Appl Phys A (2009) 95: 453–456
DOI 10.1007/s00339-008-4905-4
Atypical behaviour of the surface hardness and the elastic
modulus of a phosphate glass matrix under 193 nm laser
irradiation
Irini Michelakaki · Stavros Pissadakis
Received: 10 June 2008 / Accepted: 8 September 2008 / Published online: 2 October 2008
© Springer-Verlag 2008
Abstract The effect of 193 nm excimer laser radiation on
the Knoop hardness and the elastic modulus of an ultra-
phosphate glass is presented here. The experimental results
reveal that the glass matrix undergoes a significant soften-
ing and volume dilation process for highly accumulated en-
ergy doses, where the Knoop hardness reduces by more than
15%, while following a single photon absorption rule. Fur-
ther, during the early stages of the exposure a slight harden-
ing process is observed. Finally, the elastic modulus is cor-
related with respect to the measured Knoop hardness.
PACS 61.80.Ba · 61.82.Ms · 62.20.de · 62.20.mj ·
42.70.Ce
Recently, there has been a significant interest in the pho-
tosensitivity of phosphate glass matrices using high inten-
sity, ultraviolet laser radiation. Phosphate glasses are con-
sidered as promising host matrices for the development of
high output, active waveguide and fibre devices, due to their
great rare earth solubility without sacrificing emission life-
time [1–3]. However, the photosensitivity of those glasses
has been only recently investigated using ultraviolet [4] and
infrared [5] laser sources. These studies included the inves-
tigation of the photosensitivity of fluorophosphate [6], ultra-
phosphate [4] and ion-sensitised [7] matrices, by employ-
ing a variety of diagnostics for gaining insight into specific
physical mechanisms and structural modifications. We have
I. Michelakaki · S. Pissadakis ()
Institute of Electronic Structure and Laser, Foundation for
Research and Technology-Hellas, Vasilika Vouton, P.O. Box
1527, Heraklion 71 110, Greece
e-mail: pissas@iesl.forth.gr
Fax: +30-2810-391318
demonstrated in the past the photosensitivity of an Er/Yb co-
doped phosphate glass using 248 nm excimer [4] and more
recently using 213 nm Nd:YAG laser radiation [8], while
other researchers have extended the investigations using
193 nm laser radiation [9, 10]. The above studies were fo-
cused on the refractive index dynamics and changes, which
in turn were attributed to mainly two underlying physical
mechanisms: those of colour centres absorption bands and
volume modification effects.
Herein, we present a photosensitivity study of a hybrid
phosphate glass using 193 nm, 10 ns laser radiation, where
we focus on the modification of the mechanical and struc-
tural properties induced in the matrix. Our study will address
the radiation induced changes of the surface hardness of the
glass, and it will be expanded to the investigation of the ef-
fect of accumulated radiation damage in the elastic modulus
of the material. The changes in these mechanical properties
will be monitored by measuring the Knoop hardness (HK)
of the exposed glass. Similar studies have been recently pre-
sented for fused silica [11] and in the past for other silicate
glasses [12], under infrared femtosecond irradiation, where
the effect of matrix compaction was quantified. The phos-
phate glass exposed is the alumino-ultra-phosphate IOG1,
fabricated by Schott USA and co-doped with Er and Yb.
The IOG1 glass is optimised for being ion-exchangeable us-
ing K+ and Ag+ ions, for developing low loss, high power
lasers and amplifiers. The magnitude and the evolution of
the Knoop hardness and elastic modulus changes presented,
herein, can provide a useful basis for a deeper insight into
the photosensitivity of phosphate glass matrices, by means
of underlying physical processes involved, as well as of re-
fractive index changes and structural modifications induced
after large irradiation doses.
The exposures were performed using a TUI 193 nm ex-
cimer laser emitting at 50 Hz, 10 ns, 9 mJ pulses. Exposures
454
Fig. 1 SEM picture of indentation embossed in an IOG1 glass sample
exposed using 188 mJ/cm2 energy density and 108000 pulses (50 gf
load, 20 s)
of circular spot areas greater than 1.8 mm2 were performed,
for allowing an easy accommodation of the indentation mea-
surements and avoiding indentations close to the edges of
the beam spot. The glass samples exposed had a thickness of
1 mm and contained 2.3% wt. Er2 O3 and 3.6% wt. Yb2 O3 .
The exposure to 193 nm excimer laser radiation resulted in
significant photodarkening of the glass, which extended into
a depth of several tens of microns below the sample sur-
face. The Knoop hardness measurements were preformed
using a Matsuzawa, MXT70, digital micro-hardness inden-
tation microscope, and applying a 50 gf load for 20 s inden-
tation time. Under these micro-indentation conditions the
HK of the pristine glass was measured to be ≈380; a figure
which is in agreement with the data provided by the manu-
facturer [13]. Heavier loads of 200 gf were applied for esti-
mating the bulk modulus of the glass; however, such loads
led to spontaneous crack generation, observed for a signifi-
cant number of the samples received. For reducing statistical
errors more than 15 indentations were applied on each sam-
ple examined. The main experimental errors apply in our
measurements are related to the homogeneity of the glass
and the beam profile of the laser spot. The average indenta-
tion spot for the 50 gf load applied had typical dimensions
of ≈41 × 6 µm (see Fig. 1), as measured by both optical
and scanning electron microscopy (SEM). The depth of in-
dentation was no greater than 1.6 µm for the softer sam-
ple examined, under 50 gf load. Also, micro-Raman spectral
measurements were performed close to or inside the inden-
tation prints, for investigating structural changes induced in
the glass.
The dependence of Knoop hardness on the energy den-
sity, the number of pulses and accumulated energy density
of the laser exposure is presented in Fig. 2a, 2b and 2c. As
I. Michelakaki, S. Pissadakis
Fig. 2 Knoop hardness versus (a) energy density, (b) number of
pulses, (c) accumulated energy density of IOG1 glass exposed using
193 nm, 10 ns excimer laser radiation
it is shown in Fig. 2, the behaviour of the Knoop hardness is
characterised by two regimes:
1. In the early regime the HK of the glass matrix rapidly
increases by a factor of 5% reaching a maximum point,
whereas for prolonged exposures or higher energy den-
sities the surface hardness undergoes a substantial de-
crease, reaching HK values of the order of 330.
2. The last regime is characterised by a linear trend, with-
out reaching saturation for the experimental conditions
applied, indicating that the underlying structural trans-
formation mechanism is not supported by a single type
of defect.
By fitting the HK data of Fig. 2c that exhibits values lower
than that of the pristine glass, to a simple power law NFb ,
a b factor of 0.96 is obtained, denoting a single photon ab-
sorption photosensitivity process.
The non-monotonic behaviour observed in the HK data
versus exposure conditions can be correlated with the
co-existence of a number of counteracting photosensitiv-
ity mechanisms, similar to Type IIA that is observed in
Atypical behaviour of the surface hardness and the elastic modulus of a phosphate glass matrix
Fig. 3 Elastic modulus versus energy density of IOG1 glass exposed
using 193 nm, 10 ns excimer laser radiation
highly doped germanosilicate optical fibres [14]. In gen-
eral, the photosensitivity of phosphate glasses using ul-
traviolet lasers has been associated with the PO4 unit re-
organisation, and specifically the PO bond cleaving which
primarily leads to the creation of strong absorption bands
at the visible and near-ultraviolet wavelengths. However,
prolonged exposures under high energy densities can fur-
ther promote the PO bond cleaving and the glass de-
polymerisation, by breaking the long phosphate network
chains [9]. The photon with a wavelength of 193 nm has
energy greater than the band gap of the material, therefore,
no specific phosphorus-oxygen or glass modifier related de-
fect is preferentially exhausted; but rather the whole glass
network is photo-dissociated leading to significant spatial
re-arrangements [15]. In our case, 473 nm Ar-ion laser,
micro-Raman measurements shown a ≈4% broadening of
the two fundamental peaks located at 704 cm−1 (POP sym-
metric bond) and 1184 cm−1 (PO2 symmetric bond), com-
pared to that of the pristine glass; denoting the generation
of a broad band of defects. On the other hand, the initial
increase of the Knoop hardness may be associated with the
fast exhausting of a specific defect in the glass matrix or the
relaxation of strain due to the casting method followed. For
the former assertion, the responsible effect could be a non-
bridging oxygen-type defect [6, 15], while for the latter, the
possibility of relaxing structural surface singularities might
be the case [16].
By adopting the approach of Marshall et al. [17], an es-
timation of the effect of the 193 nm irradiation on the elas-
tic modulus E of the exposed glass was carried out. Ad-
ditional indentations were performed by applying heavier
loads of 200 gf for imprinting larger dimension indentations
on the exposed glass samples which in turn allowed con-
sistent measurement of the small diagonal of the diamond-
shape imprint. The variations of the elastic modulus versus
the energy density of the exposure are presented in Fig. 3.
Using the approach of Marshall et al., the E value for the
pristine sample was estimated to be 76.9 GPa for a slope fac-
tor α = 0.45 [17]; figure significantly higher than the value
455
Fig. 4 Elastic modulus versus Knoop hardness of IOG1 glass samples
exposed using 193 nm, 10 ns excimer laser radiation. The 200 gf, in-
dentations leaded to a Knoop hardness figure of 351 for the pristine
glass
provided by the manufacturer (61.23 GPa) [13]. Therefore,
the elastic modulus data provided here are rather suitable
for extracting comparative trends and not absolute values.
The modulus data E follow the same declining trend for
increasing energy densities, confirming the occurrence of a
glass softening and volume dilation process in the exposed
glass [9], contrary to that observed for the case of the pris-
tine silicate glass matrix under high intensities or radiation
dose exposure conditions [11, 18]. An exception to the com-
monly observed compaction model has been presented for
the case of hydrogen loaded silica, where the exposure to
248 nm radiation induced a volume expansion, possibly cor-
related with the presence of a strong photorefractive stress
component emerging from the SiH and SiOH species [19].
A similar effect may also contribute in the volume expan-
sion behaviour observed herein. The extensive formation of
strong absorption bands in the glass associated with the gen-
eration of hole and electron centre defects by the 193 nm ra-
diation might induce similar charge migration and trapping
photorefractive effects resulting in macroscopic volume ex-
pansion.
The heavier load micro-indentations revealed more in-
teresting findings related to the structural changes induced
by the 193 nm radiation into the glass matrix. While pris-
tine glasses suffered crack propagation along the long di-
agonal at a rate of 40–50% approximately, the indentations
imprinted on the highly exposed glasses exhibited a substan-
tially lower crack generation percentage, which reached fig-
ures of the order of 10% for samples exposed to 188 mJ/cm2
energy densities. On the other hand, the indentations per-
formed in “hardened” samples exposed using low energy
density of 17 mJ/cm2 exhibited rapid crack propagation at
a rate of ≈90%, rendering the specific measurement incon-
sistent. In other words, the exposed glass exhibited different
fracture toughness under different exposure conditions [20],
while further, the elastic modulus figure followed a linear
type correlation with the Knoop hardness data measured
456
(see Fig. 4). Therefore, one may assume a rough trend re-
lated to the elastic modulus of the exposed glass by inter-
preting the HK measured changes.
Summarising, the Knoop hardness and the elastic mod-
ulus of the commercial Schott IOG1 phosphate glass were
measured after exposure to nanosecond 193 nm excimer
laser radiation. Significant and non-monotonic reduction of
the Knoop hardness was observed, which indicated glass
softening and volume dilation effects due to the laser irra-
diation processing. That glass softening process was further
supported by the Young modulus measurements, which in
turn followed a clear reduction trend. Similar results on the
HK behaviour after exposure to 248 nm, femtosecond laser
radiation, as well as an extended study on the photosensitiv-
ity of the above glass will be presented elsewhere [21].
Acknowledgements S.P. gratefully acknowledges Leo Gilroy
(Schott, USA) for kindly providing the glass samples, as well as Vicky
Vamvakaki and Nikos Chaniotakis (Laboratory of Analytical Chem-
istry, Chemistry Department, University of Crete) for performing the
micro-Raman measurements.
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