Journal of Crystal Growth 128 (1993) 1236-1244 North-Holland

j. . . . . . . . C R Y S T A L

GROWTH

Effect of impurities on the processes of crystal growth

K. Sangwal
Department of Physics, Technical University of Lublin, Ul. Nadbystrzycka 38, 20-618 Lublin, Poland

The influence of impurities inherently present in growth media and deliberately added to them on crystal growth is manifested during the process of crystallization in a number of ways. Impurities change growth rates, shape and thickness of growth layers and growth habit, and are trapped as impurity striations and large clusters of impurities and inhomogeneities. Some of these effects of impurities are reviewed for growth of bulk single crystals.

I. Introduction

Influence of foreign particles present in growth media has long been recognized to change growth habits of crystals. After the publication of the classic monograph by Buckley [1], studies on the effects of impurities were diverted to understand the mechanisms involved in changing the growth habit on microscopic level [2-5]. The first phase of important experimental works in this direction was published during the late fifties and early sixties [4-8], when structural interpretation of habit modification in terms of the formation of a two-dimensional adsorbed-impurity layer structurally similar to the growing crystal face, and kinetic interpretations involving adsorption of impurity molecules at the sites of kinks and steps were advanced [4-13]. The second phase of investigations on impurity effects started from the works of Davey and Mullin [14], who studied layer displacement rates as a function of impurity concentration, and confronted the experimental data with different kinetic models of impurity adsorption. The last phase of the studies on impurities starting from the early eighties deals with the design of structurally specific additives, called tailor-made impurities [15]. Any foreign substance other than the crystallizing compound is considered as an impurity. Thus a solvent used for growth and any other compound deliberately added to the growth medium or inherently present in it is an impurity.

Different terms, such as additive, admixture, surfactant, inhibitor or poison, are used in the literature for foreign substances other than the solvent. Irrespective of its concentration, a deliberately added impurity is called additive, but by the term admixture we mean an impurity added in relatively large amounts. A surfactant may be any chemical compound active on the surface in changing the growth behaviour. An impurity can accelerate or decelerate the growth process and the one that decelerates growth is called a poison or an inhibitor. The literature on the effects of impurities on crystal growth is quite multifarious, and has been reviewed several times [16-22] since the publication of Buckley's monograph [1]. The experimental data on impurities deal with the following topics: habit modification and morphodroms [4,5,23-27], kinetic data on face growth rates [7-12,28-47] and layer displacement rates [13,14,48-50], observation of the presence of dead bones at low impurity concentrations [28-33,36, 38,46,47], ex-situ [40,41,48-50] and in-situ observation of crystal faces [13,14,43,46-48,51], nucleation and precipitation kinetics [52-54], and chemical constitution of impurity species and chemistry of adsorption in solution growth [37,48,49,56-59]. Although it is well known that solvents and foreign substances other than the crystallizing compound change the growth characteristics of a crystallizing compound, our knowledge of the

0022-0248/93/$06.00 1993 - Elsevier Science Publishers B.V. All rights reserved

K. Sangwal / Effect of impurities on processes of crystal growth

1237

structure of the growth media and of the nature of the impurity species in the liquid state remains incomplete even today. Consequently, despite volumenous literature on the effects of additives and solvents, the mechanisms of their action during growth are obscure. The aim of this paper is to survey our present understanding of the processes of adsorption of impurities during growth. We will not discuss here the role of solvent in growth nor the effect of impurities on three-dimensional nucleation. The impurities considered are foreign substances deliberately added to or inherently present in a growth medium.

2. Mechanisms of impurity adsorption

Foreign substances which influence crystal growth processes can. in general, be divided into tailor-made, polyelectrolyte (multifunctional) and electrolyte (single-functional) impurities [20,21]. Tailore-made, polyelectrolyte and simple electrolyte impurities have molecular weights of about 104 , 10 3 and 102, respectively. The former two types of impurities are composed of long chains, while impurities of the last type are quite small, usually up to 2-3 atomic dimensions. In growth media (e.g. solutions) their chemical structure can undergo a change, but the above order of the size of the "effective" impurity species is maintained. Therefore, it may be considered that molecules of tailor-made and polyelectrolyte impurities adsorbed on a surface are practically immobile, while in the case of simple electrolyte impurities the adsorbing species may be mobile or immobile. 2.1. Adsorption on F faces Adsorption of an impurity on an F face may affect three parameters [17], namely, the thermodynamic and kinetic terms involved in the growth models, and the crystal solubility. The thermodynamic parameter in the growth models is the surface energy, 7. Consideration of adsorption process in terms of adsorption isotherms and adsorption equilibrium reveals that impurities adsorption leads to a decrease in y [5]. A decrease

in 3' leads to an increase in the nucleation rate, J, in the two-dimensional nucleation models and to a decrease in the radius, re, of critically-sized two-dimensional nucleus and consequently the spacing, Yo, between neighbouring spiral steps [17]. The growth rate, R, based on these models, is thus increased. The kinetic term, on the other hand, in the growth theories is directly connected with the velocity, Vs, of motion of steps on the crystal surface [17]. Impurities adsorbed on the surface decrease this velocity by decreasing the values of retardation factors associated with distances between neighbouring steps and kinks. From the above, it follows that the theoretical models of growth predict opposite effects of impurities on growth kinetics. The thermodynamic effect tends to increase the growth rate while the kinetic effects tends to decrease it. Experimental results [7,11,17,19] indeed support this inference. On the other hand, it is difficult to predict the effect of impurities on crystal solubility. However, it can be shown that the effect of an impurity on solubility suppliments changes caused by thermodynamic and kinetic parameters. At low concentrations, the effect of impurities on solubility is usually negligible [8,10-12,29]. Davey [17] pointed out that, for low supersaturations, the layer displacement rate, vs, and the growth rate, R, increase at small additive concentrations and decrease as the additive concentration is raised; but that with an increase in impurity concentrations, Cimp, at relatively high supersaturations, additive adsorption decreases these rates in the whole impurity concentration range.

%
I,oal"~..Z~..~
10

20 30 40 50 Cimp( X lOJg/I) Fig. 1. Dependence of linear growth rates R of (10t)) and (111) faces of Pb(NO3) 2 grown from aqueous supersaturated solutionson concentrationCim p of methylblue [7],

1238

K. Sangwal / Effect of impurities on processes of crystal growth

Fig. 1 illustrates the dependence of linear growth rates of (100) and (111) faces of Pb(NO3) 2 grown from aqueous solutions in the presence of methyl blue. With increasing impurity concentration, an initial increase followed by decreasing growth rate is observed in the case of both surface-active additives composed of large molecules and ionic salts [7,11,41]. In the case of impurities involving relatively small entities, a regular decrease in v~ and R due to the dominating effect of the kinetic parameters is usually observed [7,8,11,17,34,35, 40,41]. The above consideration of the simultaneous effects of thermodynamic and kinetic parameters is valid for any impurity which is capable of adsorbing at kinks as well as on the surface terrace. It is easy to realize two extreme cases of impurity particles in terms of the adsorption sites. Mobile impurity particles are capable of adsorbing at kinks, while immobile impurity particles will mainly adsorb at the surface terrace. However, in both cases some contribition due to adsorption at ledges is also possible. The number nma x of sites available for adsorption on a surface at given conditions is constant, but, for a particular concentration of the impurity, Cimp, a fraction 0 of the nmax sites available for adsorption is occupied by the impurity particles. Denoting the number of adsorbed sites by had s, the coverage of adsorption sites 0 may be expressed by
0 = n a d s / n max" (1)

initiating the formation of a two-dimensional layer of the adsorbed impurity. Thus, with increasing impurity concentration, one has the following two situations, namely, 0 << 1 and 0 > 1.

2.1.1. Adsorption at low impurity concentrations (i.e. 0 << 1) In this situation, two extreme cases, i.e. adsorption at kinks (mobile impurities) and the surface terrace (immobile impurities), may be distinguished. The models of impurity adsorption considering kinks and the surface terrace deal with the kinetic aspect of adsorption of impurities on an F face, neglecting the thermodynamic effects. Assuming that kinks are the preferred adsorption sites, following Bliznakov [6,7], we consider that a part of the adsorption sites is occupied by the impurity particles, while the remaining sites remain uncovered. The movement of a growth ledge is ensured simultaneously by different rates of attachment of growth entities at unoccupied and occuppied sites. These different attachment rates result in ledge displacement rates v 0 and voo, respectively. The effective displacement rate, v, of the ledge is then
v = v0(1 - 0) + v=O, or the coverage of adsorption sites 0 = (v 0 - v ) / ( v 0 - v~). (3) (2)

The parameter 0 is essentially similar to the surface coverage 0 of adsorption isotherms. When all available sites on the surface are adsorbed, 0 = 1. Since usually a small amount of the impurity decreases the rate of ledge motion enormously, it can be believed that in the case of adsorption at kinks, ledges or surface terrace, 0 << 1. With increasing impurity concentration, 0 increases until 0 = 1 when all adsorption sites are occupied. However, with further increase in impurity concentration, 0 can exceed unity and the surplus potent inhibiting species tend to form aggregates around some adsorption sites, thereby

The coverage of adsorption sites may be described by the usual adsorption isotherms. A similar type of equation may be given in terms of lateral displacement rate R of a face. It is found that in most cases Langmuir and Temkin isotherms are followed by the growth kinetics [7,9,10,14,34,35,40,41]. According to these isotherms, the coverage of adsorption sites 0 increases with an increase in impurity concentration Cimp. Consequently, growth rates v and R monotonically decrease with increasing impurity concentration Cim p. An entirely different mechanism holds when impurities strongly adsorb on the surface rather than at kinks. In the case of immobile particles, when the advancing ledge contacts an impurity particle, it tends to curl around this particle. The

K. Sangwal / Effect of impurities on processes of crystal growth

step will stop when the average distance between the adsorbed species d < 2r c (where r c is the radius of critically sized nucleus), while it squeezes between a pair of impurity particles when d > 2 re. The configuration of straight ledges is thus modified by the impurity particles and their average velocity will be smaller than v 0 and R 0 (where R 0 is the face growth rate in the absence of the impurity). This mechanism, due to Cabrera and Vermilyea [3], predicts that the displacement of a ledge in growth medium containing an impurity can occur only above a critical value of supersaturation ratio (C/Co)* , and that the value of the supersaturation ratio (C/Co)* increases with increasing impurity concentration Cimp, and is expressed by
b

1239

xl

:K

(12 04 e;

0.6 08

(%)

[ I / I n ( c / C o ) * ] 2= ( Z/cimp) + B,

(4)

Fig. 2. Two different types of RQr) dependences with dead zones above supersaturation or* whose value increases with impurity concentration eimp in the growth medium. (a) R(~r) curves of (110) face of paraffin C36H74 from petroleum ether solutions containing dioctadecylamine impurity; impurity concentration for curves from left to right is 0, 55.3, 133 and 175 pprn. (b) R(~r) curves of (100) face of KDP crystals from aqueous solutions of different purities. After (a) refs. [18,29] and (b) ref. [32].

where A and B are constants. There are many experimental observations of the existence of critical supersaturation or* (where l n ( c / c o) = cr = (c - Co)/Co), below which no growth takes place (dead zones) [28-33,36,3840,44,46], and the value of or* increases with the impurity concentration in the solution [2833,36,38-40,43]. For supersaturations or > ~r*, the growth rate curves for different concentrations of an impurity are similar [18,29,32], and may be described by the usual growth rate equations with corrected supersaturation (or - ~r *) instead of the applied supersaturation ~ (fig. 2a). However, with increasing impurity concentration, the RQr) dependence may become less and less steep (fig. 2b) due to contribution from increasing surface energy or changing activity of sources of steps. Some interesting results at very low impurity concentrations deal with fluctuations in face growth rates with time [43,44,46,60] and supersaturation [60], and with anomalies in rates of layer displacement with supersaturation [44,52,60]. In the case of growth of KDP in the presence of A13+ and Cr 3+ impurities [36], even two values of critical supersaturations o.1 and (72 have been reported. Supersaturation o-2 corresponds to or* in the Cabrera-Vermilyea model. Fig. 3 shows the dependence of linear growth rate of the (100) face of KDP for A13+ impurity on supersatura-

tion expressed as A t under conditions of natural convection. At a given impurity concentration, in the supersaturation range 0 < A t < A t I growth

[2

0.~
x
v

'

i At1

; ~t2

at(K) Fig. 3. Dependence of linear growth rate R of the (100) face of KDP for different concentrations of AI3+ impurity on supersaturation expressed as At under conditions of natural convection[36].For curves from left to right, impurityconcentations are 0, 10 4 and 10 3 wt%. Note that, at a given impurity concentration, in the supersaturation range 0 < At < At1, growth does not occur; but in the range At I < At < At2,
the face grows slowly following the BCF dependence: R cz (At) 2.

1240

K. Sangwal / Effect of impurities on processes of crystal growth

does not occur, but in the range At 1 < At < At 2 the face grows slowly following the dependence: Rct (At) 2. However, for the supersaturation At > At 2, the rate R c t (At - At2 )m with 1 < m < 2. The data of At I and At 2 on concentration Cimp of AI 3+ and Cr 3+ impurities showed [62] that both of them may be represented by eq. (4), but the fit is better for At 2 than for At 1. It was suggested [36] that for At < At 2 growth is determined by the kinetic step, while that for At > At 2 it is diffusion-controlled. 2.1.2. Adsorption at high impurity concentrations (i.e. 0 >> 1) 2.1.2.1. Formation of two-dimensional adsorption layer. When the concentration of an impurity in the growth medium is high, the above mechanisms of adsorption involving kinks and surface terrace cease to be important. In this case, decrease in the growth rate of a face is possible due to the inaccessibility of growth units to the surface by the formation of a uniform two-dimensional layer of the adsorbing impurity. This layer has a crystallographic similarity with the growing face [4,5,25]. The formation of adsorption layer is favourable in systems involving large inhibiting species, because the interaction between a large inhibiting species and an adsorption site is expected to be relatively weak. Consequently, in the case of large impurity particles, the impurity concentration required for inhibiting the movement of ledges is also high. Experimental results of several investigations [7,9,17,34,35,40,41] convincingly demonstrate that growth rates of crystals growing in the presence of impurities always decrease with an increase in the impurity concentration. However, in the case of growth rates of the (100) and (111) faces of KC1 crystals growing in the presence of CdC12 and PbC12 impurities [34,35], the decrease in growth rate is much larger at low impurity concentrations than that at higher impurity concentrations (fig. 4). This type of dependence suggests [59] that kink/terrace adsorption and surfacelayer adsorption take place in low and high impurity concentration intervals, respectively.

2
{ioo}

10"

ci~ ( 102tool/1)
Fig. 4. Dependence of growth rates R of the (100) and (111) faces of KCI crystals at ~r = 3.6% on concentration Cimp of CdC12 at two different temperatures [35]. Note that for each face the decrease in R with increasing Cimp is steep below a particular value of Cimp typical of a face and temperature, while it is small beyond this particular Cimp.

2.1.2.2. Formation of surface macroclusters. In systems where two-dimensional impurity layers are not formed, localized insoluble three-dimensional impurity clusters may be produced on the surface of a crystal. These impurity clusters are the cause of the so-called irregular growth for supersaturations ~r exceeding some critical values ~r0. Irregular growth corresponding to irregular growth morphology results when some parts of the face of a crystal grow according to the usual growth mechanisms involving two-dimensional nucleation or dislocations with or without impurity adsorption, while growth of other parts is entirely blocked by the impurity [18,40]. Surfaces growing with the participation of three-dimensional impurity clusters may exhibit hillocks on them [61]. Thus irregular growth is essentially due to nonuniform adsorption of the impurity on the growing surface. Typical examples of the dependence of growth rate of crystals grown from solutions containing different concentrations of impurities on supersaturation is shown in fig. 5. At a particular impurity concentration, growth is completely stopped below %, but beyond this value the growth rate shows the usual supersaturation dependence in the presence of an impurity follow-

K. Sangwal / Effect of impurities on processes of crystal growth

1241

ing Cabrera-Vermilyea mechanism of impurity adsorption. In the presence of an impurity, the growth rate is lower than that in systems without the impurity in the first case (fig. 5a), while it is nearly equal in the second case (fig. 5b). In general, in the case of formation of localized insoluble three-dimensional impurity clusters, the following situations are possible: Case I. In the first situation, in addition to the usual reduction of growth rate of a face by small impurity particles, the impurity clusters act as additional obstacles for the motion of growth layers. Then both types of adsorption species, say A and B, are adsorbed simultaneously on the surface to an extent 0a and 0 B, respectively. Assuming that mixed Langmuir adsorption isotherm holds in this case, it can be shown [62] that there exists another critical value of supersaturation ratio (C/Co)** for the motion of a ledge, which is given by
** c " *72

=,

/
v

01

ff

02

03

Ol

02
c~

03-

A' +

In

- In

0B

Fig. 5. Typical R(o-) curves for different faces of sodium perborate crystals growing from aqueous solutions containing surfactant (sodium salt of butyl ester of oleic acid), showing two types of dead zones. For the curves from left to right, impurity concentrations in both (a) and (b) are: 0, 15, 30 and 75 ppm of the surfactant. The (011) and (100), and (101) and (001) faces of sodium perborate show dependences of the type of (a) and (b), respectively. The growth rate is lower than that in systems without the impurity in (a), while it is nearly equal in (b) above a supersaturation ~ r * * > ~ * (cf. fig. 2). After refs. [18,30,31].

(Sa)
or

ln(c/Co) ** ln(c/Co)*

1
=

A' + - CA

(5b)

where A' and B' are constants, c A is the concentration of A, and the supersaturation ratio (C/Co)* is given by eq. (4) for the impurity species A. From this equation the following conclusions can be drawn: (a) In the region of formation of impurity clusters where 0B = 0, eq. (5a) reduces to relation (4) of the Cabrera-Vermilyea mechanism. (b) For a constant value of CA, the supersaturation barrier increases with increasing 0 B. (c) For constant values of both 0 B and ca, ln(c/Co)** - ln(c/Co)* = constant. (d) For a constant values of 0B, the supersaturation barrier decreases with an increase in c A, and
vice versa.

The experimental data of fig. 5a correspond to case (c), those of fig. 5b to case (b), and those of figs. 2a and 2b to case (a).

Eq. (5) reveals that, for 0 B -o 0, ln(c/Co)** ln(c/Co)*>O, and that the ratio ln(c/Co)** / In(c/Co)* of critical supersaturations decreases with increasing concentration c A. This supersaturation difference is associated with the formation of B species as a result of agglomeration of A species on the surface. When c A > CB, growth proceeds following the usual growth mechanisms for supersaturations above In(c/Co)**. Case H. In this case too, the A species join the clusters of B species but now c B > c A. Then a situation may arise when the impurity clusters (or precipitates) supply additional sources of steps for growth. Thus rather than a decrease, there is an increase in the growth rate of a face with impurity concentration Cimp. Assuming the formation of three-dimensional impurity nuclei on the surface and an absence of adsorption of A by the Bliznakov or Cabrera-Vermilyea mechanism, the face growth rate may be given by [41] R = R o + a exp(-bc~mp), (6)

1242

K. Sangwal / Effect of impurities on processes of crystal growth

.=i .~E_ 3 _=
-4

~ o

the surface due to a structural similarity between them. T h e character of an S or K face resembles that of an F face, and a face grows by the free development of growth layers [27,63]. However, transition of a K face to an F face may also involve the piling up of growth layers on the F faces of the growth morphology. T h e piling up of the steps results in an S-type face, rather than the original K-type face consisting of only kinks [27].

3. C o n c l u d i n g

remarks

-1.5

-14

_ _

-13 -12 lncimp (mol/mol)

Fig. 6. Dependence of linear growth rate R along (001) directions of KDP crystals grown from aqueous solutions at o- = 13% on concentration Cim p of () C r 3+ and (x) Fe 3+ ions [41]. Both impurities follow the same dependence.

where R 0 is the face growth rate in the absence of the impurity, and a, b and n are constants. W h e n bc~mp >> 1, eq. (6) may be written as
R : ( R o + a) - bc.~m p.

This review has been confined to the effects of impurities on the proceeses of growth of bulk crystals with naturally developing faces from solutions. However, the mechanisms of adsorption of impurities described here are not restricted to the growth of bulk crystals. T h e y are equally valid in the case of growth of epitaxial layers, and different types of surface morphologies r e p o r t e d in the literature (see ref. [22] for the review) may be explained in terms of these mechanisms.

(7)
References

Experimental evidence in support of this mechanism is available for the growth of N a N O 3 in the presence of Co 2 ions [12] and K D P in the presence of Cr 3+ and Fe 3+ ions at relatively high supersaturations [41]. Fig. 6 illustrates the experimental d e p e n d e n c e of R for K D P crystals.
2.2. Adsorption on S and K faces

In contrast to the growth of F faces by the displacement of ledges on the surface terrace, growth of S and K faces takes place by a statistical deposition of growth molecules at growth sites (i.e. kinks), resulting in the displacement of a face in a direction normal to it. Because of the statistical nature of deposition, even at low concentrations of an impurity, adsorption will be quite effective at kinks of the K faces and at ledges of the terrace of the S faces. A t high impurity concentrations, S and K faces can also a p p e a r in the morphology of a crystal when adsorption takes place by the formation of a two-dimensional impurity adsorption layer on

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K. Sangwal / Effect of impurities on processes of crystal growth

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