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Heavily Boron-Doped Silicon Single Crystal Growth: Boron Segregation

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1999 Jpn. J. Appl. Phys. 38 L223

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Jpn. J. Appl. Phys. Vol. 38 (1999) pp. L 223–L 225
Part 2, No. 3A, 1 March 1999
°1999
c Publication Board, Japanese Journal of Applied Physics

Heavily Boron-Doped Silicon Single Crystal Growth: Boron Segregation

Toshinori TAISHI ∗ , Xinming H UANG, Masayoshi K UBOTA1 , Tomio K AJIGAYA1 ,
Tatsuo F UKAMI2 and Keigo H OSHIKAWA
Faculty of Education, Shinshu University, Nishinagano, Nagano 380-8544, Japan
1 Sumitomo Metal Mining Co., Ltd, Suehirocho, Ome 198-0025, Japan
2 Faculty of Engineering, Shinshu University, Wakasato, Nagano 380-8553, Japan

(Received December 7, 1998; accepted for publication January 21, 1999)

Heavily boron-doped silicon single crystals have been grown successfully by the Czochralski (CZ) method. The limit of
boron concentration in the silicon melt for dislocation-free silicon crystal growth and segregation with heavy boron doping
were investigated. It was found that a dislocation-free silicon crystal could be obtained even when the initial boron concen-
tration in the silicon melt was up to 3.8 × 1020 atoms/cm3 with a solidified fraction of about 0.5. The lowest resistivity of the
dislocation-free B-doped silicon crystal was about 0.7 mÄ·cm. It is confirmed that the equilibrium segregation coefficient of
boron decreases from 0.8 with heavy boron doping.
KEYWORDS: Czochralski growth, dislocation-free Si crystal, heavy B-doping, segregation coefficient, boron concentration, re-
sistivity

Recently, various elements such as boron and antimony
are used as dopants for heavily doped Czochralski (CZ) sil-
icon crystal growth, and the heavily doped silicon wafers are
widely used as substrates (mainly after epitaxy processing)
for large-scale integrated circuit devices (LSI). In order to re-
alize further integration and higher performance of the elec-
tronic devices, a high quality of the heavily doped silicon
wafer is demanded. However, in regard to each dopant with
heavy doping, (i) the concentration limit of the dopant for
dislocation-free single crystal growth, (ii) segregation during
the crystal growth, (iii) distributions of the dopant in the radial
direction of the wafers, (iv) variations of lattice parameters,
and (v) oxygen behaviors are poorly known.
Oxygen precipitate behavior in silicon wafers with a boron
concentration of less than 1.0 × 1019 atoms/cm3 ,1, 2) and oxi-
dation stacking fault (OSF) ring and crystal originated parti-
cles (COP) in wafers3) with a boron concentration of less than
2.0 × 1019 atoms/cm3 have been reported. It has also been re-
ported that single crystal wafers with a boron concentration
of up to 1 × 1020 atoms/cm3 were used to measure the de-
pendence of the lattice constant on the boron concentration.4)
In other words, a single crystal with a boron concentration of
1 × 1020 atoms/cm3 has already been obtained. There was,
however, no further description of sample preparation, such
as crystal growth conditions, in the literature. On the other
hand, a very important parameter for investigating the boron
distribution in the silicon crystal, the equilibrium segregation
coefficient of boron, is still poorly known, although a value
of 0.8 is generally accepted,5) especially in the case of heavy
boron addition.
In this study, boron segregation concerning with heavily B-
doped CZ-Si crystal growth will be investigated.
Heavily B-doped silicon crystals with various boron con-
centrations were grown by the Czochralski method. A fur-
nace with a high-purity carbon heater was used for melting
the silicon. The carbon heater was 210 mm in diameter and
could provide a high temperature of up to 1570◦ C. The heater
was externally covered by a carbon heat shield. A Pt–Rh ther-
mocouple was incorporated between the heater and the heat
∗ Permanent address:
Faculty of Engineering, Shinshu University, Wakasato,
Nagano 380-8553, Japan.
L 223
shield to control the temperature. Two kilograms of commer-
cial high-purity polysilicon was charged in a high-purity silica
crucible 180 mm in diameter. Granulated boron with a purity
of 99.5% was charged in the crucible simultaneously in the
range from 1 × 1018 to 1 × 1021 atoms/cm3 to obtain the de-
sired boron concentration in the silicon melt. Immediately
below the silica crucible was another Pt–Rh thermocouple for
measuring the temperature of the silicon melt. A h100i di-
rectional single silicon crystal 13 mm in diameter was used as
the seed. The crystals were grown at growth rates of about
1 mm/min by manual control, and the diameter of the crystals
as controlled at about 70 mm. The rotation rates of the crys-
tal and the crucible were maintained constant at 20 rpm and
−10 rpm, respectively. The crystal growth was carried out in
a high-purity argon atmosphere (more than 99.9995%) with
an argon flow rate of 15 l/min, and the argon pressure was
controlled at 20 Torr during the whole process.
The grown crystals were cut into wafers 1 mm thick, using
a slicing machine of the inside-blade type. The resistivity of
all the silicon wafers was measured by a resistivity measure-
ment instrument with four-point probes (KYOWARIKEN K-
705RM, Japan). The instrument was recalibrated by measur-
ing some standard resistances with resistivities ranging from
96.5 mÄ·cm to 106 Ä·cm, and the accuracy of the measure-
ment was estimated to be ±3%. The resistivity of the sili-
con wafers was converted into boron concentration using the
ASTM F723-88 curve.6) The boron concentration of some
typical silicon wafers was also analyzed by inductively cou-
pled plasma atomic emission spectroscopy (ICP-AES). All
the single crystals were examined by X-ray topography.
It was found that a dislocation-free crystal which was iden-
tified by the X-ray topography could only be grown when the
initial boron concentration in the silicon melt was less than
3.8 × 1020 atoms/cm3 with a solidified fraction of about 0.5,
and the resistivity of the corresponding silicon wafers was
about 0.7 mÄ·cm. When the initial boron concentration, C B0 ,
in the silicon melt was more than 6.3 × 1020 atoms/cm3 , all
the crystal habit lines disappeared during the necking process,
thus a single silicon crystal could not be grown if the boron
concentration was larger than this value. When C B0 was in
the range of 3.8–6.3 × 1020 atoms/cm3 , silicon single crystals
could initially be grown, but all of them became polycrystals
L 224 Jpn. J. Appl. Phys. Vol. 38 (1999) Pt. 2, No. 3A T. TAISHI et al.

during the crystal growth.

The segregation phenomenon of boron in heavily B-doped
CZ-Si crystal growth was investigated by comparing the
boron concentrations in the silicon crystals and the corre-
sponding silicon melts. Figure 1 shows some typical results of
the two. C BS in Fig. 1 represents the boron concentrations in
the different silicon crystals grown from melts with different
C B0 . The C BS was measured from wafers cut from different
crystals with the same solidified fraction, g = 0.05. The open
circles in Fig. 1 represent those obtained from single crystals
and the closed circles those from polycrystals. The data were
mainly obtained using resistivity measurements. The largest
boron concentration in Fig. 1 (4.2 × 1020 atoms/cm3 ) was also
measured using the ICP-AES and the two measurement re-
sults were consistent within an accuracy of 6%. The dotted
line in Fig. 1 is plotted assuming that the segregation coeffi-
cient of boron is 0.8. It is clear that all the values of C BS were
smaller than the values in the dotted line and the shift became
larger with increasing boron concentration, especially when
Fig. 1. Relationship between the boron concentration in the silicon melts
C BS was larger than 1.4 × 1020 atoms/cm3 . The results indi- and in the corresponding silicon crystals when the solidified fraction was
cated that the boron segregation coefficient was smaller than g = 0.05.
0.8 in the heavily B-doped silicon crystal growth, although
the value of 0.8 was generally accepted. The segregation co-
efficient depended on the boron concentration in the silicon
melt or silicon crystal. The larger the boron concentration is,
the smaller the boron segregation coefficient would be.
The boron segregation coefficient has also been investi-
gated from another aspect. A dislocation-free crystal grown
from a silicon melt with the initial boron concentration of
C B0 = 2.5 × 1020 atoms/cm3 , was cut along its axial direc-
tion and several vertical wafers were obtained. The resistivity
of the vertical wafers was measured along the axial direction,
and the dependence of boron concentration on the solidified
fraction, g, of the crystal was obtained, as shown in Fig. 2.
The dotted line was calculated by assuming the boron segre-
gation coefficient to be 0.8. It can be seen that the distribu-
tion of boron concentration in the present experiment is much
lower than the calculated results. The data shown in Fig. 2 are
analyzed using
C(g) = kC B0 (1 − g)k−1 , (1)
where C(g) is the boron concentration in the silicon crystal
Fig. 2. Dependence of boron concentration on the solidified fraction, g, of
with a solidified fraction of g and segregation coefficient k.7) a crystal grown from the silicon melt with an initial boron concentration of
The analyzed result shows that the boron segregation coeffi- 2.5 × 1020 atoms/cm3 .
cient was approximately 0.52. The results calculated using
eq. (1) with k = 0.52 are also plotted in Fig. 2. It can be seen
that the measured results fit very well with the calculated re- pends on the crystal growth conditions such as the growth rate
sults using k = 0.52 when g is small, but they shift slightly and rotation rate. The segregation coefficient of a dopant is
with increasing g. This result agrees with the result that the usually analyzed using the theory put forth by Burton et al.8)
boron segregation coefficient decreases with increasing boron (BPS theory), and it is easy to understand that the effective
concentration in the silicon melt, which has already been ob- segregation coefficient, keff , should be a value between the
tained from the data shown in Fig. 1. equilibrium segregation coefficient k0 and 1. In other words,
Further analysis is carried out by comparing the results k0 of boron in the heavily B-doped silicon crystal growth was
shown in Figs. 1 and 2. A value of 0.54 for the boron seg- at least smaller than the effective segregation coefficient ob-
regation coefficient can be obtained from the data in Fig. 1 tained experimentally, as shown above, and was not unexpect-
with C B0 = 2.5 × 1020 atoms/cm3 , which is the same value as edly smaller than 0.8.
that used in Fig. 2. The results show that the boron segrega- All the crystals described above were grown under almost
tion coefficients obtained by the two kinds of analyses were the same growth conditions, therefore the parameters used in
almost the same (k = 0.52 and 0.54). BPS theory8) for analysis of the segregation coefficient should
All the results on the segregation coefficient analyzed be the same. It can be suggested, therefore, that the k0 of
above represented effective segregation coefficients. keff de- boron in the heavily B-doped silicon crystal growth should
 Jpn. J. Appl. Phys. Vol. 38 (1999) Pt. 2, No. 3A
have the same tendency as the effective segregation coeffi-
cient except for the absolute values being slightly smaller.
It can also be verified from the phase diagram of the silicon-
boron system that the k0 of boron in the heavily B-doped sil-
icon crystal growth depends on the boron concentration and
decreases with increasing boron concentration.9) The highest
boron concentration in solid silicon is about 3 at.%, and the
corresponding value in the liquid is 8 at.%. A result of about
k0 = 0.38 can easily be obtained after a simple calculation.
This value is even smaller than half the hitherto-known value
of 0.8.
If k0 = 0.8 is assumed to be correct in the lightly B-
doped silicon crystal growth, it can be suggested that the equi-
librium segregation coefficient of boron decreases gradually
from 0.8 with increasing boron concentration, and finally be-
comes 0.38.
It is described above that a silicon single crystal could not
be grown if the boron is added at a concentration of more
than 6.3 × 1020 atoms/cm3 in the silicon melt. The reason
for the polycrystallization still remains a mystery. How-
ever, as explained above, the boron segregation coefficient
decreased considerably in the heavily B-doped silicon crys-
tal growth. Then, it is not difficult to visualize that the phe-
nomenon of constitutional supercooling occurred during the
crystal growth. Constitutional supercooling occurs easily if
the equilibrium segregation coefficient of the dopant is small
and the initial concentration of the dopant is very large.10)
We can, therefore, assume that constitutional supercooling is
the reason for the polycrystallization. Further analysis of the
problem is currently in progress.
The main results of this study are summarized as follows.
Heavily B-doped silicon crystals with various boron concen-
trations have been grown by the Czochralski method. It is
found that there is a boron concentration limit for dislocation-
T. TAISHI et al. L 225
free silicon crystal growth and a silicon single crystal could
not be grown when the initial boron concentration in the sili-
con melt was larger than 6.3 × 1020 atoms/cm3 . Boron segre-
gation in the heavily B-doped silicon crystal growth has also
been investigated. The results show that the effective segre-
gation coefficient and equilibrium segregation coefficient de-
crease considerably with increasing boron concentration in
the silicon melt.
Acknowledgments
This work was supported by JSPS Research for the Future
Program in the Area of Atomic Scale Surface and Interface
Dynamics under the Project of “Dynamic Behavior of Sili-
con Atoms, Lattice Defects and Impurities near Silicon Melt-
Crystal Interface”.
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