Band Gap Transition Research Articles

Sliding-reversible bandgap modulation in irreversible asymmetric multilayers

The electronic bandgap of a material is often fixed after fabrication. The capability to realize on-demand and nonvolatile control over the bandgap will unlock exciting opportunities for adaptive devices with enhanced functionalities and efficiency. We introduce a general design principle for on-demand and nonvolatile control of bandgap values, which utilizes reversible sliding-induced polarization driven by an external electric field to modulate the irreversible background polarization in asymmetric two-dimensional (2D) multilayers. The structural asymmetry can be conveniently achieved in homobilayers of Janus monolayers and heterobilayers of nonpolar monolayers, making the design principle applicable to a broad range of 2D materials. We demonstrate the versatility of this design principle using experimentally synthesized Janus metal dichalcogenide multilayers as examples. Our first-principles calculations show that the bandgap modulation can reach up to 0.3 eV and even support a semimetal-to-semiconductor transition. By integrating a ferroelectric monolayer represented by 1T″′-MoS2 into a bilayer, we show that the combination of intrinsic ferroelectricity and sliding ferroelectricity leads to multi-bandgap systems coupled to multi-step polarization switching. The sliding-reversible bandgap modulation offers an avenue to dynamically adjust the optical, thermal, and electronic properties of 2D materials through mechanical and electrical stimuli.

Indirect-to-direct bandgap transition in GaP semiconductors through quantum shell formation on ZnS nanocrystals

Although GaP, a III-V compound semiconductor, has been extensively utilized in the optoelectronic industry for decades as a traditional material, the inherent indirect bandgap nature of GaP limits its efficiency. Here, we demonstrate an indirect-to-direct bandgap transition of GaP through the formation of quantum shells on the surface of ZnS nanocrystals. The ZnS/GaP quantum shell with a reverse-type I heterojunction, consisting of a monolayer-thin GaP shell grown atop a ZnS core, exhibits a record-high photoluminescence quantum yield of 45.4% in the violet emission range (wavelength = 409 nm), validating its direct bandgap nature. Density functional theory calculations further reveal that ZnS nanocrystals, as the growth platform for GaP quantum shells, play a crucial role in the direct bandgap formation through hybridization of electronic states with GaP. These findings suggest potential for achieving direct bandgaps in compounds that are constrained by their inherent indirect energy gaps, offering a strategy for tailoring energy structures to significantly improve efficiencies in optoelectronics and photovoltaics.

Mobile intrinsic point defects for conductive neutral domain walls in LiNbO3.

Conductive ferroelectric domain walls (DWs) hold great promise for neuromorphic nanoelectronics as they can contribute to realize multi-level diodes and nanoscale memristors. Point defects accumulating at DWs will change the local electrical transport properties. Hence, local, inter-switchable n- and p-type conductivity at DWs can be achieved through point defect population control. Here, we study the impact of point defects on the electronic structure at neutral domain walls in LiNbO3 by density functional theory (DFT). Segregation of Li and O vacancies was found to be energetically favourable at neutral DWs, implying that charge-compensating electrons or holes can give rise to n- or p-type conductivity. Changes in the electronic band gap and defect transition levels are discussed with respect to local property engineering, opening the pathway for reversible tuning between n- and p-type conduction at neutral ferroelectric DWs. Specifically, the high Curie temperature of LiNbO3 and the significant calculated mobility of O and Li vacancies suggest that thermal annealing and applied electric fields can be used experimentally to control point defect populations, and thus enable rewritable pn-junctions.

Lattice constant, bandgap energy, absorption coefficient and dielectric function of the antimony-rich InBixSb1-x alloy using first-principles calculations

So far, little is known about the electronic and optical properties of InBixSb1-x. In this work, the first-principles calculations are performed to research the lattice constant, the bandgap energy, the absorption coefficient and the dielectric function of the antimony-rich InBixSb1-x. The results show that the bowing coefficient for the lattice constant is merely −0.012 Å. According to the band structures, it is found that the Sb-rich InBixSb1-x possesses a direct bandgap at G point. Its bandgap reduction is due to the ascending of the valence band maximum (VBM) and the descending of the conduction band minimum (CBM). For the sake of providing a good description for the bandgap energy in the Sb-rich range, the modified valence band anticrossing (MVBAC) model plus a linear equation is utilized. The result shows that the predicted positive to negative bandgap transition occurs at x = 0.13. Besides, the valence band offset between InSb and InBi is identified to be 0.27eV. For the optical properties, it is found that the Bi component is effective in raising the static dielectric constant of InBixSb1-x. However, it has a minor effect on the transition ability of the electrons. In the Sb-rich component range, the critical point energies E0+Δ0E1, E1+Δ1E2 and E1′ are found to shift toward the low energy direction. The result of the absorption spectra supports this opinion as increasing Bi component leads to a redshift of the absorption spectra. The adjustable bandgap energy and the optical properties of InBixSb1-x demonstrate that it is a strong candidate for fabricating the photodetectors in the 8–12 μm spectral region.

Optical and structural transformations in polyethylene terephthalate (PET) films subjected to Ag[formula omitted]-ion implantation and subsequent Au[formula omitted]-ion irradiation

We report on the dual effects of ion implantation and swift heavy ion on the optical and structural characteristics of polyethylene terephthalate (PET) films using UV–Vis spectrophotometry, FTIR and X-ray diffraction measurements. Samples were first implanted with 150 keV Ag+-ions at different fluences of 1 ×1016, 5 ×1016, and 1 ×1017 ions/cm2, and thereafter irradiated with 30 MeV Au7+-ions at different fluences, while analysing elemental depth profile in situ on the Time of Flight Heavy Ions Elastic Recoil Detection (ToF-Hi-ERDA) instrument. The elemental depth profile measurements showed considerable atomic depletion of hydrogen from 36% down to below 6% and oxygen from 18% to about 5%. The proportion of carbon increased from 45% to over 87%. The optical bandgap decreased with increasing ion implantation fluence and reduced even further on irradiation with 30 MeV 197Au7+-ions. The most notable outcome of the implantation was the onset of the precipitation of gold nanoparticles (Au-NPs) in the PET matrix, marked by Localised Surface Plasmon Resonance effects, coincided with a relatively significant drop in the bandgap energy. This latter effect could only be best explained as the result of these Au-NPs in the PET. This suggests that optical bandgap tuning in polymer films, usually achievable through high fluence implantation at low energy (i.e., keV), could also be realized through low fluence irradiation with MeV energy ions. It is surmised that, for the noble metals, NP-induced bandgap modification in PET precludes the need for high fluence to achieve the same. This has the obvious advantage of bandgap alterations at much lower structural damage to the target polymer. As reported by FTIR results, one can observe structural changes with the formation of new chemical bonds on thin films. X-ray diffraction results exhibited one prominent peak corresponding to the (100) plane, which varies in intensity with increased implantation fluence, suggesting a change in the crystallinity of the PET. The decrease in (100) peak or crystallinity was well connected with the presence and decrease of 847, 970, and 1471 cm−1 peaks, which were assigned to the ethylene glycol molecular groups.

Nonequilibrium bandgap modification in porphyrin-based metal-organic frameworks revealed by transient absorption spectroscopy

Modifying the equilibrium bandgap has proven to be an effective strategy for optimizing photocarrier properties in metal-organic frameworks (MOFs). In this work, we have investigated the nonequilibrium bandgap modification in cobalt porphyrin-based MOF (Co-TCPP MOF) nanofilms through transient absorption spectroscopy. Our results reveal a captivating redshift–blueshift crossover in the nonequilibrium bandgap of Co-TCPP MOFs, with a staggering maximum shifting value of approximately 170 meV, achieved with an excitation fluence of 96 μJ/cm2. This phenomenon sets the stage for further investigations into harnessing nonequilibrium bandgap modification as a powerful tool for tailoring photocarrier properties. Another key facet of our research is the revelation that the bandgap modification effect observed in Co-TCPP MOFs is strongly dependent on the excitation fluence and is absent in disordered porphyrin molecules. This observation suggests a correlation between the bandgap modification and the amplified many-body interactions present within the ordered MOF structure, thus offering valuable insights into the intricate relationship between bandgap modification, excitation fluence, and ordered MOF structures.

Optimization of novel plate acoustic metamaterials and modulation of the low-frequency bandgap

Based on the local resonance mechanism, five new acoustic metamaterial plate structures with low-frequency bandgaps are proposed in this paper. The two new structures obtained by heuristic structural design are capable of suppressing vibrations over a large frequency range in the low-frequency range of 0-400 Hz, which is promising for practical applications. The mechanism of bandgap generation is found to be a shift in the form of local resonance. Among the three original models, model C has the smallest transmission coefficient T min of −154.6. Analysis of the group and phase velocity diagrams reveals that the change in frequency has a great influence on the energy transfer, speed and direction of the wave in the structure. The heuristic structural design allows the mass block of model B1 to undergo angular state changes, which ultimately realizes the regulation of the bandgap position and the total bandgap width within a certain range. It is also found that the variation of the bandgap properties has a certain regularity with the change of the structural parameters.

Theoretical design of high-performance guiding and filtering devices using photonic comb-like waveguides with defective resonators

This paper uses the Transfer Matrix Method (TMM) to investigate the transmission rate and the photonic band structure of one-dimensional photonic comb-like waveguides (CWGs) system. This study is crucial as it provides valuable insights into the properties of photonic waveguides, which can be leveraged to design high-performance guiding, filtering and multiplexing devices. The primary objective of our study is to comprehend the impact of defects on the transmission and band structure of CWGs. Specifically, how changes the geometrical and material properties of defective resonators affect defect modes in photonic band gaps. By modifying the relative permittivity and length of these defective resonators, we observed a shift of defect modes to lower frequencies. This work shows, for the first time, the influence of these defects on defect modes and their potential applications in the development of high-performance guidance and electromagnetic filtering devices.

Electronic and adsorption properties of halogen molecule X2 (X=F, Cl) adsorbed arsenene: First-principles study

The geometry, electronic structure, and adsorption properties of halogen molecule X2(X = F, Cl) on arsenene were investigated using first-principles calculations. The adsorption of molecules was considered at various sites and in various orientations on the pristine arsenene (p-As) surface. Both molecules show chemisorption and the crystal orbital Hamiltonian population (COHP) analysis reveals the formation of strong X-As bonds. In particular, the adsorbed molecules spontaneously dissociate into atomic halogen atoms, with a diffusion barrier of 1.91 (1.72) eV for F2(Cl2). The adsorbed X2 molecules induced distortions in the local geometry due to strong interaction with arsenene. Importantly, the formation of X-As bonding remarkably changed the electronic properties, evidenced by the decrease of the actual band gap due to the emergence of defect states within the band gap. For instance, the F2 adsorbed arsenene system (F2-As) exhibited an average band gap of 1.17 eV, and Cl2 adsorbed arsenene (Cl2-As) showed an average band gap of 0.83 eV. In particular, indirect to direct band gap transition was observed for some adsorption configurations. The reduction in band gap resulted in the enhancement of electrical conductivity. These findings suggest that the electronic properties of arsenene can be tuned by halogen decoration.

Hybrid Eu(II)-bromide scintillators with efficient 5d-4f bandgap transition for X-ray imaging

Luminescent metal halides are attracting growing attention as scintillators for X-ray imaging in safety inspection, medical diagnosis, etc. Here we present brand-new hybrid Eu(II)-bromide scintillators, 1D type [Et4N]EuBr3·MeOH and 0D type [Me4N]6Eu5Br16·MeOH, with spin-allowed 5d-4f bandgap transition emission toward simplified carrier transport during scintillation process. The 1D/0D structures with edge/face -sharing [EuBr6]4− octahedra further contribute to lowing bandgaps and enhancing quantum confinement effect, enabling efficient scintillation performance (light yield ~73100 ± 800 Ph MeV−1, detect limit ~18.6 nGy s−1, X-ray afterglow ~ 1% @ 9.6 μs). We demonstrate the X-ray imaging with 27.3 lp mm−1 resolution by embedding Eu(II)-based scintillators into AAO film. Our results create the new family of low-dimensional rare-earth-based halides for scintillation and related optoelectronic applications.

Strain-tunable electronic and optical absorption in the MXenes nanolayers: A DFT approach

Computational simulations using density functional theory (DFT) were performed to show that biaxial strain engineering within the range of −8% to +8% is an effective method for modifying the fundamental properties of two-dimensional (2D) transition metal carbides (MXenes). In this work, we computationally explored the effect of both compressive (0 to −8%) and tensile (0 to +8%) strain on the structural, electronic, and optical properties of M2CO2 MXenes (M = Ti, Zr, Sc and Hf) nanolayers. When compressive strains are applied, the charge transfer between layers increases because of decreased interlayer coupling. Conversely, tensile strains result in the opposite behavior. The strain-tunable band gap effect in Mo2CO2 nanolayers is revealed by investigating the valence band maximum (VBM) and conduction band minimum (CBM) in the band structure under biaxial strain. It is observed that the indirect-to-direct band gap transition occurs when the tensile strain is applied to Sc2CO2 and Ti2CO2 nanolayers. In most samples, the energy gap increases with an increase in tensile strain and decreases with an increase in compressive strain. The optical absorption coefficient indicates considerable absorption in the visible to ultraviolet (UV) region. Additionally, the absorption can be influenced by biaxial strains. In particular, under compressive strains (−8%) and Z-polarized light, the UV absorption peak in Hf2CO2, Ti2CO2, and Zr2CO2 reaches 68 %, 78 %, and 113 % respectively. The results indicate that these M2CO2 MXenes nanolayers will have significant potential for applications in tunable optoelectronic devices.

Indirect to direct band gap engineering of cubic bromide perovskite AlMgBr3 under pressure: First-principles calculations for enhanced optoelectronic applications

Through first principles, the structural, electronic, optical, mechanical, and thermodynamic properties of AlMgBr3 at different pressures are investigated for the first time. At 0 GPa, cubic AlMgBr3 is an indirect band gap insulator (Eg = 3.958 eV). Interestingly, its band gap type changes from an indirect band gap to a direct band gap at 5 GPa, making it a more favorable material for optoelectronic device applications. In addition, as the pressure increases, the conduction band electrons move downward, resulting in a reduction of the band gap, and the band gap transition from the ultraviolet to visible region. The optical properties show that AlMgBr3 has a high dielectric constant, refractive index, and conductivity, which is favorable for its application in solar cells, waveguides and other optoelectronic devices. The phase transition point of AlMgBr3 was determined to be 39.6 GPa based on the mechanical stability conditions, and the mechanical properties revealed the ductility, anisotropy and machinability of AlMgBr3. By using the quasi-harmonic Debye model, the effect of temperature and pressure on the bulk modulus, coefficient of thermal expansion, isobaric heat capacity, Debye temperature, and entropy were also calculated. It is worth mentioning that the electronic, optical, mechanical and thermodynamic properties of AlMgBr3 have been significantly enhanced under pressure.

A theoretical analysis of the effect of hydrostatic pressure on cerium oxide for renewable energy applications

The characteristics of cubic cerium oxide (CeO2) have been investigated using density functional theory (DFT) using the PBE-GGA exchange–correlation functional. This study mainly focused on the structural, elastic, and optoelectronic properties of the CeO2 under the application of external hydrostatic pressure. It is observed that lattice constants and volume tend to decrease with increasing pressure. Based on the observed trends in lattice constants variations, CeO2 exhibits compressibility at high-pressure conditions, although it remains structurally unchanged throughout the pressure range of 0 to 100 GPa. Applying pressure within the range of 0 to 100 GPa reveals a distinct characteristic associated with the emergence of electronic bandgap opening. The material displays an indirect energy bandgap, with its magnitude increasing from 2.659 eV to 4.055 eV under rising pressure. To deeply understand the impact of external pressure on the optical behaviour of CeO2, extensive investigation has been conducted on several optical parameters such as the dielectric function, refractive index, optical reflectivity, absorption coefficient, optical conductivity, and loss function throughout the energy range up to 50 eV. However, there is a tendency for optical parameters to show sharpening peaks that shift somewhat towards higher energies. Furthermore, we have also tested the impact of bandgap modulation induced in CeO2 by proposing a CsSnBr3-based solar cell with the One-Dimensional Solar Cell Capacitance Simulator software. Based on our findings, the use of cubic cerium oxide may find its potential to enhance the performance of optoelectronic and renewable energy devices.

Design of an on-chip germanium cavity for room-temperature infrared lasing

Germanium (Ge) is one of the most promising material platforms to enable the realization of monolithically integrated laser on silicon because it is a group-IV material with a pseudo-direct-band structure that can be converted into direct-bandgap either through the application of tensile strain or via the tin (Sn) incorporation in Ge. The bandgap modification enhances the light emission efficiency of Ge, where lasing can also be observed if a suitable cavity preserving the strain can be realized. In fact, several different research groups have reported lasing from strained Ge and GeSn optical cavities, however they all report lasing at low temperatures and room-temperature lasing, which is the ultimate goal required for a fully integrated laser, has not been demonstrated yet. In this work, we design an on-chip germanium cavity that has all the ingredients combined to make the room-temperature lasing possible. The design includes a 4.6% uniaxially tensile strained Ge gain medium embedded in a Fabry-Perot like cavity composed of two distributed Bragg reflectors. 3-dimensional (3D) Finite Element Method (FEM) based strain simulations together with a proposed fabrication methodology provides a guideline for the realization of the structure. Furthermore, 3D Finite Difference Time Domain (FDTD) simulations demonstrate that the designed structure is suitable for the room-temperature lasing in a wavelength range of 2410–2570 nm. 3D FEM-based heat transfer simulations performed for the designed cavity verifies the eligibility of the room-temperature operation paving the way for a possible demonstration of on-chip laser that could take part in the fully integrated infrared systems for a variety of applications including biological and chemical sensing, as well as security such as alarm systems and free-space optical communications.

Unveiling thermally driven photoluminescence in CVD grown MoS[formula omitted] dendritic flake

High-quality MoS2 nanostructures were fabricated via chemical vapor deposition technique on SiO2/Si substrate. In this paper, the effect of temperature on the photoluminescence behavior of MoS2 dendritic flake is addressed. We scrutinized the photoluminescence spectra of monolayer and multilayer regions of MoS2 in the temperature range 300 K–680 K. Monolayer and multilayer behavior of MoS2 flakes are confirmed by Raman and Photoluminescence spectroscopy. The excitonic peaks from the multilayer regime become less intense and show a red shift compared to the monolayer PL spectra. Thermally-induced bandgap modulation of MoS2 is demonstrated. The excitonic intensity and peak positions reveal pronounced temperature-dependent changes. These changes are explicable through the increased electron–phonon interaction and lattice rearrangements. Furthermore, first principle calculations are employed to glean insight into the impact of atomic rearrangements on the band gap behavior of MoS2. Our research presents a detailed understanding of thermally driven band gap modulation of monolayer and multilayer MoS2, which is essential for designing optoelectronic devices.

Spinel nickel ferrite (NiFe2O4) materials synthesized via spray-pyrolysis for electrochemical supercapacitor application

To explore potential applications of NiFe2O4-based supercapacitors in various energy storage systems, including portable electronic devices, electric vehicles, and grid energy storage, highlighting the advantages and challenges of using NiFe2O4 in these applications. To identify and propose future research directions for further improving the performance of NiFe2O4 supercapacitors. In the study focuses on optimizing concentration of synthesis to achieve desirable structural and electrochemical properties, characterizing the synthesized materials, and assessing their specific capacitance, energy density, power density, cycle stability, and rate capability. The different molar precursor solutions were utilized for the formation of NiFe2O4 thin films by using the cost-effective spray pyrolysis technique. The impact of different molarities on the structural, morphological, elemental, optical, and charge storage performance of NiFe2O4 thin films has been studied. In the XRD studies identified the cubic crystalline structure with Fd-3 m space group symmetry of NiFe2O4. The FE-SEM shows the grain-like surface morphology of NiFe2O4 thin films. The EDAX study reveals that NiFe2O4 thin films were stoichiometric. Bandgap energy values of the thin films were observed in the range of 1.97 to 2.2 eV with allowed direct band gap transitions. The maximum specific capacitance for NiFe2O4 thin film was found to be 707 Fg−1 at 2 mVs−1 with the wider potential window of − 0.8 to + 1 .6 V in 1 M KOH aqueous electrolyte. GCD study confirms the pseudocapacitive behavior of NiFe2O4 thin films. The maximum specific energy and specific power were found to be 83.88 WhKg−1 and 5.294 KWkg−1 at a current density of 0.002 Ag−1. Such as spinel ferrite NiFe2O4 thin film electrodes as an excellent candidate material for electrochemical supercapacitor applications.

New Insights into the Guanine Functionalization of ssDNA-Coated SWCNTs

Single-walled carbon nanotubes (SWCNTs) are a class of nanomaterials that due to their unique physical and chemical properties hold great promise for use in future nanoelectronics, engineered smart materials, and biomedical applications. The discovery of the guanine functionalization reaction1 that allows for tailored band gap modulation of carbon nanotubes has sparked interest in prospects for new applications and improved photophysical insights.In this work, we build upon knowledge gained by previous studies of guanine functionalization to use this reaction as a tool to better understand the nature of these hybrids. Using sorted samples, we analyze E11 spectral shapes of band-gap modified SWCNTs to infer single-site exciton perturbations. These results are correlated with Raman spectra to estimate the fraction of guanine sites that become covalently bonded. Further information is obtained from experimental studies of ionic strength dependence and molecular dynamics simulations of ssDNA-wrapped SWCNT structures prior to guanine functionalization.(1) Zheng, Y.; Bachilo, S. M.; Weisman, R. B. Controlled Patterning of Carbon Nanotube Energy Levels by Covalent DNA Functionalization. ACS Nano 2019. https://doi.org/10.1021/acsnano.9b03488.

(Nanocarbons Division Richard E. Smalley Research Award) Fluorescence of Single-Walled Carbon Nanotubes: From Discovery to Real-World Applications

The unique physical and chemical properties of single-walled carbon nanotubes (SWCNTs) continue to inspire extensive research by many basic and applied researchers. One of the most remarkable features of SWCNTs is their variety of pi-electronic structures associated with specific diameters and roll-up angles. Approximately two-thirds of these structural species are semiconducting and display near-infrared photoluminescence (fluorescence) through direct band gap transitions. I will describe the discovery of this SWCNT fluorescence and the assignment of specific spectral features to physical nanotube structures. Several illustrations of using SWCNT emission spectroscopy in research will then be described, including characterizing sample compositions, capturing images and spectra of single nanotubes in physical and biological environments, and guiding covalent tailoring of nanotube excitonic properties. Finally, I will present an update on an emerging technology for industrial strain measurement that uses SWCNTs as strain sensors that report through spectral shifts in their emission spectra.

Statistics of Lyapunov exponent in random Fibonacci multilayer

Abstract We numerically investigated the localization properties of band-gap and band-edge modes in a one-dimensional random Fibonacci optical multilayer. The statistics of the Lyapunov Exponent (LE) reveal distinct behaviors of localization effects for band-edge and band-gap modes as a function of disorder strength. In particular, a deviation from the single parameter scaling theory (SPST) of localization was observed within a frequency window corresponding to the band-gap of an ordered Fibonacci multilayer. To provide a physical explanation for the violation of SPST, a close correlation between the frequency distribution of the resonant modes in the band-gap and the variance of the LE has been found. The spatial distribution of resonant modes has been reported and discussed. Finally, the dynamics of the gap closing of the two main band-gaps as a function of the disorder strength has been analyzed.

Electronic and optical properties of the GeS/GeSe heterostructure tuned by in-plane strain

Constructing new two-dimensional (2D) van der Waals (vdW) heterostructures has been widely employed as a convenient and effective strategy for tuning the optoelectronic properties, which is of great significance for applications in integrated nano-optoelectronic devices. In this work, we design a GeS/GeSe vdW heterostructure and systematically investigate its electronic and optical properties by using first-principles calculations. Our results indicate that the pristine GeS/GeSe heterostructure possesses an indirect band gap (∼0.98 eV) and exhibits an intrinsically type-I band alignment. Furthermore, the optoelectronic properties of the GeS/GeSe heterostructure can be effectively modulated by applying in-plane strain. Specifically, an indirect to direct band gap transition and a type-I to type-II band alignment transition can be synchronously realized, when the tensile strain along zigzag direction reaches 2%. Furthermore, the calculated dielectric function also reveals an obvious strain effect on the optical properties of the GeS/GeSe heterostructure. The light absorption coefficient of the GeS/GeSe heterostructure along the zigzag direction can reach to 106 cm−1 level, as the compressive in-plane strain reaches −5%. These findings are expected to play a guidance role in the future design of the optoelectronic devices based on 2D anisotropic heterostructures.