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CRYSTAL

GROWT H

Journal of Crystal Growth 131 (1993) 431—438
North-Holland

Microsegregation in crystal growth from the melt:
an analytical approach
J.P. Garandet
DTA / CEREM/DEM/SMGP/LET,

Commissariat

a l’Energie Atomique,

Centre d’Etudes Nucléaires de Grenoble, 85X,

F-38041 Grenoble Cedex, France
Received 5 January 1993; manuscript received in final form 22 March 1993

The influence of interface velocity variations on microsegregation is modelled analytically using a boundary layer formulation
and a perturbation approach. The theoretical correlations between interface velocity and concentration fluctuations are seen to
compare well with existing numerical and experimental data, meaning that the solute boundary layer formalism is well adapted to
the study of microsegregation. A possible field of application of this work is the derivation of the allowable pulling device
instabilities in a crystal growth furnace.

1. Introduction
Solute segregation at the microscopic level is
often a major problem for the crystal growth of
application oriented materials [1]. For instance, it
is well known that rotation of the sample in an
asymmetrical thermal field, pulling device instabilities or vibrations lead to time-dependent vanations of the interface velocity which in turn
often result in striations.
Another possible mechanism for microsegregation is related to unsteady convection in the melt,
It can act either directly on the solutal field, as in
the case of g-jitter during solidification in microgravity [2] or indirectly when the temperature
fluctuations associated with the flow modify the
growth velocity and thus the composition of the
alloy.
Kinetic effects on faceted interfaces are also to
be considered. High lateral growth velocities at
macrosteps or local interface breakdown due to
an excessive undercooling can result in transient
solute incorporation [3], but a detailed study of
these microscopic problems is outside the frame
of our present work.
0022-0248/93/$06.OO © 1993

A correlation between interface and composition fluctuations was obtained numerically by
Wilson [4,51
in the early eighties for a sinusoidal
growth rate in an idealized Czochralski configuration. An interesting result was that microsegregation scaled linearly with the amplitude of the
velocity variations even up to the point of backmelting.
An hybrid analysis was carried out by Van Run
[61and Favier and Wilson [71.Convection is accounted for using a stagnant film model, and the
solution to the time dependent problem is then
found numerically using either finite differences
[6] or finite elements [71.Both approaches were
seen to compare very well with Wilson’s data.
A solution to the general problem, involving
an analytical derivation of the correlations between the interface velocity, temperature and
concentration variations is very difficult to find.
One of the reasons is that, without any simplifying assumptions, the time dependent heat and
mass transfer equations are generally non-linear.
As a consequence, the two outstanding efforts
in the field [8,91 both relied on a perturbation
approach. Another common feature of these two

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Using Wilson’s [121definition. One of the main interests of this boundary layer concept is that it is possible to account very simply for the convection phenomena in the melt. (1) and (3) become: d2C dC D—~-+ V dZ~ ‘dZ ~ ~SF~ c C~. in crystal growth from the melt With the Z-axis oriented from the interface into the liquid. one of the main problems being that the solution of the stagnant film model led to a discontinuity of the solute flux at Z 6SF’ To quote their words. 2. dZ (1) dZ was solved along with the boundary conditions: Z=0 (interface): (4) (5) = = — C(0) C~ 6= (6) the physical meaning of 6 rests on stable physical D — Z —s —I =V (dC 1 1(1-k)C(0). We shall then focus on the limiting case of low frequency perturbations in section 3 before turning to the general problem in section 4. D— Vett~ (7) d dZ2 ~- = . [101). A necessary prerequisite is to modify the stagnant film model first introduced by Burton. “the somewhat arbitrary quantity 65F may = be characterized by defining it so that it yields the same dependence of the composition upon the growth parameters that is given by the exact solution”. BPS obtained an analytical solution to the above set of equations and then proceeded to propose a simple stagnant film model that could account for the macrosegregation phenomena. Wilson [121showed that this idea was not correct. Indeed. as rightly recognized by the authors. Afterwards however. The results are discussed and a comparison with the existing numerical and experimental data will he presented in section 5. grounds. k and C~. but a lot of misunderstanding and confusion can still be found in the literature. the fluid velocity in their idealized Czochralski configuration being given by the approximate analytical expression of Cochran [111 In a frame moving with the interface. even if we know that convection is present. Our opinion is that the effect of diffusion and convection is to force all the significant composition variations to take place in a region of extent 6 the solutal boundary layer in the vicinity of the interface. stand for the interface and convective velocities. Gurandet 132 / Microsegregation models is that the effect of convection is accounted for via a stagnant film model. in their pioneering work. W. Prim and Slichter (BPS. W is necessarily negative. Our solution will thus be valid all over the convecto-diffusive solute transport range. and concentration in the fluid phase far away from the interface. = BPS did not ascribe any physical meaning to 6~. which will be done in section 2. D. this approach. An additional advantage of our analysis with respect to previous work is that the algebra involved is much simpler. BPS considered a steady state. is only correct when convection dominates mass transfer.1.1’. = (2) (3) V1. solute diffusion and partition coefficients.respectively. The boundary layer concept Let us briefly recall the basis of the stagnant film model. — d2C dC D—+[V 2 1—W(Z)]—-—=0. Indeed. the bulk of the liquid being assumed to be homogeneous. let us suppose that mass transport is purely diffusive in a region of extent 6s~in front of the interface. Our purpose in this paper is to extend the previous analytical results using a physically sound boundary layer approach. one-dimensional concentration problem. making it easier to use for the practician. dZ )~ ~: C C~. the externally supplied parameter 65F was widely interpreted as the length scale of “diffusion dominated mass transport”. the governing mass transfer equation. let us consider the “diffusion controlled” mass transfer equation: 2C dC 0. Eqs.

in(10)). at no additional cost in terms of mathematical complexity. but we shall now see that this boundary layer concept can be fruitfully used in the study of microsegregation.J.141that the characteristic equation governing the variations of 6 is = — — D/6 = V1 — W(6). from eqs. transport will be said to be diffusion controlled (‘~~>> W(6). A way to interpret (9) is todiffusive say that. we shall assume that the frequency of the fluctuations is low enough for the system to follow them. it is possible to write down a time dependent version of eq. The boundary conditions being again eqs. aC/at time scale T much larger than 6 be negligible with respect to DII2C/aZ2. It is then possible to define an effective partition coefficient keff as the melt 433 A lot of misunderstanding could probably have been avoided. In other words. viz. the solution is (1 k)V 1c~. (11) — — — = — = = ~. depending on the relative magnitudes of V 1 and W(6). and that the growth rate I/~(t)is given by: V1(t) ~7~(i +m(t)). the difference is mere intellectual satisfaction.P. fr~ W(6)). t)] az ~. if BPS had 65F~introduced Of course. (13) m(t) being a modulation around the average value V~. W(6(t). t). (9)). the 6 characteristic length scale of the probindeed 1cm. J’~~V1). (9) Eq. but a first advantage is that there is no discontinuity of the concentration derivative in this formulation. W(6) towards the front. C(Z) (1 k)V 1 ~ + i 1 exp~ D ) — = — — ~_ j (8) So far we have merely changed the arbitrary parameter necessary to match the exact solution of BPS at the interface. the time-dependent mass transfer equation in a one-dimensional frame moving with the interface at a rate V1(t) is aC at a~C 2 D az + [V1(t) 3C — W(Z.yet to be defined. Garandet / Microsegregation in crystal growth from where a constant effective velocity fr~. It is interesting to note [13. or convection controlled (V1 W(6). us where the convecto-diffusive parameter ~ V16/D V1/V~~~ measures the respective contributions of convection and diffusion to mass transport. a typical D/6 balances the overall fluid motion V. (7) is thus justified on physical grounds. (1). The substitution in eq. ( t) — W( 6(t). (9) was seen to compare very well with existing numerical and experimental [13—15]. Moreover. t) W(6(t)). D/V1). (6) and (8). we get ~ D/6. If both solidification and convection velocities are unsteady. The low frequency limit In this section.141 that in the developed convective (~1~n 1 or65F6 is 65F~ Underregime this restriction. an effective velocity J”~instead of for steady state problems. The time-averaged value of the boundary = = 1 — (1 k D/6 (t) (10) keff kC(0) C~ — Order of magnitude arguments indicate that if the concentration variations take place ovenwilla 2/D. Once 6(t) has been derived. (9): — k) ~‘ = = ~ = = = . has been substituted to the V1 W(Z) — term in eq. (2) and (3). Besides.velocity at the boundary layer edge. In that case. we suppose that the composition instantaneously reacts to a change of the growth conditions. it is possible to show from scaling analysis arguments [13. now suppose that the convective contribution does not depend explicitly on time. eq. D/6 is then expected to be close to data V 1 W(Z) at the boundary layer scale 6. t) standing for the effective convection velocity at the time dependent boundary layer scale 6(t) (see eq. (12) with W(6(t). but this result certainly does not hold when diffusion becomes important.assumed smaller than unity to avoid backmelting. meaning that the characteristic length in the exponential is as it should be the boundary layer thickness. Moreover. 3. it is possible to use the convecto-diffusive parameter ~i(t) 6(t)V1(t)/D the Let effective partition coefficient formula (eq.

thus: C(Z.3 0. as expected. eqs. — (‘~(t) ~SS — (15) where ~ is the average interface composition derived setting i =i in eq. The general problem k=O. exp(iwt).9 I Fig. The main vanables of the problem (composition field.7 0. 1 for various values of the partition coefficient k. If we now suppose the variations of the W(6(t)) term to be small. (7) will be the relevant mass transfer equation. (10). it was assumed that the stagnant film thickness did not depend on interface velocity.m’lt velocity changes. layer thickness ~ can then he derived from eq. the approach of refs. P. we shall assume that the boundary layer thickness of the steady state prob1cm 5° is a given parameter. relative concentration variation 1 k~O. [8.4 - 0. but significant differences are observed when diffusion becomes important.91.6 Our purpose here is to derive a correlation 0.4 —— 0.8 0. It can also be considered as the low frequency limit for the general problem we shall now address. (15) was earlier obtained in the frame of the stagnant film model [11.e. the fluctuation of fr~reduces to V~l. interface and effective velocity) are expanded into Fourier series up to the order one. More interesting for our present purposes.91 is certainly correct in the convective regime limit (6 ~< D/VI or i ~< 1) and it will be used to check the validity of our solution there. As was done previously in the analytical efforts already quoted [8. (16a) V~ V1°+ V1t exp(iwt). We shall here drop this hypothesis. assumed small with respect to the zeroth order contributions. (15) is useful for prediction purposes.434 . the time-dependent version of eq. Due to our solutal boundary layer formulation. (lOb) (lbc) = being the pulsation of the perturbations. Since we focus only on the influence of variations of the interface velocity.1 0.6 —~-~- 0. However. I.5 ~ c — 0 0. we find that the concentration fluctuation for low amplitude growth rate changes is = k ) ~(1 ~) I ~(l —k)~ c’5sifl(t). Relative microsegregaiion versus i in the low ‘requency limit for various values of the segregation coefficient.2 0. we shall not dwell on the related temperature problem and the interested reader is referred to the earlier papers for a derivation of the influence of thermal oscillations on growth rate.e.8 ‘~- 4.Oi 0. the key improvement being that our results arc expected to hold whatever the convecto-diffusive state of the melt. An expression similar to eq.1 0. the first order governing w = . The relative concentration variation is plotted in fig. The zeroth order solution is simply eq.1. i. (8). D/6 V1 W(6). for i ranging from 0 to I. In refs. both approaches yield the same transient behaviour when convection dominates mass transport (i ~< 1). Using ~(t) thus defined as an input in the effective partition coefficient formula. (12) and (13) yield = ~( I) (14) + = 1 +ni(t)~1 — — — where i V16/D..2 k—O. V. However.9].~1=V. (9).YF+ V. r) =C°(Z) +C’(Z) exp(iwt). Gurundet / Microsegregaoon in crystal growth from the . Eq. i. keeping in mind that it is only valid when the boundary layer reacts instantaneously to interface between interface velocity and concentration variations.5 0. [8. setting fr~ D/6°. we shall rely on a perturbation approach.

their relative amplitude depending on three non-dimensional parameters: - ~ = in crystal growth from the melt Fq =w(6°)2/D. and the driving term V 1’ exp(iwt). (21).3 —3 As noted in ref.° .16]. The general solution is thus = = — which can be made to coincide with the published results [1. • The convective regime. a particular solution of eq.5 (21) —.~0)). Taking the limit Fq —* eq. (18) to determine A. a complex parameter: = [ 1 ( 4iw(6°)2)i/2] 11+ 1+ 1260 435 interface velocity variations are proportional.i° and k = o. Discussion 1 — 0) We now make use of eq. We find that the concentration and —2 —i 0 log 1 2 3 4 (Fq~ Fig. look a little unfriendly. (21) may published correlations (eqs.Z). ~°=5°V1 Eq. (17) is simply C. respectively. and we finally get for the value of C’ at the interface: V 1(1 —k)C~ 1 C:=_D+(lk)V0 ( iV. . C1=0. 2. we can proceed to a systematic presentation of the predicted correlations.9] are expected to be hold. k. (18) dZ 1 - = — An additional requirement is that the perturbation C’ vanishes far away from the interface: Z—~. (14a) and (14b) in ref. (21) reduces to eq. Norm of the relative concentration variation versus non-dimensional frequency for three values of . (41) and (42) in ref. I D 1—i (22) ~=Vi Setting dC°/dZ —B exp(—Z/6°).~ (iB/w) exp(—Z/6°). Garandet / Microsegregation equations in the bulk and at the interface are. 1— —(1 +m 0)6° (20) Now that we have gained confidence in the validity of eq. the occurrence of imaginary terms defines the phase difference between the interface concentration. = C’ =A exp(m. Shown in fig. high frequency range (~O ~ 0.°(lk)/D. eqs. two limiting cases can be considered: . [8]. Fq —v 0. The low frequency limit. [8]. Fq —s ~) where the previous solutions [8. 2 is the frequency dependence of the modulus of the relative concentration vania— The above expression can be transformed into C C~ V1 1 V. (15).P.Z) + iB ( —exp~ Z 5. To check the validity of our result.oi. (21) becomes ~(1_k)~Fq~/2 ~. 1 > — -1 -1. (19) The solution to the homogeneous problem is simply: C~ A exp(m. it is easy to show that eq.5 — (i~i0/2Fq)[1 X ~[1+(l+4iFq)1/2] — (1 + 4iFq)iz”2] ~ -2 —(1—k)~° —2. with B V~°C. but it is indeed quite simple with respect to the previously 0/D. (13a).J. (40).9. [9]). A being an integration constant yet unknown and m. 2C’ D dC’ dC° D ddZ2 + ~T iwCt V 1t (17) dC’ (1 k)(V 0C1 + v~tC0).

The associated phase shift of fig.)) tions for three values of the steady state convecto-diffusive parameter.7] in the early eighties.54 ((.436 .1 and finally decrease as = = = Fq ~ However. (13). (22)) Fq limits. i° 0. 0.( t) A sin(wt). The variations are monotonic. for purely diffusive mass transport (see fig. a maximum in the medium frequency range could have been expected. (21) and the numerical Table I (~onipartson between our analytical predictions and Wilson’s numerical results 171 -2 5 .3 and 0. For high values of Fq. 3. i°—0. i. The relative composition variations first increase with frequency. hut the cornposition variations always seem to increase with 1 kH Turning to a comparison with the numerical data.5 and — FigS. P. with n. A fully time-dependent analysis was carried out. Cr CCr ~ r- N 6— oL~— I I ~ 3 2 1 0 log 1 2 3 4 4 5 (-q) Fig.01. A priori more surprising is the result obtained for i° 1.~____________________________________ 4 3 —2 1 0 1 2 3 J° Fq k 4 log ~3r Fig. An alternative presentation of’ these results is proposed in fig. in the low frequency range. Garandet C ~ / Mic-ro.9. 3 also exhibits a monotonic decrease. but it lags ~/4 behind in the high frequency limit. assurning a variation following eq. Norm of the relative concentration variation versus non-dimensional frequency for the case — I (purely diffusive mass transport) and k ((1)1. 4). 1)33 6. Shown in table I is a comparison between the - predictions of our eq. where w stands for the angular velocI — — - 5L - ity of crystal rotation. the expected Fq I 2 power law being observed above a cutoff frequency Fq 1. the effect of fluctuating growth rate in a Czochralski configuration was thoroughly studied by Wilson [4. 11) 028 ((II 026 11.0515 0. the relative concentration fluetuations increase linearly with i°. using i~ as a variable. we took k 0.e.1)!.03 that a maximum can he ohserved. (21)) (numericall 1). 4.5. 5. Interface velocity/concentration phase shifi sersus non-dimensional frequency for the case Jo = ((. (15)) and high (ccl.09 001 ~ 1)78 2 54 2. in all cases. the concentration fluctuation is able to follow the variation of the interface velocity.1.1.0505 (H’ . since microsegregation vanishes both in the low (eq.07 1.it is only for Fq smaller than 0.25 (H / ( (‘iH leg. then pass through a maximum around Fq 0. The influence of the partition coefficient has not been checked in detail. Norm of the relative concentration sariation versus the convecto-diffusive parameter tor three values ol Fq and k —‘ (1.segregation in crystal growth from the roe/i T C’ 51 ~ Cr) r~ -~ U-.

As for the experimental data.069 0. we were able to derive a correlation between interface velocity and concentration fluctuations. 6.097 0. D. Rouzaud. We thus think that our modelling can be used in practice. this approach stands on stable physical grounds.44 0.35 0.J. Garandet / Microsegregation in crystal growth from the melt 437 E 0 C) 51 _50 cv E 0 a 19 ~0 3x10 a) o 0 0 • •~ 0 •• (b) —. [17]).023 0.J.023 C~/C. as the two growth cycles were somewhat different (see fig. Even though we know that microsegregation remains proportional to A up to the point of back melting [4].06 1171 1181 [181 [191 with the predictions of eq.147 0. [7].° C~/C° (eq. [17] in 1973. We also demonstrated the possibility of accounting for the effect of convection in the melt via a solute boundary layer formalism.38 k 0. (21) is fair.023 0. Prim and Slichter stagnant film model [10].26 Fq 3. Favier are gratefully acknowledged. Further work by the MIT team [18. Acknowledgements Fruitful discussions on the topic with Drs. results for the three cases presented in ref. (21)) (experimental) 0. As opposed to the Burton. l~~1~’~O • ~ 0 ••••• - 40 — 30 a. Two sets of data were obtained from ref. for instance to assess the allowable pulling device instabilities in a crystal growth furnace. Using a perturbation analysis.21].38 6. Camel and J. A typical output of this procedure is plotted in fig.045 0.49 5. The author would also like to . The agreement Table 2 Comparison between our analytical predictions and the experimental results [17—19] J° 0.~. a very important paper was published by Witt et al.P. - 20 — 010 = 0 2xtO’9 Icycle I i — 0 1 tb) 2 3 2I cycle I I I 3 cycle I 0 4 5 6 7 8 9 10 II 12 13 14 15 16 17 18 19 cc Length of crystal grown (pm1x280 (01 0 0 Fig.37 0.058 0. 2 in ref. All the results are summarized in table 2.087 0.9]. As the boundary layer concept was also successfully applied to radial problems [20.094 0. we think that it is a very powerful key to the modelling of segregation phenomena in melt crystal growth.19] on this topic featured Sb doped Si alloys. The algebra involved was seen to be quite simple with respect to the previous theoretical treatments [8. Concluding remarks Our purpose in this paper was to propose an analytical approach to the microsegregation prob1cm. [18]. thus supporting the possibility of a linear approach even out of its range of validity stricto sensu. These authors were able to measure simultaneously the dopant distribution (via spreading resistance) and the microscopic interface velocity (via the distance between striations induced by current pulses sent at a given frequency) in Czochralski grown Ga doped Ge. only the experiments performed without backmelting being considered here. Quantitative growth rate and microsegregation analysis on a Ga doped Ge crystal (experimental result from ref. the maximum discrepancy being roughly 50%.08 0. A. [18]).61 5. the agreement is well beyond what could have been expected. 6.

F. . The present work was conducted within the frame of the GRAMME agreement between the CNES and the CEA.iiid (‘haracterizittion.J. A. for their help in improving the presentation of the manuscript. nd D ( I imcl in II indbook oh D. (‘omera and . Amsterdam. R (‘ Prim and W. Wilson. Amsterdam. [IS] A. Soc. Gatoi. [4] 1.J. V.0. I Ouazzani and I (‘rysil Growth 97 (989) 285 ~ C’~’ Amplitude of growth rate modulation Solute composition (mass or mole traction) Steady state interface composition (mass or mole fraction) Zeroth order interface composition (mass or mole fraction) I ‘ .segregation in crystal growtbt /rom the tile/i thank his friends 0. J. Crystal Growth S ( I 969) 227. (oehran. J ..T. (arrutllers and Al’.I Fluctuation of interface and effective velocities (m ~ Z Space coordinate normal to interface (m) S - Solute boundary layer thickness (m) Zeroth order solute boundary layer thickness (m ) Stagnant film thickness in BPS model (m) Convecto-diffusive parameter (0 ~ i ~ Quasi-steady-state convecto-diffusive parameter [12] L.F. Crystal Growth 114 (1991) 593.1. [21] JR Garandet.1.365. [3] AN.1. [2] . Fluctuation of the interface composttion (mass or mole fraction) I) Solute diffusion coefficient (rn s ) Fq Non-dimensional frequency k Solute partition coefficient m( I ) Modulation of growth rate W Dimensional velocity component on Z axis (m -- ~ -.G. Wilt. [9] 1). [IS] 3. T.35 H [.P.J. [17] A. C. (hem Phys 21 (1953) 987.(rysI~l Growth 11(6 (1990) 437. [14] Crystal 1 P Ci irGrowth.I. Rouz~iud. [8] DII. (ryslal ( ~ussIbi (1989) 571.W.I. 1211 (1973) 1119. I-lu ne and F. Crystal Growth 48 I 1980) 4. [Icetrochem. .11 Averageorder intirtact velocity (m s (m Zeroth interface velocity V.0.J . Garandet.438 . i5 w Zeroth order convecto-diffusive parameter Frequency of perturbation (s I References I”~oiuenclature [I] JR. 30 (1934) .0 01 Wikon. .Flee— trochem Soc. 126 (1979) 2240. Gatos and WA. I 6] D.G. . Alexander. lids.1. to he published). Murgai. Garatu/et / Micro.P Sliehter. Z. ~ — I) I) 511 ~. Crystal Growth 47 11979) 68IL [7] JJ [~ 1(3.T. T. Garandei.M.1. (‘rystal Growth 48 (1980) 451.1). R. Murgai. G:irandet. P.. I i Rosenberiiet. J.1. van Run. (‘rystal Growth 113 (1991) 587. Thevcnard. [C. . Wesldor~~. Wilt. J.I) - ~ —.1.(. Ilenz. I 2. Duffar and [1 Camel. sriEd. Wilson. J.C).1.1. lurle (North-I lolland. Jake man and ER. Crystal Growth 44 (197$) 247. . Mullin (North— A C I lolland.1. 5_I) V~~-Effective diffusion velocity (rn V Interface velocity (m I V.1’. Soc l~3(19761 114 [19] A. Gatos and A. J. Wilt. [13] J.I . and F. J. [6] A. (‘rvstal Growth 108 (I 991) 572. Crystal Growth 125 (1992)112. ~aviei.. . [20] J.1 Crystal (irowth 5$ I 1982) I lurlc. . A. l. F. mdcl iiVol. and [.1. J. I IC’. Jakcman.J. l’ikc 3-stIll (irowih 3/4 (1968) 633.. IJeda and il). 197S). (‘ambridge Phil. Wilson. Proc. Eleetroclicm. Soc. Rouzaud. Favic r. M. .ichtcnsteigcr and Il. in: (rystal ( ~rowIli . [I Ii W. [11)1 IA Burton. Danilewskv nil K.1.P. Duffar and . . J.