Large Binding Energy Research Articles

Adsorption of dissolved gases (CO, H2, CO2) produced by partial discharge in converter transformer oil by CuO(1, 2) and Ag2O(1, 2) clusters doped with MoTe2: A DFT study

Density functional theory (DFT) was used to analyze the effect of (CuO)n, (Ag2O)n (n=1, 2) cluster-doped MoTe2 on the three gases (CO, H2 and CO2) adsorption performance and characteristics. MoTe2 has large bond length and low binding energy, which can simultaneously achieve high sensitivity to target molecules and excellent reversibility at room temperature. By analyzing the modified MoTe2, compared with the initial MoTe2, the reduced energy band structure of band gap, the increased adsorption energy, more charge transfer, and the increased conductivity of DOS, all reflect that the doping of metal oxides enhances the adsorption and sensing performance of MoTe2 for the three gases. The adsorption capacity of CuO-MoTe2 and (Ag2O)2-MoTe2 for the three gases is: CO>H2>CO2, while the adsorption capacity of (CuO)2-MoTe2 and Ag2O-MoTe2 for the three gases is: CO>CO2>H2. Finally, the adsorption effects of the four modifications were compared and feasibility analyzed through molecular orbitals, recovery time, sensitivity and work function, and corresponding conclusions were drawn. The results of this study provide a theoretical basis for detecting dissolved gases in oil generated by partial discharge of converter transformers.

Enhanced trion emission from WS2 monolayers directly exfoliated on Ag nanohole arrays

The extraordinarily large exciton binding energies of transition metal dichalcogenides (TMDs) have attracted significant attention in both fundamental scientific research and innovative technology development. TMD-metal nanostructures have been fabricated to control excitonic behaviors as well as improve the light-matter interaction in TMDs. WS2 monolayers are integrated with periodic Ag nanohole (AgNH) arrays prepared using a template stripping method. The ultrasmooth and contamination-free surface of the template-stripped Ag layer allows for the direct exfoliation of WS2 flakes on the AgNHs. Surface plasmon excitation increases optical absorption in WS2/AgNH, as evidenced by reflectance, PL, and Raman measurements, along with numerical calculations. Furthermore, the AgNH structures significantly increase the trion-to-exciton emission ratios from the WS2 monolayers on them. Nanoscopic surface photovoltage mapping of WS2/AgNH using Kelvin probe force microscopy can visualize electron accumulation at the suspended WS2 region under light illumination, which triggers the formation of trions. All the results highlight the capability of WS2/AgNH to boost trion emission through plasmon-induced concentrated light and a built-in potential gradient. This work introduces a simple and efficient strategy for fabricating TMD-metal integrated systems to control their excitonic behaviors.

Enhanced π-electron transport in graphitic carbon nitride (g-C3N4) by constructing biochar-welded donor-acceptor (D-A) configuration for photocatalytic conversion of biomass

g-C3N4 has broad prospects in photocatalytic upgrading of biomass but suffers from the large exciton binding energy and high charge recombination rate. Herein, we integrated the biomass-derived carbocyclic rings with heptazine units via π-conjugation, constructing biochar-welded electron donor (D)-acceptor (A) structures in g-C3N4. This structure can induce intrinsic driving forces that promoted electron delocalization and transport. Meanwhile, the interlayer π-π stacking interaction of the carbocyclic rings provided a channel for electrons to migrate on the vertically layered structure. The g-C3N4 with biochar-welded D-A configuration exhibited an improved yield of 87.52 % for xylonic acid from biomass monosaccharide. The mechanism study confirmed the dominant role of superoxide radicals (·O2-) and distinguished singlet oxygen (1O2) from the generation path, demonstrating the supporting role of 1O2 originated from an energy transfer process. This work proposed a universal strategy to construct g-C3N4-based photocatalysts with D-A configuration to achieve efficient photocatalytic reforming of biomass.

Deciphering the Catalytic Mechanism of Peroxidase-like Activity of Iron Sulfide Nanozymes.

Iron sulfide nanomaterials represented by FeS2 and Fe3S4 nanozymes have attracted increasing attention due to their biocompatibility and peroxidase-like (POD-like) catalytic activity in disease diagnosis and treatments. However, the mechanism responsible for their POD-like activities remains unclear. Herein, taking the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) by H2O2 on FeS2(100) and Fe3S4(001) surfaces, the catalytic mechanism was investigated in detail using density functional theory (DFT) calculations and experimental characterizations. Our experimental results showed that the catalytic activity of FeS2 nanozymes was significantly higher than that of Fe3S4 nanozymes. Our DFT calculations indicated that the surface iron ions of iron sulfide nanozymes could effectively catalyze the production of HO• radicals via the interactions between Fe 3d electrons and the frontier orbitals of H2O2 in the range of -10 to 5 eV. However, FeS2 nanozymes exhibited higher POD-like activity due to the surface Fe(II) binding to H2O2, forming inner-orbital complexes, which results in a larger binding energy and a smaller energy barrier for the base-like decomposition of H2O2. In contrast, the surface iron ions of Fe3S4 nanozymes bind to H2O2, forming outer-orbital complexes, which results in a smaller binding energy and a larger energy barrier for the base-like decomposition of H2O2. The charge transfer analysis showed that FeS2 nanozymes transferred 0.12 e and Fe3S4 nanozymes transferred 0.05 e from their surface iron ions to H2O2, respectively. The simulations were consistent with the experimental observations that the FeS2 nanozymes had a greater affinity for H2O2 compared to that of Fe3S4 nanozymes. This work provides a theoretical foundation for the rational design and accurate preparation of iron sulfide functional nanozymes.

Chirality-Dependent Dynamic Evolution for Trions in Monolayer WS2.

Monolayer transition metal dichalcogenides exhibit valley-dependent excitonic characters with a large binding energy, acting as the building block for future optoelectronic functionalities. Herein, combined with pump-probe ultrafast transient transmission spectroscopy and theoretical simulations, we reveal the chirality-dependent trion dynamics in h-BN encapsulated monolayer tungsten disulfide. By resonantly pumping trions in a single valley and monitoring their temporal evolution, we identify the temperature-dependent competition between two relaxation channels driven by chirality-dependent scattering processes. At room temperature, the phonon-assisted upconversion process predominates, converting excited trions to excitons within the same valley on a sub-picosecond (ps) time scale. As temperature decreases, this process becomes less efficient, while alternative channels, notably valley depolarization process for trions, assume importance, leading to an increase of trion density in the unpumped valley within a ps time scale. Our time-resolved valley-contrast results provide a comprehensive insight into trion dynamics in 2D materials, thereby advancing the development of novel valleytronic devices.

Photoluminescence of Monolayer WSe2 Enhanced by the Exciton Funnel Effect and the Interfacial Carrier Tunneling Effect When Integrated with 3D Si Wrinkled Structures

Quantum optics and photonic quantum-information technologies require emitters that have good stability and brightness, coupled with fabrication scalability and on-chip integrability. Most quantized emitters are presently based on 1D and 3D sources. Recently, monolayer transition metal dichalcogenides (TMDCs) hosting spatially localized excitons with narrow linewidths have garnered great interest. Advantages such as large binding energies and long room-temperature lifetimes of intralayer excitons suggest that TMDCs are promising candidates for use in optical devices. Here, we propose an emitter based on a 2D WSe2 semiconductor monolayer integrated with a periodic 3D Si-based wrinkled pattern. Carriers confined within the wrinkled pattern can be electrically and optically pumped, and funneled, to boost emission from the 2D WSe2 layer. This in turn acts as a monochromated quantum light source for the Si or any Si-based quantum optic and photonic information technologies. The brightness of the emission is enhanced by a factor greater than 40 compared with monolayer WSe2 on conventional flat SiGe. Moreover, these monolayer 2D/3D semiconductor composite heterostructures are fully scalable and promisingly efficient chip-integrated emitters.

The relationship between hydrogen storage capacity and 4d transition metal-carbon surface binding energy

This study explores the correlation between the strength of 4d-transition metal (TM)/surface binding energy (BE) and the hydrogen storage capacity in decorated (TM@CNF) and doped (TM/CNF) carbon nanoflakes. The findings reveal smaller TM-CNF distances and larger BE for doped cases. These TM-CNF bond characteristics impact the storage capacity, with doped cases outperforming in Mo/CNF and Tc/CNF and decorated in Y@CNF and Zr@CNF scenarios. This contrasting performance underscores the difficulty in finding a surface/dopant combination for efficient storage, where the BE cannot be weak due to its stability and also cannot be too strong due to the loss of storage capacity.

Evaluation of Aging Effects of Zinc Oxide on the Optical Properties of Porous Silicon-Zinc Oxide Heterojunction Photodetector Device

Porous silicon is very important for integrated technology because of its many superior properties, such as suitability for mass production, easy and controlled production, and adjustable electrical and optical properties. Semiconductors with metal oxides, such as indium oxide, indium tin oxide, tin oxide, and zinc oxide, are highly preferred in optical devices. Among these metal oxides, zinc oxide is preferred for photodetectors because of its stable crystal structure and large exciton binding energy of 60 meV. Researchers have conducted studies on photodetectors with porous silicon-zinc oxide heterojunction structures. The importance of the stable operation of devices has been emphasized. Therefore, in this study, a porous silicon-based zinc oxide heterojunction structure suitable for photodetector production was formed, and the effect of aging on zinc oxide was investigated over time. As a result of the investigation, it was observed that the intensity decreased approximately 2.5 times at the end of 365 days owing to the aging of zinc oxide. In addition, UV spectroscopy measurements were performed to investigate the optical properties that affect their operation as photodetectors. Because the PS-ZnO heterojunction functions as a detector in the UV region, the absorption and reflectivity of the PS-ZnO heterojunction were investigated, especially in the UV region. From the measurements, it was observed that aging decreased absorption and increased reflectance. These findings underscore the negative impact of aging on photodetector performance.

In-situ TEM characterization and atomistic simulation of cavity generation and interaction in tungsten at 800 °C under dual W2+/He+ irradiation

In this work, we have investigated the role of pre-existing nano-scale cavities and irradiation sequence in helium clustering, and in the evolution of the cavity population in tungsten at 800 °C, by performing in-situ Transmission Electron Microscopy (TEM) characterizations under dual-beam W2+(600 keV)/He+(10 keV) irradiation to a total dose of 0.351 dpa, and supported by atomistic simulations. Pre-existing cavities, induced by single W2+ irradiation to 0.256 dpa, were seen to attract induced defects from subsequent irradiations, resulting in enhanced cavity size and a reduced number density in sequential irradiation when compared to concurrent irradiation. Such cavities developed faceted geometries and saturated in number density at an additional 0.051 dpa induced by He+ exposure in the sequential irradiation. In contrast, concurrent irradiations generate a denser cavity distribution that showed no sign of saturation or faceting up to the total irradiation damage of 0.351 dpa. In addition, Molecular Dynamics and Statics simulations were performed using LAMMPS software. These showed the pre-existing cavities to be trapping sites for helium atoms. Despite the large binding energy of ∼6 eV of those cavities, He-He interactions still occurred beyond the effective radius of such sinks, leading to additional He-He clustering not seeded by neighbouring cavities. These results point to the importance of selecting the irradiation conditions to simulate synergistic ion effects on cavity formation and evolution in plasma-facing tungsten-base materials.

The binding energy distribution of H2S: why it is not the major sulphur reservoir of the interstellar ices

Abstract Despite hydrogen sulfide (H2S) has been predicted to be the major reservoir of S-bearing species on the icy mantles of interstellar grains, no solid H2S has been detected so far. A crucial parameter that governs whether or not a species remains frozen onto the grain mantles is its binding energy (BE). We present a new computational study of the H2S BE on a large amorphous water ice surface, constituted by 200 water molecules. The resulting H2S BE distribution ranges from 57 K (0.5 kJ/mol) to 2406 K (20.0 kJ/mol), with the average μ = 984 K (8.2 kJ/mol). We discuss the reasons why the low bound of the newly computed BE distribution, which testifies to the very weak interaction of H2S with the ice surface, has never been found by previous theoretical or experimental works before. In addition, the low H2S BEs may also explain why frozen H2S is not detected in interstellar ices. Following previous molecular dynamics studies that show that the energy of reactions occurring on ice surfaces is quickly absorbed by the water molecules of the ice and conservatively assuming that 10% of the HS + H → H2S formation energy (-369.5 kJ/mol) is left to the newly formed H2S, its energy is more than twice the largest BE and 5 times the average BE and, hence, H2S will most likely leave the water surface.

Oxygen-Vacancy-Mediated Large Binding Energy Exciton Dissociation in Nb3O7(OH) Nanorods with High Electron Mobility for CO2 Photoreduction.

Despite the excellent performance of Nb3O7(OH) in dye-sensitized solar cells and catalysis, its charge separation, transport, and structural properties remain poorly understood. Herein, the Nb3O7(OH) nanorods were prepared, and their structural characteristics, optoelectronic properties, and carrier mobility were also analyzed and investigated through a series of complex characterizations. Theoretical prediction suggested that the exciton binding energy of Nb3O7(OH) could be as high as 100.49 meV. The temperature-dependent photoluminescence (PL) of Nb3O7(OH) nanorods revealed two activation energies, and a higher proportion of long-lived components observed in the photoluminescence decay indicated effective electron trapping. That is, two energy states were present, hindering photogenerated charge recombination and promoting photocatalytic action. Current-voltage characteristics of the Nb3O7(OH) nanorod film were analyzed, revealing an ultrahigh carrier mobility of ∼310 cm2/V·s, ensuring fast and efficient electron transfer. Furthermore, Nb3O7(OH) nanorods were employed to reduce CO2, resulting in the effective production of CO and CH4. Overall, considering the presence of hydroxyl pairs on the surface of Nb3O7(OH), which facilitate the formation of the frustrated Lewis acid-base pairs and the activation of CO2, together with its effective electron trapping and charge transport, give Nb3O7(OH) nanorods a promising potential for CO2 reduction.

Atomic-scale visualization of the interlayer Rydberg exciton complex in moiré heterostructures

Excitonic systems, facilitated by optical pumping, electrostatic gating or magnetic field, sustain composite particles with fascinating physics. Although various intriguing excitonic phases have been revealed via global measurements, the atomic-scale accessibility towards excitons has yet to be established. Here, we realize the ground-state interlayer exciton complexes through the intrinsic charge transfer in monolayer YbCl3/graphite heterostructure. Combining scanning tunneling microscope and theoretical calculations, the excitonic in-gap states are directly profiled. The out-of-plane excitonic charge clouds exhibit oscillating Rydberg nodal structure, while their in-plane arrangements are determined by moiré periodicity. Exploiting the tunneling probe to reflect the shape of charge clouds, we reveal the principal quantum number hierarchy of Rydberg series, which points to an excitonic energy-level configuration with unusually large binding energy. Our results demonstrate the feasibility of mapping out the charge clouds of excitons microscopically and pave a brand-new way to directly investigate the nanoscale order of exotic correlated phases.

Stark Effects of Rydberg Excitons in a Monolayer WSe2 P-N Junction.

The enhanced Coulomb interaction in two-dimensional semiconductors leads to tightly bound electron-hole pairs known as excitons. The large binding energy of excitons enables the formation of Rydberg excitons with high principal quantum numbers (n), analogous to Rydberg atoms. Rydberg excitons possess strong interactions among themselves as well as sensitive responses to external stimuli. Here, we probe Rydberg exciton resonances through photocurrent spectroscopy in a monolayer WSe2 p-n junction formed by a split-gate geometry. We show that an external in-plane electric field not only induces a large Stark shift of Rydberg excitons up to quantum principal number 3 but also mixes different orbitals and brightens otherwise dark states such as 3p and 3d. Our study provides an exciting platform for engineering Rydberg excitons for new quantum states and quantum sensing.

Design of High-Performance Inorganic-Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al13 and Dianhydrides.

Novel inorganic-organic hybrid complexes Al13-X (X represents the dianhydrides PMDA, NTCDA, and PTCDA) are theoretically designed and studied using density functional theory (DFT) and time-dependent DFT. These conjugated dianhydrides containing four acceptor carbonyl groups are commonly used as electron acceptor materials. These compounds possess large binding energies, reflecting the sufficient binding of Al13 to the dianhydride molecule. The binding nature of the complexes is of charge transfer type, i.e., electrons are transferred from the aluminum cluster to the dianhydride. All of the aimed complexes have large mean polarizability (α0) and first hyperpolarizability (β0). The β0 values are explained on the basis of electronic transitions in crucial excited states using the TD-DFT method. Additionally, the hole-electron distribution was analyzed, revealing the nature of electronic excitation. Absorption spectra analysis shows that these complexes have an excellent infrared (IR) transparent region (1000-5000 nm). Therefore, these inorganic-organic hybrid complexes with high stability can be considered as potential candidates for new IR nonlinear optical molecules.

Green Synthesis and Characterization of Zinc Oxide Nanoparticles by Using Numerous Plants: A Review

Nanotechnology deals with the production and usage of material with nanoscale dimension. The nanoscale dimension provides nanoparticles with a large surface area to volume ratio and thus very specific properties. Zinc oxide nanoparticles (ZnO NPs) had been in recent studies due to its large bandwidth and high exaction binding energy and it has potential applications like antibacterial, antifungal, anti-diabetic, antiinflammatory, wound healing, antioxidant and optic properties. Due to the large rate of toxic chemicals and extreme environment employed in the physical and chemical production of these NPs, green methods employing the use of plants, fungus, bacteria and algae have been adopted. This review is a comprehensive study of the synthesis and characterization methods used for the green synthesis of ZnO NPs using different biological sources.

Exploring layer thinning of exfoliated β-tellurene and room temperature photoluminescence with large exciton binding energy revealed in β-TeO2

Due to its tunable bandgap, anisotropic behavior, and superior thermoelectric properties, device applications using layered tellurene (Te) are becoming more attractive. Here, we report a thinning technique for exfoliated tellurene nanosheets using thermal annealing in an oxygen environment. We characterize different thinning parameters, including temperature and annealing time. Based on our measurements, we show that controlled layer thinning occurs in the narrow temperature range of 325–350 °C. We also show a reliable method to form β-tellurene oxide (β-TeO2), which is an emerging wide bandgap semiconductor with promising electronic and optoelectronic properties. This wide bandgap semiconductor exhibits a broad photoluminescence (PL) spectrum with multiple peaks covering the range of 1.76–2.08 eV. This PL emission, coupled with Raman spectra, is strong evidence of the formation of 2D β-TeO2. We discuss the results obtained and the mechanisms of Te thinning and β-TeO2 formation at different temperature regimes. We also discuss the optical bandgap of β-TeO2 and show the existence of pronounced excitonic effects evident by the large exciton binding energy in this 2D β-TeO2 system that reach 1.54–1.62 eV for bulk and monolayer, respectively. Our work can be utilized to have better control over the Te nanosheet thickness. It also sheds light on the formation of well-controlled β-TeO2 layered semiconductors for electronic and optoelectronic applications.

Highly efficient deep-blue emitting CsPbBr3 nanoplatelets synthesized via surface ligand-mediated strategy

Two-dimensional (2D) CsPbBr3 nanoplatelets (NPLs) have attracted great attention as one of promising semiconductor nanomaterials due to their large exciton binding energy and narrow emission spectra. However, the labile ionic and weakly bound surfaces of deep-blue emitting CsPbBr3 NPLs with wide bandgap result in their colloidal instability, thus degrading their optical properties. It is challenging to obtain deep-blue emitting CsPbBr3 NPLs with excellent optical properties. In this study, high-quality blue-emitting CsPbBr3 NPLs with tunable thickness were prepared adopting the DBSA-mediated confinement effect based on the hot-injection method. Thanks to the coordination interaction of − SO3− of DBSA ligand and the Pb2+ on the surface of the CsPbBr3 NPLs, as well as the effective passivation of Br vacancy defects on the surface of NPLs by OAm-Br, the obtained pure-blue CsPbBr3 NPLs and deep-blue CsPbBr3 NPLs show high photoluminescence quantum yield (PLQY) of 92 % and 81.2 %, respectively. To the best of our knowledge, this is the highest PLQY recorded for deep-blue emitting CsPbBr3 NPLs with two monolayers [PbBr6]4− octahedra. Furthermore, the agglomeration of CsPbBr3 NPLs due to ligand loss induced by moisture, oxygen, and irradiation was also suppressed by the dual passivation effect of DBSA and OAm-Br. Our work provided a new approach to developing high-performance and stable deep-blue emitting CsPbBr3 perovskite nanoplatelets.

Inorganic-Organic Hybrid Layered Semiconductor AgSePh: Quasi-Solution Synthesis, Optical Properties, and Thermolysis Behavior.

Two-dimensional inorganic-organic hybrid layered semiconductors are actively studied because of their naturally formed multiquantum well (MQW) structures and associated optical, photoelectric, and quantum optics characteristics. Silver benzeneselenolate (AgSePh, Ph = C6H5) is a new member of such hybrid layered materials, but has not fully been exploited. Herein, we present a quasi-solution method to prepare high quality free-standing AgSePh flake-like microcrystals by reacting diphenyl diselenide (Ph2Se2) with silver nanoparticles. The resultant AgSePh microflakes exhibit room-temperature (RT) resolvable MQW-induced quasi-particle quantization and interesting optical properties, such as three distinct excitonic resonance absorptions X1 (2.67 eV), X2 (2.71 eV), and X3 (2.83 eV) in the visible region, strong narrow-line width blue photoluminescence at ∼2.64 eV (470 nm) from the radiative recombination of the X1 exciton state, and a large exciton binding energy (∼0.35 eV). Furthermore, AgSePh microcrystals show high stability under water, oxygen, and heat environments, while above 220 °C, they will thermally decompose to silver and Ph2Se2 as evidenced by a combination of thermogravimetry and differential scanning calorimetry and pyrolysis-coupled gas chromatography-mass spectrometry studies. Finally, a comparison is extended between AgSePh and other metal benzeneselenolates, benzenethiolates, and alkanethiolates to clarify differences in their solubility, decomposition/melting temperature, and pyrolytic products.

Oxygen Vacancy‐Rich Defects Porous Cu2MgO3/Mg0.78Cu0.22O Composite with Sinter‐Resistant and Highly Reactive for Long‐Duration High‐Temperature Thermochemical Energy Storage

AbstractHigh‐temperature thermochemical energy storage based on metal oxides is the key technology to reducing the levelized costs of electricity of the next‐generation concentrated solar power plants. CuO/Cu2O has wide availability and high energy density, but severe sintering leads to low reactivity. In this study, an innovative approach to modulate the oxygen vacancy content to change the surface properties and crystal structure to enhance the sintering resistance and redox reversibility is proposed. The re‐oxidation degree is increased from 46% to 99%, and the energy release rate is increased by 3.5 times. It remains 99.9% reduction and 97.1% oxidation activity after 3000 cycles, which is very valuable for engineering applications. Cu2MgO3 and Mg0.78Cu0.22O are prone to form oxygen vacancies, which promotes the formation of porous structures. Mg0.78Cu0.22O helps Cu2MgO3/CuO/Cu2O deliver more O through the surface. Mg0.78Cu0.22O is firmly and uniformly dispersed on the CuO/Cu2O surface after long cycling. They have a large binding energy, more charge transfer and enhanced bond energy at the interface. The mechanism of composite in increasing the sintering temperature and long‐term reaction stability is revealed from experimental and theoretical calculations, which provides a new idea for the rational design of thermochemical energy storage materials.

Group III (In/Ga)-V (P/As)-VI (S/Se) Monolayers: A New Class of Auxetic Semiconductors with Highly Anisotropic Electronic/Optical/Mechanical/Thermal Properties.

We present a theoretical design of a class of 2D semiconducting materials, namely, group III (In/Ga)-V (P/As)-VI (S/Se) monolayers, whose global-minimum structures are predicted based on the particle swarm optimization method. Electronic structure calculations suggest that all group III-V-VI monolayers exhibit quasi-direct semiconducting characteristics with desirable band gaps ranging from 1.76 to 2.86 eV (HSE06 functional). Moreover, most group III-V-VI monolayers possess highly anisotropic carrier mobilities with large anisotropic ratios (3.4-6 for electrons, 2.2-25 for holes). G0W0+BSE calculations suggest that these monolayers show high optical anisotropy and relatively large exciton binding energies (0.33-0.75 eV), comparable to that (0.5 eV) of MoS2 monolayer. In particular, the GaPS monolayer manifests strikingly anisotropic I-V curves with a large ON/OFF ratio of ∼105 (106 for the GaPS bilayer) and anisotropic lattice thermal conductivity. Furthermore, the GaPS monolayer is predicted to exhibit both in-plane and out-of-plane negative Poisson ratios (NPRs) and prominent anisotropic Young moduli.