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Appl. Phys.

A 37, 1-17 (1985)


Physics A

Surfaces ""

9 Springer-Verlag 1985

Point Defects, Diffusion Processes, and Swirl Defect Formation in Silicon
T. Y. Tan IBM Th. J. Watson Research Center, Yorktown Heights, NY 10598, USA U. Grsele Siemens Research Laboratories, D-8000 Miinchen 83, Fed. Rep. Germany
Received 20 November 1984/Accepted 16 January 1985

Abstract. The paper consists of three parts. In the first part we review the basic experimental and theoretical results which shaped our present knowledge on point defects and diffusion processes in silicon. These results concern on one side oxidation effects which established that silicon self-interstitials and vacancies coexist in silicon and on the other side diffusion of gold into dislocation-free silicon which allowed to determine the self-interstitial contribution to silicon self-diffusion and to estimate the corresponding vacancy contribution. In the second part we discuss topics for which an understanding is just emerging within the framework of coexisting self-interstitials and vacancies: reaching of local dynamical equilibrium between self-interstitials and vacancies; rough estimates of the thermal equilibrium concentrations of self-interstitials and vacancies and their respective diffusivities, and finally, various possibilities to generate an undersaturation of self-interstitials. In the third part we examine swirl defect formation in silicon in terms of vacancies and selfinterstitials. PACS: 61.70, 66.30, 85.30

Atomic diffusion in silicon can proceed via both direct and indirect mechanisms. Impurity atoms having no strong bonding interactions with silicon atoms are located exclusively on interstitial sites and in their process of migration jump directly between these sites. Species such as hydrogen, helium, or many metallic impurities, such as copper and lithium are supposed to diffuse in this manner. Oxygen atoms, although possessing strong bond interactions with silicon atoms are also believed to diffuse directly by jumping between the bond-centered interstitial positions. By contrast, the diffusion of substitutional impurities (e.g., of the commonly used group-III or group-V dopants, B, A1, or P, Sb, As, respectively) and self-diffusion require intrinsic point defects such as vacancies (V) or self-interstitials (I) as diffusion vehicles. Whereas in the case of metals there is general agreement that vacancies are sufficient to explain selfdiffusion, the situation became less clear-cut in the case

of silicon when in 1968 Seeger and Chik [1] suggested that besides vacancies also self-interstitials play an essential rSle in diffusion processes in silicon. Based on the observation that surface oxidation of silicon leads to the growth of interstitial-type stacking faults as well as to an enhancement of boron and phosphorus diffusion Hu [2] suggested that these elements are diffusing partly via vacancies and partly via self-interstitials. In fact, as discussed in Sect. 1 further investigations and analyses of the effects of oxidation on the growth of stacking faults and on the diffusion of dopants have shown beyond reasonable doubt that self-interstitials and vacancies coexist under thermal equilibrium as well as under oxidizing conditions. These investigations finally stopped the controversy whether vacancies only, self-interstitials only, or coexisting vacancies and self-interstitials govern substitutional dopant and self-diffusion in silicon. Presently the remaining arguments center around

by thermal nitridation of silicon. In. 10. and Sect. for references see [3]. 9] 1 GCv = c qc q . (6) (7) In (7) G~ is the fractional I-component of the dopant diffusivity D ' under thermal equilibrium conditions defined as G~= D~/Ds. On one side. Finally.. but by an appropriate analysis of the diffusion of gold into dislocation-free silicon this can be accomplished as discussed in Sect. where D{ and D~r are the respective diffusion components involving self-interstitials or vacancies. 2. e.(Dox-.DI(CI/CI ) + Dv(Cv/C v ). 3 we deal with the question of how long it takes at a given temperature until local dynamical equilibrium between vacancies and self-interstitials is established. 10-12] I. In slightly updated form the reasoning is as follows: The growth of interstitial-type OSF requires a supersaturation of self-interstitials or an undersaturation of vacancies. 6. 10-12] s __ s eq s eq Dox. Available oxidation experiments do not allow a splitting of silicon self-diffusion into the contributions via vacancies and via self-interstitials. Ga. in Sect. (3) Surface oxidation of silicon single crystals leads to oxidation-enhanced diffusion (OED) of B. 1 Hu [115] discussed possible deviations f r o m (2) . 13]. show that during surface oxidation silicon self-interstitials are injected from the SiO/Si2 interface into the silicon. oxidation-retarded diffusion of Sb requires an undersaturation of those point defects governing Sb diffusion. On the other side. Oxidation Effects D'=D~+D~. P. therefore. By surface oxidation selfinterstitials are injected into the silicon and react with vacancies according to I+V~O. which perturbs the point defect concentrations as discussed above. G~ is expected and have been found to depend on the specific dopant as well as on temperature and on the position of the Fermi-level [3. 7. (4) If dynamical equilibrium according to (2) is reached the normalized diffusivity enhancement A sox--.D~)/Ds s (5) may be expressed in terms of the self-interstitial supersaturation ratio sx=(G-c~q)/c~ q as [11. to oxidation-retarded diffusion (ORD) of Sb as well as to the generation and growth of interstitial-type oxidation-induced stacking faults (OSF). 3. Section 4 is devoted to an estimate of the thermal equilibrium concentrations C ~ q and C~q ofselfinterstitials and vacancies and their respective diffusivities D~and Dv as a function of temperature. During oxidation. As soon as local dynamical equilibrium is reached the mass action law yields for the actual point defect concentrations C~ and Cv [8. As first pointed out by Hu [2] these phenomena need to be considered together and.g. and As. we will present some suggestions how the fairly complex experimental results on the formation of swirl defects may be understood in terms of the coexistence of vacancies and self-interstitials and their agglomeration during the growth and cooling of silicon crystals. (1) quantitative aspects of the individual contributions of vacancies and self-interstitials to the various diffusion processes. This may be understood by assuming that without oxidation both self-interstitials and vacancies are present in their respective thermal equilibrium concentrations C~q and C~q. In Sect. as observed in the case of surface oxidation. when analysed properly. In the presence of coexisting self-interstitials and vacancies the diffusivity D ~of a substitutional dopant is given by [2. (2) Equation (2) shows that under these circumstances a supersaturation of self-interstitials ( C t > C [ q) is coupled with a corresponding vacancy undersaturation (Vv<C%q). Since O R D of Sb [4-7] occurs under the same oxidation conditions as OED of the other dopants. A1. the dopant diffusivity changes to [3. Tan and U.2 T. 5 to various possibilities to realize an undersaturation of self-interstitials. where 0 denotes the undisturbed lattice. it can be concluded that surface oxidation leads to a supersaturation of self-interstitials and that these dopants diffuse predominantly via an interstitialcy mechanism.Y. From O R D it can therefore be concluded that surface oxidation leads to an undersaturation of vacancies and that Sb diffuses predominantly by a vacancy mechanism. Grsele oxidation obviously induces simultaneously a selfinterstitial supersaturation and a vacancy undersaturation. 12] A~x= (2G~+ G~s~--1)s~/(1 + si). oxidation-enhanced diffusion of substitutional dopants indicates a supersaturation of those point defects which serve as diffusion vehicles for these dopants.

This means that Sb diffuses almost entirely ( ~ 98%) via a vacancy mechanism. Predictions of normalized diffusion changes A~. / / / / / 1. A plot of (8) is shown in Fig. or closely related expressions [7.5 I t -1 A~x /. see / //is' $ -0. 10. Nevertheless. The value of A~. 11. G] values for other dopants as determined by various authors [7. 31].1. In this q way. 1 for three G~values. 5] a self-interstitial undersaturation (si < 0) associated with a corresponding supersaturation of vacancies (Sv > 0) may be realized. q (9) ~2 (dRsF~ = _(DIC~q+ DvC~q)~T J + DIC~qsI_ Dv Cveq Sv.0Sb in Si Fig. This can actually be done by measuring the growth kinetics of OSF under the same oxidation conditions prevailing in the OED/ORD experiments. data from Mizuo and Higuchi [4]. 37-39] but even more so the different methods of calculating s~ from measured OSF data.g. Diffusion Processes. Open circles. for oxidation of (111) surfaces at high temperatures and long times. 18] from the shrinkage rate of OSF in an inert atmosphere sx=Sv=0. data from Tan and Ginsberg [31] From appropriate experiments on OED/ORD G~may be determined provided the oxidation-induced supersaturation ratio sx of self-interstitials may be determined.c~q)/c~ according to (7) q Fig. The dimensionless quantity aofe contains all factors related to interaction potentials between point defects and the Frank partial dislocation binding the OSF and turns out to be approximately 2 [3. 2 [4. there is an obvious trend that the fractional interstitialcy diffusion component G~ increases with increasing temperature. The fitting parameter is G~ which turns out to be around 0. 25-31] at the same temperature s~ may be determined [10.0 I 1. this part of the figure is given.. 7 the stacking fault energy (0.8 • 10-9 [11].52eV/kT)t-1/4s 1/4. 15] controlled growth regime of the growing oxide film on top of an (100) silicon surface [11] s~ ~6. 2. 14. 10. Since s~ is timedependent. the measured normalized diffusion enhancement (or retardation) is a time-averaged value A~x which still fulfils to a good approximation (7) if a time-averaged value '2~ is used instead of S02.Point Defects. 5 for a discussion of effects occurring in an N2 atmosphere [19-25]. or for surface nitridation discussed in Sect.~ = o. The quantity aeff(DiC~q+DvC~r q) can be determined [10.38• f2 the atomic volume (2• 10 -2a cm3). filled circles. 17]. 7.C~q)/C~. 11. The quantity go2 may be obtained from (10) by replacing the pre-exponential factor by 8.5 M / . 11]. An independent determination by Antoniadis and Moskowitz [7] yields G~0. . For a semicircular OSF (as an approximation for those OSF usually occurring at the silicon surface during oxidation) the change of its radius RSFwith time t is given to a good approximation by [14.5- 9 1-2G~ G~ . 32-36] (Table 1) show a laroe scatter which partly reflects the scatter in the experimental data [5."~. 1. From measured growth rates in an oxidizing atmosphere [2.6 x lO-9exp(2. 7.02.02. Fitting of data on oxidation-retarded diffusion of antimony in (100) Si wafers via (7) with G~= 0.10].015. provided (2) holds and that either sI is sufficiently small o r DIC~q>~DvC~r [15]. one obtains for example in the diffusion- . and Swirl Defect Formation in Silicon 3 T oMizuo Higuchi and (1981) 9Tan and Ginsberg (1983) 0.. 10. too. . (10) A~eff \ d t (8) where A is the area per atom in the stacking fault (6. due to an oxidation-induced self-interstitial supersaturation st = (C1-.026eV/atom) [16]. and Sv the vacancy supersaturation ratio defined analogously to s~ by Sv= ( C v . is either positive (OED) or negative (ORD) depending on the values of G~ and sv Since under certain conditions [e. A fitting of data on ORD of Sb at 1100 ~ is shown in Fig.

0" 0..35 0.(n3 = Cv. D%_. 36. 10] Guerrero [34] Fair [33] Matsumoto et al.45 G~On) G~ (P) 0. (14) (15) (16) Q.52 0.5 0.4 0.42 0. could be obtained by measuring the influence of oxidation on self-diffusion.(n) + \"l. G~.18 0.(n) D~+ ~ ci+(n) • LJV+..16 0. we may write (13) as D'(n) = (01o + D~o) + (D~++ D~+) n~ Depending on the specific dopant.51 0. it has been found that the dependence of D~ on the electron concentration n (or the hole concentration p related to n via n p = n~.6 1100 0.6-0.22 ( T.0 0.(n)/Q.5-1. V . for B. 10] Guerrero [34] Fair [33] Matsumoto et al.30 G~ (As) 0. or D~ may be negligibly small.g. [7. (12) Therefore. [7] Tan and.2-0.7 0. I =. Cv+(nO] C v .8 0.8-1. and Sb as calculated by various authors (from O ED/O RD and O SF data available in the literature) based on different calculation procedures T[~ G~ 03) 950 0. G6sele [11] 0.42 0. as yet no such experiments have been performed. 0. DL.2-0.22 0.25 0. in principle [14]. where n~is the intrinsic carrier concentration) is given by [1. 36] Guerrero [34] Fair [33] Matsumoto et al. Equation (12).55 0.4 Table 1. (17) which is just the form of (12).45 0. Ga. Experimentally. [114] Mathiot and Pfister [35] Antoniadis et al. Before discussing a completely different way to obtain information on DIC~q and D v C ~ q via the diffusion of Au in silicon we shortly comment on the implications of the coexistence of vacancies and self-interstitials on the doping dependence of D~.32 0. which is used in process simulation programs (e.3 0. [32] G6sele and Tan [14] GSsele and Tan [14] GSsele and Tan [14] Antoniadis et al.55 0.27 ( 0.1 0. Fractional interstitialcy diffusion components. [7.35 0.12 .25 0.14 0.3 G~(Sb) Although. in the Stanford program SUPREM [43])..34 0.19 0.34 0.23 0.15 0.Y. By n + ( D ~ .Ci_ (ni) + Dv. Q= (n)/Q= (n3 = Cv: (n)/Cv: (ni) = ( n / n f .38 G~ (Ga) G[ (A1) 0.19 0.. GSsele 1000 0. V = we get D'(n) = (D~o+ D~o) + {us CI.Cv_ (ni) ] { G =(n) Cv =(n) + ~ui--' ~ ~ +D~r Cv:(nM " (13) The relative changes of the concentrations of charged point defects with doping are independent of their specific level position in the band gap and given by [1] CI +(n)/ G +(ni) = Cv +(n)/ Cv +(ni) = nJn .3 0.. P.. 40-42] D~(n)=D~o+D~+ +DL n +D~= .015 0. [32] G6sele and Tan [14] Antoniadis et al.(n)/Cv.+ D~r +(D~= +D~r (~) z . Tan and U. V ~ V +. I-. [32] GSsele and Tan [141 Mathiot and Pfister [35] Antoniadis et al.09 0.. may be explained in terms of various charge states of the point defects carrying diffusion.02 0.(n3 = n/nl.17 1050 0. . A1.24-0. [7.7 Mathiot and Pfister [35] Antoniadis et al. 10. As.42 0. the corresponding splitting of the uncorrelated self-diffusion coefficient D sD = DIC~q -'}-DvC~r q (11) assuming the presence ofI ~ I +.12 0.35 0.38 0.64).17 0. some of the quantities D~.16 0.19 0.

However.1 found. This results clearly demonstrates that self-interstitials are involved in the diffusion process. Finally. Therefore. The vacancies are replenished by the diffusion of vacancies from the silicon surface which acts as a vacancy source under these circumstances.1 ~c ~ / oc'~ with the effective diffusivity Def given by t D e .~ mine that DvCv/DICIe q . 20) only (19) operates sufficiently fast. then this mechanism creates an undersaturation of vacancies during the diffusion of Au into silicon. 53] Ci= C~n (Ca: Aul concentration).~ L" / ~ ' s " (25) Within this mechanism diffusion of the gold into dislocation-free silicon creates self-interstitials in supersaturation which diffuse to the silicon surface which acts as sink for supersaturated self-interstitials. The thermal equilibrium concentration (solubility) of Au~. An example of a gold diffusion profile in dislocationfree silicon above 800 ~ as measured by Stolwijk et al. Diffusion of Gold into Dislocation-Free Silicon (23a) (23b) (23c) Gold atoms.1 DIe f f _ ~ . the two mechanisms differ in the way the interchange between interstitial and substitutional positions is accomplished. 45. 53.1 or/and via the Frank-Turnbull mechanism [50-52.~/OIG")D~c~q/ G q . 20. A much better fitting was obtained by the use of (22).1.1 either on substitutional (Au~) or on interstitial sites (Aui).~~ C~ >> c~qc[q) 1/2 . The two mechanism have in common that long-range transport of Au atoms occur via migration of the highly mobile Au i which may either jump from interstitial site to interstitial site or from an interstitial site to a substitutional site becoming Au~. In the kick-out mechanism the interchange involves silicon selfinterstitials I according to [45.DiffusionProcesses. 46. 19. ( 2. which under thermal equilibrium conditions are incorporated in silicon [44. (19) If DIC~q is negligibly small compared to DvC~z (22) q yields a constant effective Aus diffusivity [50.~1 at 1000~ and ~0. (20) If operative. it can be expected that Gf is doping dependent as has actually been observed [13].~ + Z)vC~.1 DVf -. 46. In (22) contributions to the Au~-Au: interchange process due to both kick-out and Frank-Turnbull mechanism are accounted for. However. which requires that at least two of the three reactions [1. In deriving (22) the following approximations and assumptions have been made [3. C~q.n~ t / V " "c~e~/e'~q ef V/~-'s 9 (24) The same result holds if D~C~q is not negligible but among the reactions (1. 5 measured in an experiment on Au diffusion into dislocation-free silicon may approximately be described by [53. = ( C . we mention that D~ and D~ of (3) represent the sum over the various charge states of the point defects involved.1 Au~ ~ Au~ + I.1 are sufficiently fast [3. 3.1. it does not exclude that vacancies are contributing to selfdiffusion since the strong dependence of D~ffon C-2 in (22) reduces the effects due to DvC~q by this factor for most parts of in-diffusion experiments where C < 1 and C -2 >>1. C~q'. This result did not only show that vacancies are contributing to silicon self-diffusion but also allowed to detereq . is negligible compared to the solubility C~q of Au~. [53. whereas the diffusivity of Aus may be neglected compared to that of Au~. V. We now assume that local dynamical equilibrium between I.Point Defects. and Au~ is established. 51.2nI " -r' I -. In the Frank-Turnbull mechanism the interchange involves vacancies V according to [50-52] Au~ + V ~ Au~. that while almost perfect fitting was obtained for short-time diffusion data small but observable deviations occurred for long-time diffusion data if (25) was used. may diffuse via the kick-out mechanism [3.5 at 1100 ~ . e. Morehead et al. [49-1. 53. 19. 19. Under this condition the normalized Au~ concentration C = CJC~ q to be The same result holds if DvC~q is not negligible but among the reactions (1. 45-49. is shown in Fig.and Swirl DefectFormation in Silicon We remind the reader that (12) just shows that charged point defects are involved in the diffusion. Indeed.. It can be seen that the profile can not be described by a constant diffusivity according to (24) but is satisfactorily fitted by the use of (15). Aui. 20) only (20) is operating sufficiently fast. (22) and analogous for D}.g. but nothing can be learned on the relative contributions of selfinterstitials and vacancies in the various charge states. If DvC~q is negligibly small compared to DIC~q (22) yields a strongly concentration-dependent diffusivity [3.

Fig. Solid fine: fitting via (25) for the kick-out mechanism.. G r s e l e I I I l 0. The fairly large scatter indicates that while (27) is certainly in the right order of magnitude. (26) As will be discussed in Sect.~ 0.t. 31] shown in Fig. \ k IU which is plotted together with (26) in Fig. 56] From their gold diffusion data Stolwijk et al. In Fig. Hu [65] suggested such an energy barrier of "a few to several eV" so that vacancies and self-interstitials would behave independently even at temperatures near the melting point. reciprocal q temperature according to [14]. which basically give the sum of DIC~ q and DvC~rq (for details. 59] but the data available are much less accurate than in the case of gold. 4 the results on DvC}q obtained from these experiments are also shown. In that case only reaction (20) will be operating and an erfc-type profile should show up. The DIC~ q determined from these Pt data are compatible with (26). we expect that at T < 900 ~ reaction (1) becomes ineffective and for still lower temperatures reaction (19) also becomes ineffec- . Tan a n d U. Self-diffusion c o m p o n e n t s DIC~q and DvC~r vs. \ ". 54]. By performing similar experiments for shorter oxidation times (5 to 60 min) Antoniadis IO-ZO 9 Stolwijket al. (1983) ~Kitagawa al.. A comparison of(26) and (27) with tracer and other more direct measurements of silicon selfdiffusion [60-63].1 tive [14. Gold concentration profile after an 1 hour diffusion into dislocation-free silicon at 900 ~ according to Stolwijk et al.4.1.5 " '. (1983) ~ OMoreheadet al. show good agreement within the large scatter of these data and for the temperature range ( g 850 ~ point) where such tracer data are available. 10-is 10. therefore. N~" 10-22 6 7 8 9 104/T [1( "1] 10 i. 53. D a t a from [49.84 eV/kT) cm 2 s. Wertheim [64] assumed the existence of an energy barrier against self-interstitial-vacancy recombination in silicon in order to explain the observation that the rate of A-center production by high energy electron irradiation strongly depends on the irradiation temperature. but in the case of nickel only the Frank-Turnbull mechanism is operating in the temperature-range in which Ni precipitation experiments have been performed [55-57]. Platinum in silicon also diffuses via the kick-out mechanism [58. Later on. 0. more accurate data are required to get an as reliable estimate for DvC~rq a s for DIC~ q. This data point together with the data of Morehead et al. a possible recombination barrier cannot be too high. Wilcox et al. 3. [49].18 ~C e~ Vq xl ~ "~ \ I I 3. 51.\/ x\ / DiCieq > 10-14 g %. 3.1. 55.05 li I 20 50 x [pm ] Fig. 4.'.6 exp ( . The experiments on ORD of Sb [4. [49] determined the quantity DIC[ q a s DIC[q = 914 exp (--4. (1964)& IYoshida and Saito (1967) I I I i I \7' l '%J. see [3]). Y . 2 demonstrate that for oxidation times longer than a few hours at ll00~ local dynamical equilibrium is reached. dashed line: fitting via (24) for the Frank-Turnbull mechanism 4 Tloci 1300 i t 1100 i % g T ~5 i 900 i 800 ~ 700 i 10"12 \ . 0982) et TWilcox et al. [51] found such a case at 700 ~ With their data and an extrapolation of the Au~ solubility to this temperature an estimate of DvC}q at 700 ~ can be obtained. Nickel in silicon diffuses similarly as Au.6 T . [53] yields the crude estimate [14] DvC~rq .03 eV/kr) cm 2 s. 4. (27) I / I I 2 I 5 I 10 "\ %"t 100 0. Kinetics of Reaching Local Dynamical Equilibrium Between Vacancies and Self-Interstitials After knowing that vacancies and self-interstitials coexist in silicon and under certain conditions are present in local dynamical equilibrium according to (2) the question arises how long it takes at a given temperature until this dynamical equilibrium is established.

S i interface but it takes about 1 h at 1100 ~ for I-V-recombination to proceed to such an extent that dynamical equilibrium is reached. In this picture the factor 10 s by which the experimental v a l u e "Cdy differs from ~Tdi estimated from (2) arises n f from the Bolzmann factor exp(AG/kT).4 eV/kT) (30) for an enthalpy barrier AH.Point Defects.g.4 eV assuming that in the expression Fig. e.. for establishing local dynamical equilibrium between vacancies and self-interstitials is given by "Cbar ~' (O/4nDSOrw) exp(1. A convenient source of self-interstitials is a growing oxide.e. from an entropy barrier against I . and Swirl Defect Formation in Silicon and Moskowitz I-7] showed that (2) is not fulfilled immediately when oxidation starts. Waite's theory of diffusion-controlled reactions I66] has been used to estimate the time Zdif required to establish the dynamical equilibrium in the AntoniadisMoskowitz experiment. by [67] 27dif ~.DiffusionProcesses. then the concentrations CI and Cv. dashed line: entropy barrier limited recombination (31) for an entropy barrier AS. and 170 days for 1000~ 950 ~ and 900 ~ respectively. It is seen that Zbar according to (30) increases rapidly with decreasing temperature and attains values of 2.V recombination. 0 5 S which is about 10 s times shorter than the observed time Zdy of n about an hour. . Solid line: enthalpy barrier limited recombination (30). Another even more promising possibility is the A G = A H . The diffusion retardation approaches the value expected for dynamical equilibrium at about 60m in. Therefore.TA S (29) the entropy contribution TAS is negligibly small By contrast. 17. 3. [67] proposed that the main part ofA G originates from the term TS.e. and by "Cbar . T [~ 1100 900 i i 7 7"~ t07 T i . Calculated recombination-barrier limited time Zbarrequired for reaching local dynamical equilibrium between vacancies and self-interstitials as a function of reciprocal temperature.V recombination is controlled by the overcoming of a barrier that exceeds Gibbs free energy of diffusion (of the faster diffusing ones of the point defects) by G. 5. The temperature dependence of the barrier-limited reaction time. With D sD~ 10-1 s cm 2 S. and 22 days for 1000~ 950 ~ and 900 ~ The long times estimated for "Cryn at temperatures below 1100 ~ simply mean that ifa perturbation of the point defect concentrations occur. These observations may be rationalized as follows: during oxidation self-interstitials are injected into the silicon by the SiO 2 . i. 5 using D sD of (11) with (26) and (27). that (2) is fulfilled. after short times of oxidation there is not yet a vacancy undersaturation. Antoniadis and Moskowitz [7] interpreted the difference between Zdy and Zdif in terms of an enthalpy ~ barrier corresponding to AH ~ 1. "Char. so that the oxidation-induced self-interstitial supersaturation enhances Sb diffusion via the small I-component of its diffusivity (GI ~ 0.1::: 103 t~ T 106 105 ! / ~/// ! /! 102 101 104 100 10 3 (28) 7 8 104/T [K-1] 9 =. At ll00~ they found a small OED of Sb for a 5 min oxidation which gives way to an ORD for an oxidation period longer than 10 min. We therefore expect that in future oxidation experiments at 1000~ or lower temperatures Sb should show OED for oxidation times t ~ Zbar. ~ (~2/4rcDSDrlv)exp (A S/k) (31) . Both estimates are plotted in Fig. i.1 and a recombination radius of r i v ~ 5 • (28) yields " C d i f ~ 0 . it can be concluded that I . if no recombination barrier were present. Equation (32) leads to somewhat lower values but still to 1. The virtual independence of self-interstitials and vacancies for typical times of experiments at temperatures below about 1000 ~ offers the possibility to measure the diffusivities of point defects injected into the silicon. where exp (A S/k) ~ 105. in (4).02). have to be considered as being independent of each other for usual times of experiments of a few hours or shorter. based on a consideration of the large preexponential factor associated with D sD. G6sele et al. where AS is negative. This consideration applies to the analysis of O E D / O R D and of OSF growth/shrinkage experiments. f 2 / 4 ~ z D S D r i v . As a consequence.

.D.e.9 c m 2 s .8 self-interstitial injection mechanism of phosphorus diffusing into silicon starting from a high surface concentration [68-70]. q eq (37) where C eq is the solubility of substitutional gold in silicon in dimensionless atomic fractions [4. l T. DI. such a reaction is not available. 14] C~r < Cs = 18 e x p ( . induced by the oxidation process at the wafer backside. 9]. on one hand.Y. c)..~(DIC[ + DvCv )/De'ff . B. has been determined [49] and that via vacancies.~ eq (34) eq if c~q>>c[ q.(OiCi + D v C eq eq v ) / ( C I -k c~rq). DvC~q.. and c[q < qC~q. 6). (33) provided C[ q >>C~q. O v could be determined similarly if we knew of a surface reaction injecting vacancies at temperatures below 1000~ Presently. (32) may be used for an estimate of C~q. upper limits for C~r and C~q q between 900 ~ and 1200 ~ have been obtained via the conditions (23b.2. B) or retardation (Sb) of dopants at the frontside ofa siliconwaferoxidizedat the backside as a function ofwafer thickness d for 500 and 4000min according to Mizuo and Higuchi [5. G6sele back-side oxidation FZ. O R D instead of OED) indicates that local dynamical equilibrium between vacancies and self-interstitials has been established.98 eV/kT). V C I ~ ( D I C I +DvCv)/Deft. (36) From the experiments on the diffusion of gold in silicon. These features show that it takes a certain time until the point-defect concentration changes. eq . or Sb implanted into the silicon from the frontside of the wafer. It turns out that the time dependence of the oxidation-induced point-defect concentration changes at the frontside is a measure for an effective point-defect diffusivity (holding for a situation where local dynamical equilibrium between vacancies and selfinterstitials is established) approximately given by [14]. 6. The effect of backside oxidation on frontside dopant diffusion increases with time and decreases with increasing wafer thickness d for a given time t (Fig. as has also been done by Taniguchi et al. The opposite behavior of Sb compared to that of P and B (i. This situation appeared to change when in recent oxidation experiments Mizuo and Higuchi [5. From experiments on the diffusion of gold in silicon the uncorrelated silicon self-diffusion coefficient via selfinterstitials DIG[q. [73] who tried to determine the temperature dependence of O I in a slightly different experimental set-up involving oxidation-induced stacking faults. 72] give a value of 3 x 10 . The interpretation of DI'f as DI is not likely to be v correct for the following reason: Since.~ eq eq I. C~.0 5 0. Since at 1100~ roughly DIG ~DvCv holds (32) also yields [54] Di~DLfV/2 and IV Dv. A splitting of the products DIC~q and DvC~q into their individual factors has not been possible on a sound experimental basis. (32) Fig.1 for Dto'v at 1100 ~ f Mizuo and Higuchi [5.5 0 0 ~ o 0 100 I 200 I 300 I 400 I 500 d [ iJm] .'ff/2 for c~q>~c~r q (35) for c~q>>c[q. eq DIe'fv~. Such experiments will be used in the next section for estimating O I. In a most recent paper Mathiot and Pfister [71] claim that based on their computer simulation results vacancy-interstitial recombination occurs readily and that OED of Sb at short oxidation times should be attributed to the interaction of intrinsic point defects with dopants rather than to a recombination barrier. eq eq eq IV Cv ~. arrive at its frontside where they are measured by the corresponding changes in the dopant diffusivities..~ . 4000 rain 500 rain 1.1. 72] interpreted Dte'f simply as v DI. Estimates of Dv. 6. Tan and U. on the other hand. and C[ q q. 2. 6. DtC[ q and DvC~. or for an estimate of C~q. Diffusion enhancement (P. (38) . These limits are [3. as described in Sect. ' - 4. 6] measured a pointdefect related diffusivity and interpreted it as Dv In their experiments at 1100 ~ Mizuo and Higuchi [5. 6] This and other similar experiments of Mizuo and Higuchi [5.q are reasonably well known.0 ~ \ N. 6] investigated the influence of a backside oxidation on the diffusivity of P. has been estimated [14].siticon 1100"C DoSx D-'. The frontside was covered by an SiaN 4 film in order to prevent point defect generation by frontside oxidation. From the limited information available we cannot judge the validity of their results and therefore refrain from a further discussion.

as a fimction of q. 800 i k "~ 1017 ~ . and Swirl Defect Formation in Silicon . if reasonable q error bars are assumed. Crude estimate o f vacancy (Dy) and self-interstitial (D0 diffusivitiesas a function of reciprocal temperature. The uncertainty of the individual values is at least of the order of a factor of ten where q is a factor < 1 [which follows from (23c) and the corresponding experimental data] given e. The diffusion of these self-interstitials into or across a silicon wafer may be measured via their effect on the diffusion o f substitutional dopants. 6] at 1100 ~ for oxidation-induced point defects. (39) (40) behavior of phosphorus-induced point defects. 8. (. T [oc] 9 l 1400 i 1200 t ~ 1000 E . 7 and 8. 5. Fig. 31) and Fig.g. 72] is in clear contradiction to the condition for C~q expressed in (38) for q ~ 1. For typical diffusion times of 30 min in the T [~ 1300 1100 T 10.v for D v rather than for Dv Since C~q is fairly close to C~q at 1100 ~ but nevertheless has to be smaller than C eq over the whole temperature range from 900 ~ to 1200 ~ we conclude that the activation enthalpy of C~.1. (in q atomic fractions) and Dv shown in Figs. whereas the corresponding C?rq from (36) is compatible with condition (37) for C~. C~ and of self-interstitials. Diffusion Processes. Such experiments have been performed by Lecrosnier et al. The uncertainty of the values of DI and Dv is at least of the order of a factor of ten . 7. an estimate of D I at 950~ or lower temperatures may be obtained from the diffusion 10-14 1046 6 7 8 9 10 11 12 104/T [K-I] . reciprocal temperature.. This results in a corresponding vacancy undersaturation and an effective point-defect diffusivity DIe'f in the order of D v ~ D~ as described by v (32). Thus we arrive at the crude estimate for C~. C~q = 4 exp ( . 6. The time to establish dynamical equilibrium at 900 ~ is at least in the order of days as follows from (30.. 3 the diffusional behavior of self-interstitials injected at 900~ is different from that of selfinterstitials injected at 1100 ~ At 1100 ~ the selfinterstitials in supersaturation react with vacancies (which at this temperature are present in thermal equilibrium in a much higher concentration than selfinterstitials) and establish a dynamical equilibrium with vacancies. by about 0. As discussed in Sect.1 exp ( . The diffusion of phosphorus into silicon starting from a high surface concentration leads to the generation of a self-interstitial supersaturation [68-70]. compared to other diffusivitiesin silicon. [74] at 900 ~ in a similar way as by Mizuo and Higuchi [5. D~>>D eq and that consequently the r.4 900 800 700 600 500 "E .003 at 1000 ~ C~q derived via (35) from the data of Mizuo and Higuchi [5. An analogous procedure for estimating C[ q o r O I is not feasible since c [ q < C~q at 1100 ~ and only an upper limit of C[ q but not C[q itself may be derived from experiments on gold diffusion in silicon.2 eV/kT). Crude estimate of thermal equilibrium concentrations of vacancies. As mentioned in Sect. effective diffusivity D etf gbt this temperature is a measure i. Fig. 13 . Dv = 0.2 eV/kT) cm 2 s. At 1100~ such a situation is present for oxidation-induced [4-7] as well as for phosphorusinduced [68-70] self-interstitials. C[q. 3. is closed to that of q C eq.3 thermal equilibrium concentration of vacancies and self-interstitials in Si 1016 101' 10t4 7 8 9 104/T [K-1] . We therefore conclude.Point Defects.s 10_6 a 10-8 10-10 10-12 The uncertainties of these quantities in the temperature ranges given in the figures are at 1east in the order of a factor of ten. that at eq eq 1000 ~ Cv >>CI .

1 at 900 ~ than at higher temperatures (e. Point defectgeneration(or absorption)mechanism during surface oxidation of silicon. 7 and 8. we assume that c[q> C~r at the q melting temperature T.~n v. Therefore.or phosphorusinduced self-interstitials at sufficiently low temperatures and short times at which dynamical equilibrium between vacancies and self-interstitials has not yet been reached.:. i:. 6) during crystal growth under appropriate growth conditions.-\ V/////~.T/Z///A 02[ I/////. An evaluation of the experiments ofLescrosnier et al. 5. the situation may be described by the left-hand side of Fig.~:. . i ] .[.~"1x 10. 81-83]. Tan and U. 18. s~~//A t x2 02" ~/. .. Possibility (i) is operating at such high temperatures and long times (e.5eV [76]) indicates the correct direction but is quantitatively not very meaningful at present.g.. At lower temperatures self-interstitials L%ff.. as given in (39-42) are values averaged over various charge states and it can reasonably be expected that with decreasing temperatures the charge states with As yet we have dealt with self-interstitial injection induced by surface oxidation or phosphorus diffusion leading to a self-interstitial supersaturation and a corresponding vacancy undersaturation.. induced by oxidation or wafer-backside damage.YY'x~'.b..1 and with the known value of D~C[q an estimate of Cfq(900 ~ 1.. ~ . 812.41U////I T . may influence device processing much more severely and over much larger distances at lower than at higher temperatures. and Tan and G6sele [87]. ~ ~ contrary to what is expected for a simple thermally activated diffusion process.. 9a and b. and DI q. C[q. Unfortunately.7 cm / s. This assumption is based on an analysis [54] of the formation of interstitial-type dislocation loops ("A-swirl defects". e.I V A self-interstitial perturbation may therefore spread much faster at lower temperatures (e.Y.10 experiments of Lecrosnier et al. [74] yields [75] an estimate of DI(900 ~ ~ 10. 80. Theoretical calculations of activation enthalpies of C~q.. s I con". for obtaining the temperature dependence of D~ and C[q. "~ .~z~ move independent of the presence of vacancies with their own diffusivity D~which is much higher than De'ft. (41) (42) T.Xi.g..2 :-.~/////~ \:. Let us shortly summarize what we presently know on the spreading of a perturbation in the self-interstitial concentration: At sufficiently high temperatures and long times (e. Cf q g 108 exp(-4..00)for thick oxidesand/or high temperatures [14. analogous experiments at other temperatures are not available. with DI ~ 10. As a possible mechanism why the S i . .. 1 for si < 0.. We mention explicitly that the assumption c[q(Trn) > c~q(Tm) is still highly controversial and certainly the weak point in the estimated temperature dependencies of C~q and DI. :. a comparison with measured activation enthalpies for vacancy diffusion below room temperature (which are <0..."~" :.si0 ~~llu_.5 x 10-11 in atomic fractions. 1100 ~ 1 h) local dynamical equilibrium between vacancies and self-interstitials prevails and the perturbation spreads with the effective diffusivity nI. as suggested by Francis and Dobson [80]. (a)for thin oxides and/or n-~)/~. Dr.. 80.: b) Fig. 87] . C~q. 9.. G6sele lower activation enthalpies take over. Realizing a Self-Interstitial Undersaturation shown in Figs.4 eV/kT) cm 2 s. corresponding to c[q(900~ 10alcm -3.S i 02...s e x p ( .5 h at 1160 ~ [31]) that local dynamical equilibrium between vacancies and selfinterstitials always is established. At lower x ox/.1.0. [74] at 900 ~ the interaction of phosphorus-induced self-interstitials with vacancies is negligible and the self-interstitials can spread with their own diffusivity Dz.):. _/////~ | l P'/////AFP27"A x.:i)~'~reaction I. (ii) Surface oxidation in the presence of a sufficiently high percentage of a chlorine-containing compound in the oxidizing atmosphere [15. ' . see also Sect.g. so that.7 cm 2 s.g./~.. with ni. v . For realizing a self-interstitial undersaturation (coupled with a vacancy supersaturation at sufficiently high temperatures) presently three different possibilities are known: (i) Surface oxidation at high temperatures for long times especially for (111) surface orientation [31.'/. Therefore. (iii) Growing of a surface film of amorphous Si3N4 by thermal nitridation [84-86]. we remind the reader that C~r Dv..4 eV/kT). DI ~ 10.S i t 2 acts differently at high temperatures and long times than at lower temperatures and for shorter times is indicated in Fig. o) L..9 cm 2 s-1 at 1100 ~ . ~.. Finally. This has the interesting consequence that a point-defect perturbation.'. A more reliable estimate may hopefully be obtained in the future by systematically measuring the spreading of oxidation..~ '•02 T b"~..v.' . and D~ in various charge states are just appearing in the literature and indicate values roughly in the order given by (39-42) for some charge states but rather different ones for others [77-79].::":.I ~i':"-.g.

75 > 0. in which A~x is negative. has the advantage that a knowledge of sl from OSF data is not required. negative) si values. The possibility (iii) that thermal nitridation of silicon surfaces may lead to an undersaturation of selfinterstitials has only recently been noticed [84-86]. namely the injection of self-interstitials into the substrate [86]. A distinction between these two point-defect perturbation processes has been achieved by Fahey et al. amorphous Si3N 4 films on top of silicon wafers have thoroughly been investigated mainly because of their possible use in metal-insulator field effect transistors [88].90 > 0.13 .5 + 0.Si interface. Equation (43) leads. Thin. e.90 >0. The stress effect is now overcompensated by the depletion of Si atoms from the S i O 2 . All these three phenomena indicate a nitridation-induced self-interstitial undersaturation (si < 0) coupled with a corresponding vacancy supersaturation (Sv > 0) which could be due either to a self-interstitial depletion or to a vacancy injection. Under these conditions the local equilibrium (2) was not reached and we can hence conclude that nitridation depletes self-interstitials instead of injecting vacancies. An extensive discussion of the influence of chlorine on OSF growth and shrinkage may be found in [15].85 > 0. 80] and diffusion-enhancement of antimony (G~<0.(1 + A~x)2] 1/2 (43) which follows from (7) [-14]. chlorine reacts with the silicon at the S I O 2 . In the case of possibility (ii) of creating a self-interstitial undersaturation.29 . Lower bounds of the fractional interstitialcy diffusion components. 92]. This may easily be understood by considering (8) for appropriate (e.5) [31.SiO2 interface counterdiffuses the 02 molecules coming from the SiO2 surface.95 > 0. 85]. then the oxide is transformed into oxynitride 1-91. for some substitutional dopants as derived from retarded-diffusionphenomena via(43). In contrast. nitridation of an uncovered silicon surface leads.95 for P at 1267~ see Table 2. it could not yet been decided whether the SiO z . Diffusion Processes. and Swirl Defect Formation in Silicon Table 2. Equation (43). provided local dynam- . If an oxide film covers the silicon surface during the nitridation process.5) the occurrence of a diffusionretardation allows to calculate a lower limit of Gf via G~> 0. The SiO2 formation occurs somewhere in the SiO 2 film. The volume expansion coupled with the SiO2 formation is the driving force for self-interstitial injection. A' is equal to A~x in the case of oxidation and to the corresponding quantity in the case of nitridation Dopant P P P Ga A1 B B T [~ 1100 1150 1267 1150 1150 1100 1200 Lowest As observed -0. 1-83] Francis and Dobson [80] Mizuo and Higuchi [37] Mizuo and Higuchi [38] Mizuo et al. G~.S i interface.511 .S i interface. Nabeta et al. Since the effect of chlorine is most pronounced at temperatures above about 1100 ~ where dynamical equilibrium between vacancies and self-interstitials is established fairly quickly. [86] who observed nitridation-retarded diffusion of P and B at 1010 ~ for nitridation times of 30rain.36 -0.55 -0.0. An increasing chlorine content in the oxidizing atmosphere first leads to a decreasing injection of self-interstitials and then finally even to an undersaturation of self-interstitials. and the corresponding volume expansion is adapted viscoelastically. and (43) we have estimated lower limits of G~ for B and P (Table 2). to G~>0. e. [83]. 86]. At higher temperatures and for long oxidation times Si from the S i . For long oxidation times at high temperatures diffusionretardation of phosphorus (G~>0.88 > 0.5) [-31] has been observed. [85] Hill [81] 11 temperatures and for short times the SiO 2 formation occurs at the S i O 2 . which is nothing else but a vacancy injection or/and a selfinterstitial depletion in the silicon crystal..27 Gf > 0.58 . Equation (43) may also be used in the case of nitridation-retarded diffusion. nitridation-retarded diffusion of P and B [85. at 1100 ~ to enhanced shrinkage ofpre-grown OSF [84.83 Reference Mizuo et al. 86] and to nitridation-enhanced diffusion of Sb [85. Technologically a chlorine (or chlorine compound) containing ambient is used to reduce or even prevent the growth of oxidation-induced stacking faults. and we will not pursue this subject any further.g. The effect of oxynitridation on point-defect generation is basically the same as for normal oxidation.g. [-85] Nabeta et al.S i interface mainly absorbs self-interstitials or mainly injects vacancies. since vacancy injection would have resulted in enhanced diffusion of all dopants independent of their Gf values.0.Point Defects.g. For dopants diffusing predominantly via selfinterstitials (G~>0. Using the data of Hill [81].0.55 .0. Such Si3N4 films can be produced by direct thermal nitridation of silicon in an ammonia ambient [89-92]..

already some time ago a slightly higher OSF shrinkage rate was observed for N2 than for Ar annealing [24]. we conclude that the nitridation reaction cannot proceed at the SiaN4-Si interface and cause self-interstitial depletion at the same time.12 ical equilibrium between vacancies and selfinterstitials is established. In the following section we will also deal with perturbed self-interstitial and vacancy concentrations. (43) yields G{>0. such as carbon [102]. The higher OSF shrinkage rate for (100) than for (111) oriented wafers is qualitatively consistent with the orientation effects of oxidation: the (100) Si surface acts as a more effective self-interstitial source (oxidation) or sink (nitridation) than the (111) surface [33. 6. which they termed D defects. the nature of B defects could not yet been determined experimentally. which can now reasonably be attributed to a small nitridationinduced selfinterstitial undersaturation. Example of swirl defect distribution in a float-zone grown silicon crystal of about 40 mm diameter [103] defects were first noted by Plasket [93] and Abe et al. but no experimental proof is available. Hayafuji et al. Rocksnoer and Van den Boom [99] found an additional type of swirl defects. 10. not been possible to relate the logarithmic nitride film growth [91] to the constant nitridationinduced shrinkage rate of OSF [84]. For a given G value no defects form for very low v. [85] found that an N2 ambient.Si interface to the Si3N4 free surface. and for even further increased v finally D defects form. This process would account for the depletion of Si selfinterstitials which may at least partly. As yet no quantitative treatment of self-interstitial depletion during nitridation is available.Si interface (Fig. An example is shown in Fig. An example is shown in Fig. Swirl T. In contrast. The formation of swirl defects is dependent on the crystal growth rate v and the temperature gradient G near the crystal-liquid interface.Y. the effect of surface orientation (of Si wafers without SiO2 coverage) on the shrinkage of OSF in N2 ambients [21] may be due to nitridation effects. these perturbations are not due to surface processes such as oxidation. 11. based on their different sizes and different behavior in lithium decoration experiments: the larger A-swirl defects and the smaller B-swirl defects. It has. By electron microscopy the A defects were identified as interstitialtype dislocation loops or loop clusters [97. for still higher values of v. Swirl Defect Formation Swirl defects are micro-defects which are formed during crystal growth in dislocation-free silicon. De Kock [95. Within this concept the volume increase associated with the SiaN 4 formation can easily be adapted at the free surface of the SiaN4 fdm. but due to the changing temperature during the growth process of silicon single crystals. or in short A and B defects. Therefore. Therefore. 81]. since B defects could not be detected in an electron microscope without copper decoration. A and B defects disappear and the crystal is defect free again. Whereas the driving force for oxidation-induced selfinterstitial injection can be attributed to the volume expansion of 120% associated with the S i O 2 formation at the SiO2 . when v increases. Tan and U. [84] proposed that nitridation proceeds primarily via silicon cation migration from the SiaN 4 . 10. Eq. slightly but noticeably influences the diffusion of dopants. even without any addition of ammonia. . a small correction to the analysis of OSF shrinkage in an N 2 ambient and to (10) may be required. There is also a delicate dependence of swirl defect formation on dopants [101] and on impurities. There exist some indirect indications that D defects are vacancy agglomerates. The term "swirl" defects derives from their swirl distribution pattern in wafers cut perpendicular to the growth axis of the crystal. 96] observed these defects by x-ray topography following lithium or copper decoration. As summarized in Table 2. In contrast to all the previous cases. 9a). the situation is less clear in the case of thermal nitridation. which we will not discuss in this paper.9 for P and B at 1100~ in accordance with previous estimates [14]. G6sele Fig. Similarly. He distinguished between two types. 98] which refuted the earlier suggestion that these defects are vacancy agglomerates [96]. The role of the temperature gradient G is the opposite to that of v and hence to a first approximation swirl defect formation depends basically on the parameter v/G [100]. Nitridation of silicon also is associated with a volume expansion of about 20%. In fact. for example. constitute the Si cations moving to the SiaN4 surface. Mizuo et al. A and B defects form. [94] in float-zone grown silicon.

namely vacancies. The main points of Voronkov's model are: i) Self-interstitials and vacancies coexist in Si and. w g 104 \ 102 li'lH I I I f I I fl I 1 2 3 4 5 6 T growth rate v [mm rain-1] Fig. v) The model of Voronkov [108] assumes that both self-interstitials and vacancies coexist and are present in local dynamical equilibrium at high temperatures. B defects are considered as precursors of the A defects. already on a qualitative basis. iii) The model of Chikawa and Shirai [106. Because of temperature fluctuations in the liquid... and D-type swirl defects as a function of growth rate v in 23 mm thick pedestal pulled silicon crystals according to Roksnoer and Van den Boom [99] Contrary to all the other models. if either selfinterstitials or vacancies have a concentration in excess of the other point defect species. After discussing the assumptions we will give an improved description of the diffusion problem of point defects involved in swirl defect formation and present some qualitative results based on this description. then swirl defects form by the condensation of the excess amount of the appropriate species. by incorporating diffusion fluxes of point defects parallel to the growth direction.. and a dynamical equilibrium between both types of defects at high temperatures. iii) The difference in the self-interstitial and vacancy concentrations at Ts is determined by their diffusion processes and local dynamical equilibrium via recombination and thermal creation of vacancy-interstitial pairs. are given by their appropriate thermal equilibrium concentrations. as soon as crystal growth is resumed and the droplets have solidified. Possible mechanisms may be trapping of self-interstitials due to a deviation of point-defect concentrations in the outermost layer of the growth interface from the equilibrium bulk value [105] or due to structural and density differences between the solid and the liquid [106]. . Within this model no conclusion is drawn on the dominant species of thermal equilibrium point defects.-. which is responsible for the formation of A defects. ii) The model of Petroff and de Kock [98] attributes swirl defect formation to the incorporation of a nonequilibrium concentration of self-interstitials into the crystal at the solid-liquid interface. [97. Vacancies do not play a role at all in this model. Within this model self-interstitials condense into A defects and vacancies into B defects. ii) At a freezing temperature Tr < T. The model constitutes a quantitative attempt to explain the occurrence of the various types of swirl defects and their dependence on v/G. for crystal growth. Voronkov's treatment contains two invalid but essential assumptions which render most of his results obsolete. Consequently. Example ofthe concentration ofA-.and Swirl Defect Formation in Silicon The following models for swift defect formation have been suggested: i) The model of F611 et al. 107] assumes that during remelt processes liquid droplets are formed in the crystalline silicon in a superheated region behind the solid-liquid interface.Diffusion Processes. upon cooling of the crystal. the Voronkov model [108] contains the basic ingredients required by our present-day understanding of point defects in silicon. Unfortunately.).. This initiates a flow of self-interstitials and impurities into the droplets and of vacancies away from the droplets. there is an excess amount of self-interstitials. 103] is based on the assumption that self-interstitials are the dominant thermal equilibrium point defects in silicon. 102. i. Swirl defect formation is attributed to the agglomeration of self-interstitials which are present in the concentration C~q(Tm)at Tm and become supersaturated when the crystal is cooled down. l 1. iv) The model of Hu [65] assumes that vacancies and self-interstitials coexist under thermal equilibrium conditions and that there is a barrier of a few to several eV which prevents that vacancy-interstitial recombination occurs easily. both self-interstitials and vacancies become supersaturated. In addition. self-interstitials..) and c~q(T.e. c~q(T. 13 T E 108 B-defects A-defects c~ 106 . Additional trapping due to this remelt phenomenon has been proposed. A and B defects are considered as being of interstitial-type and D defects as vacancy agglomerates. the self-interstitial and vacancy concentrations at the melting temperature T. The first of the two invalid assumptions in Voronkov's treatment concerns the use of the quantity A C O= C I Cv (44) . The volume decrease upon melting causes a tensile stress in the lattice surrounding the droplets. he managed to describe at least qualitatively the experimentally observed v/G dependence of swift defect formation.Point Defects. Because of the different density of liquid and solid silicon. a growing crystal can experience alternating growth and remelt cycles.. B-.

(52) AJ ( T) = Dt( T) [ c[q( Tm) . In the limiting case v = 0 the use of (47) leads to CI = c~q(Tm) and Cv = c~q(Tm) everywhere in the crystal independent of the local temperature T which decreases with increasing distance to the solidliquid interface instead of v -- f'eqg"eq'l'~s = 0. The -~t ~.c~q(r)]. In the two limiting cases that either local equilibrium is established or that CI and Cv are independent of each other (i. AJ=O thereby neglecting diffusion currents induced by temperature gradients..c~q)-Dv(Cv . for which C~~ C~q and Cv g Cv . for short times or low temperatures) it may easily be shown that Ct and Cv depend on v.[c~r -. For v~oo we get A C(T) = [c[q(Tm). then in some specific cases (45) and (46) could lead to different predictions as to which type of point defects will agglomerate. whereas this equilibrium is established in the case of v = 0.~ c~q(T) and Cv ~ c~q(T). . otherwise the quantity which governs the growth of interstitial. As mentioned above.c~q)/dx - (46) In (46) AJ is proportional to the net point defect flux into an agglomerate. Therefore. (53) The local dynamical equilibrium (2) is not attained in this case.d T =0 (57) . In the latter case the recombination terms drop and (49) may be written in terms of T as the independent variable as dT ( ot 2 dC I \ dx ] dT dx =0" + vi d-T- contains all the essential physics needed for dealing with the present diffusion problem. (47) Dvd(C v - c~r -. (51) where the integration constant H depends on v.or vacancy-type agglomerates is A J = J I . We note that (45) is the proper quantity only if the agglomeration proceeds to completion at Ty. It is somewhat involved to describe the diffusion of intrinsic point defects in a temperature gradient rigorously [109.v(C I- Cv) = H.: kr~0. and G via v/G.. 110] but to a first approximation an expression of the type j = ..e. The second invalid assumption in Voronkov's treatment concerns the diffusion flux of point defects which he writes in the simple form j ~ . dx A C>O indicates self-interstitial agglomeration and AC < 0 vacancy agglomeration.C eq) (48) (54) (55) holds.J v .v aCv ..( C v .V ~ -.O.. is the reaction coefficient for establishing dynamical equilibrium between vacancies and selfinterstitials. the quantities Ci(x) and Cv(x) are independent of time and the appropriate diffusion dT dx z +V dT (56) An analogous equation holds for Cv. G6sele to determine the point-defect species which agglomerates. Y . (50) In (49. for which AC=O. . For an observer in a coordinate system fixed relative to the solid-liquid interface the crystal moves along the x-axis with a constant speed v. ~ D I ( C I .Q~ Cv~ -.14 T . 50) k.C~rq) 9 equations are given by d ( D d(Ci-c~q)'~ ' ) -. (56) reduces to dT / + \ G ] .D grad C. T a n a n d U.C~ q) .c~rq(T)]. "-'v I (49) (45) . Subtraction of (49) and (50) and integration yields O.~v at Tf may be excluded. Based on the quantity A Co it cannot be explained why no swirls form at very low growth speeds v..D grad (C .C~q). From here on a solution can only be obtained by numerical integration (which we will not pursue in this paper) except in the two cases v~oo and v=0. For a constant temperature gradient G = dT/dx near the solid-liquid interface. in these cases (45) holds if agglomeration proceeds to completion at Ty and (46) otherwise. If vacancies and self-interstitials may be considered as independent.--oq proper quantity which should be used instead of (44) is A C = ( C I .Dv(T ) [C~rq(Tm).c[q(T)] -. In this coordinate system after sufficiently long times 8C~/at = aCv/Ot = 0 holds.c[q(T)] . The relations (45) and (46) lead to the same result as long as local dynamical equilibrium according to (2) is established.d( C . the unlikely case that accidentally c'oq"-".

C~ (58) and at the freezing temperatures ( T : ~ l l 0 0 ~ for A and B defects. Within our assumptions C1> C[q [and hence Cv < C~q based on (2)] is at least fulfilled from T.C[ q acquires a large enough value in the temperature range from T. Accepting the hypothesis that D defects are vacancy agglomerates. (2) is obviously fulfilled. and Swirl Defect Formation in Silicon 15 b Tm showing that CI and analogously Cv depend on v and G in the form v/G as experimentally observed.. we can explain that for some reasonably small v/G values A C > 0 is obtained. ORD. the situation depicted in Fig. An examination of approximate analytical solutions of (49. (a)For low v/G values for which local equilibrium between V and I is established leading to AC>O at T:. ( G . in principle. 50) based on a piece-wise joining of approximate solutions.Point Defects. in the limiting cases v = 0 Eq. The above discussion showed that it is not only possible to get an insight into the v/G dependence of swirl defect formation but also that the concentrations and diffusivities required are in a semiquantitative way consistent with the corresponding values derived from results on OED. Diffusion Processes. i.. For explaining a change in the sign of A C at least qualitatively we have to assume that local dynamical equilibrium breaks down as v/G increases to large values. (b) For large v/G values for which local equilibrium between I and V breaks down at Th leading to AC< 0 at T: C~ ~> ~.x4 o: /X\ cleq XX lIT I/T X.. The situation is depicted in Fig. 12b in which for simplicity it has been assumed that the deviation does not occur gradually but that (2) breaks down completely and suddenly at a temperature Th.. Cv at the appropriate freezing temperature T: has practically the same value as at Th and hence we may obtain (Cv-C~rq)>0 at T:. ' Tf T CI . 12a and b. This conclusion has been arrived at by a qualitative examination of the diffusion problem (49. T:~900 ~ for D defects F100]) C~a >>C[ a and DI >> . For the case of local dynamical equilibrium subtraction of (49) and (50) and applying the same procedure as above yields the same dependence on v/G. Thus. and Au diffusion in silicon. This behavior is helpful in fulfilling AC < 0. If the diffusion currents of vacancies and self-interstitials and the effect of pulling the crystal with a speed v are taken into account it turns out that a change from CI > C[ q to CI < C[ q does not take place at To (except in the limiting case v/G~O) but at a lower temperature. Based on a break down of the local dynamical equilibrium (2) we have found one case which can.. Vacancy agglomeration requires that A C < 0 at T:. Van Run [111] has calculated that the disappearance of the remelt phenomenon also has a dependence on v/G which is not surprising. When v/G is increased to some fairly large values then the point defects start to deviate from the local dynamical equilibrium (2). to TO.. in principle and qualitatively. to To where C[q(TO) = c~q(TO). to T: where the defects are frozen in [54]. we have to explain a change in A C from positive (interstitial-type A and B defects) to negative (vacancy-type D defects) with increasing v/G. thermal diffusion of selfinterstitials back towards the higher temperature regions of the crystal is more effective than the corresponding diffusion process of vacancies thus leading to a much smaller CI at T: than present at Th. explain that AC changes sign with increasing v/G.. Since now vacancy-interstitial recombination is no longer effective and Dv is very small. Schematic diagrams showing CI and Cv as functions of reciprocal temperature during cooling after crystal growth. Fig. 50) demonstrates that such a change in the sign of AC can not be produced with the assumption that the local dynamical equilibrium (2) is always established from T. since the thermal conduc- . For this case we need to assume that at T.. whereas for v--+oo the two types of point defects can be considered as being independent of each other. However. This temperature can be lower than T: provided Q . 12a which shows that A C > 0 at T: may be realized for sufficiently small values of v/G.C ~ q) > 0 at T:.e. we explicitly caution the reader that other possibilities and mechanisms of swirl defect formation may exist especially since the vacancy nature of D defects has not yet been proven. As mentioned above. 4. Dv (59) (60) The conditions expressed in (59. A similar situation also holds for CI.. 60) are compatible with our results derived from the diffusion of Au in silicon and from OED/ORD experiments as discussed in Sect. Under the above conditions. Tm Tg i Tf Tg Tj. Since D I >) D v f r o m Th to Tf.

U. A lot remains to be done before a reliable qualitative and quantitative treatment of swirl defect formation will be available. Higuchi: Jap. 11. 36. 37. H.. Matsumoto. Narayan and T. 35. Wang (North-Holland. 43.B.Y. by S. Antoniadis. Phys. 1 (1980) U. Kashiwagi: J. 739 (1981) S. e. 5. Soc. New York 1981) p.16 tion equation has a similar form as our Eqs. Yoshinaka. Phys. Moskowitz: J. 3066 (1964) R. 27.W. 42. 15.. U. Techn. 7996 (1979). Rev.S. Sugita. 21. P. Appl. 73 Y.R. M. Part B.G. Phys. 455 (1968) 2. 44 (1977) W. T. 53. 17. 45. New York 1984) p. Mehrer. Swirl defect formation in terms of the agglomeration of vacancies and selfinterstitials is not yet satisfactorily understood. G. A. Similarly. ed. Y. Lett. 39. 3747 (1977) H. 1567 (1974) 3. T. 315 7. Mizuo. 2850 (1972) E. G6sele: J. Leroy: J. 194 (1983) D. ed. Ishikawa. Fair: In Impurity Doping Processes in Silicon.and B-swirl defect [102. Murarka: Phys. 53. 38. Niimi: J. Mizuo. H. Phys. 29. Microscopy 118. 129. Higuchi: J. Boston 1983) p. New York 1981) p. The values of the fractional interstitialcy diffusion components of substitutional dopants are not yet k n o w n with sufficient accuracy. Hashimoto. R. Phys. A. B 16. J. 104] or to an indirect influence on swirl defect formation via the temperature gradient as expressed. by D. J. 8. 30. Lett. Oldham (Martinus Nijhoff.Y. Sakino. 2243 (1980) U. G6sele S. 20.J. Ghezzi: J. W. Mizuo. In conclusion. Suppl. Sanders. R. Appl. 97 (1983) K.Y.C. Phys.A. G6sele. Mathiot. Phys. Sci.Y. a complete description of swirl defect formation will certainly have to account for the experimentally observed influence of impurities on the nucleation of A. Equations (49. Soc. Declerck. Tan. 881 (1969) H. Lett. Soc.Y. 55. Lett. 1093 (1982) T. 41. 20. 50). Corda. K. S. 50. Soc. F. H. Solidi 29. Acknowledgements. 35. 10.J. 32. 1 S. New York 1981) p. 22. S. 1031 (1981) HJ. e. Tan. Phys. Jap. ed. Guerrero: Ph. Phys. Therefore. Nowick (Academic. 4 D. 16. Y. Mizuo. 165 (1975) T. Appl. Much more theoretical work is needed in this area. Kahng (Academic. ed. Appl. Huffand E. 31. U. 7. U. 18. Appl. Sci. 26. 21. Soc. 50) m a y be solved numerically but due to the large n u m b e r of adjustable parameters the resulting solutions cannot be expected to be very reliable. Tan. Frank: In Defects in Semiconductors. 3742. Appl. Phys. Electrochem. 2292 (1982) S.R. P. Wu. Taniguchi. the recently observed correlation of A-defect striation spacing in longitudinal slices to the periodicities of temperature fluctuations in the melt [112] m a y either be attributed to an introduction of an excess of non-equilibrium point defects. (49.J. H.S. Matsumoto. Antoniadis. 4767 (1982) B. in (57) within the model presented above. Tan and U. 129. G6sele. 333 I. 24. J. Alexander.F. 127. H. ed. 46 (1977) S. Claeys. London 1973) p. we have described an improved version of V o r o n k o v ' s model [108] of swirl defect formation based on the agglomeration of vacancies and selfinterstitials. Grsele. Appl. J. Murch and A. I. 797 (1979) J~. Appl. 28. G. Phys. Shaw (Plenum Press. G. Mag. Antoniadis: J. 2. T. by P. by D. Princeton. Conclusions There is n o w general agreement that b o t h vanacies and self-interstitials are present under thermal equilibrium conditions and contribute to self. Phys. 331 (1982) S. ed. and W. Fair: In Applied Solid State Science. 19. the v/G dependence of swirl defect formation does not exclude a relation to remelt phenomena. Higuchi: Denki Kagaku (J. 14. 113]. Thesis. 53. H.D.g. Mag. 12. 9.P. 54. Queisser. 2849 (1977) S. Washburn: J. 40. 20. Soc. 1 E. Stat.-K. 448 (1983) S. 13. 27.) 50. Shaw: Phys. Ishikawa: Fujitsu Scientific and Technical Journal (March 1977) p. 10.W. Ishikawa. Dobson: Philos. van Overstraeten: Appl. 129.G. T. Conti. University of Vienna (1984) D. Morehead: Appl. Phys. (b)72.B. Kurosawa. Prussin: J. although the improved model of V o r o n k o v appears to be a step in the right direction. G. A. Vac.M. S. Electrochem. Sift1 (Electrochem. Dobson: Philos. Electrochem. 747 (1978) L.Y. Electrochem. Appl. 56 (1982) Y.Y. R. Antognetti. Most of the present authors' results were obtained while one &them (U. H. J. Phys. Silicon Integrated Circuits. Grsele. 45 T. 63 . 25. ed.. 6. Lambert. 34. A 31.M. Shimizu. Yoshinaka. 40. Sugita: Jap. Ele~trochem. 17. 4. ed. References 1.) was working at the Max-Planck-Institute for Metal Research in Stuttgart. 11 (1975) S. Hu: In Diffusion in Semiconductors. A. H. Ginsberg: Appl. Mizuo. Antoniadis: In Process and Device Simulation for MOS-VLSI Circuits.M. Higuchi: Jap. Aoshima: J. Wendler: J. Phys. 3518 (1984) D.P. Higuchi: J. Murarka. G6sele: Appl. Mat. The authors appreciate numerous discussions with colleagues on the subjects of this paper. Appl. Tan. 616 (1982) T.g. 6788 (1982) S. by J. Hu: Appl.G. Electrochem. S. Niimi: J. by F. Hu: J. Phys.and dopant diffusion. H.G. by remelt phenomena [98. In addition. 35. 705 (1975) S. W. H.. Chik: Phys. 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