Fusion Engineering and Design 81 (2006) 301–306

Helium irradiation effects for deuterium retention

in boron coating films
T. Takeda a,∗ , A. Yoshikawa a , M. Oyaidzu a , T. Nakahata a ,
Y. Nishikawa a , H. Kimura a , Y. Onishi a , H. Miyauchi a ,
Y. Oya b , A. Sagara c , N. Noda c , K. Okuno a
a Radiochemistry Research Laboratory, Shizuoka University, Oya 836, Shizuoka 422-8529, Japan
b Radioisotope Center, The University of Tokyo, Yayoi 2-11-16, Bunkyo-ku, Tokyo 113-0032, Japan
c National Institute for Fusion Science, Oroshi-cho 322-6, Toki, Gifu 509-5292, Japan

Received 1 February 2005; received in revised form 23 August 2005; accepted 23 August 2005
Available online 20 December 2005

Abstract

TDS analyses have been performed in order to examine helium irradiation effects for deuterium retention in boron coating
films prepared by PACVD. It is clarified that the deuterium retention is reduced due to the irradiation prior to deuterium. There
is no correlation between the retention variations of deuterium and helium, and thus the helium occupation seems hardly to
contribute to the reduction. The third peaks in the TDS spectra shift on the high temperature side with the irradiation fluence.
It is presumed that helium irradiation forms certain layers by knocking on boron atoms, in which deuterium retention is partly
restricted, and trapped deuterium needs higher energy for the desorption.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Helium irradiation prior to deuterium; Deuterium retention; Boron coating film; PACVD; TDS

1. Introduction tamination. Ever since that, boronization has also been

It is very important for future fusion devices to
achieve high density and high confinement plasmas.
Boronization, one of inner wall conditioning, was first
fulfilled to improve plasma performance at TEXTOR
[1], and proved to be effective to reduce impurity con-
∗ Corresponding author. Tel.: +81 54 238 6436;
fax: +81 54 238 3989.
E-mail address: sttaked@ipc.shizuoka.ac.jp (T. Takeda).
applied to other fusion experimental devices [2–15],
such as DIII-D, JT-60, LHD, NSTX. On the other hand,
there have still been some critical issues, for example,
hydrogen isotope retention and recycling. The walls,
coated with boron films by plasma-assisted chemi-
cal vapor deposition (PACVD) [16], are exposed to
energetic particles of fusion plasmas. Therefore, it is
necessary to clarify the chemical interactions between
boron and hydrogen isotopes, as various chemical
states and/or bonds can be formed.

0920-3796/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.fusengdes.2005.08.049
302 T. Takeda et al. / Fusion Engineering and Design 81 (2006) 301–306

We have examined such chemical interactions, sim- Table 1

ulating deuterium irradiation for boron coating films Typical parameters
deposited on pure silicon substrates in a high vac- PACVD condition
uum chamber. In our previous studies [17–20], thermal B10 H14 gas flow rate 2.5 sc cm
He gas flow rate 3.8 sc cm
desorption spectroscopy (TDS) analyses exhibited two Total gas pressure 26.7 Pa
desorption processes of deuterium, and it was revealed Radio frequency 13.6 MHz
that deuterium retention decreases as the film tem- Discharge power 50 W
perature during the irradiation (hereinafter referred to Substrate temperature 673 K
as “irradiation temperature”) increases. X-ray photo- Deposition duration 60 min
Ion-beam condition
electron spectroscopy (XPS) analyses proved that two He+ energy 1 keV
chemical bonds, namely B–D terminal and B–D–B Flux 1.4 × 1018 m−2 s−1
bridges, exist in the films. Moreover, it was suggested Fluence 0.63–10.0 × 1021 m−2
that helium irradiation prior to deuterium affects B–D D2 + energy 1 keV
rather than B–D–B, though its effects for deuterium Flux 1.4 × 1018 m−2 s−1
Fluence 5.0 × 1021 m−2
retention were not studied adequately. Beam diameter 4 mm
In this paper, we present the TDS spectra and the Irradiation temperature 323–823 K
desorption amounts of deuterium and helium for boron
coating films in the various cases of helium irradia-
tion prior to deuterium, and discuss its effects for the with very little hydrogen, XPS analyses with argon-ion
deuterium retention. beam sputtering showed typical features as follows: the
thickness is about 300 nm, boron and carbon content
are 94% and 4%, respectively.
2. Experimental
2.2. Ion-beam irradiation and TDS analysis
2.1. Sample preparation
Ion-beam irradiations and TDS analyses were car-
Boron coating films were prepared by a PACVD ried out in a high vacuum chamber in the following
device (illustrated in detail in Ref. [20]). Slab substrates procedure: (i) a boron film sample with an electrical
of highly pure single crystal silicon (purity 99.999%, heater is inserted to a mounting bracket; (ii) the sample
size 10 mm × 10 mm) are mounted and heated around is heated for the thermal annealing duration of 10 min
673 K in the chamber, which is evacuated below at 1053 K to remove a large amount of hydrogen; (iii)
10−6 Pa by a pumping unit (composed of a rotary and a helium-ion beam is vertically irradiated to the sam-
a turbo pump). A highly pure decaborane gas (B10 H14 , ple at a given temperature by an ion-beam gun, and
purity 99.9%) vaporized at 403 K is used as boron sequentially a deuterium-ion beam is used at the same
source, being diluted by a highly pure helium gas temperature at the same position, which can be iden-
(purity 99.9%). During the injection of the mixture gas, tified with their beam spots. Table 1 also shows the
plasmas are produced by RF-glow discharges between ion-beam condition; (iv) the TDS analysis is performed
an electrode (diameter 120 mm) fixed at the upper side with a high-resolution quadrupole mass spectrometry
and the inner wall. The total pressure and the film thick- (QMS) below 10−6 Pa, which can discriminate a slight
ness are monitored through a baratron pressure gauge difference between helium and deuterium masses. The
and a quartz oscillator, respectively. Table 1 shows the sample temperature rises up to 1053 K at a rate con-
PACVD condition. stant of 0.5 K s−1 , being automatically controlled by a
We noted that boron films produced by PACVD programmable thermo-controller. Simultaneously, des-
are amorphous with trapped hydrogen (a-B:H) [21,22]. orption rates of helium and deuterium are separately
The film samples were transported to other vacuum measured.
devices through a glove box adjacent to the chamber The above procedure was repeated with changing
under the argon atmosphere, which was enclosed in the sample, the helium-ion fluence, and the irradiation
a transfer vessel without air exposure. For the films temperature. Eventually, the TDS spectra of helium
 T. Takeda et al. / Fusion Engineering and Design 81 (2006) 301–306 303

these spectra prove that helium and deuterium masses

are individually detected at the same time. As the irra-
diation temperature increases, the spectral intensity
becomes weak gradually, and P3 shifts toward high
temperature. On the other hand, the helium spectra are
extremely weak in the ion-irradiation temperature of
523 K or more. This indicates that helium is hard to be
trapped around 523 K or more. Desorption amounts of
deuterium and helium, estimated from Figs. 1 and 2,
are plotted with respect to the irradiation temperature in
Fig. 3. Due to the helium-ion irradiations, the deuterium
amount to the deuterium-ion fluence of 5.0 × 1021 m−2
is reduced from 51% to 33% in 323 K, and from 30% to
16% in 523 K. The deuterium amount with the helium-
ion irradiation decreases more gradually than that with-
out it. The helium amounts to the helium-ion fluence
Fig. 1. TDS spectra of deuterium in various irradiation temperatures
without helium-ion irradiation.

and deuterium were individually calibrated by using

standard leak gases of helium and deuterium. The des-
orption amounts, that is, the retention amounts were
obtained by the integral of each the calibrated spec-
trum with respect to time.

3. Results and discussion

3.1. Dependence on irradiation temperature

Fig. 1 shows TDS spectra of deuterium in various

irradiation temperatures without helium-ion irradia-
tion. Basically, the spectra appear to consist of at least
three peaks, named P1, P2 and P3. The P3 positions
are close to that of polycrystalline boron [17], and
seem to characterize the film structure. The films pre-
pared in the present experiment may be composites of
amorphous and polycrystalline boron. From our pre-
vious study [17–20] and Refs. [21,22], trapping sites
of P1 and P3 can be identified as B–D–B bridge and
B–D terminal bond, respectively, though that of P2 is
unknown. As the irradiation temperature increases, P3
shifts toward high temperature whereas P1 is almost
stationary. There is a possibility that the deuterium des-
orption from B–D sites consists of multiple processes.
Fig. 2 shows TDS spectra of deuterium (a) and
helium (b) in various irradiation temperatures in the Fig. 2. TDS spectra of deuterium (a) and helium (b) in various irra-
helium-ion fluence of 5.0 × 1021 m−2 . Apparently, diation temperatures in the helium-ion fluence of 5.0 × 1021 m−2 .
304 T. Takeda et al. / Fusion Engineering and Design 81 (2006) 301–306

Fig. 3. Desorption amounts of deuterium and helium vs. irradiation

temperature.

of 5.0 × 1021 m−2 are 3.9% in 323 K, and 0.49% in Fig. 4. TDS spectra of deuterium in various helium-ion fluences in
the irradiation temperature of 323 K.
523 K. The decrease between these is much steeper
than that above 523 K. It is obvious that there is no cor- not to the helium occupation but to the structural
relation between the amount variations of deuterium transformation.
and helium. This indicates that the helium occupa- Fig. 6 shows TDS spectra of deuterium in various
tion in the films hardly contributes to the reduction of helium-ion fluences in the irradiation temperature of
the deuterium amounts. In 823 K, isothermal annealing 523 K. It is seen that the spectral intensities become
effects seem dominant because the deuterium retention very week due to the helium-ion irradiations. As the
is almost the same amount in both cases. fluence increases, P2 decays somewhat, and P3 shifts
clearly toward high temperature, which means that the
3.2. Dependence on helium-ion fluence helium-ion irradiation affects the desorption process
of deuterium by transforming the film structure. Des-
Fig. 4 shows TDS spectra of deuterium in vari- orption amounts of deuterium and helium are plotted
ous helium-ion fluences in the irradiation tempera- with respect to the fluence in Fig. 7. The deuterium
ture of 323 K. It is exhibited that the spectra dynam-
ically change with fluence. The spectral intensities are
extremely weak from the fluence of 0.63 × 1021 m−2 .
P1 is almost stationary to heating temperature except
for the case of 5.0 × 1021 m−2 . P2 and P3 shift toward
high temperature, and the shift width of P3 is greater
than that of P2. Desorption amounts of deuterium and
helium are plotted with respect to the fluence in Fig. 5.
The deuterium amounts, reduced by the helium-ion
irradiations, vary up and down whereas the helium
amount increases linearly. The minimum of the deu-
terium amount is 21% to the deuterium-ion fluence. The
helium amounts are less than the reduction amounts
of deuterium, and are not inversely proportional to
the deuterium amounts. These mean that the deu-
terium retention does not depend on the helium reten- Fig. 5. Desorption amounts of deuterium and helium vs. helium-ion
tion. Possibly, the deuterium reduction is attributed fluence in the irradiation temperature of 323 K.
 T. Takeda et al. / Fusion Engineering and Design 81 (2006) 301–306
Fig. 6. TDS spectra of deuterium in various helium-ion fluences in
the irradiation temperature of 523 K.
amounts from 1.25 × 1021 m−2 are almost stable and
16–18% to the deuterium-ion fluence; meanwhile, the
helium amount increases linearly in much lower level.
The helium amounts are much less than the reduction
amounts of deuterium, and are not inversely propor-
tional to the deuterium amounts. It is likely that the
helium-ion irradiation transforms the film structure,
which also restricts the deuterium retention.
It has been found that boron-coating film is in amor-
phous states based on icosahedral clusters [23]. Since
incident helium-ions knock on boron atoms in the film,
they may yield the other clusters in amorphous and/or
polycrystalline states, and certain layers may form
Fig. 7. Desorption amounts of deuterium and helium vs. helium-ion
fluence in the irradiation temperature of 523 K.
305
especially near the surface. It has theoretically been
predicted that there can be various boron clusters [24],
which mainly have interatomic distances between 1.5
and 2.0 Å. Hence it is presumed that the certain lay-
ers restrict deuterium retention partly, and deuterium
trapped in the layers needs higher energy for the des-
orption.
4. Summary
We examined helium irradiation effects for deu-
terium retention in boron coating films prepared by
PACVD. TDS analyses were performed in the various
cases of helium irradiation prior to deuterium. It
became clear that the deuterium retention is reduced
due to the helium irradiation. Dependences on the irra-
diation temperature showed that the retained amount of
deuterium with the helium irradiation decreases more
gradually than that without the helium irradiation.
Dependences on the helium-ion fluence showed that
the retention amount varies on a complicated manner
at the irradiation temperature of 323 K, but is almost
stable in 523 K except for the case of non-helium
irradiation. The retained amounts of helium were less
than the reduction amounts of deuterium, and there
was no correlation between the amount variations of
deuterium and helium. The third peak in the TDS
shifted toward high temperature with the fluence of
the helium irradiation. Therefore, it is presumed that
helium irradiation forms certain layers by knocking
on boron atoms, in which deuterium retention is partly
restricted, and trapped deuterium needs higher energy
for the desorption.
Acknowledgements
This work was supported by the NIFS Collaborative
Research Program.
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