Auger Electron Spectroscopy Research Articles

Characterization of the Tyranno SA4 third generation SiC fiber surface and comparison with Tyranno SA3 and HNS fibers

AbstractWhile presenting similar properties, the Hi‐Nicalon Type S (HNS) and Tyranno SA3 (TSA3) SiC fibers exhibit different mechanical behaviors when used as reinforcement in SiC/SiC composites. Indeed, the HNS‐reinforced composites exhibit a pseudoductile mechanical behavior whereas the TSA3‐based composites show low ductility. Even though the differences in their grain size and surface roughness could explain a part of this phenomenon, the chemical composition and microstructure of the fibers outermost surface play a key role. The recent availability of the new Tyranno SA4 (TSA4) SiC fiber allowed the processing of composites showing the expected pseudoductile mechanical behavior in ceramic matrix composites, even without an interphase. Therefore, this result shows that the TSA4 surface should be different from its predecessors. In order to characterize the surface, X‐ray photoelectron spectroscopy (XPS), auger electron spectroscopy (AES), and transmission electron microscopy (TEM) were performed on the HNS, TSA3, and TSA4 fibers. The presence of an organized boron nitride layer of dozens of nanometers in thickness on the TSA4 fiber surface was evidenced. This layer already acts as an interphase material, guaranteeing cracks deflection, and is responsible for the pseudoductile behavior of composites made of this new fiber, reducing the interfacial shear stress at the fiber/matrix interface.

Bulk-to-surface segregation measurements of Cu and S in a Ni-Cu(S) ternary system with Auger electron spectroscopy

The bulk-to-surface segregation measurement of Cu and S in Ni0.813Cu0.187 alloy crystals was investigated by using Auger electron spectroscopy (AES) to monitor the surface concentration of Cu and S during the constant temperature segregation measurement. The constant temperatures were carried out in the temperature range 770 K to 860 K at a 30 K interval. The results show that the initially both Cu and S segregated to the surface and the first segregation rate of Cu is higher than that of S. Once the Cu reached the maximum surface coverage, it started to desegregate until Cu was replaced by S. The segregation measured profile data with a constant temperature heating method were fitted by the modified Fick’s model extracted the bulk diffusion coefficient as DCu in Ni = 5.8 × 10−14exp(−160.1 kJ/RT) m2/s, DS in Ni = 1.2 × 10−2exp(–222.1 kJ/RT) m2/s, The segregation parameters obtained in this work were compared well with experimental data values obtained from published elsewhere.

Standard Approaches to XPS and AES Quantification—A Summary of ISO 18118:2024 on the Use of Relative Sensitivity Factors

ABSTRACTQuantitative analysis of electron spectroscopy data from techniques such as Auger electron spectroscopy (AES) and X‐ray photoelectron spectroscopy (XPS) typically requires the use of relative sensitivity factors (RSFs). Virtually, all routine XPS experiments attempt to turn peak intensities into elemental or chemical compositions using RSFs. The comparability and reproducibility of surface chemical analysis by electron spectroscopies therefore require the standardisation of RSFs and their use. RSFs may be determined either from theoretical calculations based on photo‐ionisation cross‐sections or empirically through direct measurement of homogeneous reference samples of known composition. The accurate use of sensitivity factors, even empirically determined RSFs, requires accounting for the effect of material differences on relative intensities, the so‐called ‘matrix effects’. ISO 18118:2024 is the most recently revised version of the ISO standard for the use and determination of empirical RSFs for quantitative analysis of homogeneous materials by AES and XPS. This article provides a summary of the new, updated standard and the methods described therein, noting in particular the revisions made since the previous edition, ISO 18118:2015.

3R-CuCrO2 delafosite: crystal growth, crystal structure, dielectric and DC conductivity properties

Single-crystal samples of the 3R-CuCrO2 phase (R3m, a = 2.9613(2) Å, c = 17.098(2) Å) with a delafossite structure were grown by the flux method. Structural parameters were refined by X-ray structural analysis. The elemental composition of the grown crystals was confirmed by Auger electron spectroscopy. A threshold electric field switching effect from a high-resistance to a low-resistance state was discovered. The effect is characterized by a jump in electrical resistance (up to 5 orders of magnitude at E = 4.7 kV/cm, T = 120 K) and S-shaped current–voltage characteristics with a region of negative differential resistance. The temperature dependences of dielectric permittivity and dielectric loss tangent exhibit a Debye-type relaxation process with an activation energy of 0.51(3) eV. The observed features of dc conductivity, current–voltage characteristics, and dielectric properties interpreted on the basis of the existence of charge carriers in a small polaron state and the destruction of this state by the electric field.

Observation of novel carbon nanocorals during the synthesis of graphene and investigations on their composition, morphological and structural properties

Novel carbon nanocorals (CNCs) are observed during the synthesis of graphene on copper substrates by thermal chemical vapor deposition, using precursor gas acetylene (C2H2) and carrier gas argon (Ar). CNCs have unique structure and investigations are carried out on structural and elemental compositions by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray excited Auger electron spectroscopy (XAES), energy dispersive X-ray spectroscopy (EDS), field emission scanning electron microscopy (FESEM), and high resolution transmission electron microscopy (HRTEM). The graphitic nature of the CNCs is evident from characteristic D, G, and 2D bands obtained from Raman spectrum. Elemental composition analysis by XPS shows presence of sp2 and sp3 hybridized carbon whereas XAES quantifies percentage of sp2 and sp3 hybridized carbon. FESEM micrographs show a uniform distribution of densely packed CNCs throughout the sample, and formation of groups of CNCs with distinct contours on the surface. The cross-sectional FESEM shows stacking of large number of graphene layers with dendrites. HRTEM analysis further supports observations of FESEM and elaborates structural morphology of the CNCs. Synthesis, characterization and analysis of the properties of carbon nanocorals are reported here, for the first time.

Promoting subsurface Sn incorporation at Nb(100) oxide surface sites leading to homogeneous Nb3Sn film growth for superconducting radiofrequency applications

For next-generation superconducting radiofrequency (SRF) cavities, the interior walls of existing Nb SRF cavities are coated with a thin Nb3Sn film to improve the superconducting properties for more efficient, powerful accelerators. The superconducting properties of these Nb3Sn coatings are limited due to inhomogeneous growth resulting from poor nucleation during the Sn vapor diffusion procedure. To develop a predictive growth model for Nb3Sn grown via Sn vapor diffusion, we aim to understand the interplay between the underlying Nb oxide morphology, Sn coverage, and Nb substrate heating conditions on Sn wettability, intermediate surface phases, and eventual Nb3Sn nucleation. In this work, Nb-Sn intermetallic species are grown on a single crystal Nb(100) in an ultrahigh vacuum chamber equipped with in situ surface characterization techniques including scanning tunneling microscopy, Auger electron spectroscopy, and x-ray photoelectron spectroscopy. Sn adsorbate behavior on oxidized Nb was examined by depositing Sn with submonolayer precision on a Nb substrate held at varying deposition temperatures (Tdep). Experimental data of annealed intermetallic adlayers provide evidence of how Nb substrate oxidization and Tdep impact Nb-Sn intermetallic coordination. The presented experimental data contextualize how vapor and substrate conditions, such as the Sn flux and Nb surface oxidation, drive homogeneous Nb3Sn film growth during the Sn vapor diffusion procedure on Nb SRF cavity surfaces. This work, as well as concurrent growth studies of Nb3Sn formation that focus on the initial Sn nucleation events on Nb surfaces, will contribute to the future experimental realization of optimal, homogeneous Nb3Sn SRF films.

Effect of О<sub>2</sub><sup>+</sup> Ion Implantation on the Elemental and Chemical Composition of the Si(111) Surface

Using the methods of secondary ion mass spectrometry, elastic peak electron spectroscopy and Auger electron spectroscopy, the elemental and chemical composition of the surface, concentration profiles of the distribution of atoms over the depth of silicon implanted with O2+ ions with energy E0 = 1 keV at a dose of D = 6 × 1016 cm–2 were studied. It was found that oxides and suboxides of Si (SiO2, Si2O and SiO0.5) were formed in the ion-doped layer, and it also contained unbound O and Si atoms. Post-implantation annealing at 850–900 K led to the formation of a stoichiometric SiO2 layer ~25–30 Å thick.

Analysis of the Influence of Formation of Pd Silicides on Surface Layers of Si on the Diffusion of Atoms of Contacting Metal

4-probe measurements of surface resistivity, measurements of dark and light current-voltage characteristics, the possibilities of using a thin PdSi film to obtain perfect nano-sized ohmic contacts on the Si(111) surface have been investigated using Auger electron spectroscopy methods in combination with ion etching of the surface. It has been shown that the depth of Ni diffusion in the Ni-Si (111) system is 400 ‑ 500 Å at indoor temperature, and 70 – 80 Å in the Ni-PdSi-Si (111) system. The quality of the ohmic contact in the latter case does not change up to T = 800 K and withstands luminous flux illumination up to F = 1100 lux. It is shown that the resistivity of the PdSi film passes through a minimum at T = 900 – 1000 K. An analysis of the results obtained will be given in the article.

Modeling the influence of the duration of water vapor pulses on the properties of hafnium oxide synthesized by atomic layer deposition method

The work experimentally and theoretically analyzes the process of atomic layer deposition of hafnium oxide with the participation of water vapor as an oxidizing agent. The study of infrared absorption, Auger spectroscopy and luminescence shows that with increasing water pulse duration, the concentration of oxygen vacancies decreases and the composition tends to stoichiometric, which is given by the formula HfO2. Modeling of gas dynamics and kinetics of film synthesis by atomic layer deposition was performed, which showed the dependence of the coverage of the film surface with oxygen on the pulse duration and deposition temperature. A comparison of calculations with experimental results made it possible to estimate the magnitude of the kinetic coefficients of the synthesis processes that describe the observed experimental dependences and to show that the larger of the two temperatures of the atomic layer deposition window is associated with water desorption.

Elimination of V‐Shaped Pits in Thick InGaN Layers via Ammonia‐Assisted Face‐to‐Face Annealing

InGaN, a group‐III nitride semiconductor, is expected to be widely used in the field of optoelectronics, owing to its excellent physical properties. However, InGaN has various limitations. This study reports face‐to‐face annealing (FFA) using vapor‐phase and in‐plane mass transport to improve the surface flatness of an InGaN template. InGaN layers are grown on a GaN template that is grown on a c‐plane sapphire substrate using metal–organic vapor‐phase epitaxy. NH3‐assisted FFA is performed at 1050 °C for 20 min, causing V‐pits to vanish from the InGaN template despite their initial density of 3.3 × 108 cm−2. The surface condition of the lower InGaN layer is worse than that of the upper InGaN layer due to the FFA‐induced upward mass transport from the lower layer, thereby eliminating the V‐pits. Compositional analysis of the upper layer through Auger electron spectroscopy and energy‐dispersive X‐ray spectroscopy reveals In peaks despite high‐temperature annealing, thus confirming the presence of InGaN. The results of this study offer possibilities for future InGaN crystal growth and InGaN‐based device fabrication.

Toward Controlled Fluidized Bed – Chemical Vapor Deposition of Boron Nitride: Thermochemical Analysis and Microstructural Investigations

AbstractThis study examines the optimization and characterization of stoichiometric and carbon‐free boron nitride interphase coatings using triethylamine borane complex as a precursor in the Fluidized Bed Chemical Vapor Deposition process. It highlights the importance of optimizing chemical vapor deposition parameters to control coating formation, limit carbon contamination, and assess the feasibility of stoichiometric boron nitride from triethylamine borane complex coatings. The study investigates the thermal decomposition of triethylamine borane complex and its effect on carbon contamination through theoretical thermodynamic calculations, corroborated by Fourier‐transform infrared spectroscopy. Analysis shows a consistent, uniform microstructure. Auger electron spectroscopy and X‐ray photoelectron spectroscopy confirm the presence of boron, nitrogen, carbon, and oxygen, with negligible carbon inclusions. Transmission electron microscopy and electron energy loss spectroscopy reveal a low‐crystalline, isotropic structure. Carbon‐rich areas in boron nitride coatings indicate intricate chemical interactions during deposition, while disordered structures highlight the need to understand the effects of structural variations. Despite using a high‐carbon precursor, boron nitride coatings are remarkably stoichiometric with low carbon and oxygen contamination, demonstrating the benefits of non‐chlorinated precursors.

(Keynote) Unified Quantum Theory of Electrochemical Kinetics Based on Coupled Ion-Electron Transfer

A general theory of coupled ion–electron transfer (CIET) is presented, which unifies quantum kinetics of electron transfer (ET) with classical kinetics of bond-breaking ion transfer (IT) in a general framework of non-equilibrium thermodynamics [1]. In the limit of large reorganization energy, the theory predicts Marcus kinetics of “electron-coupled ion transfer” (ECIT). In the limit of large ion-transfer energies, the theory predicts generalized Butler–Volmer kinetics of “ion-coupled electron transfer” (ICET), where the charge transfer coefficient and exchange current are connected to microscopic properties of the electrode/electrolyte interface. In the ICET regime, the reductive and oxidative branches of Tafel’s law are predicted to hold over a wide but finite range of overpotentials, bounded by the ion-transfer energies for oxidation and reduction, respectively. The probability distribution of transferring electron energies in CIET smoothly interpolates between a shifted Gaussian distribution for ECIT (as in the Gerischer–Marcus theory of ET) to an asymmetric, fat-tailed Meixner distribution centered at the Fermi level for ICET. The latter may help interpret asymmetric line shapes in x-ray photo-electron spectroscopy (XPS) and Auger electron spectroscopy (AES) for oxidized metal surfaces in terms of shake-up relaxation of the ionized atom and its image polaron by ICET. In the limit of large overpotentials, the theory predicts a transition to inverted Marcus ECIT, leading to a universal reaction-limited current for metal electrodes, dominated by barrierless quantum transitions. Uniformly valid, closed-form asymptotic approximations are derived that smoothly transition between the limiting rate expressions for ICET and ECIT for metal electrodes, using simple but accurate mathematical functions. The theory is applied to lithium intercalation in lithium iron phosphate (LFP) and found to provide a consistent description of the observed current dependence on overpotential, temperature and concentration, learned from x-ray images [2]. CIET theory thus provides a critical bridge between quantum electrochemistry and electrochemical engineering.[1] M. Z. Bazant, Unified quantum theory of electrochemical kinetics by coupled ion-electron transfer, Faraday Discussions 246, 60-124 (2023).[2] H. Zhao, H. D. Deng, A. E. Cohen, J. Lim, Y. Li, D. Fraggedakis, B. Jiang, B. D. Storey, W. C. Chueh, R. D. Braatz, and M. Z. Bazant, Learning heterogeneous reaction kinetics from X-ray movies pixel-by-pixel, Nature 621, 289-294 (2023). Figure 1

Effect of MgO/ZnO ratio on the formation process of MgxZn1-xO ceramics

The structural characteristics, chemical composition, and element spatial distribution in MgxZn1-xO ceramics were investigated using X-ray diffraction, scanning electron microscopy, Auger electron spectroscopy, energy-dispersive X-ray spectroscopy, and cathodoluminescence techniques. The study revealed that the morphology of the ceramic samples, as well as the mechanism of solid solution formation, depend on the relative contribution of both oxides in the charge. It was discovered that hexagonal and cubic phases of the solid solution were found to form simultaneously. An increase in the MgO content in the charge results in the magnesium content rise in the hexagonal grains continuously, reaching approximately 13 at.%. It was discovered an enrichment of grain boundaries with zinc and magnesium playing a significant role in doping ZnO and MgO grains. Obtained results allowed to propose two mechanisms involved in the formation of solid solution ceramics: i) diffusion of Mg and Zn along grain boundaries, followed by their incorporation into ZnO or MgO grains, respectively, and ii) interdiffusion of Mg into ZnO and Zn into MgO due to direct contact of ZnO and MgO grains. The second mechanism appears to dominate when both ZnO and MgO contribute comparably, increasing the probability of their direct contact. This study significantly advances the understanding of the process of the formation of MgxZn1-xO ceramics under thermodynamic conditions. These insights are crucial for optimizing the doping process and improving the material properties, thereby promoting innovations in the ceramics industry.

Grain boundary segregation for the Fe-P system: Insights from atomistic modeling and Bayesian inference

In this work we re-assess experimental data for grain boundary (GB) segregation of P in bcc Fe with thermodynamic and statistical methods. The data are based on Auger-Electron-Spectroscopy (AES) measurements which have provided P GB concentrations for various bulk contents and temperatures for ferrite. While in the previous investigations of this system a single-site McLean equation was used to extract segregation enthalpy and entropy, we employ multi-site segregation models as suggested by atomistic simulations. We use a recently introduced methodology based on inter-atomic potentials to calculate the segregation energy spectrum, as well as vibrational entropy and solute-solute interactions of P in polycrystalline Fe, thereby obtaining a three-dimensional distribution of energy, entropy and interactions. Using this trivariate distribution we predict P GB concentrations and compare them to the experimental measurements. Furthermore, we calibrate the parameters of physical models of increasing complexity to the experimental data with an inverse modeling approach based on Bayesian inference. While it is not possible to seamlessly link the results from AES to atomistic modeling, our investigation provides significant new insights for thermodynamic modeling of GB segregation. The vibrational entropy deduced from experiment differs from physics based atomistic simulations even when taking the spectral nature of energy, entropy and interactions into account. However, the correlations of the quantities are in good agreement when considering the trivariate model. Our investigation highlights the need for new and more accurate experimental datasets of GB segregation.

Structure of Silicon Wafers Planar Surface before and after Rapid Thermal Treatment

Presently it is important to remove mechanically disturbed layer on wafer surface during creation of up-to-date microelectronic products. Rapid thermal treatment with optical pulses of second duration is one of the applicable methods for removing disturbances in crystal lattice emerging after ion implantation. However the crystal structure of mechanically disturbed layer on wafer planar side is still unclear. Researches by transmission electronic method, analysis of diffraction reflection curve and electronic Auger spectroscopy has failed to provide reliable data about the state of crystal lattice in surface layer of at least 30 nm thickness. Hence it was impossible to suggest a model of solid phase recrystallization and to present its mathematical description. The goals of the work were as follows: – identify of silicon crystal lattice state in surface layer of 30 nm thickness before and after rapid thermal treatment by backward reflected electrons diffraction method using raw Si wafers surface; – analysis of contamination element composition on the surface of raw silicon before and after rapid thermal treatment; – model development for solid phase recrystallization of surface disturbed layer after rapid thermal treatment and its mathematical description. Images of back ward reflected electrons diffraction using surface layer of raw silicon wafers' of 30 nm thickness and also the results of the planar surface of raw silicon wafers' cleaning from impurities are provided. Processes reducing the activating energy of mechanically disturbed silicon layer recrystallization process were suggested and its mathematical description was provided. Parameters of rapid thermal treatment mitigating the thermal impact on silicon wafer for recrystallization of mechanically disturbed layer on its planar surface ware defined.

Influence of Hardwood Lignin Blending on the Electrical and Mechanical Properties of Cellulose Based Carbon Fibers.

Carbon fibers (CFs) are fabricated by blending hardwood kraft lignin (HKL) and cellulose. Various compositions of HKL and cellulose in blended solutions are air-gap spun in 1-ethyl-3-methylimidazolium acetate (EMIM OAc), resulting in the production of virtually bead-free quality fibers. The synthesized HKL-cellulose fibers are thermostabilized and carbonized to achieve CFs, and consequently their electrical and mechanical properties are evaluated. Remarkably, fibers with the highest lignin content (65%) exhibited an electrical conductivity of approximately 42 S/cm, surpassing that of cellulose (approximately 15 S/cm). Moreover, the same fibers demonstrated significantly improved tensile strength (∼312 MPa), showcasing a 5-fold increase compared to pure cellulose while maintaining lower stiffness. Comprehensive analyses, including Auger electron spectroscopy and wide-angle X-ray scattering, show a heterogeneous skin-core morphology in the fibers revealing a higher degree of preferred orientation of carbon components in the skin compared to the core. The incorporation of lignin in CFs leads to increased graphitization, enhanced tensile strength, and a unique skin-core structure, where the skin's graphitized cellulose and lignin contribute stiffness, while the predominantly lignin-rich core enhances carbon content, electrical conductivity, and strength.

Laser induced ultrafast Gd 4f spin dynamics at the surface of amorphous CoxGd100-x ferrimagnetic alloys

We have investigated the laser induced ultrafast dynamics of Gd 4f spins at the surface of CoxGd100-x alloys by means of surface-sensitive and time-resolved dichroic resonant Auger spectroscopy. We have observed that the laser induced quenching of Gd 4f magnetic order at the surface of the CoxGd100-x alloys occur on a much longer time scale than that previously reported in “bulk sensitive” time-resolved experiments. In parallel, we have characterized the static structural and magnetic properties at the surface and in the bulk of these alloys by combining Physical Property Measurement System (PPMS) magnetometry with X-ray Magnetic Circular Dichroism in absorption spectroscopy (XMCD) and X-Ray Photoelectron spectroscopy (XPS). The PPMS and XMCD measurements give information regarding the composition in the bulk of the alloys. The XPS measurements show non-homogeneous composition at the surface of the alloys with a strongly increased Gd content within the first layers compared to the nominal bulk values. Such larger Gd concentration results in a reduced indirect Gd 4f spin-lattice coupling. It explains the “slower” Gd 4f demagnetization we have observed in our surface-sensitive and time-resolved measurements compared to that previously reported by “bulk-sensitive” measurements.

Drop–Dry Deposition of SnO2 Using Na2SnO3 and Fabrication of SnO2/NiO Transparent Solar Cells

In this work, SnO2 thin films are deposited by drop–dry deposition (DDD), which is a simple, low-cost chemical technique for thin film deposition. The deposition solution contains Na2SnO3 as the Sn source, and is highly stable without spontaneous reactions in the solution. The solution is dropped on a substrate heated to 60°C on a heater plate. According to Auger electron spectroscopy, the deposit will be stoichiometric SnO2. The film is n-type and transparent in the visible range. The pn heterostructure is fabricated by depositing SnO2 on p-type NiO. The NiO film is also fabricated by DDD. Ni(OH)2 is deposited using a solution containing Ni(NO3)2 and NaOH, and then is converted to NiO by annealing at 400°C. The SnO2/NiO structure is transparent in the visible range and shows clear rectification properties and photovoltaic effects. Thus, a transparent solar cell is successfully fabricated by DDD.

Fabrication of monolayer h-BN/LaB6 heterostructure thin film with low work function and high chemical stability

To expand the applications of low work function materials, high chemical stability is necessary to prevent the surface from unfavorable reactions. We developed a 20-nm-thick lanthanum hexaboride (LaB6) thin film covered by a monolayer hexagonal boron nitride (h-BN), which exhibits not only low work function but also high chemical stability. Results demonstrated that the h-BN/LaB6 heterostructure can be formed by vacuum annealing a nitrogen-doped LaB6 thin film. The formation process was investigated using Auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (HREELS), and X-ray absorption near edge structure (XANES) spectroscopy. We have elucidated that the doped nitrogen atoms and boron atoms in the film thermally diffuse into the surface during annealing, thereby forming the monolayer h-BN on the surface. Work function was measured using scanning tunneling microscopy (STM). From a practical perspective, chemical stability was evaluated with a heating temperature necessary for restoring the low work function state after air exposure. The work function was comparable to that of the clean LaB6(100) surface. Moreover, it recovered at a much lower temperature than the cleaning temperature of the LaB6(100) surface. We anticipate that this material development will facilitate implementation of the low work function material.

Quantification of alloy atomic composition sites in 2D ternary MoS2(1-x)Se2x and their role in persistent photoconductivity, enhanced photoresponse and photo-electrocatalysis

Engineering transition metal dichalcogenides-based semiconducting two-dimensional (2D) layered materials for photo(electro)chemical (PEC) hydrogen evolution reaction (HER) by water splitting is an enduring challenge. Here, alloy-assisted photoconductivity and photoresponse from CVD-grown MoS2(1-x)Se2x (MSSE) 2D ternary atomic layered alloy-based photodetector device is presented for the realization of PEC HER. The explicit role of ‘S–Se’ and ‘Se2’ atomic alloy sites including chalcogen-induced vacancy defects on the photoconductivity/photoresponse and PEC HER performance of MSSE 2D alloy is investigated. Alloy formation, atomic site-by-site ‘Se’ composition and atomic structure are characterized using Raman/Photoluminescence (PL) spectroscopy, high-angle annular dark field (HAADF)- scanning transmission electron microscopy (STEM) extensively and supported with Auger Electron Spectroscopy (AES) mapping. Further, the local density and concentration of S–Se, Se2 atomic sites and defects were quantitatively estimated using HAADF-STEM image analysis in correlation with AES and it is found between the range of ∼15–20 % in MSSE alloy. A 10-fold high photoresponsivity in the case of MSSE concerning as-grown MS having fast photocurrent growth time and the prolonged decay time originates from the ‘Se’ and this alloy assisted states to enhance the PEC performance of MSSE alloy. The enhanced PEC HER activity of MSSE alloy was identified in terms of overpotential and current density. In addition, increased density of states as a function of ‘Se’ alloying, shifts in a p-band centre and lowers ΔGH* according to density functional theory calculations, which makes MSSE alloy an efficient HER activity. Further, the PEC stability and presence of the ‘S–Se’ and ‘Se2’ alloying and their role towards HER have been correlated by the spectral line shape analysis of PL and Raman spectra from post-PEC HER catalysts. These experimental and theoretical findings establish the role of chalcogen, and transition metal-based 2D alloy, leading to the design of new PECs of engineered 2D atomic layer interfaces.