Effect of Dimensionality on The Electronic Properties of SnSe: A Density Functional Theory Study

This study investigated the structural and electronic properties of bulk, bilayer, and monolayer SnSe using the density functional theory (DFT) method. We succeeded in calculating the bandgap and identifying accurately the transformation of the band structure from bulk to monolayer systems using generalized gradient approximation. An increase in the lattice parameter a and a decrease in the lattice parameter b were observed when the bulk dimensions were reduced to a monolayer. The reduction of van der Waals interactions when the dimensions of a system are reduced is the main factor that causes changes in lattice parameters. The indirect bandgap of bulk SnSe (0.56 eV, 0.3∆→0.7Σ) becomes wider in the monolayer system (0.94 eV, 0.2∆→0.8Σ). Bandgap widening is predicted due to the emergence of the quantum confinement effect in low-dimensional systems. Furthermore, we found the formation of a quasi-degenerate minimum conduction band in the monolayer SnSe. With the formation of these bands, we predict the monolayer SnSe will have better thermoelectric properties than the bulk or bilayer system. This study provides an in-depth understanding of the electronic structure of SnSe and its correlation to thermoelectric properties.

Nanocrystals of Metal Halide Perovskites and Their Analogues as Scintillators for X-ray detection

Scintillators are widely used for X-ray detection in various fields, such as medical diagnostics, industrial inspection and homeland security. Nanocrystals of metal halide perovskites and their analogues showed great advantages as X-ray scintillators due to their cheap manufacturing, fast decay time, and room temperature scintillation from quantum confinement effect. However, there are still many challenges unsolved for further industrialization. Herein, it is necessary to summarize the progress of scintillators based on nanocrystals of metal halide perovskites and their analogues. In first section, the scintillation mechanism and key parameters are outlined. Then, various nanocrystals of metal halide perovskites and their analogues used as scintillators are reviewed. Finally, the challenges and outlook are discussed. It is believed that nanocrystals of metal halide perovskites and their analogues are favorable for large-area and flexible X-ray detectors.

Recent Progress and Approaches on Transition Metal Chalcogenides for Hydrogen Production

Development of efficient and affordable photocatalysts is of great significance for energy production and environmental sustainability. Transition metal chalcogenides (TMCs) with particle sizes in the 1–100 nm have been used for various applications such as photocatalysis, photovoltaic, and energy storage due to their quantum confinement effect, optoelectronic behavior, and their stability. In particular, TMCs and their heterostructures have great potential as an emerging inexpensive and sustainable alternative to metal-based catalysts for hydrogen evolution. Herein, the methods used for the fabrication of TMCs, characterization techniques employed, and the different methods of solar hydrogen production by using different TMCs as photocatalyst are reviewed. This review provides a summary of TMC photocatalysts for hydrogen production.

Study on chemical synthesis of SnSSe nanosheets and nanocrystals

Two kinds of raw material combination for the hot injection method were investigated for the chemical synthesis of SnSSe nanosheets and nanocrystals, which are low-toxic optoelectronic materials. When SnSe quantum dots were synthesized by mainly using oleic acid as Se precursor solvent, the quantum dots changed from spherical to cubic as the size increased. The growth condition dependence of the nanocrystal formation process was discussed. When SnSSe nanocrystals were synthesized by mainly using trioctylphosphine as Se precursor solvent, it was found that the nanocrystal shape changed from dot to rod or sheet by reducing the proportion of S. The bandgap energy did not simply depend on the composition ratio of S but was affected by the change in the nanocrystal shape depending on the quantum confinement effect.

Nanocrystallized Ge-Rich SiGe-HfO2 Highly Photosensitive in Short-Wave Infrared

Group IV nanocrystals (NCs), in particular from the Si–Ge system, are of high interest for Si photonics applications. Ge-rich SiGe NCs embedded in nanocrystallized HfO2 were obtained by magnetron sputtering deposition followed by rapid thermal annealing at 600 °C for nanostructuring. The complex characterization of morphology and crystalline structure by X-ray diffraction, μ-Raman spectroscopy, and cross-section transmission electron microscopy evidenced the formation of Ge-rich SiGe NCs (3–7 nm diameter) in a matrix of nanocrystallized HfO2. For avoiding the fast diffusion of Ge, the layer containing SiGe NCs was cladded by very thin top and bottom pure HfO2 layers. Nanocrystallized HfO2 with tetragonal/orthorhombic structure was revealed beside the monoclinic phase in both buffer HfO2 and SiGe NCs–HfO2 layers. In the top part, the film is mainly crystallized in the monoclinic phase. High efficiency of the photocurrent was obtained in a broad spectral range of curves of 600–2000 nm at low temperatures. The high-quality SiGe NC/HfO2 matrix interface together with the strain induced in SiGe NCs by nanocrystallization of both HfO2 matrix and SiGe nanoparticles explain the unexpectedly extended photoelectric sensitivity in short-wave infrared up to about 2000 nm that is more than the sensitivity limit for Ge, in spite of the increase of bandgap by well-known quantum confinement effect in SiGe NCs.

Fast and Effective Catalytic Degradation of an Organic Dye by Eco-friendly Capped ZnS and Mn doped ZnS nanocrystals

Undoped and Mn-doped ZnS nanocrystals encapsulated with thioglycolic acid were synthetized and characterized with different techniques, and finally tested in the photodegradation of a methyl orange in aqueous solution under UV and sunlight irradiations. FTIR and X-ray diffraction results confirmed the functionalization of these nanocrystals surface by thioglycolic acid and the formation of crystalline structures of ZnS and Mn-doped ZnS with cubic and hexagonal phases. Calculated average size of ZnS nanocrystals was in the range of 2 - 3 nm. It was observed a blue shift of the absorbance threshold and the estimated bandgap energies were higher than that of Bulk ZnS thus confirming the quantum confinement effect of charge carriers. Photoluminescence spectra of ZnS nanocrystals exhibited emission in the range of 410- 490 nm and the appearance of an additional emission band around 580 nm (2.13eV) connected to the 4𝑇1→ 6𝐴1 transition of the Mn2+ions. Photodegradation of methylene orange with undoped and Mn-doped ZnS-TGA nanocrystals was investigated. Dye adsorption prior to photocatalysis using nanocrystals was studied via kinetic experiments and statistical physics models. The maximum dye adsorption capacity on doped ZnS-TGA was ~ 26.98 mg/g. The adsorption kinetic was found to follow the pseudo-second-order kinetic model.According to the statistical physics results, the calculated adsorption energy was 22.47-23.47 kJ/mol and it showed that the dye adsorption was associated to the hydrogen interaction where the removal process was feasible and multi-molecular. The photocatalytic activity of undoped ZnS nanoparticles under UV irradiation showed better efficiency than doped nanocrystals thus indicating that manganese doping generated a dropping of the photocatalytic degradation of the dye. Dye degradation efficiency of 81.37% using ZnS-TGA nanocrystals was achieved after 6 min, which indicated that ZnMnS-TGA nanocrystals may be considered as an alternative low cost and environmental friendly material for facing water pollution caused by organic compounds via photodegradation processes.

The Quantum Calculation for Valence Band Structure of Strained Zinc-blende GaN Using Six-Band Based k·p Method

The variations of valence band energy with stress effects in zinc-blende GaN are proposed in this paper. The calculations are based on a six-band strain dependent k·p Hamiltonian, and can be self-consistently solved by Schrödinger-Poisson equation. Accurate physical pictures are given for the quantized valence subband structure under biaxial and uniaxial stress in (001) surface along the [110] direction accounting the quantum confinement effect. The warping of the energy profile results in carrier distribution change. This research will be beneficial for improving the hole mobility and the selective of optimum stress for group-III nitride semiconductor based devices.

Electronic, Optical, and Thermoelectric Properties of Bulk and Monolayer Germanium Tellurides

Electronic, optical, and thermoelectric properties of germanium tellurides (GeTe) were investigated through a series of first-principles calculations of band structures, absorption coefficients, and thermoelectric transport coefficients. We consider bulk GeTe to consist of cubic and rhombohedral phases, while the two-dimensional (2D) GeTe monolayers can form as a 2D puckered or buckled honeycomb crystals. All of the GeTe variants in the bulk and monolayer shapes are excellent light absorbers in a wide frequency range: (1) bulk cubic GeTe in the near-infrared regime, (2) bulk rhombohedral GeTe and puckered monolayer GeTe in the visible-light regime, and (3) buckled monolayer GeTe in the ultraviolet regime. We also found specifically that the buckled monolayer GeTe exhibits remarkable thermoelectric performance compared to the other GeTe phases due to a combination of electronic band convergence, a moderately wide band gap, and unique 2D density of states from the quantum confinement effect.

Excellent Room-Temperature Thermoelectricity of 2D GeP3: Mexican-Hat-Shaped Band Dispersion and Ultralow Lattice Thermal Conductivity

Although some atomically thin 2D semiconductors have been found to possess good thermoelectric performance due to the quantum confinement effect, most of their behaviors occur at a higher temperature. Searching for promising thermoelectric materials at room temperature is meaningful and challenging. Inspired by the finding of moderate band gap and high carrier mobility in monolayer GeP3, we investigated the thermoelectric properties by using semi-classical Boltzmann transport theory and first-principles calculations. The results show that the room-temperature lattice thermal conductivity of monolayer GeP3 is only 0.43 Wm−1K−1 because of the low group velocity and the strong anharmonic phonon scattering resulting from the disordered phonon vibrations with out-of-plane and in-plane directions. Simultaneously, the Mexican-hat-shaped dispersion and the orbital degeneracy of the valence bands result in a large p-type power factor. Combining this superior power factor with the ultralow lattice thermal conductivity, a high p-type thermoelectric figure of merit of 3.33 is achieved with a moderate carrier concentration at 300 K. The present work highlights the potential applications of 2D GeP3 as an excellent room-temperature thermoelectric material.

Mesoporous TiO2 Implanted ZnO QDs for the Photodegradation of Tetracycline: Material Design, Structural Characterization and Photodegradation Mechanism

A sol-gel method was used to prepare a mesoporous TiO2 implanted with a ZnO quantum dot photocatalyst (TZQ) for the photodegradation of tetracycline (TC) under fluorescent light irradiation. Scanning electron microscopy (SEM) shows the presence of cavities on the photocatalyst surface due to the use of starch as a synthetic template, where the nitrogen sorption results indicate that TZQ contains mesopores with reduced size (ca. 4.3 nm) versus the pore size of the parent meso-TiO2 (ca. 7.5 nm). The addition of ZnO quantum dots (QDs) resulted in spherically-shaped binary composite particles in layers onto the surface of TiO2. The coexistence of the ZnO QDs and TiO2 phase was observed using high resolution-transmission electron microscopy (HR-TEM). The photodegradation of TC was carried out in a homemade reactor equipped with two fluorescent lights (24 W each) and within 90 min of irradiation, 94.6% of TC (40 mg L−1) was photodegraded using 250 mg L−1 of TZQ at pH 9. The major reactive oxygen species identified from the scavenging tests were O2●− followed by HO●. The deconvolution of the photoluminescence spectrum of TZQ indicates the presence of a strong quantum confinement effect (QCE) of the ZnO QDs, a defect related to Ti-species and oxygen. The analysis of the intermediates detected by LC-time-of-flight/mass spectrometry (LC/TOF-MS) suggest two photodegradation pathways. The pathways were validated using the Fukui function approach and the Wheland localisation approach. This simple and efficient photocatalytic technology is anticipated to benefit small-scale animal husbandries and aquaculture operators that have limited access to sustainable water treatment technology.