Study of the bandgap renormalization in Ga-doped ZnO films by means of optical absorption under high pressure and photoelectron spectroscopy

Abstract In this paper we investigate the band gap renormalization in heavily Ga-doped ZnO thin films deposited by pulsed laser deposition on C -plane sapphire and mica substrates. Thin films were studied by ultraviolet photoelectron spectroscopy and also by optical measurements under high pressure. The Fermi-level shift, as obtained from ultraviolet photoelectron experiments, exhibits a relatively small and positive shift (about 0.3 eV) with respect to the valence band for increasing electron concentrations up to 1021 cm−3. The optical gap exhibits a much larger increase (0.6 eV) for the same concentration range. Absorption measurements under pressure show that the pressure coefficient of …

Investigation of acceptor levels and hole scattering mechanisms in p-gallium selenide by means of transport measurements under pressure

The effect of pressure on acceptor levels and hole scattering mechanisms in p-GaSe is investigated through Hall effect and resistivity measurements under quasi-hydrostatic conditions up to 4 GPa. The pressure dependence of the hole concentration is interpreted through a carrier statistics equation with a single (nitrogen) or double (tin) acceptor whose ionization energies decrease under pressure due to the dielectric constant increase. The pressure effect on the hole mobility is also accounted for by considering the pressure dependencies of both the phonon frequencies and the hole-phonon coupling constants involved in the scattering rates.

Investigation of conduction-band structure, electron-scattering mechanisms, and phase transitions in indium selenide by means of transport measurements under pressure

In this work we report on Hall effect, resistivity and thermopower measurements in n-type indium selenide at room temperature under either hydrostatic and quasi-hydrostatic pressure. Up to 40 kbar (= 4 GPa), the decrease of carrier concentration as the pressure increases is explained through the existence of a subsidiary minimum in the conduction band. This minimum shifts towards lower energies under pressure, with a pressure coefficient of about -105 meV/GPa, and its related impurity level traps electrons as it reaches the band gap and approaches the Fermi level. The pressure value at which the electron trapping starts is shown to depend on the electron concentration at ambient pressure an…

Mesoporous iron phosphate/phosphonate hybrid materials

Abstract Relatively high surface area pure mesoporous iron-phosphorus oxide-based derivatives have been synthesized through an S + I − surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from iron atrane complexes and phosphoric and phosphonic acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from iron phosphate up to hybrids involving approximately 30% of organophosphorus entities (phosphonates or diphosphonates). X-ray powder diffraction, transmission elect…

Nanotexturing To Enhance Photoluminescent Response of Atomically Thin Indium Selenide with Highly Tunable Band Gap.

Brotons-Gisbert, Mauro et al.

Highly fluorescent and photostable organic- and water-soluble CdSe/ZnS core-shell quantum dots capped with thiols

Highly fluorescent organic- and water-soluble CdSe/ZnS core-shell quantum dots (QDs) with thiol ligands chemisorbed on the QD surface were synthesized by the replacement of amine ligands by alkyl thiols under very mild conditions. The QDs exhibited an even greater photostability than the initial core-shell amine capped QDs.

Solution-Processed Ni-Based Nanocomposite Electrocatalysts: An Approach to Highly Efficient Electrochemical Water Splitting

In this study, we report an up-scalable and low-cost solution-processed method to in situ synthesize an earth-abundant non-stoichiometric NiOx-based electrocatalytic film for water oxidation. The catalytic activity was found to be inversely proportional to the baking temperature, which varied from 50 to 500 °C. We found the formation of a hybrid nanocomposite thin film of NiOx nanocrystals (<2 nm size) inside an acetate-based organic matrix at low temperatures (<200 °C). The defective and short-range structural order of the NiOx-based nanocomposite electrocatalysts, compatible with lattice stress, low electrical conductivity, and high density of catalytically active surface species, and hig…

Boosting Long-Term Stability of Pure Formamidinium Perovskite Solar Cells by Ambient Air Additive Assisted Fabrication

Due to the high industrial interest for perovskite-based photovoltaic devices, there is an urgent need to fabricate them under ambient atmosphere, not limited to low relative humidity (RH) conditions. The formamidinium lead iodide (FAPI) perovskite α-black phase is not stable at room temperature and is challenging to stabilize in an ambient environment. In this work, we show that pure FAPI perovskite solar cells (PSCs) have a dramatic increase of device long-term stability when prepared under ambient air compared to FAPI PSCs made under nitrogen, both fabricated with N-methylpyrrolidone (NMP). The T80 parameter, the time in which the efficiency drops to 80% of the initial value, increases f…

Study of the Secondary Electron Yield in Dielectrics Using Equivalent Circuital Models

[EN] Secondary electron emission has an important role on the triggering of the multipactor effect; therefore, its study and characterization are essential in radio-frequency waveguide applications. In this paper, we propose a theoretical model, based on equivalent circuit models, to properly understand charging and discharging processes that occur in dielectric samples under electron irradiation for secondary electron emission characterization. Experimental results obtained for Pt, Si, GaS, and Teflon samples are presented to verify the accuracy of the proposed model. Good agreement between theory and experiments has been found.

Au-ZnO Nanocomposite Films for Plasmonic Photocatalysis

Nanocomposites based on plasmonic nanoparticles and metal-oxide semiconductors are emerging as promising materials for conversion of solar energy into chemical energy. In this work, a Au–ZnO nanocomposite film with notably enhanced photocatalytic activity is successfully prepared by a single-step process. Both ZnO and Au nanoparticles are synthesized in situ during baking of the film spin-coated from a solution of Zn(CH3COO)2 and HAuCl4. Furthermore, it is shown that this precursor solution can be formulated as a nanoink for the generation of micropatterns by microplotter printing, opening the way for the miniaturization of devices with enhanced properties for photocatalysis, optoelectronic…

Optical contrast of 2D InSe on SiO2/Si and transparent substrates using bandpass filters

The particular optical and electronic properties recently reported for 2D InSe depict this 2D material as being very versatile for future electronic and optoelectronic devices with tunable and optimized functionalities. For its fundamental study and the development of practical applications, rapid and accurate identification methods of atomically thin InSe are essential. Here, we demonstrate an enhancement of the optical contrast between InSe nanosheets and the underlying SiO2/Si substrate by illuminating with a 40 nm wide bandpass filter centered at 500 nm. Moreover, we study the optical contrast of 2D InSe on transparent substrates. Our results suggest that a good optical contrast is achi…

Ionic liquid modified zinc oxide injection layer for inverted organic light-emitting diodes

Abstract We have demonstrated a novel approach for fabricating efficient hybrid organic–inorganic light emitting diodes (HyLEDs) by introducing dopants into solutions processable metal oxides as an interfacial layer. The doped ZnO is prepared by adding ionic liquid (IL) to a precursor solution for the ZnO. In this way a heavily doped ZnO:ILs cathode was obtained that enhances the electron injection properties and assures a good wetting of the organic active materials.

Deep oxidation of volatile organic compounds using ordered cobalt oxides prepared by a nanocasting route

Ordered Co3O4 with high surface area (until 173 m2/g) has been successfully obtained through a nanocasting route using mesoporous KIT-6 silica as a hard template and tested in the deep oxidation of a series of representative volatile organic compounds (VOCs): propane as a model of short chain alkane and toluene as a model of monoaromatic hydrocarbon. It has been demonstrated that the catalytic activity for VOC deep oxidation is very elevated and its catalytic stability at moderate temperatures very good. However, the role of the ordered structure in the catalytic performance does not seem to be beneficial. The enhanced catalytic activity has been explained in terms of both the high surface …

Effect of annealing on Zn1−xCoxO thin films prepared by electrodeposition

Polycrystalline thin films of Zn"1"-"xCo"xO with different cobalt (Co) content were grown on indium tin oxide (ITO) substrates by cathodic electrodeposition technique and subsequently annealed in air at 400^oC. The effect of annealing in their structural, optical and chemical properties has been characterized by X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Raman scattering and optical spectroscopy. Our measurements indicate that moderate annealing increases the crystal quality of the films. The films are highly transparent in the visible range and evidence an increase of the band gap and of the intensity of three typical Co absorptio…

Precatalyst or dosing-device? The [Pd2{μ-(C6H4) PPh2}2{μ-O2C(C6H5)}2] complex anchored on a carboxypolystyrene polymer as an effective supplier of palladium catalytically active nanoparticles for the Suzuki-Miyaura reaction

Abstract A new catalyst has been synthesized from the precursor [Pd2{μ-(C6H4) PPh2}2 {μ-O2C(C6H5)}2] immobilized on a carboxypolystyrene polymer that exhibits an excellent dispersion of the Pd (II) centers, reusability, and catalytic activity in front of phenyl bromides. The activity of this new material was studied in detail for the Suzuki-Miyaura reaction and compared to that of Pd nanoparticles (NPs) supported on UVM-7 (a mesoporous silica), and Pd NPs stabilized with polyvinylpirrolydone. The homogeneous/heterogeneous character of the catalytic process was determined from the results of the hot-filtration, centrifugation, poisoning, three phases tests, and from differential sensitivity …

Laser ablation of a silicon target in chloroform: formation of multilayer graphite nanostructures

With the use of high-resolution transmission electron microscopy, selected area electron diffraction and x-ray photoelectron spectroscopy methods of analysis we show that the laser ablation of a Si target in chloroform (CHCl3) by nanosecond UV pulses (40 ns, 355 nm) results in the formation of about 50–80 nm core–shell nanoparticles with a polycrystalline core composed of small (5–10 nm) Si and SiC mono-crystallites, the core being coated by several layers of carbon with the structure of graphite (the shell). In addition, free carbon multilayer nanostructures (carbon nano-onions) are also found in the suspension. On the basis of a comparison with similar laser ablation experiments implement…

Enhancing the photocatalytic properties of PbS QD solids: the ligand exchange approach.

Surface engineering of nanomaterials is a promising tool towards the design of new materials for conversion of solar energy into chemical energy. In this work, we examine the influence of ligand exchange on the photocatalytic performance of solution-processed PbS films. We test different ligands such as oleylamine (OAm), 1,2-ethanedithiol (EDT), 3-mercaptopropionic acid (MPA) and tetrabutylammonium iodide (TBAI). The study demonstrates that PbS films capped with MPA and EDT exhibit 3.5-fold enhanced photocatalytic performance for the photodecomposition of methyl orange upon sunlight exposure. Both band energy alignment and charge carrier transport have a strong impact on the generation of r…

Engineering light emission of two-dimensional materials in both the weak and strong coupling regimes

Abstract Two-dimensional (2D) materials have promising applications in optoelectronics, photonics, and quantum technologies. However, their intrinsically low light absorption limits their performance, and potential devices must be accurately engineered for optimal operation. Here, we apply a transfer matrix-based source-term method to optimize light absorption and emission in 2D materials and related devices in weak and strong coupling regimes. The implemented analytical model accurately accounts for experimental results reported for representative 2D materials such as graphene and MoS2. The model has been extended to propose structures to optimize light emission by exciton recombination in…

Tetrahedral versus octahedral Mn site coordination in wurtzite and rocksalt Zn1−xMnxO investigated by means of XAS experiments under high pressure

Abstract We present the results of x-ray absorption measurements carried out in Zn 1− x Mn x O thin films under high pressure. The Mn environment remains essentially the same for nominal Mn concentrations given by x = 0.05 , 0.1, 0.15 and 0.25. Both the XANES (X-ray Absorption Near Edge Structure) and EXAFS (Extended X-ray Absorption Fine Structure) indicate that Mn occupies the Zn site, being surrounded by four oxygen atoms at 2.02±0.01 A. The substitutional hypothesis is reinforced by comparing the differences between the ambient (wurtzite) and high pressure (rocksalt) spectra, which correspond to tetrahedral and octahedral Mn environments.

Cathodic electrodeposition of ZnCoO thin films

We report on the characterization of ternary Zn1–xCoxO alloy crystalline films grown by electrodeposition onto FTO-coated substrates. The Zn1–xCoxO films have hexagonal wurtzite structure as shown by X-ray diffraction measurements. The Co incorporation into the ZnO lattice is confirmed by the presence of absorption peaks assigned to Co in trigonal crystal field. X-ray photoemission spectroscopy indicates that as-grown films have a considerable concentration of not-fully oxidized metallic Co in the surface that correlates with the O concentration in the surface. Finally, Raman measurements of as-grown films indicate that they are polycrystalline with grains of nanometric size showing short-r…

Optical, X-ray absorption and photoelectron spectroscopy investigation of the Co site configuration in Zn1−xCoxO films prepared by pulsed laser deposition

Abstract In this paper, we investigate the Co site configuration in Zn1−xCoxO thin films by means of different spectroscopic techniques. Thin films were prepared by pulsed laser deposition with Co proportion from 1% to 30%. The Co 2p doublet observed in the X-ray photoelectron spectra exhibits the spin–orbit splitting and shake-up satellites typical of Co+2 ionization states. X-ray absorption spectra at the Co K-edge, taken in fluorescence mode, unambiguously show that Co atoms are in tetrahedral configuration substituting for Zn over the whole composition range. Optical absorption spectra provide further evidence of the tetrahedral coordination of Co cations, both through the internal tran…

Reversible Chemisorption of Sulfur Dioxide in a Spin Crossover Porous Coordination Polymer

The chemisorption of sulfur dioxide (SO2) on the Hofmann-like spin crossover porous coordination polymer (SCO-PCP) {Fe(pz)[Pt(CN)4]} has been investigated at room temperature. Thermal analysis and adsorption-desorption isotherms showed that ca. 1 mol of SO2 per mol of {Fe(pz)[Pt(CN)4]} was retained in the pores. Nevertheless, the SO2 was loosely attached to the walls of the host network and completely released in 24 h at 298 K. Single crystals of {Fe(pz)[Pt(CN)4]}·nSO2 (n ≈ 0.25) were grown in water solutions saturated with SO2, and its crystal structure was analyzed at 120 K. The SO2 molecule is coordinated to the Pt(II) ion through the sulfur atom ion, Pt-S = 2.585(4) Å. This coordination…

Thin film growth and band lineup of In2O3 on the layered semiconductor InSe

Thin films of the transparent conducting oxide In2O3 have been prepared in ultrahigh vacuum by reactive evaporation of indium. X-ray diffraction, optical, and electrical measurements were used to characterize properties of films deposited on transparent insulating mica substrates under variation of the oxygen pressure. Photoelectron spectroscopy was used to investigate in situ the interface formation between In2O3 and the layered semiconductor InSe. For thick In2O3 films a work function of φ = 4.3 eV and a surface Fermi level position of EF−EV = 3.0 eV is determined, giving an ionization potential IP = 7.3 eV and an electron affinity χ = 3.7 eV. The interface exhibits a type I band alignmen…

Effects of Nid-levels on the electronic band structure of NixCd1-xO semiconducting alloys

NixCd1-xO has a ∼3 eV band edge offset and bandgap varying from 2.2 to 3.6 eV, which is potentially important for transparent electronic and photovoltaic applications. We present a systematic study of the electronic band structure of NixCd1-xO alloys across the composition range. Ion irradiation of alloy samples leads to a saturation of the electron concentration associated with pinning of the Fermi level (EF) at the Fermi stabilization energy, the common energy reference located at 4.9 eV below the vacuum level. The composition dependence of the pinned EF allows determination of the conduction band minimum (CBM) energy relative to the vacuum level. The unusually strong deviation of the CBM…

Pressure dependence of the optical properties of wurtzite and rock-salt Zn1–xCoxO thin films

In this paper we investigate the electronic structure of Zn 1-x Co x O by means of optical absorption measurements under pressure. Thin films of Zn 1-x Co x O with different Co content (from 1 to 30%) were prepared by pulsed laser deposition on mica substrates. Absorption spectra exhibit three main features that are clearly correlated to the Co content in the films: (i) absorption peaks in the infrared associated to crystal-field-split internal transitions in the Co 3d shell, with very small pressure coefficients due to their atomic character; (ii) a broad absorption band below the fundamental edge associated to charge transfer transitions, that exhibit relatively large pressure coefficient…

Resonant laser spectroscopy of localized excitons in monolayer WSe_2

Coherent quantum control and resonance fluorescence of few-level quantum systems is integral for quantum technologies. Here we perform resonance and near-resonance excitation of three-dimensionally confined excitons in monolayer WSe2 to reveal near-ideal single-photon fluorescence with count rates up to 3 MHz. Using high-resolution photoluminescence excitation spectroscopy of the localized excitons, we uncover a weakly fluorescent exciton state ∼5  meV blue shifted from the ground-state exciton, providing important information to unravel the precise nature of quantum states. Successful demonstration of resonance fluorescence paves the way to probe the localized exciton coherence in two-dime…

One-step growth of isolated CdO nanoparticles on r-sapphire substrates by using the spray pyrolysis methodology

In spite of the remarkable properties of CdO, there are only a few reports on CdO nanostructures, especially on isolated NPs. In this paper, we analyze the growth of isolated CdO nanoparticles (NPs) on 0.5° miscut r-sapphire substrates by using the spray pyrolysis methodology in its classical configuration. A systematic study has been performed to optimize the growth parameters such as precursor concentration, growth time, spray rate and growth temperature to obtain CdO NPs (size: 6–10 nm to 35–100 nm depending on the growth conditions). The study shows the control over the size and density of the CdO nanoparticles that can be achieved by adjusting the growth parameters. The CdO nanoparticl…

Growth and characterization of ZnO1−xSx highly mismatched alloys over the entire composition

Alloys from ZnO and ZnS have been synthesized by radio-frequency magnetron sputtering over the entire alloying range. The ZnO1−xSx films are crystalline for all compositions. The optical absorption edge of these alloys decreases rapidly with small amount of added sulfur (x ∼ 0.02) and continues to red shift to a minimum of 2.6 eV at x = 0.45. At higher sulfur concentrations (x > 0.45), the absorption edge shows a continuous blue shift. The strong reduction in the band gap for O-rich alloys is the result of the upward shift of the valence-band edge with x as observed by x-ray photoelectron spectroscopy. As a result, the room temperature bandgap of ZnO1−xSx alloys can be tuned from 3.7 eV to …

Functionalized Gold Nanoparticles as an Approach to the Direct Colorimetric Detection of DCNP Nerve Agent Simulant

New functionalized gold nanoparticles have been synthesized and their ability to act as colorimetric molecular probes for the naked-eye detection of nerve agent simulant DCNP has been studied. The detection process is based on the com

Strongly-coupled PbS QD solids by doctor blading for IR photodetection

Solution-processed QD solids are emerging as a novel concept for high-performance optoelectronic devices. In this work, doctor blading is proposed for the fabrication of strongly-coupled QD solids from a PbS nanoink for photodetection at telecom wavelengths. The key step of this procedure is the solid-state ligand exchange, which reduces the interparticle distance and increases the carrier mobility in the resulting strongly-coupled QD solid. This is accomplished by replacing the original long oleylamine molecules by shorter molecules like 3-mercaptopropionic acid, as confirmed by FTIR, TGA and XPS. Further, a detailed investigation with XPS confirms the air-stability of the QD solids and th…

CuInS2 Films for Photovoltaic Applications Deposited by a Low-Cost Method.

We report an atmospheric-pressure deposition method for preparing well-adhered and compact CuInS 2 films. The precursor film is obtained by a solution-coating technique and is subjected to a low-cost and safe one-step reduction-sulfurization treatment. A maximum thickness of 300 nm is achieved per layer, and up to three layers were sulfurized at a time. The obtained films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and visible-near-infrared (vis-NIR) spectrophotometry.

Optical Contrast and Raman Spectroscopy Techniques Applied to Few-Layer 2D Hexagonal Boron Nitride

The successful integration of few-layer thick hexagonal boron nitride (hBN) into devices based on two-dimensional materials requires fast and non-destructive techniques to quantify their thickness. Optical contrast methods and Raman spectroscopy have been widely used to estimate the thickness of two-dimensional semiconductors and semi-metals. However, they have so far not been applied to two-dimensional insulators. In this work, we demonstrate the ability of optical contrast techniques to estimate the thickness of few-layer hBN on SiO2/Si substrates, which was also measured by atomic force microscopy. Optical contrast of hBN on SiO2/Si substrates exhibits a linear trend with the number of h…

Oxidative Addition of Halogens on Open Metal Sites in a Microporous Spin-Crossover Coordination Polymer

Anisotropy of the refractive index and absorption coefficient in the layer plane of gallium telluride single crystals

Refractive index and absorption coefficient of GaTe for light polarized in the optical axis directions in the layer plane are determined from transmission measurements. The refractive index is determined in the wavelength range from 0.7 to 25 μm and the absorption coefficient in the range of energies from 1.6 to 2 eV at room temperature and at 30 K. The optical constants are found to be anisotropic in the layer plane. The refractive index dispersion is interpreted through a Phillips-Van Vechten model and the Penn gaps for each direction are found to be E pg (⊥b) = 3.37 eV and E pg (∥b) = 3.58 eV. In the long-wavelength region a polar phonon contribution is also taken into account. The absor…

Trapping of three-dimensional electrons and transition to two-dimensional transport in the three-dimensional topological insulator Bi2Se3under high pressure

This paper reports an experimental and theoretical investigation on the electronic structure of bismuth selenide (Bi2Se3) up to 9 GPa. The optical gap of Bi2Se3 increases from 0.17 eV at ambient pressure to 0.45 eV at 8 GPa. The quenching of the Burstein-Moss effect in degenerate samples and the shift of the free-carrier plasma frequency to lower energies reveal a quick decrease of the bulk three-dimensional (3D) electron concentration under pressure. On increasing pressure the behavior of Hall electron concentration and mobility depends on the sample thickness, consistently with a gradual transition from mainly 3D transport at ambient pressure to mainly two-dimensional (2D) transport at hi…

Optical and photovoltaic properties of indium selenide thin films prepared by van der Waals epitaxy

Indium selenide thin films have been grown on p-type gallium selenide single crystal substrates by van der Waals epitaxy. The use of two crucibles in the growth process has resulted in indium selenide films with physical properties closer to these of bulk indium selenide than those prepared by other techniques. The optical properties of the films have been studied by electroabsorption measurements. The band gap and its temperature dependence are very close to those of indium selenide single crystals. The width of the fundamental transition, even if larger than that of the pure single crystal material, decreases monotonously with temperature. Exciton peaks are not observed even at low temper…

Thickness identification of atomically thin InSe nanoflakes on SiO2/Si substrates by optical contrast analysis

Abstract Single layers of chalcogenide semiconductors have demonstrated to exhibit tunable properties that can be exploited for new field-effect transistors and photonic devices. Among these semiconductors, indium selenide (InSe) is attractive for applications due to its direct bandgap in the near infrared, controllable p- and n-type doping and high chemical stability. For its fundamental study and the development of practical applications, rapid and accurate identification methods of atomically thin nanosheets are essential. Here, we employ a transfer matrix approach to numerically calculate the optical contrast between thin InSe flakes and commonly used SiO2/Si substrates, which nicely re…

Electronic structure of p-type ultraviolet-transparent conducting CuScO2 films

Abstract We investigate the electronic structure of CuScO 2 thin films grown on sapphire and mica substrates by pulsed laser deposition. X-ray diffraction and microanalysis confirm that the films have the expected delafossite crystal structure and stoichiometric proportions. The electronic structure is investigated by means of X-ray and ultraviolet photoelectron spectroscopy. Electronic states in the range 0–1350 eV are identified, making reference to theoretical density-of-states calculations up to 80 eV. Photoelectron spectra near the Fermi energy confirm the p-character of the films. Optical absorption spectroscopy shows that the films are transparent up to 3.7 eV and exhibit an intense …

Orbital origin and matrix element effects in the Ag/Si(111)-()R30° Fermi surface

The Fermi surface (FS) of the Ag/Si(1 1 1)-3×3 reconstruction with an excess of Ag has been mapped by angle resolved photoemission spectroscopy with polarized light in a wide region of the reciprocal space and with different detection geometries. In contrast to previous results, a strong polarization dependence is observed. Applying the dipole selection rules, it is found that the surface state at the Fermi level, S1 state, has odd symmetry with respect to the mirror plane of the honeycomb-chained triangle structure, indicating that it is mainly derived from Ag 5px and 5py orbitals. This conclusion is revised in the new frame of a inequivalent-triangle structure for the Ag/Si(1 1 1)-3×3 at …

Growth and characterization of self-assembled Cd1−xMgxO (0 ≤ x ≤ 1) nanoparticles on r-sapphire substrates

In this work, the growth of isolated Cd1−xMgxO nanoparticles on r-sapphire substrates is extended to the entire range of Mg content (0 ≤ x ≤ 1) using the spray pyrolysis method. The sizes of the Cd1−xMgxO nanoparticles were in the ranges 4–6 nm and 15–30 nm (with a nanoparticle density of 1010 cm−2). The composition of the nanoparticles was determined using transmission electron microscopy energy dispersive X-ray analysis (TEM-EDAX), while the compound formation was confirmed using X-ray photoelectron spectroscopy. A systematic decrease in the a lattice parameter of Cd1−xMgxO on increasing the Mg content substantiated the successful incorporation of Mg2+ ions into the cubic CdO lattice. Sin…

Influence of the pH on the synthesis of reduced graphene oxide under hydrothermal conditions

Here we describe the important role played by the pH on the morphology and structure of the reduced graphite oxide (rGO) samples obtained by hydrothermal treatment of the previously prepared GO. The nature of the resulting samples has been studied on the basis of a complete battery of experimental techniques.

Influence of the preparative route on the properties of WOx–ZrO2 catalysts: A detailed structural, spectroscopic, and catalytic study

Abstract Two series of tungstated zirconia (WZ) solid acids covering a wide range of tungsten surface densities ( δ, W at/nm2 ) were prepared by nonconventional impregnation and coprecipitation routes, leading to samples with enhanced surface area ( ∼ 70 – 120 m 2 / g ) on annealing at 973–1073 K. The materials were thoroughly characterized by N2 physisorption , XRD, Raman, XPS, H 2-TPR, and DR UV–vis spectroscopy. The catalytic behavior of the Pt-promoted WZ catalysts (1 wt% Pt) was evaluated for the hydroconversion of n-hexadecane used as model feed representative of Fischer–Tropsch waxes. Both series of catalysts displayed a pronounced maximum in the reaction rate and a minimum in the se…

Role ofp-dands-dinteractions in the electronic structure and band gap of Zn1−xMxO (M=Cr, Mn, Fe, Co, Ni, and Cu): Photoelectron and optical spectroscopy and first-principles band structure calculations

We report an investigation on the effect of $p$-$d$ and $s$-$d$ interactions in the electronic structure, and especially in the band-gap value, of wurtzite wide-gap diluted magnetic semiconductors Zn${}_{1\ensuremath{-}x}$${M}_{x}$O ($M=\mathrm{Cr}$, Mn, Fe, Co, Ni, Cu). Thin films prepared by pulsed laser deposition are investigated by means of optical absorption at low-temperature and photoelectron spectroscopy. Pure wurzite phase is shown to be maintained for Co and Mn concentrations up to 25$%$ and for Cr up to 10$%$, while in the case of Fe, Ni, and Cu, other phases are present for concentrations higher than 5, 2, and 1$%$, respectively. The band gap of the Zn${}_{1\ensuremath{-}x}$${M…

Quantum-well states in ultrathin Ag(111) films deposited onto H-passivated Si(111)-(1x1) surfaces

Ag(111) films were deposited at room temperature onto H-passivated Si(111)-(1x1) substrates, and subsequently annealed at 300 C. An abrupt non-reactive Ag/Si interface is formed, and very uniform non-strained Ag(111) films of 6-12 monolayers have been grown. Angle resolved photoemission spectroscopy has been used to study the valence band electronic properties of these films. Well-defined Ag sp quantum-well states (QWS) have been observed at discrete energies between 0.5-2eV below the Fermi level, and their dispersions have been measured along the GammaK, GammaMM'and GammaL symmetry directions. QWS show a parabolic bidimensional dispersion, with in-plane effective mass of 0.38-0.50mo, along…

Formation of Si/SiO2 Luminescent Quantum Dots From Mesoporous Silicon by Sodium Tetraborate/Citric Acid Oxidation Treatment

We propose a rapid, one-pot method to generate photoluminescent (PL) mesoporous silicon nanoparticles (PSiNPs). Typically, mesoporous silicon (meso-PSi) films, obtained by electrochemical etching of monocrystalline silicon substrates, do not display strong PL because the silicon nanocrystals (nc-Si) in the skeleton are generally too large to display quantum confinement effects. Here we describe an improved approach to form photoluminescent PSiNPs from meso-PSi by partial oxidation in aqueous sodium borate (borax) solutions. The borax solution acts to simultaneously oxidize the nc-Si surface and to partially dissolve the oxide product. This results in reduction of the size of the nc-Si core …

Self-assembled MgxZn1−xO quantum dots (0 ≤ x ≤ 1) on different substrates using spray pyrolysis methodology

By using the spray pyrolysis methodology in its classical configuration we have grown self-assembled MgxZn1−xO quantum dots (size [similar]4–6 nm) in the overall range of compositions 0 ≤ x ≤ 1 on c-sapphire, Si (100) and quartz substrates. Composition of the quantum dots was determined by means of transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDAX) and X-ray photoelectron spectroscopy. Selected area electron diffraction reveals the growth of single phase hexagonal MgxZn1−xO quantum dots with composition 0 ≤ x ≤ 0.32 by using a nominal concentration of Mg in the range 0 to 45%. Onset of Mg concentration about 50% (nominal) forces the hexagonal lattice to undergo a p…

Improving Long Term Stability of Pure Formamidinium Perovskite Solar Cells by Ambient Air Additive Assisted Fabrication

Nanoscale strain-engineering and optics of quantum emitters in a two-dimensional semiconductor

We present deterministic fabrication of a two-dimensional lattice of quantum emitters in an atomically thin semiconductor. Resonant laser spectroscopy of these emitters reveals localized exciton states that exhibit stable, bright and high-purity single photon emission.

Tin-related double acceptors in gallium selenide single crystals

Gallium selenide single crystals doped with different amounts of tin are studied through resistivity and Hall effect measurements in the temperature range from 30 to 700 K. At low doping concentration tin is shown to behave as a double acceptor impurity in gallium selenide with ionization energies of 155 and 310 meV. At higher doping concentration tin also introduces deep donor levels, but the material remains p-type in the whole studied range of tin doping concentrations. The deep character of donors in gallium selenide is discussed by comparison of its conduction band structure to that of indium selenide under pressure. The double acceptor center is proposed to be a tin atom in interlayer…

Optical and electronic properties of 2H−MoS2 under pressure: Revealing the spin-polarized nature of bulk electronic bands

Monolayers of transition-metal dichalcogenide semiconductors present spin-valley locked electronic bands, a property with applications in valleytronics and spintronics that is usually believed to be absent in their centrosymmetric (as the bilayer or bulk) counterparts. Here we show that bulk $2\mathrm{H}\text{\ensuremath{-}}\mathrm{Mo}{\mathrm{S}}_{2}$ hides a spin-polarized nature of states determining its direct band gap, with the spin sequence of valence and conduction bands expected for its single layer. This relevant finding is attained by investigating the behavior of the binding energy of $A$ and $B$ excitons under high pressure, by means of absorption measurements and density-functi…

In Situ Synthesis of Conducting Polymers: A Novel Approach toward Polymer Thermoelectrics

The efficient conversion of thermal energy into electricity by means of durable and scalable solid-state thermoelectric devices has been a well stablished aim. Electrically conducting polymers have...

Ultrapure laser-synthesized Si nanoparticles with variable oxidation states for biomedical applications

We employ a method of femtosecond laser fragmentation of preliminarily prepared water-dispersed microcolloids to fabricate aqueous solutions of ultrapure bare Si-based nanoparticles (Si-NPs) and assess their potential for biomedical applications. The nanoparticles appear spherical in shape, with low size dispersion and a controllable mean size, from a few nm to several tens of nm, while a negative surface charge (−35 mV ± 0.10 according to z-potential data) provides good electrostatic stabilization of colloidal Si-NP solutions. Structural analysis shows that the Si-NPs are composed of Si nanocrystals with inclusions of silicon oxide species, covered by a SiOx (1 < x < 2) shell, while the to…

Charge Transport in Trap-Sensitized Infrared PbS Quantum-Dot-Based Photoconductors: Pros and Cons

Control of quantum-dot (QD) surface chemistry offers a direct approach for the tuning of charge-carrier dynamics in photoconductors based on strongly coupled QD solids. We investigate the effects of altering the surface chemistry of PbS QDs in such QD solids via ligand exchange using 3-mercaptopropionic acid (MPA) and tetrabutylammonium iodide (TBAI). The roll-to-roll compatible doctor-blade technique was used for the fabrication of the QD solid films as the photoactive component in photoconductors and field-effect phototransistors. The ligand exchange of the QD solid film with MPA yields superior device performance with higher photosensitivity and detectivity, which is due to less dark cur…

Self-Assembled Zinc Oxide Quantum Dots Using Spray Pyrolysis Methodology

Self-assembled ZnO quantum dots (QDs) have been obtained on different substrates by using the atmospheric spray pyrolysis methodology under well-defined growth conditions. The evolution of size and...

In Situ Synthesis of Polythiophene and Silver Nanoparticles within a PMMA Matrix: A Nanocomposite Approach to Thermoelectrics

The processability of organic thermoelectric materials plays a crucial role due to their clear advantages of applicability in large-scale areas compared to traditional inorganic counterparts. A promising way to process thermoelectric materials based on conductive polymers is through in situ polymerization in an insulating polymer matrix. This work shows an interpenetrating polymeric network based on polythiophene, silver nanoparticles (Ag NPs), and poly(methyl methacrylate) (PMMA) produced by the oxidative polymerization of terthiophene by an oxidizing silver salt in a PMMA matrix. Ag NPs are in situ synthesized simultaneously as a byproduct. The reaction occurs very fast in the solid state…

Quantum size confinement in gallium selenide nanosheets: band gap tunability versus stability limitation

Abstract Gallium selenide is one of the most promising candidates to extend the window of band gap values provided by existing two-dimensional semiconductors deep into the visible potentially reaching the ultraviolet. However, the tunability of its band gap by means of quantum confinement effects is still unknown, probably due to poor nanosheet stability. Here, we demonstrate that the optical band gap band of GaSe nanosheets can be tuned by ∼120 meV from bulk to 8 nm thick. The luminescent response of very thin nanosheets (&lt;8 nm) is strongly quenched due to early oxidation. Oxidation favors the emergence of sharp material nanospikes at the surface attributable to strain relaxation. Simul…

Gas-phase selective oxidation of chloro- and methoxy-substituted toluenes on TiO2–Sepiolite supported vanadium oxides

Abstract Catalytic behaviour of vanadium oxide systems (5–20 wt.% V2O5) supported on TiO2–Sepiolite (with titania loading around the theoretical monolayer, 12 wt.%, 12Ti–Sep) and, as reference, on Sepiolite calcined (Sepc) in the p-substituted toluene derivatives selective oxidation was studied. In all the catalysts studied p-chloro (p-ClBA) and p-methoxybenzaldehyde (p-MeOBA) were the main products. The yields to benzaldehydes obtained with %V/12Ti–Sep are comparable with some of those reported in the literature under similar kinetically controlled experimental conditions (Sp-ClBA = 70% and X = 19% were obtained at 653 K on 20 V/12Ti–Sep). The activity for benzaldehyde derivatives formatio…

Enhanced H2O2 production over Au-rich bimetallic Au-Pd nanoparticles on ordered mesoporous carbons

1 figures, 3 tables.-- © 2014. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/

Layered double hydroxide (LDH)–organic hybrids as precursors for low-temperature chemical synthesis of carbon nanoforms

A low-temperature route for the chemical synthesis of diverse carbon nanoforms, including nano-onions and multi-walled nanotubes, is described. The method involves thermal decomposition of a sebacate-intercalated NiFe LDH at 400 °C and benefits from the catalytic activity of FeNi3 nanoparticles generated in situ.

Two-Dimensional Indium Selenide for Sulphur Vapour Sensing Applications

Surface-to-volume ratio in two-dimensional (2D) materials highlights among their characteristics as an inherent and intrinsic advantage taking into account their strong sensitivity to surface effects. For this reason, we have proposed in this work micromechanically exfoliated 2D nanosheets of InSe as an optical vapour sensor. As a proof of concept, we used 2-mercaptoethanol as the chemical analyte in vapour phase to monitor the change of the InSe photoluminescence (PL) before and after exposure to the analyte. For short vapour exposure times (at low analyte concentration), we found a PL enhancement of InSe nanosheets attributed to the surface localization of Se defects. For long vapour expo…

Transport properties of nitrogen doped p‐gallium selenide single crystals

Nitrogen doped gallium selenide single crystals are studied through Hall effect and photoluminescence measurements in the temperature ranges from 150 to 700 K and from 30 to 45 K, respectively. The doping effect of nitrogen is established and room temperature resistivities as low as 20 Ω cm are measured. The temperature dependence of the hole concentration can be explained through a single acceptor‐single donor model, the acceptor ionization energy being 210 meV, with a very low compensation rate. The high quality of nitrogen doped GaSe single crystals is confirmed by photoluminescence spectra exhibiting only exciton related peaks. Two phonon scattering mechanisms must be considered in orde…

Optical and dielectric properties of MoO 3 nanosheets for van der Waals heterostructures

Two-dimensional (2D) insulators are a key element in the design and fabrication of van der Waals heterostructures. They are vital as transparent dielectric spacers whose thickness can influence both the photonic, electronic, and optoelectronic properties of 2D devices. Simultaneously, they provide protection of the active layers in the heterostructure. For these critical roles, hexagonal Boron Nitride (hBN) is the dominant choice due to its large bandgap, atomic flatness, low defect density, and encapsulation properties. However, the broad catalogue of 2D insulators offers exciting opportunities to replace hBN in certain applications that require transparent thin layers with additional opti…

Enhanced optical response of InSe nanosheet devices decorated with CsPbX3 (X = I, Br) perovskite nanocrystals

Abstract The combination of several two-dimensional materials opens the door for the creation of cooperative nanodevices with functionalities that complement to each other and even compensate the weaknesses of the individual components. Two-dimensional indium selenide (InSe) shows one of the largest tunability bandgap found in two-dimensional materials with application in optoelectronics. However, the intrinsic out-of-plane luminescent dipolar nature limits its implementation in devices operating in vertical configuration. All-inorganic CsPbX3 (X = Br, I) cubic nanoparticles offer high absorption and emission quantum yields and great integrability with two-dimensional materials. Combining t…

Photoelectron lifetime determination of Ag(1 1 1) films at the Fermi surface

The electronic properties of 10 monolayers Ag(111) films deposited onto Si(111)-7 x 7 substrates at room temperature have been studied by scanning the photoelectron intensity at the Fermi level in different symmetry directions. The main features observed in these profiles correspond to Lorentzian-like peaks produced by the pass of the sp band through the Fermi level. A simple model has been developed, which connects the photoemission peak linewidth with the lifetime of photoelectrons excited from the Fermi level. The obtained inverse photoelectron lifetime values have been found to be in excellent agreement with the typical values of the Ag single crystals. These results support the fact th…

Femtosecond laser fragmentation from water-dispersed microcolloids: toward fast controllable growth of ultrapure Si-based nanomaterials for biological applications

International audience; An ultrashort laser-assisted method for fast production of concentrated aqueous solutions of ultrapure Si-based colloidal nanoparticles is reported. The method profits from the 3D geometry of femtosecond laser ablation of water-dispersed microscale colloids, prepared preliminarily by the mechanical milling of a Si wafer, in order to avoid strong concentration gradients in the ablated material and provide similar conditions of nanocluster growth within a relatively large laser caustics volume. We demonstrate the possibility for the fast synthesis of non-aggregated, low-size-dispersed, crystalline Si-based nanoparticles, whose size and surface oxidation can be controll…

In-situ synthesis of thiophene-based multifunctional polymeric networks with tunable conductivity and high photolithographic performance

Abstract Design of novel multifunctional polymeric materials combining electrically conducting properties with patterning capability is a significant challenge in materials science. Herein, we report on the synthesis of multifunctional interpenetrating polymer networks (IPN) by the in-situ oxidative polymerization of thiophene-based monomers with Cu(ClO 4 ) 2 inside a novolac-based photoresist. The resulting IPNs show conductivities up to 20 S/cm depending on the monomer properties. Among them, 3,3‴-Dihexyl-2,2’:5′,2’’:5″,2‴-quaterthiophene (DH4T) is chosen because it has the largest conjugation length and excellent solubility in organic solvents. Moreover, it renders a low percolation thre…

Atrane complexes chemistry as a tool for obtaining trimodal UVM-7-like porous silica

[EN] The use of atrane complexes as hydrolytic precursors enables the homogeneous incorporation of manganese (25Si/Mn48) throughout the porous walls of the nanoparticles of a surfactant-templated bimodal mesoporous silica (UVM-7). The subsequent leaching of the manganese nanodomains allows adding controlled microporosity to the host silica framework. The resulting final silica material presents three pore systems structured at different length scales: interparticle textural-type macroporosity (ca. 43.2nm), ordered intraparticle mesoporosity (ca. 2.63nm; after template removal), and well-dispersed microporosity (< 2nm; as consequence of the lixiviation of the Mn-rich domains). The good dispe…

Correlation between optical and transport properties of Ga-doped ZnO thin films prepared by pulsed laser deposition

Abstract In this paper we report on the correlation between the transport and optical properties of Ga-doped ZnO films epitaxially grown on C-oriented sapphire substrates by means of pulsed laser deposition. Thin films with electron concentrations ranging between 10 20 and 10 21  cm −3 were prepared from targets containing 0.25–5 at.% Ga. The Ga content in the thin films was estimated by XPS, from the ratio between the intensities of the 2p peaks of Ga and Zn. The electron concentration in the films is very close to the Ga content for films prepared from low Ga content targets even at high deposition temperature. For Ga contents in the target larger than 1%, the Ga content in the films incr…

Extrinsic Effects on the Optical Properties of Surface Color Defects Generated in Hexagonal Boron Nitride Nanosheets

Hexagonal boron nitride (hBN) is a wide-band gap van der Waals material able to host light-emitting centers behaving as single photon sources. Here, we report the generation of color defects in hBN nanosheets dispersed on different kinds of substrates by thermal treatment processes. The optical properties of these defects have been studied using microspectroscopy techniques and far-field simulations of their light emission. Using these techniques, we have found that subsequent ozone treatments of the deposited hBN nanosheets improve the optical emission properties of created defects, as revealed by their zero-phonon linewidth narrowing and reduction of background emission. Microlocalized co…

Buildup and structure of theInSe∕Ptinterface studied by angle-resolved photoemission and x-ray absorption spectroscopy

The atomic structure and the electronic nature of the $\mathrm{In}\mathrm{Se}∕\mathrm{Pt}$ interface have been studied by x-ray absorption spectroscopy and angle-resolved photoemission, respectively. By these measurements, it has been found that Pt atoms equally incorporate into two trigonal-prismatic intralayer positions existing within the InSe layer, although, at low Pt coverage, Pt atoms seem to prefer one of these sites, where they have a lower interaction with Se atoms. The atomic structure of the $\mathrm{In}\mathrm{Se}∕\mathrm{Pt}$ interface appears to determine its electronic behavior as Pt deposition increases. At initial stages of Pt diffusion, isolated Pt atoms act as a surface …

Out-of-plane orientation of luminescent excitons in two-dimensional indium selenide.

Van der Waals materials offer a wide range of atomic layers with unique properties that can be easily combined to engineer novel electronic and photonic devices. A missing ingredient of the van der Waals platform is a two-dimensional crystal with naturally occurring out-of-plane luminescent dipole orientation. Here we measure the far-field photoluminescence intensity distribution of bulk InSe and two-dimensional InSe, WSe2 and MoSe2. We demonstrate, with the support of ab-initio calculations, that layered InSe flakes sustain luminescent excitons with an intrinsic out-of-plane orientation, in contrast with the in-plane orientation of dipoles we find in two-dimensional WSe2 and MoSe2 at room-…

CCDC 929061: Experimental Crystal Structure Determination

Related Article: Zulema Arcís-Castillo, Francisco J. Muñoz-Lara, M. Carmen Muñoz, Daniel Aravena, Ana B. Gaspar, Juan F. Sánchez-Royo, Eliseo Ruiz, Masaaki Ohba, Ryotaro Matsuda, Susumu Kitagawa, and José A. Real|2013|Inorg.Chem.|52|12777|doi:10.1021/ic4020477