Growth and characterization of nanostructured Al2O3/YAG/ZrO2 hypereutectics with large surfaces under laser rapid solidification

The preparation of large bulk oxide eutectics with homogeneous and dense structure in nano-scale by melt growth method is a difficult challenge. Fully dense, homogeneous and crack-free ternary nanostructured Al₂O₃/YAG/ZrO₂ hypereutectic plate with large surface is successfully obtained by laser remelting. The hypereutectic in selected composition presents an ultra-fine eutectic-like microstructure consisting of alternating interpenetrating Al₂O₃, YAG and ZrO₂ lamellae with mean interphase spacing of about 150 nm, which is much smaller than the ternary eutectic composition grown at the same growth conditions. With the increase of laser scanning rate, the lamellar spacing is rapidly decreased. The minimum value obtained is 50 nm. The analysis indicates that the strong faceted growth behavior and cooperative branching of the component phases related with high entropies of fusion and large kinetic undercooling during laser rapid solidification are the primary formation reasons for the irregular eutectic growth morphology. Furthermore, the unique cellular microstructure with complex structure is also observed at high growth rate, and their formation mechanism and effect of the composition on the microstructure are discussed.     

On the orientational relationship between eutectic α-Fe2Si5 and ϵ-FeSi

The undirectional solidification of the eutectic between α-Fe₂Si₅ and ?-FeSi was carried out. The temperature gradient at the liquid-solid interface was 70°C/cm. Microstructures of the aligned composite were fibrous and lamellar, for last and slow growth rates respectively. The growth direction of α and the preferred axial orientation relationships between α and ? were determined for both structures.     

Study on crystallization kinetics of Al65Cu20Ti15 amorphous alloy

The crystallization behavior and thermal stability of amorphous phases of Al₆₅Cu₂₀Ti₁₅ alloy obtained by mechanical alloying were investigated by using in-situ X-ray diffraction and differential scanning calorimetry (DSC) under non isothermal and isothermal conditions. The result of a Kissinger analysis shows that the activation energy for crystallization is 1131 kJ/mol. The higher stability against crystallization of Al₆₅Cu₂₀Ti₁₅ amorphous alloy is attributed to the stronger interaction of atoms in the Al-Cu-Ti system and formed of complicated compound like Al₅CuTi₂ and Al₄Cu₉ as primary phases. The isothermal crystallization was modeled by using the Johnson-Mehl-Avrami (JMA) equation. The Avarami exponents suggest that the isothermal crystallization is governed by a three-dimensional diffusion-controlled growth.     

Crystallization behaviours ofCo100−1(x+y)NbxBy amorphous alloys

The crystallization behaviours of Co_100?1(x+y)Nb_xB_y amorphous alloys were investigated by means of differential thermal analysis and a conventional X-ray diffractometer. The crystallization sequences are discussed in terms of the equilibrium phase diagram of the ternary alloy system.Assuming crystallization occurs as a result of nucleation and growth, the stabilizing effect of eutectic phase separation on the crystallization is shown by introducing the effective free energy of the critical nucleus.     

The microstructure development in arc-melt and melt-spun Fe50Ni10Cu20P10Si5B5 immiscible alloy

A six-component Fe₅₀Ni₁₀Cu₂₀P₁₀Si₅B₅ immiscible alloy was arc-melt in argon and it was melt-spun from various temperatures. The morphology and chemical composition of the cross-section of the ingot and melt-spun ribbons were analysed with a scanning electron microscope SEM/EDS. The melt-spun ribbon was investigated by a transmission electron microscope (TEM). The melting range of the alloy was investigated by means of differential thermal analysis (DTA) and for reference, the temperature change during free cooling of the alloy was controlled by pyrometer in the melt spinning device. The slow cooling rate resulted in the fractal surface structures formed by the Fe-rich regions and Cu-rich regions typical for the alloying system with a miscibility gap. The structures of the melt-spun ribbons were dependent on ejection temperatures before the melt spinning. The lower ejection temperatures resulted in the formation of the structures separated into Fe-rich and Cu-rich regions. This was due to rapid cooling within the miscibility gap. Ejection at higher temperatures led to the formation of a uniform amorphous/crystalline composite.     

Single crystals growth and absorption spectra of Cr-doped Al2−xInx(WO4)3 solid solutions

The growth conditions of pure and Cr³⁺-doped Al_2−xIn_x(WO₄)₃ single crystals, using top-seeded solution growth (TSSG) technique, have been studied. A series of experiments have been performed at different In concentrations, x=0.0, 0.3, 0.6 and 1.0, as well as at different concentrations of Cr³⁺ (0.0, 0.1, 0.2, 0.5 and 1.0) in at% with respect to the initial total concentration of Al and In in the starting solutions. The basic parameters of the crystal growth are varied over a wide range: seed orientation, speed of rotation, axial and radial temperature differences in the solution and the solution cooling rate. The investigated relations between the basic defects in the crystals and these parameters result in determination of the optimal conditions for growth of defect-free crystals. Distribution coefficients of Al, In and Cr have been determined, so the growth of crystals with given compositions is possible. Values of Dq/B (crystal field strength) for the various crystal compositions are calculated from the optical absorption spectra. The calculated values show that the discussed solid solutions have weak crystal field and are suitable for media with broadband emission spectra.     

Eutectic crystallization of aluminium nickel alloys

The directional crystallization of eutectic Al Ni alloys was studied. Variations of the growth rate caused significant change of the microstructure and mechanical behaviour of eutectic alloys. On the base of a Tiller's analysis involving the voluminal ratio of the two phases the interphase boundary energy σ_αβ is obtained.     

Structural and electrical properties of Germanium-doped Sb70Te30 eutectic thin films

Ge-doped Sb₇₀Te₃₀ eutectic films show high potential for high transfer rate recording and non-volatile memory applications. Their potential applications are based on the difference in optical and electrical properties between the crystalline and amorphous phases. However, the structure and crystallization mechanism of such films is not yet well understood.The aim of this work is to study the amorphous-to-crystalline phase transformation mechanism in eutectic thin films of pure Sb₇₀Te₃₀ and doped with 2, 5 and 10 at% of Ge. Results of isokinetics and isothermal annealing were carried out using various techniques: four-probe electrical, optical reflectance and X-ray measurements.The results of optical and electrical measurements of Ge doped Sb₇₀Te₃₀ eutectic films showed that the addition of Ge increases both, the crystallization temperature and the effective activation energy of crystallization and that the mechanism of crystallization does not depend on Ge contents.In amorphous films, Ge acts as impurity center and does not affect the optical band gap value, but decreases the pre-exponential factor in the thermally activated conductivity. In crystalline films, Ge is probably incorporated into the Sb₇₀Te₃₀ structure and Ge vacancy are responsible for p-type metallic conduction, which increases with increasing the Ge content.     

Crystallization process on amorphous GeTeSb samples near to eutectic point Ge15Te85

One of most important properties of some tellurium-based chalcogenide glasses is the optical and electrical switching between two states: the glass and the crystalline state. The understanding in these systems of the glass to crystal transition and its transformation kinetics is essential for their application in non-volatile memories. GeTeSb and GeTe amorphous samples of compositions close to the eutectic point Ge₁₅Te₈₅ were obtained by rapid solidification from the liquid state employing melt spinning technique. The glass forming ability of this system, for this cooling technique, is restricted to a small composition range nearby the binary eutectic. The crystallization kinetics of the samples was studied by means of differential scanning calorimetry (DSC) under both isothermal and continuous heating regimes. The quenched samples and the crystallization products have been characterized by X-ray diffraction with Cu(Kα) radiation. The crystallization temperature, activation energy, crystallization enthalpy and the dependence of these properties on concentration are reported. The crystallization study of Ge₁₅Te₈₅ glasses shows: a primary crystallization of Te superimposed with a secondary crystallization of GeTe. The addition of Sb (5 at.%) to the eutectic point Ge₁₅Te₈₅ modifies this behavior: the crystallization of Ge₁₃Sb₅Te₈₂ glasses consists on the crystallization of Te and Ge₂Sb₂Te_5. The crystallization of the ternary glasses was modeled.     

Crystallization kinetics of the Zr61Al7.5Cu17.5Ni10Si4 alloy using isothermal DSC and TEM observation

The crystallization behavior and microstructure development of the Zr₆₁Al_7.5Cu_17.5Ni₁₀Si₄ alloy during annealing were investigated by isothermal differential scanning calorimetry, X-ray diffractometry and transmission electron microscopy. During isothermal annealing of the Zr₆₁Al_7.5Cu_17.5Ni₁₀Si₄ alloy at 703 K, Zr₂Cu crystals with an average size of about 5 nm were first observed during the early stages (30% crystallization) of crystallization by TEM. The Zr₂Cu crystal size increased with annealing time and attained an average size of 20 nm corresponding to the stage of 80% crystallization. In addition, the change in particle size with increasing annealing time exhibited a linear relationship between grain growth time and the cube of the particle size for the Zr₂Cu type crystalline phase. This indicates that the crystal growth of the Zr₆₁Al_7.5Cu_17.5Ni₁₀Si₄ alloy belongs to a thermal activated process of the Arrhenius type. The activation energy for the grain growth of Zr₂Cu is 155 ± 20 kJ/mol in the Zr₆₁Al_7.5Cu_17.5Ni₁₀Si₄ amorphous alloy. The lower activation energy for grain growth in compared to that for crystallization in Zr₆₅Cu₃₅ 440 kJ/mol crystal corresponds to the rearrangement of smaller atoms in the metallic glass, Al or Si (compare to Zr).     

Phase lead determined growth of 〈100〉 — textured germanium crystallites in eutectic Ag?Ge alloys

Al Si type eutectics (Al Si, Ag Si, Ag Ge, Zn Ge) form 〈100〉 — textured eutectic dendrites of the semiconductor phase when a certain growth rate R and liquid temperature gradient G are held. The spacings of these eutectic dendrites λ follow the relationship: λ = (r_λ ≈︁ 0.2; g ≈︁ 0.5). The exponents of this relationship can be explained by the model of phase lead determined growth. This model is based on the consideration of the analogy to dendrite growth. The Al Si type eutectics have geometrically similar morphologies for determined G^x/R-relations (x = 1.25 in the case of Ag Ge) and the relation λ²R = const. is valid. In this paper the Ag Ge eutectic will be discussed in close detail.     

Eutectic crystallization of aluminium copper alloys (II). Influence of impurity elements

The directional crystallization of eutectic Al–Cu alloys with Fe additions under molten salts has been studied. According to Tiller's theory the specific interphase boundary energy σ_αβ was estimated for eutectic Al–Cu alloys with three concentrations of additive. Values of σ_αβ depend on Fe-concentration. Small additions of Fe modify the eutectic structure in two directions: a) enlargement of interlamellar spacings. b) formation of rod-like structure.     

Thickness dependence of crystallization and melting kinetics of eutectic Sb70Te30 phase change recording film

As the thickness of eutectic Sb₇₀Te₃₀ phase change recording film was reduced, the crystallization temperature and activation energy for crystallization would increase, while the melting temperature and activation energy for melting would decrease. Accordingly, the archival stability and recording sensitivity can be improved. However, the recording speed for direct over write will be slowed down. Based upon the Johnson-Mehl-Avrami equation, it was found that the increase of film thickness would increase the nucleation rate of eutectic Sb₇₀Te₃₀ recording film and make the crystallization process become more nucleation-dominated.     

Effect of Al addition on the crystallization of a-AlxSi1−x (0.025 x 0.100) by electron-beam irradiation

Si crystals and nano-rods were formed in Al-added amorphous Si films (a-Al_xSi_1−x; 0.025 x 0.100) by the irradiation of a focused electron-beam; the films were in situ heated to be kept at 400 °C and the current density of the electron-beam was 15.7 pA/cm². The size, shape, and concentration of the Si crystallites were varied sensitively with the Al content as well as the irradiation time. Under the electron-beam irradiation, crystallization occurred to produce polycrystalline phases in the a-Al_0.025Si_0.975 film, while rod-shaped Si nanostructures were formed in the a-Al_0.050Si_0.950 and a-Al_0.100Si_0.900 film. It is evident that the removal of Al and as a result the atomic rearrangements and/or local restructuring in the Al/a-Si film are critically affected by the electron-beam irradiation, which lead to the local crystallization and growth of Si nanocrystallites.     

Characterisation of ALCVD Al2O3-ZrO2 nanolaminates, link between electrical and structural properties

Al₂O₃ and ZrO₂ mixtures for gate dielectrics have been investigated as replacements for silicon dioxide aiming to reduce the gate leakage current and reliability in future CMOS devices. Al₂O₃ and ZrO₂ films were deposited by atomic layer chemical vapor deposition (ALCVD) on HF dipped silicon wafers. The growth behavior has been characterized structurally and electrically. ALCVD growth of ZrO₂ on a hydrogen terminated silicon surface yields films with deteriorated electrical properties due to the uncontrolled formation of interfacial oxide while decent interfaces are obtained in the case of Al₂O₃. Another concern with respect to reliability aspects is the relatively low crystallization temperature of amorphous high-k materials deposited by ALCVD. In order to maintain the amorphous structure at high temperatures needed for dopant activation in the source drain regions of CMOS devices, binary Al/Zr compounds and laminated stacks of thin Al₂O₃ and ZrO₂ films were deposited. X-ray diffraction and transmission electron microscope analysis show that the crystallization temperature can be increased dramatically by using a mixed oxide approach. Electrical characterization shows orders of leakage current reduction at 1.1-1.7 nm of equivalent oxide thickness. The permittivity of the deposited films is determined by combining quantum mechanically corrected capacitance voltage measurements with structural analysis by transmission electron microscope, X-ray reflectivity, Rutherford backscattering, X-ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectroscopy. The k-values are discussed with respect to formation of interfacial oxide and possible silicate formation.     

Fabrication of (1 1 1)-oriented Si layers on SiO2 substrates by an aluminum-induced crystallization method and subsequent growth of semiconducting BaSi2 layers for photovoltaic application

We have prepared (1 1 1)-oriented Si layers on SiO₂ (fused silica) substrates from amorphous-Si(a-Si)/Al or Al/a-Si stacked layers using an aluminum-induced crystallization (AIC) method. The X-ray diffraction (XRD) intensity from the (1 1 1) planes of Si was found to depend significantly on growth conditions such as the thicknesses of Si and Al, deposition order (a-Si/Al or Al/a-Si on SiO₂), deposition technique (sputtering or vacuum evaporation) and exposure time of the Al layer to air before the deposition of Si. The crystal orientation of the Si layers was confirmed by θ−2θ, 2θ XRD and electron backscatter diffraction (EBSD). The photoresponse properties of semiconducting BaSi₂ films formed on the (1 1 1)-oriented Si layers by the AIC method were measured at room temperature. Photocurrents were clearly observed for photon energies greater than 1.25 eV. The external quantum efficiencies of the BaSi₂ were also evaluated.     

Study of the structural insertion of Al in the Al2O3-SiO2 and Nd2O3-Al2O3-SiO2 glass systems

Glasses in the Al₂O₃-SiO₂ and Nd₂O₃-Al₂O₃-SiO₂ systems were prepared by the sol-gel method. The gel-glass evolution was studied using near-infrared (NIR) and ultraviolet-visible (UV-VIS) spectrophotometry, X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). The results obtained indicate a relationship between the sample compositions, the treatment temperature and the Al coordination. In the samples of the Nd₂O₃-Al₂O₃-SiO₂ system the densification of the structure, when the treatment temperature increases, leads to the segregation of neodymium oxide particles.     

Enhanced plasticity of a Zr50Cu48Al2 bulk metallic glass

In this work, a Zr₅₀Cu₄₈Al₂ bulk metallic glass (BMG) with improved glass forming ability and mechanical properties was synthesized by adding a small amount of Al to a Zr-Cu binary glass-forming alloy. The as-cast Zr₅₀Cu₄₈Al₂ glassy rod does not exhibit macroscopic failure under compression at room temperature indicating the excellent plasticity of the BMG. The deformation behavior of the BMG was studied intensively by examining the true stress-strain curve and the surface morphology of the post-deformation sample. The effect of minor Al addition on the mechanical properties including the fracture stress, the modulus, and the kinetic characteristics of the BMG was also investigated. The enhanced plasticity of the BMG is considered to be related to its reduced fragility parameter m value.     

Glass formation in the ternary Zr-Zr2Cu-Zr2Ni system

Glass formation and glass forming ability in the ternary Zr-Cu-Ni system were studied systematically. For Cu mold casting, the critical size for glass formation was found to be 1 mm in a relatively wide composition range of 56-64  at.% Zr, 16-26 at.% Cu and 16-24 at.% Ni. The phases competing with glass formation were found to be Zr, Zr₂Cu and Zr₂Ni. Despite the fact that Cu and Ni are completely miscible with each other, they cannot be regarded as simple substitution to each other in the case of glass formation in the Zr-Zr₂Cu-Zr₂Ni ternary eutectic system.     

Synthesis, spectroscopic characterisation and X-ray structure of [trans-Co(en)2(NO2)2]2(Cr2O7)

Dark red crystals of bis[trans-dinitrobis(ethylenediamine)cobalt(III)] dichromate, [trans-Co(en)₂(NO₂)₂]₂(Cr₂O₇) have been obtained by slowly allowing to mix the solutions of potassium dichromate and trans-dinitrobis(ethylenediamine)cobalt(III) nitrate in 1:2 molar ratio in aqueous medium. Elemental analyses and spectroscopic techniques (IR, UV/visible, ¹H and ¹³C NMR) were used for characterizing the complex salt. The complex salt crystallizes in the orthorhombic space group Fdd2 with unit cell dimensions a = 24.778(2) ?, b = 30.457(2) ?, c = 6.5364(5) ?, Z = 8, V = 4932.8(7) ?³, R₁ = 0.0617 and wR₂ = 0.1518. X-ray structure determination revealed an ionic structure consisting of cationic cobaltammine [trans-Co(en)₂(NO₂)₂]NO₃ and dichromate anion. It is the first crystal structure of this cation with a dianion.