Electronic Absorption Research Articles

Twisted graphene superlattices: resonating valence bond states and magnetic properties

Resonating valence bond (RVB) states are fundamental for understanding quantum spin liquids in two-dimensional (2D) systems. The RVB state is a collective phenomenon in which spins are uncoupled. 2D lattices such as triangular, honeycomb, and dice lattices were investigated using the Hubbard model and exact diagonalization method. We analyzed the total spin, spin–spin correlation functions, local magnetic moments, and spin and charge gaps as a function of on-site Coulomb repulsion, electron concentration, and electronic hopping parameters. Phase diagrams showed that RVB states can live in half-filled and hole-doped anisotropic triangular lattices. We found two types of RVB states: one in the honeycomb sublattice and the other in the centered hexagons in the triangular lattices. Owing to the novel discovery of exotic magnetic ordering in triangular moiré patterns in twisted bilayer graphene and transition metal dichalcogenide systems, our results provide physical insights into the onset of magnetism and possible spin liquid states in these layered materials.

Construction and Electrochromic Properties of Two-Dimensional Covalent Organic Frameworks with Donor-Acceptor Structures of Triphenylamine and Bipyridine

Abstract The stacking between layers of a two-dimensional covalent organic framework (COF) leads to overlapping π orbitals, which enables charge carriers to be transported quickly through these pre-designed π orbitals. The two-dimensional COF featuring donor-acceptor interactions represents a straightforward approach for fabricating a high-performance organic electrochromic device. In this paper, N, N, N', N'-tetrad(4-aminophenyl)-1,4-phenylenediamine (TPDA) with electron-rich structure and 2,2'-bipyridine-5,5'-dialdehyde (BPDA) with strong electron absorption ability were used as the construction unit. COFTPDA-BPDA electrochromic materials with donor-acceptor structure were synthesized by Schiff base reaction, which can achieve reversible switching from red to dark gray. The color/fade time of the film at 474 nm wavelength is 6.8 s/11.9 s. The contrast retention rate of the film can reach 97.6% after 20 potential cycles, the memory time is as long as 4278 s. The present study demonstrates that constructing a donor-acceptor (D-A) structural unit with conjugated triphenylamine as the electron donor linked to bipyridine electron-withdrawing groups enhances charge transfer and redox reactions. With the success of this design strategy, the construction of the D-A structure is an important methodology for improving the electrochromic properties of materials.

Over 500°C stable transparent conductive oxide for optoelectronics

AbstractHigh‐temperature stable transparent conductive oxides (TCOs) are highly desirable in optoelectronics but are rarely achieved due to the defect generation that is inevitable during high‐temperature air annealing. This work reports unprecedented stability in aluminum and fluorine co‐doped ZnO (AFZO) films prepared by pulse laser deposition. The AFZO can retain a mobility of 60 cm2 V−1 s−1, an electron concentration of 4.5 × 1020 cm−3, and a visible transmittance of 91% after air‐annealing at 600°C. Comprehensive defect characterization and first principles calculations have revealed that the offset of substitutional aluminum by zinc vacancy is responsible for the instability observed in aluminum‐doped ZnO, and the pairing between fluorine substitution and zinc vacancy ensures the high‐temperature stability of AFZO. The utility of AFZO in enabling the epitaxial growth of (AlxGa1−x)2O3 film within a high‐temperature, oxygen‐rich environment is demonstrated, facilitating the development of a self‐powered solar‐blind ultraviolet Schottky photodiode. Furthermore, the high‐mobility AFZO transparent electrode enables perovskite solar cells to achieve improved power conversion efficiency by balancing the electron concentration‐dependent conductivity and transmittance. These findings settle the long‐standing controversy surrounding the instability in TCOs and open up exciting prospects for the advancement of optoelectronics.image

Unraveling Lattice-Distortion Hardening Mechanisms in High-Entropy Carbides.

Uncovering the hardening mechanisms is of great importance to accelerate the design of superhard high-entropy carbides (HECs). Herein, the hardening mechanisms of HECs by a combination of experiments and first-principles calculations are systematically explored. The equiatomic single-phase 4- to 8-cation HECs (4-8HECs) are successfully fabricated by the two-step approach involving ultrafast high-temperature synthesis and hot-press sintering techniques. The as-fabricated 4-8HEC samples possess fully dense microstructures (relative densities of up to ≈99%), similar grain sizes, clean grain boundaries, and uniform compositions. With the elimination of these morphological properties, the monotonic enhancement of Vickers hardness and nanohardness of the as-fabricated 4-8HEC samples is found to be driven by the aggravation of lattice distortion. Further studies show no evident association between the enhanced hardness of the as-fabricated 4-8HEC samples and other potential indicators, including bond strength, valence electron concentration, electronegativity mismatch, and metallic states. The work unveils the underlying hardening mechanisms of HECs and offers an effective strategy for designing superhard HECs.

Pyrobacteriopheophorbide-a derivatives possessing various hydrophilic esterifying groups at the C17-propionate residues for photodynamic therapy.

Aiming at the application to photodynamic therapy, natural bacteriochlorophyll-a was converted to chemically stable free-base derivatives possessing different kinds of hydrophilic C17-propionate residues. These semi-synthetic bacteriochlorins were found to have self-assembling ability in an aqueous environment and formed stable J-type aggregates in a cell culture medium containing 0.2% DMSO. The electronic absorption spectra of all the sensitizers showed Qy absorption maxima at 754 nm in DMSO as their monomeric states, while a drastic shift of the red-most bands to ca. 880 nm was observed in the aqueous medium. The circular dichroism spectra in the medium showed much intense signals compared to those measured in DMSO, supporting the formation of well-ordered supramolecular structures. By introducing hydrophilic side chains, the bacteriochlorin sensitizers could be dispersed in the aqueous medium as their J-aggregates without the use of any surfactants. Cellular uptake efficiencies as well as photodynamic activities were evaluated using human cervical adenocarcinoma HeLa cells. Among the 11 photosensitizers investigated, the best result was obtained for a charged derivative possessing trimethylammonium terminal (17-CH2CH2COOCH2CH2N+(CH3)3I-) and photocytotoxicity of EC50 = 0.09 μM was achieved by far-red light illumination of 35 J/cm2 from an LED panel (730 nm).

Recent Development and Advancement in Quantum Dots in Pharmaceutical and Biomedical Fields for the Delivery of Drugs

Abstract: Nanoscale semiconductors known as quantum dots (QDs) are essential for drug testing because they bridge the gap between nanotechnology and the testing of drugs. QDs are a valuable tool in theranostics and treatment because of their unique physicochemical features. Due to their photoluminescence and electronic properties, including broad and continuous absorption spectra, narrow emission spectra from visible to near-infrared wavelengths, and long-lasting and high brightness, they are suitable probe materials for use in (bio)sensing (immunological) platforms. Several studies use QDs due to their optical, magnetic, electrical, photochemical, and biological features that allow them to be employed in various scientific domains. When utilized in drug delivery systems, fluorescent markers, such as QDs, can track the metabolism of drugs in the human body. Many medicinal applications, such as disease diagnosis and medication research, can benefit from these fluorescent tests. In this review article, the application of QD in drug delivery and immunoassay sensing has been described in detail.

Effect of Acceptor Traps in GaN Buffer Layer on Source/Drain Contact Resistance in AlGaN/GaN High Electron Mobility Transistors

As‐grown GaN buffer layers have a significant electron concentration, which causes an increase in leakage current and a decrease in the breakdown voltage, VBR, of GaN High Electron Mobility Transistors (HEMTs). To prevent this, deep acceptor traps of density, NAT, are added to the GaN layer during growth. While a study on the effect of NAT on VBR is available in the literature, that on the effect of NAT on contact resistance, Rc, of source/drain contacts is lacking. Herein, the following is established using technology computer‐aided design simulations calibrated with measured current–voltage characteristics of ungated AlGaN/GaN structures: 1) Rc increases significantly with NAT and with the depth of the trap level from the conduction band. For trap level 2.5 eV below the conduction band, Rc doubles for an increase in NAT from 1 × 1016 to 5 × 1017 cm−3. 2) The variation of Rc with temperature is non‐monotonic. Over a temperature range of 300–450 K, Rc is nearly constant with temperature for NAT = 1 × 1016 cm−3 and decreases by 20% for NAT = 5 × 1017 cm−3, when traps are 2.5 eV below the conduction band. Also, the degradation of the transfer and output characteristics of GaN HEMTs due to a notable increase in Rc due to NAT is investigated.

Tailoring epsilon-near-zero wavelength and nonlinear absorption properties of CdO thin films by Mo doping

Cadmium oxide (CdO) has recently attracted attention as a material with controllable properties tailored for optoelectronic and nanophotonic devices due to its superior mobility. However, its potential application in near-infrared (NIR) remains to be explored. In this work, we demonstrate that the epsilon-near-zero (ENZ) wavelength and nonlinear optical properties of CdO films can be effectively tuned by Mo doping. The results show that Mo doping increases the electron concentration as well as improve the crystalline quality of CdO. With increasing Mo doping, we achieve blueshifts of the ENZ wavelength from 2.89 to 1.56 μm. The nonlinear absorption (NLA) behavior at 1550 nm changes from reverse saturable absorption to saturable absorption with increasing Mo content. Moreover, significant improvement in NLA performance with nonlinear absorption coefficient β = −72 cm/GW is observed at the highest doping content. Our work shows that doped CdO films with tunable optoelectrical and nonlinear optical properties can be an ideal candidate for optoelectronic and nanophotonic application in the NIR region.

Effects of locally-gradient Co-doping on the electron properties of Bi2Te2.1Se0.9+0.33wt.% Co composite

Interconnected effects of the locally-gradient Co-doping and electron scattering by filler inclusions has been for the first time observed in thermoelectric Bi2Te2.1Se0.9 + 0.33 wt.% Co composite, prepared via spark plasma sintering (SPS) of matrix and filler powders at temperatures TS=573, 598, 623, 648, 673 and 698 K and at the same time t = 2.5 min. During SPS-process, initial Co inclusions, randomly distributed inside the Bi2Te2.1Se0.9 matrix, act as electron doping sources. High-temperature diffusion embedding of Co atoms in the Bi2Te2.9Se0.1 structure results in increasing electron concentration. This diffusion process corresponds to diffusion from limited doping sources, which are spatially separated inside the Bi2Te2.9Se0.1 matrix. Separate filler inclusion is each such source. Concentration profiles of Co distribution were applied to extract a diffusion coefficient, DCo, of Co atoms inside Bi2Te2.9Se0.1. The DCo increases with TS in accordance with Arrhenius law. Owing to locally-gradient distribution of doping Co atoms, the Co-doping is locally-gradient doping. Initial inclusions, consisting of only Co atoms, are gradually transforming into the “core Co@shell CoTe2” inclusions. This transformation is related to diffusion of Co atoms that is accompanied by subsequent solid-state Co+2Te→CoTe2 reaction. Room-temperature weighted mobility of electrons increases with growing TS. This behavior of mobility can be originated from electron scattering by magnetic moments of the Co cores.

Correlation of the properties of quasi-ternary Ni-based superalloys computed from DFT to elemental properties enabling predictions on the behavior of metallic alloying elements

Research on multicomponent superalloys derived from Ni3Al shows that certain elemental additions congregate at the boundary of the γ/γ′ interface while certain others partition into either the γ or the γ′ phases. Such microstructural features have a strong bearing on the performance of the superalloy. However, no established correlations exist as of now, that can help predict such a behavior. The present work addresses this issue by examining the properties of the quasi-ternary alloys of Ni3Al and brings out correlations to selected lumped parameters related to the elemental properties. Computation of thermodynamic properties of 11 alloys of quasi-ternary Ni24Al7X system was carried out from first principles using Wien 2k and Gibbs2 code on a supercell constructed with 32 atoms. Elements X substituted at the Al site are selected from the information derived from the literature. Systematic variations are shown to occur in compressibility and heat of formation ΔH of the alloys with average electron concentration, elemental radii and/or electronegativity of the constituent elements in the alloys. Analysis of the data computed for a supercell on ΔH of quasi-ternary Ni31X alloys of Ni (the γ phase) and the ΔH of Ni24Al7X alloys (the γ′ phase) explains the possible reason for the enrichment of elements like Re and W at the γ/ γ′ interface. Trends in the observed correlations correctly predict the experimental observations on alloying effects reported from spectroscopic studies on quasi-ternary alloys of Ni3Al. The scope of predicting alloying behavior based on basic elemental properties gains significance in the design of superalloys.

Synthesis of N2-Type Superatomic Molecules.

Exploration of multiple bonds between superatoms remains an uncharted territory. In this study, we present the synthesis and characterization of N2-type superatomic molecules featuring triple bonds between two superatoms. The successful synthesis of M2Au17 (M = Pd, Pt) nanoclusters hinged upon the photoinduced fusion of MAu12 superatoms, achieved through sequential electron transfer and detachment of [AuPR3]+ species. Solid-state structures were confirmed via X-ray crystallography, while their electronic structures were elucidated through density functional theory (DFT) calculations. Analysis of electronic absorption properties, coupled with time-dependent DFT calculations, unveiled a symmetry-dependent electron transition nature between superatomic molecular orbitals, akin to that observed in conventional molecules.

New bioactive titanium(IV) derivatives with their DFT, molecular docking, DNA/BSA interaction, antioxidant and in-vitro investigations

A set of four new metallacyclic complexes titanium(IV) associated with Schiff bases (SBs) (1a- 1d) obtained by the specific reactions of β-diketones such as acetylacetone (acacH) and benzyl acetone (bzacH) and aminophenol derivatives while treating Ti(OPri)4 and these SBs individually in 1:2 stoichiometry under 8 h reflux condition in anhydrous benzene to afford as reddish powder (2a-2d). These products have been purified in repeated washings of dry n-hexane afterwards, subjected to characterization by suitable spectroscopic techniques (NMR, IR, UV–Vis and HRMS). These hexacoordinated complexes appeared as distorted octahedral geometry from computational data studies. The synthesized titanium(IV) complexes were screened for their antioxidant abilities where 2c and 2d exhibited remarkable activity as IC50 values. The DNA & BSA binding properties of the complexes (2a-2d) have also been investigated through electronic absorption and molecular docking analysis. The obtained results indicated clearly that the complexes got bound with DNA via groove binding mode according to the intrinsic binding constant values (Kb = 1.5 × 104 M−1 to 7.5 × 105 M−1). Derivative 2c was examined in-vitro on a panel of cancerous cell line − breast cancer and human colon cell lines MCF-7 to reflect IC50 results as 53.92 μg/mL and HT-29 33.43 μg/mL, respectively.

Ultrafast Events of Photoexcited Iron(III) Chloride for Activation of Benzylic C-H Bonds.

The usage of rare-earth-metal catalysts in the synthesis of organic compounds is widespread in chemical industries but is limited owing to its environmental and economic costs. However, recent studies indicate that abundant-earth metals like iron(III) chloride can photocatalyze diverse organic transformations using blue-light LEDs. Still, the underlying mechanism behind such activity is debatable and controversial, especially in the absence of ultrafast spectroscopic results. To address this urgent challenge, we performed femtosecond time-resolved electronic absorption spectroscopy experiments of iron(III) chloride in selected organic solvents relevant to its photocatalytic applications. Our results show that the long-lived species [Fe(II) ← Cl•]* is primarily responsible for both oxidizing the organic substrate and reducing molecular oxygen through the diffusion process, leading to the final product and regenerating the photocatalyst rather than the most widely proposed free chloride radical (Cl•). Our study will guide the rational design of efficient earth-abundant photocatalysts.

The behaviour and properties of some acid-base indicators: a review

This review focuses on Seven Acid-Base Indicators from the azo class and from the second type: Methyl Orange; Methyl Red; Methyl Yellow; Alizarin Yellow R; Alizarin Yellow GG; Tropaeolin O and Magneson I. These indicators show different colors involving the chemical reaction in aqueous solutions as results as change the acidity of solution causing the formation two different structure forms one in acid form and another in basic forms with possibility formation of resonance structures. Different variables such as temperature; ionic strength; solvents; concentrations; pressure; substituent’s; position of function group and surfactant that influence on the behavior of Acid-Base indicators were explained. The electronic absorption spectral, equilibrium, terminological aspects and characteristics as well as the possible schemes of formation two compounds at isosbestic point are discussed. The contributions of different methods using to estimate the dissociation constant for it is discussed.

Prediction of the Cohesion Energy, Shear Modulus and Hardness of Single-Phase Metals and High-Entropy Alloys.

In order to facilitate the prediction of some physical properties, we propose several simple formulas based on two parameters only, the metallic valence and metallic atomic radii. Knowing the composition, for single-phase alloys, the average parameters can be calculated by the rule of mixture. The input parameters can be obtained from tabulated databases. Adopting from the literature the results of Coulomb crystal model for metals and single-phase high-entropy alloys, we have derived formulas for the shear modulus (G) and the cohesion energy (Ecoh). Based on these parameters separately, we set up two formulas to estimate the hardness in the case of pure metals. For single-phase (solid-solution) HEAs, by simplifying the Maresca and Curtin model, we obtained a formula for estimating the hardness, which takes into account the atomic misfit in addition to G. The maximal hardness for single-phase HEA is approximately 600 kg/mm2 and is obtained for a composition with a valence electron concentration of approximately 6 ÷ 7.

Methoxylated bis(pentafluorophenyl)boron‐β‐diketonates: Synthesis, Optical Properties and Hydrolytic Stability

AbstractA series of methoxylated bis(pentafluorophenyl)boron‐β‐diketonates (dkB(C6F5)2) with intense emission has been synthesized and characterized by a variety of physicochemical methods. The photophysical properties of the synthesized compounds were thoroughly investigated by electronic absorption, steady‐state, and time‐resolved fluorescence spectroscopy in both solution and solid state. The studied compounds exhibit solvatochromic behavior attributed to the intramolecular charge transfer (ICT) nature of the first excited state. The formation of exciplexes between DBMB(C6F5)2 and benzene derivatives was also studied. Notably, the studied compounds display a complex luminescence profile in the solid state, featuring fluorescence, delayed fluorescence and phosphorescence emission. Furthermore, the hydrolytical stability of the complexes was assessed, demonstrating excellent resistance to hydrolysis. Estimated rate constants, determined at 60 °C, are significantly lower (90‐2000 times) than those observed for the well‐studied dibenzoylmethanatoboron difluoride (DBMBF2). The incorporation of pentafluorophenyl substituents at the boron atom enables the synthesis of highly fluorescent and hydrolytically stable boron chelate complexes, suitable for sensing and bioimaging applications in water‐containing environments.

A Multi-Parameter Tunable and Compact Plasmon Modulator in the Near-Infrared Spectrum

To keep pace with the demands of modern photonic integration technology, the electro-optic modulator should feature multi-parameter tunable components and a compact size. Here, we propose a hybrid structure that can modulate the multi-parameters of surface plasmon polaritons (SPPs) simultaneously with a compact size by controlling the electron concentration of indium tin oxide (ITO) in the near-infrared spectrum. The length, width and height of the device are only 15 μm, 5 μm and 9 μm, respectively. The numerical results show that when the electron concentration in ITO changes from 7.5 × 1026 m−3 to 9.5 × 1026 m−3, the variation in amplitude, wavelength and phase are 49%, 300 nm and 347°, respectively. The demonstrated structure paves a new way for multi-parameter modulation and the realization of ultracompact modulators.

Quantitative measurement of spatial distribution of effective refractive index induced by local electron concentration at a nano slit

Abstract Surface plasmon polaritons (SPPs) have found their key applications in high-sensitivity biomolecular detection and integrated photonic devices for optical communication via light manipulation at nanostructures. Despite their broad utility, SPPs are known to be accompanied by other complex near-field propagation modes, such as quasi-cylindrical waves (QCWs) and composite diffracted evanescent waves (CDEWs), whose electromagnetic and quantum propagation effects have not been comprehensively understood especially regarding their mutual interaction with SPPs. In this study, we addressed this complexity by employing a nano groove structure and a high-stability broadband femtosecond laser as a light source, the spatial phase distribution around the nano slit edge was measured with relative stability of a 4.6 × 10−11 at an averaging time of 0.01 s. Through this spatial phase spectrum, we precisely measured the nonlinear distribution of effective refractive index changes with an amplitude of 10−2 refractive index units at the edge of the nano slit–groove structure. These results reveal that the near-field effects on local electron concentration induced by nanostructure’s discontinuity can be quantitatively measured, which can contribute to a deeper understanding of SPP phenomena in nanostructures for the optimal design and utilization of the SPP effects in diverse nano-plasmonic applications.

Microstructural and chemical dependences of fracture toughness in stainless steel welds at 4.2 K

In this study, 316LN-Mn and 316LN plates were welded by gas tungsten arc welding. The fracture toughness of 316LN-Mn and 316LN steel welds at the cryogenic-temperature of 4.2 K was evaluated by focusing on the effects of microstructures and chemical elements. The results showed that both steel welds did not experience stress-induced martensite transformation during deformation. At 4.2 K, the microbands and dislocation pileup at grain boundaries blocked dislocations, thus reducing the fracture toughness of the welds. The embedded nano-twin clusters inhibited void initiation in the nano-grained matrix and formed a crack-bridging ligament behind the crack, which contributed to higher fracture toughness. It was found that microstructures with dominant equiaxed grains at an average grain size of 30 μm had the highest fracture toughness. While chemically, the reduction of manganese content blurred the outline of the electron density map, reduced the valence electron concentration, resulting in unstable austinites, which informed the significance of manganese content control in design and selection of weld metals.

A Fundamental Perspective on the Selective Zn Substitution in Ternary Ordered Intermetallic Compound Cu 6 Zn 2 Sb 2

The unique site substitution of Zn in the structure of tetragonal and atomically ordered Cu6Zn2Sb2, followed by the formation of Cu5Zn3Sb2, has been addressed from fundamental perspectives. First principles energy calculations, and semi‐empirical electronic structure calculations using the density of states, crystal orbital Hamilton population, crystal orbital bond index and Mulliken population analysis were performed to understand the observed substitution pattern and the narrow homogeneity range of the titled compound. Mulliken and Löwdin’s approach of charge analysis explain the experimentally proved ‘coloring’ based on the ‘site energy’ argument. The concept of ‘topological charge stabilization’ has been introduced in this context. Valence electron concentration and the optimization of the partially covalent Cu‐Sb interactions also play pivotal role in the electronic stability of the titled phase.