Energy Shift Research Articles

Epitaxial SiGeSn grown on Si by ion implantation

We have formed SixGe1−x−ySny compounds on Si substrates by ion implantation and annealing and investigated their concentration profiles, crystallization, and optical properties. Ge and Sn ions were implanted in the range (2.5–10) × 1016 Ge/cm2 at 65 keV, and (1.0–4.0) × 1016 Sn/cm2 at 100 keV, resulting in a peak implant dose at a depth of 50 nm for both species. Epitaxially regrown SixGe1−x−ySny layers (110 nm thick) were produced with Ge and Sn contents that allowed bandgap tuning in the (0.88–1.1) eV range. Shifts in photoelectron binding energies (Si 2p, Ge 3d, and Sn 3d) were consistent with ternary compound formation. Sn segregation was observed for annealing temperatures ≥600 °C. A significant increase in the optical absorption coefficient (×104 cm−1 for λ = (800–1700) nm) was observed for SiGe, SiSn, and SiGeSn alloys, with SiGeSn having coefficients several orders of magnitude higher than for Si. Contributions of segregated Sn to these properties were observed. Metastable SixGe1−x−ySny layers were achieved, which may point to a promising route to mitigate Sn incorporation challenges for near-infrared detectors.

Photovoltaic response promoted via intramolecular charge transfer in triphenylpyridine core with small acceptors: A DFT/TD-DFT study

Currently, A−π−A configured molecules (TTP1-TTP6) were designed from the reference compound (TPPR) by modifying the terminal acceptors for photovoltaic materials. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) using the M06/6-311G(d,p) functional were employed to analyze the photonic and electronic properties of the newly designed derivatives. Various analyses; frontier molecular orbitals (FMOs), density of states (DOS), absorption spectra (λmax), transition density matrix (TDM), binding energy (Eb), hole-electron and open circuit voltage (Voc) were performed to explore the photovoltaic properties of triphenylpyridine based compounds. The structural modulation with acceptor moieties significantly tuned their HOMO and LUMO levels, resulting in reduced band gaps (2.833–3.037 eV). They also exhibited broader absorption spectra (λmax) ranging from 482.560 to 514.756 nm as compared to the reference compound (486.289 nm). Notably, TPP3 showed the good photovoltaic response as it displayed the least energy gap (2.833 eV) with lower binding energy (0.415 eV) and bathochromic shift (512.798 nm) in absorption spectra as compared to all other derivatives. Beside this, a comparative study with spiro-OMeTAD and P3HT standard hole transport materials illustrated that these materials can also be utilized as effective photovoltaic materials.

Fully relativistic derivation of the thermal Sunyaev-Zel'dovich effect

We present the first fully and inherently relativistic derivation of the thermal Sunyaev-Zel'dovich effect. This work uses the formalism historically applied to compute radiation spectra emerging from inverse Thomson/Compton sources of x-ray radiation. Comparing our results to the traditional approach based on relativistically-corrected classical Kompaneets equation, we find small, but systematic differences. Most notable are the modest (⩽10%) differences in the crossover frequency where the spectral distortion due to the Sunyaev-Zel'dovich effect vanishes, and the quadratic scaling of the energy shift with the electron cloud temperatures.

Mitigating Band Tailing in Kesterite Solar Absorbers: Ab Initio Quantum Dynamics.

Open-circuit voltage deficits are limiting factors in kesterite solar cells. Addressing this issue by suppressing band tailing and nonradiative charge recombination is essential for enhancing the performance. We employ ab initio nonadiabatic molecular dynamics to elucidate the origin of band tailing and charge losses and propose a mitigation strategy. The simulations show that Cu-Zn disorder, associated with antisite defect clusters [CuZn+ZnCu], is a significant source of band tailing in kesterites, as evidenced by the much larger Urbach energy in disordered than ordered kesterites. Cu-Zn disorder gives rise to new sulfur-centered coordination polyhedra, increases structural inhomogeneity, changes electrostatic potential at sulfur centers, and shifts the S(3p) orbital energy. Differences in the S(3p)/Cu(3d) and S(3p)/Sn(5s) hybridization strengths and the S(3p) orbital energy shift reduce the band gap by 0.37 eV. Furthermore, Cu-Zn disorder enhances vibrational motion of sulfur anions and surrounding cations, increasing band gap fluctuations by 15 meV. The stronger electron-phonon interactions reduce charge carrier lifetimes and limit the kesterite solar cell efficiency. Partial substitution of Zn with Cd facilitates structural ordering and significantly suppresses band tailing, particularly in disordered systems. The improvement can be attributed to the larger atomic radius and mass of Cd, which weakens bonding around the anion, suppresses S-related vibrations within the covalent tetrahedra, and reduces nonadiabatic coupling, thereby increasing charge carrier lifetimes. The reported results establish the key influence of cation disorder on band tailing and reduced charge carrier lifetimes in kesterites and highlight cation disorder engineering as a strategy to achieve high-efficiency kesterite solar cells.

Changes in electronic structure within NiSx (0.60 < x < 1.53) compound series

In this article, changes in electronic properties of NiSx series of films with different sulfur content (x = S/Ni) are studied using X-ray (XPS) and ultra-violet (UPS) photoelectron spectroscopy techniques. NiSx (0.60 < x < 1.53) films are synthesized on native oxide of Si(111) substrates via reactive deposition of Ni and S in an ultra-high vacuum chamber by varying the sulfur pressures and substrate temperatures. The binding energy (BE) of Ni2p3/2 core level, the separation between the Ni2p3/2 main peaks and satellite peaks, and the Ni3d valence band binding energies are all found to vary nearly linearly with the sulfur content in NiSx series of compounds, suggesting a direct dependence of Ni electronic charge on the sulfur content. The shift of the Ni3d and S3p states (to higher and lower BE, respectively) with an increase in the S content provides experimental confirmation of the theoretical prediction previously reported (Wen et al., 2020) [1]. All NiSx films showed density of states (DOS) at the Fermi level, indicating their metallic nature. The Ni2p3/2 binding energy shift of NiSx films are much smaller than that of oxide-based compounds, confirming the significantly more covalent nature of the sulfides. NiSx film grown on Si (111) substrate showed nickel silicide interface formation. This study provides information on the growth and trends in the electronic properties of NiSx relevant for their applications in catalysis, energy storage, and electronic devices.

High-Throughput Spectroscopy of Geometry-Tunable Arrays of Axial InGaAs Nanowire Heterostructures with Twin-Induced Carrier Confinement.

Predicting the optical properties of large-scale ensembles of luminescent nanowire arrays that host active quantum heterostructures is of paramount interest for on-chip integrated photonic and quantum photonic devices. However, this has remained challenging due to the vast geometrical parameter space and variations at the single object level. Here, we demonstrate high-throughput spectroscopy on 16800 individual InGaAs quantum heterostructures grown by site-selective epitaxy on silicon, with varying geometrical parameters to assess uniformity/yield in luminescence efficiency, and emission energy trends. The luminescence uniformity/yield enhances significantly at prepatterned array mask opening diameters (d0) greater than 50 nm. Additionally, the emission energy exhibits anomalous behavior with respect to d0, which is notably attributed to rotational twinning within the InGaAs region, inducing significant energy shifts due to quantum confinement effects. These findings provide useful insights for mapping and optimizing the interdependencies between geometrical parameters and electronic/optical properties of widely tunable sets of quantum nanowire heterostructures.

Noise analysis of a quasi-phase-matched quantum frequency converter and higher-order counter-propagating SPDC

Quantum frequency conversion (QFC) will be an indispensable ingredient in future quantum technologies. For example, large-scale fibre-based quantum networks will require QFC to interconnect heterogeneous building blocks like emitters, channels, memories, and detectors. The performance of existing QFC devices – typically realized in periodically poled nonlinear crystals – is often severely limited by parasitic noise that arises when the pump wavelength lies between the inter-converted wavelengths. Here we comprehensively investigate the noise spectrum of a QFC device pumped by a CW 1064 nm laser. The converter was realized as a bulk periodically poled potassium titanyl phosphate (ppKTP) crystal quasi-phase-matched for conversion between 637 nm and 1587 nm, which was also polished and coated to resonantly enhance the pump field by a factor of 50. While Raman scattering dominates the noise background from 1140 nm to 1330 nm, at larger energy shifts (beyond 60 THz), parasitic spontaneous parametric down-conversion (SPDC) is the strongest noise source. Further, the noise spectrum was contaminated by a regular succession of narrow-band peaks, which we attribute to a heretofore unidentified higher-order counter-propagating SPDC processes – with quasi-phase-matching orders up to 44 evident in our measurements. This work provides a comprehensive overview of the limiting noise sources in QFC devices that use quasi-phase-matched crystals and will prove an invaluable resource in guiding their future development.

Renewable Energy in Nepal: Current State and Future Outlook

Nepal’s energy mix is predominantly based on traditional and inefficient biomass and fossil fuels. As a result, there is a notable prevalence of energy scarcity in the country. Within the literature, there exists a lack of a comprehensive review of the potential of renewable energy in the country while the relatively less contribution of renewable energy resources, making the country more vulnerable to adopt a more carbon-intensive energy policy. Consequently, in this study, we conduct a thorough review of existing literature to provide a comprehensive assessment of the current status of renewable energy and the energy mix in Nepal. We also discussed the potential for the country to transition to a sustainable energy system. This review analysis exclusively focused on scholarly articles and research reports that specifically addressed the topic of renewable energy in Nepal. Despite the rapid decline in the cost of solar photovoltaics, Nepal’s renewable energy share currently stands at only 3.2%. This paper argues that Nepal needs proactive and favorable strategies and policies to effectively implement clean energy, based on the given premises and the country’s aspirations for sustainable energy. This involves a substantial amount of solar power production combined with battery storage, supplemented by storage methods such as off-river pumping hydropower technology. The study emphasizes the significance of renewable energy in achieving the United Nations’ Sustainable Development Goals (SDGs). This review also emphasizes the obstacles in the advancement of Nepal’s renewable energy industry and offers suitable policy suggestions to address these obstacles, hence facilitating a sustainable shift in energy.

An improbable driver of “just transitions”? Union power in the coal heartland of Western Australia ‘s climate and energy shift

Much scholarship in the nascent field of climate crisis and labour assumes that trade unions can readily become agents of “just transition” to post‑carbon energy systems but simply lack a willingness to do so. We investigate this problem more deeply by asking: under what precise circumstances might unions drive “just transitions”? Drawing upon a case study of one union's effort to build a just transition in the energy generation sector of one fossil-fuel reliant region in Australia, we show that union leaders have seen themselves as agents of change, capable of driving internal change and deploying power resources for a just transition. This transition from a carbon energy system is, however, fragile because the shape of a post-transition region remains unclear and sits in the hands of capital and the state.

Variations in the optical and thermoelectric behavior of ZnCo2O4 nanostructures as a function of synthesis temperature

Zinc cobalt oxide nanostructures were synthesized by electrochemical deposition of zinccobalt alloy at various bath temperatures (15, 30, 45 and 60 ˚C) and its hydrothermal oxidation at 100 ˚C. X-ray diffraction pattern and Raman spectroscopy data reveals the formation of spinal structure of ZnCo2O4. Photoluminescence spectra of the samples exhibit broad peaks with a red shift in the emission energy. Diffused reflectance spectroscopy measured the band gap of the synthesized materials; band gap is 3.06, 3.03, 3.02 and 2.99 eV, for samples electrodeposited at 15, 30, 45 and 60 ˚C, respectively. Optical conductivity of synthesized materials decreases with increasing deposition layers while reflectance shows opposite trend. Thermoelectric set up measures the change in potential difference through synthesized materials when different temperatures are applied and an increment in potential were observed. Seebeck co-efficient and power factor are also studied as function of bath temperature.

Copper-saturated chitosan beads (CuSCBs) for Enhanced phosphate removal

This study investigates the sequential use of non-cross-linked chitosan beads (CBs) for copper and phosphate adsorption, emphasizing copper site saturation and selective phosphate binding. Initially, CBs were loaded with copper until saturation was achieved, where all available sites were occupied by copper at an initial concentration of 100 mg/L. These copper-saturated chitosan beads (CuSCBs) were subsequently applied for phosphate adsorption, achieving a maximum adsorption capacity of 85.89 mg/g at pH 5. X-ray Photoelectron Spectroscopy (XPS) analysis revealed a shift in the Cu2O binding energy to lower values upon phosphate adsorption, indicating that phosphate ions interact primarily with the copper ions intercalated on the CBs rather than the chitosan matrix. Additionally, the nitrogen spectra showed no shift, confirming that the amine groups of chitosan do not participate in phosphate binding. The findings suggest a 1:1 interaction ratio between copper and phosphate ions, with each phosphate ion binding to one copper ion, creating a stable and selective adsorption site. The adsorption data fit the Langmuir isotherm and pseudo-second-order kinetic models, suggesting a homogeneous monolayer adsorption mechanism driven by chemisorption, where each copper site on the chitosan surface selectively binds one phosphate ion. Furthermore, the CuSCBs demonstrated minimal copper leaching and retained 90 % of their phosphate adsorption capacity over multiple adsorption–desorption cycles, highlighting their potential as effective and reusable adsorbents for water treatment applications targeting copper and phosphate removal.

Probing structural and electrochemical properties of a 2D CoMoO4@hBN nanocomposite as pseudocapacitive electrode for high-performance supercapacitors

The effectiveness of energy storage is largely determined by the electrode material's performance in critical areas. Enhancements in ion transport, cyclic stability, rate capability, and specific capacitance directly boost the supercapacitors' overall performance and broaden their application potential. This study aims to enhance these properties by incorporating hexagonal boron nitride (hBN) into cobalt molybdate (CoMoO4) material in a 1:1 stoichiometric ratio. The CoMoO₄@hBN nanocomposite was synthesized using a hydrothermal method followed by ball milling. The X-ray diffraction (XRD) analysis confirmed the formation of a single-phase CoMoO4@hBN composite, with a significant increase in crystallite size from 18.21 nm in pure CoMoO₄ to 25.6 nm, along with a slight shift in diffraction peaks, indicating enhanced crystallinity and structural defects due to the substitution of oxygen with boron atoms. Raman spectroscopy revealed that the composite retains the characteristic peaks of both CoMoO₄ and hBN, with stable sharp peaks at 936 cm−1 (Mo=O bond) and 1367 cm−1 (E2g peak of hBN) even after 20 depth measurements, confirming successful conjugation and consistent vibrational properties. The X-ray photoelectron spectroscopy (XPS) showed a slight shift in Co 2p and Mo 3d binding energies to higher values, suggesting improved electronic interactions between CoMoO4 and hBN, which could enhance the composite's conductivity. The electrochemical analysis demonstrated that incorporating h-BN significantly boosts the electrode's performance compared to pristine CoMoO4, with about 37 % increase in specific capacitance at 1 A g−1, reduced charge transfer resistance (0.11 Ω), and superior cyclic stability with 96 % capacitance retention after 5000 cycles. These findings indicate that hBN enhances both the electrical conductivity and structural integrity of CoMoO4, positioning the CoMoO4@hBN composite as a promising material for high-performance supercapacitors.

Layer-number and strain effects on the structural and electronic properties of PtSe2 material

Bandgap engineering of low-dimensional materials forms a robust basis for advancements in optoelectronic technologies. Platinum diselenide (PtSe2) material exhibits a transition from semi-metal to semiconductor (SM-SC) when going from bulk to monolayer. In this work, density functional theory (DFT) with various van der Waals (vdW) corrections has been tested to study the effect of the layer-number on the structural and electronic properties of the PtSe2material. The considered vdW corrections gave different results regarding the number of layers at which the SM-SC transition occurs. This variation is due to the different interlayer distances found for each correction, revealing the sensitivity of the bandgap to this distance in addition to the layer number. In fact, the bandgap increases with the increasing of the interlayer distance, due to the energy shift of conduction and valence bands dominated by Se-pzorbitals. According to the comparison with the available experimental data, the vdW corrections vdW-DF and rVV10 gave the most accurate results. Moreover, the control of the interlayer distance via vertical compressive strain led to the bandgap tuning of semiconductor PtSe2BL. Indeed, a semi-metal character of PtSe2BL can be obtained under 17% vertical strain. Our work shows a deep understanding of the correlation between the structural and electronic properties, and thus a possibility to tune the bandgap by strain means.

Microstructural characteristics of aluminosilicate minerals in cement clinker prepared from coal gangue, carbide slag, and desulfurization gypsum

Utilizing solid waste to prepare cement clinker with low-calcium minerals is crucial for the low-carbon evolution of cementitious materials. In this study, a belite-ye’elimite-ternesite cement clinker was prepared using coal gangue, carbide slag, and desulfurization gypsum instead of non-renewable resources. The evolution law of the silica-alumina mineral phase in cement clinker under different calcining temperatures was tested and analysed. The results show that the predominant mineral phases in cement clinker consist of belite, ye’elimite, and ternesite at 1200 °C to 1250 °C. The composition of cement clinker transforms into belite and ye’elimite as the calcination temperature increases to 1300–1400 °C. At 1400 ℃, the content of belite in cement clinker reaches a remarkable 85 %. The results of XPS and NMR spectra showed that the chemical binding energy and chemical shift of Al in the cement clinker changed after calcination, representing the transformation of the aluminate in kaolinite, with [AlO6], to ye’elimite, with [AlO4]. The peak fitting results of 29Si NMR spectra semi-quantitatively describe the transition process of the silicate mineral phase from kaolinite to ternesite and then to belite. Morphologically, the increase in calcination temperature leads to a significant enlargement of the grain size of belite in cement clinker. This study can provide a basis for research on the phase regulation of cement clinker composed mainly of low-calcium minerals.

Unraveling the Origin of Elemental Chemical Shift and the Role of Atomic Hydrogen in a Surface Ullmann Coupling System.

The Ullmann coupling of aryl halides is a powerful method in the on-surface synthesis of functional materials. Understanding its basic aspects and influencing factors can aid in the use of this tool for the fabrication of intriguing structures. In this study, we unveil (1) the origin of the shift in the elemental binding energy (BE) and (2) the functions of atomic hydrogen (AH) in a typical Ullmann coupling system using combined spectroscopy and microscopy techniques. During debromination of the aryl halide precursor, the work function (WF) alteration is correlated with the surface Br amount. The WF change instead of C-Ag formation is proposed to play a dominant role in the shift of the molecular C 1s BE. AH dosing onto organometallic chains leads to chain decomposition and surface Br removal. In contrast, AH dosing onto covalent poly(para-phenylene) (PPP) chains results in superhydrogenation in addition to Br removal. The C 1s BE shift is attributed to both WF change and superhydrogenation effects. Thermal annealing restores the PPP chains by eliminating superhydrogenation, which causes the C 1s BE to shift to a high BE. This study provides deep insights into the mechanisms of Ullmann coupling on surfaces, highlighting the significant role of WF alterations and AH treatments in these processes.

Unveiling Doppler effects and charge phenomena in the elastic scattering of keV electrons on polystyrene

Recoil energy is a phenomenon that is observed in various spectroscopy experiments. Elastic Peak Electron Spectroscopy (also known as Electron Compton Scattering) studies the shape of the elastic peak resulting from electron scattering from solid targets. As the atoms move around their equilibrium position, they scatter the distribution of recoil energies, resulting in a broadening of the elastic peak known as Doppler broadening. Since the hydrogen peak has the largest recoil energy shifts due to the low mass of hydrogen, Elastic Peak Electron Spectroscopy is ideal for the detection of hydrogen. The most important aspects of this method for the detection of hydrogen include electron-induced hydrogen desorption and, in dielectric materials, charge phenomena. This work focuses on the elastic peak spectra of keV electrons impinging on polystyrene, with particular interest in the changes in line shape due to the Doppler effect and surface charge during electron irradiation.

Reducing Dielectric Confinement Effect Enhances Carrier Separation in Two-Dimensional Hybrid Perovskite Photocatalysts.

Two-dimensional organic-inorganic hybrid perovskites (OIHPs) with alternating structure of the organic and inorganic layers have a natural quantum well structure. The difference of dielectric constants between organic and inorganic layers in this structure results in the enhancement of dielectric confinement effect, which exhibits a large exciton binding energy and hinders the separation of electron-hole pairs. Herein, a strategy to reduce the dielectric confinement effect by narrowing the dielectric difference between organic amine molecule and [PbBr6]4- octahedron is put forward. The Ethanolamine (EOA) contains hydroxyl groups, resulting in the positive and negative charge centers of O and H non-overlapping, which generated a larger polarity and dielectric constant. The reduced dielectric constant produces a smaller exciton binding energy (71.03 meV) of (C2H7NO)2PbBr4 ((EOA)2PbBr4) than (C8H11N)2PbBr4 ((PEA)2PbBr4 (156.07 meV), and promotes the dissociation of electrons and holes. The increasing of lifetime of photogenerated carrier in (EOA)2PbBr4 are proved by femtosecond transient absorption spectra. Density functional theory (DFT) calculations have also indicated that the small energy shift of the total density of states (DOS) between the C/H/N and the Pb/Br in (EOA)2PbBr4 favors the separation of electrons and holes. In addition, this work demonstrates the application of (PEA)2PbBr4 and (EOA)2PbBr4 in the field of photocatalytic CO2 reduction.

Abnormal Response of Indirect Excitons to Non‐Uniform Elastic Strain in MoS2 Flakes

AbstractRegulating the electronic structures and carrier dynamics in 2D materials via elastic strain is a fascinating avenue for tailoring their optoelectronic properties at atomic scale. Here, the abnormal response of indirect excitons to non‐uniform elastic strain in MoS2 flakes is reported. The non‐uniform elastic strain in the MoS2 flakes is introduced by transferring them to pre‐prepared convex cross structures on a SiO2/Si substrate, where the topography and strain distribution are determined by atomic force microscopy and Raman spectroscopy, respectively. It is observed that the emission energy of the indirect excitons shows an unexpected blue‐shift followed by a red‐shift with increasing the local tensile strain, which is in sharp contrast to the linear red‐shift of the direct excitons. Density functional theory calculations reveal that the abnormal energy shift of the indirect excitons in the MoS2 flakes arises from the strain‐induced competition between two indirect bandgap transitions and the spatial exciton funnel effect in the non‐uniform strain field. This work provides new insights into the elastic strain effect on the indirect excitons in 2D semiconductors, which possesses potential applications in flexible optoelectronic devices.

Synthesis of 2‐Aryl‐2H‐1,2,3‐triazoles via P(OMe)3‐Promoted Intramolecular Transannulation of 4‐Diazenylisoxazol‐5(4H)‐ones

AbstractTrimethyl phosphite promotes the synthesis of 2,4,5‐trisubstituted 2H‐1,2,3‐triazoles. The protocol developed affords a two‐step method towards triazoles from available reagents. 3,4‐Disubstituted isoxazolones are initially coupled with diazonium tetrafluoroborates. The subsequent reaction is triggered by a single electron transfer from the phosphite to the diazenylisoxazolone under heating or blue LED irradiation at room temperature. The radical anion cascade proceeds via a ring opening/decarboxylation/cyclization sequence. The synthesized triazoles show promising fluorescence in the region from 340 nm to 450 nm with a quantum yield up to 81.6%. The emission energy depends slightly on the substituent nature at the triazole carbon atoms. If an electron‐donor group is introduced into the N2 substituent of the triazole ring, it results in a bathochromic shift of the luminescence energy.

Resonant transport in a double-barrier heterostructure AlxGa1−xAs/GaAs and mass discontinuity: a semiclassical path integral approach

In this paper, we investigate the dependence of the resonant carrier transport in an AlGaAs/GaAs double-barrier heterostructure on the electron’s effective mass discontinuity between the well and the barrier layer. We use a one-dimensional model for the effective potential and consider the activation of the resonant tunneling mechanism when a bias is applied between the emitter and the collector. We calculate the system’s Green’s function through semiclassical path integration to obtain the complex spectrum. Electron’s effective mass discontinuity affects our calculations through the contributions of the various propagations inside the heterostructure and the multiple reflections from the turning points. Our findings show that the lowest resonance energy decreases linearly with increasing bias, while the real energy shift of the resonance decreases in a non-linear manner with the mass discontinuity. We also observe that the resonant transport time increases nearly linearly with the mass discontinuity. These results demonstrate the impact of the carrier’s inertia enhancement on the resonance characteristics and are consistent with established concepts in quantum mechanics and previously published works. Furthermore, we identify a critical bias value that distinguishes the behavior of the symmetric and asymmetric heterostructure. Additionally, the derivative of the transport time with respect to mass discontinuity is found to be independent of the applied bias. Our results provide concise analytical relationships involving parameters such as barrier and well thickness and shape, enabling the prediction and optimization of various nanoscale devices’ performance.