Thermally induced stress in GaN layers with regard to film coalescence

Thermally induced plane stress in GaN layers of different thicknesses, grown by metalorganic vapour phase epitaxy on sapphire, is investigated. Thin layers, characterized by isolated grains, are found to be stress-free. With increasing layer thickness, however, grains start to coalesce and stress can build up when the samples are cooled down following growth. As soon as the coalescence process is completed and a compact film has been formed, a maximum stress level is reached which does not further increase for still thicker layers. Therefore, it is proposed that grain edges enable non-compact films to elastically relieve in-plane stress.     

Transmission electron microscopy study of defects in AlN crystals with rough and smooth surface grains

Defects present in (0 0 0 1) textured polycrystalline AlN grown by the sublimation–recombination method were analyzed using transmission electron microscopy (TEM) methods. Grains in the polycrystalline boule had either a smooth or a rough surface. The rough surface grains had mainly edge dislocations, whereas the smooth surface grains had some sub-grain boundaries and were mostly free of dislocations. Dislocations at the grain boundaries were pinned and could not be annihilated.     

In situ time-resolved X-ray diffraction study of octacalcium phosphate transformations under physiological conditions

The present study is focused on the in vitro investigation of octacalcium phosphate (OCP) transformations when mixed with physiological solution (aqueous isotonic 0.9% NaCl) by the energy dispersive X-ray diffraction technique. This technique allowed in situ monitoring of the processes taking place in this system in real time. It was demonstrated that when OCP is mixed with physiological solution, it undergoes two simultaneous processes: (1) amorphous-into-crystalline OCP transformation (37%), and OCP average grain size growth from 22 up to 35 nm; (2) partial phase transformation of OCP (33%) into hydroxyapatite (HA), and HA average grain growth up to 5 nm. Both processes take place simultaneously with the same characteristic time (2.90±0.25) h.     

Fourier analysis based phase shift interferometric tomography for three-dimensional reconstruction of concentration field around a growing crystal

The present work is concerned with the three-dimensional reconstruction of concentration field around a crystal growing from its aqueous solution using Fourier analysis based phase shift interferometric tomography. Projection data of convective field around a growing NaClO₃ crystal have been recorded using a Mach–Zehnder interferometer. A new numerical method based on the concept of real time phase shift interferometry has been employed for the analysis of the interferograms. By interpreting the interferograms as projection data, the 3-D distribution of salt concentration has been determined using principles of tomography. Study shows that the Fourier analysis-based phase shift method is a novel approach for crystal growth studies as it requires only one interferometric image for the determination of full phase information as opposed to the conventional real time phase shift interferometry wherein at least three or more phase-shifted interferograms are needed. Results have been presented in the form of interferograms, path-integrated concentration contours and three-dimensional concentration profiles over select horizontal planes above the growing crystal. Based on the reconstruction results, distribution of salt concentration in the crystal vicinity is determined and an appropriate mechanism of buoyancy-induced fluid movement in the growth chamber is discussed.     

Three-dimensional global analysis of thermal stress and dislocations in a silicon ingot during a unidirectional solidification process with a square crucible

A three-dimensional global model was used to obtain the solution of a thermal field within the entire furnace during a unidirectional solidification process of multicrystalline silicon with a square crucible. Then the thermal stress distribution in the silicon ingot was solved. Based on the solution of thermal stress, relaxation of stress and multiplication of dislocations were performed by using the Haasen–Alexander–Sumino model (HAS model). The influence of crucible constraint on stress levels and dislocations was investigated. It was found that the crucible constraint had significant influence on the thermal stresses and dislocations in the ingot. The results indicated that it is important to reduce the crucible constraint in order to relax thermal stresses and reduce dislocations in a silicon ingot during the solidification process.     

Synthesis of AlN from Li3N and Al: Application to vapor phase epitaxy

We performed synthesis of AlN using Al and Li₃N. In this method, there are two problems that must be solved for obtaining single-phase AlN. One of them is suppression of Li₃AlN₂ formation and the other is precipitation of LiAl from the residual source materials during the cooling process. In the present work, we analyzed phase stability of products and found that AlN was stable at high temperatures and low Li–N/Al molar ratios. However, the products still contained LiAl and Al. Therefore, we examined the effectiveness of vapor phase epitaxy for separating AlN from the extra phase (LiAl and Al formed from residual source materials). From the experimental results, feasibility of vapor phase epitaxy was confirmed. That is, we can deposit only an AlN layer on a sapphire substrate by optimizing the growth conditions, i.e., temperature range above 1150 °C and Li–N/Al molar ratio less than 1.     

Extended defects in bulk GaN and III-nitrides grown on this substrate

A short review of the structural perfection of high-pressure grown bulk crystals is given. As-grown undoped and Mg-doped crystals are described. The dependence of defect arrangement and quality of the surface on growth polarity is described. A high perfection of homoepitaxial layers grown on these substrates is shown. However, growth of thick layers by HVPE may lead to the formation of differently arranged dislocations and the formation of low angle grain boundaries associated with cracks. It is shown that the introduction of dopant or growth of mismatched layers on undoped high-pressure substrates may lead to the formation of additional defects.     

Growth and characterization of ferromagnetic shape memory alloy Co50Ni20FeGa29 single crystals

Single crystals of Co₅₀Ni₂₀FeGa₂₉ with B2 phase have been obtained in a deep supercooling condition. The interface-facets and the segregation effect lead to the formation of ordered defects that store a directional internal stress. These defects give to a large energy barrier that leads to a very sharp martensitic transformation within a temperature window of only 2 K. The single crystals show good shape memory effect and superelasticity, which are anisotropic between the growth direction [0 0 1] and its equivalent direction [0 1 0]. The anisotropic behaviors are attributed to the directional internal stress caused by the ordered defects.     

Crystal growth of Co46Ni27Ga27 ferromagnetic shape memory alloys with large single-variant set

The present work proposes a directional solidification method based on liquid melt cooling (LMC) technique to prepare large grain with single-variant set in Co–Ni–Ga alloys. The competitive growth from equaixed grains to steady columnar crystals with 1 1 0 orientation along the axis was observed. The directionally solidified rod has a uniform chemical composition. It can be also found that the unidirectional lamellar martensitic variants were well aligned in a whole grain, forming a single-variant state. Furthermore, the needle-like Ni₃Ga-type γ′ precipitates were formed in alloy with lower growth velocity, and it exhibited the complicated microstructural evolution. At the lowermost part of rod-like crystal, a large number of precipitates were dispersed both in grain interiors and at boundaries but its amount decreased when the columnar crystals were formed and gradually increased again from bottom up to top in the whole rod.     

Dislocations and grain boundaries in semiconducting rubrene single-crystals

Assessing the fundamental limits of the charge carrier mobilities in organic semiconductors is important for the development of organic electronics. Although devices such as organic field effect transistors (OFETs), organic thin film transistors (OTFTs) and organic light emitting diodes (OLEDs) are already used in commercial applications, a complete understanding of the ultimate limitations of performance and stability in these devices is still lacking at this time. Crucial to the determination of electronic properties in organic semiconductors is the ability to grow ultra-pure, fully ordered molecular crystals for measurements of intrinsic charge transport. Likewise, sensitive tools are needed to evaluate crystalline quality. We present a high-resolution X-ray diffraction and X-ray topography analysis of single-crystals of rubrene that are of the quality being reported to show mobilities as high as amorphous silicon. We show that dislocations and grain boundaries, which may limit charge transfer, are prominent in these crystals.     

Mixed-phase solidification of thin Si films on SiO2

Mixed-phase solidification (MPS) is a new beam-induced solidification method that can produce large-grained and highly (1 0 0)-surface textured polycrystalline Si films on SiO₂. The grains resulting from this mixed-phase solidification (MPS) method, which was conceived based on a well-known phenomenon of coexisting solid–liquid regions in radiatively melted Si films, are found to be essentially devoid of various intragrain defects that always plague, and subsequently degrade the utility of large-grained Si films previously obtained using other crystallization techniques. It is experimentally shown that multiple exposures are required in order to generate such a polycrystalline microstructure from an initial amorphous precursor. The observed trends are conceptually explained in terms of the melt being initiated primarily at grain boundaries in polycrystalline films, and melting and solidification subsequently proceeding laterally at interface-location specific rates as determined by the local thermodynamic factors, which include the anisotropic surface and interfacial energies of the grains, and the unusual local thermal profile—all transpiring within a near-equilibrium but nonisothermal and dynamic environment that needs to address the thermal and stability requirements associated with the coexisting solid–liquid regions.     

Subtle interplay between polytypism and preferred growth direction alignment in GaN nanorods non-catalytically grown on Si(1 1 1) substrates by using hydride vapor phase epitaxy

GaN nanorods were grown on Si(1 1 1) substrates by using hydride vapor phase epitaxy, and the crystallographic characteristics associated with their preferred growth directions were investigated by utilizing synchrotron X-ray reciprocal space mapping in a grazing incidence geometry and scanning electron microscopy. Crystallographic analysis reveals that the nanorods containing both wurtzite and zinc blende phase tend to have narrower distribution of the preferred growth directions than those containing only wurtzite phase. This tendency is partly attributed to the subtle interplay between polytypism and the preferred growth directions of GaN nanorods.     

Analysis of the growth of RF sputtered ZnO thin films using the optical reflective second harmonic generation

Reflective second harmonic generation (RSHG) is used to analyze the growth condition of poly crystal zinc oxide (ZnO) film with a c-axis orientation, grown on the Si substrate by RF magnetron sputtering technique. It elucidates physical phenomena exhibited by growing ZnO thin films. Connecting with analytical results of the characteristic parameters derived from the X-ray patterns and SEM images, the relationship between the RSHG intensity and the substrate temperature reveals that the effect of the grain boundaries is the domination of the RSHG mechanism. The inclined structures of ZnO films on the Si substrate are explained with reference to these RSHG patterns.     

X-ray characterization of detached-grown germanium crystals

Germanium (1 1 1)-oriented crystals have been grown by the vertical Bridgman technique, in both detached and attached configurations. Microstructural characterization of these crystals has been performed using synchrotron white beam X-ray topography (SWBXT) and double axis X-ray diffraction. Dislocation densities were measured from X-ray topographs obtained using the reflection geometry. For detached-grown crystals, the dislocation density is on the order of 10⁴ cm⁻² in the seed region, and decreases in the direction of growth to less than 10³ cm⁻², and in some crystals reaches less than 10² cm⁻². For crystals grown in the attached configuration, dislocation densities were on the order of 10⁴ cm⁻² in the middle of the crystals, increasing to greater than 10⁵ cm⁻² near the edge. The measured dislocation densities are in excellent agreement with etch pit density (EPD) results. Broadening and splitting of the rocking curve linewidths was observed in the vicinity of subgrain boundaries identified by X-ray topography in some of the attached-grown crystal wafers. The spatial distribution of rocking curve linewidths across the wafers corresponds to the spatial distribution of defect densities measured in the X-ray topographs and EPD micrographs.     

High-velocity banding structure in the laser-resolidified hypoperitectic Ti47Al53 alloy

Stability analysis of a growing solid/liquid interface is the fundamental concept of modern solidification theory. Here, serial laser rapid solidification experiments were performed on a hypoperitectic Ti₄₇Al₅₃ alloy to explore the dendritic growth behavior near the limit of high-velocity absolute stability. SEM and TEM techniques were carried out to investigate the microstructure and identify the phase composition. By adopting an improved sampling method of TEM, the growth morphology evolution of the laser-resolidified layer was observed directly and high-velocity banding structure was firstly detected in Ti–Al peritectic alloys. The high-velocity banding structures are parallel to the solid/liquid interface (normal to the growth direction) and made of the oscillation structures grown alternatively in modes of cell and plane morphologies. In light bands with cellular growth mode, all dislocation assembles are parallel to the growth direction and forms the cell boundaries, while all dislocation distributes randomly in dark bands. The determined growth velocity range for the appearance of high-velocity banding structures is about 0.51.1 m s⁻¹ according to the rapid solidification experiments, and the origin of the banding agrees well with the prediction of the CGZK phenomenological model (Acta Metal. Mater. 40 (1992) 983).     

Edge-defined film-fed growth of Yb:YVO4 single crystal plates

The applicability of the edge-defined film-fed growth (EFG) technique for Yb_xY_(1−x)VO₄ (x=0.05, 0.1 and 1) was approved by successful growth of crystals up to 80 mm in length as the thin plates. Low-angle grain boundaries and the crystal coloration as main defects were found. Optimal seed orientation was suggested on the strength of vanadate crystal plate morphology. Optical properties, chemical composition and the crystalline quality were investigated.     

Defect characterization and composition distributions of mercury indium telluride single crystals

A mercury indium telluride (MIT) ingot was grown by the vertical Bridgman method. The defects in MIT crystals were characterized by the chemical etching method. A defect etchant for MIT crystals was developed. The etch pits of dislocations, microcracks and boundary was observed by scanning electron microscopy. It was elucidated that the etch pits density of dislocations of MIT wafers was about 4×10⁵ cm⁻². Te and In reduced at the grain boundaries, but were homogeneously distributed within the grains in the as-grown MIT crystals. The distribution of In in MIT crystals along the growth direction and radial direction was analyzed by electronic probe microscopy. It was found that In concentration was higher in the initial part and lower in the final part of the MIT ingot, which indicated that the segregation coefficient of In in MIT crystals was 1.15. The radial In concentration increased from the center to edge of the wafers and homogeneous in the middle part.     

Reducing dislocation density in GaN films using a cone-shaped patterned sapphire substrate

The threading dislocation (TD) density in GaN films grown directly on flat sapphire substrates is typically >10¹⁰/cm², which can deteriorate the properties of GaN-based LEDs significantly. This paper reports an approach to reducing the TD density in a GaN layer using a variety of patterned sapphire substrates (PSS). A cone-shaped PSS produced by metal organic chemical vapor deposition (MOVCD) was used for GaN deposition. Three types of GaN specimens were prepared at the initial nucleation stage, middle growth stage and final growth stage. The TDs generated on the cone-shaped PSS were analyzed by transmission electron microscopy (TEM) and a strain mapping simulation using HRTEM images, which evaluated the residual strain distribution. A large number of TDs were generated and the residual strain by the lattice distortions remained above the top of the cone-shaped regions. However, no TDs and residual strain were observed at the slope of the cone-shaped regions. This might be due to the formation of a GaN layer by lateral overgrowth at the slope of the cone-shaped regions, resulting in less lattice mismatch and incoherency between the GaN and sapphire. In conclusion, the TD density in the GaN layer could be reduced significantly, approximately 10⁷/cm², using the cone-shaped PSS.     

Environmental SEM investigation on surface defects in 0.92Pb(Zn1/3Nb2/3)O3–0.08PbTiO3 single crystal

In this paper, the technique of environmental scanning electron microscopy (ESEM) has been employed to investigate the surface defects of the (1 1 1) appearing face in 0.92Pb(Zn_1/3Nb_2/3)O₃–0.08PbTiO₃ (PZN–8%PT) crystals. From the ESEM images, we succeeded in observing and studying the growth hillocks and etch pits, low-angle grain boundaries, and sub-grain boundaries in (1 1 1) face, which were related to the generation of dislocation and stacking faults, respectively. On the other hand, an image of a unique multi-layer lamellar structure and fine step structure obtained in the (1 1 1) face reveals that the dominant fast growth mechanism of PZN–8%PT crystal grown by the flux method is a sub-step mechanism, unlike the screw dislocation growth mechanism.     

Estimation of growth rate in unidirectionally solidified multicrystalline silicon by the growth-induced striation method

Multicrystalline silicon was grown by unidirectional solidification method using the accelerated crucible rotation technique. The application of the accelerated crucible rotation technique in unidirectional solidification method induced growth striations across the axial direction of the grown crystal. This striation pattern was observed from carbon concentration distribution, obtained by using Fourier transform infrared spectroscopy. The generated striation pattern was found to be weak and discontinuous. Some striations were absent, probably due to back melting, caused during each crucible rotation. From the growth striations and applied time period in crucible rotation, the growth rate was estimated by using Fourier transformation analysis.