Growth from the vapour by surface nucleation

The experimental conditions under which cadmium sulphide is grown from the vapour to form crystals having a (11.0) singular growth faces are calculated. This is done assuming that growth proceeds on these faces by one-dimensional surface nucleation. Calculations based on this assumption are compared with experimental observations on the habit of CdS, and the relationship between growth rate and supersaturation, and shown to be consistent with these.     

Influence of phenol on the habit of sodium chloride crystals

The influence of phenol on the habit of sodium chloride crystals was studied quantitatively. At small concentrations the presence of phenol has no influence whatsoever on the growth rate of the (100) face. At greater concentrations this growth rate increases. Spiral growth was observed on the (100) face by surface dissolution. Phenol slows down the growth rate of the (111) face, the energy barrier being about 600 cal/mole. Roughening of this face is observed when crystallization takes place from pure solutions and in the presence of small amounts of phenol. At a phenol concentration of 0.065 mole/l the growth rates of the (100) and (111) faces become equal.     

Metastability and crystal growth kinetics on L‐arginine phosphate

Stability of saturated L‐Arginine Phosphate (LAP) solution studied as a function of supercooling rate and crystal growth kinetics investigated as a function of supersaturation are reported in this communication. Solution stability was studied by observing the metastable zone width at different cooling rates employing a polythermal method. Analysis of the experimental data yielded the kinetic constant of nucleation and the order of nucleation. Crystal growth rates studied on small seed crystals with regular morphology, under normal growth conditions and at different supersaturation levels were found to satisfy BCF surface diffusion model. Crystal growth rates were investigated normal to the (100), (010) and (00 ) faces. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microstructures on {111} faces of stannic iodide single crystals

Single crystals of stannic iodide (SnI₄) havebeen grown using the controlled reaction between SnCl₂ and KI by diffusion process in silica gel medium. Orange to reddish octahedral stannic iodide crystals up to 3–4 mm in size have been grown at room temperature. Optical studies have been made on the various surface structures of {111} faces of the asgrown crystals. On octahedral faces of these crystals, triangular-shaped hillocks with growth layers in the 〈110〉 directions have been observed. Occasionally, growth spirals on octahedral faces have also been reported. Close loops of growth fronts have been investigated and have been interpreted. It has been suggested that two-diemensional nucleation, spreading and pilling up of triangular growth layers is mainly responsible for the growth and occasionally the growth is due to screw dislocations. The implications are discussed.     

Electrocrystallization of silver: Growth kinetics of screw-dislocation-free (100) crystal faces

At given conditions, especially at higher supersaturation, the growth rate of a close packed, perfect crystal face depends on the formation rate of two-dimensional nuclei and on the propagation rate of the monoatomic layers. This multinuclear multilayer growth as well as the advancement rate of growth steps have been studied experimentally on electrocrystallization of silver. The advancement rate of mono- and polyatomic growth steps has been measured on screw dislocation-free (100) crystal faces. For low overvoltages a linear dependence of the rate on overvoltage has been found. A strong influence of the surface condition of the crystal face — “fresh” or “aged” on the step advancement rate has been established. It was also found that on a “fresh” surface mono- and polyatomic steps advance with the same rate. The average monoatomic step spacing of the polyatomic step has been determined. The kinetic constants of the step growth rate are established and a conclusion regarding the mechanism of electrolytic deposition of silver is drawn. The initial current—time curves were recorded on applying potentiostatic pulses on a perfect crystal face. The shape of these curves coincides very well with those theoretically calculated for the cases of multinuclear growth. On the basis of the theoretical dependences, one can determine from these curves the formation rate J of two-dimensional nuclei at a given overvoltage η since the rate of step advancement is known. A linear dependence of log J on 1/η has been established. The values of the pre-exponential term in Volmer's equation and the specific edge energy of the two-dimensional nucleus have been determined. The surface condition of the crystal face influences strongly also the process of two-dimensional nucleation.     

Yb∶YAl3(BO3)4晶体形貌与生长速度的关系

观察测量了不同生长速度(相应于不同降温速度)自发成核生长的Yb∶YAl3(BO3)4晶体形貌。粒度较大(>2mm)的晶体不管降温速度快慢形态都很简单,只发育六方柱｛1120｝和菱面体｛1011｝;粒度较小(<2mm)的晶体形态随降温速度增快而变复杂,发育一些罕见的高指数晶面。说明在生长速度较快的条件下,在晶体生长早期,一些高能面发育,在晶体生长后期已尖灭了,晶体生长的大部分时间是在低能面｛1120｝和｛1011｝上进行的。对比了不同生长条件下晶面的粗糙度,随着降温速度的增快,六方柱面｛1120｝和菱面体面｛1011｝由光滑变粗糙,顶面｛0001｝永远是粗糙的。从晶体结构上定性地探讨了3种晶面的杰克逊因子α及生长机理     

Desymmetrization of the polyhedral crystal shape of tetragonal lysozyme due to face-growth rate fluctuations

We have studied the desymmetrization of the polyhedral crystalline shape of tetragonal lysozyme crystals due to the growth rate differences of the equivalent {1 0 1} planes. Using atomic force microscopy, we have observed the evolution of the multifaceted structures composed of four equivalent {1 0 1} faces during growth. In our growth condition, lateral step flow, where a large density of dislocations acts as a source of steps, is the dominant growth mechanism. The measured step flow velocities are almost independent of the separation between the neighboring steps, revealing that the local face normal growth rate is determined by the local step density. By tracing the motion of the vertex surrounded by the {1 0 1} faces, we have found that the desymmetrization of the crystalline shape is due to the large fluctuation of the local face normal growth rate, which is comparable in magnitude to the average growth rate.     

Heteroepitaxial growth of ZnS on GaP by the close-spaced technique

Heteroepitaxial growth of ZnS on GaP substrates was achieved with high growth rate by the close-spaced technique. Source temperatures were between 900 and 1150° C. The apparent enthalpy change of 36.6 kcal/mol obtained from the temperature dependence of the evaporation rate of source ZnS powder suggests that the material transport is carried out via the reaction between the source and hydrogen by diffusion and convection. The dependence of the growth rate on the substrate orientation is (100) > (111)Ga > (111)P, and the growth rates on these faces at a source temperature of 1000° C are about 1.6, 0.85, and 0.4 μm/min, respectively. The growth kinetics on the (111)Ga face are close to the mass transport limited case. The growth kinetics on the (111)P face are close to the surface reaction limited case, and that on the (100) face are almost the mass transport limited case. The surface morphology and X-ray analysis show that the crystal structure depends on the orientation of the substrate. The (0001) oriented α (hexagonal) modification of ZnS is obtained on the (111)Ga face, the (111) oriented β (cubic) modification on the (111)P face, and the (100) oriented β modification on the (100) face in the studied range of temperature.     

Fundamental aspects of VLS growth

The kinetics and the mechanism of the vapor-liquid-solid (VLS) growth are discussed. Emphasis is placed on the dependence of the growth rate on the whisker diameter. It is found that the rate decreases abruptly for submicron diameters and vanishes at some critical diameter d_c ? 0,1 μm according to the Gibbs-Thomson effect. A new method for simultaneous determination of kinetic coefficients and of supersaturations has been developed. The method can be used to measure the coefficients of some materials as well as the temperature dependence of the coefficient for silicon and the activation energy of the process. From the dependence of supersaturation on the diameter we conclude that whiskers grow by a poly-nuclear mechanism. The periodic instability of the diameter is discussed and the rate-determining step is analysed. We conclude that phenomena on the liquid-solid interface are the decisive ones. In determining the role of liquid phase in vapor growth we measured the “liquid phase effectivity coefficient” as a function of crystallization condition; the coefficient typically was about 10²?10³. It is stressed that the liquid phase reduces the activation energy both on vapor-liquid interfaces (for chemical reactions) and on liquid-solid interfaces (for nucleation). The liquid phase ensures growth rates as high as 1 cm/sec, provided there are no barriers between the interfaces. The growth mechanism of the side faces was studied, and it was observed that the faces grow mainly by a chain mechanism rather than by two-dimensional nucleation. In work on surface diffusion in the VLS whiskers growth by CVD, we found that the whiskers grow mainly by direct deposition rather than by diffusion on the side faces. It is concluded that the VLS mechanism is important also for the vapor growth of platelets, films, and bulk crystals.     

Oriented growth of whiskers of AIIIBV compounds by VLS-mechanism

The oriented growth of GaAs, GaP, InAs and GaInAs whiskers on the same (GaAs, GaP) or different (InAs/GaAs, GaInAs/GaAs) substrates was studied. A detailed morphological study of GaAs whiskers on polar A(III), B(111 ) and non-polar (001), (011) substrates was performed. The growth conditions for ordered (perpendicular to substrate) growth on the A(111) and B(111 ) faces were determined. There were found discrete spectra of whisker systems on all substrates with the preferential growth of “arsenic” B{111 } faces. The dependence of the growth rate on the whisker diameter is typical for the vapour-liquid-solid (VLS) mechanism and is used for the determination of kinetic coefficients for polar faces. There was observed a periodic instability in growth of InAs and GaInAs whiskers.     

Growth kinetics on the (100) and (001) faces of TGS crystals

The growth kinetics and mechanisms on the (001) and (100) faces of TGS crystals were investigated. A phase contrast microscope with a CCD camera was used to observe the growth of the crystal. We found the growth on the (001) and (100) faces at high supersaturation was mainly controlled by a BCF surface diffusion mechanism. The kinetic data for the (100) face were also fitted by the nucleation and layer growth model of two-dimension nucleation at high supersaturation. Some important growth parameters for TGS crystals, such as edge energy, activation energy, and so on, were estimated.     

Growth of faces of K2Co x Ni1 – x(SO4)2 · 6H2O mixed crystals

Data on the morphology and normal growth rate of the (110) and (001) faces, velocities of step motion, and slopes of dislocation hillocks on the (001) face of K₂Co _x Ni₁– _x (SO₄)₂ · 6H₂O crystals at different supersaturations of solutions with a Co/Ni ratio equal to 1: 1 or 1: 2 have been obtained using a Michelson interferometer. The morphology of the (110) faces is found to be the same for solutions of both compositions. Powerful dislocation sources with large Burgers vectors dominate on the (001) face. The morphology of the (001) surface is rougher than that of (110), especially in a 1: 2 solution at high supersaturation. The (110) faces grow more slowly as compared with (001). The kinetic coefficients of steps on the (001) face are identical in the 1: 1 and 1: 2 solutions. The influence of the kinetic and morphological characteristics of (001) faces on the single-crystal quality is analyzed.

     

Effect of organic impurities on the surface morphology and growth mechanism of KBP crystals (C8H5O4K)

The surface morphology of the (010) face of potassium biphthalate (KBP) crystals grown from aqueous solutions under the supersaturation ranging within 0.029–0.04 has been studied by the methods of optical and electron microscopies. It was revealed that the (010) surface has polygonal growth macrohills of the dislocation nature, small hillocks developing by the mechanism of successive two-dimensional nucleation, and numerous two-dimensional nuclei. The density of small hillocks (10⁴–10⁵ cm^?2) exceeds the dislocation density in KBP crystals by one to two orders of magnitude. It is shown that at low supersaturations, the (010) face grows simultaneously by the dislocation mechanism and the mechanism of successive two-dimensional nucleation. It is also established that the tangential velocity of growth-step motion on the (010) face increases in the presence of organic impurities. This effect can be used as one of the factors increasing the growth rates of crystal faces at low impurity concentrations (the so-called catalytic effect of impurities).     

Atomic Force Microscopy Studies on Growth Mechanisms and Defect Formations on {110} Faces of Cadmium Mercury Thiocyanate Crystals

Growth mechanisms and defect formations on {110} faces of cadmium mercury thiocyanate crystals grown at 30°C (σ=0.24) were investigated by using atomic force microscopy (AFM). It was found that, under this condition, spiral dislocation controlled mechanism and 2D nucleation mechanism operates simultaneously and equally during growth, which is completely different from the traditional 2D nucleation and dislocation source controlled mechanisms. A number of 2D nucleus are formed at the large step terraces generated by dislocation sources, leading to the unequal growth rates of the elementary steps and thereby “step bunches” arecaused. Various defects are formed under this growth condition, which is assumed to result from the incongruence between the steps generated by different sources. A new kind of 2D defect, corresponding to one growth layer in height, was observed for the first time.     

Distinct Growth Phenomena Observed on Zinc Cadmium Thiocyanate Crystals by Atomic Force Microscopy

Atomic force microscopy is used to investigate the surface morphology of the prismatic (100) face of ZCTC crystal grown at 30°C at a supersaturation of 0.16. This surface is distinctly formed by periodic “macrosteps” that advance along different directions and join with each other leading to the interlaced growth layers with an inclination of about 137°. These two “macrostep” trains well correspond to the pyramidal faces of (0 ) and (01 ) in orientation, therefore they probably propagate from the edges of these faces. The “macrosteps” are practically formed by highly dense steps at the front with regular elementary steps in between. The alternation of “macrosteps” and elementary steps vividly reflects Chernov's “kinematic waves of steps” theory (Chernov , (1984)) on a nanometer scale. Wide indentations and long clefts are generated at the “macrosteps”. The former is generated by twodimensional nucleation growth at a relatively faster growth rate than that of the underlying layer. The latter is probably caused by step trains generated by individual growth sources that have not merged.     

Growth and selective etching studies on NaBrO3 crystals

Surface studies on (111) faces of sodium bromate crystals grown from aqueous solution show the presence of growth steps. A new etchant consisting of a mixture of 8 parts of glacial acetic acid and 2 parts of formic acid, to which 3 mg/cc of cupric nitrate is added, reveals the dislocation sites on (111) faces of these crystals. The etching action on (111) and (111 ) faces is different. Different microhardness values are recorded on (111) and (111 ) faces of these crystals. The difference in etching action as well as in microhardness values on (111 ) and (111) faces is discussed.     

Über die Züchtung von ZnS-, ZnSe- und ZnTe-Einkristallen unter Anwendung der chemischen Transportreaktion

In connection with investigations on the synthesis of ZnS, ZnSe and ZnTe single crystals by chemical transport using iodine as transport agent in sealed tubes the mechanism of mass-transport and the relationship between material-transport and growth process were studied. In this way the optimum conditions for growing single crystals were found. The dependence of the transport rate on the undercooling ΔT, on the diameter of the ampoule and on the pressure in the system is described. Relative large crystals in good quality could be propared by influencing the nucleation and the growth process by help of well defined transport rates. In all cases crystals with sphalerite structure only were obtained. The habit with the most common faces (110), (111) and (211) was found to be predominant. The dominant habit is responsive to variations in the experimental parameters. The crystal perfection have been determined by etch patterns and by X-ray topography.     

BGO熔体急冷自发结晶形貌

本文研究了BGO熔体在急冷的条件下自发结晶的显露形貌.在急冷的条件下,组成BGO的各个面族自由发育.{321}面族、{211}面族和{111}面族都是按[GeO4]4-四面体以顶角相连的化学键链生长发育的,生长速度快,优先显露,在熔体急冷时保留下来.表面形貌显露不完整的{100}面族是[GeO4]4-四面体以棱相连所对应的面族,生长速度较慢,尚未显露完全熔体就已冷却.从生长速度考虑,在实际生长晶体时以[321]、[211]、[111]方向生长可以获得较快的速度.     

InAs nanowire growth on oxide-masked 〈111〉 silicon

Here we investigate the growth of InAs nanowires on 〈111〉 Si substrates masked by SiO_x using metal–organic chemical vapor deposition. We study 〈111〉 (axial) and 〈1?10〉 (radial) growth of InAs NWs by varying growth duration, temperature, group-III molar flows, V/III ratio, mask material, mask opening size, and inter-wire distance. We find that growth takes place without an In droplet and the process evolves through three successive phases: nucleation of an InAs cluster, followed by two distinct nanowire growth phases. These two growth phases have different axial and radial growth rates, which originate in a transition from having In supply dominated by the open Si area in the first phase towards an In supply from the vapor/oxide mask in the second growth phase. The linear relation found between nanowire length and diameter vs. time in the last growth phase indicates that 〈111〉 growth is not surface diffusion limited as is usually the case for catalyzed growth. A high yield of vertical nanowires is obtained if group-III flow is above and V/III ratio below threshold values, in addition to having an arsenic-terminated Si surface. Furthermore, we observe that 〈111〉 and 〈1?10〉 growth is surface kinetically limited below 520 °C and 540 °C, respectively, with activation energies of 20 and 6.5 kcal/mol. This difference in activation energies limits the selectivity of the 〈111〉 to 〈1?10〉 growth to 25:1 under optimized conditions, which must be considered when fabricating axially modulated structures. However, we find that by placing wires in large arrays it is possible to completely stop the 〈1?10〉 growth rate in favor of the 〈111〉 growth rate.     

In situ atomic force microscopy studies of growth mechanisms and surface morphology of zinc thiourea sulfate crystals

In situ atomic force microscopy (AFM) has been utilized in studies of the growth mechanism on the (100) face of zinc tris (thiourea) sulphate (ZTS) crystals growing from solution. The growth on the (100) face of pure ZTS crystal is mainly controlled by two dimensional (2D) nucleation mechanisms, under which the hillock is formed through layer‐by‐layer growth. It is easier to form 2D nuclei at edge dislocation and the apex of steps. The growth of 2D nucleus is in accord with nucleation‐spreading mode. The growth rate along the 〈010〉 direction is faster than that along 〈001〉 direction, both of which increase firstly and then decrease with the spread of nucleus. The kinetic coefficients of one nucleus have been roughly estimated to be 3.6 × 10⁻⁴ cm/s and 1.8 × 10⁻⁴ cm/s in two directions, while the activation energy E was calculated to be 53.7 kJ/mol and 55.4 kJ/mol, respectively. The 2D nuclei can be generated under lower supersaturation with the addition of EDTA. If there are several hillocks growing together, step bunches will form when the steps moving in the same direction meet each other, while the meeting of steps that move in the inverse direction will result in the separation of steps. The ability of nucleation of edge dislocation outcrops are different even they are close to each other on the same surface. When the nucleus was generated at the edge dislocation sites, it cannot spread speedily until finishes an “incubation period”. Moreover, the detour of microsteps was observed due to the existence of pits. If the microcrystals attached on the surface block the step advancement, or leave the surface or are covered by the macrosteps, the pits are formed. If the macrosteps advanced across the pits, the pits will be covered and the liquid inclusions may form. However, if the microcrystal forming in the pit grow up and expose on the surface, the pit will not be covered by macrosteps. The formation of solid inclusions may be caused by the microcrystals being embedded into the single steps which move layer‐by‐layer.