Experimental and theoretical study of band structure of InSe andIn1−xGaxSe(x<0.2)under high pressure: Direct to indirect crossovers
This paper reports on the pressure dependence of the absorption edge of indium selenide and ${\mathrm{In}}_{1\ensuremath{-}x}{\mathrm{Ga}}_{x}\mathrm{Se}$ alloys $(xl0.2)$ up to the pressure at which precursor effects of the phase transition prevent further transmission measurements. The absorption edge could be divided into three components exhibiting different pressure coefficients: one corresponding to a direct transition that could be analyzed through the Elliot-Toyozawa theory, and two supplementary edges with quadratic dependence on the photon energy. The first component is attributed to the direct transition at the Z point of the rhombohedral Brillouin zone. One of the quadratic abso…
Study of the Partial Substitution of Pb by Sn in Cs-Pb-Sn-Br Nanocrystals Owing to Obtaining Stable Nanoparticles with Excellent Optical Properties.
Halide perovskites are revolutionizing the photovoltaic and optoelectronic fields with outstanding performances obtained in a remarkably short time. However, two major challenges remain: the long-term stability and the Pb content, due to its toxicity. Despite the great effort carried out to substitute the Pb by a less hazardous element, lead-free perovskite still remains more unstable than lead-containing perovskites and presents lower performance as well. In this work, we demonstrate the colloidal preparation of Cs–Pb–Sn–Br nanoparticles (NPs) where Sn is incorporated up to 18.8%. Significantly, we have demonstrated that the partial substitution of Pb by Sn does not produce a deleterious e…
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…
High Optical Performance of Cyan‐Emissive CsPbBr3 Perovskite Quantum Dots Embedded in Molecular Organogels
This is the pre-peer reviewed version of the following article: High Optical Performance of Cyan‐Emissive CsPbBr3 Perovskite Quantum Dots Embedded in Molecular Organogels, which has been published in final form at https://doi.org/10.1002/adom.202001786. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions." Perovskite quantum dots (PQDs) have fascinating optoelectronic properties, such as high photoluminescence quantum yield (PLQY) for a broad range of materials, and the possibility to obtain different bandgaps with the same material or halide combinations. Nevertheless, blue‐emissive materials generally present…
Polarity Effects on ZnO Films Grown along the Nonpolar[112¯0]Direction
The surface electrical properties of ZnO thin films grown along the nonpolar $[11\overline{2}0]$ direction have been investigated by Kelvin probe microscopy on a nanometer scale. Two different charge domains, with a 75 meV work function difference, coexist within the ZnO surface, which is covered by rhombohedral pyramids whose sidewalls are shown to be ${10\overline{1}1}$-type planes. The presence and relative orientation of the two kinds of charge domains are explained in terms of the atomic arrangement at the ${10\overline{1}1}$ polar surfaces.
Anomální Ramanovy módy v teluridech
[EN] Two anomalous broad bands are usually found in the Raman spectrum of bulk and 2D Te-based chalcogenides, which include binary compounds, like ZnTe, CdTe, HgTe, GaTe, GeTe, SnTe, PbTe, GeTe2, As2Te3, Sb2Te3, Bi2Te3, NiTe2, IrTe2, and TiTe2, as well as ternary compounds, like GaGeTe, SnSb2Te4, SnBi2Te4, and GeSb2Te5. Many different explanations have been proposed in the literature for the origin of the anomalous broad bands in tellurides, usually located between 119 and 145 cm(-1). They have been attributed to the intrinsic Raman modes of the sample, to oxidation of the sample, to the folding of Brillouin-edge modes onto the zone center, to the existence of a double resonance, like that …
Self-assembled metal-oxide nanoparticles on GaAs: infrared absorption enabled by localized surface plasmons
Abstract Metal-oxides hold promise as superior plasmonic materials in the mid-infrared compared to metals, although their integration over established material technologies still remains challenging. We demonstrate localized surface plasmons in self-assembled, hemispherical CdZnO metal-oxide nanoparticles on GaAs, as a route to enhance the absorption in mid-infrared photodetectors. In this system, two localized surface plasmon modes are identified at 5.3 and 2.7 μm, which yield an enhancement of the light intensity in the underlying GaAs. In the case of the long-wavelength mode the enhancement is as large as 100 near the interface, and persists at depths down to 50 nm. We show numerically t…
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…
Numerical study of the growth conditions in an MOCVD reactor: application to the epitaxial growth of HgTe
Abstract In order to analyse the epitaxial growth by metalorganic chemical vapour deposition (MOCVD) of mercury telluride, HgTe, a 2D numerical model has been developed to simulate the gas flow in a horizontal MOCVD reactor. This model takes into account the Navier–Stokes equations coupled with the heat transfer and mass transport of chemical species. For the mathematical resolution of the governing equations a commercial solver, which can be run in a conventional personal computer, has been used. The study carried out presents a discussion about the dominant growth regime in a MOCVD growth as a function of different parameters: substrate temperature, total flow, partial pressure of precurs…
Photoluminescence in ZnO:Co2+ (0.01%–5%) Nanoparticles, Nanowires, Thin Films, and Single Crystals as a Function of Pressure and Temperature: Exploring Electron–Phonon Interactions
This work investigates the electronic structure and photoluminescence properties of Co2+-doped ZnO and their pressure and temperature dependences through high-resolution absorption and emission spe...
A numerical study of thermal conditions in the THM growth of HgTe
A numerical simulation of the travelling heater method (THM) process in the growth of HgTe is carried out. The whole system (furnace, ampoule and charge) is taken into account in the frame of a quasi-steady-state model. The mass conservation condition for the solute in the liquid zone permits the determination of the rate of advance of the crystallisation isotherm as a function of the heater position. We claim to study the evolution of different magnitudes along the growth process, searching for the physical reasons which could be at the origin of defects in the form of thin layers observed in some growing experiences. To solve the governing equations of fluid flow, heat transfer and mass t…
Induced crystallographic changes in Cd1−xZnxO films grown on r-sapphire by AP-MOCVD: the effects of the Zn content when x ≤ 0.5
High-resolution X-ray diffraction, scanning electron microscopy and transmission electron microscopy techniques were used to investigate, as a function of the nominal Zn content in the range of 0–50%, the out-of-plane and in-plane crystallographic characteristics of Cd1−xZnxO films grown on r-plane sapphire substrates via atmospheric pressure metal–organic chemical vapor deposition. The study is conducted to search for knowledge relating to the structural details during the transition process from a rock-salt to a wurtzite structure as the Zn content increases in this CdO–ZnO system. It has been found that it is possible to obtain films exhibiting a single (001) cubic orientation with good …
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…
Hybrid multiple diffraction in semipolar wurtzite materials: (\bf 01\overline{1}2)-oriented ZnMgO/ZnO heterostructures as an illustration
X-ray diffraction has been widely used to characterize the structural properties (strain and structural quality) of semiconductor heterostructures. This work employs hybrid multiple diffraction to analyzer-oriented Zn1−xMgxO layers grown by molecular beam epitaxy on ZnO substrates. In such a low-symmetry material system, additional features appear in symmetric reflection scans, which are described as arising from hybrid multiple diffraction. First, the Bragg conditions necessary for these high-order processes to occur are introduced and applied to explain all the observed satellite reflections, identify the planes that contribute and computea priorithe angles at which they are observed. Fur…
A Controllable and Highly Propagative Hybrid Surface Plasmon-Phonon Polariton in a CdZnO-based Two-Interface System
The development of new nanophotonic devices requires the understanding and modulation of the propagating surface plasmon and phonon modes arising in plasmonic and polar dielectric materials, respectively. Here we explore the CdZnO alloy as a plasmonic material, with a tunable plasma frequency and reduced losses compared to pure CdO. By means of attenuated total reflectance, we experimentally observe the hybridization of the surface plasmon polariton (SPP) with the surface phonon polariton (SPhP) in the air-CdZnO-sapphire three-layer system. We show how through the precise control of the CdZnO thickness, the resonance frequencies of the hybrid surface plasmon-phonon polariton (SPPP) are tune…
Crystal Growth of HgSe by the Cold Travelling Heater Method
We report on the low-temperature synthesis and growth of HgSe crystals making use of the cold travelling heater method. Ingots so obtained are analyzed by means of scanning microscopy, including EDAX and backscattered electron modes, and X-ray diffraction techniques.
Quenching and blue shift of UV emission intensity of hydrothermally grown ZnO:Mn nanorods
Abstract ZnO:Mn alloyed nanorods (Mn nominal concentration – 3–5 wt%) were synthesized by using hydrothermal process at an optimized growth temperature of 200 °C and a growth time of 3 h. The XRD, SEM and Raman, FTIR investigations reveal that ZnO:Mn (Mn – 3–5 wt%) retained hexagonal wurtzite crystal structure with nanorod morphology. The HRTEM and SAED analysis confirm the single crystalline nature of hydrothermally grown ZnO and ZnO:Mn (5 wt%) nanorods. The ZnO:Mn nanorods (Mn – 0–5 wt%) displayed optical band gap in the range 3.23–3.28 eV. The blue shift of UV emission peak (PL) from 393 (ZnO) to 386 nm and quenching of photoluminescence emission in ZnO:Mn is due to the Mn incorporation …
Structural and morphological characterization of the Cd-rich region in Cd1-xZnxO thin films grown by atmospheric pressure metal organic chemical vapour deposition
Abstract We have analysed the growth, morphological and structural characterization of Cd1-xZnxO thin films grown on r-sapphire substrates by atmospheric pressure metal organic chemical vapour deposition, mainly focusing on the Cd-rich rock-salt phase for its promising optical and technological applications. The evolution of the surface morphology and crystalline properties as a function of Zn content has been studied by means of high resolution x-ray diffraction and electron microscopy techniques. Monocrystalline (002) single-phase cubic films were obtained with Zn contents up to 10.4%, and with a low density of dislocations as a consequence of the optimized crystal growth process. Particu…
Thermal Creation of Defects in GaTe
Photoluminescence spectra of as-grown and annealed GaTe single crystals in the 0.7–1.8 eV range have been analyzed at different temperatures. Annealing up to 200 °C produces an increase in the recombination intensity of an excitonic characteristic. The annealing at 400 °C generates an intense optically active recombination in the infrared region (0.76 eV). The thermal generation of defects is possible, owing to the low melting temperature of GaTe (800 °C).
Engineering Sr-doping for enabling long-term stable FAPb1xSrxI3 quantum dots with 100% photoluminescence quantum yield
The Pb substitution in quantum dots (PQDs) with lesser toxic metals has been widely searched to be environmentally friendly, and be of comparable or improved performance compared to the lead-perovskite. However, the chemical nature of the lead substitute influences the incorporation mechanism into PQDs, which has not been explored in depth. In this work, we analyzed Sr-doping-induced changes in FAPbI3 perovskites by studying the optical, structural properties and chemical environment of FAPb1−xSrxI3 PQDs. The substitution of Pb by 7 at% Sr allows us to achieve FAPb1−xSrxI3 PQDs with 100% PLQY, high stability for 8 months under a relative humidity of 40–50%, and T80 = 6.5 m…
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...
Band structure of indium selenide investigated by intrinsic photoluminescence under high pressure
This paper reports on photoluminescence experiments in $n$-type indium selenide $(T=300\phantom{\rule{0.3em}{0ex}}\mathrm{K})$ under hydrostatic pressure up to 7 GPa at low and high excitation densities. Photoluminescence measurements at low excitation density exhibit a broad band around the energy of the direct band gap of $\mathrm{InSe}$ and with the same pressure dependence. The reversible increase of its linewidth above $1\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ is associated to a direct-to-indirect band-gap crossover between valence band maxima. The reversible decrease of its intensity above $4\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ is interpreted as evidence of a direct-to-indirect b…
Growth of ZnO crystals by vapour transport: Some ways to act on physical properties
Nowadays, the growth of ZnO by vapor transport in silica ampoules is generally made in presence of graphite. As it has been already shown, this means that the growth process is carried out in presence of a Zn excess. In order to control that and act, as a consequence, on the physical properties of crystals we have performed a systematic study of the growth process in a wide range of Zn excess compositions using well defined experimental conditions. As a preliminary characterization, optical absorption and electrical properties have been analyzed at room temperature. The results show how some physical properties of as-grown ZnO crystals can be changed in a controlled way by an adequate combi…
Growth and characterization of Mg 1‐x Cd x O thin films
In this paper, we study the growth of thin films of the Mg1–xCdxO alloy in the Mg-rich range of compositions by using the metal organic chemical vapour deposition (MOCVD) method at low pressure. X-ray diffraction (XRD) has been used to analyse the compound formation and the progressive incorporation of Cd2+ ions into the cubic MgO lattice. Both, layers with a single-cubic phase of Mg1–xCdxO and layers with a phase separation, where Cd1–xMgxO and Mg1–xCdxO coexist, have been studied. Finally, a morphological study of the layers has been carried out by using scanning electron microscopy (SEM) and the layers' composition has been measured by energy dispersive X-ray analysis (EDX). (© 2016 WILE…
MOCVD growth of CdTe on glass: analysis of in situ post-growth annealing
Abstract In this paper, we analyse the growth by MOCVD of CdTe on glass substrates using in situ post-growth annealing. First, in order to perform a systematic study, polycrystalline layers of CdTe were deposited by MOCVD on glass substrates. The structure and morphology of the layers was investigated as a function of different growth parameters, temperature, VI/II precursor molar ratio and substrate position on the susceptor. An activation energy of Ek=20.7 kcal/mol was obtained from the experimental data. In order to better understand the process and the effects of different growth parameters, a numerical model that simulated the gas flow in the reactor, was developed. Secondly we analyse…
Phase segregation in Mg$_{x}$Zn$_{1-x}$O probed by optical absorption and photoluminescence at high pressure
The appearance of segregated wurtzite Mg$_x$Zn$_{1-x}$O with low Mg content in thin films with $x>0.3$ affected by phase separation, cannot be reliably probed with crystallographic techniques owing to its embedded nanocrystalline configuration. Here we show a high-pressure approach which exploits the distinctive behaviors under pressure of wurtzite Mg$_x$Zn$_{1-x}$O thin films with different Mg contents to unveil phase segregation for $x>0.3$. By using ambient conditions photoluminescence (PL), and with optical absorption and PL under high pressure for $x=0.3$ we show that the appearance of a segregated wurtzite phase with a magnesium content of x $\sim$ 0.1 is inherent to the wurtzit…
Growth of tin oxide thin films composed of nanoparticles on hydrophilic and hydrophobic glass substrates by spray pyrolysis technique
Abstract In this paper, we have demonstrated the growth of tin oxide (SnO 2 ) thin films composed of nanoparticles on hydrophobic (siliconized) and hydrophilic (non-siliconized) glass substrates by using the spray pyrolysis technique. X-ray diffraction (XRD) analysis confirmed the formation of SnO 2 thin films with tetragonal rutile-phase structure. Average particle size of nanoparticles was determined to be in the range of 3–4 nm measured from the front view images obtained by a field emission gun scanning electron microscope (FESEM), while the size of nanoparticle clusters, when present, were in the range of 11–20 nm. Surface morphology of SnO 2 films grown over hydrophobic substrates rev…
Morphology and Band Structure of Orthorhombic PbS Nanoplatelets: An Indirect Band Gap Material
PbS quantum dots and nanoplatelets (NPLs) are of enormous interest in the development of optoelectronic devices. However, some important aspects of their nature remain unclear. Recent studies have revealed that colloidal PbS NPLs may depart from the rock-salt crystal structure of bulk and form an orthorhombic (Pnma) modification instead. To gain insight into the implications of such a change over the optoelectronic properties, we have synthesized orthorhombic PbS NPLs and determined the lattice parameters by means of selected area electron diffraction measurements. We have then calculated the associated band structure using density functional theory with Perdew–Burke–Ernzerhof functional fo…
Controlling the Phase Segregation in Mixed Halide Perovskites through Nanocrystal Size
Mixed halide perovskites are one of the promising candidates in developing solar cells and light-emitting diodes (LEDs), among other applications, because of their tunable optical properties. Nonetheless, photoinduced phase segregation, by formation of segregated Br-rich and I-rich domains, limits the overall applicability. We tracked the phase segregation with increasing crystalline size of CsPbBr3–xIx and their photoluminescence under continuous-wave laser irradiation (405 nm, 10 mW cm–2) and observed the occurrence of the phase segregation from the threshold size of 46 ± 7 nm. These results have an outstanding agreement with the diffusion length (45.8 nm) calculated also experimentally f…
Unravelling the Photocatalytic Behavior of All-Inorganic Mixed Halide Perovskites: The Role of Surface Chemical States
Within the most mesmerizing materials in the world of optoelectronics, mixed halide perovskites (MHPs) have been distinguished because of the tunability of their optoelectronic properties, balancing both the light-harvesting efficiency and the charge extraction into highly efficient solar devices. This feature has drawn the attention of analogous hot topics as photocatalysis for carrying out more efficiently the degradation of organic compounds. However, the photo-oxidation ability of perovskite depends not only on its excellent light-harvesting properties but also on the surface chemical environment provided during its synthesis. Accordingly, we studied the role of surface chemical states …
ZnO films grown by MOCVD on GaAs substrates: Effects of a Zn buffer deposition on interface, structural and morphological properties
Abstract Integration of ZnO with the well-developed GaAs technology presents several aspects that need to be previously analyzed and considered. The large lattice mismatch between ZnO and GaAs and its different crystallographic structure lead to many structural defects. In addition, their potential chemical reactivity is another source of complexity and an academic challenge. Recently some interesting contributions on this subject have been carried out by Liu and co-workers. As an additional step to the knowledge of the ZnO/GaAs heterostructure, we have deepened on the study of the morphology and orientation of ZnO thin films grown by atmospheric pressure metal-organic chemical vapour depos…