Semiconductor ZnSe Research Articles

Synergistic implementation of efficient adsorption-diffusion-conversion in lithium-sulfur batteries via built-in electric field constructed by transition metal selenides

The adsorption of lithium polysulfides (LiPSs), the transport of lithium ions, and the redox kinetics collectively play pivotal roles in determining the application of lithium-sulfur (Li-S) batteries. Herein, a defect-rich p-Co3Se4/n-ZnSe p-n junction (ZCSNC) is engineered by chemical vapor deposition (CVD)-selenation. The n-type semiconductor ZnSe and the p-type semiconductor Co3Se4 contained in ZCSNC effectively anchor LiPSs and promote the catalytic reaction kinetics through synergistic effects, respectively. Meanwhile, the presence of heterogeneous interfaces in the p-n junction and the difference in work functions spontaneously form a built-in electric field, which promotes the transport and transfer of lithium ions and LiPSs. Therefore, the ZCSNC functional material contributes to improving the electrochemical performance of Li-S batteries through the process of adsorption-diffusion-conversion. The Li-S cells with ZCSNC-modified separators show excellent rate performance (741.1 mAh/g at 5C) and long-lasting cycling performance (only 0.04 % capacity decay per cycle over 1000 cycles). Notably, the ZCSNC still has excellent rate discharge capacities (683.9 and 649.7 mAh/g at 2C, respectively) at high sulfur loading and low temperature of 0 °C. This study illustrates that a p-n junction containing a built-in electric field can effectively modulate the kinetics of redox reactions of LiPSs through synergistic interactions.

NC Meets CN: Porous Photoanodes with Polymeric Carbon Nitride/ZnSe Nanocrystal Heterojunctions for Photoelectrochemical Applications.

The utilization of photoelectrochemical cells (PEC) for converting solar energy into fuels (e.g., hydrogen) is a promising method for sustainable energy generation. We demonstrate a strategy to enhance the performance of PEC devices by integrating surface-functionalized zinc selenide (ZnSe) semiconductor nanocrystals (NCs) into porous polymeric carbon nitride (CN) matrices to form a uniformly distributed blend of NCs within the CN layer via electrophoretic deposition (EPD). The achieved type II heterojunction at the CN/NC interface exhibits intimate contact between the NCs and the CN backbone since it does not contain insulating binders. This configuration promotes efficient charge separation and suppresses carrier recombination. The reported CN/NC composite structure serves as a photoanode, demonstrating a photocurrent density of 160 ± 8 μA cm-2 at 1.23 V vs a reversible hydrogen electrode (RHE), 75% higher compared with a CN-based photoelectrode, for approximately 12 h. Spectral and photoelectrochemical analyses reveal extended photoresponse, reduced charge recombination, and successful charge transfer at the formed heterojunction; these properties result in enhanced PEC oxygen production activity with a Faradaic efficiency of 87%. The methodology allows the integration of high-quality colloidal NCs within porous CN-based photoelectrodes and provides numerous knobs for tuning the functionality of the composite systems, thus showing promise for achieving enhanced solar fuel production using PEC.

Investigating structural and optoelectronic properties of Cr-substituted ZnSe semiconductors

The optoelectronic and structural characteristics of the Zn1−xCrxSe (0 ≤ x ≤ 1) semiconductor are reported by employing density functional theory (DFT) within the mBJ potential. The findings revealed that the lattice constant decreases with increasing Cr concentration, although the bulk modulus exhibits the opposite trend. ZnSe is a direct bandgap material; however, a change from direct to indirect electronic bandgap has been seen with Cr presence. This transition is caused by structural alterations by Cr and defects forming, which results in novel optical features, including electronic transitions. The electronic bandgap decreases from 2.769 to 0.216 eV, allowing phonons to participate and improving optical absorption. A higher concentration of Cr boosts infrared absorption and these Cr-based ZnSe (ZnCrSe) semiconductors also cover a wider spectrum in the visible range from red to blue light. Important optical parameters such as reflectance, optical conductivity, optical bandgap, extinction coefficient, refractive index, magnetization factor, and energy loss function are discussed, providing a theoretical understanding of the diverse applications of ZnCrSe semiconductors in photonic and optoelectronic devices.

STRUCTURAL, ELECTRONIC, AND OPTICAL PROPERTIES INVESTIGATION OF ZnSe CUBIC SPHALERITE COMPOUNDS USING DENSITY FUNCTIONAL THEORY (DFT)

Theoretical investigation of the structural, elastic, electronic and optical properties of ZnSe using the plane-wave pseudo potential formalism method of density functional theory with local density approximation (LDA) and generalized gradient approximation (GGA) as exchange-correlation potentials (DFT). The optimal structure of the binary semiconductor ZnSe crystallized in the complex phase of sphalerite was determined by studying the energy as a function of the basic unit volume. The calculated equilibrium lattice constants, bulk moduli and volumes are in reasonable agreement with the available experimental results. The electronic and chemical bonding properties were investigated by calculating the band structure, density of states and Mulliken population. We found that for ZnSe, the band gap of LDA is 1.33 eV and that of GGA is 1.34 eV. In addition, optical properties (absorption coefficients) were calculated.

Achieving high-rate and long-life Zn metal anodes via constructing interfacial gradient heterostructure

The practical application of aqueous zinc-ion batteries (AZIBs) is hampered by dendrite growth and side reactions. Herein, we designed an interfacial gradient heterostructure protective layer (MXene/ZnSe), comprising a conductive MXene nanosheets and an semiconductors ZnSe nanoparticles, to reconstruct the Zn anode surface. Theoretical calculations and experiments show that the interfacial gradient can rearrange the energy bands to facilitate electron/ion transfer. The protective layer not only mitigates the corrosion of Zn anode, but also induces uniform Zn deposition. Therefore, the elaborate gradient heterostructure enables the MXene/ZnSe@Zn symmetric cell to have an excellent long lifespan over 7700 cycles at 20 mA cm−2, surpassing most of the MXene-based related materials reported in the literature. When paired with the commercial V2O5, the MXene/ZnSe@Zn//V2O5 cell achieves an exceptional capacity of 230 mAh/g at 5 A/g. This work paves a new yet powerful tactic for designing a multi-functional gradient heterostructure with strong interface effect toward high-rate and calendar-life AZIBs.

Zinc selenide based dual-channel SPR optical biosensor for HIV genome DNA hybridization detection

Simultaneous measurement of human immunodeficiency virus (HIV) genome DNA hybridization and the DNA melting temperature in a prism-based surface plasmon resonance (SPR) biosensor is modeled theoretically using a simple dual-channel construction. The proposed sensor consists of a BK7 prism coated with silver as a plasmonic material. The metal surface is divided into two channels to detect medium refractive index (RI) and temperature. One half is covered with zinc selenide (ZnSe) semiconductor to enhance the hybridization detection sensitivity and to protect silver from oxidation. The other half is covered with polydimethylsiloxane (PDMS) polymer to detect the temperature variations. The proposed sensor is optimized numerically, and the optimum structure provides an excellent sensitivity of 208 deg/RIU, thanks to the use of the ZnSe layer, which is greater than double the reported dual-channel prism-based sensor in thickness. The polymer channel shows high sensitivity to the temperature variations of − 0.125 deg/°C, which is nearly 10 times the response of the RI channel to temperature variations. The data obtained from the polymer channel is used to compensate for the thermal perturbations of the sensing medium RI, and at the same time, to monitor the increments of the temperature in order to avoid reaching the DNA melting temperature. A mathematical expression is provided to consider the effect of the temperature variations on the RI of the sensing medium to get a better accurate detection process. The DNA hybridization detection of HIV is theoretically discussed in detail starting from the preparation of the sensing medium with the different ingredients until the hybridization between probe and complementary target DNA (ct-DNA) molecules.

Solid State Excitation‐Emission Spectroscopy for the Non‐Destructive Analysis of Band‐Gap & Defect States in Inorganic and Organic Semiconductors

AbstractA new approach to analyze band‐gap and defect states within semiconductors is reported. Solid state excitation‐emission matrices are used to deconvolve spectral signatures that will be superimposed in 1D spectral space; for example, the 570 nm emission peak in ZnO whose emissive state is of a different physical nature depending on the excitation wavelength used. The broad applicability of the technique is shown for a library of widely studied inorganic semiconductors CdS, CdSe, ZnS, ZnSe, ZnO (analytical standard and nanorods), and TiO2. Anthracene is included as a representative example of an organic semiconductor. The developed approach can identify spectral features from the band gap, defects, and trace impurities and provide information on the relative contributions of the different emission pathways. The technique, based on using a plate‐reader conventionally used for the study of biological samples in solution has applicability in both academic and industrial settings for semiconductor studies and quality control applications.

Surface-enhanced Raman spectroscopic activity study on topological ZnSe nanostructures

Topological nanomaterials generally exhibit different defect structures, high specific surface areas, and varying bandgaps. These special geometries, energy-level structures, and interfacial interaction properties provide possibilities to explore interesting properties in the surface-enhanced Raman scattering (SERS). Such properties offer unexplored possibilities for exploring interesting physics and materials science in the field of SERS physical property research and further enhancing substrate materials’ SERS activity. In this paper, the ZnSe topological nanowire crystallite structure was grown using the chemical vapor deposition method, twin defects were introduced, and a topological branched structure that caused the corresponding changes in SERS activity was systematically investigated. On topological ZnSe nanowires, rhodamine 6G (R6G), methylene blue (MB), and crystalline violet (CV) molecules were detected using Raman spectroscopy. The Raman signal enhancement of MB on topological branched nanowires was about 1.9 times that of the trunk nanowires. Finally, the national standard measurement of malachite green (MG) content in water bodies were realized. The results suggest that semiconductor ZnSe topographical nanowires are an emerging class of SERS substrates, and a thorough investigation into the relationship between material structure and SERS performance in specific topological regions will provide new evidence for the principle of chemical enhancement of SERS, as well as recommendations for developing precisely functionalized SERS substrate nanomaterials.

The interaction between semiconductor ZnSe quantum dots and graphene oxide: Ultrafast charge transfer dynamics

In this article, by connecting positively charged cysteamine-coated ZnSe quantum dots (QDs) with either negatively charged graphene oxide (GO) or reduced graphene oxide (RGO), we have assembled ZnSe-GO and ZnSe-RGO composite materials, respectively. We used time-correlated single photon counting (TCSPC) and femtosecond transient absorption (TA) to study the effects of GO/RGO on the fluorescence and carrier transport dynamics of ZnSe QDs. We confirmed that the strong excited state interaction between GO/RGO and ZnSe QDs could significantly quench the exciton fluorescence of ZnSe QDs. Picosecond ultrafast electron transfer from ZnSe QDs to GO/RGO surfaces has been found, and it can decrease the bleaching signal intensity of ZnSe QDs and accelerate the recovery of the bleaching signal as well. Moreover, we found that the energy level change caused by the GO reduction reduced the energy level difference between RGO and ZnSe QDs, which implies broader application prospects for ZnSe-RGO vs. ZnSe-GO composite.

Extreme learning machine computational method of modeling energy gap of doped zinc selenide nano-material semiconductor

Zinc selenide (ZnSe) semiconductor belongs to a class of wide energy gap material with low visible region optical absorption, high optical coefficient (nonlinear) and fascinating optoelectronic as well as photocatalytic features which foster and strengthen its applications in resisting thermal shock, photoelectric fields (which include dielectric mirrors, shot wavelength lasers and light emitting diode), buffer layer of solar cell and many photocatalytic environmental cleanliness applications. Nanostructured ZnSe semiconductors occupy a special place in application domain due to the characteristic features attached to the crystallite size of the material which include high fluorescence quantum yields, solvent dispersibility and adjustable emission color among others. Effective utilization of nanostructured ZnSe semiconductor involves tuning of its energy gap through doping mechanisms which is accompanied with distortion in the parent lattice structure. In this contribution, extreme learning machine (ELM) computational intelligent method is proposed for predicting the band gap energy of doped ZnSe nanostructured semiconductor using the material crystallite size and lattice parameter as descriptors to the models. The developed ELM based model using sine (Sine), sigmoid (Sig) and transig (Trang) activation functions were compared with the existing SVR-GA and SPR models in the literature using various performance metrics. The developed Sine-ELM model shows superior performance over Sig-ELM, Trang-ELM, SVR-GA (2021) and SPR (2021) models with performance improvement of 12.74%, 64.89%, 68.87% and 75.62% using mean squared error (MSE) metric for testing data samples. The superiority of the model developed was further justified through validation with external set of data. The precision and superiority of the ELM based models developed would eventually ease quick characterization and tuning of energy gap of ZnSe nanostructured semiconductors for various applications.

Structural Dynamics of Short Ligands on the Surface of ZnSe Semiconductor Nanocrystals.

ZnSe semiconductor nanocrystals (NCs) with a size comparable to their Bohr radius are synthesized, and the native capping agents with long hydrocarbon tails are replaced with short thiocyanate (SCN) ligands through a ligand exchange method. The structural dynamics of SCN ligands on the surface of ZnSe NCs in solution is investigated by ultrafast infrared spectroscopy. Vibrational population relaxation of SCN ligands is accelerated due to the specific interaction with the positively charged sites on the surface of NCs. The orientational anisotropy of the bound SCN ligands decayed at a rate much faster than that in the control solution containing Zn2+ cations. From the wobbling-in-the-cone model analysis, we found that the SCN ligand undergoes wobbling orientational diffusion with a relatively large cone semiangle on the surface of ZnSe NCs, and the overall orientational diffusion of bound SCN is found to be strongly dependent on the size of ZnSe NCs.

Investigate and Calculation Electron Transfer Rate Constant in the N749 Sensitized Dye Contact to ZnSe Semiconductor

The dye–semiconductor interface between N749 sensitized and zinc semiconductor (ZnSe) has been investigated and studied according to quantum transition theory with focusing on the electron transfer processes from the N749 sensitized (donor) to the ZnSe semiconductor (acceptor). The electron transfer rate constant and the orientation energy were studied and evaluated depended on the polarity of solvents according to refractive index and dielectric constant coefficient of solvents and ZnSe semiconductor. Attention focusing on the influence of orientation energies on the behavior of electron transfer rate constant. Differentdata of rate constant was discussion with orientation energy and effective driving energy for N749-ZnSe system. Furthermore, the electron transfer rate constant is increased with less orientation energy at less effective driving energy while the electron transfer rate constant increased with large orientation energy with large effective driving energy, as seen as the electron transfer rate reach to 1.3109 × 1011 with less orientation energy has 0.188708eV at effective driving energy E=0.22eV comparing the rate reach to 9.7207× 10−96 with driving energy E=1.89eV and same orientation energy. In general, the electron transfer rate constant increases with increases the coupling coefficient of system, its indicate that alignment of energy levels are very good between N749 sensitized metal and ZnSe semiconductor.

Correlating ZnSe Quantum Dot Absorption with Particle Size and Concentration.

The focus on heavy metal-free semiconductor nanocrystals has increased interest in ZnSe semiconductor quantum dots (QDs) over the past decade. Reliable and consistent incorporation of ZnSe cores into core/shell heterostructures or devices requires empirical fit equations correlating the lowest-energy electron transition (1S peak) to their size and molar extinction coefficients (ε). While these equations are known and heavily used for CdSe, CdTe, CdS, PbS, etc., they are not well established for ZnSe and are nonexistent for ZnSe QDs with diameters <3.5 nm. In this study, a series of ZnSe QDs with diameters ranging from 2 to 6 nm were characterized by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), UV-vis spectroscopy, and microwave plasma atomic emission spectroscopy (MP-AES). SAXS-based size analysis enabled the practical inclusion of small particles in the evaluation, and elemental analysis with MP-AES elucidates a nonstoichiometric Zn:Se ratio consistent with zinc-terminated spherical ZnSe QDs. Using these combined results, empirical fit equations correlating QD size with its lowest-energy electron transition (i.e., 1S peak position), Zn:Se ratio, and molar extinction coefficients for 1S peak, 1S integral, and high-energy wavelengths are reported. Finally, the equations are used to track the evolution of a ZnSe core reaction. These results will enable the consistent and reliable use of ZnSe core particles in complex heterostructures and devices.

Nondegenerate two-photon absorption in ZnSe: Experiment and theory

We experimentally and theoretically investigate the non-degenerate two-photon absorption coefficient $\beta(\omega_1,\omega_2)$ in the prototypical semiconductor ZnSe. In particular, we provide a comprehensive data set on the dependence of $\beta(\omega_1,\omega_2)$ on the non-degeneracy parameter $\omega_1/\omega_2$ with the total frequency sum $\omega_1+\omega_2$ kept constant. We find a substantial increase of the two-photon absorption strength with increasing $\omega_1/\omega_2$. In addition, different crystallographic orientations and polarization configurations are investigated. The nonlinear optical response is analyzed theoretically by evaluating the multiband semiconductor Bloch equations including inter- and intraband excitations in the length gauge. The band structure and the matrix elements are taken an eight-band k.p model. The simulation results are in very good agreement with the experiment.

Transfer mechanisms in semiconductor hybrids with colloidal core/shell quantum dots on ZnSe substrates

Hybrid systems consisting of colloidal CdS/ZnS core/shell quantum dots on ZnSe semiconductor substrates have been studied by continuous-wave and nanosecond time-resolved photoluminescence. On the basis of kinetic calculations, we studied the interplay between the possible transfer processes in these hybrids. The considered transfer mechanisms were resonance energy transfer, photon reabsorption, electron and hole tunneling. Depending on the size of the CdS cores the dominating transfer mechanism is changing. Carrier tunneling was found only for quantum dots in direct contact to the substrate. For large quantum dots a hole tunneling was found, whereas in case of small dots the fast electron tunneling is decisive. Eventually, we were able to determine the conduction band offset between CdS and ZnSe to 0.56 eV at 10 K.

Optical harmonic generation on the exciton-polariton in ZnSe

We study optical harmonic generation on the 1S exciton-polariton in the semiconductor ZnSe. Intense and spectrally narrow exciton resonances are found in optical second (SHG), third (THG), and fourth (FHG) harmonic generation spectra. The resonances are shifted to higher energy by 3.2 meV from the exciton energy in the linear reflectivity spectrum. Additional resonances are observed in the THG and FHG spectra and assigned to combinations of incident and backscattered photons in the crystal. Rotational anisotropy diagrams are measured and further information on the origin of the optical harmonic generation and the involved exciton states is obtained by a symmetry analysis using group theory in combination with a microscopic consideration.

Design and Characterization of a Sharp GaAs/Zn(Mn)Se Heterovalent Interface: A Sub-Nanometer Scale View.

The distribution of magnetic impurities (Mn) across a GaAs/Zn(Mn)Se heterovalent interface is investigated combining three experimental techniques: Cross-Section Scanning Tunnel Microscopy (X-STM), Atom Probe Tomography (APT), and Secondary Ions Mass Spectroscopy (SIMS). This unique combination allowed us to probe the Mn distribution with excellent sensitivity and sub-nanometer resolution. Our results show that the diffusion of Mn impurities in GaAs is strongly suppressed; conversely, Mn atoms are subject to a substantial redistribution in the ZnSe layer, which is affected by the growth conditions and the presence of an annealing step. These results show that it is possible to fabricate a sharp interface between a magnetic semiconductor (Zn(Mn)Se) and high quality GaAs, with low dopant concentration and good optical properties.

Phonons correction of the energy and photoionization cross section in polar semiconductors and hollow nanoparticles

Abstract

Twin-ZnSe nanowires as surface enhanced Raman scattering substrate with significant enhancement factor upon defect.

Semiconductor-based surface enhanced Raman scattering (SERS) substrate design has attracted much interest due to the excellent photoelectronic and biochemical properties. The structural change caused by twin in semiconductor will have an influence on improving the Raman signals enhancement based on the chemical mechanism (CM). Here, we demonstrated the twin in semiconductor ZnSe nanowires as an ultrasensitive CM-based SERS platform. The SERS signals of the rhodamine 6G (R6G) and crystal violet (CV) molecules adsorbed on twin-ZnSe nanowires could be easily detected even with an ultralow concentration of 10-11 M and 10-8 M, respectively, and the corresponding enhancement factor (EF) were up to 6.12 × 107 and 3.02 × 105, respectively. In addition, the charge transfer (CT) between the twin-ZnSe nanowires and R6G molecule has been demonstrated theoretically with first-principles calculations based on density-functional theory (DFT). These results demonstrated the proposed ZnSe nanowires with twin as SERS substrate has a broader application in the field of biochemical sensing.

Spin-related optical behaviors of dilute magnetic semiconductor ZnSe:Ni(II) nanobelts

There are varied spin states in dilute magnetic semiconductors, and carriers are not the only elementary excitations that carry the spin. This article reports a study of spin interactions in excitons of ZnSe:NiI(II) nanostructures. High-quality ZnSe:NiI(II) nanobelts (NBs) prepared by chemical vapor deposition show a zinc blende structure by x-ray diffraction and Raman spectroscopy. The temperature-dependent photoluminescence spectra of doped NBs show independent free exciton (FX) and exciton magnetic polaron (EMP) peaks at room temperature with ferromagnetically coupled Ni ions. A single-mode lasing profile was obtained with femtosecond laser excitation due to condensation of EMPs over a threshold. The luminescence lifetimes at different pump powers indicated different relaxation profiles, confirming the formation of coherent EMP aggregates. At a slightly higher dopant concentration, a weak peak at the high-energy side of the FX peak showed up separately at low temperature; this should be the magnetic polaron emission band from the antiferromagnetically coupled Ni(II) pair binding with a FX (antiferromagnetic magnetic polaron). These results illustrate the typical spectroscopic characteristics of spin–spin magnetic coupling, exciton–spin or phonon interactions in dilute magnetic semiconductor nanostructures, showing that their different coupled spin types could work as exciton binders for their collective excitons, with possible use in spin nanophotonic devices and quantum modulations.