SWELLING OF S10 2 QUARTZ INDUCED BY ENERGETIC HEAVY IONS

C. TRAUTMANN 1 , J.M. COSTANTINI 2 , A. MEFTAH 3 , K. SCHWARTZ 1

4 5
J. P. STOQUERT , AND M. TOULEMONDE

1 Gesellschaft fuir Schwerionenforschung, Planckstr. 1, 64291 Darmstadt, Germany,

C.Trautmann@gsi.de
2
DPTA/PMC, BP 12, 91680 Bruy6res-Le-Chdtel, France
3 ENSET, BP 26 Merj-eddib, 21000 Skikda, Algeria
4 Laboratoire PHASE, 67037 Strasbourg - cedex 2, France
5 CIRIL, Laboratoire commun CEA/CNRS, BP 5133, 14070 Caen-cedex 5, France

ABSTRACT

A pronounced swelling effect occurs when irradiating SiO 2 quartz with heavy ions (F, S, Cu,
Kr, Xe, Ta, and Pb) in the electronic energy loss regime. Using a profilometer, the out-of-plane
swelling was measured by scanning over the border line between an irradiated and a virgin area of
the sample surface. The step height varied between 20 and 300 nm depending on the fluence, the
electronic energy loss and the total range of the ions. From complementary Rutherford
backscattering experiments under channelling condition (RBS-C), the damage fraction and
corresponding track radii were extracted. Normalising the step height per incoming ion and by the
projected range, a critical energy loss of 1.8 ± 0.5 keV/nm was found which is in good agreement
with the threshold observed by RBS-C. Swelling can be explained by the amorphisation induced
along the ion trajectories. The experimental results in quartz are compared to swelling data
obtained under similar irradiation conditions in LiNbO 3.

INTRODUCTION

Radiation induced volume expansion is a general effect which has been discovered in various
solids in the late fifties. The swelling under irradiation can result from point defects, but also from
defect aggregates or from phase transitions. In the case of point defects, the swelling mechanism
is well understood [1,2], while for more complex defects, i.e. under irradiation at higher doses, it
is described only phenomenologically. In this regime, the relative volume changes are larger and,
depending on the material, can reach several percent (e.g. 15% for quartz) [3]. Swelling occurs in
a wide range of irradiation conditions (e.g. temperature, dose, and dose rate) and under various
particle beams such as electrons, neutrons or ions [4-8]. More recently, swelling has been
observed when irradiating A12 0 3 [9] and LiNbO 3 [10-12] with energetic heavy ions. The
macroscopic volume increase of the bulk material was clearly attributed to the damage produced
by electronic excitations. The goal of our study was to extend the swelling tests to SiO 2 crystals.
It should be mentioned that in quartz, the damage under heavy ion irradiation has been studied by
various techniques [7,13-15]. Evidence was given that along the ion trajectory a cylindrical zone
of amorphous silica is formed having a diameter of a few nanometers. The experimental data are

123
Mat. Res. Soc. Symp. Proc. Vol. 504 0 1998 Materials Research Society
in good agreement with the thermal spike model which describes the track as a cylindrical zone
resulting from rapid quenching of a liquefied phase along the ion path [ 15].
In order to perform systematic measurements of the out-of-plane swelling in Si0 2 , we
irradiated quartz with various ion species in the energy regime between 15 and 830 MeV. The
swelling tests were complemented by RBS-C analysis from which the damage fraction at
different ion fluences was deduced. By combining the two techniques, we followed the data
analysis as presented by Canut et al in ref. [10]. Extending this analysis, it was possible to extract
an energy loss threshold for swelling. Finally, we will compare ion induced swelling and damage
effects in quartz and in LiNbO 3 .

EXPERIMENTAL CONDITIONS AND PHYSICAL CHARACTERISATIONS.

Irradiation

We used single crystals of synthetic quartz of a thickness of about 1.5 mm. The polished
surface (optical quality) of the samples was covered with a 50 nm thin carbon layer in order to
avoid electrostatic charging during irradiation or analysis. The irradiations were performed using
lighter ions ( 19F, 32S, and 63Cu) at the 7 MV tandem Van de Graaff in Bruy~res-le-Chdtel and
heavier ions (84 Kr, 129 Xe, 181Ta, and 208Pb) at the medium energy line of the GANIL accelerator
in Caen. All irradiations were performed at room temperature under normal incidence. In some
cases, thin aluminium foils were placed in front of the samples in order to vary the energy and
energy loss of the ions when impinging on the sample surface. By limiting the maximum energy
of the ion beam to 4 MeV/u, significant velocity effects were avoided [16]. A complete list of the
irradiation parameters is given in Table I, where the values for the energy loss dE/dx and the ion
range were calculated with the TRIM 91 code [17]. The flux of the ion beam was of the order of
109 ions s-Icm- 2 at the tandem Van de Graaff accelerator and 3 x 108 ions s-Icm- 2 at the GANIL
accelerator. The maximum applied ion fluence 0 depended on the ion species and was, e.g.,
4 x1011 and 2 X10 14 ions/cm 2 for Pb and F ions, respectively. During the irradiation, all crystals
were partially masked in order to analyse the damage of an irradiated area in direct comparison
with a virgin area of the same sample.

Table I. Parameters of ion irradiation, the damage cross section Ad and track radius R
ion energy dE/dx range Ad= 7t R2 radius R reference
(MeV/u) (keV/nm) (gtm) (10-13 cm 2 ) (nm)
F 0.79 2.4 7.1 0.11 ±0.03 0.6±0.1 [14]
S 1.56 4.7 11.7 1.2 ± 0.3 2.0 ± 0.3 [14]
Cu 0.79 9.1 8.7 2.6 ± 0.5 2.9 ± 0.03 [14]
Kr 3.3 12.0 27.7 3.3 ± 1.0 3.2 ± 0.5 [14]
Xe 1.5 17.0 14.7 5.0 ± 1.0 4.0 ± 0.4 [14]
Ta 0.8 17.6 13.2 11.2 ± 1.5 6.0 ± 0.8
1.5 21.1 19.6 8.9 ± 1.0 5.3 ± 0.6 presentwork
4.6 24.5 48.0 8.5 ± 1.0 5.2 ± 0.6
Pb 1.2 21.9 15.7 11.2± 1.5 5.5 ± 0.5
4.0 27.6 38.8 8.9 ± 1.0 5.2+0.5 present work

124
Step height measurements:

The swelling effect was studied using a profilometer (Dektak 8000) where a high precision
stage moves the sample beneath a diamond-tipped stylus. The out-of-plane swelling 1 was
measured by scanning over the border line between an irradiated and a virgin area of the sample
surface (Fig. 1). Depending on the ion fluence, the electronic energy loss and the total range of the
ions, 1 varied between 20 and 300 nm. The surface roughness of the crystals was in the order of 5
nm. For each sample, a mean step height was extracted from several measurements.
The evolution of the step height as a function of the ion fluence is presented in Figure 2. After
an initial linear increase, the swelling saturates at high ion fluences where the ion tracks begin to
overlap. This saturation effect was observed only when a sufficiently high fluence was obtained
such as in the case of Ta ions (2x10' 2 cm-2) and F ions (1X10 14 cm- 2). For all other ion species,
the swelling effect was restricted to the linear regime.

0.20 i i i i 0.15 1 I i I
0.15
=L . 0.10
S0.10
0.05
S0.05
0.00 0.00 I I I
0 100 200 300 400 500 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
2
scan [gtm] fluence [1012 ions/cm ]
Fig. 1. Profilometer scan from the irradiated Fig. 2. Step height as a function of the fluence
(4.6 X10 13 F-ions/cm 2 ) (left) to the virgin of the Ta ions (0.8 MeV/u).
(right) area of the crystal.

Damage analysis by Channelling Rutherford Backscattering

The radiation damage of the irradiated crystals was analysed by means of Rutherford
backscattering under channelling condition (RBS-C). The experiments were performed at the
4 MV Van de Graaff accelerator (Strasbourg) using 2 MeV He+ ions and a backscattering angle
of 170%. Figure 3 shows a typical RBS-C spectrum of a non-irradiated (curve a) and an irradiated
area (curve b) of a Si0 2 quartz sample in channelling condition along the (0001) direction. Due to
the damage induced by the ions, the backscattering yield increases, but is still below the yield of a
randomly oriented crystal (curve c).
Using the surface approximation, the backscattering yield X was measured by extrapolating the
energy evolution of the yield over the first 500 nm up to the mean energy of the random edge.
The damage fraction Fd of the material is given by
Fd = (Xi -Xv) / (Xr - Xv), (1)
where Xi and Xv are the backscattering yield under channelling condition of the irradiated and of
the virgin sample, respectively, and Xr corresponds to the yield of the randomly-oriented crystal.

125
 I I I I I I I
400 0.3 Kr
c
+ 300 - 0.2 Xe
0 -
200" b
S0.1
100 Cu-
0 0a0. 1
200 400 600 800 0.0 0.1 0.2 0.3 0.4
channel damage fraction
Fig. 3. RBS spectra of backscattered He ions Fig. 4. Swelling versus damage fraction for
on Si0 2 quartz in channelling conditions (0001): Cu, Xe, and Kr ions with a total range of 8.7,
(a) virgin sample (b) sample irradiated with 14.7 and 27.7 gm, respectively.
Pb ions (2.3 1011 cm-2 at 1.2 MeV/u)
(c) virgin sample in random orientation.
Assuming that at higher ion fluences 0, the overlapping of tracks leads to a damage distribution
which can be described by a Poisson law
Fd = 1 - exp (- Ad X 0) (2)
we can deduce the mean cross section Ad of the damage. Since the damage zone along each ion
trajectory has a cylindrical geometry, the track radius R can be determined from Ad = it R2 .
RBS-C data analysed accordingly are listed in Table 1. The track radii of Ta and Pb ions at
different energies exhibit a maximum variation of the radius of around 15% for the studied
energy regime from 0.8 to 4.6 MeV/u and 1.25 to 4.0 MeV/u, respectively. This observation
supports the assumption that, in our situation, the track radius can be regarded as almost constant
along the full length of the ion path.

DATA ANALYSIS AND DISCUSSION:

Combining the data from the swelling and the RBS-C measurements, it becomes evident that
the step height has a linear dependence on the damage fraction Fd. Figure 4 demonstrates this
relation for the irradiation with Cu, Xe and Kr ions. Moreover, the slope of the curve becomes
steeper for larger range of the ions. The same observation has been made in LiNbO 3 [9,10]. In
order to compare quantitatively our results to the effects observed in LiNbO 3 , the step height 1
was normalised by the damage fraction Fd and then plotted versus the total range L of the ions
(Fig. 5). Although the data exhibit some scattering, in particular for the lighter ions in quartz, both
materials follow a linear dependence. The line fit intercepts the range axis at Lo=5 gtm (Fig. 5)
indicating that the damage responsible for swelling is not produced along the full range of the ion
path. The slope of the curve has a value of about 0.04 and corresponds to the relative dimensional
change l/L. Using this presentation, it is surprising to note that Si0 2 and LiNbO 3 show
qualitatively and quantitatively the same dimensional change.
In our experimental set-up, the free expansion of the irradiated volume is limited by the
constraint of the undamaged substrate. Therefore, the induced swelling occurs mainly normal to
the sample surface and corresponds to a relative decrease of the mass density. The density

126
decrease can be understood on the basis of the finding that tracks in quartz consist of amorphised
regions [14]. As a consequence of the transition from the crystalline to the amorphous phase,
each individual track undergoes a volume expansion finally leading to a macroscopic out-of-plane
swelling.
In order to test the correlation between swelling and the energy loss of the ions, we determined
the relative contribution of each single ion per unit damage length. This was done by dividing the
initial rate of swelling (Al / Aý) by the projected ion range L and plotting it versus the mean
energy loss. Since the ions were stopped in the crystals, we used the energy loss averaged along
the ion path obtained from dividing the initial energy by the total range of the ions. If we fit the
experimental data by a linear curve, a threshold for the energy loss of (dE/dx)c = 1.8±0.5 keV/nm
was found. The given error includes considerations that the critical energy loss is not surpassed
along the full length of the ion path. In the case of the light ions (F, S, and Cu), we took this part
of the trajectory into account as possibly not contributing to the swelling. It should be noted that
the threshold of swelling is in good agreement with the value determined from the RBS-C
analysis of the damage induced with low-velocity ions [14].
,-,
16
1.6 I1 I i1 i12. . - 2.5 i i , /•
* LiNbO3 0 _
=L 1.2- 0 SiO2 02.0

S- 9 - "" 1.5
0.8 9 1.5
1.0
" 0.4 0
0 o0 0.5
o.o F - I I I 1 1 0.0
0 10 20 30 40 50 0 5 10 15 20 25
range [jim] mean dE/dx (keV/nm)
Fig. 5. Step height normalised by the damage Fig. 6. The initial swelling (A1/AO) normalised
fraction Fd as a function of the ion range for by the ion range L versus the mean energy loss
Si0 2 in quartz and LiNbO 3 [11]. dE/dx in Si0 2 quartz.

CONCLUSIONS

Swelling effects have been found when irradiating Si0 2 quartz with various heavy ions in the
electronic energy loss regime. For high fluences when track overlapping becomes significant, the
step heights show saturation effects. The out-of-plane swelling depends both on the induced
damage fraction and on the range of the ions. From a detailed analysis of the swelling data, a
critical energy loss of 1.8±0.5 keV/nm was extracted. Below this value, the damage along the ion
path does not contribute to the expansion of the sample dimension. The observed macroscopic
swelling can be interpreted in terms of a decrease of the mass density of around 4%. This is
supported by the finding that energetic ions induce amorphisation along their trajectories [14]. The
quantitative analysis of swelling and damage creation gives evidence that both oxides, Si0 2 quartz
and LiNbO 3 undergo similar structural modifications under heavy ion irradiation.

127
REFERENCES:

1. R. Balzer, H. Peisl and W. Waidelich, Phys. Stat. Sol. 15, p. 495 (1966).
2. F. Agullo-Lopez, C.A.R. Catlow and P. D. Townsend, in Point defects in Materials,
Academic Press , pp. 149 (1988).
3. L. Douillard and J. P. Duraud, J. Phys. III France 6, p. 1677 (1996).
4. S.L. Chan, L.F. Gladden and S.R. Elliott, in The Physics and Technology of Amorphous
Si_9, edited by R.A.B. Devine, Plenum Press, pp. 83 (1987).
5. F.W. Clinard (Guest Editor) MRS Bulletin 22, N°4 (1997).
6. D.S. Bilington and J.H. Crawford, in Radiation Damage in Solids, Princeton University
Press, Princeton (1961).
7. L. Douillard, F. Jollet, J.P. Duraud, R.A.B. Devine and E. Dooryhee, Rad. Eff. Def. Sol.
124, p. 351 (1992).
8. W. Primak, Phys. Rev. B 14, p. 46 79 (1976).
9. R.Brenier, B. Canut, S.M.M.Ramos and P. Thdvenard, Nucl. Instr. Meth. Phys. Res. B 90,
p. 339 (1994).
10. B. Canut, R. Brenier, A. Meftah, P. Moretti, S. Ould Salem, S.M.M. Ramos, P. Th6venard
and M. Toulemonde, Nucl. Instr. Meth. Phys. Res. B 91, p. 312 (1994)
11. B. Canut, S.M.M. Ramos, R. Brenier, P. Th6venard, J.L. Loubet and M. Toulemonde,
Nucl. Instr. Meth. Phys. Res. B 107, p. 194 (1996).
12. S.M.M. Ramos, B. Canut, M. Ambri, C. Clement, E. Dooryhee, M. Pitival, P. Th6venard
and M. Toulemonde, Nucl. Instr. Meth. Phys. Res. B 107, p. 254 (1996).
13. R.L. Fleischer, P.B. Price and R.M. Walker, Nuclear Tracks in Solids: Principles and
Applications, University of California, Berkeley, (1975).
14. A. Meftah, F. Brisard, J.M. Costantini, E. Dooryhee, M. Hage-Ali, M. Hervieu,
J.P. Stoquert, F. Studer and M. Toulemonde, Phys. Rev. B 49, p. 12457 (1994).
15. M. Toulemonde, J.M. Costantini, Ch. Dufour, A. Meftah, E. Paumier, and F. Studer, Nucl.
Instr. Meth. Phys. Res. B 116, p. 37 (1996).
16. A. Meftah, F. Brisard, J.M. Costantini, M. Hage-Ali, J.P. Stoquert, F. Studer and
M. Toulemonde, Phys. Rev. B 48, p. 920 (1993).
17. J.P. Biersack and L.G. Haggmark, Nucl. Instr. Meth. 174, p. 257 (1980).

128