S4-3 (L. N.) Ext. Abs.
the 13th International Workshop on Junction Technology 2013
Thermal Behavior of Residual Damage in Low-Dose Implanted Silicon after
High-Temperature Rapid Thermal Annealing
Akihiko Sagara and Satoshi Shibata
Panasonic Corporation
3-1-1, Yagumo-nakamachi, Moriguchi, Osaka 570-8501, Japan
Phone: +81-6-6906-4916 Fax: +81-6-6906-3407 E-mail: sagara.akihiko@jp.panasonic.com
1. Introduction
Along with the development of the Si semiconductor
industry, numerous studies have been carried out on the
defects that remain after ion-implantation processes [1]. For
15 –2
example, in the case of high-dose (~10 cm ) implantation,
dislocation loops can be created even after annealing. These
defects are typically evaluated by transmission electron
microscopy (TEM) and have been confirmed as a reason for
13 –2
junction leakage [2][3]. Even in low-dose (< 10 cm )
implantation, some intrinsic point defects remain at
relatively low annealing temperatures (< 700 ˚C). These
defects have been conventionally analyzed and investigated
by optical and electrical characterization techniques, such
as photoluminescence (PL) and deep transient level
spectroscopy (DLTS) [4]-[6]. In contrast, residual damage
in low-dose implanted and high-temperature annealed Si
has not been detected and reported. Therefore, it is believed
that there is no damage remains in this condition, and, if
exists, it has no influence on device performance. Little
attention has been paid to the defects that remain after
low-dose implantation processes.
In our previous studies, we have shown the presence of
residual damage when using a rapid thermal process as heat
treatment. Cathodoluminescence (CL) analysis clearly
13
revealed a non-radiative decay center in low-dose (10
–2
cm ) arsenic (As) implanted Si after high-temperature
(1100 ˚C) rapid thermal annealing (RTA) [7]. This defect
has been identified by positron annihilation spectroscopy
analysis as a vacancy-type defect (PAS). Moreover, it has
been shown that this defect is transformed into an
oxygen-related defect by a non-equilibrium reaction with
oxygen (O2) in the annealing chamber during the extremely
rapid cooling step in the RTA sequence [8].
In this study, we analyze the thermal behavior of the
defects remaining after RTA. We prepared low-dose
implanted and high-temperature RTA-applied Si wafers.
We also applied additional furnace annealing (FA) as
equilibrium heat treatment at various temperatures. The
defects were characterized using a carrier lifetime
measurement system in addition to the CL and PAS
methods. The details of the defects and their evolution
during annealing will be discussed by comparison with
carrier properties obtained by sheet resistance
measurements.
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2. Experimental
Figure 1 shows the process of making of the samples
used in this investigation. The base material was a p-type
Cz-Si wafer and a thermal oxide layer was grown to a
+
thickness of about 40 nm. As ions were implanted through
13 –2 +
the oxide layer at 150 keV to a dose of 1.0×10 cm . B
12
ions were also implanted at 250 keV to a dose of 1.0×10
–2 12 –2
cm and 400 keV to a dose of 1.0×10 cm . These samples
were annealed at the top temperature of 1100 ˚C for 30
seconds using a hot-wall type RTA system. The heating-up
rate and cooling-down rate were set at 40 ˚C/sec and 80
˚C/sec respectively. Additional FA was applied at 300 - 900
˚C in steps of 100 ˚C. The top temperature was held for 60
minutes. The heating and cooling rates were slower than
with the RTA system: 8 ˚C/min and 4 ˚C/min respectively.
An oxide-layer-grown sample was prepared as reference.
We also prepared samples without RTA treatment, which
were FA-applied at 800 - 900 ˚C immediately after
implantation, for comparison. CL spectra were analyzed
using a scanning electron microscope (SEM) with a single
monochromator and InGaAs multi-channel detector. All CL
measurements were performed at 15 K. For PAS analysis,
the oxide layers were removed using hydrofluoric (HF)
acid. The Doppler broadening spectra of the positron
annihilation radiation were measured as a function of the
incident positron energy. The low-momentum part of the
spectrum was characterized by the S parameter, which was
defined as the number of annihilation events over the
energy range of 511 keV ± ΔE (where ΔE = 0.76 keV).
This S parameter is an index of
SiO2 40 nm
SiO2-grown
p-type Cz-Si
Impurity
As 150keV 1× 1013 cm-2
Implantation B 250keV 1× 1012 cm-2
B 400keV 1× 1012 cm-2
Rapid Thermal
Annealing (RTA) 1100 ˚C, 30 sec
↑40 ˚C/sec, ↓80 ˚C/sec
Furnace
Annealing (FA) 300~900 ˚C, 60 min
↑8 ˚C/min, ↓4 ˚C/min
Figure 1. Fabrication of the samples used in this investigation.
 S4-3 (L. N.) Ext. Abs. the 13th International Workshop on Junction Technology 2013

the number and size of vacancy-type defects [9]. Effective 1.2

Normalized TO-line Intensity (a.u.)

minority carrier lifetime was measured using a 9.35-GHz (a) RTA+FA reference (b) FA only
microwave transmittance measurement system and 1.0
analyzed on the basis of carrier diffusion and annihilation Annealing conditions
0.8 RTA: 1100˚C, 30sec.
theories [10][11]. A 635-nm CW laser diode light, with its FA: 300-900˚C, 60min.
2
intensity set at 1.5 mW/cm , was used to generate carriers.
The microwaves transmitted through the samples were 0.6
rectified using a high-speed diode and integrated. The
detection accuracy of the transmissivity was ± 0.1% in the 0.4
present system [12]. The sheet resistance was measured FA:
0.2 800-900˚C
using Frontier Semiconductor RsL300 non-contact 60min.
photovoltage-based equipment. [13] The wavelength and
0
Rs frequency of the modulated LED were 700 nm and 100 0 100 200 300 400 500 600 700 800 900 800 900
kHz respectively. The 1000 iterated measurements of each FA temperature (˚C)
measurement point improved the repeatability by up to Figure 3. Comparisons of TO-line intensity of the samples after
0.08%. annealing. (a) RTA + FA. (b) FA. All intensities are normalized
by those of the reference sample.

3. Results and discussion

peaks can be seen other than these TO and TO+OΓ-lines, it
Figure 2 shows the CL spectra of reference, can be concluded that the defect density is low just after the
as-implanted, and the annealed samples subjected to FA in oxide layer has grown. In contrast, the intensity of TO-line
addition to RTA. Two emission lines, labeled TO and is reduced after implantation and a W-line is newly
TO+OΓ, can be observed in the spectrum of the reference detected in the spectrum. W-line emission is considered to
sample. These lines are typical of band-to-band transition be originated from Si self-interstitial clusters [14]-[17].
followed by the emission of transverse optical (TO) This defect-related line reflects the development of implant
phonons and optical phonons at k = 0 (OΓ) [14]. Since no damage caused by the impact of accelerated ions. When
this implanted sample was annealed using the RTA system
at a high temperature of 1100 ˚C, the W-line disappeared
T=15K and the TO-line reappeared. This indicates that the implant
Annealing conditions
damage had been annealed out and the crystallinity had
TO RTA: 1100˚C, 30sec. been regained to some extent. However, the intensity of the
FA: 300-900˚C, 60min. TO-line gives new information on the residual defects.
TO+OΓ Figure 3 shows a comparison of the TO-line intensity of the
RTA+FA900˚C
samples after annealing. Note that the repeatability of
TO-line intensity, obtained by taking the average of 5
RTA+FA800˚C
measurements, was realized to within about 6% by
optimizing the optical systems and controlling the
RTA+FA700˚C
CL intensity (a.u.)

fluctuation of the sample temperature. Its intensity was

H normalized by the value of the reference sample, for
RTA+FA600˚C
comparison. The TO-line intensity of the only-RTA-applied
sample (i.e., additional FA temperature was 0 ˚C) is clearly
RTA+FA500˚C much lower than that of the reference sample. This suggests
that the TO-line emission had been suppressed by
RTA+FA400˚C non-radiative decay centers, i.e., some kind of defect and/or
crystal disorder. This provides strong evidence of the
RTA+FA300˚C presence of residual damage, as we had discovered in
previous studies [7]. In contrast, the TO-line intensity of the
RTA samples with additional FA at 300 ˚C and 400 ˚C gradually
W increased with increased annealing temperature. This
as-impla. indicates that the vacancy-type defects mentioned above
tended to be removed and the total number of defects was
reference suppressed after FA. When the FA temperature was set at
1100 1200 1300 1400 1500 500 - 600 ˚C, an H-line was observed, as shown in Figure 2.
Wavelength (nm) Although the origin of this H-line is not entirely clear, it
Figure 2. CL spectra of reference, as-implanted and the annealed appears to be due to some kind of point defect related to
samples subjected to FA in addition to RTA. interstitial carbon or interstitial oxygen [14][18]. This

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 S4-3 (L. N.) Ext. Abs. the 13th International Workshop on Junction Technology 2013
defect line disappeared after FA at 700 - 900 ˚C. The
TO-line intensity was drastically increased and saturated at
the value of the reference sample. This demonstrates that
crystallinity is likely to be regained to almost the same
level as the reference sample. For comparison, the samples
to which FA had been applied instead of RTA were
prepared and measured by CL. Only TO and TO+OΓ-lines
were detected in the spectra (not shown). The TO-line
intensities of these samples were slightly lower than those
of the samples subjected to RTA before FA at 700 - 900 ˚C,
as shown in Figure 3. This result indicates that some kind
of damage is present in the only-FA-applied sample (i.e.,
without RTA). The difference between these samples was
the presence or absence of RTA at 1100 ˚C, the maximum
temperature of the annealing process. We therefore
presume that a maximum temperature of annealing of 800 -
900 ˚C was insufficient to remove the implant damage
and/or activate impurities. Therefore, high-temperature
RTA appears to be necessary before FA to suppress the
creation of defects.
Several samples were evaluated by PAS, and the S
parameters as a function of incident positron energy E are
shown in Figure 4. The mean implantation depth of
positrons in Si crystal is calculated and described at the
upper x-axis in the same Figure [9]. The S value of the
only-RTA-applied sample was higher than that of the
reference sample, and it was distributed near the surface
region up to a few hundreds of nm. This provides further
evidence of the presence of damage as suggested by the CL
results; and a part of this damage was identified as
vacancy-type defects. When additional FA was applied
after RTA, the S value gradually decreased with increasing
FA temperature, and finally its distribution in the
FA-applied sample at 700 ˚C coincided exactly with the
Mean Implantation depth
of positrons (nm)
10 50 100 300 500
0.560
□ reference
0.555 ● RTA
◆ RTA+FA300˚C
▲ RTA+FA700˚C
S parameter
0.550
Annealing conditions
RTA: 1100˚C, 30sec.
FA: 300,700˚C, 60min.
0.545
0.540
0.535
0 2 4 6 8 10
Positron Energy (keV)
Figure 4. S parameters as a function of incident positron energy E
for RTA and FA-applied samples. A plot of the reference sample
is also shown for comparison. Mean implantation depth of
positrons in Si crystal are calculated and recorded on the upper
x-axis.
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≈
103
reference
carrier lifetime (usec)
102
Effective minority
101
Annealing conditions
RTA: 1100˚C, 30sec.
FA: 700-900˚C, 60min.
100
≈
0 700 800 900
FA temperature (˚C)
Figure 5. Effective minority carrier lifetime of some of the
annealed samples subjected to FA in addition to RTA
reference sample’s profiles. This result clearly indicates
that vacancy-type defects were abolished after FA at 700 ˚C.
This conclusion matches the CL analysis.
Figure 5 shows the effective minority carrier lifetime of
several samples. Carrier lifetime is very sensitive to the
total number of defects and crystal quality. Compared to
the reference sample, the lifetime of the only-RTA-applied
sample was one order lower. This is the influence of the
residual damage detected by CL and PAS measurements. In
contrast, the lifetime of the samples to which additional FA
had been applied at 700 ˚C was one order higher than the
only-RTA-applied sample, and was saturated with
increasing annealing temperature from 700 ˚C to 900 ˚C.
This suggests that almost all the defects that act as lifetime
killers in the lattice were removed by additional FA at 700
˚C or higher. This result also corresponds to the
expectations arrived at after CL measurements.
The sheet resistance variation of all annealed samples is
shown in Figure 6. Unlike the only-RTA-applied samples,
the sheet resistance of the samples applied with additional
FA fell with increasing FA temperature. Since it was
confirmed by PAS analysis that the vacancy-type defects
gradually disappeared in the temperature range of 300 - 400
˚C, this reduction of sheet resistance might be due to a
reduction in carrier-trapping sites. In contrast, a significant
change of the sheet resistance was observed in the samples
annealed at 500 - 600 ˚C. In this temperature range, the CL
results confirmed that intrinsic point defects were being
created. This means that the variation in sheet resistance is
due to the creation of defect levels related to point defects
in the band gap that are likely to act as carrier-trapping sites
which keep the sheet resistance still higher. When the
temperature of additional FA was set at 700 - 900 ˚C, the
sheet resistance decreased and seemed to level off at a
lower level. This result clearly indicates that most
carrier-trapping sites, i.e., residual defects, were removed
by additional FA at 700 ˚C or higher, as shown by using
various techniques for measuring its characteristics. Th e
sheet resistance under this particular annealing condition
47
 S4-3 (L. N.) Ext. Abs. the 13th International Workshop on Junction Technology 2013

2150 Yoshikawa for analyzing the SIMS profiles. We are also grateful
(a) RTA+FA (b) FA only to K. Ito and E. Igaki for their support.
Sheet resistance (orm/sq.)

2100
Annealing conditions
2050 RTA: 1100˚C, 30sec.
FA: 300-900˚C, 60min. References
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[1] See review, K.S. Jones, S. Prussin, and E.R. Weber, Appl.
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Figure 6. Sheet resistance of the samples after annealing. (a) RTA [5] O.O. Awadelkarim, A. Henry, B. Monemar, J.L. Lindstrom,
+ FA. (b) FA. Y. Zhang, and J.W. Corbett, Phys. Rev. B 42, 5635 (1990).
[6] S. Libertino, S. Coffa, and J.L. Benton, Phys. Rev. B 63,
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might thus correspond to the expected value under [7] A. Sagara, M. Hiraiwa, S. Shibata, R. Sugie, and K. Yamada,
conditions where the implant impurities are fully activated. AIP Proc. 1321, 225 (2008).
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th
only-FA-applied sample was slightly lower than that of the Proceedings of the 12 International Workshop on Junction
samples to which RTA had been applied before FA at 700 - Technology, 81 (2012).
900 ˚C. We surmise this to be due to insufficient activation [9] A. Uedono, K. Tsutsui, S. Ishibashi, H. Watanabe, S. Kubota,
of B at the FA temperature of 800 - 900 ˚C. This conclusion Y. Nakagawa, B. Mizuno, T. Hattori and H. Iwai, Jpn. J.
is also consistent with the trend of the TO-line intensity as Appl. Phys. 49, 051301 (2010).
evaluated by CL analysis. [10] T. Sameshima, H. Hayasaka, and T. Haba, Jpn. J. Appl. Phys.
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[11] T. Sameshima, T. Nagao, S. Yoshidomi, K. Kogure, and M.
4. Conclusions Hasumi, Jpn. J. Appl. Phys. 50 03CA02 (2011).
[12] T. Sameshima, K. Betsuin, T. Mizuno, and N. Sano, Jpn. J.
We analyzed the thermal behavior of residual damage Appl. Phys. 51 03CA04 (2012).
13 –2
in low-dose (< 10 cm ) As and B implanted Si after [13] V.N. Faifer, M.I. Current, T.M.H. Wong and V.V. Souchkov,
high-temperature (1100 ˚C) RTA after applying additional J. Vac. Sci. Technol. B 24(1) 414-420 (2006).
FA at 300 - 900 ˚C. The characterization techniques we [14] G. Davies, Phys. Rep. 176, 83 (1989).
selected were CL, PAS, lifetime, and sheet resistance [15] G. Davies, E.C. Lightowlers and Z.E. Ciechanowska, J.
measurement. All the results revealed the following new Phys. C 20, 191 (1987).
information about the defects. Vacancy-type defects were [16] P.K. Giri, S. Coffa and E. Rimini, Appl. Phys. Lett. 78, 291
gradually removed in the temperature range of 300 - 400 ˚C. (2001).
In contrast, several kinds of point defects were created at [17] P.K. Giri, Semicond. Sci. Technol. 20, 638 (2005).
500 - 600 ˚C. These defects were confirmed to be [18] C.E. Jones, E. S. Johnson, W. D. Compton, J.R. Noonan,
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improved, exceeding that of the only-FA-applied samples
without RTA. The reason is presumed to be that the
maximum temperature of FA (800 - 900 ˚C) is insufficient
to activate and/or remove the implant damage.
High-temperature RTA is thus necessary before FA to be
able to activate the impurities and reduce residual damage
after the implantation process.

Acknowledgements

We would like to express our gratitude to Prof. A. Uedono for

performing the PAS measurements and to Prof. T. Sameshima for
FC measurements and their analysis. We would like to thank F.
Kawase and T. Ishisaki for preparing the samples and S.

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