Band Gap Materials Research Articles

A Full‐Scale Analysis of Absorption Edges in Dye‐Doped Nonlinear Optical Polymers

AbstractA full‐scale analysis of the absorption edges by modified Tauc‐Lorentz models is essential in determining the optical bandgap and Urbach energy of semiconductors, transparent conductors, ionic compounds, and dielectric materials. This technique has not yet been applied to analyzing organic nonlinear optical (NLO) materials. This problem is tackled by preparing high‐quality films of guest–host NLO polymers with a wide thickness range from sub‐micron to 200 microns, allowing accurate measurement of full‐spectral absorption coefficients of NLO materials over four orders of magnitude by the UV‐VIS‐NIR spectroscopy. The Tauc model and a new Monolog–Lorentz model are used to study the optical absorption edge of guest‐host NLO polymers containing various push‐pull chromophores and the dependence of optical bandgap and Urbach edge on the structure and composition of materials is analyzed. The results reveal the critical transition of the Urbach exponential tail to a low energy tail that overlaps with vibrational overtones of materials at the telecom wavelengths. Determining the fundamental absorption region of organic NLO films in this study provides quantitative insight into the research to harness the resonance‐enhanced nonlinear coefficients of materials by operating at the wavelengths near the band edge with the control of optical loss.

Reduced internal stress of quasi-single crystalline Na4Fe3(PO4)2P2O7 electrode enhancing sodium-ion kinetics

A NASICON-type quasi-single crystalline Na4Fe3(PO4)2P2O7 (SC) cathode material was successfully synthesized via a freeze-drying method. The as-optimized SC sample displays both outstanding rate performance (107.9 and 88.5 mAhg−1 at 0.1C and 5C, respectively) and excellent cycling stability (88.1 % of capacity retention after 1000 cycles at 1C). Reduced sodium ion migration path of as-prepared SC cathode material effectively enhanced the kinetics of Na+ upon cycling. More importantly, the SC structure could suppress nearly 50 % of internal strain, prodigiously reducing the local stress accumulation accompanied by the inhomogeneous sodium concentration gradient during the charging/discharging processes. The smaller the stress accumulation, the more stable the crystal structure would be obtained, which maintained a more superb mechanical stability of the SC cathode material. At the same time, a high-spin state of Fe in the SC sample was confirmed by both of electron paramagnetic resonance and temperature-dependent magnetization susceptibility, indicating that the eg orbital occupation of Fe2+ could be regulated to optimize the bond strength between the reduction and oxidation processes. As a consequence, the band gap of SC material has decreased from 1.66 to 1.45 eV, and the electronic conductivity has increased from 6.0 to 32.4 μS/cm. It is believed that the SC cathode material could be a competitive candidate material for sodium ion batteries.

Atomic and Electronic Structures of Co-Doped In2O3 from Experiment and Theory.

The synthesis and properties of stoichiometric, reduced, and Co-doped In2O3 are described in the light of several experimental techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ultraviolet (UV)-visible spectroscopy, porosimetry, and density functional theory (DFT) methods on appropriate models. DFT-based calculations provide an accurate prediction of the atomic and electronic structure of these systems. The computed lattice parameter is linearly correlated with the experimental result in the Co concentration ranging from 1.0 to 5.0%. For higher Co concentrations, the theoretical-experimental analysis of the results indicates that the dopant is likely to be preferentially present at surface sites. The analysis of the electronic structure supports the experimental assignment of Co2+ for the doped material. Experiments and theory find that the presence of Co has a limited effect on the material band gap.

Unconventional Band Structure via Combined Molecular Orbital and Lattice Symmetries in a Surface-Confined Metallated Graphdiyne Sheet.

Graphyne (GY) and graphdiyne (GDY)-based monolayers represent the next generation 2D carbon-rich materials with tunable structures and properties surpassing those of graphene. However, the detection of band formation in atomically thin GY/GDY analogues has been challenging, as both long-range order and atomic precision have to be fulfilled in the system. The presentwork reports direct evidence of band formation in on-surface synthesized metallated Ag-GDY sheets with mesoscopic (≈1µm) regularity. Employing scanning tunneling and angle-resolved photoemission spectroscopies, energy-dependent transitions of real-space electronic states above the Fermi level and formation of the valence band are respectively observed. Furthermore, density functional theory (DFT) calculations corroborate the observations and reveal that doubly degenerate frontier molecular orbitals on a honeycomb lattice give rise to flat, Dirac and Kagome bands close to the Fermi level. DFT modeling also indicates an intrinsic band gap for the pristine sheet material, which is retained for a bilayer with h-BN, whereas adsorption-induced in-gap electronic states evolve at the synthesis platform with Ag-GDY decorating the (111) facet of silver. These results illustrate the tremendous potential for engineering novel band structures via molecular orbital and lattice symmetries in atomically precise 2D carbon materials.

“Microwave approach and thermal decomposition: A sustainable way to produce ZnO nanoparticles with different chemo-physical properties”

Two different synthetic approaches such as thermal decomposition method and microwave-assisted procedure were compared for the synthesis of nanosized ZnO. The two procedures were tested using zinc acetate as precursor as is, or in the presence of two coadjutants, one of anthropic origin (melamine) and one derived from the reuse of agricultural waste (wine extracts). All the samples were physico-chemically characterized in order to evaluate the influence of the synthesis conditions on the properties of the materials that were characterized by N2 adsorption/desorption at 77 K and Field Emission-Scanning Electron microscopy measurements for evaluating the morphology, X-ray diffraction for examining the crystalline structure and X-Ray photoelectron spectroscopy for evidencing the surface composition of the nanoparticles. In order to verify the influence of the synthesis procedure on the electrical and optical properties of the ZnO nanoparticles, forecasting their use in photocatalytic applications, also the band gap of materials was evaluated by means of UV–Vis spectroscopy and Tauc plot. A final comparison of all the results allowed to evidence advantages and disadvantages of the procedures under study pointing out the importance of deepen the study of microwave-based synthetic approaches.

A Simple and Promising Prediction Model to Analyze the Optical Properties of Organic Photovoltaic Materials

Optimizing light utilization is crucial in organic photovoltaics. Understanding the intricate connection between the optical properties and the chemical structure of organic materials is pivotal yet challenging in this regard. Herein, over 2800 published reports with a database of ≈300 organic non‐fullerene acceptors (NFAs) are surveyed and a mathematical model suitable for predicting and analyzing the optical properties of organic photovoltaic materials is established. The model is used to predict the optical properties of representative NFAs within experimental error, including four newly synthesized organic materials to validate the model. In addition, the reliability and applicability of the model through data transformation are demonstrated and it is found that the addition of double bonds and asymmetry in the chemical structure does not necessarily reduce the optical bandgap of organic materials. Based on the model, the strong noncovalent interaction is more significant than the weak noncovalent interaction and asymmetry on the reduction of the bandgap, which provides new insights into the design and development of organic photovoltaic materials with tunable optical properties.

Combined Machine Learning and High-Throughput Calculations Predict Heyd-Scuseria-Ernzerhof Band Gap of 2D Materials and Potential MoSi2N4 Heterostructures.

We present a novel target-driven methodology devised to predict the Heyd-Scuseria-Ernzerhof (HSE) band gap of two-dimensional (2D) materials leveraging the comprehensive C2DB database. This innovative approach integrates machine learning and density functional theory (DFT) calculations to predict the HSE band gap, conduction band minimum (CBM), and valence band maximum (VBM) of 2176 types of 2D materials. Subsequently, we collected a comprehensive data set comprising 3539 types of 2D materials, each characterized by its HSE band gaps, CBM, and VBM. Considering the lattice disparities between MoSi2N4 (MSN) and 2D materials, our analysis predicted 766 potential MSN/2D heterostructures. These heterostructures are further categorized into four distinct types based on the relative positions of their CBM and VBM: Type I encompasses 230 variants, Type II comprises 244 configurations, Type III consists of 284 permutations, and 0 band gap comprises 8 types.

Predicting the properties of perovskite materials by improved compositionally restricted attention-based networks and explainable machine learning

Understanding the unique properties of perovskite materials is crucial in advancing solar energy technologies. Factors like heat of formation and bandgap significantly influence the light absorption capability and stability of perovskite solar cells. However, it is time-consuming and labor-intensive to obtain the properties of perovskites using traditional experimental or high-throughput computational methods. As a prospective method, machine learning can find regularities in the given training data and give accurate prediction results. In this article, we use deep learning models based on attention mechanisms and elemental features to predict the heat of formation and bandgap of perovskite materials. Random Forest and Gradient Boosted Regression Tree models have also been used for interpretable predictions of properties. The compositionally restricted attention-based network was improved by introducing a densely connected network and optimizing the network structure to increase data processing capabilities. The experiment results show that the mean absolute errors of the heat of formation and bandgap on the test sets are decreased by 5.77% and 3.37% respectively. The optimized model also shows better performance when used for classification tasks. In addition, we use the gradient boosting regression tree model and the shapley additive explanations tool to conduct an interpretable analysis, explaining the impact of different features on the predictions of the properties.

Impact of annealing on Cu2O doped with Na/Co: Structural, optical, and electrochemical consequences

Impact of annealing on Cu2O doped with Na/Co: Structural, optical, and electrochemical consequences

Quaternary conducting Cs/GO/PANi hydrogel composites: A smart material for room temperature hydrogen sensing

Hydrogen sensors are essential for hydrogen energy technology development and safety monitoring. However, hydrogen sensing is difficult because it requires effective and fast detection of tiny quantities of hydrogen. In situ oxidative radical polymerization is used in this study to combine polyaniline (PANi) with a chitosan/graphene oxide (Cs/GO) hydrogel, which is very good at conducting electricity, to make it sensor. FTIR, XRD, SEM, and UV were used to evaluate the material's functional groups, crystal structure, morphology, and bandgap. This work shows that Cs/GO/PANi can synthesise a hydrogel-based sensor. Electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and chronoamperometry (CA) were used to evaluate electron transfer mobility, redox behaviour, and hydrogen sensing. Using a hydrogen source with a concentration of 0.5–2.5 M KOH, the hydrogen sensor's response time, recovery sensitivity, and limit of detection were found to be 0.4 s, 0.8 s, 54.3748 μAM, and 3.5520 μM, respectively. Under conventional conditions, the experiment demonstrated significant sensing capabilities at ambient temperature. According to the research, the sensor works so well because of the π-π stacking interaction, the irregular structure, and the way the GO-based hydrogel and PANi work together.

Investigation of photosensitive and photodetector characteristics of n-TPA-IFA/p-Si heterojunction structure

n-TPA-IFA organic material was synthesized and deposited on p-Si by spin coating method to produce n-TPA-IFA/p-Si heterojunction diode. We determined that the dielectric constant and energy band gap of TPA-IFA organic material were 3.91 and 3.37 eV by DFT/B3LYP/6-311G(d,p) method using on Gaussian 09 W, respectively, and the carrier type of TPA-IFA organic semiconductor material was also n-type at room temperature from temperature-dependent hall effect measurements. Using forward and reverse bias I–V measurements in the dark and under various light intensities, we examined the key electrical characteristics of the n-TPA-IFA/p-Si heterojunction diode, including Φb\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\Phi }_{b}$$\\end{document} and n\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$n$$\\end{document}. It was determined that the rectification ratio (RR) was approximately 104. The reverse current's observed increasing behavior with increasing light indicates that the produced heterojunction diode can be utilized as a photodiode, detector, or sensor. The values of n, Φb\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\Phi }_{b}$$\\end{document}, and Io were determined using I–V data in dark as 1.34, 0.91 eV, and 7.25 9 10–12 A, respectively. On the other hand, when the n-TPA-IFA/p-Si heterojunction diode is exposed to 100 mW/cm2 illumination, these parameters were obtained as 1.85, 0.80 eV, and 5.11 9 10–10 A, respectively. Photovoltaic parameters such as short circuit current (Isc) and open circuit voltage (Voc) were determined as 0.018 mV, 0.08 A and 0.050 mV, 0.29 A under 20 mW/cm2 light and 100 mW/cm2 light intensity, respectively. The photodetector properties of n-TPA-IFA/p-Si heterostructure were explored at different light intensities, and the photoresponsivity (R), photosensitivity (PS), specific detectivity (D∗\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${D}^{*}$$\\end{document}), and linear dynamic range (LDR) of the heterojunction changed with reverse voltage and light intensity. It was found that as light intensity increased, the linear dynamic range (LDR), a crucial characteristic for image sensors, increased as well (10.15 dB and 18.84 dB for 20 and 100 mW/cm2).

Demystifying metal-assisted chemical etching of GaN and related heterojunctions

GaN and related semiconductors have become an increasingly prominent material for a wide range of active and passive devices from optoelectronics to high frequency and power electronics as well as photocatalysis. Regardless of the application, anisotropic etching is required for micro and nano structuring, currently performed by reactive ion etching (RIE). Alternately, metal-assisted chemical etching (MacEtch) is an open-circuit plasma-free anisotropic etching method that has demonstrated high aspect ratio device structures devoid of plasma-induced damage found in RIE. This paper presents an in-depth study of the ensemble electrochemical mechanisms that govern the photo-enhanced MacEtch process of GaN and related heterojunctions. Through in-depth experimental investigations, modeling and simulations, the effects of local cathode and anode design, energy-band alignments, and solution chemistry on MacEtch are correlated with the underlying electronic mechanisms of carrier generation, annihilation, transport, and extraction, establishing a fundamental framework for parametrized prediction of system behavior. These findings carry profound implications for tailored design of photoelectrochemical processes employed not just for uniformly etching wide/ultrawide bandgap materials but more broadly for semiconductor-based photocatalytic reactions in general. One-pot photo-enhanced MacEtching of AlInGaN multi-heterojunction device structures including superlattices and multi-quantum wells are demonstrated.

Metal oxide-dispersed PDMS nanocomposite films with enhanced heat-shielding ability and optical transparency

Coatings that transmit visible light and shield near-infrared (NIR) rays of sunlight have potential applications in smart windows, thermal camouflage, and heat shielding encapsulations. Here, we report metal oxide-dispersed polymer nanocomposites as potential coating materials that possess a combination of NIR reflection and visible light transmission. Film coatings (∼600 μm) comprising nanocrystalline zinc oxide (ZnO), titanium dioxide (TiO2), and cupric oxide (CuO) in the range of 0–2 wt% in polydimethylsiloxane (PDMS) matrix are fabricated. At optimal compositions, these coatings provided up to 52 % reduction in the interior air temperature, measured at distances ∼3 cm beneath the surface, while, at the same time, retaining up to 70 % of visible light transparency. The NIR reflection may be attributed to a combination of the band gap of the pigment material and the difference between the refractive indices of the pigments and the polymer matrix. We present a design map that highlights different regimes of heat-shielding and light transmission space for PDMS nanocomposite films. The performance, when compared with existing reports, suggests that films fabricated in this work outperform previously reported polymeric coatings in providing a combination of heat shielding and optical transparency.

Zinc-modified barium stannate micro-rods: Investigating structural, morphological, and optical features

In the present study, we have synthesized pristine and Zn-doped (0.025, 0.05, 0.075, 0.10) barium stannate (BSO) micro-rods via the hydrothermal method. The prepared samples have been analyzed for their structural, optical, and morphological properties using X-ray diffraction technique (XRD), UV–Vis diffuse reflectance spectroscopy, field emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray spectroscopy (EDX). Our Rietveld refinement examination of the XRD data verifies that the samples are single-phase, with a cubic crystal structure. Additionally, the lattice parameters determined align closely with the existing literature. Furthermore, the FE-SEM analysis unveiled the presence of well-defined rod-shaped structures accompanied by particle agglomeration across the surface. Further, the EDX analysis confirmed the presence of key elements, providing crucial insights into the material's chemical makeup. Especially noteworthy was the UV-DRS analysis, demonstrating a direct correlation between increased Zn doping concentrations and a concurrent reduction in the band gap values. This adjustment aligns the material's band gap with those commonly found in key components utilized in DSSC and PSC cells, suggesting promising applications in these crucial technological domains.

Synthesis and characterization of absorption-enhanced alumina solid particle materials for direct irradiation solar-thermal conversion

Based on solar-thermal application more than 1000 °C, a novel combination of sol-gel synthesis and stepwise calcination to prepare metal-ion doped alumina composite particles as heat transfer media were proposed, enhancing solar energy absorption and lowering preparation temperature. Investigations focused on the elemental distribution, phase composition, oxidation states, optical properties and thermal stability of the composites, which were doped with Cr, Co, Cu, Fe, and Mn metal ions in a 100:5 M ratio. The first-principles calculations elucidate the mechanism behind the impact of transition metal ions on alumina’s optical properties. Results show that introducing a small quantity of metal atoms results in new impurity energy levels and electron states around EF = 0. Specifically, the band gap energy of Cu- and Mn–Al2O3 decreases from 6.017 eV to 4.464 eV and 2.170 eV, respectively. Correspondingly, the absorptivity of these composite particles increases from around 20 %–76.6 %. And Tauc analysis indicates a decrease in the optical band gap of the particle materials from 5.37 eV to a range of 2.88–4.90 eV. Additionally, doping with Mn, Fe, and Cu accelerates the in-situ formation of α-Al2O3 crystals, with a phase transition temperature below 1000 °C and a crystallinity exceeding 93 %. Thermal stability tests show that the particles are highly stable, exhibiting a mere 0.49 % mass change between 30 °C and 1200 °C. The stepwise inert annealing strategy and metal-iron doping positively influence the optical performance of alumina, synthesizing long-term high-temperature stable alumina ceramic particles with absorptance enhancement and a low α-Al2O3 phase transition temperature. These attributes make a favorable choice for solar-thermal applications in direct irradiation.

Critical assessment of G0W0 calculations for 2D materials: the example of monolayer MoS2

Two-dimensional (2D) materials combine many fascinating properties that make them more interesting than their three-dimensional counterparts for a variety of applications. For example, 2D materials exhibit stronger electron-phonon and electron-hole interactions, and their energy gaps and effective carrier masses can be easily tuned. Surprisingly, published band gaps of several 2D materials obtained with the GW approach, the state-of-the-art in electronic-structure calculations, are quite scattered. The details of these calculations, such as the underlying geometry, the starting point, the inclusion of spin-orbit coupling, and the treatment of the Coulomb potential can critically determine how accurate the results are. Taking monolayer MoS2 as a representative material, we employ the linearized augmented planewave + local orbital method to systematically investigate how all these aspects affect the quality of G0W0 calculations, and also provide a summary of literature data. We conclude that the best overall agreement with experiments and coupled-cluster calculations is found for G0W0 results with HSE06 as a starting point including spin-orbit coupling, a truncated Coulomb potential, and an analytical treatment of the singularity at q = 0.

Visible light-induced photocatalytic degradation of methylene blue dye using pure phase bismuth ferrite nanoparticles

The degradation of organic dyes in wastewater has become a significant environmental issue, requiring the development of degradation technologies that are both effective and environmentally friendly. The present study employed the sol-gel approach to synthesize nanoparticles of phase pure bismuth ferrite (BiFeO3). The nanoparticles were assessed for their ability to efficiently degrade methylene blue (MB) dye, especially under visible light irradiation. The X-ray diffractogram (XRD) confirmed the formation of BiFeO3 nanoparticles, with an average crystallite size of 48 nm. The material's band gap, with a value of 1.84 eV, demonstrates its capacity to effectively absorb light, including wavelengths within the visible spectrum. Scanning electron microscopy (SEM) was used to identify porous aggregated particles. Both Raman and Fourier transform infrared spectroscopy (FTIR) confirm the successful synthesis of pure BiFeO3 in the desired phase. The BiFeO3 photocatalyst exhibited a significant surface area and isotherms of type IV, a characteristic typically observed in mesoporous materials, as determined by the Brunauer-Emmett-Teller (BET) analysis. The efficacy of BiFeO3 nanoparticles in facilitating the decomposition of MB in a water-based solution was evaluated by visible light photocatalysis. An efficiency degradation of 98.49 % was recorded for MB within 2 h.

Strain tunability of the properties of Fe-doped lithium niobate for optoelectronic applications: Theoretical insights

This work elucidates the impact of strain on the optical and electronic properties of Fe-doped lithium niobate using density functional theory. The Fe-doped lithium niobate is applied with the tensile and compressive strain (10% and 20%) and optical properties are analyzed. Lithium niobate, a large bandgap material (bandgap 3.56 eV), has absorption limited to the UV region of the optical spectrum only. For the Fe-doped lithium niobate, the bandgap is 1.38 eV, with low absorption in the visible region. The computed results show that the tensile and compressive strains have significantly narrowed down the bandgap of Fe-doped lithium niobate in compression to the unstrained structures. The decrease in the bandgap is largest for the tensile strain of 20% among all the applied strains. Further, visible light absorption is also improved due to the application of strain. The improvement in visible light absorption is highest for the tensile strain of 20% with absorption completely shifted in the desired visible region. The improved visible absorption due to the applied strain makes Fe-doped lithium niobate a potential candidate for optoelectronics and solar applications.

Structural, optical and electrical studies of non-toxic oxide- RMnO3 [R=Y, Er, Yb] hexagonal manganite thin-films

Recently, ferroelectric-photovoltaics have come under the spotlight as a potential class of materials for application in photovoltaic devices. However, the broad bandgap of these ferroelectric-photovoltaic materials causes them to have modest photocurrents[1]. To overcome this challenge hexamanganites can be used to achieve high photovoltaic efficiency as it has a small band gap. Here we present a stable, non-toxic, and cost-efficient hexamanganite RMnO3 [R=Y, Er, Yb] thin films prepared by spray pyrolysis method. The formation of the single phase is confirmed by X-ray diffraction analysis. Morphological studies show grains are uniform and closely packed and the grain size increases with the decrease in ionic radii of rare earth ions. A narrow optical band gap of nearly 1.5 eV is observed for the films. The results of this investigation show that Ultraviolet ray irradiation can be used to tune the bandgap. With a carrier concentration of around 10+14 cm−3, Hall measurements proved that the films are p-type semiconductors. This research illuminates the exploration of stable oxide semiconductors with a small band gap for applications in futuristic solar cells.

Enhanced ferroelectric photovoltaic performance of Bi2FeCrO6 thin films for neuromorphic computing applications

Nowadays, ferroelectric photovoltaic synapses have attracted great attention due to its polarization controllable and self-powered features. However, the large bandgaps of ferroelectric oxide materials limit its application. This study focuses on the enhancement of ferroelectric photovoltaic properties and the synaptic application of Bi2FeCrO6 (BFCO) device. It is found that the bandgap of BFCO can be modulated by Cr alloying, which causes its photovoltaic effect in the visible region to exceed that of BiFeO3 (BFO) significantly. The short-circuit current density (JSC) of BFCO device in the visible region increases by about 100 times than that of BFO. Furthermore, the polarization modulation and multi-states response are demonstrated by an external electric field. For BFCO ferroelectric photovoltaic synapse, long-term potentiation/depression (LTP/LTD) measurements show an excellent synaptic plasticity of the polarization modulation. The simulated image recognition rate using the MNIST dataset reaches a high accuracy of 96.06%. This work has expanded the potential application of ferroelectric photovoltaic synapse in the visible region.