Band Modification Research Articles

Enhanced thermoelectric performance in p-type AgBiSe2 through carrier concentration optimization and valence band modification

Enhanced thermoelectric performance in p-type AgBiSe2 through carrier concentration optimization and valence band modification

Effect of Morphology Modification of BiFeO3 on Photocatalytic Efficacy of P-g-C3N4/BiFeO3 Composites.

This current study assessed the impacts of morphology adjustment of perovskite BiFeO3 (BFO) on the construction and photocatalytic activity of P-infused g-C3N4/U-BiFeO3 (U-BFO/PCN) heterostructured composite photocatalysts. Favorable formation of U-BFO/PCN composites was attained via urea-aided morphology-controlled hydrothermal synthesis of BFO followed by solvosonication-mediated fusion with already synthesized P-g-C3N4 to form U-BFO/PCN composites. The prepared bare and composite photocatalysts' morphological, textural, structural, optical, and photocatalytic performance were meticulously examined through various analytical characterization techniques and photodegradation of aqueous rhodamine B (RhB). Ellipsoids and flakes morphological structures were obtained for U-BFO and BFO, and their effects on the successful fabrication of the heterojunctions were also established. The U-BFO/PCN composite exhibits 99.2% efficiency within 20 min of visible-light irradiation, surpassing BFO/PCN (88.5%), PCN (66.8%), and U-BFO (26.1%). The pseudo-first-order kinetics of U-BFO/PCN composites is 2.41 × 10-1 min-1, equivalent to 2.2 times, 57 times, and 4.3 times of BFO/PCN (1.08 × 10-1 min-1), U-BFO, (4.20 × 10-3 min-1), and PCN, (5.60 × 10-2 min-1), respectively. The recyclability test demonstrates an outstanding photostability for U-BFO/PCN after four cyclic runs. This improved photocatalytic activity exhibited by the composites can be attributed to enhanced visible-light utilization and additional accessible active sites due to surface and electronic band modification of CN via P-doping and effective charge separation achieved via successful composites formation.

Topological properties of a class of generalized Su–Schrieffer–Heeger networks: Chains and meshes

We analyze the topological properties of a family of generalized Su-Schrieffer-Heeger (SSH) chains and mesh geometries. In both the geometries the usual staggering in the distribution of the two overlap integrals is delayed (in space) by the inclusion of a third (additional) hopping term. A tight-binding Hamiltonian is used to unravel the topological phases, characterized by a topological invariant. While in the linear chains, the topological invariant (the Zak phase) always appears to be quantized, in the quasi-one dimensional strip geometries and the generalized SSH mesh patterns the quantization of the Zak phase is sensitive to the strength of the additional interaction (the ‘extra’ hopping integral). We study its influence thoroughly and explore the edge states and their robustness against disorder in the cross-linked generalized SSH mesh geometries. The systems considered here can be taken to model (though crudely) two-dimensional polymers where the cross-linking brings in non-trivial modification of the energy bands and transport properties. In addition to the topological features studied, we provide a prescription to unravel any flat, non-dispersive energy bands in the mesh geometries, along with the structure and distribution of the compact localized eigenstates. Our results are analytically exact.

ELECTRON IRRADIATED PI2610 POLYIMIDE FILMS ON MONOCRYSTALLINE SILICON

The optical and strength properties of electron-irradiated films of a polyimide composition (polyimide PI2610) deposited on the surface of single-crystalline silicon wafers of the KDB-10 grade by centrifugation were studied. Irradiation with electrons with an energy of 5 MeV was carried out on a linear accelerator U-003 in the dose range 1·1014 – 2·1015 cm–2. It has been experimentally established that at an irradiation dose of Ф = 1∙1014 cm–2, relaxation of elastic stress fields in the polyimide film is observed, which is expressed in modification of the shape of bands with maxima at 1349 and 1700 cm–1, caused by vibrations of the C–N–Cst bond and the C=O double bond imide ring. Polyimide PI-2610 films on silicon are quite stable when irradiated with electrons. A noticeable transformation of the ATR spectrum at a dose of 2∙1015 cm–2 was observed only in the region of stretching vibrations of C–H and O–H bonds, which is due to radiation-induced processes on by-products of polyimide synthesis and residual solvents. No noticeable decrease in the intensity of absorption bands caused by vibrations of the skeleton of the aromatic ring, imide ring, single and double C–C and C–O bonds, and imide C=O bonds was observed.

ZIF-8 incorporated CeO2-CdS quantum dots @ 2D g-C3N4 nanosheets as a staggered type II heterojunction for decolouration of a set of dyes

Dye toxins, emitted by industries, pose a significant threat to living beings and aquatic life by absorbing light radiation and inhibiting the growth of essential bacteria and microbes, making their removal crucial for health of living beings and flora and fauna. This research endorsed a hydrothermal synthetic route for the photocatalyst CeO2/CdS/g-C3N4 @ZIF8 (or CCdGZ) fabrication to remove a set of hazardous dyes from wastewater streams. Corresponding Analytical methods evaluated the successfully developed CCdGZ photocatalyst's structural, morphological, and compositional properties. Powder X-ray photoelectron (PXRD) analysis showed the structural properties of CCdGZ and the quantum dot nature of the CeO2-CdS hybrid in the heterostructure with a crystallite size of 0.16 nm. The photocatalyst's optical responses were examined using UV–vis spectrophotometry and the UV-diffuse reflectance spectroscopy (UV-DRS) technique. Tauc's plot determined the energy band gap of the CCdGZ to be ∼2.64 eV, confirming a slight modification of the valence band (VB) and conduction band (CB) edges of the moieties CeO2, CdS, and g-C3N4. Thus, the heterostructure's moieties synergised to produce photocatalytic degradation. Under visible light irradiation, the photocatalyst CCdGZ photodegraded Victoria blue R (VBR) dye by 96.54% in 55 min. Photodegradation followed pseudo-first-order kinetics with a specific reaction rate of 0.06159 min−1 {coefficient of determination (R2) = 0.99847}. The corresponding TOC removal was 83.27%, while COD got reduced to 78.98% of its initial magnitude. Multiple reaction parameters, heterostructure reusability (over 89% efficient till the 5th run), the scavengers' experiment, inorganic ion effects, and water matrices were also evaluated. The study concludes with a photocatalytic reaction mechanism that explains the moieties' roles. This study designs a heterostructure photocatalyst that disintegrates emerging non-degradable organic pollutants in the UV–visible range, is recoverable, and has better photostability.

Optical manipulation of the topological phase in ZrTe5 revealed by time- and angle-resolved photoemission

High-resolution time- and angle-resolved photoemission measurements were conducted on the topological insulator ZrTe5. With strong femtosecond photoexcitation, a possible ultrafast phase transition from a weak to a strong topological insulating phase was experimentally realized by recovering the energy gap inversion in a time scale that was shorter than 0.15 ps. This photoinduced transient strong topological phase can last longer than 2 ps at the highest excitation fluence studied, and it cannot be attributed to the photoinduced heating of electrons or modification of the conduction band filling. Additionally, the measured unoccupied electronic states are consistent with the first-principles calculation based on experimental crystal lattice constants, which favor a strong topological insulating phase. These findings provide new insights into the longstanding controversy about the strong and weak topological properties in ZrTe5, and they suggest that many-body effects including electron–electron interactions must be taken into account to understand the equilibrium weak topological insulating phase in ZrTe5.

MSM UV photodetector with low dark current based on GaInO/SrTiO3 heterojunction

Doping and heterojunction manufacturing processes are widely employed techniques for modifying the energy band of wide band gap semiconductors. In this work, the sol-gel method was employed to introduce indium (In) into Ga2O3, leading to the formation of the GaInO (GIO) thin film, which was subsequently combined with SrTiO3 (STO) to form the heterojunction. The heterojunction was utilized for the fabrication of metal-semiconductor-metal (MSM) structured ultraviolet (UV) photodetectors (PDs). The existence of a built-in electric field (Ebi) generated by the heterojunction at the contact interface of GIO and STO can diminish the density of majority carriers in dark conditions, consequently leading to a decrease in the dark current. The photo-to-dark suppression ratio of GIO/STO exceeds three orders of magnitude (1.157 × 103), and the dark current of the composite GIO/STO MSM UVPDs (0.178 nA) is one order of magnitude lower than that of the individual GIO (4.028 nA) at 5V bias. Additionally, the Ebi may accelerate the exciton separation for photo-generated exciton, thereby accelerating the response speed. The GIO/STO device demonstrates a shorter rise time of 1.21 s and a decay time of 0.42 s. The utilization of both energy band modification methods offers promising prospects for the application of GIO/STO MSM UVPDs.

Spin and valley-polarized multiple Fermi surfaces of α -RuCl3/bilayer graphene heterostructure

We report the transport properties of α-RuCl3/bilayer graphene heterostructures, where carrier doping is induced by a work function difference, resulting in distinct electron and hole populations in α-RuCl3 and bilayer graphene, respectively. Through a comprehensive analysis of multi-channel transport signatures, including Hall measurements and quantum oscillation, we unveil significant band modifications within the system. In particular, we observe the emergence of spin and valley-polarized multiple hole-type Fermi pockets, originating from the spin-selective band hybridization between α-RuCl3 and bilayer graphene, breaking the spin degree of freedom. Unlike the α-RuCl3/monolayer graphene system, the presence of different hybridization strengths between α-RuCl3 and the top and bottom graphene layers leads to an asymmetric behavior of the two layers, confirmed by effective mass experiments, resulting in the manifestation of valley-polarized Fermi pockets. These compelling findings establish α-RuCl3 proximitized to bilayer graphene as an outstanding platform for engineering its unique low-energy band structure.

Influence of Bi doping on the electronic structure of (Ga,Mn)As epitaxial layers

The influence of the addition of Bi to the dilute ferromagnetic semiconductor (Ga,Mn)As on its electronic structure as well as on its magnetic and structural properties has been studied. Epitaxial (Ga,Mn)(Bi,As) layers of high structural perfection have been grown using low-temperature molecular-beam epitaxy. Post-growth annealing of the samples improves their structural and magnetic properties and increases the hole concentration in the layers. Hard X-ray angle-resolved photoemission spectroscopy reveals a strongly dispersing band in the Mn-doped layers, which crosses the Fermi energy and is caused by the high concentration of Mn-induced itinerant holes located in the valence band. An increased density of states near the Fermi level is attributed to additional localized Mn states. In addition to a decrease in the chemical potential with increasing Mn doping, we find significant changes in the valence band caused by the incorporation of a small atomic fraction of Bi atoms. The spin–orbit split-off band is shifted to higher binding energies, which is inconsistent with the impurity band model of the band structure in (Ga,Mn)As. Spectroscopic ellipsometry and modulation photoreflectance spectroscopy results confirm the valence band modifications in the investigated layers.

ZnO nanoparticles impregnated with Hibiscus sabdariffa L. extract: Characterization and antimicrobial activity

Zinc oxide can be a vehicle for the encapsulation of bioactive compounds obtained from Hibiscus sabdariffa L by-products due to its mesoporous structure. The nanoparticles obtained with zinc nitrate showed an average particle size of 120 mn, when impregnated with ultrasound-assisted extract of Jamaican by-product did not show morphological alterations, however; it was observed that there is a modification of the ZnO energy bands attributed to the interactions between ZnO and the extract molecules. T1.0% and T1.5% presented higher inhibition on Listeria Monocytogenes, Staphylococcus aureus, Escherichia coli and Staphylococcus mutans compared to T0.5% and EUSJ. The results show that the synthesis process and the impregnation of Jamaican by-product extracts have interesting antibacterial properties associated with the potentiating effect of ZnO and extract, which can be a starting point for further studies on some applications or other types of microorganisms

A Review on Pulsed Laser Fabrication of Nanomaterials in Liquids for (Photo)catalytic Degradation of Organic Pollutants in the Water System.

The water pollution caused by the release of organic pollutants has attracted remarkable attention, and solutions for wastewater treatment are being developed. In particular, the photocatalytic removal of organic pollutants in water systems is a promising strategy to realize the self-cleaning of ecosystems under solar light irradiation. However, at present the semiconductor-based nanocatalysts can barely satisfy the industrial requirements because their wide bandgaps restrict the effective absorption of solar light, which needs an energy band modification to boost the visible light harvesting via surface engineering. As an innovative approach, pulsed laser heating in liquids has been utilized to fabricate the nanomaterials in catalysis; it demonstrates multi-controllable features, such as size, morphology, crystal structure, and even optical or electrical properties, with which photocatalytic performances can be precisely optimized. In this review, focusing on the powerful heating effect of pulsed laser irradiation in liquids, the functional nanomaterials fabricated by laser technology and their applications in the catalytic degradation of various organic pollutants are summarized. This review not only highlights the innovative works of pulsed laser-prepared nanomaterials for organic pollutant removal in water systems, such as the photocatalytic degradation of organic dyes and the catalytic reduction of toxic nitrophenol and nitrobenzene, it also critically discusses the specific challenges and outlooks of this field, including the weakness of the produced yields and the relevant automatic strategies for massive production.

Direct Observation of Locally Modified Excitonic Effects within a Moiré Unit Cell in Twisted Bilayer Graphene.

Bilayer graphene, which forms moiré superlattices, possesses distinct electronic and optical properties owing to its hybridized energy band and the emergence of van Hove singularities depending on its twist angle. Extensive research has been conducted on the global characteristics of moiré superlattices induced by their long-range periodicity. However, the local properties, which differ owing to the variations in the three-dimensional atomic arrangement, within a moiré unit cell have been rarely explored. In this study, we demonstrate the highly localized excitation of carbon 1s electrons to unoccupied van Hove singularities in twisted bilayer graphene by electron energy loss spectroscopy using a monochromated transmission electron microscope. The core-level excitations associated with the van Hove singularities exhibit a systematic twist-angle dependence analogous to optical excitations. Furthermore, local variations in the core-level van Hove singularity peaks, which can originate from the core-exciton lifetimes and band modifications corresponding to the local stacking geometry within a moiré unit cell, are unambiguously corroborated.

Band Modification and Localized Lattice Engineering Leads to High Thermoelectric Performance in Ge and Bi Codoped SnTe-AgBiTe2 Alloys.

SnTe, emerging as an environment-friendly alternative to conventional PbTe thermoelectrics, has drawn significant attention for clean energy conversion. Here, a high peak figure of merit (ZT) of 1.45 at 873K in Ge/Bi codoped SnTe-AgBiTe2 alloys is reported. It is demonstrated that the existence of Ge, Bi, and Ag facilitate band convergence in SnTe, resulting in remarkable enhancement of Seebeck coefficient and power factor. Simultaneously, localized lattice imperfections including dislocations, point defects, and micro/nanopore structures are caused by incorporation of Ge, Bi, and Ag, which can effectively scatter heat carrying phonons with different wavelengths and contribute to an extremely low κL of 0.61Wm-1 K-1 in Sn0.92 Ge0.04 Bi0.04 Te-10%AgBiTe2 . Such high peak ZT is achieved by decouples electron and phonon transport through band modification and localized lattice engineering, highlighting promising solutions for advancing thermoelectrics.

Fungal Screening for Potential PET Depolymerization

Approximately 400 billion PET bottles are produced annually in the world, of which from 8 to 9 million tons are discarded in oceans. This requires developing strategies to urgently recycle them. PET recycling can be carried out using the microbial hydrolysis of polymers when monomers and oligomers are released. Exploring the metabolic activity of fungi is an environmentally friendly way to treat harmful polymeric waste and obtain the production of monomers. The present study addressed: (i) the investigation of potential of strains with the potential for the depolymerization of PET bottles from different manufacturers (crystallinity of 35.5 and 10.4%); (ii) the search for a culture medium that favors the depolymerization process; and (iii) gaining more knowledge on fungal enzymes that can be applied to PET recycling. Four strains (from 100 fungal strains) were found as promising for conversion into terephthalic acid from PET nanoparticles (npPET): Curvularia trifolii CBMAI 2111, Trichoderma sp. CBMAI 2071, Trichoderma atroviride CBMAI 2073, and Cladosporium cladosporioides CBMAI 2075. The fermentation assays in the presence of PET led to the release of terephthalic acid in concentrations above 12 ppm. Biodegradation was also confirmed using mass variation analyses (reducing mass), scanning electron microscopy (SEM) that showed evidence of material roughness, FTIR analysis that showed band modification, enzymatic activities detected for lipase, and esterase and cutinase, confirmed by monomers/oligomers quantification using high performance liquid chromatography (HPLC-UV). Based on the microbial strains PET depolymerization, the results are promising for the exploration of the selected microbial strain.

Band modification towards high thermoelectric performance of SnSb2Te4 with strong anharmonicity driven by cation disorder

As a typical (IV–VI)x(V2VI3)y compound, the tetradymite-like layered SnSb2Te4-based compounds have attracted increasing attention in the thermoelectric community owing to the intrinsically low lattice thermal conductivity. Nevertheless, the effect of cations disorder on the inherent physical characteristics remains puzzling, and its inferior Seebeck coefficient is the bottleneck to achieving high thermoelectric performance. In this work, the thermoelectric properties of polycrystalline InxSn1−xSb2(Te1−ySey)4 (0 ≤ x ≤ 0.1, 0 ≤ y ≤ 0.15) samples are comprehensively investigated. In conjunction with the calculated band structure and experimental results, the Seebeck coefficient and power factor are markedly improved after the introduction of indium and selenium, which originates from the combined effects of the emergent resonant states and converged valence bands along with optimal carrier concentration. Additionally, compared with the ordered lattice structure, the disordered cations occupancy in SnSb2Te4 further strengthens lattice anharmonicity and reduces phonon group velocity verified by first-principles calculations, securing intrinsically low lattice thermal conductivity. Finally, a record zT value of ∼0.6 at 670 K and an average zT of ∼0.4 between 320 and 720 K are obtained in the In0.1Sn0.9Sb2Te3.4Se0.6 sample, being one of the highest zT values among SnSb2Te4-based materials. This work not only demonstrates that SnSb2Te4-based compounds are promising thermoelectric candidates, but also provides guidance for the promotion of thermoelectric performance in a broad temperature range.

Development of Transition Metal Incorporated Bismuth‐Based Oxide Semiconductors as Potential Candidates for Solar Assisted Water Splitting Applications

AbstractPhotocatalysis is a traditional approach for solving energy crises and environmental pollution control problems. Visible light‐sensitive transition metal incorporated bismuth‐based metal oxides have enough potential to act as photoelectrodes in the communal of solar energy conversion and environmental remediation. These transition metal incorporated Bi‐based metal oxides are of practical importance due to their efficient photocatalytic activity, high stability, low cost and non‐toxicity. The latest efforts towards the limitations for improvement in performances of these materials can be controlled by different factors e. g., surface morphology, band gap, size, crystallinity, charge separation efficiency and rate of the charge transfer, etc. The alignment of band position or modification of band energy can also play an important role for these materials. Here, we primarily focus on the detailed discussion of transition metal incorporated bismuth‐based oxide semiconductors with suitable modifications – their fabrication and applications to enhance the photoelectrochemical activity.

Band Engineering of Photocatalytic BiVO4 with Modified Vanadium States via Potassium Chloride Addition during Hydro-Thermal Synthesis and Post-Annealing

The monoclinic BiVO4 in a powder state was prepared via a hydrothermal method, with the addition of KCl as a structure-directing agent. The as-prepared sample was calcined at different temperatures (400–600 °C), either in the air or in Ar gas. It is found that, though the morphology and crystal structure mostly remain unchanged, the bandgap properties are modified during calcination. A detailed analysis of the surface chemical states and optical absorption properties reveals the involvement of tetravalent vanadium ions and oxygen vacancies as the cause of the band modification. The bandgap properties are to be found tunable via changing the calcination condition, as well as the KCl concentration in the precursor. The photocatalytic properties of BiVO4 samples are greatly enhanced with the addition of KCl in the precursor, but degraded by post-annealing, where the residual Cl in the calcined sample may act as an inhibitor. The enhanced photoactivity is explained in terms of favorable faceting, bandgap modification, and heterojunction of BiVO4/BiOCl.

Isolation of Thermophilic Bacteria and Investigation of Their Microplastic Degradation Ability Using Polyethylene Polymers.

Microplastics (MPs) pose potential public health challenges because of their widespread occurrences in all environmental compartments. While most studies have focused on the occurrence fate of microplastics in wastewater treatment systems, the biodegradation of microplastics in wastewater is generally little understood. Therefore, we used two Gram-positive and thermophilic bacteria, called strain ST3 and ST6, which were identified by morphological, biochemical, physiological, and molecular analyses, to assess the growth and biodegradation potential of two different sized (50 and 150 m) polyethylene particles. The degradation was monitored based on structural and surface morphological changes. According to 16S rRNA analyses, ST3 and ST6 were identified as Anoxybacillus flavithermus ST3 and Anoxybacillus sp. ST6, respectively. The occurrence of cracks, holes, and dimensional changes was detected by scanning electron microscopy. Moreover, critical characteristic absorption band formation and modifications were determined by Fourier transform infrared spectroscopy. In addition to these, it was found that Anoxybacillus flavithermus ST3 and Anoxybacillus sp. ST6 produced high level of alpha-Amylase. These results showed that thermophilic bacteria are capable of the biodegradation of microplastics and production of alpha-Amylase.

Effects of transition metal dopants (Mo and W) on electrical and optical properties of CdO thin films

Cadmium oxide (CdO) is known to have the highest electron mobility among common transparent conductive oxides (TCOs). Here, we carried out a systematic investigation on the properties of CdO films doped with transition metal donors, namely Mo (CMO) and W (CWO) which have been reported to enhance the mobility in In2O3. We find that the electron concentration N in as-grown CMO and CWO increases with dopant concentration to> 1021 cm−3. While the mobility μ increases with rapid thermal annealing (RTA) temperature, N decreases when the temperature is> 400 °C, suggesting that Mo and W are unstable donors. The stronger affinity of the Mo and W to diffuse out in an O2 environment results in an even stronger decrease in N when annealed in O2. Isothermal RTA at 300 °C further reveals that H interstitial donors incorporated during room temperature film growth are unstable at temperature< 300 °C. Overall, both CMO and CWO can achieve a low resistivity of ∼1.5 × 10−4 Ω-cm with μ > 100 cm2/V-s and N∼3.5 × 1020 and 4 × 1020 cm–3, respectively, as well as an overall transmittance> 80% up to λ > 1600 nm with x ≲ 0.01 after RTA at 600 °C in N2. Finally, changes in optical absorption edges Eopt of CMO and CWO are consistent with the modification of the conduction band (CB) due to anticrossing interactions of the dopant d–states with the CdO CB, which also flattens the CB dispersion which dramatically lowers the μ at high x.

Coupling modification of Fermi level, band flattening and lattice defects to approach outstanding thermoelectric performance of ZnO films via tuning In and Ga incorporation

Band structure modification is found one of the state-of-the-art strategies to control electrical, thermal transport properties, and optimize performance of thermoelectric (TE) materials. Despite being a high-temperature n-type TE material, low-dimensional ZnO structures, specifically thin films normally possess a poor performance due to instability, low electrical, and high thermal conductivities. Herein, it is found that the trade-offs between TE parameters of ZnO films can be simultaneously abated by co-doping In and Ga. The dual incorporation of In and Ga enhances crystallinity, thermal stability, and TE properties up to 573 K. Tuning In and Ga contents not only optimizes carrier concentration associating with Fermi level modification, but also engineers lattice defects contributing to scattering transport mechanisms. Furthermore, the In3+ compensation at substitutional sites, specifically at high temperature, significantly increases density-of-state effective mass due to conduction band flattening. As a result, the coupling modification of Fermi level, band flattening, and lattice defects leads to maintaining electrical conductivity at a medium degree, increasing Seebeck coefficient, and decreasing thermal conductivity, respectively. The TE dimensionless figure of merit (ZT) and power factor (PF) of the films deposited from the In0.01Ga0.04Zn99.95O compound significantly boost to 0.2 and 745.2 µW/mK2 at 573 K, respectively. These values are 1328 and 536% higher than pristine ZnO film; 400 and 258% greater than Ga single-doped ZnO film, respectively. It proposes that our ZnO-based thin films approach the high ZT region (ZT ≥ 0.2) of advanced nanostructured ZnO-based bulks.