turn, changes the rate for He(23S1) and He2(a3Σu +) conversion. The helium metastable induced desorption of adsorbed water causes a decay of the metastable density along the plasma channel due to quenching.

Ultrafast Excitonic Transitions in Enantiopure and Racemic Squaraine Thin Films

ABSTRACTWhile chirality is a prevalent character of numerous biological and synthetic organic molecules, its selective absorption of circularly polarized light, known as circular dichroism (CD), is typically small due to intrinsically weak coupling between magnetic and electric dipoles. However, thin films of aggregated, enantiopure prolinol‐derived squaraine molecules (ProSQ‐C16) exhibit an unusually large excitonic CD signal, although the underlying mechanism is not yet known. In this study, we employ steady‐state and ultrafast transient absorption spectroscopy to investigate the nature and dynamics of excitons in aggregates of enantiopure and racemic ProSQ‐C16 thin films. Highly resembling transient responses of enantiopure thin films under excitations at different photon energies strongly indicate that a single type of aggregate dominates the linear optical response, that is, a strong red‐shifted (J‐like) and weak blue‐shifted (H‐like) absorption band. On the other hand, the transient properties of the racemic thin film deviate from this pattern and remain largely ambiguous. The short lifetime of excited states and coherent oscillations present in the dynamics of the transient absorption signal indicate that the early time dynamics are governed by a transition towards a dark intermediate state, which might arise from intermolecular charge transfer with potential contributions from the coupling of excitons to the vibrations. This non‐radiative relaxation pathway explains the unusually weak fluorescence of the predominately J‐like behaving aggregate. Our findings conclusively show that the chiral aggregate structure has a strong impact on the optical and dynamic response of the excitons and underline the significance of non‐Frenkel exciton states for the optical properties of anilino squaraine dyes.

Magnetron Sputtering Formation of Germanium Nanoparticles for Electrochemical Lithium Intercalation.

In the drive towards increased lithium based battery capacity, germanium is an attractive material due to its very high lithium storage capacity, second only to silicon. The persistent down-side is the considerable embrittlement accompanying its remarkable volume expansion of close to 300 %. A proven method to accommodate for this lattice expansion is the reduction of the size towards the nanoscale at which the fracturing is prevented by "breathing". In this work we employed a novel magnetron sputtering gas aggregation nanoparticle generator to create unprecedented layers of well-defined germanium nanoparticles with sizes below 20 nm. The electrochemical lithium intercalation was monitored by a suite of techniques under which Raman spectroscopy, which provided clear evidence of the presence of lithium inside the germanium nanoparticles. Moreover, the degree of lattice order was measured and correlated to the initial phases of the lithium-germanium alloy. This was corroborated by electron diffraction and optical absorption spectroscopy, of which the latter provided a strong dielectric change upon lithium intercalation. This study of low lithium concentrations inside layers of well-defined and very small germanium nanoparticles, forms a new avenue towards significantly increasing the lithium battery capacity.

The CH3D Absorption Spectrum Near 1.58 μm: Extended Line Lists and Rovibrational Assignments

Monodeuterated methane (CH3D) contributes greatly to absorption in the 1.58 μm methane transparency window. The spectrum is dominated by the 3ν2 band near 6430 cm−1, which is observed in natural methane and used for a number of planetary applications, such as the determination of the D/H ratio. In this work, we analyze the CH3D spectrum recorded by high-sensitivity differential absorption spectroscopy in the 6099–6530 cm−1 region, both at room temperature and at 81 K. Following a first contribution to this topic by Lu et al., the room-temperature line list is elaborated (11,189 lines) and combined with the previous 81 K list (8962 lines) in order to derive about 4800 empirical lower-state energy values from the ratio of the line intensities measured at 81 K and 294 K (2T-method). Relying on the position and intensity agreements with the TheoReTS variational line list, about 2890 transitions are rovibrationally assigned to twenty bands, with fifteen of them being newly reported. Variational positions deviate from measurements by up to 2 cm−1, and the band intensities are found to be in good agreement with measurements. All the reported assignments are confirmed by Ground-State Combination Difference (GSCD) relations; i.e., all the upper-state energies (about 1370 in total) have coinciding determinations through several transitions (up to 8). The energy values, determined with a typical uncertainty of 10−3 cm−1, are compared to their empirical and variational counterparts. The intensity sum of the transitions assigned between 6190 and 6530 cm−1 represents 76.9 and 90.0% of the total experimental intensities at 294 K and 81 K, respectively.

Building Asymmetric Zn−N3 Bridge between 2D Photocatalyst and Co‐catalyst for Directed Charge Transfer toward Efficient H2O2 Synthesis

AbstractTwo‐dimensional (2D) polymeric semiconductors are a class of promising photocatalysts; however, it remains challenging to facilitate their interlayer charge transfer for suppressed in‐plane charge recombination and thus improved quantum efficiency. Although some strategies, such as π–π stacking and van der Waals interaction, have been developed so far, directed interlayer charge transfer still cannot be achieved. Herein, we report a strategy of forming asymmetric Zn−N3 units that can bridge nitrogen (N)‐doped carbon layers with polymeric carbon nitride nanosheets (C3N4−Zn−N(C)) to address this challenge. The symmetry‐breaking Zn−N3 moiety, which has an asymmetric local charge distribution, enables directed interfacial charge transfer between the C3N4 photocatalyst and the N‐doped carbon co‐catalyst. As evidenced by femtosecond transient absorption spectroscopy, charge separation can be significantly enhanced by the interfacial asymmetric Zn−N3 bonding bridges. As a result, the designed C3N4−Zn−N(C) catalyst exhibits dramatically enhanced H2O2 photosynthesis activity, outperforming most of the reported C3N4‐based catalysts. This work highlights the importance of tailoring interfacial chemical bonding channels in polymeric photocatalysts at the molecular level to achieve effective spatial charge separation.

Pseudospins revealed through the giant dynamical Franz-Keldysh effect in massless Dirac materials

The dynamical Franz-Keldysh effect, indicative of the transient light-matter interaction regime between quantum and classical realms, is widely recognized as an essential signature in wide bandgap condensed matter systems such as dielectrics. In this theoretical study, we applied time-resolved transient absorption spectroscopy to investigate ultrafast optical responses in graphene, a zero-bandgap system. We observed in the gate-tuned graphene that the massless Dirac materials notably enhance intraband light-driven transitions, significantly leading to the giant dynamical Franz-Keldysh effect compared to the massive Dirac materials, a wide bandgap system. In addition, employing the angle-resolved spectroscopy, it is found that the unique polarimetry orientation, i.e., perpendicular polarizations for the pump and the probe, further pronounces the optical spectra to exhibit the complete fishbone structure, reflecting quantum pseudospin natures of Dirac cones. Our findings expand the establishment of emergent transient spectroscopy frameworks into not only zero-bandgap systems but also pseudospin-mediated quantum phenomena, moving beyond dielectrics.

Visualizing the Structure and Dynamics of Transition Metal-Based Electrocatalysts Using Synchrotron X-Ray Absorption Spectroscopy.

As the global energy structure evolves and clean energy technologies advance, electrocatalysis has become a focal point as a critical conversion pathway in the new energy sector. Transitional metal electrocatalysts (TMEs) with their distinctive electronic structures and redox properties show great potential in electrocatalytic reactions. However, complex reaction mechanisms and kinetic limitations hinder the improvement of energy conversion efficiency, highlighting the necessity for comprehensive studies on structure and performance of electrocatalysts. X-ray Absorption Fine Structure (XAFS) spectra stand out as a robust tool for examining the electrocatalyst's structures and performance due to its atomic selectivity and sensitivity to local environments. This review delves into the application of XAFS technology in characterizing TMEs, providing in-depth analyses of X-ray Absorption Near-Edge Structure (XANES) spectra, and Extended XAFS (EXAFS) spectra in both R-space and k-space. These analyses reveal intrinsic structural information, electronic interactions, catalyst stability, and aggregation morphology. Furthermore, the paper examines advancements in in-situ XAFS techniques for real-time monitoring of active site changes, capturing critical intermediate and transitional states, and elucidating the evolution of active species during electrocatalytic reactions. These insights deepen our understanding on structure-activity relationship of electrocatalysts and offer valuable guidance for designing and developing highly active and stable electrocatalysts.

Investigation of Single Atom Catalysts by X‐Ray Absorption Spectroscopy

Investigation of Single Atom Catalysts by X‐Ray Absorption Spectroscopy

Surface Coordination Chemistry of Graphitic Carbon Nitride from Ag Molecular Probes.

Graphitic carbon nitride (g-C3N4) has gained significant attention for its catalytic properties,especiallyin the development of Single Atom Catalysts (SACs).However,the surface chemistry underlying the formation of these isolated metal sites remains poorly understood.In thisstudyweemploy Surface OrganoMetallic Chemistry (SOMC) together with advanced microscopic and spectroscopic techniquesfor an in-depth analysis of functionalizedg-C3N4materials, where tailored organosilver probe molecules are used to monitor surface processes and characterize resulting surface species. Amulti-technique approach-including high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM), X-ray absorption spectroscopy (XAS), and multinuclear solid-state Nuclear Magnetic Resonance spectroscopy (ssNMR),coupled with density functional theory (DFT) calculations- identifies three primary surface speciesin Ag-functionalized g-C3N4:bis-NHC-Ag+, dispersed Ag+sites, andphysisorbed molecular precursor.These findings highlight a dynamic grafting process and provide insights into the surface coordination chemistryof functionalizedg-C3N4materials.

Self-Trapped Excitons in 3R ZnIn2S4 with Broken Inversion Symmetry for High-Performance Photodetection.

Exploring novel materials with intrinsic self-trapped excitons (STEs) is crucial for advancing optoelectronic technologies. In this study, 2D 3R-phase ZnIn2S4, featuring broken inversion symmetry, is introduced to investigate intrinsic STEs. This material exhibits a broadband photoluminescence (PL) emission with a full width at half maximum of 164nm and a large Stokes shift of ≈0.6eV, which arises from the distortion of [ZnS4]6- tetrahedral unit induced by the symmetry breaking and strong electron-phonon coupling. The photophysical properties of the STEs exhibit a high Huang-Rhys factor (15.0), rapid STEs formation time (166fs), and extended STEs lifetime (1039ps), as demonstrated by experimental evidence from temperature-dependent PL, Raman spectroscopy, and ultrafast absorption spectroscopy. Additionally, STE-induced photoconductiveeffect is elucidated, indicating that intrinsic STEs in 3R-ZnIn2S4 can provide a synergistic effect that enhances absorption capacity, localization, and lifetime by capturing the self-trapped hole state. Consequently, the 2D 3R-ZnIn2S4 photodetector exhibits remarkable broad-spectrum photosensitivity, including a photo-switching ratio of 11286, response times of less than 0.6ms, responsivity of 15.2AW-1, detectivity of 1.02×10¹¹ Jones, and external quantum efficiency of 5032% under 375nm light. These findings provide new ideas for exploring materials with intrinsic STEs to achieve novel high-performance photodetector applications.

Sensitive Self-Driven Single-Component Organic Photodetector Based on Vapor-Deposited Small Molecules.

Typically, organic solar cells (OSCs) and photodetectors (OPDs) comprise an electron donating and accepting material to facilitate efficient charge carrier generation. This approach has proven successful in achieving high-performance devices but has several drawbacks for upscaling and stability. This study presents a fully vacuum-deposited single-component OPD, employing the neat oligothiophene derivative DCV2-5T in the photoactive layer. Free charge carriers are generated with an internal quantum efficiency of 20 % at zero bias. By optimizing the device structure, a very low dark current of 3.4 · 10-11Acm-2 at -0.1V is achieved, comparable to the dark current of state-of-the-art bulk heterojunction OPDs. This optimization results in specific detectivities of 1· 1013Jones (based on noise measurements), accompanied by a fast photoresponse (f-3dB = 200kHz) and a broad linear dynamic range (>150dB). Ultrafast transient absorption spectroscopy unveils that charge carriers are already formed at very short time scales (<1ps). The surprisingly efficient bulk charge generation mechanism is attributed to a strong electronic coupling of the molecular exciton and charge transfer states. This work demonstrates the very high performance of single-component OPDs and proves that this novel device design is a successful strategy for highly efficient, morphological stable and easily manufacturable devices.

Cation Vacancy-Mediated Ultrafast Hole Transport in CuBi2O4 Photocathodes.

In this study, the ultrafast transport dynamics of the valence band hole states in CuBi2O4 (CBO) photocathodes were investigated by varying the atomic composition and manipulating their p-type character. As a comprehensive ultrafast optical transient absorption spectroscopy (TAS) investigation of compositionally manipulated CBO that combines both ex situ and in situ TAS experiments with photoelectrochemical (PEC) performance tests, the study reveals the polaron formation tendencies of the valence band (VB) holes at cationic vacancy sites. Therefore, it draws a complete picture of the ultrafast hole transport dynamics and provides valuable insights into the hindrance of the photocurrent generated in CBO.

Exploring Ultrafast Carrier Dynamics in Photoelectrochemical Water Splitting Using Transient Absorption Spectroscopy

AbstractHydrogen fuel produced from water splitting using sunlight remains one of the cleanest and most sustainable energy sources. However, photoelectrochemical hydrogen production faces several challenges, including poor sunlight absorption, deficient charge carrier lifetime and transfer rates, and very sluggish kinetics of the water oxidation half‐reaction. To address these challenges, researchers have concentrated on enhancing the efficiency of photoelectrochemical water splitting. A critical factor in this enhancement is a deeper understanding of the fundamental processes involved in photoabsorption and the subsequent oxidation evolution reaction. The advent of ultrafast lasers has enabled the detailed tracking of charge carriers within materials after sunlight absorption, including their separation and migration to the surface for water oxidation. Ultrafast transient absorption spectroscopy is a powerful technique that allows real‐time observation of the behavior of excited states and charge carriers on femtosecond to nanosecond timescales. Recent studies utilizing ultrafast transient absorption spectroscopy are explored to investigate the dynamics of charge carriers in photoelectrochemical water splitting, providing insights into the mechanisms that lead to the design of enhanced photoanodes with improved efficiency.

Tuning Electron-Transfer Driving Force in Photosynthetic Special Pair Models.

Visible-light excitation of a family of bimetallic ruthenium polypyridines with the formula [RuII(tpy)(bpy)(𝜇-CN)RuII(py)4L]n+ (RuRuLn+), where L = Cl-, NCS-, DMAP and ACN, was used to prepare photoinduced mixed-valence (PI-MV) MLCT states as models of the photosynthetic reaction center. Ultrafast transient absorption spectroscopy allowed to monitor photoinduced IVCT bands between 6000 and 11000 cm-1. Mulliken spin densities resulting from DFT and (TD)DFT computations revealed the modulation of the charge density distribution depending on the ligand substitution pattern. Results are consistent with PI-MV systems ranging from non-degenerate Class II to degenerate Class III, with electronic couplings between 1000 and 3500 cm-1.These findings guide the control electron localization-delocalization in charge-transfer/charge-separated excited states, like those involved in the photosynthetic reaction center.

Microscale chemical imaging to characterize and quantify corrosion processes at the metal-electrolyte interface

We introduce an experimental setup to chemically image corrosion processes at metal-electrolyte interfaces under stagnant, confined conditions—relevant in a wide range of situations. The setup is based on a glass capillary, in which precipitation of corrosion products in the interfacial aqueous phase can be monitored over time with optical microscopy, and chemically and structurally characterized with microscopic synchrotron-based techniques (X-ray fluorescence, X-ray diffraction, and X-ray absorption spectroscopy). Moreover, quantification of precipitates through X-ray transmission measurements provides in-situ corrosion rates. We illustrate this setup for iron corrosion in a pH 8 electrolyte, revealing the critical role of O2 and iron diffusion in governing the precipitation of ferrihydrite and its transformation to goethite. Corrosion and coupled reactive transport processes can thus be monitored and fundamentally investigated at the metal-electrolyte interface, with micrometer-scale resolution. This capillary setup has potential applications for in-situ corrosion studies of various metals and environments.