On the void distribution and size in shaped sapphire crystals

Ribbon and rod sapphire pulling has been performed in three different crystal growth equipments in order to study the effect of the installation, of the atmosphere, of the die shape, of the feed material and of the pulling rate on the distribution, number and diameter of the characteristic voids (micro‐bubbles) in the crystals. The location of the bubbles in the crystals depends on the die geometry; however, in most cases they are essentially located close to the crystal periphery and then can be efficiently removed by lapping. After statistical analysis of the results, it is demonstrated that the number of gas moles incorporated in the crystals, inside the voids, is totally independent of any growth parameter. It is also shown that the bubble diameter depends only on the pulling rate. Consequently, for a given pulling rate, the number of bubbles auto‐adjusts in order to satisfy the constant molar gas incorporation. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gas bubbles in shaped sapphire

Shaped sapphire single crystals almost always contain a typical defect: small bubbles also known as “micro-voids”. The goal of this paper is to review the existing literature and give a survey of our recent work on this specific defect. As a conclusion to our review we propose a mechanism for bubble formation and its occurrence and distribution in shaped sapphire.The bubbles contain CO which originates as a result of complex reactions between the molten alumina, Mo crucible and graphite pieces. The CO dissolves in the molten alumina and is probably present as a saturated solution whatever the growth conditions. Then the dissolved gas is rejected at the solid–liquid interface and bubble nucleation occurs where the concentration of CO is highest. Therefore, the location of the bubbles in the crystal is governed by the hydrodynamics in the meniscus, which include Marangoni convection. The bubble is finally incorporated in the crystal when it reaches a critical size which depends only on the growth rate.When a central capillary channel is used, the bubbles are located in a layer close to the surface of the crystal from where they can be easily removed by polishing. Also, all the literature agrees on the fact that interface destabilization at high velocity results in the presence of bubbles throughout the entire crystal and should be avoided.     

The influence of thermal screens on the temperature distribution,thermal stress,and defect structure during growth of shaped sapphire crystals

The ways in which a block structure is formed in shaped sapphire single crystals grown from melt by the Stepanov method are considered. The measured temperature distributions and results of a mathematical modeling of the heat exchange in the growth zones, as well as the calculated thermoelastic fields and measured residual stresses, are reported. The possibility of effectively controlling the thermal fields and growth of block-free crystals by choosing optimal screening is shown for single crystals in the form of tubes and basal-plane-faceted ribbons.     

The mechanism of formation of light-scattering centers in sapphire crystals grown in gas atmospheres

The mechanism of the formation of light-scattering centers in sapphire crystals grown by horizontal directed crystallization in gas atmospheres reducing with respect to the Al₂O₃ melt was studied. The experimental regularities here significantly differ from those observed upon formation of other conventional defects in sapphire crystals (vacancy pores, gas bubbles, and so on). It is shown that the known formation mechanisms of macroscopic ≥1 mm) inclusions in crystals are not acceptable in this case. Using the model of bulk crystallization is proposed to describe the obtained regularities.     

Mathematical modeling of impurity distribution in the melt meniscus in the growth of profiled sapphire crystals

The distribution of impurities in the growth of profiled sapphire crystals is simulated. The distribution of impurities was calculated with the use of the diffusion equation with convective terms. The melt flow was found by solving the Navier-Stokes equation. The distributions of impurities over the melt meniscus are obtained at different crystallization rates. The maximum concentration supersaturation in the meniscus is studied as a function of its geometric parameters.     

Haze in sapphire crystals grown by SAPMAC method

Haze defect in SAPMAC method grown sapphire crystal was studied in detail. It is shown that haze is composed by a large number of CO₂ bubbles, and haze always appears in the axis region of the crystal since the bubbles formed in front of the crystallization surface are most always draged to the convection rolls in front of the central part of the crystallizaiton surface by melt and then engulfed by the rolls. Moreover, the effects of pulling rate on the formation of haze were analyzed and means for restraining haze was suggested. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Redistribution of thermoelastic stresses in shaped crystals: Numerical simulation

The shape of crystals was considered for the first time as an important factor controlling thermoelastic stresses during crystal growth. It was found on the basis of numerical simulation that thermoelastic stresses can be redistributed by varying the shape of a crystal during growth. In this way, large weakly stressed regions can be obtained in the crystal owing to the formation of locally stressed regions. As an example, a model of a sapphire ribbon (50 × 175 mm²) divided by waists into three plates (50 × 50 mm²) is discussed. Different crystallographic orientations and slip systems are considered.     

Growth of sapphire crystals for optoelectronics from alumina in a protective medium

This paper reports on the results obtained during the development of the technological process of growth of sapphire crystals for optoelectronics through horizontal directional crystallization in a gaseous argon medium at a pressure of 800 mmHg. The sapphire crystals intended for the use in optoelectronics have been grown from purified molten alumina according to the authors’ technology. It has been demonstrated that, under conditions of a high temperature gradient across the crystallization front and at a low content of reducing components (H₂, CO) in the growth medium, it is possible to grow sapphire crystals satisfying the requirements of optoelectronics.     

Specific features of the morphology and distribution of gas inclusions in single-crystal sapphire ribbons grown by the Stepanov method

The distribution of gas inclusions in single-crystal sapphire ribbons with different crystallographic orientations, grown by the Stepanov method, is analyzed. In all ribbons gas inclusions are observed only in thin surface layers located at a depth of about 100 μm. One characteristic feature is the presence of several zones with different distributions and morphologies of inclusions. We observed inclusions of the two types: cylindrical pores and microbubbles. The differences in the morphology and zonality of the gas-inclusion distribution are consistent with the α-Al₂O₃ crystallography.     

Sapphire shaped crystals for waveguiding,sensing and exposure applications

Second half of the XX century was marked by a rapid development of sapphire shaped crystal growth technologies, driven by the demands for fast, low-cost, and technologically reliable methods of producing sapphire crystals of complex shape. Numerous techniques of shaped crystal growth from a melt have been proposed relying on the Stepanov concept of crystal shaping. In this review, we briefly describe the development of growth techniques, with a strong emphasize on those that yield sapphire crystals featuring high volumetric and surface quality. A favorable combination of physical properties of sapphire (superior hardness and tensile strength, impressive thermal conductivity and chemical inertness, high melting point and thermal shock resistance, transparency to electromagnetic waves in a wide spectral range) with advantages of shaped crystal growth techniques (primarily, an ability to produce sapphire crystals with a complex geometry of cross-section, along with high volumetric and surface quality) allows fabricating various instruments for waveguiding, sensing, and exposure technologies. We discuss recent developments of high-tech instruments, which are based on sapphire shaped crystals and vigorously employed in biomedical and material sciences, optics and photonics, nuclear physics and plasma sciences.     

Singular ring‐shaped distribution of Nd in NdxY1‐xVO4 crystals grown by floating zone method

A singular ring‐shaped distribution of high Nd concentration was observed in Nd‐doped YVO₄ single crystals grown by the floating zone (FZ) method. The ring‐shaped distribution appeared 500‐1000 μm inside from the rim of the crystals. Results of growth experiments by the anisotropic heating floating zone (AHFZ) method showed that the Nd concentration was high at the high‐temperature side of the grown crystals. We found a small concave projection at a part of the convex solid‐liquid interface by quenching the molten zone during growth. The cause of the singular ring‐shaped distribution of the Nd‐rich area was discussed in relation with the concave projection at the interface and the convection in the molten zone. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Modeling habit forms of sapphire crystals using the principles of periodic-bond-chain method

The potential of the periodic-bond-chain method for calculating the sequence of manifestation of faces of corundum single crystals is considered. The leading role of the faces of the pinacoid, high rhombohedron, and hexagonal prism is demonstrated. The calculation results are compared with the experimental data on faceting the lateral surface of cylindrical sapphire single crystals grown by the Stepanov method and with the faceting data for crystals grown by the flux method and natural crystals.

     

Heterogeneous gas bubble formation during GaP solution growth

The gas bubble formation on seed surface, during growth of GaP crystals from the solution, is considered on the basis of the model for heterogeneous nucleation. It is shown that the bubble formation in this case could be a consequence of the interaction between gallium oxide, Ga₂O₃, and gallium generating gaseous gallium protoxide, Ga₂O₃, during heating. The size of the bubbles incorporated in the crystal depends on the kinetics of this reaction and the dissolution rate of Ga₂O₃ in liquid gallium. The values of forces that act on gaseous bubbles in the liquid zone are estimated. It is shown that the migration behaviour of these bubbles is mainly determined by Archimed and thermocapillary forces and depends on growth situations. The methods for avoiding bubble formation in GaP solution growth are suggested.     

The distribution of impurities in lysozyme crystals

The effective distribution coefficient, K_Ieff, of turkey egg white lysozyme into host hen egg white lysozyme crystals was measured for varying levels of relative supersaturation, impurity concentrations and temperatures. Turkey egg white lysozyme served as a test impurity of high homology to hen egg white lysozyme. K_Ieff increased with increasing host protein concentration and temperature, consistent with a kinetically controlled incorporation process. The principles of slow crystal growth rate to limit impurity incorporation were applied to a commercial source of lysozyme with concomitant improvement in purity of re-crystallized protein.     

New advances and developments in the Stepanov method for the growth of shaped crystals

The main recently developed versions of the Stepanov method are analyzed, and a brief review of the main achievements in the growth of shaped crystals is given.     

Supersmooth and modified surface of sapphire crystals: Formation,characterization, and applications in nanotechnologies

The results of studying the state of the surface of sapphire crystals by a complex of methods in different stages of crystal treatment are considered by an example of preparing sapphire substrates with a supersmooth surface. The possibility of purposefully forming regular micro- and nanoreliefs and thin transition layers using thermal and thermochemical impacts are considered. The advantages of sapphire substrates with a modified surface for forming heteroepitaxial CdTe and ZnO semiconductor films and ordered ensembles of gold nanoparticles are described. The results of the experiments on the application of crystalline sapphire as a material for X-ray optical elements are reported. These elements include total external reflection mirrors and substrates for multilayer mirrors, output windows for synchrotron radiation, and monochromators working in the reflection geometry in X-ray spectrometers. In the latter case, the problems of the defect structure of bulk crystals sapphire and the choice of a method for growing sapphire crystals of the highest structural quality are considered.     

Convection in melts and impurity distribution in semiconductor crystals

Impurity distributions in semiconductor melts and crystals grown from these melts are experimentally and numerically studied on an example of Ga-doped Ge crystals. It is shown that inhomogeneous dopant distribution is observed in the form of striations and is caused by the convective flows in the melt and their nonstationary rearrangement in the vicinity of the crystallization front. The character of heat and mass transfer under the microgravity conditions is predicted. The necessity of precision experiments under terrestrial and, especially, space conditions is emphasized.     

Basal twinning as a room temperature plastic deformation mode of chromium- and titanium-doped sapphire crystals

The degree of basal twinning caused by indentation was determined quantitatively on a series of chromium and titanium doped sapphire crystals with variours dopant contents. It depends on the dopant content significantly. The effect of titanium ions in reducing the degree of twinning is more pronounced than that of chromium dopants. This “size effect” of the dopant ions is consistent with the mechanism of basal twinning as reported by KRONBERG .