Etching Studies on Potassium Dichromate (KBC) Crystals

An investigation of the revelation of dislocations in potassium dichromate (KBC) crystals by etching in water, alcohls, and in inorganic acids mixes with acetone and alcohols is carried out. It is observed that several solutions including water, alcohols and organic acids produce disslocation etch pits on various faces of KBC crystals. Observations of twining and dissolution anisotorpy of (001) faces are also presented. Etching of (001) cleavage faces of same crystals in an etchant composed from 1 part HNO₃ and 3 parts acetone indicates the possible growth of another phase at low temperatures.     

Etching Figures in Neodymium Gallate and Yttrium Aluminate Crystals

The dislocations existing in single crystals of neodymium gallate and yttrium aluminate grown by the Czochralski technique have been studied by means of etch pits. The data concerning their solubility in cases of different directions of a face orientation, various treatment temperatures and several enchant types are reported. The investigation of etch pits in the twinned YAlO₃ and NdGaO₃ crystals showed that twins are formed during a growth process. In the [110]‐pulled NdGaO₃ crystals the discrepancy between the twin and matrix parts of a crystal is accommodated by the dislocation congestion and the dislocation low‐angle boundaries whereas in [010]‐pulled YAlO₃ crystals the microcracks perform this function.     

Microstructures of Tin Iodide Single Crystals Grown in Silica Gels

Single crystals of tin iodide (SnI₂) have been grown in silica gels. A detailed microtopographical study of {100} faces have been described. Horizontal striations are predominant on these faces for most of the crystals, while few of them show vertical striations. The horizontal striations are associated with the two-dimensional nucleation theory whereas the vertical striations relate to the growth fronts. Growth layers modified by the presence of misaligned microcystals have been illustrated. The natural etch pits on {100} faces of the crystal are attributed to the dissolution of crystals in the acid set gel. In the light of these observations, the mechanism of the development and growth of these faces have been assessed and the implications are discussed.     

Static magnetic fields in semiconductor floating-zone growth

Heat and mass transfer in semiconductor float-zone processing are strongly influenced by convective flows in the zone, originating from sources such as buoyancy convection, thermocapillary (Marangoni) convection, differential rotation, or radio frequency heating. Because semiconductor melts are conducting, flows can be damped by the use of static magnetic fields to influence the interface shape and the segregation of dopants and impurities. An important objective is often the suppression of time-dependent flows and the ensuing dopant striations. In RF-heated Si-FZ-crystals, fields up to 0.5Tesla show some flattening of the interface curvature and a reduction of striation amplitudes. In radiation-heated (small-scale) Si-FZ crystals, fields of 0.2–0.5Tesla already suppress the majority of the dopant striations. The uniformity of the radial segregation is often compromised by using a magnetic field, due to the directional nature of the damping. Transverse fields lead to an asymmetric interface shape and thus require crystal rotation (resulting in rotational dopant striations) to achieve a radially symmetric interface, whereas axial fields introduce a coring effect. A complete suppression of dopant striations and a reduction of the coring to insignificant values, combined with a shift of the axial segregation profile towards a more diffusionlimited case, are possible with axial static fields in excess of 1Tesla. Strong static magnetic fields, however, can also lead to the appearance of thermoelectromagnetic convection, caused by the interaction of thermoelectric currents with the magnetic field.     

Role of microcrystals in the growth and development of prism faces of cultured quartz (II.) Detached microcrystals

Results of microtopographical investigations on prism faces of cultured quartz crystals grown by hydrothermal crystallization techniques, undertaken with a view to determine the influence of microcrystals which get attached to the growing host prism face and then get detached, at some stage of growth, from or still remain attached to the host face, with special reference to the role played by them in the growth and development of host prism faces in particular and the quartz crystals in general, are discussed. The study is an extension of, and obviously to be dealt in continuation with, the earlier one (Part-I, see JOSHI , KOTRU ). Polygonal cavities of various shapes and structures observed on the prism faces are described. Mechanism of formation of the polygonal cavities is explained. Also described are pyramidal depressions, striations, growth hillocks, and etch pits within the cavities on the growing host prism faces. Some of the observed structures within the cavities are attributed to the imprints of the surface structures on the faces of detached microcrystals of quartz. Evidence of growth within the cavities is offered and the implications of such a growth are discussed. Evidence of micro-etching in the cavities is suggestive of the possibilities of some of the grown cultured quartz crystals to get etched in the autoclave. Two different suggestions are made for the interpretation of the origin of etch pits within the cavities, and there is support for the view that they are as a result of etching, only at a time when the supply quartz gets exhausted, of some of the grown crystals where the growing chamber is the hottest.     

Long-term Crystal Growth under Microgravity during the EURECA-1 Mission (II) THM Growth of Sulphur-doped InP

Long-term crystal growth experiments were successfully performed under microgravity conditions during the first flight of the unmanned EURECA-1 mission in the automatic mirror furnace (AMF). Two crystals of sulphur-doped InP with [001] and [111] orientation respectively were grown from indium solution by the travelling heater method (THM). The absence of time dependent buoyancy-driven convection is documented by the lack of type I striations in the space-grown crystals. The sulphur concentration is measured by spatially resolved photoluminescence. As expected, the macrosegregation can be described by a pure diffusion-controlled model which is in good agreement with the findings from the first German spacelab mission D1. Compared to the earth-grown reference samples, both of the space-grown InP crystals show strong disturbances such as inclusions and type II striations. The morphological instabilities are similar to growth disturbances already known from the space-grown MD-ELI-01 from the D1 mission.     

Growth and dissolution of BaFCl crystals

Single crystals of BaFCl have been growth by flux technique using BaF₂ and BaCl₂. Etching with formic acid revealed dislocation etch pits on (001) cleavage faces of the crystals, at room temperature. The influence of etching parameters such as undersaturation, temperature and concentration of poison in the etchant is studied. Decreasing the undersaturation of formic acid by reducing the percentage of water and increasing the temperature of the etchant were found not to have any effect on the morphology of etch pits. However, as the CdCl₂ poison concentration is gradually increased, the orientation of the pits change from 〈100〉 to 〈110〉 at high concentration.     

Revealing extended defects in HVPE-grown GaN

In this communication we will summarize the results of a complementary study of structural and chemical non-homogeneities that are present in thick HVPE-grown GaN layers. It will be shown that complex extended defects are formed during HVPE growth, and are clearly visible after photo-etching on both Ga-polar surface and on any non-polar cleavage or section planes. Large chemical (electrically active) defects, such as growth striations, overgrown or empty pits (pinholes) and clustered irregular inclusions, are accompanied by non-uniform distribution of crystallographic defects (dislocations). Possible reasons of formation of these complex structures are discussed. The nature of defects revealed by selective etching was subsequently confirmed using TEM, orthodox etching and compared with the CL method. The non-homogeneities were studied in GaN crystals grown in different laboratories showing markedly different morphological characteristics.     

Distinction between topography of prism faces of natural and cultured quartz crystals

Results of detailed microtopographical studies on prism faces of a large number of natural and hydrothermally grown quartz crystals are described, illustrated and discussed. In the light of these results distinction between prism faces of the two varieties of quartz is assessed. Horizontal striations, parallelogram shaped and low angle tetrahedral growth pyramids are reported as characteristic features on prism faces of natural quartz crystals, whereas hexagonal and square shaped pyramids are shown to be characteristic features on prism faces of cultured quartz crystals. Evidence of independent growth on prism faces of both the varieties of quartz crystals are given. A wide variety of growth forms, like oriented snail shaped hillocks, pentagonal elevations, rectangular spiral patterns, screw ledges, missile-like structures, influence of impurities on advancing growth fronts, microdiscs patterns and etch patterns due to chemical etching are explained.     

Studies on twin boundaries in calcite crystals

Natural single crystals of calcite have been cleaved along (100) planes and cleavage faces have been etched in 2% and 3% citric acid solutions. Etching produces twin boundaries oriented in 〈010〉 directions. The etch pits on the two sides of the twin boundary are oppositely oriented. It has been conjectured that the rows of pits might have been formed due to etching of dislocations on twin boundaries. One to one correspondence of twin boundaries has been established on matched cleavage faces. This is further confirmed by studying the induced twin regions produced on a (100) cleavage plane by indenting that plane itself. The implications are discussed.     

Chiral Etch Pits on Sodium Chlorate Crystals

Microtopography of {100}, {110}, {111}, and {210} surfaces of sodium chlorate crystals etched in various solvents has been studied by optical microscopy. It has been established that etch pits formed on left- and right-handed crystals are chiral, and directions of dissolution steps reveal bond chains of the structure.     

X-ray topographic study of quartz crystals with induced growth striations

The method of “induced growth striations” was applied to the hydrothermal growth of quartz crystals. Striations were due to a periodical modulation of the growth temperature induced and investigated by means of the X-ray Lang topography and plane wave reflection topography. The results show that the X-ray topographic methods are a sensitive tool for the characterization of the growth striations, which are produced generally by Al impurities. The application of the method of induced growth striations to quartz crystals and the characterization of these crystals with optical and X-ray topographical methods allow a deeper understanding of the crystal growth behaviour.     

Selective etching of ZnTe in HF:H2O2:H2O solution: Interpretation of extended defect‐related etch figures

HF:H₂O₂:H₂O solution (40%wt.HF: 30wt.%H₂O₂: H₂O, 3:2:1 by volume) was used to reveal extended defects (line, face and volume defects) in bulk ZnTe crystals grown from Te solution. The etch patterns were analyzed based on their size, shape and distribution. The etch figures, both in the shape of pits and hillocks with high resolution, show forms controlled by the symmetries of the respective faces were produced. Two different sizes of pits were observed, the larger‐size pits correspond to dislocations penetrating the surface, however, the smaller‐size texture pits are produced on the defect‐free region, which serve as standard pits on respect faces. The face defects, such as grain boundaries, sub‐grain boundaries, dislocation walls, twins and stacking faults, can be all displayed clearly. Another essential feature of the etchant is that, it can effectively dissolve Te‐rich phase (Te inclusion/precipitates), which makes it promising to reveal the shape of this volume defect.     

Surface structures of fluorite crystals

Optical studies have been made of the microstructures on the natural {100} and {111} faces of natural fluorite crystals. The protrudance of triangular elevations, growth pyramids, and natural etch pits have been observed on a large number of crystals. It is suggested that fluorite crystals grown by two-dimensional spreading and piling of growth layers parallel to {100} faces. The natural etch pits on {100} and {111} faces suggest that they have been produced as a result of a dissolution process in nature. The natural faces have been etched in the laboratory and it is established that the pits indicate the existence of linear defects in the crystals. The implications are discussed.     

Shape of thermal etch pits and crystal structure in tellurium crystals

During the systematic study of thermal etching of tellurium crystals, various shaped thermal etch pits were observed on the {101 0} cleavage faces of this crystal. An attempt has been made to explain the shape of non-dislocation and dislocation etch pits. A simple model based on crystal structure and bonding of atoms has been suggested to explain the shape of etch pits.     

Etching behaviour of calcium fluoride crystals in hydrochloric acid vapour

Etching of octahedral cleavage faces of calcium fluoride crystals in hydrochloric acid vapour has been investigated. It is observed that dislocation etch pits and non-dislocation elevations are formed. The morphology of etch pits obtained by vapour etching is observed to be different from that obtained by weak acid solutions. The results are discussed in terms of the prevailing etching conditions.     

Evidence of slip in calcium fluoride single crystals

Natural single crystals of calcium fluoride have been cleaved along (111) planes and the cleavage faces have been etched in 0.2 N nitric acid solution. Etching produces rows of equally spaced etch pits running in <110>directions. One-to-one correspondence of glide bands has been established on the matched faces and on the three different flakes of the same crystal. This is further confirmed by studying the rosette structure produced on a (111) cleavage plane by indenting that plane itself. The active slip planes are found to be {110}. The implications are discussed.     

碲锌镉单晶体的(110)面蚀坑形貌观察

本文报道了一种能够在室温下择优腐蚀碲锌镉(CZT)单晶体(110)晶面的腐蚀液配方,并对富Cd生长的CZT晶体蚀坑形貌进行了扫描电镜观察.结果表明晶体(110)面腐蚀坑形状为三角形,并初步对蚀坑的成因进行了分析,估算出CZT(110)面蚀坑密度约为103～105/cm2数量级.这说明富Cd原料的改进布里奇曼法可以生长出低蚀坑密度的CZT单晶体.     

Etching of CaF2 single crystals in silica gels

Etching of {111} cleavage faces of CaF₂ crystals in aqueous solution of 50% HCl is carried out in citric acid set silica gel, and the kinetics of growth of etch pits at the sites of dislocations is investigated as a function of temperature, time of etching and height of gel column above the crystal surface. It is observed that the transient period required to initiate etch pit at the sites of a dislocation decreases (1) at particular temperature, with a decrease in gel height, and (2) for a particular gel height, with an increase in the temperature of etching. It is also observed that the morphology of dislocation etch pits remains triangular irrespective of the gel height and the temperature of etching. The results are compared with those of solution etching and discussed.     

Solution growth and comparative characterization of L‐HFB single crystals

Single crystals of L‐histidine tetrafluoroborate (C₆H₁₀N₃O₂BF_{4 ,} L‐HFB) were grown by solution growth method using two different temperature profiles: conventional, in which the growth temperature was kept constant at 30°C and rapid, in which it was increased in steps of 1 K per day while keeping the other growth conditions same. Crystals grew in nearly 30 and 10 days in the two methods, respectively. The crystals were transparent and showing its characteristic morphology. Both types of crystals were characterized by XRD for their structural comparison. Surface morphology and growth features of the crystals were studied by SEM. Features of two dimensional layer growth steps, rectangular etch pits, slip lines and bands, etc. were observed. The presence of various functional groups and their bonding were studied by FTIR in the range 4000‐400 cm^‐1. Thermal stability of the crystals was determined by thermo‐gravimetric and differential thermal analysis. The generation of green light due to second harmonic generation for fundamental λ =1064 nm has been confirmed in both cases. Dielectric constant measurement was carried out in the range 20Hz‐2MHz. In the UV‐Vis studies, high transmittance and a shorter ‘lower cut off' value (232 nm) were observed. The effect of rapid growth on the structural, morphological and optical properties of the crystals were studied and compared to those of crystals grown in conventional way. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)