Structural characterization of Ga-doped Mg0.1Zn0.9O layers grown on ZnO/α-Al2O3 templates by P-MBE

In this study, structural properties of epitaxial Ga-doped Mg_0.1Zn_0.9O layers grown on ZnO/α-Al₂O₃ templates by plasma-assisted molecular beam epitaxy have been investigated by high-resolution transmission electron microscopy (HRTEM), and high resolution X-ray diffraction (HRXRD). From analysis of the diffraction pattern, the monocrystallinity of the Mg_0.1Zn_0.9O layer with hexagonal structure is confirmed. The orientation relationship between Mg_0.1Zn_0.9O and the template is determined as (0 0 0 1)_Mg0.1Zn0.9O(0 0 0 1)_ZnO(0 0 0 1)_Al2O3 and [ [ ]_ZnO[ . The density of dislocations near the top surface layers measured by plan-view TEM is about 3.610¹⁰ cm⁻², one order of magnitude higher than the value obtained for ZnO layers on α-Al₂O₃ with a MgO buffer. Cross-sectional observation revealed that the majority of threading dislocations are in the [0 0 0 1] line direction, i.e. they lie along the surface normal and consist of edge, screw, and mixed dislocations. Cross- sectional TEM and X-ray rocking curve experiments reveal that most of dislocations are edge dislocations. The interface of Mg_0.1Zn_0.9O and ZnO layers and the effect of excess Ga-doping in these layers have been also studied.     

The most stable crystal structure and the formation processes of an order-disorder (OD) intermetallic phase in the Mg–Al–Gd ternary system

The most stable crystal structure for an 18R-type order-disorder (OD) intermetallic phase in the Mg–Al–Gd ternary system and its formation processes by annealing at 525?°C have been investigated by means of transmission electron microscopy and scanning transmission electron microscopy. The most energetically favourable polytype at 525?°C is found to be the structurally simplest one, a maximum degree of order polytype (monoclinic, 1M, space group: C2/m), described with a single stacking vector in stacking six-layer structural blocks. The formation of this simplest polytype occurs in the sequence of (i) enrichment of Gd and Al in four consecutive close-packed planes while keeping the hexagonal close-packed stacking of the AB-type, (ii) formation of Al₆Gd₈ clusters in the four consecutive atomic planes, introducing a stacking fault in the middle of the four consecutive atomic planes, (iii) thickening by the formation of Gd and Al-enriched four consecutive planes at a distance of two or three close-packed Mg atomic planes from the pre-existing Gd and Al-enriched four consecutive atomic planes so as to form six-layer and, sometimes seven-layer structural blocks, (iv) in-plane ordering of Al₆Gd₈ clusters in the four consecutive atomic planes and the stacking of structural blocks in the preferential stacking positions to form the OD structure, and (v) elimination of different structural blocks (other than six-layer ones) and the long-range ordering in the stacking of structural blocks.     

Stability of the long-period stacking order in Mg3ln AND Mg3(In1−yCdy) alloys

The stability of the stacking ordered structures of close-packed layers in Mg-In alloys near Mg₃In and pseudo-binary alloys Mg₃(In_1?yCd_y) for 0 ? y ? 1 is studied from a standpoint based on the pseudopotential theory. An expression of the structure-dependent energy for an arbitrary type of layer stacking is given by the method described in the previous papers [1,2]. The numerical results explain well the observed trends in the composition and pressure dependences of stacking sequence; the orders of appearance of stacking variants are 3R → 12R → 2H with an increasing Mg-content for Mg-In alloys near Mg₃In, 12R → 18R → 2H with an increasing Cd-content for Mg₃(In_1?yCd_y) and 12R → 18R → 24R with an increasing pressure for Mg₃ln. Speaking in detail, however, the present calculation fails to reproduce a 12R-structure (β₁-phase) at 25% In in the Mg-In system, an 18R-structure of Mg₃(In_0.65Cd_0.35) and an 18R-structure of Mg₃In found under pressure of 20–55 kb, although the energy differences are small in all the cases. From the analysis of components of the structure-dependent energy, it is concluded that the favorable type of layer stacking is determined predominantly by a contribution from the band-structure energy term of a state with the disordered arrangement of constituent atoms and also that an energy required to the alternation of stacking of layers is apparently smaller than the ordering energy. If a specific layer sequence is characterized by a hexagonality, the alloys vary their sequences in such a way that the hexagonality increases from zero (3R) to unity (2H) as the electron-to-atom ratio of the alloys decreases from 2·3 to 2·0.The Ewald and Madelung constants are calculated for various types of layer structure. Both constants change linearly with hexagonality, without regard to period, symmetry and layer sequence.     

Zn1−x Mg x O (0≤x≤0.05) nanowalls grown on catalyst-free sapphire substrates by high-pressure PLD and their photoluminescence properties

We report the growth of Zn_1?x Mg _x O (x=0, 0.02, 0.05 at.%) nanowalls on sapphire substrates without any metal catalysts by a high-pressure pulsed laser deposition (PLD). The influences of the experimental parameters like growth pressure, temperature, and target-substrate distance on the growth of Zn_1?x Mg _x O nanowalls were systemically studied and the growth mechanism was discussed. It was found that large area and uniform Zn_1?x Mg _x O nanowalls with c-orientation can be grown on sapphire substrates when the growth temperature and pressure were 950 °C and 400 Torr at a target-substrate distance of 2 cm. A thin layer assisted vapor-solid (VS) process was proposed for Zn_1?x Mg _x O nanowalls growth. The photoluminescence spectrum shows the bandgap of Zn_1?x Mg _x O nanowall was effectively expanded together with defect-related levels formation in a forbidden gap, which also induced enhancement of visible emission.     

Magnetic properties of off-stoichiometric R2Co3Zn14 (R=Y,Gd) single crystals

Single crystal X-ray diffraction data indicate that the R₂Co₃Zn₁₄ (R=Gd, Y) phase crystallizes non-stoichiometrically with a mixed occupancy of Co/Zn atoms on the 12-coordinated transition metal site and one of the three zinc sites. The crystals are rhombohedral with R-3m space group. Magnetization measurements provide no evidence of localized 3d electron moment in Y₂Co_2.3Zn_14.7 which is non-magnetic down to 1.8 K. Thermodynamic and transport measurements on two Gd₂Co_3+xZn_14−x crystals reveal that the extra cobalt influences temperature below which the samples enter into an antiferromagnetic state: T_N=31.5(3) K for Gd₂Co₃Zn₁₄ and 28(1) K for Gd₂Co_4.2Zn_12.8. A lower magnetic ordering temperature of T_mag=6.0(2) K is common in both Gd samples.     

First-principles calculations of structural,electronic and thermal properties of Zn1−x Mg x S ternary alloys

Structural, electronic and thermal properties of Zn_1?x Mg _x S ternary alloys are studied by using the full potential-linearized augmented plane wave method (FP-LAPW) within the density functional theory (DFT). The Wu-Cohen generalized gradient approximation (WC-GGA) is used in this approach for the exchangecorrelation potential. Moreover, the modified Becke-Johnson approximation (mBJ) is adopted for band structure calculations. The dependence of the lattice constant, bulk modulus and band gap on the composition x showed that the first exhibits a small deviation from the Vegard’s law, whereas, a marginal deviation of the second from linear concentration dependence (LCD). The bowing of the fundamental gap versus composition predicted by our calculations agrees well with the available theoretical data. The microscopic origins of the gap bowing are explained by using the approach of Zunger and co-workers. Thermal effects on some macroscopic properties of Zn_1?x Mg _x S alloys are also investigated using the quasi-harmonic Debye model, in which the phononic effects are considered. As, this is the first quantitative theoretical prediction of the thermal properties of Zn_1?x Mg _x S alloys, no other calculated results and furthermore no experimental studies are available for comparison.     

The effect of the static atomic displacements on the structure factors of weak reflections in cubic semiconductor alloys

We show that the static atomic displacements (SDs) from the average crystal sites, which exist in all III–V and II–VI semiconductor alloys where atoms having different covalent radii share a mixed sublattice, have a large effect on the structure factors (SFs) of the weak reflections (h + k + l = 4n + 2) of the cubic crystals of such alloys. Using atomistic simulations, this effect is studied quantitatively for 25 ternary alloys. Parameters describing the variations in the SFs with alloy composition for both electrons and X-rays are given. The sign of the difference between SFs calculated with and without SDs is the same for most alloys with a type-III or type-II mixed sublattice and reverses for a type-V mixed sublattice. Non-zero imaginary parts appear for reflections with all indices non-zero. We use a simple approximation to explain these results, to provide general rules for the effect of the SDs and to estimate its magnitude. We also study quantitatively the large effect of the SDs in quaternary Ga_{1? x} In _x As_{1? y} N _y alloys with y ? 1. Our calculations explain part of the difference between the experiments and the standardly calculated SFs of Ga _1?x In _x As alloys. They show that the SDs must be taken into account, particularly when such ‘quasiforbidden’ reflections are used to measure alloy composition by electron microscopy.     

First-principles study of structrural and corrected band properties of wurtzite Zn1-xCdxO and Zn1-xMgxO systems

A first-principles method based on density functional theory(DFT),a generalized gradient approximation(GGA),and a projector-augmented wave(PAW) are used to study the structual and band properties of wurtzite Zn1-xCdxO and Zn1-xMgxO(0 ≤x≤1) ternary alloys.By taking into account all of the possible structures,the band gaps of Zn1-xCdxO and Zn1-xMgxO alloys are corrected and compared with experimental data.     

Investigations on structural and optical properties of Zn1−xGdxS nanoparticles

Zn_1−xGd_xS (x = 0.00, 0.02 and 0.04) nanoparticles were synthesized by facile chemical co-precipitation method using PVP as a surfactant. ZnS nanoparticles could be doped with Gd ions during synthesis without altering the XRD patterns of ZnS. Also, the pattern of the powders showed cubic zincblende structure. The particle size obtained from the XRD studies lies in the range 3-5 nm, whereas from TEM analysis it is 4 nm for x = 0.02 sample. The UV-Vis absorption spectra revealed that Zn_1−xGd_xS nanoparticles exhibit strong confinement effect as the blue shift in the absorption spectra with that of the undoped ZnS. The photoluminescence spectra showed enhanced luminescence intensity and the entry of Gd into host lattice.     

高温高压下Mg_xZn_(1-x)O固溶体的制备

研究了高温高压下制备MgxZn1-xO(0.30x0.60)固溶体的过程.在1000—2000℃和4—5.6GPa的条件下,制备出稳定的单一立方相MgxZn1-xO(x=0.4,0.5,0.6)固溶体,解决了常压下MgxZn1-xO的分相问题.通过X射线衍射仪和扫描电子显微镜等测试手段,对MgxZn1-xO样品进行了表征,阐明了立方相MgxZn1-xO的形成机制,给出了高压下MgxZn1-xO固溶体的温度与组分相图.     

Growth of cubic MgxZn1−xO alloy films by electron beam evaporation

We report the growth of cubic Mg_xZn_1−xO alloy thin films on quartz by electron beam evaporation. It can be found that all the samples have sharp absorption edges by the absorption measurements. X-ray diffraction measurements indicate the Mg_xZn_1−xO films are cubic phase with preferred orientation along the (1 1 1) direction. Energy dispersive spectrometry (EDS) demonstrates that the Mg concentration in Mg_xZn_1−xO films is much higher than the ceramic target used, and the composition can be tuned in a small scope by varying the substrate temperature and the beam electric current. The reasons of this phenomenon are also discussed.     

Surface oxidation behavior of MgNd alloys

The oxidation kinetics of MgNd alloys oxidized in pure O₂ at high temperatures has been investigated. The results revealed two stages of the reaction: A fast initial oxidation was followed by a slow oxide growth with a parabolic kinetics. For MgNd alloys (Nd = 25 wt.%), the oxidation rate increased with the enhancement of the oxidation temperature. A sudden ignition was found for this alloys oxidized at 873 K up to about 80 min. Moreover, the increase of the Nd content would harm the oxidation resistance of the MgNd alloys. By Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis, it was found that a triplex structure of oxide film formed. The outer layer was composed of MgO, Nd₂O₃ and Nd(OH)₃, the middle layer mainly consisted of MgO and Nd₂O₃, and the inner layer was the transitional layer made of MgO, Nd₂O₃ and the content of the substrate. The protective oxidation was associated with the formation of the dense Nd₂O₃/MgO layer during isothermal oxidation process. The oxidation mechanisms for the formation of oxide film are discussed.     

The structure of a long-period stacking phase in an Mg–Al–Y alloy studied by electron microscopy

A new phase with a 10H-type long-period stacking (LPS) structure was found in an Mg₇₅Al₁₀Y₁₅ alloy annealed at 823?K. The LPS structure in the Mg₇₅Al₁₀Y₁₅ alloy annealed at 823?K for 2?h has an ordered arrangement of L1₂-type structural Al₆Y₈ clusters on the two-dimensional plane parallel to the c-plane of hexagonal Mg lattice and a disordered arrangement along the c-axis, whereas a perfectly ordered structure along the c-axis, which has a period with two times of that of the 10H-type LPS structure, was established by annealing at 823?K for 24?h. The structural model of the ordered LPS phase is proposed by high-resolution images taken with a Cs-corrected scanning transmission electron microscope and also electron diffraction patterns.     

Oxygen flux influence on the morphological, structural and optical properties of Zn1−xMgxO thin films grown by plasma-assisted molecular beam epitaxy

The Zn_1−xMg_xO thin films were grown on Al₂O₃ substrate with various O₂ flow rates by plasma-assisted molecular beam epitaxy (P-MBE). The growth conditions were optimized by the characterizations of morphology, structural and optical properties. The Mg content of the Zn_1−xMg_xO thin film increases monotonously with decreasing the oxygen flux. X-ray diffractometer (XRD) measurements show that all the thin films are preferred (0 0 2) orientated. By transmittance and absorption measurements, it was found that the band gap of the film decreases gradually with increasing oxygen flow rate. The surface morphology dependent on the oxygen flow rate was also studied by field emission scanning electron microscopy (FE-SEM). The surface roughness became significant with increasing oxygen flow rate, and the nanostructures were formed at the larger flow rate. The relationship between the morphology and the oxygen flow rate of Zn_1−xMg_xO films was discussed.     

Dielectric study on Zn1−x Mg x O ceramic materials prepared by the solid-state route

The present work investigates the structural and dielectric properties of Zn_1?x Mg _x O composites prepared by the standard sintering method at 1200 °C during 24 h and doped with different weight percentages of MgO (x = 0–40 %). For this purpose, the scanning electron microscopy (SEM) was used to study the effect of the magnesium’s proportion on the morphology and crystallinity of the obtained samples. The SEM observations have shown rougher surfaces of the samples covered by grains having prismatic shapes and different sizes. The dielectric properties of the ceramics were investigated by spectroscopic impedance at different temperatures and frequencies, thus showing a frequency-dependent dispersion of the permittivity constants and dielectric losses. From these measurements, the relaxation processes were identified and their activation energies extracted. Dielectric responses were correlated with the microstructure and chemical composition of the ZnMgO composites. The mechanisms of ac conductivity are controlled by the polaron hopping and the electron tunneling models. Concerning the tunneling model, two types corresponding to the overlapping large polaron tunneling model for the composites Zn_0.9Mg_0.1O and Zn_0.8Mg_0.2O and the small polaron tunneling model for the composites Zn_0.64Mg_0.36O (in the frequency range 1.7 × 10⁴ Hz–1 MHz) and Zn_0.6Mg_0.4O were observed. Besides, one type of hopping model corresponding to the correlated barrier hopping for the composites ZnO and Zn_0.64Mg_0.36O (in the frequency range 6 × 10²–1.7 × 10⁴ Hz) was noted.     

Optical and structural properties of Zn1−x Mg x O ceramic materials

This paper reports structural, optical and cathodoluminescence characterizations of sintered Zn_1?x Mg _x O composite materials. The effects of MgO composition on these film properties have been analyzed. X-ray diffraction (XRD) confirms that all composites are polycrystalline with prominent hexagonal wurtzite structure along two preferred orientations (002) and (101) for the crystallite growth. Above doping content x = 10 %, the formation of the hexagonal ZnMgO alloy phase and the segregation of the cubic MgO phase start. From reflectance and absorption measurements, we determined the band gap energy which tends to increase from 3.287 to 3.827 eV as the doping content increases. This widening of the optical band gap is explained by the Burstein–Moss effect which causes a significant increase of electron concentration (2.89 × 10¹⁸?5.19 × 10²⁰ cm^?3). The luminescent properties of the Zn_1?x Mg _x O pellets are studied by cathodoluminescence (CL) at room and liquid nitrogen temperatures under different electron beam excitations. At room temperature, the CL spectra of the Zn_1?x Mg _x O composites exhibit a dominant broad yellow-green light band at 2.38 eV and two ultraviolet emission peaks at 3.24 and 3.45 eV corresponding to the luminescence of the hexagonal ZnO and ZnMgO structures, respectively. For the doped ZnO samples, it reveals also new red peaks at 1.72 and 1.77 eV assigned to impurities’ emissions. However, the CL spectra recorded at 77 K show the presence of excitonic emission peaks related to recombination of free exciton (X _A), neutral donor-bound excitons (D⁰X) and their phonon replicas. The CL intensity and energy position of the green, red and ultraviolet emission peaks are found to depend strongly on the MgO doping content. The CL intensity of the UV and red emissions is more enhanced than the green light when the MgO content increases. CL imaging analysis shows that the repartition of the emitting centers in Zn_1?x Mg _x O composites is intimately connected to the film composition and surface morphology.     

利用ICP法测定ZnMgO薄膜的Mg组分

利用电感耦合等离子体(ICP)装置对分子束外延(MBE)法在Sapphire衬底上生长的Zn_1-xMg_xO薄膜的Mg组分进行了测试. 经理论分析，得到使用1次和2次检量式所确定的Zn_1-xMg_xO薄膜中的Mg组分的差异. 将采用1次检量式的ICP测定与EPMA测定结果进行对照，表明当Mg组分x≤0.5时二者的测试结果相当一致，由此证明ICP测试结果的正确性. 关键词： ZnMgO薄膜 Mg组分 分子束外延(MBE) 电感耦合等离子体(ICP)     

Corrosion and passivation behavior of Mg-Zn-Y-Al alloys prepared by cooling rate-controlled solidification

Highly corrosion-resistant nanocrystalline Mg-Zn-Y-Al multi-phase alloys have been prepared by consolidation of rapidly solidified (RS) ribbons. The relation between corrosion behavior and microstructure evolution of Mg-Zn-Y-Al alloys with a long period stacking ordered phase has been investigated. In order to clarify the influence of rapid solidification on the occurrence of localized corrosion such as filiform corrosion, several Mg_96.75Zn_0.75Y₂Al_0.5 (at.%) alloys with different cooling rates are fabricated by the gravity casting, copper mould injection casting and melt-spinning techniques and their corrosion behavior and microstructures are examined by the salt water immersion test, electrochemical measurements, GDOES, XRD, SEM and TEM. To clarify the effect of aluminium addition on the improvement in corrosion resistance of the alloys, several Mg_97.25−xZn_0.75Y₂Al_x alloys with different aluminium contents are fabricated by consolidating RS ribbons and the formation of corroded films on the Mg-Zn-Y-Al alloys have been investigated. Rapid solidification brings about the grain refinement and an increase in the solid solubility of zinc, yttrium and aluminium into the magnesium matrix, enhancing microstructural and electrochemical homogeneity, which in turn enhanced corrosion resistance. The addition of aluminium to magnesium can modify the structure and chemical composition of surface films and improves the resistance to local breakdown of the films.     

Ternary alloys CdyZn1 ? yO and MgxZn1 ? xO as materials for optoelectronics

Thin films of Cd _y Zn_{1 − y} O and Mg _x Zn_{1 − x} O (y = 0−0.35, x = 0−0.45) ternary alloys have been grown by pulsed laser deposition onto sapphire substrates. The record solubility limits of Cd (y = 0.3) and Mg (x = 0.35) have been achieved in hexagonal zinc oxide. The mismatch of the lattice parameters a of Cd_0.2Zn_0.8O and Mg_0.35Zn_0.65O does not exceed 1%; in this case, the band gap discontinuity is 1.3 eV. The surface roughness of the films does not exceed 2.5 nm at x = 0−0.27 and y = 0−0.20.