Optical gain and entanglement through dielectric confinement and electric field in InP quantum dots.

Quantum dots are widely recognized for their advantageous light-emitting properties. Their excitonic fine structure along with the high quantum yields offers a wide range of possibilities for technological applications. However, especially for the case of colloidal QDs, there are still characteristics and properties which are not adequately controlled and downgrade their performance for applications which go far beyond the simple light emission. Such a challenging task is the ability to manipulate the energetic ordering of exciton and biexciton emission and subsequently control phenomena such as Auger recombination, optical gain and photon entanglement. In the present work we attempt to engineer this ordering for the case of InP QDs embedded in polymer matrix, by means of their size, the dielectric confinement and external electric fields. We employ well tested, state of the art theoretical methods, in order to explore the conditions under which the exciton-biexciton configuration creates the desired conditions either for optical gain or photon entanglement. Indeed, this appears to be feasible for QDs with small diameters (1 nm, 1.5 nm) embedded in a host material with high dielectric constant and additional external electric fields. These findings offer a new design principle which might be complementary to the well-established type II core-shell QDs approach for achieving electron-hole separation.

Rational Design of Tetrahedral Derivatives as Efficient Light-Emitting Materials Based on "Super Atom" Perspective.

Traditional semiconductor quantum dots of groups II-VI are key ingredients of next-generation display technology. Yet, the majority of them contain toxic heavy-metal elements, thus calling for alternative light-emitting materials. Herein, we have explored three novel categories of multicomponent compounds, namely, tetragonal II-III2-VI4 porous ternary compounds, cubic I2-II3-VI4 ternary compounds, and cubic I-II-III3-V4 quaternary compounds. This is achieved by judicious introduction of a "super atom" perspective and concurrently varying the solid-state lattice packing of involved super atoms or the population of surrounding counter cations. Based on first-principles calculations of 392 candidate materials with designed crystal structures, 53 highly stable materials have been screened. Strikingly, 34 of them are direct-bandgap semiconductors with emitting wavelengths covering the near-infrared and visible-light regions. This work provides a comprehensive database of highly efficient light-emitting materials, which may be of interest for a broad field of optoelectronic applications.

Design Principle for Tetrahedral Semiconductors and Their Functional Derivatives: Cation Stabilizing Charged Cluster Network.

Colloidal quantum dots (QDs) of groups II-VI and III-V are key ingredients for next-generation light-emitting devices. Yet, many of them are heavy-element-containing or indirect bandgap, causing limited choice of environmental friendly efficient light-emitting materials. Herein, we resolve this issue by exploring potential derivatives of the parent semiconductors, thus expanding the material space. The key to success is the discovery of a principle for designing those materials, namely, cation stabilizing charged cluster network. Guided by this principle, three novel categories of cubic materials have been predicted, namely, porous binary compounds, I-II-VI ternary compounds, and I-II-III-V quaternary compounds. Using first-principles calculations, 65 realistic highly stable candidate materials have been theoretically screened. Their structural and compositional diversity enables a wide tunability of emitting wavelength from far-infrared to ultraviolet region. This work enriches the family of tetrahedral semiconductors and derivatives, which may be of interest for a broad field of optoelectronic applications.

Efficient Band-Edge Emission from Indirect Bandgap Semiconductor Quantum Dots upon Shell Engineering.

Environmentally friendly colloidal quantum dots (QDs) of groups III-V are in high demand for next-generation high-performance light-emitting devices for display and lighting, yet many of them (e.g., GaP) suffer from inefficient band-edge emission due to the indirect bandgap nature of their parent materials. Herein, we theoretically demonstrate that efficient band-edge emission can be activated at a critical tensile strain γc enabled by the capping shell when forming a core/shell architecture. Before γc is reached, the emission edge is dominated by dense low-intensity exciton states with a vanishing oscillator strength and a long radiative lifetime. After γc is crossed, the emission edge is dominated by high-intensity bright exciton states with a large oscillator strength and a radiative lifetime that is shorter by a few orders of magnitude. This work provides a novel strategy for realizing efficient band-edge emission of indirect semiconductor QDs via shell engineering, which is potentially implemented employing the well-established colloidal QD synthesis technique.

On the Quantum Confinement Effects in Ultrathin PdO Films by Experiment and Theory.

Radio frequency magnetron sputtering conducted in a high vacuum with a base pressure of 1×10-6 mbar was used to deposit ultrathin palladium films on Corning glass. The thickness of these films ranged from 0.4 to 13 nanometers. PdO films were produced after being post-annealed in a furnace at temperatures of 530 degrees Celsius in the presence of air. The results of an atomic force microscopy study showed that the material possessed a high crystalline quality with a low roughness. When looking at Tauc plots to determine the position of the direct optical band gap, the thicker films show a value that is relatively close to 2.2 eV. When the film thickness was reduced all the way down to 0.7 nm, a significant "blue shift" of more than 0.5 eV was observed. In order to provide a more in-depth understanding of the experiment, theoretical calculations based on the Hartree-Fock approximation as applied to an electron-hole system were performed in the framework of the effective mass approximation. The findings are regarded as empirical proof of the existence of quantum confinement effects.

Twisting Enabled Charge Transfer Excitons in Epitaxially Fused Quantum Dot Molecules.

A heterojunction with type-II band alignment has long been considered as a prerequisite to realize charge transfer (CT) excitons which are highly appealing for exploration of quantum many-body phenomena, such as excitonic Bose-Einstein condensation and superfluidity. Herein, we have shown CT excitons can be activated via twisting in epitaxially fused heterodimer quantum dot (QD) molecules with quasi type-II band alignment, and even in QD homodimer molecules, therefore breaking the constraint of band alignment. The enabling power of twisting has been revealed. It modulates the orbital spatial localization toward charge separation that is mandatory for CT excitons. Meanwhile, it manifests an effective band offset that counterbalances the distinct many-body effects felt by excitons of different nature, thus ensuring the successful generation of CT excitons. The present work extends the realm of twistroincs into zero-dimensional materials and opens a novel pathway of manipulating the properties of QD materials and closely related molecular systems.

Size Engineering of Trap Effects in Oxidized and Hydroxylated ZnSe Quantum Dots.

Environmentally friendly blue-emitting ZnSe quantum dots (QDs) are in high demand for next-generation light-emitting devices. Yet, they suffer longstanding optical instability issues under aerobic conditions. Herein, we have demonstrated the existence of oxidization or hydroxylation on the QD surface when QDs are subjected to oxygen exposure, which potentially introduces highly localized in-gap states. Those states result in a dense number of surface-related, weak-intensity "dark" exciton states at the emission edge. Remarkably, there exists a critical diameter (Dc ≈ 8.5 nm) at which the deepest trap level reaches resonance with the highest occupied molecular orbital state. Beyond this critical diameter, the effects of those trap states are minimized, and the emission edge is dominated by high-intensity, bulk-to-bulk-like "bright" exciton states. The present work provides a novel strategy for designing highly stable QD emitters via size engineering, which are broadly applicable to other closely related QD systems.

Direct sunlight-driven enhanced photocatalytic performance of V2O5 nanorods/ graphene oxide nanocomposites for the degradation of Victoria blue dye.

Herein, we report the synthesis and characterizations of Vanadium pentoxide (V2O5) nanorods/graphene oxide (GO) nanocomposite as efficient direct solar light driven photocatalyst for the enhanced degradation of victoria blue (VB) dye. The nanocomposite was synthesized by sonochemical process and characterized using several analytical methods in order to study the structural, morphological, compositional, optical and photocatalytic properties. The X-ray diffraction studies confirmed the orthorhombic structure of V2O5 while the morphological examinations revealed the growth of V2O5 nanorods and 2D GO sheets. Interestingly, the UV studies ratify that the bandgap of the nanocomposite was reduced compared to pure GO and V2O5. Interestingly, the interaction of the V2O5 nanorods with the graphene oxide substrate and its effect on the electronic properties of the combined system, have been examined by means of theoretical calculations, based on the so called Geometry, Frequency, Noncovalent, eXtended Tight Binding (GFN-xTB) method. Studying the photocatalytic behavior of nanocomposite, we observe an almost complete degradation (97.95%) of Victoria Blue (VB) dye under direct sunlight illumination within just 90 min. The outstanding nanocomposite photocatalytic efficiency was due to the excellent transfer of interfacial charge and the suppressed recombination of charge-carrier. The kinetics of the degradation process was also analyzed by calculating the rate constant and half-life time. Finally, a possible mechanism has also been discussed for the degradation process of VB dye using nanocomposite under direct sunlight irradiation.

Adsorptive removal of antibiotic ofloxacin in aqueous phase using rGO-MoS2 heterostructure.

This paper reports the synthesis, characterization and detailed adsorption studies of rGO-MoS2 heterostructure. The heterostructure was explored for the adsorption of ofloxacin from the aqueous phase. Detailed studies were conducted to study the effect of crucial parameters such as pH of drug solution, adsorbent dose, temperature and initial drug concentration on the adsorption capacity. Even with a low surface area of 17.17 m2/g, the adsorbent exhibited maximum removal efficiency of 95% at a dose of 0.35 g/L and an initial drug concentration of 10 mg/L in 240 min. Thermodynamic study revealed the values for ∆H0 and ∆G0 to be - 101.15 and - 7.47 kJ/mol respectively, indicating that the process is spontaneous and exothermic in nature. The heterostructure adsorbent exhibited remarkable reusability and stability up to five cycles. The heterostructure combines excellent adsorption capabilities arising from the two-dimensional structures of rGO and MoS2 with the stronger and more specific interaction with the drug molecules which results in better performance towards the removal of the drug. The excellent performance of the heterostructure indicates that combining 2D materials can be a good strategy for producing highly efficient materials towards the adsorptive removal of pollutants.

Band Gap Measurements of Nano-Meter Sized Rutile Thin Films.

Thin Titanium films were fabricated on quartz substrates by radio frequency magnetron sputtering under high vacuum. Subsequent annealing at temperatures of 600 ∘C in air resulted in single-phase TiO2 with the structure of rutile, as X-ray diffraction experiment demonstrates. Atomic-force microscopy images verify the high crystalline quality and allow us to determine the grain size even for ultrathin TiO2 films. Rutile has a direct energy band gap at about 3.0-3.2 eV; however, the transitions between the valence and conduction band are dipole forbidden. Just a few meV above that, there is an indirect band gap. The first intense absorption peak appears at about 4 eV. Tauc plots for the position of the indirect band gap show a "blue shift" with decreasing film thickness. Moreover, we find a similar shift for the position of the first absorbance peak studied by the derivative method. The results indicate the presence of quantum confinement effects. This conclusion is supported by theoretical calculations based on a combination of the effective mass theory and the Hartree Fock approximation.

A Study of Quantum Confinement Effects in Ultrathin NiO Films Performed by Experiment and Theory.

Ultrathin NiO films in the thickness range between 1 and 27 nm have been deposited on high-quality quartz substrates by direct magnetron sputtering under a rough vacuum with a base pressure of 2 × 10-2 mbar. The sputtering target was metallic Ni; however, due to the rough vacuum a precursor material was grown in which most of Ni was already oxidized. Subsequent short annealing at temperatures of about 600 °C in a furnace in air resulted in NiO with high crystallinity quality, as atomic force microscopy revealed. The images of surface morphology showed that the NiO films were continuous and follow a normal grain growth mode. UV-Vis light absorption spectroscopy experiments have revealed a blue shift of the direct band gap of NiO. The band gap was determined either by Tauc plots (onset) or by the derivative method (highest rate of absorbance increase just after the onset). The experimental results are interpreted as evidences of quantum confinement effects. Theoretical calculations based on Hartree Fock approximation as applied for an electron-hole system, in the framework of effective mass approximation were carried out. The agreement between theory and experiment supports the quantum confinement interpretation.

Electronic and Optical Properties of Ultrasmall ABX3 (A = Cs, CH3NH3/B = Ge, Pb, Sn, Ca, Sr/X = Cl, Br, I) Perovskite Quantum Dots.

Perovskite quantum dots (QDs) constitute a novel and rapidly developing field of nanotechnology with promising potential for optoelectronic applications. However, few perovskite materials for QDs and other nanostructures have been theoretically explored. In this study, we present a wide spectrum of different hybrid halide perovskite cuboid-like QDs with the general formula of ABX3 with varying sizes well below the Bohr exciton radius. Density functional theory (DFT) and time-dependent DFT calculations were employed to determine their structural, electronic, and optical properties. Our calculations include both stoichiometric and nonstoichiometric QDs, and our results reveal several materials with high optical absorption and application-suitable electronic and optical gaps. Our study highlights the potential as well as the challenges and issues regarding nanostructured halide perovskite materials, laying the background for future theoretical and experimental work.

Morphology control of exciton fine structure in polar and nonpolar zinc sulfide nanorods.

Electron-hole exchange interaction in semiconductor quantum dots (QDs) splits the band-edge exciton manifold into optically active ("bright") and passive ("dark") states, leading to a complicated exciton fine structure. In the present work, we resolve by atomistic million-atom many-body pseudopotential calculations the exciton fine structure in colloidal polar and nonpolar zinc sulfide (ZnS) nanorods (NRs). We explore that polar NRs with high symmetry exhibit vanishing fine structure splitting (FSS), and are therefore ideal sources of entangled photon pairs. In contrast, nonpolar NRs grown along [Formula: see text] and [Formula: see text] directions with reduced symmetries have significant FSS, which can even reach up to a few mili electron volts. However, such large FSS can be effectively minimized to a few micro electron volts, or even less, by a simple morphology control.

Excitonic optical properties of wurtzite ZnS quantum dots under pressure.

By means of atomistic empirical pseudopotentials combined with a configuration interaction approach, we have studied the optical properties of wurtzite ZnS quantum dots in the presence of strong quantum confinement effects as a function of pressure. We find the pressure coefficients of quantum dots to be highly size-dependent and reduced by as much as 23% in comparison to the bulk value of 63 meV/GPa obtained from density functional theory calculations. The many-body excitonic effects on the quantum dot pressure coefficients are found to be marginal. The absolute gap deformation potential of quantum dots originates mainly from the energy change of the lowest unoccupied molecular orbital state. Finally, we find that the exciton spin-splitting increases nearly linearly as a function of applied pressure.

Near-band-edge exciton polarization change in ZnO nanowires.

Using the atomistic pseudopotential method complemented by configuration interaction calculations, we have studied the electronic and optical properties of ZnO nanowires (NWs) in the presence of quantum confinement effects. Our results indicate that the near-band-edge exciton experiences a crossover from an in-plane polarized A-exciton (for D≥ 3 nm) to an out-of-plane polarized C-exciton (for D < 3 nm) due to quantum confinement. This transition leads to a non-monotonic variation of Stokes shift, exhibiting a maximum value around the critical diameter of 3 nm. The observed behavior is analyzed by a stepwise inclusion of correlation effects, leading to a comprehensive description of the excitonic fine structure.

Interfacial impregnation chemistry in the synthesis of nickel catalysts supported on titania.

The interfacial chemistry of the impregnation step involved in the preparation of nickel catalysts supported on titania is presented. Several methodologies based on deposition data, pH measurements, potentiometric mass titrations, and microelectrophoresis have been used in conjunction with diffuse reflectance UV/Vis/NIR spectroscopy, simulations, and semiempirical quantum chemical calculations. Three mononuclear inner-sphere complexes were formed at the compact layer of the "titania/electrolyte solution" interface: A monosubstituted, dihydrolyzed complex above a terminal oxo group, a disubstituted, dihydrolyzed complex above two terminal adjacent oxo groups, and a disubstituted, nonhydrolyzed complex above one terminal and one bridging adjacent oxo groups. The monosubstituted, dihydrolyzed complex predominates. The contribution of the disubstituted configurations is also important at very low Ni(II) surface concentration, but it decreases as the Ni(II) surface concentration increases. In addition, bi- and trinuclear inner-sphere complexes were formed. The receptor site involves one bridging and two terminal oxo groups in the first case and two bridging and three terminal oxo groups in the second case. The relative surface concentrations of these configurations increase initially with Ni(II) surface concentration and then remain practically constant. The understanding of these interfacial processes at a molecular level is very important to shift the catalytic synthesis from an art to a science as well as to obtain strict control of the impregnation step and, to some extent, of the whole preparative sequence. This study is very relevant to the synthesis of submonolayer/monolayer nickel catalysts supported on TiO(2) following equilibrium deposition filtration (otherwise called equilibrium adsorption).

Interfacial impregnation chemistry in the synthesis of cobalt catalysts supported on titania.

The interfacial chemistry of the impregnation step involved in the synthesis of cobalt catalysts supported on titania was investigated with regard to the mode of interfacial deposition of the aqua complex [Co(H(2)O)(6)](2+) on the "titania/electrolyte solution" interface, the structure of the inner-sphere complexes formed, and their relative interfacial concentrations. Several methodologies based on the application of deposition experiments and electrochemical techniques were used in conjunction with diffuse-reflectance spectroscopy and EPR spectroscopy. These suggested the formation of mononuclear/oligonuclear inner-sphere complexes on deposition of the [Co(H(2)O)(6)](2+) ions at the "titania/electrolyte solution" interface. The joint application of semiempirical quantum-mechanical calculations, stereochemical considerations, and modeling of the deposition data revealed the exact structure of these complexes and allowed their relative concentrations at various Co(II) surface concentrations to be determined. It was found that the interface speciation depends on the Co(II) surface concentration. Mononuclear complexes are formed at the compact layer of the "titania/electrolyte solution" interface for low and medium Co(II) surface concentrations. Formation of mono-hydrolyzed Ti(2)O-TiO and the dihydrolyzed TiO-TiO disubstituted configurations is very probable. In the first configuration one water ligand of the [Co(H(2)O)(6)](2+) ion is substituted by a bridging surface oxygen atom and another by a terminal surface oxygen atom. In the second configuration two water ligands of the [Co(H(2)O)(6)](2+) ion are substituted by two terminal surface oxygen atoms. Binuclear and trinuclear inner-sphere complexes are formed, in addition to the mononuclear ones, at relatively high Co(II) surface concentrations.

Mapping the surface (hydr)oxo-groups of titanium oxide and its interface with an aqueous solution: the state of the art and a new approach.

In this article the "titanium oxide/electrolyte solution" interface is studied by taking in advantage the recent developments in the field of Surface and Interface Chemistry relevant to this oxide. Ab-initio calculations were performed in the frame of the DFT theory for estimating the charge of the titanium and oxygen atoms exposed on the anatase (1 0 1), (1 0 0), (0 0 1), (1 0 3)(f) and rutile (1 1 0) crystal faces. These orientations have smaller surface energy with respect to other ones and thus it is more probable to be the real terminations of the anatase and rutile nanocrystallites in the titania polycrystalline powders. Potentiometric titrations for obtaining "fine structured" titration curves as well as microelectrophoresis and streaming potential measurements have been performed. On the basis of ab-initio calculations, and taking into account the relative contribution of each crystal face to the whole surface of the nanocrystals involved in the titania aggregates of a suspension, the three most probable surface ionization models have been derived. These models and the Music model are then tested in conjunction with the "Stern-Gouy-Chapman" and "Basic Stern" electrostatic models. The finally selected surface ionization model (model A) in combination with each one of the two electrostatic models describes very well the protonation/deprotonation behavior of titania. The description is also very good if this model is combined with the Three Plane (TP) model. The application of the "A/(TP)" model allowed mapping the surface (hydr)oxo-groups [TiO(H) and Ti(2)O(H)] of titania exposed in aqueous solutions. At pH>pzc almost all terminal oxygens [TiO] are non-protonated whereas even at low pH values the non-protonated terminal oxygens predominate. The acid-base behavior of the bridging oxygens [Ti(2)O] is different. Thus, even at pH=10 the greater portion of them is protonated. The application of the "A/TP" model in conjunction with potentiometric titrations, microelectrophoresis and streaming potential experiments allowed mapping the "titania/electrolyte solution" interface. It was found that the first (second) charged plane is located on the oxygen atoms of the first (second) water overlayer at a distance of 1.7 (3.4) A from the surface. The region between the surface and the second plane is the compact layer. The region between the second plane and the shear plane is the stagnant diffuse part of the interface, with an ionic strength dependent width, ranging from 20 (0.01 M) up to 4 A (0.3 M). The region between the shear plane and the bulk solution is the mobile diffuse part, with an ionic strength dependent width, ranging from 10 (0.01 M) up to 2 A (0.3 M). At I>0.017 M the mean concentration of the counter ions is higher in the stagnant than in the mobile part of the diffuse layer. For a given I, removal of pH from pzc brings about an increase of the mean concentration in the interfacial region and a displacement of the counter ions from the mobile to the stagnant part of the diffuse layer. The mean concentration of the counter ions in the compact layer is generally lower than the corresponding ones in the stagnant and mobile diffuse layers. The mobility of the counter ions in the stagnant layer decreases as pH draws away from pzc or ionic strength increases.