Effect of Carbon Concentration and Growth Conditions on Oxygen

Precipitation Behavior in n-type Cz-Si

Takuto Kojima1*, Ryota Suzuki1, Kosuke Kinoshita1, Kyotaro Nakamura1, Atsushi Ogura1,
Yoshio Ohshita2,Isao Masada3, and Shoji Tachibana3
1
Meiji University, Kawasaki, Kanagawa, 214-8571, Japan
2
Toyota Technological Institute, Nagoya, Aichi 468-8511, Japan
3
Tokuyama Corporation, Shunan, Yamaguchi 745-8648, Japan

Abstract — The behavior of oxygen precipitates under solar cell BSL-I bulk lifetime measurement system, along the crystal
fabrication processes and the effect on device performance were length for the typical CZ-A and CZ-B. As clearly shown the
investigated using TEM observation. Samples were prepared with improved crystal CZ-B exhibits the higher lifetime covering
different carbon concentration and with two sets of growth
conditions. The number of precipitates correlates monotonically almost complete region.
with the carbon concentration. When the initial carbon
concentration is high, the cell efficiency is improved by decreasing
the carbon concentration. When the initial carbon concentration
is reduced to smaller than 1016 cm-3, the oxygen precipitate grows
largely and introduces dislocation. Precipitates grown in a plate
form introduce dislocations to the surroundings at a high density,
while dislocation density is relatively small around the precipitates
polyhedral-grown on the basis of an octahedron. Under the growth
conditions for introducing a plate-like precipitate, the cell
efficiency was not improved even if the carbon concentration was
reduced.

I. INTRODUCTION
Oxygen in Cz silicon agglomerates into precipitates and the
precipitates grow during crystal growth and device processes,
and it becomes a major deterioration factor of carrier lifetime
[1]. Oxygen precipitates (OPs) change morphology by heat
treatment depending on the growth and process conditions.
Recombination enhancement at oxygen precipitates has been
attributed to the defect levels at the Si/SiOx interface and/or
gettered metals [2-4]. However, the precipitation behavior in
the actual solar cell process and the influence on the devices are
not sufficiently discussed.
In this study, the dynamics of oxygen precipitation by solar
cell processes and the influence on the devices are discussed
from the transmission electron microscope (TEM) evaluation.
Two sets of growth conditions were used to investigate the
influence of the initial state of precipitation.
Fig. 1. Lifetime and resistivity profiles along the crystal length for
the typical CZ-A and CZ-B.
Substrates sliced from the top of the ingots, containing high
concentration of oxygen, were used in the experiment.
Concentrations of substitutional carbon at parts of the ingots
were measured by FT-IR, and the initial concentrations of
carbon in the melt were calculated assuming normal
segregation. The used wafers were named A0 to A5, and B0 to
B2 for the substrates from CZ-A and CZ-B growth conditions
in descending order of carbon concentration, respectively. The
wafers were processed into bifacial n-PERT cells. The
fabrication process includes thermal processes at
approximately 1000 °C for boron diffusion and oxidation.
Density of OPs were determined by TEM observation. The
morphology of OPs was also observed.

III. RESULTS AND DISCUSSION

II. EXPERIMENTAL PROCEDURE
N-type ingots were produced under two sets of growth
conditions, conventional (CZ-A) and improved (CZ-B), using
polysilicon feedstock with different carbon concentrations. The
crystal diameters are 220 mm with 1 m long. The same growth
furnace was used under both CZ-A and CZ-B conditions, and
the overall growth time was set to the same length. Figure 1
shows the lifetime and resistivity profiles, measured by Sinton
Before the cell fabrication process, OPs were not observed by
TEM, whereas after the cell fabrication process, OPs of >10 nm
were observed in all the samples. The numbers of OPs in a
10,000× field of view by TEM were counted to determine the
density of OPs at the center part of the wafers (Fig. 2). The
density is calculated assuming thickness the observed ion-
milled sample is 30 nm. For both sets of growth conditions, the
carbon concentration and OP density showed approximately

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linear correlation, while the OP density in the CZ-B substrates 㻌
were nearly one order magnitude smaller than those of CZ-A. 20
The density of OPs could be reduced by modification of thermal CZ-A
history in crystal growth. 19
㻌0.1 CZ-B

Efficiency (%)
0.01 1 㻔㼜㼜㼙㼍㻕 18

No. of OPs in 10,000x FoV

14
10 10 3
17
CZ-A A0
OP density (cm-3)

CZ-B 16

㻌
10 13 A1 10 2
15
B0
B1 14

㻌
A2 13
1012 A3 101 1011 1012 1013 1014
B2 -3
A4 OP density (cm )
A5

1011
1014 1015 1016
C concentration (cm-3)
Fig. 2. Oxygen precipitate density for different carbon
concentrations and growth conditions. The Error bars represent
variations in counting OPs in an identical FoV.
The conversion efficiencies of the fabricated solar cells are
shown in Fig. 3. When the initial carbon concentration is the
highest (A0 and B0), there is no difference in conversion
efficiency between CZ-A and CZ-B growth conditions. The cell
efficiency was improved by decreasing the carbon
concentration, up to 16.5 % (Voc = 599 mV, Jsc = 36.2 mA/cm2,
and FF = 0.762) in CZ-A cells and 17.8% (Voc = 629 mV, Jsc
= 37.5 mA/cm2, and FF = 0.754) in CZ-B cells. The
improvement was greater in CZ-B, whereas in CZ-A, it was
saturated under approximately 5 × 1015 cm-3.
0.01
㻌0.1
20
CZ-A
19
CZ-B
Efficiency (%)
Fig. 4. Cell performance of the n-PERT bifacial cells shown in Fig.
1017 3 against OP density in Fig. 2.
The relation between cell efficiency (in Fig. 3) and OP
density (in Fig. 2) is shown in Fig. 4. In CZ-B, the deterioration
per one OP is larger than that of CZ-A when the OP density is
about 7 × 1012 cm-3 at high carbon concentration (B0). On the
other hand, at low density, OPs in CZ-B wafers become much
more harmless. The degradation per OP may be derived from
the size, morphology, and/or OP-induced defects. Therefore,
TEM observation for each OP was carried out.
The results of high magnification 〈110〉 TEM observation on
the precipitates are shown in Fig. 5. The observed dislocations
are indicated by yellow arrows. In A0 and B0 with the highest
carbon concentration, small octahedral or truncated-octahedral
precipitates of approximately 10 nm were observed. The small
precipitates do not introduce dislocations. When the initial
carbon concentration becomes smaller than 1016 cm-3, the
1 㻔㼜㼜㼙㼍㻕 oxygen precipitate grows largely and produces so-call “punch-
out” dislocations. In B2 with a small precipitation density, the
precipitate grows larger than B1, and dislocations are generated
around. On the other hand, in A2, dislocations were distributed

18 with high density around plates of precipitates. Similar plate-

like precipitates with dislocations were also observed in A3 to
17 A5.
16
㻌

15

14

13
1014 1015 1016 1017
-3
C concentration (cm )

Fig. 3. Cell performance of the n-PERT bifacial cells for different

carbon concentrations and the growth conditions.

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 Fig. 5. 〈110〉 TEM images at oxygen precipitates in A2, B1, and B2. Yellow arrows point dislocations.
From the results, when the initial carbon concentration is
small, the density of the precipitate becomes small and grows
largely. The OP density is so high that the distance between
OPs is smaller than or comparable to diffusion length of
interstitial oxygen (Oi) during thermal processes. Therefore,
when OP density is high, mobile oxygen is competed by
adjacent OPs for size growth. Precipitates that do not introduce
dislocations also degrade cell efficiency, but plate-like
precipitates that introduce dislocations at high density suppress
efficiency even at low density. The precipitates growing on the
basis of the octahedron are considered to have a moderate
introduction of dislocation and the influence on cell
performance is relatively small.
IV. SUMMARY
The behavior of oxygen precipitates under solar cell
fabrication process and the effect on device performance were
investigated using TEM observation. Samples were prepared
with different carbon concentration and with two sets of growth
conditions. The number of precipitates correlates
monotonically with the carbon concentration. When the initial
carbon concentration is high, the cell efficiency is improved by
decreasing the carbon concentration. When the initial carbon
concentration becomes smaller than 1016 cm-3, the oxygen
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precipitate grows largely and introduces dislocation.
Precipitates grown in a plate form introduce dislocations to the
surroundings at a high density, while dislocation density is
relatively small in precipitates polyhedral-grown on the basis of
an octahedron. Under the growth conditions for introducing a
plate-like precipitate, the cell efficiency was not sufficiently
improved even if the carbon concentration was reduced. As a
result, the CZ-B has been much improved compared to
conventional CZ-A not only in their initial life time but also
after cell fabrication processes with less degradation.
ACKNOWLEDGMENT
Part of this study was supported by New Energy and
Industrial Technology Development Organization (NEDO).
We also thank Dr. H. Hashiguchi of JEOL for his support in
TEM observation.
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[4] J. D. Murphy, M. Al-Amin, K. Bothe, M. Olmo, V. V. Voronkov,
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