Journal of Nuclear Materials 451 (2014) 356–360

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Journal of Nuclear Materials

journal homepage: www.elsevier.com/locate/jnucmat

Helium defects interactions and mechanism of helium bubble

growth in tungsten: A molecular dynamics simulation
Xiao-Chun Li a,b, Yi-Nan Liu b, Yi Yu b, Guang-Nan Luo a, Xiaolin Shu b,⇑, Guang-Hong Lu b
a
Institute of Plasma Physics, Chinese Academy of Sciences, Hefei, Anhui 230031, China
b
School of Physics and Nuclear Energy Engineering, Beihang University, Beijing 100191, China

a r t i c l e i n f o a b s t r a c t

Article history: Molecular dynamics simulations have been performed to investigate the interactions between helium
Received 3 September 2013 (He) and defects in tungsten (W). The binding energy between He and He cluster is shown to be positive,
Accepted 19 April 2014 which increases with increasing He cluster size. Both the W self-interstitial atoms (SIAs) and the vacancy
Available online 26 April 2014
can promote the He cluster formation. The binding energies of a He, a vacancy and an SIA W to a
He–vacancy cluster (HenVm) in W are also investigated, which depend on the n/m ratio. According to
these results, we propose the formation and growth mechanism of He bubbles, which involves the pro-
cedures of He–vacancy cluster formation, the capturing of vacancies, then He atoms, and vacancies again.
The mechanism provides a good reference to understand the initial stage of the He bubble formation and
growth in W.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction site preference of He in a W grain boundary (GB) [5], indicating

The final application of nuclear fusion energy mainly relies on
the development of key materials in fusion devices, in which the
choice of the plasma facing materials (PFMs) is one of the critical
issues. Tungsten (W) and W alloys are considered as the most
promising candidates for PFMs because of their good thermal prop-
erties, such as high melting temperature and low sputtering
erosion, and they will be widely used in the next generation of
fusion reactors [1]. However, the blistering phenomena at the
W-PFM surface induced by the extremely high flux of low-energy
hydrogen (H) and helium (He) irradiation will greatly influence
the plasma stability and the PFMs lifetime. The He atoms behaviors
in W is also affected by the high concentration of vacancy and self-
interstitial atoms (SIA) induced by high energy neutron radiation,
and the small He–vacancy clusters play an important role in the
nucleation of He bubble.
According to the first-principles calculation by Becquart and
Domain [2,3], the most stable interstitial configuration for He is
at the tetrahedral site. According to their calculations, the migra-
tion barrier of He in bulk W is around 0.06 eV, and He atom can
be easily trapped by other He atoms. The most stable configuration
for He in W is at the vacancy site, and He tends to occupy the cen-
ter of vacancy [4]. Zhou et al. have investigated the energetics and
⇑ Corresponding author.
E-mail address: shuxlin@buaa.edu.cn (X. Shu).
that He prefers to segregate in the W GB and it is quite hard for
He to dissolve in the W GB. The H–He interaction in W was also
studied, which shows that He can suppress H blistering [6]. The
effective volume and relative stability of He at different interstitial
sites can be quantitatively characterized by the He-induced lattice
stresses in metals [7]. Liu et al. have performed a first-principles
computational tensile test [8] and the results suggest that the pres-
ence of He has great effect on the structure and bonding properties
of W. Henriksson et al. have studied the He cluster formation in W
by molecular dynamics (MD) simulations [9], the initial blistering
behavior [10], as well as the difference in the formation of H and
He clusters in W [11,12]. Our pervious work indicates that a
vacancy could trap more than 13 He atoms, which suggests that
vacancy is a strong trapping center for He atoms [13]. On the other
hand, more studies focused on the He behaviors in iron (Fe) by
both MD [14–17] and first-principles [18–21] simulations.
Due to the lack of suitable W–He potentials, little work has been
done on the He-defects interaction in W via MD simulations.
Recently, new W–He potentials have been developed including
both EAM potentials [22,23] and a bond order potential [13]. In this
paper, we perform MD and molecular statics (MS) simulations to
investigate the He-defects interactions in W, the binding energies
of a He, a vacancy and a self-interstitial W to a He–vacancy cluster
in W are also demonstrated. The results are quite helpful to under-
stand the mechanism for the helium bubble growth in W under a
fusion environment.

http://dx.doi.org/10.1016/j.jnucmat.2014.04.022
0022-3115/Ó 2014 Elsevier B.V. All rights reserved.
 X.-C. Li et al. / Journal of Nuclear Materials 451 (2014) 356–360
2. Computational method
We employ the self-developed W–W and W–He interatomic
potentials based on an analytical bond-order scheme for the
W–H–He system [13,24], and the He–He interaction of the Har-
tree–Fock-dispersion pair potential developed by Aziz et al. [25].
The potentials can reproduce various properties of the W–H–He
system such as the defect formation energies, structural properties,
and diffusion barriers determined by the first-principles. We have
especially considered the defect properties in order to make the
potentials suitable for simulating a W–H–He system with defects.
All works are performed using the MD code LAMMPS [26]. The
simulation supercell is a 10  10  10 box containing 2000 W
atoms. For all the MD simulations, we use a variable time step
algorithm that varies from 1 fs to 0.05 fs, where the maximum dis-
tance for an atom to move within one time step is 0.2 Å, and the
temperature is controlled via explicit rescaling of the velocities.
Constant pressure and periodic boundary conditions are used as
well. For static relaxation, the conjugate gradient (CG) algorithm
is used, with the stopping tolerance for energy of 109 and the
stopping tolerance for force of 109 eV/Å.
We firstly obtained the lowest configurations of vacancy cluster
(Vm), by randomly removing m W atoms in a small area to generate
hundreds of random configurations and then performing MS sim-
ulation for each configuration. In this way, we could find the lowest
configuration for vacancy cluster. Similarly, we use a random
method to find the lowest energy configurations of HenVm cluster,
Hen cluster and SiamHen cluster. For each HenVm cluster with a fixed
number of n and m, we generate different HenVm cluster configura-
tions by putting n He atoms into the vacancy cluster (Vm) ran-
domly. For each Hen cluster and SiamHen cluster, we generate
different configurations by putting m W atoms and n He atoms to
a small area. After the random configuration generation, molecular
static simulations are performed for each structure, and the lowest
energy configuration of each cluster could be obtained. Further-
more, MD simulation is employed to fully relax the system at
100 K for 10,000 time steps, followed by system quenching to
0 K. The formation energy of each HenVm cluster can be calculated
by
h i
Ef ðHen V m Þ ¼ Etot ðHen V m Þ  nECHe þ ðN  mÞECW ;
where N is the total number of W atoms in the perfect bcc crystal,
and ECW ; ECHe refers to the cohesive energy of the single W atom in
perfect bcc W crystal, and ECHe the energy of single He in vacuum,
respectively.
The binding energy of A–B can be defined as
Eb ðA þ BÞ ¼ Ef ðAÞ þ Ef ðBÞ  Ef ðA þ BÞ;
where Ef (A) and Ef (B) are the formation energy of A and B, respec-
tively. And Ef (A + B) is the formation energy of A + B, with A and B
together. Higher binding energy means stronger combination of A
and B. The binding energies of a He atom (EB(He)), a vacancy
(EB(V)) and an SIA W atom (EB(W)) to different clusters are investi-
gated. And the formation energies of Ef (He), Ef (V) and Ef (SIA) as ref-
erence are formation energies of an tetrahedral interstitial He,
isolated vacancy and h1 1 1i dumbbell SIA W, respectively.
3. Results
3.1. He interaction with He cluster
According to the previous study [13], two He atoms attract each
other in W, and the binding energy of two He atoms is 0.63 eV in
the most stable configuration with a He–He distance of 1.74 Å.
We have investigated the binding energy between He and small
357
He cluster (Hen), the He atoms number (n) ranges from 1 to 10,
and the results are shown in Fig. 1. Generally speaking, the He
binding energy will determine whether the He atom could com-
bine with more He atoms or not. When the number of He atoms
in the cluster increases from 2 to 7, the He binding energy
increases from 0.67 eV to 3.25 eV. When the cluster size is larger
than 8, the He binding energy fluctuates with the increase of He
number. Such high binding energy indicates a very strong attrac-
tive interaction between He atoms. Thus, He atoms can form He
cluster by self-trapping, and once a small He cluster is formed, it
is very difficult to separate He atoms from the cluster.
Fig. 2 gives some configurations of these Hen clusters. As shown
in Fig. 2, a single He atom will occupy the tetrahedral interstitial
site (Fig. 2(a)), three He atoms would form a triangular structure
(Fig. 2(b)), and four He atoms form a tetrahedral structure
(Fig. 2(d)). The binding energy of He with He6 cluster is the highest,
in which case a W atom is squeezed out to give He cluster more
space and induces higher binding energy, as shown in Fig. 2(g).
Overall, it is easy for He atoms to form a highly symmetrical struc-
ture, and make large deformation of the W lattice. Similar highly
symmetrical structures are also found in He–vacancy clusters
[13] and He clusters in Fe GB [27].
3.2. He interaction with SIA and vacancy
High concentration SIAs can be produced by high energy neu-
tron irradiation in the fusion environment, and SIAs may affect
the nucleation of He bubble. Thus, we investigate the binding ener-
gies of He to SIAmHen1 cluster, the SIA number (m) is 1 and 2, and
the He atoms number (n) ranges from 1 to 10. The results are
shown in Fig. 1, in comparison with the previous He binding
energy to V1Hen cluster [13].
The tendencies of the binding energies of He to SIA1Hen1 and
SIA2Hen1 cluster are similar. Taking the binding energy of He to
SIA1Hen1 cluster as an example, when the number of He atoms
in the cluster increases from 1 to 6, the He binding energy
increases from 0.5 eV to 3.0 eV, and when the cluster size is larger
than 7, the He binding energy fluctuates with the increase of He
atoms number. The structures of some SIAmHen clusters are plotted
in Fig. 3. Same as in the He cluster, all the He atoms in SIAmHen
ð1Þ cluster gather together to form a highly symmetrical structure,
and the W lattice has large deformation.
The binding energy tendency of He to Hen cluster is quite sim-
ilar to that of He to SIAmHn cluster. However, when the He number
in the cluster ranges from 2 to 6, the binding energy of He to SIAm-
ð2Þ
Fig. 1. The He binding energies as a function of the number of He atoms in the
clusters.
358 X.-C. Li et al. / Journal of Nuclear Materials 451 (2014) 356–360

Fig. 2. The configurations of Hen clusters. The larger blue spheres represent W atoms, while the smaller yellow spheres represent He atoms. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 3. The configurations of SIAmHen clusters. (a–d) are SIA1Hen clusters, and (e–h) are SIA2Hen clusters. The larger blue spheres represent W atoms, while the smaller yellow
spheres represent He atoms. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Hn cluster is 0.7 eV on average, higher than that of He to Hen
cluster, which indicates that SIAs will promote the He cluster for-
mation, and He atoms can still form He cluster by self-trapping
around SIAs.
According to the previous study of the binding energy of He to
V1Hen1 cluster [13], as a comparison with present study, when the
number of He atoms in the cluster is less than 5, the binding energy
of He–V1Hen1 cluster is much higher than the binding energy of
He to Hen cluster and He to SIAmHn cluster. After that, the binding
energies have little difference with each other when the number of
He atoms in the cluster ranges from 5 to 7. When the number of He
atoms in the cluster is larger than 8, the binding energy is similar
to each other. And the binding energies of He to V1Hen1 cluster are
all larger than 2.1 eV. Thus, the vacancy will greatly promote the
aggregation of the He atoms, and He atoms are willing to occupy
the vacancy position.
Thus, it is clear that He atoms can form He cluster by self-trap-
ping, and both SIAs and vacancy will promote the aggregation of
the He atom. He atoms will be self-trapped very easily even with-
out defects, or trapped by defects, especially vacancy. The forming
and growing process of He clusters could then be demonstrated.
When He atoms come into the W material from the surface, He
atoms will diffuse very fast (the diffusion barrier is 0.06 eV), and
once two He atoms encounter, they will combine with each other
(the binding energy is 0.63 eV). And the two-He cluster will easily
combine with another He atom (the binding energy is 1.31 eV),
during which process the two-He atoms can diffuse to another
He or the single He atom diffuses to the two-He cluster to form a
larger three-He cluster. In this way, the He cluster grows up
gradually. The defects such as SIAs and vacancies will promote this
process. Thus, the He cluster is easy to be formed in the near sur-
face of W, which is consistent with the previous simulation and
experiment results [2,11,12,28].
3.3. Formation energies of HenVm clusters
In order to obtain the defect binding energies, we investigate
the formation energies of HenVm clusters in this study, while n
and m are the numbers of He atoms and vacancies in the HenVm
cluster, with m ranging from 1 to 10 and the atomic He-to-vacancy
ratio (n/m) ranging from 1 to 9. The formation energies of HenVm
clusters as a function of the He number are shown in Fig. 4. When
 X.-C. Li et al. / Journal of Nuclear Materials 451 (2014) 356–360 359

the He-to-vacancy ratio (n/m) is less than 1, the formation energy

slowly increases with the He number. The lowest energy configu-
ration appears when He-to-vacancy ratio is 1. Fig. 5 shows the for-
mation energy of HenVm cluster as a function of the vacancy
number. When the He-to-vacancy ratio (n/m) is less than 1, the for-
mation energy of HenVm cluster slowly decreases with vacancy
number, which also indicates that the lowest energy configuration
occurs when the He-to-vacancy ratio is 1. However, when the He-
to-vacancy ratio is larger than 1, the formation energy dramatically
increases with the He-to-vacancy ratio, which is mainly caused by
the presence of He. In conclusion, the formation energy of the Hen-
Vm cluster is greatly dependent on the He-to-vacancy ratio of the
cluster, which is similar to the previous works [14,29].

3.4. Binding energies of a He atom, a W atom and a vacancy to HenVm

clusters

As we have determined the formation energy of the HenVm

cluster, the binding energies of a vacancy (EB(V)), a He atom Fig. 5. The HenVm formation energy as a function of the number of vacancies.
(EB(He)) and an SIA W atom (EB(W)) to the HenVm cluster can be
calculated. The stability of HenVm cluster can be determined by
these binding energies, which are shown in Fig. 6 as a function of
the He-to-vacancy ratio. All of the binding energies show a great
dependence on the He-to-vacancy ratio, but not the number of
vacancies in the HenVm cluster. The binding energies of a He and
a vacancy to the HenVm cluster are similar to our previous MS cal-
culations [13].
The binding energy of a He atom to the HenVm cluster (EB(He))
gradually decreases with the increasing He-to-vacancy ratio.
The He binding energy decreases from 6.0 eV to 3.0 eV when He-
to-vacancy ratio increases from 0 to 9. The energy required to
remove one He atom from the HenVm cluster can be described by
the He binding energy, thus higher binding energy means stronger
combination of the He atom to the vacancy cluster. Even when the
He-to-vacancy ratio is larger than 9, the He binding energy is still
larger than 3.0 eV. With such a high binding energy, HenVm cluster
could easily bind with more He atoms, which is consistent with the
previous first-principles calculation [4].
The binding energy of a vacancy to the HenVm cluster (EB(V))
Fig. 6. The binding energies of a He atom, a vacancy and an SIA W atom to a He–
increases dramatically with the rising He-to-vacancy ratio. The vacancy cluster in W as a function of the He-to-vacancy ratio. The solid lines are the
vacancy binding energy increases from 1.0 eV to 11.0 eV when quadratic polynomial fitting results of these binding energies.
the He-to-vacancy ratio increases from 0 to 9. With such a high
vacancy binding energy, it is energetically difficult to remove a
vacancy from the HenVm clusters. On the other hand, He–vacancy The binding energy of an SIA W to the HenVm cluster (EB(W))
clusters can be easily combined with another vacancy. greatly decreases with the increasing He-to-vacancy ratio, with
the opposite trend compared with the vacancy binding energy.
The W binding energy decreases from 12.0 eV to 2.0 eV when
the He-to-vacancy ratio is increased from 0 to 8. When the He-
to-vacancy ratio is small, the W binding energy is much higher
compared with the He binding energy and vacancy binding energy.
As a comparison of these binding energies, when the He-
to-vacancy ratio in the HenVm cluster is relatively low, the SIA W
binding energy is much higher than the vacancy and He binding
energies. In this situation, it is very easy for the He–vacancy cluster
to combine with a SIA W and reduce the vacancy number, thus the
He-to-vacancy ratio will become higher. On the contrary, when
He-to-vacancy ratio in the HenVm cluster is larger than 3, the
vacancy binding energy is much higher than the SIA and He bind-
ing energy. In this situation, it is easier for the He–vacancy cluster
to combine with another vacancy, or kick out an SIA W atoms to
the surface, and increase the size of He–vacancy cluster to reduce
the He-to-vacancy ratio. When He–vacancy ratio is greater than
6.8 in the HenVm cluster, HenVm clusters are more easily to combine
with He atoms in comparison with the SIA W.
According to the above analysis, the binding energies between
Fig. 4. The HenVm formation energy as a function of the number of He atoms. He and He, He and vacancy, He and SIA W are very high, indicating
360 X.-C. Li et al. / Journal of Nuclear Materials 451 (2014) 356–360
that He can be gathered by self-trapping. The He–vacancy cluster
could be formed by means of either He cluster squeezing out a
new vacancy or the existing vacancy capturing He atoms. Starting
with the He–vacancy cluster formation, the growth process of He
bubbles could be then demonstrated as follows. No matter how
the existing He–vacancy cluster is formed, by squeezing out
vacancy or the He trapping of existing vacancy, the original He-
to-vacancy ratio would be larger than 3, and the binding energy
of vacancy to the He–vacancy cluster is larger than those of SIA
and He, thus it is easy for the cluster to combine with a neighbor-
ing vacancy (VmHen + V = Vm+1Hen) and make the He-to-vacancy
ratio smaller. When this ratio is reduced to a value smaller than
2, the He binding energy to the cluster turns larger than that of
vacancy, thus the cluster will tend to capture more He atoms and
increase the ratio again (Vm+1Hen + Hex = Vm+1Hen+x), which leads
to the emergence of a larger He–vacancy cluster. In this way, the
He–vacancy cluster will capture more vacancies and He atoms,
thus causing the He–vacancy cluster to grow larger and larger.
Based on the above analysis, we propose the formation and
growth mechanism of He bubbles, which will go through the pro-
cedure of He–vacancy cluster formation, the capturing of vacan-
cies, then He atoms, and vacancies again. Since the He–vacancy
cluster is considered as the nuclei of the He bubble, the process
described above should be the initial stage of the He bubble forma-
tion and growth.
4. Conclusions
We have performed molecular dynamics simulations to investi-
gate the interactions between helium (He) and defects in tungsten
(W). We show that the binding energy between He and He cluster
is positive, and increases with increasing He cluster size. The
He cluster formation in W can be promoted by both the W self-
interstitial atoms (SIAs) and the vacancy. We demonstrate that
the binding energies of a He, a vacancy and an SIA W to a
He–vacancy cluster (HenVm) in W depend on the n/m ratio. The
binding energies of a He and an SIA W atom to a HenVm cluster both
decrease, while the binding energy of vacancy to a HenVm cluster
increases with the increasing n/m ratio. We propose the formation
and growth mechanism of He bubbles with the procedures of
He–vacancy cluster formation, the capturing of vacancies, then
He atoms, and vacancies again. The mechanism provides a good
reference to understand the initial stage of the He bubble forma-
tion and growth in W.
Acknowledgments
This work has been supported National Natural Science Founda-
tion of China (NSFC) Grant No. 51171008 and National Magnetic
Confinement Fusion Program with Grant No. 2013GB109002.
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