Properties of Surface Layers in Single Crystals of Calomel

Within the framework of the systematic study of differences in physical properties of the calomel (Hg₂Cl₂) single crystals before and after surface treatment, the differences in the microhardness, the residual stress in the surface layer, and the chemical etching rate were investigated on the (110) and (001) crystal faces. It has turned out that Beilby layer (B-layer) formed during surface treatment is softer, and, on the cleavage surface is harder than the underlying bulk material. The thickness of the B-layer in these samples ranged between 5 anf 7 m̈m. Further it has been found that a tensile residual stress s̀ = 14 Nm^-2 prevails in the surface layer of a polished (110) face to a depth of 70 m̈m and, after grinding, to a depth from 90 to 200 m̈m. On the other hand, a compressive stress has been found in the natural cleavage plane. Experiments on etching the Hg₂Cl₂ crystals with HCl + HNO₃ etching solution have shown that the rate of chemical etching is 2 to 4 times larger on the (110) face than on the (001) face. Differences are very strongly dependent on the experimental conditions and on the real structure of a given surface.     

Growth mechanism of crystals from aqueous solutions

Microscopic processes occurring on the surface of a growing crystal or a dissolving one were observed by microcinematography. The crystals under observation were grown either in a drop of solution by evaporation or in a constant-temperature microscope stage at a chosen supersaturation. Small (approx. 0.1 mm) and large (approx. 10 mm) crystals of NaCl, Pb(NO₃)₂, NaNO₃, CdI₂, KDP and ADP were studied. It is concluded qualitatively that the layers, in general polygonal, originating in one or several active centres, are formed on the crystal face, never at the corners or edges. – The average velocity of layer motion was studied quantitatively in dependence on their thickness and supersaturation. The layer motion at constant supersaturation considerably fluctuated. – Surface patterns created by moving layers agree in most cases with predictions of the dislocation theory. Two categories of steps were found on the surface: ”︁real”︁ macrosteps and shock waves. – The velocity of layer motion for most compounds lies within (1–10) · 10⁻⁴ cm · s⁻¹.     

The structure and melting of a lead nanocrystalline layer in reduced lead-germanate glass

A surface layer of lead nanoclusters has been obtained by thermal treatment of Pb_0.3Ge_0.7O_1.7 glass in hydrogen atmosphere. The thickness and structure of such layers depend heavily on the temperature and time of reduction. Structural studies of the lead layer have been performed with atomic force microscopy and X-ray diffraction. It has been shown that melting and solidification of lead nanoclusters induce a radical change in the surface conductivity of the reduced glass. Characteristic changes of melting and solidification temperature with Pb granules’ diameter have been found.     

Orientation relationships of aluminium nitride on sapphire

Orientation relationships of aluminium nitride on sapphire (112 6) AlN/(011 2) Al₂O₃ have been defined more exactly by X-ray diffractometry techniques. It has been found that, depending on the substrate misorientation from the surface plane (011 2), there can exist two kinds of azimuthal orientation of the epitaxial layer of AlN, namely, the projection of [0001] AlN on plane (011 2) Al₂O₃ can coincide either with [2 110] Al₂O₃ or with [21 1 0] Al₂O₃ direction. The vector field of the epitaxial layer inclination relative to the substrate misorientation has been drawn. The symmetry of this field obeys Neumann's rule. The epitaxial layer orientation has been found to depend on the sapphire substrate misorientation in direction [21 1 0].     

The role of hydration and complexing in the mechanism of impurity influence on crystal growth

The influence of impurities of chlorides and nitrates of divalent Ca²⁺ and Ba²⁺ cations on the kinetic growth of potassium dihydrophosphate KH₂PO₄ crystals at a saturation temperature of 323 K and relative supersaturation of 0.03 has been investigated experimentally. It is established that the impurity acts differently, depending on the face index, the impurity concentration, cation hydration, and the stability of the complexes formed in the solution by impurity salt ions. A model is proposed to explain the different influence of impurity ions on the growth of crystal faces. This influence is determined by the different hydration of cations and enhanced association of cations and anions of impurity salts in the surface layer with a lower dielectric constant.     

On the deposition mechanism of boron in silicon CVD epitaxy

The deposition mechanism of boron doping in CVD silicon epitaxy has been investigated by exposing silicon substrates to B₂H₆ H₂ doping gas mixtures at epitaxy temperatures and examining the effect by dopant profile measuring in an afterwards intrinsically in-situ deposited epitaxial silicon layer. It has been shown that boron is deposited increasing its concentration on the surface linearly with prolonged exposition time and desorbed by purging the surface in pure hydrogen. In the latter case its content decreases linearly proportional to the predeposited concentration. The desorbed boron builds up a secondary doping source which maintains a parasitic boron flow for reincorporation during following layer growth.     

Problems of Surface Morphology and Layer Deposition during Plasma Etching Processes (II) Si-etching in CF4-, CF4/O2-and CF4/H2 Plasmas

The plasma etching of Si in CF₄-, CF₄/O₂-and CF₄/H₂ plasmas was investigated in dependence on the etching gas, the plasma conditions (pressure, power density) and etching time in different reactors. A roughening of the surface and the formation of a “semi-amorphous” surface layer with a power-like morphology was detected by TEM-and RHEED methods. It is supposed that the surface layer has a fundamental consequence as an intermediate state in the etching mechanism.     

Microhardness of single crystals of the calomel family

Microhardness of Hg₂Cl₂, Hg₂Br₂ and Hg₂I₂ single crystals has been measured on (001) and (110) faces using the indenter after Vickers. It has been found that the microhardness of the first two homologues differs only slightly whereas the iodide is considerably softer: by about 20% on the (001) face and by about 30% on the (110) face. The average microhardness value, calculated from the values obtained on gradually rotating the indenter over 360° on the (001) face, is for Hg₂Cl₂ and Hg₂Br₂ practically equal to the microhardness of NaCl (20.3 and 19.4 compared to 19.6 · 10⁷ Pa). The average microhardness of the (110) face is for Hg₂Cl₂ and Hg₂Br₂ about 2 × lower and for Hg₂I₂ about 2.6 × lower than that of the (001) face. In the case of Hg₂Cl₂ the microhardness of the (001) face has been also calculated from crystallochemical parameters and the results have been found to be in good agreement with the value obtained experimentally for the orientation of the indenter's diagonal parallel to the [100] direction, where the data is the least influenced by the elasticity of the sample (16.6 compared to 18.6 · 10⁷ Pa).     

Effect of electrical field on growth of gallium arsenide layers from vapour phase

The effect of electrical fields on the growth rate and morphology of gallium arsenide layers in the GaAs AsCl₃ H₂ system is investigated. The fields both parallel and perpendicular to the substrate surface are used. It is found that application of the parallel field results n increase of growth rate of (111)A face but does not change that of 2° (001). The morphology of layers grown in such a field is better than that grown without any. The application of perpendicular field results in decrease of growth rate for both crystallographic orientations, the layer morphology worthening. In both cases the effect is greater when the substrate has a negative potential. Possible mechanisms of the field influence on the growth rates of gallium arsenide layers are discussed such as: supersaturation decrease because of nucleation in vapour phase and the change in the rates of surface processes.     

High-quality silicon/insulator heteroepitaxial structures formed by molecular beam epitaxy using Al2O3 and Si

Heteroepitaxial growth of γ-Al₂O₃ films on a Si substrate and the growth of Si films on the γ-Al₂O₃/Si structures by molecular beam epitaxy have been investigated. It has been found from AFM and RHEED observations that, γ-Al₂O₃ films with an atomically smooth surface with an RMS values of ∼3 Å and high crystalline quality can be grown on Si (1 1 1) substrates at substrate temperatures of 650–750°C. Al₂O₃ films grown at higher temperatures above 800°C, did not show good surface morphology due to etching of a Si surface by N₂O gas in the initial growth stage. It has also been found that it is possible to grow high-quality Si layers by the predeposition of Al layer followed by thermal treatment prior to the Si molecular beam epitaxy. Cross-sectional TEM observations have shown that the epitaxial Si had significantly improved crystalline quality and surface morphology when the Al predeposition layer thickness was 10 Å and the thermal treatment temperature was 900°C. The resulting improved crystalline quality of Si films grown on Al₂O₃ is believed to be due to the Al₂O₃ surface modification.     

Properties of Hg1‐xCdxTe epitaxial films grown on (211)CdTe and (211)CdZnTe

Hg_1‐xCd_xTe (MCT) epitaxial films have been grown employing single crystalline substrates of CdTe and Cd_0.96Zn_0.04Te with (211)Cd and (211)Te crystalline orientations. The Isothermal Vapor Phase Epitaxy (ISOVPE) technique without Hg overpressure has been used for the epitaxial growth. Substrates and films were characterized by optical microscopy, chemical etching and x ray diffraction (Laue technique). The electrical properties were determined by Hall effect measurements. The characterization results allowed to evaluate the crystalline quality of MCT films. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and chemical composition of LiB3O5 surfaces

The electronic and structural properties of LiB₃O₅ (LBO) surfaces have been studied by X‐ray photoemission spectroscopy (XPS) and reflectance high‐energy electron diffraction (RHEED). The as‐grown (110) crystal face and mechanically polished (001) surfaces have been investigated comparatively. Electronic structure of LBO has been determined on as‐grown (110) crystal face previously cleaned by chemical etching with RHEED control. The correlation of valence band structure and measured binding energies with earlier reported results has been discussed. Core‐level spectroscopy reveals strong enriching of mechanically polished LBO surface with carbon, when nanodiamond powder is used as an abrasive. So high carbon level as C:B = 0.7 has been observed at the surface while the ratio Li:B:O remains according to LBO chemical composition. The association of LBO Kikuchi‐lines with strong background has been shown by RHEED analysis of the surface. Thus, the polished LBO surface constitutes a high structure quality LBO with the inclusions of some amorphous carbon compound. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of the chemical reactions' influence on semiconductor films structure formation by the Monte-Carlo method

The investigation by the Monte-Carlo method of the growth of the silicon epitaxial film at a chloride CVD system has allowed to find out the composition of adsorption layer, the micromechanism of the reactions of Si atoms building-in into the growing crystalline layer and the growth conditions influence on the growth rate and film surface roughness. The change of adsorptive layer composition in the system SiCl₄—HCl—H₂ (fraction of adaatoms, silicon atoms built-in a crystal and molecules SiCl₂) depending on temperature has been determined. The change of silicon film growth rate depending on temperature and concentration change of SiH₂Cl₂ has been established and the contribution of growth mechanism (with participation of adatom, silicon atoms and molecules SiCl₂) into the total rate of film growth has been shown.     

Investigation of the crystallization of the system KAl(Cr)(SO4)212 H2O under various conditions

The crystallization of the isomorphous system KAl(Cr)(SO₄)₂ · 12 H₂O under various conditions has been studied. It has been found that the rate of linear crystallization of the face (100) passes through a maximum on the interval of Cr³⁺ concentrations 0.02–0.08 g ions/l which is shifted to the right with increasing temperature. Under the same conditions, the equilibrium coefficient of distribution of the microcomponent D has been determined in single crystals. D decreases with the increase of the Cr³⁺ concentration and the crystallization temperature. These results can be explained with the formation of complexes of Cr³⁺ in the solution which decreases the active concentration of the ion and are selectively adsorbed on the face (100). At the same Cr³⁺ concentration (0.058 g ion/l), the temperature dependence of the rate of growth of the face (100), as well as the influence of supersaturation on the rate of growth of the faces (100) and (111), have been studied. The apparent activation energy of crystallization of the face (100) has been determined to be E = 11.2 Kcal. · mol⁻¹. The data obtained are compared with analogical results for pure KAl(SO₄)₂ 12 H₂O.     

Precipitation of nanometer-sized SnO2 crystals and Sn depth profile in heat-treated float glass

The effect of oxygen diffusion from the atmosphere on tin depth profile in the bottom face of a soda-lime-silica float glass at temperatures above T_g was investigated. The heat treatment was performed in ¹⁸O₂/N₂ and argon (Ar) atmospheres. The significant diffusion of tin to the surface was observed for the glass heat-treated in ¹⁸O₂/N₂ atmosphere, resulting in the formation of a tin-enriched layer near the surface region. It was found that the tin was supplied from the region shallower than the ‘hump’ which is commonly observed in the tin profile of a commercial soda-lime-silica float glass. No significant change in the tin depth profile was observed for the glass heat-treated in Ar atmosphere. These results indicate that ¹⁸O diffusion into the glass, which causes the change in chemical state of tin from Sn²⁺ to Sn⁴⁺, induces the significant diffusion of tin. Furthermore, the precipitation of crystalline SnO₂ particles with a diameter of ∼1 nm was clearly recognized in the tin-enriched layer. This fact indicates that a phase separation was induced by the oxygen diffusion into the glass. Consequently, Sn²⁺ may be supplied to the surface in order to compensate for the marked decrease in Sn²⁺ concentration in the glass system. The significant diffusion of tin to the surface was suppressed by increasing the iron content in the glass. This suppression was ascribed to the increase in Sn⁴⁺ concentration as a result of the redox reaction between tin and iron because the diffusion coefficient of Sn⁴⁺ is much smaller than that of Sn²⁺.     

Growth of Pb1 ? xSmxX (X is Se or Te and x = 0.01–0.04) films on porous silicon

Films with the composition Pb_{1 − x} Sm _x X (X is Se or Te and x = 0.01–0.04) have been prepared and their structural properties have been investigated. A method for growing a buffer porous silicon layer is described. It is established that, for all samples (except for an amorphous film on the surface of porous silicon), the real film structure consists of blocks 10–50 μm in size and is independent of the porous layer morphology.     

Characterization of defects generated by di-and trivalent cations in the potassium-dihydrophosphate structure and their influence on growth kinetics and face morphology

Different types of defect sites generated by the impurities of divalent (M²⁺) and trivalent (M³⁺) metals in the structure of potassium dihydrophosphate KH₂PO₄ (KDP) were revealed by crystal-chemical analysis and computer simulation. These sites cause different deformations of the crystal matrix by generating different local strains, which enhance the inhibiting effect of impurity atoms adsorbed on the surface. This fact accounts for the different influence of di-and trivalent cations on the growth kinetics and face morphology of KDP crystals. The effect of the M³⁺ ions is associated primarily with their adsorption on the face surfaces, whereas the influence of the M²⁺ ions results from their insertion into the surface layer of the crystal.     

Nb redeposition on Si during plasma etching of Nb/SiO2/Si layers investigated by RBS

The redeposition of electrode material (Ni, Cr, Al) and material of a Nb layer on silicon surface during plasma etching of Nb, SiO₂ and Si by a CF₄ plasma has been investigated by Rutherford Back Scattering spectrometry. It is shown that a steady state exists, what causes a Nb contamination of etched Si surfaces. Obviously this steady state concentration (Nb)_ads is influenced by additional redeposition of non-etchable electrode material as Ni, Cr and Al.     

Morphological control of MgxZn1−xO layers grown on Ga:ZnO/glass substrates for photovoltaics

Mg_xZn_1?xO has been used in various photovoltaic cells because its energy bandgap can be tailored by controlling the Mg composition in this ternary compound. The Mg_xZn_1?xO layers with different surface morphologies including two-dimensional (2-D) films and one-dimensional (1-D) nanostructures are preferred for conventional p–n junction solar cells and polymer–inorganic hybrid solar cells, respectively. The Mg_xZn_1?xO layers are sequentially grown on Ga-doped ZnO (GZO) transparent conductive electrode using metalorganic chemical vapor deposition (MOCVD). The effect of the buffer layers on Mg_xZn_1?xO surface morphology is investigated. It is observed that Mg_xZn_1?xO deposited at ～500 °C on a low-temperature (～250 °C) ZnO buffer layer is in the form of 2-D dense and smooth films, whereas, on a high-temperature (～520 °C) ZnO buffer layer is in the form of 1-D nanostructures. Based on the structure characterization results, a growth mechanism in terms of nucleation and texturing is proposed to explain the buffer layer effect.     

In-situ doping of LPCVD poly silicon (II). Temperature influence

Poly silicon deposition by pyrolysis of silane under low pressure conditions has been investigated with respect to the influence of temperature when simultaneously in-situ doping of the deposited layer takes place. The growth rate of poly silicon is retarded in the presence of phosphine provided that a certain lower PH₃/SiH₄-ratio has been exceeded. It has been shown how that lower ratio depends on temperature. Increasing PH₃/SiH₄-ratio not only slows down layer growth rate but also the apparent activation energy of the layer forming reaction. An empirical equation describing the temperature dependence of that activation energy has been derived. Phosphine adsorption has been discussed as a cause of both layer growth rate and activation energy reduction. Additionally, incorporation of phosphorus during layer growth has been investigated with respect to the total amount and the electrically active concentration, the latter measured after a postdeposition anneal at 1000 °C.