MOCVD growth of CdO very thin films: Problems and ways of solution

Abstract In this paper the growth of CdO by the MOCVD technique at atmospheric pressure has been studied in order to achieve very thin films of this material on r-sapphire substrates. The growth evolution of these films was discussed and the existence of a threshold thickness, below which island-shaped structures appear, was demonstrated. Some alternatives to reduce this threshold thickness have been proposed in the frame of the analysis of the crystal growth process. The morphology and structural properties of the films were analyzed by means of SEM and HRXRD. High-quality flat CdO samples were achieved with thicknesses up to 20 nm, which is five times thinner than the values previously re…

Crystal growth of Hg1−xMnxSe for infrared detection

In this work, we report on the successfully growing Hg"1"-"xMn"xSe bulk crystals using a mixed, travelling heater method and Bridgman method, two-step procedure. Firstly, and with the aim of reducing Hg high pressure related to the high temperature synthesis reaction between the components in elemental form, HgSe crystals were synthesized and grown by the cold travelling heater method. Secondly, previously sublimated Mn and Se were incorporated to complete the desired composition. Then, the Bridgman growth was carried out by heating the alloy at a temperature of about 880^oC and lowering it at rate of 1mm/h through a gradient of 25^oC/cm. The Hg"1"-"xMn"xSe crystals were characterized by sc…

Formation and Rupture of Schottky Nanocontacts on ZnO Nanocolumns

In this paper, the electrical transport and mechanical properties of Pt/ZnO Schottky nanocontacts have been studied simultaneously during the formation and rupture of the nanocontacts. By combining multidimensional conducting scanning force spectroscopy with appropriated data processing, the physical relevant parameters (the ideality factor, the Schottky barrier height, and the rupture voltage) are obtained. It has been found that the transport curves strongly depend on the loading force. For loading forces higher than a threshold value, the transport characteristics are similar to those of large-area Schottky contact, while below this threshold deviations from strictly thermionic emission …

Preferred Growth Direction by PbS Nanoplatelets Preserves Perovskite Infrared Light Harvesting for Stable, Reproducible, and Efficient Solar Cells

Formamidinium-based perovskite solar cells (PSCs) present the maximum theoretical efficiency of the lead perovskite family. However, formamidinium perovskite exhibits significant degradation in air. The surface chemistry of PbS has been used to improve the formamidinium black phase stability. Here, the use of PbS nanoplatelets with (100) preferential crystal orientation is reported, to potentiate the repercussion on the crystal growth of perovskite grains and to improve the stability of the material and consequently of the solar cells. As a result, a vertical growth of perovskite grains, a stable current density of 23 mA cm(-2), and a stable incident photon to current efficiency in the infr…

Recombination processes in unintentionally doped GaTe single crystals

Emission spectra of GaTe single crystals in the range of 1.90–1.38 eV have been analyzed at different temperatures and excitation intensities by photoluminescence, photoluminescence excitation, and selective photoluminescence. A decrease in band gap energy with an increase in temperature was obtained from the redshift of the free exciton recombination peak. The energy of longitudinal optical phonons was found to be 14±1 meV. A value of 1.796±0.001 eV for the band gap at 10 K was determined, and the bound exciton energy was found to be 18±0.3 meV. The activation energy of the thermal quenching of the main recombination peaks and of the ones relating to the ionization energy of impurities and…

Correlative study of structural and optical properties of ZnSe under severe plastic deformation

The effect of plastic deformation on the optical and structural properties of ZnSe crystals has been investigated. The optical properties have been monitored by cathodoluminescence measurements as a function of the deformation degree. Remarkable differences in the defect-related emissions from the most severely deformed areas have been encountered. Deformation of the crystal lattice of ZnSe, associated with slip phenomena, has been studied by means of Electron Backscattered Diffraction and micro-Raman spectroscopy. The relation between the deformation and the optical properties of the ZnSe crystals has been described.

X‐ray characterization of CdO thin films grown on a ‐, c ‐, r ‐ and m ‐plane sapphire by metalorganic vapour phase‐epitaxy

CdO thin films have been grown on a-plane (110), c-plane (0001), r-plane (012) and m-plane (100) sapphire substrates by metalorganic vapour-phase epitaxy (MOVPE). The effects of different substrate orientations on the structural properties of the films have been analyzed by means of X-ray diffraction, including θ-2θ scans, pole figures and rocking curves. (111), (001) and (110) orientations are found on a-, r-, and m-sapphire respectively, while films deposited on c-plane exhibit an orientation in which no low-index crystal plane is parallel to the sample surface. The recorded pole figures have allowed determining the epitaxial relationships between films and substrates, as well as the pres…

ZnO and Related Materials

Structural characterization of CdTe layers grown on (0001) sapphire by MOCVD

Abstract We report on the growth of CdTe layers directly onto (0 0 0 1) sapphire substrates by MOCVD. The structure and morphology of the layers have been investigated as a function of growth temperature and II/VI precursor molar ratio by X-ray diffraction and scanning electron microscopy. The texture of the samples has revealed the existence of a temperature threshold, with higher growth temperatures resulting on completely (1 1 1) oriented layers. Some of these layers contained microtwins, as indicated by the extra peaks in the {4 2 2} Φ scans, leading to the existence of two different domains. The structural quality of each domain, as well as of the sample as a whole, has been determined…

Crystal growth of ZnO micro and nanostructures by PVT on c-sapphire and amorphous quartz substrates

Abstract ZnO micro and nanostructures in the form of tripods, grains, arrows and wires have been grown at temperatures as low as 500–300  ∘ C by a vapour transport method without catalysis and using a well selected value of the carrier gas flow. A transition state between grains and nanowires is reported being characterized by arrow-like structures which are constituted by a pyramidal head and a tail that is growing from the basal plane of the head. In order to understand the effect of growth conditions on the morphology of micro and nanostructures, an analysis of temperature and species concentration conditions has been carried out. In addition two different kinds of substrates have been u…

Negative U‐properties of the oxygen‐vacancy in ZnO

It is shown that the intensity of the oxygen vacancy (VO) related emission in ZnO at 2.45 eV correlates to the concentration of the donor level E4. E4 is located 530 meV below the conduction band and attributed to the VO0/++ recharging. Deep level transient spectroscopy (DLTS) experiments with optical excitation locate the VO2+/+ level position 140 meV below the conduction band and give evidence for the “negative- U” properties of the oxygen vacancies in ZnO. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

A new approach to the growth of ZnO by vapour transport

The crystal growth of ZnO by vapour transport is classically made in presence of additional species which enhance the growth process. Usually, additional species have been considered as chemical transport agents that promote a typical CVT (Chemical Vapour Transport) process. Recently, we have proposed a new interpretation of the chemical role of some of these species. This new interpretation considers that, in some cases, the additional species promote a partial consumption of the O2 provided by the ZnO decomposition and, consequently, a Zn excess is generated. This excess of Zn pressure activates the ZnO decomposition and the growth rate is enhanced. Among those species, carbon shows an ad…

VIS-UV ZnCdO/ZnO multiple quantum well nanowires and the quantification of Cd diffusion.

International audience; We report on the growth and microstructure analysis of high Cd content ZnCdO/ZnO multiple quantum wells (MQW) within a nanowire. Heterostructures consisting of ten wells with widths from 0.7 to 10nm are demonstrated, and show photoluminescence emissions ranging from 3.03 to 1.97eV. The wells with thicknesses⩽2nm have high radiative efficiencies compared to the thickest ones, consistent with the presence of quantum confinement. However, a nanometric analysis of the Cd profile along the heterostructures shows the presence of Cd diffusion from the ZnCdO well to the ZnO barrier. This phenomenon modifies the band structure and the optical properties of the heterostructure, an…

The role of surface chemical states on the photocatalytic behavior of all-inorganic mixed halide perovskite nanocrystals

Non-radiative recombination centres in catalyst-free ZnO nanorods grown by atmospheric-metal organic chemical vapour deposition

We have investigated the cathodoluminescence (CL) emission and the Raman spectra along individual ZnO nanorods grown by a catalyst-free method. The spatial correlation between the CL emission and the defect related Raman modes permits establishing a correspondence between the non-radiative recombination centres (NRRCs) and the defects responsible for the 275 cm−1 Raman band. According to this relation, the NRRCs in these nanorods are tentatively associated with complexes of zinc interstitials.

Mn2+-induced room-temperature ferromagnetism and spin-glass behavior in hydrothermally grown Mn-doped ZnO nanorods

The magnetic properties of Mn-doped ZnO (ZnO:Mn) nanorods grown by hydrothermal process at a temperature of 200 °C and a growth time of 3 h have been studied. The samples were characterized by using powder X-ray diffraction with Rietveld refinement, scanning electron microscopy, energy-dispersive X-ray analysis and SQUID magnetometry. Mn (3 wt%) and (5 wt%)-doped ZnO samples exhibit paramagnetic and ferromagnetic behavior, respectively, at room temperature. The spin-glass behavior is observed from the samples with respect to the decrease of temperature. At 10 K, both samples exhibit a hysteresis loop with relatively low coercivity. The room-temperature ferromagnetism in 5 wt% Mn-doped ZnO n…

Enhanced UV emission from ZnO nanoflowers synthesized by the hydrothermal process

ZnO nanoflowers were synthesized by the hydrothermal process at an optimized growth temperature of 200 °C and a growth/reaction time of 3 h. As-prepared ZnO nanoflowers were characterized by x-ray diffraction, scanning electron microscopy, UV–visible and Raman spectroscopy. X-ray diffraction and Raman studies reveal that the as-synthesized flower-like ZnO nanostructures are highly crystalline with a hexagonal wurtzite phase preferentially oriented along the plane. The average length (234–347 nm) and diameter (77–106 nm) of the nanorods constituting the flower-like structure are estimated using scanning electron microscopy studies. The band gap of ZnO nanoflowers is estimated as 3.23 eV, the…

Study of the ZnO crystal growth by vapour transport methods

Abstract The crystal growth of ZnO by vapour transport is classically made with the assistance of additional species that produce a gaseous mixture, the role of which remains often uncertain in the transport and growth process. Initially, in order to study the mass transport process, a numerical simulation is made to analyse which are the requirements to have an effective transport. As the pressure of each gaseous species is generally unknown, the numerical study has been performed for different total pressures. It is found that, if congruent and equilibrium conditions are assumed at the sublimation and crystallisation interfaces, effective growth conditions can only be attained for a narro…

Numerical study of the ZnO growth by MOCVD

Abstract In order to analyze the growth of zinc oxide by metalorganic chemical vapor deposition, a numerical model has been developed to simulate the gas flow in a horizontal reactor. A two-inlet system, one for the Zn precursor and the other for the oxygen one, has been studied in the framework of this numerical simulation. This model takes into account the momentum conservation equation coupled with the heat transfer and mass transport of chemical species. Different Zn precursors, DiethylZinc (DEZn), DimethylZinc (DMZn) and DimethylZinc-TriethylAmine (DMZn-TEA) and oxygen precursors, ( tert -butanol, iso -propanol and acetone) as well as carrier gases (H 2 and N 2 ) have been considered. …

ZnO/CdTe/CuSCN, a promising heterostructure to act as inorganic eta-solar cell

Abstract The ZnO/CdTe/CuSCN heterostructure was analyzed as a candidate to act as an inorganic eta -solar cell. A ZnO film consisting of single crystal nanocolumns was electrodeposited on a transparent conducting substrate which acts as n-type material. As absorber material we used CdTe, which was deposited on the ZnO columnar film by Metal Organic Chemical Vapor Deposition. In order to complete the eta -solar cell we deposited a CuSCN layer by chemical solution deposition. A conformal and uniform CdTe coverage of the ZnO columns was achieved, producing a very efficient light trapping effect. The effective absorption (∼87%) and effective reflectance (∼10%) of the complete heterostructure in…

Structural characterization of one-dimensional ZnO-based nanostructures grown by MOCVD

Various one-dimensional (1D) ZnO-based nanostructures, including ZnO nano-wires (NWs) grown using vapour-liquid-solid (VLS) process, ZnO/ZnSe core/shell, nitrogen-doped ZnO and ZnMgO NWs were grown by metalorganic chemical vapour deposition (MOCVD). Transmission electron microscopy (TEM) analysis is presented. For all the samples, a high crystalline quality is observed. Some features are emphasized such as the gold contamination of ZnO wires grown under the metal droplets in the VLS process. It is concluded that MOCVD is a suitable technique for the realization of original ZnO nanodevices.

Influence of twinned structure on the morphology of CdTe(111) layers grown by MOCVD on GaAs(100) substrates

Abstract The morphology and structure of CdTe(1 1 1) layers grown on GaAs(1 0 0) by MOCVD have been studied by atomic force microscopy (AFM) and X-ray texture analysis. Growth conditions have been chosen so that mirror-like CdTe layers are obtained. Layers whose growth times vary between 10 s and 2 h have been investigated. The X-ray texture analysis shows that the CdTe layers grown on GaAs substrates that were thermally treated at 580°C for 30 min in a H 2 atmosphere exhibit a (1 1 1) preferential orientation and are twinned. This twinned structure of the (1 1 1)CdTe layer which is observed as 60° rotated triangular crystallites in the AFM images strongly influences the surface morphology.…

Effect of Growth Temperature on the Structural and Morphological Properties of MgCdO Thin Films Grown by Metal Organic Chemical Vapor Deposition

II-VI oxides ternary alloys have attracted considerable interest of the scientific community due to the possibility of modulating their interesting optoelectronic properties. Despite this interest, MgCdO has been poorly studied. In this work, by using the metal organic chemical vapor deposition method at low pressure, we have analyzed the synthesis of thin films of this alloy. Thus, for a fixed metal-organic precursors content, a change from Mg1-xCdxO (Mg-rich phase) to Cd1-xMgxO (Cd-rich phase) has been induced when decreasing the growth temperature. The temperature range where both phases coexist has been particularly analyzed. Using X-ray diffraction analysis and scanning electron micros…

Nanogoniometry with scanning force microscopy: a model study of CdTe thin films.

In this paper scanning force microscopy is combined with simple but powerful data processing to determine quantitatively, on a sub-micrometer scale, the orientation of surface facets present on crystalline materials. A high-quality scanning force topography image is used to determine an angular histogram of the surface normal at each image point. In addition to the known method for the assignment of Miller indices to the facets appearing on the surface, a quantitative analysis is presented that allows the characterization of the relative population and morphological quality of each of these facets. Two different CdTe thin films are used as model systems to probe the capabilities of this met…

High resolution X-ray diffraction, X-ray multiple diffraction and cathodoluminescence as combined tools for the characterization of substrates for epitaxy: the ZnO case

The goal of this work is to show the capability of X-ray multiple diffraction (XRMD) to be used in combination with high resolution X-ray diffraction (HRXRD) and cathodoluminescence (CL) as an easy and simple methodology to determine structural and surface defect-related characteristics of samples that could be used as substrates for epitaxial growth. For this study ZnO {0001}-oriented samples have been used in view of their use as substrates for homoepitaxy. The miscut and bending of the samples have been analyzed by measuring the position of the X-ray diffraction peaks. The presence of multiple crystallographic domains and their characteristics have been studied by HRXRD (from the allowed…

Structural and vibrational study of Bi2Se3under high pressure

The structural and vibrational properties of bismuth selenide (Bi${}_{2}$Se${}_{3}$) have been studied by means of x-ray diffraction and Raman scattering measurements up to 20 and 30 GPa, respectively. The measurements have been complemented with ab initio total-energy and lattice dynamics calculations. Our experimental results evidence a phase transition from the low-pressure rhombohedral ($R$-3$m$) phase (\ensuremath{\alpha}-Bi${}_{2}$Se${}_{3}$) with sixfold coordination for Bi to a monoclinic $C$2/$m$ structure (\ensuremath{\beta}-Bi${}_{2}$Se${}_{3}$) with sevenfold coordination for Bi above 10 GPa. The equation of state and the pressure dependence of the lattice parameters and volume …

High-pressure studies of topological insulators Bi2Se3, Bi2Te3, and Sb2Te3

Bi2Se3, Bi2Te3, and Sb2Te3 are narrow bandgap semiconductors with tetradymite crystal structure (R-3m) which have been extensively studied along with their alloys due to their promising operation as thermoelectric materials in the temperature range between 300 and 500¿K. Studies on these layered semiconductors have increased tremendously in the last years since they have been recently predicted and demonstrated to behave as 3D topological insulators. In particular, a number of high-pressure studies have been done in the recent years in these materials. In this work we summarize the main results of the high-pressure studies performed in this family of semiconductors to date. In particular, w…

Correlation between Zn vacancies and photoluminescence emission in ZnO films.

Photoluminescence and positron annihilation spectroscopy have been used to characterize and identify vacancy-type defects produced in ZnO films grown on sapphire by metal-organic chemical-vapor deposition. The photoluminescence of the samples in the near band edge region has been studied, paying particular attention to the emission at 370.5 nm (3.346 eV). This emission has been correlated to the concentration of Zn vacancies in the films, which has been determined by positron annihilation spectroscopy. Jesus.Zuniga@uv.es Vicente.Munoz@uv.es

Intrinsic and extrinsic point-defects in vapor transport grown ZnO bulk crystals

Vapor transport grown ZnO bulk crystals were characterized by electrical, optical and magnetic resonance spectroscopy. The experiments show that the residual carrier concentration is caused by residual H, Al, Ga, and oxygen vacancies in the material. Annealing the samples in O 2 at about 1000 °C (2 atm, 20 h) reduces the H and V O donor concentration by typical one order of magnitude. The photoluminescence and DLTS results suggest a correlation between the broad unstructured emission at 2.45eV (green band) and a donor level 530 meV below the conduction band (E4).

Rock-salt CdZnO as a transparent conductive oxide

Transparent conducting oxides (TCOs) are widely used in applications from solar cells to light emitting diodes. Here, we show that the metal organic chemical vapor deposition (MOCVD)-grown, rock-salt CdZnO ternary, has excellent potential as a TCO. To assess this compound, we use a combination of infrared reflectance and ultraviolet-visible absorption spectroscopies, together with Hall effect, to determine its optical and electrical transport characteristics. It is found that the incorporation of Zn produces an increment of the electron concentration and mobility, yielding lower resistivities than those of CdO, with a minimum of 1.96 × 10 − 4 Ω · cm for a Zn content of 10%. Moreover, due to…

Near band edge recombination mechanisms in GaTe

GaTe samples of p-type have been investigated by analyzing the photoluminescence (PL) response for different excitation intensities at energies higher than the band gap. The PL intensity variation of recombination peaks as a function of the excitation intensity has been measured and fitted by a power law. The results show some particular features that do not appear in other III-V and II-VI compound semiconductors. These features can be interpreted by means of the recombination dynamics of the carriers in the band-gap edges. The expressions for the coefficients associated with different recombination rates and the relations between them are derived and used for understanding the recombinatio…

High-pressure vibrational and optical study of Bi2Te3

We report an experimental and theoretical lattice dynamics study of bismuth telluride (Bi2Te 3 )u p to 23 GPa together with an experimental and theoretical study of the optical absorption and reflection up to 10 GPa. The indirect bandgap of the low-pressure rhombohedral (R-3m) phase (α-Bi2Te 3) was observed to decrease with pressure at a rate of − 6m eV/GPa. In regard to lattice dynamics, Raman-active modes of α-Bi2Te 3 were observed up to 7.4 GPa. The pressure dependence of their frequency and width provides evidence of the presence of an electronic-topological transition around 4.0 GPa. Above 7.4 GPa a phase transition is detected to the C2/m structure. On further increasing pressure two …

Electronic structure of single-crystal rocksalt CdO studied by soft x-ray spectroscopies andab initiocalculations

Soft x-ray emission spectroscopy (XES) and x-ray absorption spectroscopy (XAS) are employed to investigate the occupied and unoccupied electronic structures in rocksalt-phase single-crystal CdO. Resonant XES at the OK edge reveals a clear Cd 4d-O 2p hybridized peak and momentum-dependent coherent contributions to the resonant emission spectra. Good agreement is obtained between the above-threshold XES and XAS spectra, and the calculated O 2p local partial density of states (PDOS). Calculation of the O 2p PDOS was performed within the GW framework of many-body perturbation theory.

Semiconductor-metal transitions in liquidIn100−xSexalloys: A concentration-induced transition

The electronic and structural properties of ${\mathrm{In}}_{100\ensuremath{-}x}{\mathrm{Se}}_{x}$ liquid alloys close to their melting points have been investigated by combining x-ray-absorption experiments with ab initio molecular-dynamics simulations. Extended x-ray-absorption fine-structure data have been acquired at both the In and Se K edges in a large concentration range $(x=20%$ to $x=50%$ of Se content). Ab initio molecular-dynamics simulations have been carried out at the two most extreme concentrations explored experimentally. Liquid InSe is found to retain a semiconducting behavior which results from a low-dimensional structure, reminiscent of that of the ambient solid phase, cha…

Optical properties of ZnMgO films grown by spray pyrolysis and their application to UV photodetection

This work presents a comprehensive optical characterization of Zn1−xMgxO thin films grown by spray pyrolysis (SP). Absorption measurements show the high potential of this technique to tune the bandgap from 3.30 to 4.11 eV by changing the Mg acetate content in the precursor solution, leading to a change of the Mg-content ranging from 0 up to 35%, as measured by transmission electron microscopy-energy dispersive x-ray spectroscopy. The optical emission of the films obtained by cathodoluminescence and photoluminescence spectroscopy shows a blue shift of the peak position from 3.26 to 3.89 eV with increasing Mg incorporation, with a clear excitonic contribution even at high Mg contents. The lin…

Structural analysis of CdO layers grown on r-plane sapphire (011¯2) by metalorganic vapor-phase epitaxy

Abstract High-quality fully relaxed CdO layers have been grown directly on r -plane sapphire by metalorganic vapor-phase epitaxy. The crystalline structure has been analyzed by high-resolution X-ray diffraction. The structural quality of the (0 0 1) oriented layers degrades as the growth temperature decreases, process which is accompanied by the appearance of pyramidal grains as revealed by scanning force microscopy. The lattice parameters, perpendicular and parallel to the sample surface, have been determined by means of reciprocal space maps taken on asymmetrical reflections and measurements of symmetrical reflections at different azimuths. The epitaxial relationships between the CdO laye…

Study of the MOCVD growth of ZnO on GaAs substrates: Influence of the molar ratio of the precursors on structural and morphological properties

Abstract ZnO thin films were grown by metal-organic chemical vapour deposition (MOCVD) on GaAs(100) and GaAs(111)A substrates. The growth experiments were performed at temperatures ranging from 290 to 500 ∘C and atmospheric pressure. Diethylzinc (DEZn) and tertiary butanol (tBuOH) were used as Zn and O precursors, respectively. The crystallinity of the grown films was studied by X-Ray Diffraction (XRD) and the thickness and morphology were investigated by Scanning Electron Microscopy (SEM). The influence of substrate orientation and molar ratio of the precursors on the crystalline orientation and morphology of the ZnO grown films was analysed.

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…

Observation of quantized subband states and evidence for surface electron accumulation in CdO from angle-resolved photoemission spectroscopy

The electronic structure of well-ordered single-crystal thin films of CdO100 has been studied using angleresolved photoemission spectroscopy. Quantized electron subbands are observed above the valence-band maximum. The existence of these states provides evidence of an intrinsic electron accumulation space-charge layer near the CdO surface, an interpretation supported by coupled Poisson-Schrodinger calculations. The origin of the accumulation layer result is discussed in terms of the bulk band structure of CdO calculated using quasiparticle-corrected density-functional theory, which reveals that the conduction-band minimum at the Brillouin-zone center lies below the charge neutrality level.

Valence-band electronic structure of CdO, ZnO, and MgO from x-ray photoemission spectroscopy and quasi-particle-corrected density-functional theory calculations

The valence-band density of states of single-crystalline rock-salt CdO(001), wurtzite $c$-plane ZnO, and rock- salt MgO(001) are investigated by high-resolution x-ray photoemission spectroscopy. A classic two-peak structure is observed in the VB-DOS due to the anion $2p$-dominated valence bands. Good agreement is found between the experimental results and quasi-particle-corrected density-functional theory calculations. Occupied shallow semicore $d$ levels are observed in CdO and ZnO. While these exhibit similar spectral features to the calculations, they occur at slightly higher binding energies, determined as 8.8 eV and 7.3 eV below the valence band maximum in CdO and ZnO, respectively. Th…

Enabling long-term stable FAPb1-xSrxI3 quantum dots with high optical performance: the effect of Sr2+ doping

Some aspects of the MOCVD growth of ZnO on sapphire using tert-butanol

The growth of ZnO on (0001) sapphire substrates using metalorganic chemical vapor deposition is reported. Diethylzinc and tertiarybutanol were used, respectively, as zinc and oxygen sources. Growth conditions are detailed such as the substrate temperature and the precursors partial pressures. The influence of the cleanness state of the MOCVD silica reactor is emphasized, since it modifies both layer quality and crystalline orientation, and since it also affects growth process steps like sapphire thermal treatment and buffer layer deposition. ZnO epitaxial layers are characterised by scanning electron microscopy (SEM) to assess the surface orientation and morphology, X-ray diffraction (XRD) …

Morphology of ZnO grown by MOCVD on sapphire substrates

A quantitative roughness and microstructural analysis of ZnO grown on sapphire by atmospheric metalorganic chemical vapor deposition (MOCVD) is presented. In order to investigate the influence of the substrate on the morphology, different sapphire orientations have been employed. Scanning force microscopy data have been analyzed for a variety of thicknesses to elucidate, if possible, the growth mechanisms involved in the growth process. Our study reveals significant differences between morphologies depending on whether the substrate surface exhibits steps (misoriented a-, c- and r-planes) or not (m-plane); however, no major differences on the calculated roughness coefficients have been foun…

Unification of the electrical behavior of defects, impurities, and surface states in semiconductors: Virtual gap states in CdO

In contrast to conventional semiconductors, native defects, hydrogen impurities, and surface states are all found to be donors in $n$-type CdO. Using this as a model system, the electrical behaviors of defects, dopants, and surface states in semiconductors are unified by a single energy level, the charge neutrality level, giving much insight into current materials and allowing a band-structure engineering scheme for obtaining desired custom electronic properties in new compound semiconductors.

Twin coarsening in CdTe(111) films grown on GaAs(100)

Abstract We present a scanning force microscopy study of twin coarsening in CdTe(1 1 1) films grown on GaAs(1 0 0). Two types of CdTe(1 1 1) twins grow epitaxially and with equal probability on the long-range wavy surface structure developed by previous in situ annealing of the GaAs(1 0 0) substrate. Due to this initial substrate wavy structure, the grain coarsening during film growth leads to a quasi-one-dimensional rippled pattern. We propose a coarsening mechanism between twins driven by the formation of stacking faults.

High pressure–high temperature phase diagram of InSe

By combining X-ray diffraction and X-ray absorption spectroscopy, the structural evolution of the InSe alloy has been explored up to 3.3 GPa and 1500 K with the use of the Paris–Edinburgh large volume cell. These conditions allowed us to study the solid and the liquid states and to measure the pressure evolution of the melting point, which increases at a rate of +120 K GPa−1. A temperature‐induced phase transition has been evidenced within the solid phase. This is the first in-situ study of the high temperature solid phase which had so far only been inferred from studies on recovered samples at ambient conditions.

Local structure in Ga1−xInxSe alloys

Abstract In this work we study the local structure of layered G a 1 − x I n x S e alloys by means of X-ray Absorption. We complement our research with a Raman study. The available alloys have compositions close to the host binaries. The dependence of XANES (X-ray Near Edge Structure) features with synchrotron polarization clearly establishes the substitutional character of the alloying cations. Interstitial atoms, if present, remain under the detection limit of the technique. EXAFS (Extended X-ray Absorption Fine Structure) demonstrates the existence of G a − I n bonds in the alloys. The cation-anion bond-lengths in the alloys remain similar to that of the pure compounds. There is no signif…

Temperature- and illumination-induced charge-state change in divacancies of GaTe

Temperature-dependent positron annihilation lifetime spectroscopy measurements have been performed in GaTe samples, with and without illumination. The average lifetime shows a monotonous temperature evolution but the lifetime decomposition shows a rich behavior. It is produced by two types of vacancy defects. The vacancy-type defects characterized by their shorter lifetime change their charge state below 100 K and when illuminating with light of an energy of 0.8 eV.

Morphology transitions in ZnO nanorods grown by MOCVD

Morphology transitions (nanorods–nanowalls and nanorods–nanotubes-layer) were induced in the growth of ZnO nanostructures by metal organic chemical vapor deposition (MOCVD) on c-sapphire, using helium as carrier gas, and dimethylzinc–triethylamine and nitrous oxide as zinc and oxygen sources, respectively. A systematic study of the influence of the VI/II ratio and precursor flow-rates on the morphology of ZnO nanorod arrays has been carried out, taking advantage of the ability of MOCVD to individually control the precursor partial pressures. Growth mechanisms are discussed to understand the evolution of the nanostructures morphology for different growth conditions. In particular, the influe…

Optical properties and microstructure of 2.02-3.30 eV ZnCdO nanowires: effect of thermal annealing

International audience; ZnCdO nanowires with up to 45% Cd are demonstrated showing room temperature photoluminescence (PL) down to 2.02 eV and a radiative efficiency similar to that of ZnO nanowires. Analysis of the microstructure in individual nanowires confirms the presence of a single wurtzite phase even at the highest Cd contents, with a homogeneous distribution of Cd both in the longitudinal and transverse directions. Thermal annealing at 550 C yields an overall improvement of the PL, which is blue-shifted as a result of the homogeneous decrease of Cd throughout the nanowire, but the single wurtzite structure is fully maintained.

Faceting and structural anisotropy of nanopatterned CdO(110) layers

CdO(110) layers with a self-organized surface structure have been grown on (10math0) sapphire (m plane) substrates by metal-organic vapor phase epitaxy. The epitaxial relationships between layer and substrate have been determined and a crystallographic model that accounts for the CdO in-plane orientation, which results in a reduced lattice mismatch when the CdO[001] direction is perpendicular to the sapphire c axis, has been proposed. Although the measured lattice parameters indicate that the layers are almost fully relaxed, an anisotropic mosaicity is detected with symmetrical rocking curves attaining minimum values when measured along the CdO[math10] direction. The layer morphology consis…

Luminescence and structural properties of defects in ion implanted ZnO

ZnO substrates and films were intentionally implanted with rare earth and transition metal ions. The influence of the implantation and subsequent air thermal annealing treatments on the structural and optical properties of ZnO samples were studied by using Rutherford backscattering spectrometry and low temperature photoluminescence techniques. Intraionic Tm-related emission was observed for bulk and ZnO films. Similarly, Eu and Tb-doped ZnO films follow the same trend observed in bulk samples. No intraionic related emission was observed for Eu-doped samples even being the ion in Zn sites and for the Tb-doped samples ion segregation was observed for thermal annealing temperatures above 800 °…

Optical active centres in ZnO samples

Abstract In recent years, there has been a resurgence in the interest in the use of ZnO (Eg ∼ 3.37 eV) as a material for a wide range of opto-emitter applications spanning visible and short wavelengths. Bulk, thin films and nanomaterials obtained using different synthesis methods have been investigated for optoelectronic and biotechnological device applications. Nominally undoped bulk samples typically present a myriad-structured near-band-edge recombination, mainly due to free/bound excitons and donor–acceptor pair transitions. Furthermore, deep level emission due to intrinsic defects and extrinsic impurities, such as transition metal ions, are commonly observed in different grades of bulk…

Structural characterization of a-plane Zn1−xCdxO (0 < x <0.085) thin films grown by metal-organic vapor phase epitaxy.

Zn1−xCdxO(11math0) films have been grown on (01math2) sapphire (r–plane) substrates by metal-organic vapor phase epitaxy. A 800-nm-thick ZnO buffer, deposited prior to the alloy growth, helps to prevent the formation of pure CdO. A maximum uniform Cd incorporation of 8.5 at. % has been determined by Rutherford backscattering spectrometry. Higher Cd contents lead to the coexistence of Zn1−xCdxO alloys of different compositions within the same film. The near band-edge photoluminescence emission shifts gradually to lower energies as Cd is incorporated and reaches 2.93 eV for the highest Cd concentration (8.5 at. %). The lattice deformation, due to Cd incorporation, has been described using a n…

Anisotropic chemical etching of semipolar \{10\bar {1}\bar {1}\}\mbox {/} \{10\bar {1}{+}1\} ZnO crystallographic planes: polarity versus dangling bonds

ZnO thin films grown by metal?organic vapor phase epitaxy along the nonpolar direction and exhibiting semipolar facets have been chemically etched with HCl. In order to get an insight into the influence of the ZnO wurtzite structure in the chemical reactivity of the material, Kelvin probe microscopy and convergent beam electron diffraction have been employed to unambiguously determine the absolute polarity of the facets, showing that facets are unstable upon etching in an HCl solution and transform into planes. In contrast, facets undergo homogeneous chemical etching perpendicular to the initial crystallographic plane. The observed etching behavior has been explained in terms of surface oxy…

Ab-Initio Studies of Electronic and Spectroscopic Properties of MgO, ZnO and CdO

We present ab-initio calculations of excited-state properties within single-particle and two-particle approaches in comparison with corresponding experimental results. For the theoretical treatment of the electronic structure, we compute eigenvalues and eigenfunctions by using a spatially nonlocal exchange-correlation potential. From this starting point, quasiparticle energies within the fully frequency-dependent G(0)W(0) approximation are obtained. By solving the Bethe-Salpeter equation, we evaluate optical properties, including the electron-hole attraction and the local-field effects. The results are compared with experimental spectra from soft X-ray emission, as well as from X-ray photoe…

Assessment of the out-plane and in-plane ordering of high quality ZnO nanorods by X-ray multiple diffraction

Abstract ZnO nanorods grown on buffered and non buffered sapphire substrates have been investigated by X-ray multiple diffraction using Renninger scans of the ZnO(0001) and ZnO(0003) forbidden reflections. In this technique the diffracted X-ray beam is simultaneously diffracted by several sets of planes, providing information on the broadening in different directions, as well as from nanorods, and from the layer on which they grow. The intensities and angular widths of peaks obtained by azimuthal and omega scans have been analyzed, making a direct comparison with conventional measurements of the full width at half-maximum of symmetric and asymmetric reflections. The analysis leads to establ…

Observation of a charge delocalization from Se vacancies inBi2Se3: A positron annihilation study of native defects

By means of positron annihilation lifetime spectroscopy, we have investigated the native defects present in ${\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$, which belongs to the family of topological insulators. We experimentally demonstrate that selenium vacancy defects $({\text{V}}_{\text{Se1}})$ are present in ${\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$ as-grown samples, and that their charge is delocalized as temperature increases. At least from 100 K up to room temperature both ${\text{V}}_{\text{Se1}}^{0}$ and ${\text{V}}_{\text{Se1}}^{+}$ charge states coexist. The observed charge delocalization determines the contribution of ${\text{V}}_{\text{Se1}}$ defects to the $n$-type conductivity of ${\mathrm{…

Surface band-gap narrowing in quantized electron accumulation layers.

An energy gap between the valence and the conduction band is the defining property of a semiconductor, and the gap size plays a crucial role in the design of semiconductor devices. We show that the presence of a two-dimensional electron gas near to the surface of a semiconductor can significantly alter the size of its band gap through many-body effects caused by its high electron density, resulting in a surface band gap that is much smaller than that in the bulk. Apart from reconciling a number of disparate previous experimental findings, the results suggest an entirely new route to spatially inhomogeneous band-gap engineering.

Spray pyrolytic deposition of ZnO thin layers composed of low dimensional nanostructures

Abstract ZnO nanolayers composed of fine nanostructures have been successively grown by spray pyrolytic deposition at 300  ∘ C over amorphous glass substrates. As deposited samples were analysed by scanning electron microscopy (SEM), showing a granular morphology with grain size in the limit of the microscope resolution. CL measurement shows a broad near band edge (3.4 eV) emission of ZnO in the UV region and the defect level emissions in the green region of the spectrum. The use of intermittent spray pyrolytic deposition is shown as an alternative to increase the homogeneity of the samples when temperatures near to the precursor pyrolytic decomposition is selected, long depositions times a…

A new CdTe/ZnO columnar composite film for Eta-solar cells

Abstract First results of CdTe deposition on ZnO films consisting of free standing single crystalline columns of several micrometers height and ∼100– 200 nm diameter are presented. The ZnO films have been obtained by electrochemical deposition on conductive glass. Morphology, structural and optical properties of the nanostructured columnar CdTe/ZnO composite films have been studied. The cadmium telluride ( 40 nm thick) deposited by vapor-phase epitaxy under dynamical vacuum is lining the ZnO columns as a continuous smooth thin film with conformal coverage. The polycrystalline CdTe layer is a mixture of cubic and hexagonal phases and is semiconductor with a direct band gap optical transition…

Front Cover: High-pressure studies of topological insulators Bi2 Se3 , Bi2 Te3 , and Sb2 Te3 (Phys. Status Solidi B 4/2013)

Sensing properties of ZnO nanostructured layers

Nanostructured ZnO layers have been deposited onto SiO 2 /Si substrates by spray pyrolysis, with previously patterned interdigitated gold electrodes. We have then measured the capacitive and resistive response against ambient parameters such as relative humidity and illumination.

The Scope of Zinc Oxide Bulk Growth

The techniques classically used for the growth of bulk ZnO crystals, melt-growth, vapour growth, solution-growth and hydrothermal growth, are reviewed. In the case of vapor growth, numerical simulations suggest that such species as H2 + H2O, CH4, Zn, C or Fe could act as sublimation activators. The electrical and structural properties of crystals obtained by these various techniques are compared.

X-ray photoemission studies of the electronic structure of single-crystalline CdO(100)

The electronic structure of single-crystalline CdO is investigated using X-ray photoemission spectroscopy. The surface is prepared by in situ Ar+ ion bombardment and annealing (IBA). The core level spectra before and after the IBA are presented, and reveal a dramatic reduction in the surface contamination. The semi-core Cd 4d level and valence band region following the IBA are also shown. The surface Fermi level is pinned 1.3 +/- 0.10 eV above the valence band maximum. (c) 2007 Elsevier Ltd. All rights reserved.

X-ray-absorption fine-structure study of ZnSexTe1−x alloys

X-ray-absorption fine-structure experiments at different temperatures in ZnSexTe1−x (x=0, 0.1, 0.2, 0.55, 0.81, 0.93, 0.99, and 1.0) have been performed in order to obtain information about the structural relaxation and disorder effects occurring in the alloys. First and second neighbor distance distributions have been characterized at the Se and Zn K edges, using multiple-edge and multiple-scattering data analysis. The first neighbor distance distribution was found to be bimodal. The static disorder associated with the Zn–Te distance variance did not depend appreciably on composition. On the other hand, the static disorder associated with the Zn–Se distance increased as the Se content dimi…

Determination of defect content and defect profile in semiconductor heterostructures

In this article we present an overview of the technique to obtain the defects depth profile and width of a deposited layer and multilayer based on positron annihilation spectroscopy. In particular we apply the method to ZnO and ZnO/ZnCdO layers deposited on sapphire substrates. After introducing some terminology we first calculate the trend that the W/S parameters of the Doppler broadening measurements must follow, both in a qualitative and quantitative way. From this point we extend the results to calculate the width and defect profiles in deposited layer samples.