ZnSe Nanocrystals Research Articles

Advanced plasmonic few-layered InSe nanosheet heterojunctions for enhanced photoelectrochemical water splitting

The selenide-based Van der Waals heterojunctions show great potential for the next generation of photoelectronic nanodevices. Herein, we construct a 2D photoanode nanocatalyst that consists of ZnSe nanocrystals with exposed active surfaces coupled with few-layered InSe nanosheets decorated by Au nanoparticles. The resultant ZnSe/AuNPs@InSe multi-heterojunction photoanode demonstrates an outstanding photocurrent density of 4.86 mAcm−2 under AM 1.5 G simulated sunlight (100 mWcm−2), which is 8 times greater than that of the pristine InSe photoanode (0.61 mAcm−2). Moreover, the lifetime of photogenerated charge carriers is extended by a factor of 3. This significant enhancement in photoelectrochemical water splitting in the near-infrared region is attributed to the surface plasmonic effect produced by the modification of Au NPs when bulk InSe is exfoliated into multi-layered flakes. The interfacial coupling effects on carrier transfer dynamics, as revealed by impedance spectroscopy assisted with the First-Principal calculations, show that this photoanode significantly minimizes the internal resistance, boosts the charge carrier separation efficiency, and promotes water oxidation.

Ultrabroadband mid-infrared emission and gas sensing of cobalt-doped chalcogenide glass ceramics.

Mid-infrared (MIR) gain materials are of great significance for the development of MIR tunable fiber lasers. Herein, for the first time, to the best of our knowledge, it is found that Ga2Se3 nanocrystals distributed in chalcogenide glass ceramics can provide new tetrahedral-coordinated sites that can be used to activate ultrabroadband MIR emissions of divalent transition metal ions, such as Co2+. Under the excitation of a 1550 nm diode laser, the transparent Ge-Ga-Se glass ceramic embedded with Co2+: Ga2Se3 nanocrystals shows an intense 2.5-5.5 µm ultrabroadband emission. The peak wavelength is located at ∼4.2 µm and the full width at half maximum exceeds 2 µm. Such emission properties, originating from the dual lattice sites of Ga3+ ions, are superior to those of transparent chalcogenide glass ceramics embedded with Co2+: ZnSe nanocrystals. Moreover, the gas detection system built based on the glass ceramic shows a sensitivity of 45.9 ppm for butane gas. Therefore, the chalcogenide glass ceramics embedded with active Co2+: Ga2Se3 nanocrystals have great potential in MIR tunable fiber lasers and gas sensing.

Annealing Effect on Structural, Optical and Electrophysical Properties of ZnSe Nanocrystals Synthesized into SiO2/Si Ion Track Template.

We report the results of synthesis of zinc selenide (ZnSe) nanocrystals into SiO2/Si track templates formed by irradiation with 200 MeV Xe ions up to a fluence of 107 ions/cm2. Zinc selenide nanocrystals were obtained by chemical deposition from the alkaline aqueous solution. Scanning electron microscopy, X-ray diffractometry, Raman and photoluminescence spectroscopy, and electrical measurements were used for characterization of synthesized ZnSe/SiO2nanoporous/Si nanocomposites. XRD data for as-deposited precipitates revealed the formation of ZnSe nanocrystals with cubic crystal structure, spatial syngony F-43m (216). According to non-empirical calculations using GGA-PBE and HSE06 functionals, ZnSe crystal is a direct-zone crystal with a minimum bandgap width of 2.36 eV and anisotropic electronic distribution. It was found that a thermal treatment of synthesized nanocomposites at 800 °C results in an increase in ZnSe nanocrystallites size as well as an increase in emission intensity of created precipitates in a broad UV-VIS spectra range. However, vacuum conditions of annealing still do not completely prevent the oxidation of zinc selenide, and a formation of hexagonal ZnO phase is registered in the annealed samples. The current-voltage characteristics of the synthesized nanocomposites proved to have n-type conductivity, as well as increased conductivity after annealing.

Comparison of the photocatalytic performance of ZnSe nanocrystals with different crystallite sizes

ZnSe nanocrystals were prepared by a hydrothermal method and their photocatalytic properties were investigated as a function of the ZnSe nanocrystal size. At the beginning of the photocatalytic reaction, the smaller-sized ZnSe nanocrystals demonstrated better H2O2 production performance (12.84 mmol g-1h−1) than the larger-sized ones (12.29 mmol g-1h−1). In the long run, the smaller-sized ZnSe nanocrystals suffered from severe photocorrosion and showed inferior H2O2 production ability.

Effect of Zn2+ ion concentration on the optoelectronic properties of chemically synthesized ZnSe nanorods

In this work, polyvinyl pyrrolidone (PVP) capped zinc selenide (ZnSe) nanorods were synthesized with varying molar concentrations of Zn precursor through chemical reaction. X-ray Diffraction (XRD) revealed the cubic polycrystalline nature of synthesized ZnSe nanostructures. Structural morphology indicated the formation of nanorods along with spherical nanoparticles with sizes ranging from 8 nm to 40 nm. The absorption spectra demonstrated a notable blue shift signifying the reduction in bandgap with the increased Zn2+ ion concentration while the refractive index showed a proportional rise. The photoluminescence (PL) spectra revealed the near bandgap emission at 416 nm along with other defect-related emissions. The conduction mechanism, assessed through I–V characteristics, suggested Richardson-Schottky or electrode limitation in the high bias region within the ZnSe nanocrystals. These findings could potentially facilitate the customization of ZnSe nanorods for optoelectronics device application.

Investigation of the processing effect parameters on the spectroscopic properties of ZnSe nanocrys-tals for hot-pressed ceramics of the Cleartran and Multispectral classes

Problem. The problem is unavailability of inexpensive ZnSe nanocrystals for hot-pressed ceramics of the Cleartran or Multispectral classes. Goal. The goal is to investigate and improve the structural features of ZnSe nanocrystals obtained by combustion synthesis during annealing in air or nitrogen. Methodology. ZnSe nanocrystals were characterized by combustion synthesis using electron scanning microscopy, X-ray diffraction analysis, electron paramagnetic resonance, and photoluminescence analysis. Results. To improve the spectroscopic properties of ZnSe nanocrystals were synthesized by combustion synthesis method (self-propagating high-temperature synthesis) with different initial current pulses, a series of thermal annealing was carried out in the temperature range Т = 200 ÷ 800 °С with a step of Т = 100 °С at atmospheric pressure, in air or in nitrogen. The developed approach makes it possible to obtain the investigated ZnSe nanocrystals with specified properties by controlling their crystal structure. The dependences of the structure, characteristics of the magnetic field, and hyperfine structure of electron paramagnetic resonance, photoluminescence spectra during annealing in air or nitrogen from temperatures of annealing were obtained. In comparison with the initial charge, the size of nanocrystals grows by ~ 20 %, the fraction of the cubic phase increases, the parameters of nanocrystals lattice grows, and the number of dislocations and microstress decrease after annealing. It is recommended to use a current pulse of ~ 40 A, and then perform annealing at a temperature of T = 800 °C in nitrogen for the synthesis of ZnSe nanocrystals with a more perfect structure. Originality. The annealing of ZnSe nanocrystals obtained by combustion synthesis in air or nitrogen was studied. Practical value. The obtained results allow using the synthesized ZnSe nanocrystals by combustion synthesis method for various optoelectronic devices or for obtaining hot-pressed ceramics of the Cleartran or Multispectral classes.

ZnCo-ZIF-based nanoarchitectonics of honeycomblike N-doped carbon for oxygen reduction reaction and supercapacitor

Nitrogen-doped carbon (NC) materials combined with transition metal nanocrystals are potential multifunctional materials for energy conversion and storage. Herein, zinc and cobalt doped zeolite imidazole frameworks (ZnCo-ZIF) were used as precursors for the synthesis of honeycomb-like NC. Due to the NaCl-assisted pyrolysis and selenylation, as-prepared honeycomb-like NC was well-distributed with ZnSe and Co nanocrystals. This unique morphology with abundant porous channels and wrinkles not only improves the dispersion and exposure of ZnSe and Co composites, but also facilitates mass and electron transfer. For oxygen reduction reaction, it exhibited a 0.976 V onset potential and a 0.923 V half-wave potential; and for supercapacitors, its specific capacitance was 915.9 F·g−1 at 1 A·g−1 in 2 M KOH. Thus, NaCl-assisted pyrolysis and selenylation can provide a feasible strategy for preparing high performance multifunctional materials.

Crystal structure and photoluminescence of ZnSe and ZnSe:Mn nanocrystals obtained by combustion synthesis

ZnSe and ZnSe:Mn nanocrystals were obtained by combustion synthesis (self-propagating high-temperature synthesis) using current pulses to initiate a reaction with amplitudes of ∼35 A and ∼40 A. The magnitude of the amplitude of the current pulse affects the size of the nanocrystals, their phase composition, the ratio of the cubic and hexagonal phases, the degree of microstresses and the density of dislocations. The inclusion of Mn dopants into ZnSe has little effect on the nanocrystal morphology and strongly influences the morphology of polycrystals. An EPR spectrum of Mn2+ ions with a hyperfine structure constant A = 6.55 mТ and a g-factor g = 2.0055, which is due to Mn2+ ions in a cubic environment, was found in self-activated and doped ZnSe and ZnSe: Mn nanocrystals. It was found that increasing the amplitude of the current pulse, which initiates the combustion synthesis reaction, increases the intensity of the diffusion processes and more effective isovalent substitution of Zn2+ ions by Mn2+ ions in the crystal lattice of ZnSe nanocrystals. The photoluminescence spectra of ZnSe and ZnSe:Mn nanocrystals were investigated, and individual emission bands were detected in the integral spectra. There were three such individual bands in the photoluminescence spectrum of ZnSe nanocrystals. Their maxima were characterized using the following parameters: λ max = 592 nm (E = 2.095 eV), λ max = 543 nm (E = 2.282 eV), and λ max = 505 nm (E = 2.455 eV). Six individual emission bands were detected in the photoluminescence spectra of ZnSe:Mn nanocrystals with the parameters: λ max = 675. 5 nm (E = 1.835 eV), λ max = 642.5 nm (E = 1.929 eV), λ max = 613 nm (E = 2.022 eV), λ max = 583.5 nm (E = 2.124 eV), λ max = 550 nm (E = 2.255 eV), λ max = 528.5 nm (E = 2.345 eV). This paper discusses the nature of the centers of radiative recombination of individual bands.

A reactivity-controlled epitaxial growth strategy for synthesizing large nanocrystals

Large ZnSe nanocrystals are expected to be promising blue-light emitters with an emission peak of 455–475 nm, which is important for the construction of display apparatus. The final size of ZnSe nanocrystals via one-step injection can be varied by the reactivity of the Zn and Se precursors; however, it has a limit of <5 nm. To describe the key factors in determining the final size of ZnSe nanocrystals, we proposed a nuclei number-considered LaMer model based on the Maxwell–Boltzmann distribution of crystal embryos. As a result, a general strategy of reactivity-controlled epitaxial growth was developed to synthesize large ZnSe nanocrystals through sequential injection of high-reactivity and low-reactivity Zn and Se precursors. The resultant ZnSe nanocrystals achieved pure blue emission between 455 and 470 nm. We further fabricated stable, large ZnSe/ZnS core–shell nanocrystals with photoluminescence quantum yields up to approximately 60%. Moreover, the reactivity-controlled epitaxial growth strategy is versatile and could be used to synthesize large ZnSe, CdSe and PbSe nanocrystals with average sizes up to 35 nm, 76 nm and 87 nm, respectively. The control of quantum-confined and classical effects in these large semiconductor nanocrystals will open up new directions for fundamental research and application exploration. Synthesizing Se-based nanocrystals with large diameters remains challenging. Here, a reactivity-controlled epitaxial growth strategy was demonstrated to synthesize nanocrystals of ZnSe, CdSe and PbSe with average diameters of 35 nm, 76 nm and 87 nm, respectively. The large ZnSe nanocrystals emitted pure blue light, which is important for display technology.

Controlled synthesis of monodispersed ZnSe microspheres for enhanced photo-catalytic application and its corroboration using density functional theory.

The present work reports enhanced photocatalytic performance of highly crystalline, monodisperse ZnSe microspheres, synthesized by the size-selective, ETDA-assisted hydrothermal method. Systematic studies on time-dependent reaction kinetics and growth parameters indicate dependency of morphology and crystal structure on the volume % of EDTA and dependency of size on the volume % of hydrazine hydrate for ZnSe microspheres. X-ray diffraction studies confirm highly crystalline cubic zinc blende crystal structure with crystallite size in the range of 10-15 nm. Diffuse reflectance spectra show blue shift having a broad absorption peak between 415 and 425 nm, with a band gap of ∼2.6 eV from the K-M plot. Photoluminescence spectra show higher ratio of near band edge emission to deep level emission, confirming the decrease in defect related emission and depicting the higher crystallinity of ZnSe. Raman spectroscopy also confirms the crystalline and pure nature of ZnSe microspheres, from the observation of a high intensity dominant peak at 248 cm-1, attributed to longitudinal optical phonon scattering. Morphological analysis using FE-SEM and HRTEM shows monodispersed microspheres having size ∼2.5 μm, made up of small ZnSe nanocrystals with ∼10 nm size and with an interplanar spacing of ∼0.32 nm, corresponding to zinc blende ZnSe(111) planes. Brunauer-Emmett-Teller analysis indicates type-IV adsorption-isotherms and hysteresis loops, confirming the presence of mesopores on the surface of ZnSe microspheres controlling the diffusion rate of the catalyst. The degradation rate constant for methylene-blue using first-order reaction kinetics confirms improvement in photocatalytic activity by a factor of 7 to 13 times higher than that of bulk ZnSe, which is attributed to the controlled, well-defined morphology of spherical microstructures made up of small-sized ZnSe nanocrystals. Density functional theory based calculations support the preferential adsorption of EDTA at the Se site of the ZnSe(111) surface with an energy of -1.90 eV. The electronic-structure plot demonstrates semiconducting behaviour with a direct band gap of ∼1.51 eV. First-principles calculations confirm enhancement in the photocatalytic water splitting activity of the ZnSe(111) surface via adsorption of intermediates. The improvement in dye degradation can be attributed to the enhanced oxidation process through the formation of intermediates such as O* (-3.13 eV) and HO* (-2.57 eV) at the Se site of the ZnSe surface.

Size-controlled growth of ZnSe nanocrystals for high-performance photocatalytic H2O2 production in pure water.

Semiconductor photocatalysis is deemed as a novel and promising process that can produce H2O2 from earth-abundant water and gaseous dioxygen using sunlight as the energy supply. The searching of novel catalysts for photocatalytic H2O2 production has received increasing attention in the last few years. Herein, size-controlled growth of ZnSe nanocrystals was realized via a solvothermal method by varying the amount of Se and KBH4. The performance of the as-obtained ZnSe nanocrystals towards photocatalytic H2O2 production depends on the mean size of the synthesized nanocrystals. Under O2-bubbling, the optimal ZnSe sample presented an excellent H2O2 production efficiency (8.596 mmol g-1 h-1), and the apparent quantum efficiency for H2O2 production reaches as high as 2.84% at λ = 420 nm. Under air-bubbling, the accumulation of H2O2 was as high as 1.758 mmol L-1 after 3 h irradiation at the ZnSe dosage of 0.4 g L-1. The photocatalytic H2O2 production performance is far superior to the most investigated semiconductors such as TiO2, g-C3N4, and ZnS.

Chelation of Zn Cations as a Method for Their Replacement by Mn, Fe, Co in ZnSe Nanocrystals

This article describes a new technique for postsynthetic doping/alloying of Mn into ZnSe nanocrystals. The key feature is that it employs diethyldithiocarbamate anion to selectively bind the host cations and promote ion exchange. The presence of Mn in the product is confirmed with photoluminescence (PL) and total reflection X‐ray fluorescence spectroscopy. The cation exchange reaction takes place at temperatures as low as 100 °C. Higher temperatures allow to incorporate the impurity in greater quantities; however, after a crossover temperature of ≈200 °C, the process gets convoluted with Ostwald ripening and sulfide deposition, as evident from electron diffraction data, high‐resolution transmission electron microscopy (HR‐TEM), and elemental analysis of the samples. Studies of PL lifetime and quantum yield confirm these findings. Preliminary success is also shown for other impurities: Fe and Co are present in the respective samples in ≈17 at% of total metal content.

Joint Studies of Spin Frustration Induced by Doping Small ZnSe Nanoparticles with Fe Atoms

AbstractAs a 1.8 nm ZnSe nanocrystal is progressively doped with 1%, 5%, and 10% Fe, it shows a progressive change in its magnetic properties from a superparamagnetic FM‐dominated exchange type to an onset of AFM exchange with evidence of spin frustration. Magnetization measurements allow to obtain exchange coupling constants that are compared to the results of a Broken‐Symmetry Density Functional Theory (BS‐DFT) model of a doped (ZnSe)34 cluster. DFT shows a capability to reproduce the experimental pattern of the increasing influence of AFM exchange as doping concentration increases. The material phase segregates at the edges where strained rhombic surface sites are the preferred doping sites of iron. Large concentrations of iron leads to the formation of Fe clusters and complex exchange patterns that result in spin frustration in some iron trimers but none in the others. The spin frustration of these complex systems by assuming mirror symmetry of the sites when fitting by using BS‐DFT formalism is classified and analyzed. While some individual J constants obtained have significant errors, the averaged exchange constants are generally in good agreement with our experimental data.

ZnSe and CdS Co-Sensitized TiO2 Nanorod Arrays as Photoanodes for Bias-Free Solar Hydrogen Evolution.

The efficient charge separation and surface state reactions are significant in enhancing the efficiency of photoelectrochemical hydrogen evolution. Herein, we report a ternary heterostructure consisting of CdS/ZnSe sensitized TiO2 nanorod as a photoanode. The heterojunction photoanode considerably widens the photon absorption spectral range and thereby enhances the photocurrent density up to 2 mA/cm2 at 1.23 V versus RHE which is 10 times higher than pristine TiO2 photoanode. The photoelectrochemical results demonstrate a high photocurrent density of 2 mA/cm2 with a photon-to-current conversion efficiency of 1.5 % at a very low applied bias (0.2 V vs RHE). The improved PEC performances of the multidimensional hybrid photoanode could be ascribed to the efficient visible-light absorption of ZnSe and CdS nanocrystals decorated on the surface of 1D TiO2 . The rapid electron-transfer properties owing to higher carrier density, low carrier transport resistance, and an extended lifetime of photoexcited carriers in the multidimensional ZnSe/CdS/TiO2 heterostructure with suppressed surface charge recombination are responsible for enhanced hydrogen evolution activities.

Ligand-Free Direct Optical Lithography of Bare Colloidal Nanocrystals via Photo-Oxidation of Surface Ions with Porosity Control.

Microscale patterning of colloidal nanocrystal (NC) films is important for their integration in devices. Here, we introduce the direct optical patterning of all-inorganic NCs without the use of additional photosensitive ligands or additives. We determined that photoexposure of ligand-stripped, "bare" NCs in air significantly reduces their solubility in polar solvents due to photo-oxidation of surface ions. Doses as low as 20 mJ/cm2 could be used; the only obvious criterion for material selection is that the NCs need to have significant absorption at the irradiation wavelength. However, transparent NCs can still be patterned by mixing them with suitably absorbing NCs. This approach enabled the patterning of bare ZnSe, CdSe, ZnS, InP, CeO2, CdSe/CdS, and CdSe/ZnS NCs as well as mixtures of ZrO2 or HfO2 NCs with ZnSe NCs. Optical, X-ray photoelectron, and infrared spectroscopies show that solubility loss results from desorption of bound solvent due to photo-oxidation of surface ions. We also demonstrate two approaches, compatible with our patterning method, for modulating the porosity and refractive index of NC films. Block copolymer templating decreases the film density, and thus the refractive index, by introducing mesoporosity. Alternatively, hot isostatic pressing increases the packing density and refractive index of NC layers. For example, the packing fraction of a ZnS NC film can be increased from 0.51 to 0.87 upon hot isostatic pressing at 450 °C and 15 000 psi. Our findings demonstrate that direct lithography by photo-oxidation of bare NC surfaces is an accessible patterning method for facilitating the exploration of more complex NC device architectures while eliminating the influence of bulky or insulating surfactants.

The luminescence characteristics of Zn1-xHoxSe QDs synthesized via a polyol-assisted microwave technique for light emitting device applications

Highly luminescent Zn1-xHoxSe (0 ≤ x ≤ 0.05) QDs were prepared using the polyol-assisted microwave approach for light-emitting device applications. The influence of the holmium atoms (Ho) on the structure and morphology of the ZnSe nanocrystals was emphasized using X-ray diffraction (XRD) and transmission electron microscope (TEM) measurements. The inclusion of the Ho-atoms in the ZnSe nanocrystals increases the particle size while preserving the cubic phase of the ZnSe nanocrystals. The inclusion of the Ho-atoms in the Zn-sites of the ZnSe nanocrystals decreases the optical bandgap. The photoluminescence measurements revealed that the introduction of the Ho-atoms in the Zn-sites of the ZnSe nanocrystals results in a redshift of the emission peaks and the increase of the luminescence intensity. Furthermore, the bandwidth of the emitted light is decreased due to the incorporation of the Ho-atoms in the ZnSe nanocrystals. The increase of the Ho-atoms concentration led to a decrease of the Stokes shift and an increase of the quantum yield reached 81%. Therefore, the developed synthetic recipe and the partial replacement of the Zn-atoms by Ho-atoms in the ZnSe crystal structure may open a new door to use the Zn1-xHoxSe QDs for LEDs application.

Tailoring Structural and Optical Properties of Cu Doped Chemically Deposited ZnSe Nanostructured Thin Films

Chemical bath deposition has been used for depositing undoped and copper doped ZnSe thin films at 343 K temperature. Growth of the thin film requires zinc sulphate cation and sodium selenosulphate anion. The preparative parameters are optimized with an aim to obtain high quality thin films. Three different concentrations of Cu source are used. XRD pattern indicates the incorporation of copper in to polycrystalline cubic ZnSe in doped thin films and is confirmed by EDAX spectrum. SEM micrographs indicate that ZnSe dispersion in the films is homogeneous. UV–visible transmission spectra of the thin films have put into evidence that the dispersion of ZnSe nanocrystals in the thin film is improved their optical transmission. Room temperature PL spectra have shown that the addition of Cu into ZnSe enhanced the emission with additional green peak other than blue band edge emission. Electrical conductivity also modified on addition of Copper.

One-dimensional ZnSe@N-doped carbon nanofibers with simple electrospinning route for superior Na/K-ion storage

One-dimensional carbon nanofibers are widely applied as anode material in the energy storage field due to its unique structure and high conductivity. In this work, one-dimensional ZnSe@N-doped carbon nanofibers (ZnSe@NC NFs) are successfully synthesized by electrospinning and annealed without extra troublesome conditions. ZnSe nanocrystals are enfolded in the N-doped carbon nanofibers, which can act as a protective layer to avoid the volume expansion of active material and promote ion transport during the cycling process. More importantly, the as-synthesized ZnSe@NC NFs are served as the anode material and display the admirable storage properties for Na/K-ion batteries. The one-dimensional ZnSe@NC NFs material shows the high capacity of 237 mAh/g for Na-ion batteries at a current density of 1 A/g for 2000 cycles. Meanwhile, it also delivers a high discharge capacity of 337 mAh/g for K-ion batteries at 0.2 A/g for 300 cycles. Additionally, it is confirmed that the pseudocapacitive contribution of the nano-structure material is up to 54.5% at a scan rate of 0.6 mV/s through the cyclic voltammetry (CV) measurement in K-ion batteries.

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.

Synthesis and Photoinduced Electron Transfer Studies of Ligand Exchanged Mn-Doped ZnSe Nanocrystals in Water

Synthesis and Photoinduced Electron Transfer Studies of Ligand Exchanged Mn-Doped ZnSe Nanocrystals in Water