Structure, bonding and electronic characteristics of amorphous Se.

Ovonic threshold switching (OTS) selectors can effectively improve the storage density and suppress the leakage current of advanced phase-change memory devices. As a prototypical OTS material, amorphous GeSe is widely investigated. But the attention paid to amorphous Se (i.e., the functional constituent in amorphous GeSe) has been very limited up to now. Here we have explored the structure, bonding and electronic characteristics of amorphous Se using ab initio molecular dynamics simulations. The results reveal that the Se atoms in amorphous Se tend to form 2-coordinated configurations, and they connect with each other to form long chains. The fraction of the vibrational density of state located in the high frequency range is relatively large, and the formation energy of the Se-Se bond is as large as 4.44 eV, hinting that the Se-Se bonds in chains possess high stability. In addition, the mid-gap state related to the OTS behavior is also found in amorphous Se despite the small proportion. Our findings enrich the knowledge of amorphous Se, which aids the applications of Se-based OTS selectors.

Structural, mechanical, electronic and optical properties of biphenylene hydrogenation: a first-principles study.

Biphenylene networks typically exhibit a metallic electronic nature, while hydrogenation can open the band gap changing it to a semiconductor. This property makes hydrogenated biphenylene a promising candidate for use in semiconductor optoelectronic materials and devices. In this work, three representative configurations of hydrogenated biphenylene, denoted by α, ß and γ, were investigated. The structural, mechanical, electronic, and optical properties of these hydrogenated biphenylene configurations were calculated by first-principles calculations. Band gaps with HSE correction were 4.69, 4.42 and 4.39 eV for α, ß, and γ configurations, respectively. Among these three configurations, ß presents the best electronic performance and special elastic properties (negative Poisson's ratio), while γ exhibits the best elastic properties. In addition, we comprehensively analyze the mechanical properties of these configurations and provide evidence that hydrogenated biphenylene possibly exhibits a negative-Poisson's-ratio along the zigzag and armchair directions when hydrogen atoms are added to biphenylene in certain ways. Furthermore, although the electronic properties of γ are weaker than those of ß, they are also excellent. In addition, the binding energies of ß and γ are relatively lower, which indicates that ß and γ are more stable. Our findings demonstrate that the hydrogenated biphenylene is a promising material with significant application potential in optoelectronic devices.

A new direct band gap Si-Ge allotrope with advanced electronic and optical properties.

Direct-band silicon materials have been a sought-after material for potential applications in silicon photonics and solar cells. Accordingly, methodologies like nanostructure engineering, alloy engineering and strain engineering have been developed. In this work, the particle swarm optimization (PSO) algorithm is used to design direct-band Si-Ge alloys. The findings of phonon computations demonstrate that all these structures are dynamically stable. In addition, ab initio molecular dynamics and elastic constant calculations are carried out, with results indicating these structures are thermodynamically stable at 300 K, as well as being mechanically stable. All of these materials exhibit semiconductor behavior with band gaps of 1.03, 0.68 and 1.37 eV for α, ß and γ phases, respectively, at the HSE06 level. The results of effective mass and mobility of carriers that are important in applications show that holes are more easily transported in all structures, with higher concentration of holes accompanied by lower carrier mobility. Different concentrations of holes nh lead to different limits in the scattering process. When nh is lower than the value of around 1016 cm-3, deformation potential scattering is dominant, while the ionized impurity scattering process limits overall mobility when nh is higher than such a value. Finally, the absorption spectra shows that both α and ß phases have isotropic optical properties in the X- and Y-directions while strong anisotropy can be seen in the Z-direction. However, the γ phase exhibits no notable isotropy. This investigation finds three direct-band and potentially CMOS compatible materials, a finding which will benefit the development of high efficiency emitters or solar cells.

High brightness silicon nanocrystal white light-emitting diode with luminance of 2060 cd/m2.

High brightness Si nanocrystal white light-emitting diodes (WLED) based on differentially passivated silicon nanocrystals (SiNCs) are reported. The active layer was made by mixing freestanding SiNCs with hydrogen silsesquioxane, followed by annealing at moderately high temperatures, which finally led to a continuous spectral light emission covering red, green and blue regimes. The photoluminescence quantum yield (PLQY) of the active layer was 11.4%. The SiNC WLED was composed of a front electrode, electron transfer layer, front charge confinement layer, highly luminescent active layer, rear charge confinement layer, hole transfer layer, textured p-type Si substrate and aluminum rear electrode from top to bottom. The peak luminance of the SiNC WLED achieved was 2060 cd/m2. The turn-on voltage was 3.7 V. The chromaticity of the SiNC WLED indicated white light emission that could be adjusted by changing the annealing temperature of the active layer with color temperatures ranging from 3686 to 5291 K.

Electronic and optical properties of hydrogen-terminated biphenylene nanoribbons: a first-principles study.

The electronic structures and optical properties of novel 2D biphenylene and hydrogen-terminated nanoribbons of different widths which are cut from a layer of biphenylene were explored via first-principles calculations. The findings of phonon computations demonstrate that such a biphenylene is dynamically stable and shows metallic properties. The crystal orbital Hamilton population analysis indicates that the tetra-ring local structure results in anisotropic mechanical properties. For 1D nanoribbons, their band gaps shrink, and a direct-indirect transition occurs in the band gap as the width increases, transforming the nanoribbon to endow them with metallic characteristics at a certain width. This is attributed to the weak coupling between the tetra-ring atoms, shrinking the direct band gap at the Y point in the Brillouin zone. Finally, the contribution of interband transitions to the dielectric function in 6-, 9-, and 12-armchair biphenylene nanoribbons (ABNRs) was identified. The lowest peak in the imaginary part of the dielectric function ε2 spectrum was mainly a contribution of a Γ-Γ transition. As the width of ABNR increases, the transitions in the x direction become stronger while the transition strength in the y direction is not significantly altered. This investigation extends the understanding of the electronic and optical properties of 2D biphenylene and 1D nanoribbons, which will benefit the practical applications of these materials in optoelectronics and electronics.

High-accuracy and rapid azimuth calibration for polarizing elements in ellipsometry by differential spectral analysis on the ellipse azimuth.

We propose an accurate and rapid azimuth calibration method for polarizing elements in ellipsometry. Over 200 calibrations were achieved simultaneously at different wavelength points in a spectral range of 550-650 nm without any calibrated element. The azimuth of the polarizer was determined from the differential spectral analysis on the ellipse azimuth of reflected light. The information of the ellipse azimuth is experimentally acquired in the spectral range by a rotating polarizing element and a spectrometer. The presented method was performed and verified with Si and Au bulk, respectively, showing reliability and feasibility for efficient and reliable calibration in ellipsometry.

Nitrogen Doped γ-Graphyne: A Novel Anode for High-Capacity Rechargeable Alkali-Ion Batteries.

High energy density is the major demand for next-generation rechargeable batteries, while the intrinsic low alkali metal adsorption of traditional carbon-based electrode remains the main challenge. Here, the mechanochemical route is proposed to prepare nitrogen doped γ-graphyne (NGY) and its high capacity is demonstrated in lithium (LIBs)/sodium (SIBs) ion batteries. The sample delivers large reversible Li (1037 mAh g-1 ) and Na (570.4 mAh g-1 ) storage capacities at 100 mA g-1 and presents excellent rate capabilities (526 mAh g-1 for LIBs and 180.2 mAh g-1 for SIBs) at 5 A g-1 . The superior Li/Na storage mechanisms of NGY are revealed by its 2D morphology evolution, quantitative kinetics, and theoretical calculations. The effects on the diffusion barriers (Eb ) and adsorption energies (Ead ) of Li/Na atoms in NGY are also studied and imine-N is demonstrated to be the ideal doping format to enhance the Li/Na storage performance. Besides, the Li/Na adsorption routes in NGY are optimized according to the experimental and the first-principles calculation results. This work provides a facile way to fabricate high capacity electrodes in LIBs/SIBs, which is also instructive for the design of other heteroatomic doped electrodes.

Origin of short- and medium-range order in supercooled liquid Ge3Sb2Te6 using ab initio molecular dynamics simulations.

Phase-change materials such as Ge-Sb-Te compounds have attracted much attention due to their potential value in electrical data storage. In contrast to the amorphous and crystalline phases, supercooled liquids are far from being deeply understood despite their inevitable role in both amorphization and crystallization processes. To this end, we have studied the dynamics properties and structural characteristics of liquid and supercooled liquid Ge3Sb2Te6 during the fast cooling process. As the temperature decreases, chemical bonds become more homogeneous, but coordination numbers of Ge, Sb and Te atoms change very little. Meanwhile, the structural order of short-range configuration is obviously enhanced. Further studies suggest that Ge-centered, Sb-centered and Te-centered configurations change to the more ordered defective octahedrons mainly by adjusting the bond-angle relationship and bond length, rather than just by changing the coordination environment. It is the more ordered octahedrons that promote the formation of medium-range order. Our findings provide a deep insight into the origin of local structural order in supercooled liquid Ge3Sb2Te6, which is of great importance for the comprehensive understanding of amorphization and crystallization processes.

Optical properties of thickness-controlled PtSe2 thin films studied via spectroscopic ellipsometry.

Platinum diselenide (PtSe2) has attracted huge attention due to its intriguing physical properties for both fundamental research and promising applications in electronics and optoelectronics. Here, we explored the optical properties of chemical vapor deposition-grown PtSe2 thin films with varied thicknesses via spectroscopic ellipsometry. The dielectric function was extracted by using a Lorentz model over the spectral range of 1.25-6.0 eV. We firstly ascribed the resonant energies, extracted from the Lorentz model, to different interband electronic transitions between valence bands and conduction bands in the Brillouin zone. A predicted exciton is observed at 2.18 eV for the monolayer and the corresponding exciton binding energy is 0.65 eV, in line with previous theoretical calculation and the measured absorption spectra. Additionally, the exciton peak shows a red shift with the increase of thickness, which is the consequence of strong interlayer interaction. These results enrich the fundamental understanding of PtSe2 and are conducive to its potential applications.

Black silicon Schottky photodetector in sub-bandgap near-infrared regime.

Sub-bandgap near-infrared silicon (Si) photodetectors are key elements in integrated Si photonics. We demonstrate such a Si photodetector based on a black Si (b-Si)/Ag nanoparticles (Ag-NPs) Schottky junction. This photodetector synergistically employs the mechanisms of inner photoemission, light-trapping, and surface-plasmon-enhanced absorption to efficiently absorb the sub-bandgap light and generate a photocurrent. The b-Si/Ag-NPs sample was prepared by means of wet chemical etching. Compared to those of a planar-Si/Ag thin-film Schottky photodetector, the responsivities of the b-Si/Ag-NPs photodetector were greatly enhanced, being 0.277 and 0.226 mA/W at a reversely biased voltage of 3 V for 1319- and 1550-nm light, respectively.

Evolution of optical properties and electronic structures: band gaps and critical points in MgxZn1-xO (0 ≤ x ≤ 0.2) thin films.

MgxZn1-xO (ZMO) thin films with tunable Mg content were deposited by atomic layer deposition (ALD) on silicon substrates at 190 °C. The elemental and structural properties were acquired by X-ray photoelectron spectroscopy, transmission electron microscopy, atomic force microscopy and X-ray diffraction. Spectroscopic ellipsometry measurements were performed to reveal the evolution of the dielectric functions and critical points in the ZMO thin films by point-by-point fit in the photon energy range of 1.2-6.0 eV. The dependence of the dielectric functions on doping content is clearly demonstrated and physically explained. The critical point energies and the types of interband optical transitions were extracted from standard lineshape analysis of the second derivatives of the dielectric functions. The critical point features were discussed in terms of band structure modification and structural homogeneity arisen by introducing the Mg dopant into the films. Controlling these transitions by changing the doping content will be of practical significance in emerging ZMO-based thin-film photonic and optoelectronic devices.

Dielectric functions and critical points of crystalline WS2 ultrathin films with tunable thickness.

Centimeter-scale WS2 ultrathin films were synthesized on sapphire substrates, and they showed highly oriented crystallographic growth along the c axis. Afterwards, the as-grown samples were systematically characterized using various detection methods. Reliable values of the roughness layer thickness and the film thickness were extracted using both atomic force microscopy (AFM) and spectroscopic ellipsometry (SE), and identified using Raman spectroscopy as well. The expansion and tensile strain along the [001] direction were discovered using X-ray diffraction (XRD) measurements. Accurate dielectric functions of WS2 films were derived from the point-by-point fitting results. The critical points (CPs) of WS2, which have not been reported so far, are precisely extracted from the standard critical point (SCP) model. Their origins are uniquely assigned to different interband electronic transitions in the Brillouin zone, including some novel optical structures above 3 eV, which were not investigated in earlier studies. In this work, it is found that dielectric functions are thickness-dependent, while CPs have an opposite nature, and their intrinsic mechanisms are revealed. The as-obtained results can be expected to help people develop more extensive applications of WS2.

Influence of hydration water on CH3NH3PbI3 perovskite films prepared through one-step procedure.

Organic-inorganic perovskites were fabricated through a one-step procedure with different levels of hydration water in precursor solutions. The optical properties of CH3NH3PbI3 films were investigated through spectroscopic ellipsometry and photoluminescence measurements. With the measured optical constants, the efficiency limit of perovskite solar cells is predicted with a detailed balance model. By comparing the optical measurement to that of planar heterojunction solar cells, we conclude that the radiative efficiency and porosity of the perovskite film significantly influence the performance of perovskite solar cells. An optimized hydration-water concentration is obtained for the 3CH3NH3I:1PbAc2•xH2O precursor solution. The results can provide guidance for further optimization of the device performance of perovskite solar cells by utilizing hydration water.

Effective method to study the thickness-dependent dielectric functions of nanometal thin film.

A new method for measuring the dielectric functions change with the thickness of nanometal thin films was proposed. To confirm the accuracy and reliability of the method, a nano-thin wedge-shaped gold (Au) film with continuously varied thicknesses was designed and prepared on K9 glass by direct-current-sputtering (DC-sputtering). The thicknesses and the dielectric functions in the wavelength range of 300-1100 nm of the nano-thin Au films were obtained by fitting the ellipsometric parameters with the Drude and critical points model. Results show that while the real part of the dielectric function (ϵ1) changes marginally with increasing film thickness, the imaginary part (ϵ2) decreases drastically with the film thickness, approaching a stable value when the film thickness increases up to about 42 nm. This method is particularly useful in the study of thickness-dependent optical properties of nano-thin film.

The fracture behaviors of monolayer phosphorene with grain boundaries under tension: a molecular dynamics study.

The fracture behaviors of monolayer phosphorene (MP) with and without a grain boundary (GB) have been explored by molecular dynamics (MD) simulations. Firstly, in the case of perfect MP, fracture mostly happens on the bond in the zigzag direction when suffering random loading. With the existence of a GB, the crack propagates perpendicular to the GB in different ways under parallel tension to the GB, whereas it propagates along the GB under perpendicular tension to the GB. Then, we found that both the fracture strength and strain decrease with increasing temperature making fracture more likely at relatively high temperatures. Finally, we also found that, similar to graphene, the effect of strain rate on both the fracture strength and strain is not significant, demonstrating that MP is a typical brittle 2D material. Overall, our findings present a useful insight into utilizing phosphorene for mechanical design in electronic devices.

The thickness-dependent band gap and defect features of ultrathin ZrO2 films studied by spectroscopic ellipsometry.

The band gap and defect features of ultrathin ZrO2 films with varying thicknesses have been investigated by spectroscopic ellipsometry through the point-by-point data inversion method. The ε2-sprectra in the 3-6 eV range are extracted based on an optical model consisting of a Si substrate/effective ZrO2 film/air ambient structure where the effective ZrO2 film is a combination of interfacial layers and ZrO2. Evident widening of the band gap with a reducing size is observed when the effective ZrO2 films are below a critical thickness, somewhere between 8.80 nm and 17.13 nm. This is due to quantum-confinement and amorphous effects. Moreover, the sub-band-gap defects at interfacial layers and in bulk ZrO2 are identified and present strong thickness dependence as well. The interfacial defects at 3.26, 4.13, 4.43, and 4.77 eV mainly exist below the critical thickness and exhibit a significant suppression with increasing film thickness. The bulk defects at 4.15 eV and 4.46 eV dominate in ZrO2 films once they are over the critical thickness. The evolution of the band gap and defects is closely related to variance in the electronic structure of amorphous ZrO2. Our results may be helpful in understanding controversial problems concerning the size effect on ultrathin high-k oxide films and exploring the further miniaturization of electronic devices based on them.

A first-principles study of the electronic structure and mechanical and optical properties of CaAlSiN3.

The mechanical properties, electronic structures and optical properties of CaAlSiN3 were investigated using the first-principles calculations. The elastic constants, bulk moduli, shear moduli, Young's moduli, and Poisson's ratio were obtained. These results indicate that CaAlSiN3 is mechanically stable and a relatively hard material. Moreover, this compound has an indirect band gap of ∼3.4 eV according to its band structure and density of states. The linear photon energy dependent dielectric functions and related optical properties including the refractive index, extinction coefficient, absorption spectrum, reflectivity, and energy loss spectrum were computed and discussed. It is shown that no sizable anisotropy is found in the optical properties of CaAlSiN3. The obtained structural estimation and some other results are in agreement with available experimental and theoretical data. This investigation is not only helpful for better understanding the electronic, mechanical and optical properties of CaAlSiN3, but also will open up the possibility of its use in device applications.

High efficiency of photon-to-heat conversion with a 6-layered metal/dielectric film structure in the 250-1200 nm wavelength region.

The optical properties and thermal stability of a 6-layered metal/dielectric film structure are investigated in this work. A high optical absorption average of > 98% is achieved in the broad spectral range of 250-1200 nm with experiment results, in good agreement with our simulated results. The samples have a typical layered structure of: SiO(2)(57.3 nm)/Ti(5.7 nm)/SiO(2) (67.1 nm)/Ti(11.6 nm)/SiO(2)(51.4 nm)/Cu(>100 nm), deposited on optically polished Si or K9-glass substrates by magnetron sputtering. The sample of the 6-layered metal/dielectric film structure has an AM1.5G solar absorptance of 95.5% with the features of low thermal emittance of 0.136 at 700K and good thermal stability, and will be potentially suitable for practical application in high-efficiency solar absorber devices in many fields.

Interpretation of Reflection and Colorimetry Characteristics of Indium-Particle Films by Means of Ellipsometric Modeling.

It is of great technological importance in the field of plasmonic color generation to establish and understand the relationship between optical responses and the reflectance of metallic nanoparticles. Previously, a series of indium nanoparticle ensembles were fabricated using electron beam evaporation and inspected using spectroscopic ellipsometry (SE). The multi-oscillator Lorentz-Drude model demonstrated the optical responses of indium nanoparticles with different sizes and size distributions. The reflectance spectra and colorimetry characteristics of indium nanoparticles with unimodal and bimodal size distributions were interpreted based on the SE analysis. The trends of reflectance spectra were explained by the transfer matrix method. The effects of optical constants n and k of indium on the reflectance were demonstrated by mapping the reflectance contour lines on the n-k plane. Using oscillator decomposition, the influence of different electron behaviors in various indium structures on the reflectance spectra was revealed intuitively. The contribution of each oscillator on the colorimetry characteristics, including hue, lightness and saturation, were determined and discussed from the reflectance spectral analysis.

The luminescence mechanism of ligand-induced interface states in silicon quantum dots.

Over decades of research on photoluminescence (PL) of silicon quantum dots (Si-QDs), extensive exploratory experiments have been conducted to find ways to improve the photoluminescence quantum yield. However, the complete physical picture of Si-QD luminescence is not yet clear and needs to be studied in depth. In this work, which considers the quantum size effect and surface effect, the optical properties of Si-QDs with different sizes and surface terminated ligands were calculated based on first principles calculations. The results show that there are significant differences in the emission wavelength and emission intensity of Si-QD interface states connected by different ligands, among which the emission of silicon-oxygen double bonds is the strongest. When the size of the Si-QD increases, the influence of the surface effect weakens, and only the silicon-oxygen double bonds still localize the charge near the ligand, maintaining a high-intensity luminescence. In addition, the presence of surface dangling bonds also affects luminescence. This study deepens the understanding of the photoluminescence mechanism of Si-QDs, and provides a direction for both future improvement of the photoluminescence quantum efficiency of silicon nanocrystals and for fabricating silicon-based photonic devices.